Method for manufacturing a laminate, method for manufacturing a circuit wiring substrate, transfer film

Abstract

The present application provides a method for manufacturing a laminate, which can inhibit excessive adhesion of a photosensitive layer after exposure to a photomask, and which also has excellent resolution of a pattern formed from the photosensitive layer. The method for manufacturing a laminate of the present application includes: a step of adhering a transfer film having a temporary support, an intermediate layer, and a photosensitive layer to a substrate, in a manner in which the surface of the photosensitive layer on the side opposite the intermediate layer of the above-described transfer film is in contact with the substrate; a step of peeling the temporary support from between the temporary support and the intermediate layer; and a step of performing an exposure process by bringing the exposed intermediate layer into contact with a mask, and further performing a development process after exposure to form a pattern, the surface free energy of the surface of the intermediate layer on the side of the temporary support being 68.0 mJ / m 2 The following.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a laminate, a method for manufacturing a circuit wiring substrate, and a transfer film. Background Technology

[0002] Because the number of steps required to obtain a given pattern is small, pattern forming methods using transfer films are widely used. Specifically, a method involves depositing 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.

[0003] For example, Patent Document 1 discloses "a method for exposing a photosensitive composition layer, characterized in that a photosensitive resin laminate having a support (A), a negative photosensitive composition layer (B) with a thickness of 1 to 35 μm and a protective layer (C) is laminated on the metal-coated surface of a metal-coated insulating plate having a metal conductor layer on one or both sides, so that the negative photosensitive composition layer (B) and the metal-coated surface of the metal-coated insulating plate are closely adhered, and when exposing ultraviolet light through a transmission photomask, the support is peeled off before exposure, and the image of the photomask is projected through a transmission lens."

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 4477077 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] Based on research conducted with reference to the exposure method described in Patent Document 1, which involves peeling off a support (temporary support) before exposure and then exposing the photomask to the exposed photosensitive composition layer (photosensitive layer), it was found that when peeling off the photomask after exposure, the photosensitive layer and the photomask sometimes adhere excessively and are difficult to peel off. Poor peelability between the exposed photosensitive layer and the photomask can lead to problems such as reduced operability due to difficulty in peeling and mask contamination caused by the adhesion of the photosensitive layer forming material. Therefore, it was found that there is a need to suppress excessive adhesion between the exposed photosensitive layer and the photomask.

[0009] On the other hand, when exposure is performed by placing the photomask in contact with the temporary support without peeling it off in order to suppress excessive adhesion between the photosensitive layer and the photomask, the presence of the temporary support causes the exposure light source to be far from the photosensitive layer. Therefore, the following problem may occur: in areas corresponding to the recesses of the pattern (e.g., in the case of a negative photosensitive layer, areas corresponding to the non-exposed areas), it is difficult to form fine patterns that suppress residue (in other words, resolution tends to deteriorate). Therefore, in research on methods to suppress excessive adhesion between the photosensitive layer and the photomask after exposure, it is necessary to ensure excellent resolution.

[0010] Therefore, the objective of this invention is to provide a method for manufacturing a laminate that can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and also has excellent resolution of the pattern formed by the photosensitive layer.

[0011] Furthermore, the present invention also aims to provide a method for manufacturing a circuit wiring board.

[0012] Furthermore, the present invention also aims to provide a transfer film suitable for an exposure method after the temporary support has been peeled off, which can suppress excessive adhesion between the photosensitive layer and the photomask after exposure and also has excellent resolution.

[0013] means for solving technical problems

[0014] The inventors have discovered that the above-mentioned problems can be solved by the following configuration.

[0015] [1] A method for manufacturing a laminate, comprising:

[0016] The process of bonding the transfer film to the substrate by contacting the surface of the photosensitive layer of the transfer film, which has a temporary support, an intermediate layer and a photosensitive layer, opposite to the intermediate layer side, with the substrate.

[0017] The process of peeling off the temporary support between the temporary support and the intermediate layer;

[0018] The process involves exposing the exposed intermediate layer to a mask for exposure, followed by a development process to form a pattern.

[0019] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2 the following.

[0020] [2] According to the manufacturing method of the laminated body described in [1], wherein,

[0021] The arithmetic mean roughness Ra of the surface of the temporary support side of the aforementioned intermediate layer is less than 50 nm.

[0022] [3] The method for manufacturing the laminated body according to [1] or [2], wherein,

[0023] The surface free energy of the intermediate layer side of the aforementioned temporary support is 25.0–50.0 mJ / m. 2 .

[0024] [4] A method for manufacturing a laminate according to any one of [1] to [3], wherein,

[0025] The aforementioned intermediate layer contains polyvinyl alcohol.

[0026] [5] According to the method for manufacturing the laminated body described in [4], wherein,

[0027] The content of polyvinyl alcohol mentioned above is 5-95% by mass relative to the total mass of the intermediate layer.

[0028] [6] A method for manufacturing a laminate according to any one of [1] to [5], wherein,

[0029] The aforementioned intermediate layer also contains polyvinylpyrrolidone.

[0030] [7] A method for manufacturing a laminate according to any one of [1] to [6], wherein,

[0031] The aforementioned intermediate layer also contains one or more compounds X selected from water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerol.

[0032] [8] The method for manufacturing the laminated body according to [7], wherein,

[0033] The content of compound X is 0.1% by mass or more and less than 30% by mass relative to the total mass of the intermediate layer.

[0034] [9] The method for manufacturing a laminate according to [7] or [8], wherein,

[0035] The above compound X contains hydroxypropyl methylcellulose.

[0036]

[10] A method for manufacturing a laminate according to any one of [1] to [9], wherein,

[0037] The thickness of the aforementioned intermediate layer is less than 3.0 μm.

[0038]

[11] A method for manufacturing a laminate according to any one of [1] to

[10] , wherein,

[0039] The thickness of the aforementioned photosensitive layer is 2.0–20 μm.

[0040]

[12] A method for manufacturing a circuit wiring substrate, comprising a method for manufacturing a laminate as described in any one of [1] to

[11] , the method for manufacturing the circuit wiring substrate comprising:

[0041] The process of forming a seed layer on a substrate to form a substrate with a seed layer;

[0042] The process involves bonding the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer, to the substrate with a seed layer by contacting the surface of the photosensitive layer opposite to the intermediate layer side of the transfer film with the seed layer, thereby obtaining a substrate having the substrate, the seed layer, the photosensitive layer, the intermediate layer, and the temporary support in sequence.

[0043] The process of peeling off the temporary support between the temporary support and the intermediate layer;

[0044] The process of exposing the aforementioned intermediate layer to a mask for exposure, and then performing a development process after exposure to form a pattern;

[0045] A process of forming a metal plating layer on the seed layer in the area where the above pattern is not configured;

[0046] The process of forming a protective layer on the aforementioned metal plating;

[0047] The process of removing the above pattern; and

[0048] The process of removing the exposed seed layer to obtain conductive fine wires.

[0049] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2 the following.

[0050]

[13] A transfer film having a temporary support, an intermediate layer and a photosensitive layer,

[0051] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2 the following,

[0052] The arithmetic mean roughness Ra of the surface of the temporary support side of the aforementioned intermediate layer is less than 50 nm.

[0053]

[14] According to the transfer film described in

[13] , wherein,

[0054] The surface free energy of the intermediate layer side of the aforementioned temporary support is 25.0–50.0 mJ / m. 2 .

[0055]

[15] The transfer film according to

[13] or

[14] , wherein,

[0056] The aforementioned intermediate layer contains polyvinyl alcohol.

[0057]

[16] According to the transfer film described in

[15] , wherein,

[0058] The content of polyvinyl alcohol mentioned above is 5-95% by mass relative to the total mass of the intermediate layer.

[0059]

[17] The transfer film according to any one of

[13] to

[16] , wherein,

[0060] The aforementioned intermediate layer also contains polyvinylpyrrolidone.

[0061]

[18] The transfer film according to any one of

[13] to

[17] , wherein,

[0062] The aforementioned intermediate layer contains one or more compounds X selected from water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerol.

[0063]

[19] According to the transfer film described in

[18] , wherein,

[0064] The content of compound X is 0.1% by mass or more and less than 30% by mass relative to the total mass of the intermediate layer.

[0065]

[20] According to the transfer film described in

[18] or

[19] , wherein,

[0066] The above compound X contains hydroxypropyl methylcellulose.

[0067]

[21] The transfer film according to any one of

[13] to

[20] , wherein,

[0068] The thickness of the aforementioned intermediate layer is less than 3.0 μm.

[0069]

[22] The transfer film according to any one of

[13] to

[21] , wherein,

[0070] The thickness of the aforementioned photosensitive layer is 2.0–20 μm.

[0071] Invention Effects

[0072] According to the present invention, a method for manufacturing a laminate capable of suppressing excessive adhesion between the photosensitive layer and the photomask after exposure, and capable of forming a pattern with excellent resolution formed by the photosensitive layer.

[0073] Furthermore, according to the present invention, a method for manufacturing a circuit wiring board can also be provided.

[0074] Furthermore, the present invention can also provide a transfer film suitable for an exposure method after the temporary support is peeled off, which can suppress excessive adhesion between the photosensitive layer and the photomask after exposure and can form a transfer film with excellent resolution patterns. Attached Figure Description

[0075] Figure 1 This is a schematic diagram illustrating an example of transfer film X1.

[0076] Figure 2 This is a schematic diagram illustrating an example of transfer film X2. Detailed Implementation

[0077] The present invention will now be described in detail.

[0078] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0079] In the numerical ranges described in this specification, the upper or lower limit value recorded within a certain numerical range can be replaced with the upper or lower limit value of other numerical ranges described in different stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value recorded within a certain numerical range can be replaced with the value shown in the embodiments.

[0080] In this specification, the term "process" refers not only to an independent process, but also to a process that performs its intended purpose even when it cannot be clearly distinguished from other processes.

[0081] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400-700nm is 80% or more, preferably 90% or more.

[0082] In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0083] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​converted using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all product names manufactured by TOSOHCORPORATION) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance, and using polystyrene as the standard substance measured by a gel permeation chromatography (GPC) analyzer.

[0084] Furthermore, unless otherwise specified in this specification, the molecular weight of the compounds with the molecular weight distribution is the weight-average molecular weight (Mw).

[0085] Unless otherwise specified, the content of metal elements in this specification refers to the values ​​measured using an inductively coupled plasma (ICP) spectrometer.

[0086] Unless otherwise specified, the refractive index in this specification is the value measured using an ellipsometer at a wavelength of 550 nm.

[0087] Unless otherwise specified, the hue in this manual refers to the value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0088] In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, "(meth)acryloyloxy" is a concept that includes both acryloyloxy and methacryloyloxy, "(meth)acrylamide" is a concept that includes both acrylamide and methacrylamide, and "(meth)acrylate" is a concept that includes both acrylate and methacrylate.

[0089] Furthermore, in this specification, "alkali-soluble" means having a solubility of 0.1g or more relative to 100g of a 1% sodium carbonate aqueous solution at a liquid temperature of 22°C. Therefore, for example, an alkali-soluble resin refers to a resin that meets the above solubility condition.

[0090] In this specification, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C. Therefore, for example, a water-soluble resin refers to a resin that meets the above solubility condition.

[0091] In this specification, "solid component" refers to the component that forms the composition layer formed using the composition. In the case where the composition contains a solvent (organic solvent, water, etc.), it refers to all components except for those containing the solvent. Furthermore, if it is a component that forms the composition layer, liquid components are also considered solid components.

[0092] [Manufacturing method of laminated bodies]

[0093] The method for manufacturing the laminate of the present invention includes:

[0094] The process of bonding the transfer film to the substrate by contacting the surface of the photosensitive layer of the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer, opposite to the intermediate layer side, with the substrate (hereinafter also referred to as the "transfer film bonding process").

[0095] The process of peeling off the temporary support between the temporary support and the intermediate layer (hereinafter also referred to as the "temporary support peeling process");

[0096] The process of exposing the aforementioned intermediate layer to a mask for exposure, followed by development after exposure to form a pattern (hereinafter also referred to as the "pattern forming process"),

[0097] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2 the following.

[0098] A key feature of the method for manufacturing the laminate of the present invention is the provision of an intermediate layer between a temporary support and a photosensitive layer, and the setting of the surface free energy of the temporary support side of the intermediate layer to a value below a predetermined range. According to the method for manufacturing the laminate of the present invention, excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed, and excellent resolution is also achieved.

[0099] Although the mechanism by which the manufacturing method of the laminate of the present invention achieves the desired effect is not yet clear, the inventors speculate that it is as follows.

[0100] First, the method for manufacturing the laminate of the present invention provides an intermediate layer between the temporary support and the photosensitive layer. Therefore, in the pattern forming process after the temporary support peeling process, the mask and the photosensitive layer do not directly contact each other due to the presence of the intermediate layer. As a result, excessive adhesion between the exposed photosensitive layer and the mask is suppressed.

[0101] Further research by the inventors on the aforementioned intermediate layer revealed the following problem: the surface free energy on the temporary support side of the intermediate layer exceeds 68.0 mJ / m. 2 In certain situations, during the temporary support peeling process, the interface between the intermediate layer and the temporary support becomes difficult to peel off. Furthermore, the photosensitive layer is partially exposed without peeling off the interface between the intermediate layer and the temporary support, and / or the surface of the intermediate layer becomes rough after peeling off the temporary support (the arithmetic mean roughness Ra of the intermediate layer surface increases). Specifically, it is clarified that when a portion of the photosensitive layer is exposed without peeling off the interface between the intermediate layer and the temporary support, excessive adhesion occurs between the exposed photosensitive layer and the mask, and the exposed mask is difficult to peel off. Moreover, it is clarified that even when exposure and development are performed after peeling off the temporary support, the following situations exist: the exposure of the photosensitive layer and / or the roughening of the intermediate layer surface (the arithmetic mean roughness Ra of the intermediate layer surface increases) hinder uniform exposure, and it becomes difficult to form fine patterns of residue in areas that suppress pattern recesses.

[0102] Hereinafter, each step of the method for manufacturing the laminate of the present invention will be described in detail. Furthermore, the descriptions of the constituent elements described below are sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0103] Furthermore, the fine patterning that further suppresses excessive adhesion between the photosensitive layer and the photomask after exposure (hereinafter also referred to as "superior mask non-adhesion") and / or suppresses residue in areas of recesses capable of forming patterns (hereinafter also referred to as "superior resolution") is also referred to as "superior effect of the present invention".

[0104] [First Embodiment]

[0105] The first embodiment of the method for manufacturing a laminated body includes, in sequence, a transfer film bonding process, a temporary support peeling process, and a pattern forming process, as shown below.

[0106] Transfer film bonding process: A process of bonding the transfer film (hereinafter also referred to as "transfer film X") to the substrate by contacting the surface of the photosensitive layer opposite to the intermediate layer side (the surface opposite to the temporary support side of transfer film X) with the substrate.

[0107] Temporary support peeling process: The process of peeling the temporary support from the intermediate layer.

[0108] Pattern forming process: A process in which the exposed intermediate layer is brought into contact with a mask for exposure, and then further developed after exposure to form a pattern (hereinafter also referred to as the "pattern forming process").

[0109] Furthermore, in the aforementioned transfer film X, the surface free energy of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 the following.

[0110] Transfer film lamination process

[0111] <Transfer Film X>

[0112] The transfer film X will be explained later.

[0113] <Transfer film lamination process>

[0114] The transfer film bonding process involves bonding the transfer film (transfer film X), which has a temporary support, an intermediate layer, and a photosensitive layer, to the substrate by contacting the surface of the photosensitive layer opposite to the intermediate layer side with the substrate. Alternatively, if the transfer film X has a structure with a protective film, the bonding process is performed after the protective film is peeled off.

[0115] During bonding, the substrate is pressed together in such a way that it contacts the surface of the photosensitive layer opposite to the middle layer side of the transfer film X.

[0116] The above-described pressing method is not particularly limited, and known transfer and lamination methods can be used. Preferably, the surface opposite to the intermediate layer side of the photosensitive layer of the transfer film X is overlapped on the substrate, and pressure and heating are applied using rollers or the like.

[0117] Well-known laminators such as vacuum laminators and automatic cutting laminators can be used during lamination.

[0118] The lamination temperature is not particularly limited, but is preferably 70 to 130°C.

[0119] The preferred substrate is a conductive substrate having a support substrate and a conductive layer disposed on the support substrate. The conductive substrate may have any layer other than the conductive layer formed on the support substrate as needed. That is, the substrate is preferably a conductive substrate having at least a support substrate and a conductive layer disposed on the support substrate.

[0120] Examples of supporting substrates include resin substrates, glass substrates, and semiconductor substrates.

[0121] As a preferred method for supporting the substrate, for example, it is described in paragraph

[0140] of International Publication No. 2018 / 155193, and this content is incorporated herein by reference.

[0122] Furthermore, when the support substrate is a resin substrate, the material of the resin substrate is preferably a cyclic olefin polymer and a polyimide, and the thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0123] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer selected from metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers, and conductive polymer layers.

[0124] Furthermore, a single conductive layer or two or more layers can be disposed on the support substrate. When two or more conductive layers are disposed, conductive layers of different materials are preferred.

[0125] As a preferred embodiment of the conductive layer, for example, it is described in paragraph

[0141] of International Publication No. 2018 / 155193, and this content is incorporated herein by reference.

[0126] The conductive substrate is preferably a substrate having at least one of a transparent electrode and a circuitous wiring. This type of conductive substrate is preferably used as a substrate for touch panels.

[0127] Transparent electrodes are preferably designed to function as electrodes for touch panels. They are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as fine metal wires such as metal meshes and metal nanowires.

[0128] Examples of fine metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0129] Metal is the preferred material for circuit wiring.

[0130] Examples of metals suitable for use as materials for circuit routing include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metals. Copper, molybdenum, aluminum, or titanium are preferred materials for circuit routing, with copper being particularly preferred.

[0131] Furthermore, in the manufacturing method of the laminate of the present invention, when the photosensitive layer in the transfer film X functions as a protective film for the electrodes of the touch panel, in order to protect the electrodes (i.e., at least one of the electrodes for the touch panel and the wiring for the touch panel), it is preferable to provide the electrodes or the like by covering them directly or in between other layers.

[0132] Temporary support stripping process

[0133] The temporary support stripping process is the process of stripping the temporary support from the intermediate layer.

[0134] <Stripping Process>

[0135] The stripping process for temporary supports is not particularly limited and can be implemented based on known methods.

[0136] For example, the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

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

[0137] <Surface free energy of the temporary support side surface in the intermediate layer>

[0138] As described above, in the transfer film X, the surface free energy of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 the following.

[0139] The surface free energy (hereinafter also referred to as "surface free energy E") of the surface on the temporary support side of the intermediate layer. I "" refers to the surface free energy of the surface of the intermediate layer on the temporary support side exposed after the temporary support is peeled off during the temporary support peeling process (the surface exposed after the temporary support is peeled off in the intermediate layer).

[0140] As surface free energy E I The upper limit is 68.0 mJ / m 2 From the viewpoint of achieving better results with the present invention, 65.0 mJ / m is preferred. 2 The preferred value is 63.0 mJ / m 2 The following is a further preferred value: 60.0 mJ / m 2 The following is a lower limit value, for example, preferably 45.0 mJ / m. 2 The above, more preferably 50.0 mJ / m 2 The above is further preferred to be 55.0 mJ / m 2 above.

[0141] In this specification, the surface free energy E of the temporary support side of the intermediate layer is... I Calculated using the following method.

[0142] (Methods for measuring and calculating surface energy)

[0143] The surface energy is given by the contact angles θ of pure water (H₂O) and diiodomethane (CH₂I₂) measured using actual measurements. H2O and θ CH2I2 And it is obtained by the Owens equation shown below (simultaneous equations (A) and (B)). In addition, the support peeling method and the type of substrate are not particularly limited when measuring the following surface energies.

[0144] (Water contact angle (θ)) H2O ))

[0145] First, the water contact angle (θ) is measured using the following method. H2O ).

[0146] After the transfer film is laminated onto the substrate, the temporary support is peeled off.

[0147] Next, at a room temperature of 25°C and a relative humidity of 50%, 12 μL of pure water was dropped onto the surface of the temporary support side of the intermediate layer (the surface exposed after the temporary support was peeled off). After 20 seconds, the contact angle was measured using a CA-D type contact angle meter (Kyowa Interface Science Co., Ltd.). The above measurements were performed a total of 5 times.

[0148] Furthermore, the arithmetic mean of the three measurements after removing the maximum and minimum values ​​from the five measurements is set as the water contact angle (θ). H2O ).

[0149] (Contact angle of diiodomethane (θ)) CH2I2 ))

[0150] Next, the contact angle (θ) of diiodomethane was measured using the following method. CH2I2 ).

[0151] After the transfer film is laminated onto the substrate, the temporary support is peeled off.

[0152] Next, at a room temperature of 25°C and a relative humidity of 50%, 12 μL of diiodomethane (manufactured by FUJIFILM Wako Pure Chemical Corporation) was dropped onto the surface of the temporary support side of the intermediate layer (the surface exposed after peeling off the temporary support). After 20 seconds, the contact angle was measured using a CA-D type contact angle meter (Kyowa Interface Science Co., Ltd.). The above measurements were performed a total of 5 times.

[0153] Furthermore, the arithmetic mean of the three measurements after removing the maximum and minimum values ​​from the five measurements was set as the contact angle (θ) of diiodomethane. CH2I2 ).

[0154] (Calculation of surface energy based on Owens' formula)

[0155] θ measured by the above method H2O and θ CH2I2 Substituting the values ​​of and γ shown in Table 1 below into the simultaneous equations (A) and (B) shown below, we obtain “γs”. d +γs h The value of is defined as surface energy.

[0156] Additionally, in the table below, when L is H2O, for example, γ L d By γ H2O d This indicates that, in the case where L is CH2I2, for example, γ L d By γ CH2I2 d express.

[0157] [Table 1]

[0158] Table 1

[0159] <![CDATA[H2O]]> 21.8 51.0 72.8 <![CDATA[CH2I2]]> 49.5 1.3 50.8

[0160] [Simultaneous Equations]

[0161] (A):

[0162] 1+cosθ H2O =2√γ S d (√γ H2O d / γ H2O，V )+2√γ S h (√γ H2O h / γ H2O，V )

[0163] (B):

[0164] 1+cosθ CH2I2 =2√γ S d (√γ CH2I2 d / γ CH2I2，V )+2√γ S h (√γ CH2I2 h / γ CH2I2，V )

[0165] <Arithmetic mean roughness Ra of the surface on the side of the temporary support in the intermediate layer>

[0166] The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer refers to the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer exposed after the temporary support is peeled off during the temporary support peeling process (the surface exposed in the intermediate layer after the temporary support is peeled off).

[0167] From the viewpoint of maximizing the effectiveness of the present invention, the upper limit of the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less. Furthermore, as a lower limit, it is preferably 0 nm or more, more preferably 1 nm or more.

[0168] In this specification, the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is a value measured by the following method.

[0169] The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer was measured using the following method. A three-dimensional optical profilometer (New View 7300, manufactured by Zygo Corporation) was used to obtain the surface profile of the object under the following conditions. MetroPro ver8.3.2 Microscope Application was used as the measurement and analysis software. Next, the Surface Map screen was displayed using the aforementioned software, and histogram data was obtained from the Surface Map screen. The arithmetic mean roughness Ra of the surface of the object was obtained from the obtained histogram data.

[0170] <Thickness of the intermediate layer>

[0171] The thickness of the intermediate layer is not particularly limited, but from the viewpoint of achieving better results in this invention, it is preferably 10 μm or less, more preferably 5.0 μm or less, even more preferably 4.0 μm or less, and especially preferably 3.0 μm or less. Furthermore, from the viewpoint of achieving better oxygen permeability, it is preferably 50 nm or more, more preferably 100 nm or more, from the lower limit of the thickness.

[0172] The thickness of the intermediate layer was calculated as the average of any 5 points measured based on cross-sectional observations using SEM (Scanning Electron Microscope).

[0173] <Surface free energy of the intermediate layer side of the temporary support>

[0174] The surface free energy (hereinafter also referred to as "surface free energy E") of the intermediate layer side surface of the temporary support S "" refers to the surface free energy of the surface of the intermediate layer side of the temporary support exposed after the temporary support is peeled off during the temporary support peeling process (the surface exposed after separation from the intermediate layer in the temporary support).

[0175] As surface free energy E S The upper limit, for example, is preferably 60.0 mJ / m 2 The preferred value is 54.0 mJ / m 2 The following is a further preferred value: 50.0 mJ / m 2 The following is a lower limit value. Furthermore, a lower limit value is preferably, for example, 20.0 mJ / m. 2 From the viewpoint of achieving better results with the present invention, 25.0 mJ / m is more preferred. 2 above.

[0176] In this specification, the surface free energy E of the intermediate layer side surface of the temporary support is...S The surface free energy E of the temporary support side of the aforementioned intermediate layer. I The value was obtained using the same method.

[0177] In addition, as the surface free energy E I and surface free energy E S It is also preferable to satisfy the following relationships (1) and / or (2).

[0178] (1) Surface free energy E I (mJ / m 2 Surface free energy E S (mJ / m 2 )

[0179] (2) Surface free energy E I (mJ / m 2 ) and surface free energy E S (mJ / m 2 The difference is 3.0–40 mJ / m 2 (Preferred value: 3.0~30mJ / m) 2 ).

[0180] Pattern Formation Process

[0181] The pattern forming process involves exposing the intermediate layer to a mask and then developing it to form a pattern.

[0182] <Exposure Processing>

[0183] The exposure process is a process of pattern exposure of the photosensitive layer of the laminate relative to the intermediate layer exposed by peeling off the temporary support.

[0184] In addition, "pattern exposure" refers to exposure that results in a patterned shape, that is, exposure with both exposed and unexposed areas.

[0185] The positional relationship between the exposed and unexposed parts in pattern exposure is not particularly restricted and can be adjusted appropriately.

[0186] In the exposure process, an exposure process is performed on the intermediate layer exposed by peeling off the temporary support, by means of a mask having an opening at a specified position.

[0187] For example, when the photosensitive layer is a negative photosensitive layer, by performing the above-described exposure process, the curing reaction of the components contained in the photosensitive layer can occur in the exposed portion of the photosensitive layer (corresponding to the opening of the mask). After the exposure process, a development process (especially an alkaline development process) is performed to remove the non-exposed portion of the photosensitive layer and form a pattern.

[0188] Furthermore, when the photosensitive layer is a negative photosensitive layer, as a light source for pattern exposure, any light in the wavelength range obtained by curing the photosensitive layer (e.g., 365nm or 405nm) can be appropriately selected and used.

[0189] The dominant wavelength of the exposure light for pattern exposure is preferably 365nm. Furthermore, the dominant wavelength refers to the wavelength with the highest intensity.

[0190] As light sources, examples include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0191] The preferred exposure level is 5–200 mJ / cm. 2 More preferably 10–200 mJ / cm 2 .

[0192] Preferred methods for use as light sources, exposure amounts, and exposure methods for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and these contents are incorporated herein by reference.

[0193] In a first embodiment of the method for manufacturing a laminate, it is preferable to remove the mask (photomask) used in the exposure process after the exposure process and before the development process.

[0194] <Developing Process>

[0195] The development process is the process of developing a patterned photosensitive layer obtained through exposure treatment to form a pattern.

[0196] The development of the aforementioned photosensitive layer can be carried out using a developing solution. For example, when the photosensitive layer is a negative photosensitive layer, the non-exposed areas of the photosensitive layer are removed by developing it with an alkaline developing solution. As a result, a pattern with the opening of the mask as a raised portion can be formed.

[0197] In the developing process, an alkaline aqueous solution is preferred as the developing solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0198] Examples of development methods include, for instance, immersion development, spray development, rotational development, and soaking development.

[0199] As a preferred developer for use in this specification, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited. As a preferred development method, for example, the development method described in paragraph

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

[0200] Post-exposure and post-baking processes

[0201] The first embodiment of the method for manufacturing the laminate may include a step of exposing the pattern obtained by developing a process (post-exposure step) and / or a step of heating (post-baking step).

[0202] In cases where both a post-exposure process and a post-baking process are included, it is preferable to perform the post-baking process after the post-exposure process.

[0203] The preferred exposure amount for post-exposure is 100–5000 mJ / cm². 2 More preferably 200–3000 mJ / cm 2 .

[0204] The preferred temperature for post-baking is 80–250°C, and more preferably 90–160°C.

[0205] The preferred baking time is 1 to 180 minutes, more preferably 10 to 60 minutes.

[0206] The position and size of the pattern formed on the substrate through the above process are not particularly limited. Preferably, the pattern is in the form of fine lines, and its width is preferably 20 μm or less, more preferably 15 μm or less. In addition, as a lower limit, it is not particularly limited, for example, it is 1 μm or more, preferably 5 μm or more.

[0207] <Transfer Film X>

[0208] Next, the transfer film X will be explained.

[0209] As a transfer film X, it has a temporary support, an intermediate layer, and a photosensitive layer, and the surface free energy of the surface of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 The following transfer films are not particularly restricted and can use known transfer films.

[0210] The following describes the implementation method of transfer film X.

[0211] The structure of the transfer film X is not particularly limited; for example, the following structures can be cited.

[0212] (1) "Temporary support / intermediate layer / photosensitive layer / protective film"

[0213] (2) "Temporary support / intermediate layer / photosensitive layer / refractive index adjustment layer / protective film"

[0214] Furthermore, in the above structures, the photosensitive layer is preferably a negative photosensitive layer. Also, the photosensitive layer is preferably a colored resin layer.

[0215] Furthermore, in the above (1) transfer film X, the intermediate layer can be formed by two layers. Specifically, it has the structure of "temporary support / second intermediate layer / first intermediate layer / photosensitive layer / protective film".

[0216] Furthermore, the pattern obtained by the manufacturing method of the laminate of the present invention, as described later, can be applied to seed layer protection patterns in circuit wiring manufacturing methods and wiring protection film patterns in wiring protection film manufacturing methods. Therefore, the transfer film X can be a transfer film for etching resist or a transfer film for wiring protection film. In addition, when the transfer film X is a transfer film for etching resist, the structure of the transfer film X is preferably, for example, the structure described in (1) above. When the transfer film X is a transfer film for wiring protection film, the structure of the transfer film X is preferably, for example, the structure described in (1) or (2) above.

[0217] From the viewpoint of suppressing bubble generation in the lamination process of the above-described laminate manufacturing method, the maximum width of the ripples in the transfer film X is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. Furthermore, the lower limit of the maximum ripple width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

[0218] The maximum width of the corrugations on transfer film X is the value measured through the following process.

[0219] First, a test sample is prepared by cutting the transfer film X to a size of 20cm long × 20cm wide along a direction perpendicular to the main surface. If the transfer film X has a protective film, the protective film is peeled off. Next, the test sample is placed on a smooth, level worktable with the surface of the temporary support facing the worktable. After placement, a three-dimensional surface image is obtained by scanning the surface of the test sample within a 10cm square area from its center using a laser microscope (e.g., a VK-9700SP manufactured by KEYENCE CORPORATION). The maximum convex height observed in the obtained three-dimensional surface image is subtracted from the minimum concave height. This process is performed on 10 test samples, and the arithmetic mean is taken as the "maximum width of the corrugations of the transfer film X".

[0220] Below, we will first explain the intermediate layer and the temporary support, and then give an example of a specific implementation to explain the overall structure of the transfer film X.

[0221] Furthermore, the transfer film X1 of the first embodiment, which is described later as a specific embodiment of the transfer film X, can preferably be used in the structure of a transfer film for etching resist, and the transfer film X2 of the second embodiment can preferably be used in the structure of a transfer film for wiring protection film.

[0222] (Middle layer)

[0223] Regarding the intermediate layer of transfer film X, the surface free energy (surface free energy E) of the surface on the temporary support side is... I The value is 68.0 mJ / m 2 the following.

[0224] In addition, the surface free energy E I It refers to the surface free energy in the surface of the intermediate layer on the temporary support side exposed after the temporary support is peeled off from the transfer film X.

[0225] Regarding surface free energy E I The preferred method and measurement method are as described above.

[0226] Furthermore, from the viewpoint of achieving better results in this invention, the upper limit of the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer of the transfer film X is preferably 50 nm or less.

[0227] In addition, the arithmetic mean roughness Ra of the surface of the temporary support side of the intermediate layer refers to the arithmetic mean roughness Ra of the surface of the intermediate layer exposed after the temporary support is peeled off from the transfer film X.

[0228] The preferred method and measurement method for the arithmetic mean roughness Ra of the intermediate layer surface are as described above.

[0229] Furthermore, from the viewpoint of achieving better results with the present invention, the upper limit of the thickness of the intermediate layer of the transfer film X is preferably 10 μm or less. The preferred method and measurement method for the thickness of the intermediate layer are as described above.

[0230] As an intermediate layer, a water-soluble resin layer comprising a water-soluble resin is preferred.

[0231] Furthermore, the intermediate layer is preferably one with oxygen barrier properties. This oxygen barrier property improves sensitivity during exposure, reduces the time load on the exposure machine, and increases productivity, making it preferable. Moreover, in the case of a negative photosensitive layer containing a free radical polymerizable compound, the photosensitive layer in the transfer film X also has the advantage of being less prone to oxygen inhibition during the polymerization reaction during exposure.

[0232] As an intermediate layer, it is preferably a layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0233] The intermediate layer preferably contains resin.

[0234] The resins described above are preferably water-soluble resins, either as a part or all thereof.

[0235] Examples of resins that can be used as water-soluble resins include, for example, polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins (e.g., water-soluble cellulose derivatives such as hydroxypropyl cellulose and hydroxypropyl methyl cellulose), acrylamide resins, polyether resins (e.g., polyepoxide resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0236] Furthermore, copolymers of (meth)acrylic acid / vinyl ester compounds can also be used as water-soluble resins. Among these, copolymers of (meth)acrylic acid / vinyl ester compounds are preferred, and copolymers of (meth)acrylic acid / allyl (meth)acrylate are more preferably used. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl ester compounds, the component ratios (mol%) are, for example, preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0237] The lower limit for the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Furthermore, the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0238] The dispersion (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0239] From the viewpoint of superior effects of the present invention and / or superior oxygen barrier properties, the water-soluble resin preferably contains one or more polyvinyl alcohols and polyvinylpyrrolidones, more preferably polyvinyl alcohols, and even more preferably any one of polyvinyl alcohols and polyvinylpyrrolidones.

[0240] Furthermore, it is preferable to use one or more of polyvinyl alcohol and polyvinylpyrrolidone, as well as one or more of water-soluble cellulose derivatives and polyethers, and more preferably to use one or more of polyvinyl alcohol and polyvinylpyrrolidone, as well as water-soluble cellulose derivatives.

[0241] As water-soluble cellulose derivatives, they are not particularly limited, and examples include hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose.

[0242] Examples of polyethers include polyethylene glycol and polypropylene glycol.

[0243] Water-soluble resins can be used alone or in combination with two or more.

[0244] The content of water-soluble resin is not particularly limited. From the viewpoint of achieving better results and / or better oxygen barrier properties, it is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the intermediate layer. Furthermore, as an upper limit, it is not particularly limited, for example, to 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and even more preferably 99% by mass or less.

[0245] Furthermore, the intermediate layer may contain other components besides the aforementioned resin.

[0246] Furthermore, the upper limit of the molecular weight of the other components mentioned above is not particularly limited, but is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, and even more preferably 2,000 or less, and particularly preferably 1,500 or less. Additionally, the lower limit is, for example, 60 or more.

[0247] As one of the other components mentioned above, the surface free energy E from the temporary support side of the easily adjustable intermediate layer... I From the perspective of [the relevant context], polyols, epoxide adducts of polyols, phenol derivatives or amide compounds are preferred, and polyols or phenol derivatives are more preferred.

[0248] The number of hydroxyl groups contained in a polyol is not particularly limited, but is preferably 2 to 10.

[0249] Examples of polyols include glycerol, diglycerol, and diethylene glycol.

[0250] Examples of alkylene oxide adducts of polyols include compounds obtained by adding ethylene oxide and propylene oxide to the aforementioned polyols. Furthermore, the average number of additions is not particularly limited, but is preferably 1 to 100, 2 to 50, and more preferably 2 to 20.

[0251] Examples of phenol derivatives include bisphenol A and bisphenol S.

[0252] Examples of amide compounds include N-methylpyrrolidone.

[0253] When the intermediate layer contains the other components mentioned above, one of the other components may be used alone, or two or more may be used.

[0254] The content of the other components mentioned above is not particularly limited. From the viewpoint of achieving better results with the present invention, the content relative to the total mass of the intermediate layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Furthermore, the upper limit is not particularly limited; for example, it is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0255] As an intermediate layer, from the viewpoint of superior effects of the present invention and / or superior oxygen barrier properties, it is preferable to include one or more of polyvinyl alcohol and polyvinylpyrrolidone, and compound X selected from water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerol. When the intermediate layer has the above composition, compound X tends to exist more unevenly on the surface of the temporary support side of the intermediate layer and / or is less likely to form a WBL (weak boundary layer) layer composed of a mixture of the intermediate layer and the photosensitive layer, and the surface free energy E of the temporary support side of the intermediate layer is lower. I And the arithmetic mean roughness Ra of the same surface can be easily adjusted to a more appropriate value. If the surface free energy E on the temporary support side of the intermediate layer... I When the arithmetic mean roughness Ra of the same surface is adjusted to a more appropriate value, the intermediate layer will not be agglomerated and destroyed when the temporary support is peeled off, and the interface between the temporary support and the intermediate layer will be easily peeled off, and a pattern with excellent resolution will be easily formed.

[0256] The composition of the intermediate layer is particularly preferred to include one or more of polyvinyl alcohol and polyvinylpyrrolidone and one or more of a water-soluble cellulose derivative and a polyether as compound X. From the viewpoint of more easily suppressing the plasticity of the intermediate layer, it is further preferred to include one or more of polyvinyl alcohol and polyvinylpyrrolidone and a water-soluble cellulose derivative as compound X. From the viewpoint of better peelability of the temporary support, it is particularly preferred to include one or more of polyvinyl alcohol and polyvinylpyrrolidone and hydroxypropyl methylcellulose as compound X.

[0257] Furthermore, polyvinyl alcohol and polyvinylpyrrolidone are preferably used simultaneously.

[0258] When the intermediate layer has the above-described composition, from the viewpoint of maximizing the effects of the present invention, the total content of polyvinyl alcohol and polyvinylpyrrolidone relative to the total mass of the intermediate layer is preferably 50% by mass or more, more preferably 70% by mass or more. Furthermore, there is no particular limitation on the upper limit, for example, it is 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and even more preferably 99% by mass or less.

[0259] Furthermore, when the intermediate layer has the above composition, the content of polyvinyl alcohol is preferably 5 to 95% by mass relative to the total mass of the intermediate layer.

[0260] Furthermore, when the intermediate layer has the above composition, the mixing ratio (mass ratio) of polyvinyl alcohol to polyvinylpyrrolidone is preferably 5 / 95 to 95 / 5, more preferably 20 / 80 to 80 / 20, more preferably 25 / 75 to 70 / 25, and especially preferably 60 / 40 to 75 / 25.

[0261] Furthermore, when the intermediate layer has the above-described composition, the content of compound X is not particularly limited. From the viewpoint of achieving better results with the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. As an upper limit, it is preferably less than 30% by mass, more preferably 15% by mass or less. When the content of compound X is less than 30% by mass relative to the total mass of the intermediate layer, phase separation of the intermediate layer forming components is easily suppressed, and surface roughening of the intermediate layer caused by this is less likely to occur, thus resulting in better resolution.

[0262] (Temporary support)

[0263] The transfer film X has a temporary support.

[0264] The temporary support is a component that supports the photosensitive layer and is eventually removed through a peeling process.

[0265] The temporary support can be a single-layer structure or a multi-layer structure.

[0266] The temporary support is preferably a thin film, more preferably a resin film. As a temporary support, the film is preferably flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat.

[0267] Examples of such films include polyethylene terephthalate films (e.g., biaxially extended polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films.

[0268] Among them, polyethylene terephthalate film is preferred as a temporary support.

[0269] Furthermore, the film used as a temporary support is preferably free from deformations such as wrinkles and scratches.

[0270] From the viewpoint of being able to expose patterns through a temporary support, it is preferable that the temporary support has high transparency, preferably with a transmittance of 60% or more at 365 nm, and more preferably 70% or more.

[0271] From the viewpoint of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, it is preferable that the temporary support has low haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0272] From the viewpoint of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, it is preferable to have a low number of particles, foreign objects, and defects contained in the temporary support. The number of particles, foreign objects, and defects with a diameter of 1 μm or more in the temporary support is preferably 50 per 10 mm. 2 The following is more preferably 10 per 10mm 2 The following is further preferred: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0273] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm. From the viewpoint of ease of operation and versatility, it is more preferably 5 to 150 μm, further preferably 5 to 50 μm, and most preferably 5 to 25 μm.

[0274] The thickness of the temporary support was calculated as the average of any 5 points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

[0275] Examples of temporary supports include biaxially stretched polyethylene terephthalate films with a thickness of 16 μm, 12 μm, and 9 μm.

[0276] Preferred forms of temporary supports include, for example, those described in Japanese Patent Application Publication No. 2014-085643, paragraphs

[0017] to

[0018] , Japanese Patent Application Publication No. 2016-027363, paragraphs

[0019] to

[0026] , International Publication No. 2012 / 081680, paragraphs

[0041] to

[0057] , and International Publication No. 2018 / 179370, paragraphs

[0029] to

[0040] , the contents of which are incorporated into this specification.

[0277] From the viewpoint of providing operability, a layer containing tiny particles (lubricant layer) can be provided on the surface of the temporary support. The lubricant layer can be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

[0278] Furthermore, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0279] The surface free energy (E) of the intermediate layer side surface of the temporary support. S The preferred value is 60.0 mJ / m 2 the following.

[0280] In addition, the surface free energy E S It refers to the surface free energy of the surface of the intermediate layer side of the temporary support exposed after the temporary support is peeled off from the transfer film X.

[0281] Regarding surface free energy E S The preferred method and measurement method are as described above.

[0282] Commercially available temporary support devices include Lumirror 16KS40, Lumirror 16FB40 (all manufactured by TORAY INDUSTRIES, INC.), Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (all manufactured by Toray Industries, Inc.).

[0283] (Overall structure of transfer film X)

[0284] Next, an example of a specific embodiment will be given to describe the overall structure of the transfer film X. Furthermore, as described above, the transfer film X1 of the first embodiment has a structure that is preferably used as a transfer film for etching resists, and the transfer film X2 of the second embodiment has a structure that is preferably used as a transfer film for wiring protection films.

[0285] Furthermore, the thickness of the photosensitive layer is not particularly limited, and is mostly 30 μm or less. From the viewpoint of achieving better results with the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less. As a lower limit, from the viewpoint of achieving excellent film strength by curing the photosensitive layer, it is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more.

[0286] The thickness of the photosensitive layer is calculated by averaging any 5 points measured through cross-sectional observation using SEM (Scanning Electron Microscope).

[0287] • Transfer film X1 of the first embodiment

[0288] Hereinafter, an example of an embodiment of the transfer film X1 of the first embodiment will be described.

[0289] Figure 1 The transfer film 10 shown in the figure has a temporary support 1, a composition layer 7 including an intermediate layer 3 and a photosensitive layer 5, and a protective film 9 in sequence.

[0290] in addition, Figure 1 The transfer film 10 shown is in the form of having a protective film 9 configured, but the protective film 9 may not be configured.

[0291] In addition, Figure 1 In this process, all layers other than the protective film 9 that can be disposed on the temporary support 1 are called composition layers 7.

[0292] The elements constituting the transfer film X1 will be described below. Furthermore, the intermediate layer and temporary support of the transfer film X1 are configured as described above.

[0293] Photosensitive layer

[0294] By transferring a photosensitive layer onto a substrate and then exposing and developing it, a pattern can be formed on the substrate.

[0295] As the photosensitive layer, a negative photosensitive layer is preferred. Furthermore, a negative photosensitive layer is a photosensitive layer in which the solubility of the exposed portion in the developer decreases upon exposure. When the photosensitive layer is a negative photosensitive layer, the resulting pattern is equivalent to a cured layer.

[0296] When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably comprises a resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive layer is a negative photosensitive layer, as described later, it is also preferable to include an alkali-soluble resin (such as polymer A) as part or all of the resin. That is, in one embodiment, the photosensitive layer preferably contains a resin comprising an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[0297] Based on the total mass of the photosensitive layer, this photosensitive layer (negative photosensitive layer) preferably contains: 10-90% by mass of resin; 5-70% by mass of polymerizable compound; and 0.01-20% by mass of polymerization initiator.

[0298] The following is a description of each component.

[0299] ...Polymer A (resin)

[0300] In the case where the photosensitive layer is a negative photosensitive layer, the resin contained in the photosensitive layer is specifically referred to as polymer A.

[0301] Polymer A is preferably an alkali-soluble resin.

[0302] From the viewpoint of achieving better resolution by suppressing the swelling of the negative photosensitive layer caused by the developer, the acid value of polymer A is preferably less than 220 mg KOH / g, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g.

[0303] The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mg KOH / g or more, more preferably 120 mg KOH / g or more, even more preferably 150 mg KOH / g or more, and especially preferably 170 mg KOH / g or more.

[0304] In addition, acid value (mgKOH / g) refers to the mass [mg] of potassium hydroxide required to neutralize 1g of sample. Acid value can be determined, for example, according to the method described in JIS K0070:1992.

[0305] Regarding the acid value of polymer A, it can be adjusted according to the types of structural units that make up polymer A and the content of structural units containing acid groups.

[0306] The weight-average molecular weight of 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. More preferably, the weight-average molecular weight is 100,000 or less, and even more preferably 60,000 or less. On the other hand, when the weight-average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregates, and the properties of the unexposed film, such as edge melting and cutting chip resistance, when used as a negative photosensitive resin laminate. More preferably, the weight-average molecular weight is 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge melting refers to the degree to which the negative photosensitive layer easily overflows from the end face of the roller when wound into a roll as a negative photosensitive resin laminate. Cutting chip resistance refers to the degree to which chips easily fly off when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the negative photosensitive resin laminate, they will be transferred to the mask in subsequent exposure processes, resulting in a defective product. The dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In this invention, dispersion is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight). In this invention, weight-average molecular weight and number-average molecular weight are values ​​measured using gel permeation chromatography.

[0307] In the negative photosensitive layer, from the viewpoint of suppressing linewidth coarsening and resolution degradation due to focus position shift during exposure, polymer A preferably contains structural units based on monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units based on monomers having aromatic hydrocarbon groups in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, relative to the total mass of polymer A. While not particularly limited to an upper limit, it is preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, when multiple polymers A are included, it is preferable that the average content of structural units based on monomers having aromatic hydrocarbon groups is within the above-mentioned range.

[0308] Examples of monomers having aromatic hydrocarbon groups include, for example, monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers having aralkyl groups or styrene are preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is styrene, the content of styrene-based structural units relative to the total mass of polymer A is preferably 20–70% by mass, more preferably 25–65% by mass, further preferably 30–60% by mass, and particularly preferably 30–55% by mass. Furthermore, when the photosensitive layer contains multiple polymers A, the content of structural units having aromatic hydrocarbon groups is calculated as a weight average.

[0309] Examples of aryl alkyl groups include substituted or unsubstituted phenylalkyl groups (with benzyl removed) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0310] Examples of monomers containing phenyl alkyl groups include ethyl methacrylate (meth)acrylate.

[0311] Examples of monomers containing a benzyl group include (meth)acrylates, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; and vinyl monomers, such as vinyl benzyl chloride and benzyl alcohol. Benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component containing an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is preferably 50–95% by mass, more preferably 60–90% by mass, further preferably 70–90% by mass, and particularly preferably 75–90% by mass, relative to the total mass of polymer A.

[0312] The polymer A, which comprises structural units based on monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing a monomer having aromatic hydrocarbon groups with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0313] Polymer A, which does not contain structural units based on monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0314] The first monomer is a monomer having a carboxyl group in its molecule. Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half ester. Among these, (meth)acrylic acid is preferred.

[0315] The content of structural units based on the first monomer in polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, relative to the total mass of polymer A.

[0316] From the viewpoints of good developability and control of edge melting, it is preferable to set the above content to 5% by mass or more. From the viewpoints of high resolution and edge shape of the photoresist pattern, and further from the viewpoints of chemical resistance of the photoresist pattern, it is preferable to set the above content to 50% by mass or less.

[0317] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate; esters of vinyl alcohol such as vinyl acetate; and methacrylonitrile. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0318] The content of the second monomer-based structural unit in polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 17 to 45% by mass, relative to the total mass of polymer A.

[0319] When polymer A contains structural units based on monomers having aralkyl groups and / or structural units based on styrene monomers, it is preferable from the viewpoint of suppressing linewidth thickening and resolution degradation due to focus position shift during exposure. For example, copolymers containing structural units based on methacrylic acid, structural units based on benzyl methacrylate, and structural units based on styrene, or copolymers containing structural units based on methacrylic acid, structural units based on methyl methacrylate, structural units based on benzyl methacrylate, and structural units based on styrene are preferred.

[0320] In one embodiment, polymer A is preferably a polymer comprising 25-55% by mass of structural units based on monomers having aromatic hydrocarbon groups, 20-35% by mass of structural units based on a first monomer, and 15-45% by mass of structural units based on a second monomer. Furthermore, in another embodiment, it is preferably a polymer comprising 70-90% by mass of structural units based on monomers having aromatic hydrocarbon groups and 10-25% by mass of structural units based on the first monomer.

[0321] Polymer A can have any of the following structures in its side chain: straight-chain, branched-chain, and alicyclic. Branched or alicyclic structures can be introduced into the side chain of polymer A by using monomers containing groups with branched side chains or monomers containing groups with alicyclic side chains. The groups with alicyclic structures can be monocyclic or polycyclic.

[0322] Specific examples of monomers containing groups having a branched structure in their side chains include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tert-butyl (meth)acrylate are more preferred.

[0323] Specific examples of monomers containing alicyclic groups in their side chains include monomers having monocyclic aliphatic hydrocarbon groups and monomers having polycyclic aliphatic hydrocarbon groups. Furthermore, (meth)acrylates having alicyclic hydrocarbon groups with 5 to 20 carbon atoms can be cited. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl ester, (meth)acrylic acid-2-adamantyl ester, (meth)acrylic acid-3-methyl-1-adamantyl ester, (meth)acrylic acid-3,5-dimethyl-1-adamantyl ester, (meth)acrylic acid-3-ethyladamantyl ester, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl ester, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylic acid-2-methyl-2-adamantyl ester, (meth)acrylic acid-2-ethyl-2-adamantyl ester, 3-Hydroxy-1-adamantyl methacrylate, octahydro-4,7-mentanoindene-5-yl methacrylate, octahydro-4,7-mentanoindene-1-methyl methacrylate, 1-menthyl methacrylate, tricyclodecane methacrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl methacrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl methacrylate, norborneol methacrylate, isoborneol methacrylate, fenyl methacrylate, 2,2,5-trimethylcyclohexyl methacrylate, and cyclohexyl methacrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentanyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and more preferably cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred.

[0324] Polymer A can be used alone or in combination with two or more polymers.

[0325] When using two or more types, it is preferable to use a mixture of two polymers A containing structural units based on monomers having aromatic hydrocarbon groups, or to use a mixture of polymer A containing structural units based on monomers having aromatic hydrocarbon groups and polymer A not containing structural units based on monomers having aromatic hydrocarbon groups. In the latter case, the proportion of polymer A containing structural units based on monomers having aromatic hydrocarbon groups relative to the total mass of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0326] Regarding the synthesis of polymer A, it is preferably carried out by adding an appropriate amount of free radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution of one or more of the monomers diluted with solvents such as acetone, methyl ethyl ketone, and isopropanol, and then heating and stirring. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is being carried out. Sometimes, after the reaction is complete, further solvent is added to adjust to the desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0327] The glass transition temperature (Tg) of polymer A is preferably 30–135°C. By using polymer A with a Tg of 135°C or lower, it is possible to suppress linewidth thickening and resolution degradation due to focus position shift during exposure. From this viewpoint, the Tg of polymer A is preferably 130°C or lower, more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to use polymer A with a Tg of 30°C or higher. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0328] The negative photosensitive layer, as polymer A, contains other resins besides those mentioned above.

[0329] Other resins that can be cited include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0330] As polymer A, an alkali-soluble resin described in the following description of the thermoplastic resin layer can be used.

[0331] The content of polymer A relative to the total mass of the negative photosensitive layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the content of polymer A to 90% by mass or less. On the other hand, from the viewpoint of improving resistance to edge melting, it is preferable to set the content of polymer A to 10% by mass or more.

[0332] Polymer compounds

[0333] When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer is preferably a polymeric compound containing polymeric groups. Furthermore, in this specification, "polymeric compound" refers to a compound polymerized by the polymerization initiator described later, and specifically refers to a compound different from polymer A described above.

[0334] As a polymerizable compound, the polymerizable groups are not particularly limited as long as they are related to the polymerization reaction. For example, groups with olefinic unsaturated groups such as vinyl, acryloyl, methacryloyl, styrene, and maleimide can be cited; as well as groups with cationic polymerizable groups such as epoxy and oxybutyl.

[0335] As a polymerizable group, it is preferably a group having an olefinic unsaturated group, and more preferably an acryloyl or methacryloyl group.

[0336] From the viewpoint that negative photosensitive layers have better photosensitivity, compounds having one or more olefin unsaturated groups (olefin unsaturated compounds) are preferred as polymerizable compounds, and compounds having two or more olefin unsaturated groups in one molecule (polyfunctional olefin unsaturated compounds) are more preferred.

[0337] Furthermore, from the viewpoint of superior resolution and exfoliability, the number of olefinic unsaturated groups in one molecule of the olefinic unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0338] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of the negative photosensitive layer, it is preferable to include a difunctional or trifunctional olefin unsaturated compound having two or three olefin unsaturated groups in one molecule, and more preferably a difunctional olefin unsaturated compound having two olefin unsaturated groups in one molecule.

[0339] From the viewpoint of excellent peelability, the content of difunctional olefin unsaturated compounds relative to the total solid content of the composition and the total mass of the negative photosensitive layer is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more. The upper limit is not particularly limited and can be 100% by mass. That is, all polymerizable compounds can be difunctional olefin unsaturated compounds.

[0340] Furthermore, as an olefinic unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0341] Polymer compound B1

[0342] The negative photosensitive layer preferably comprises a polymeric compound B1 having an aromatic ring and two olefinic unsaturated groups. Polymeric compound B1 is a difunctional olefinic unsaturated compound having one or more aromatic rings in one molecule of the aforementioned polymeric compound B.

[0343] From the viewpoint of superior resolution, the mass ratio of polymeric compound B1 in the negative photosensitive layer relative to the total mass of the polymeric compound is preferably 40% or more, more preferably 50% or more, even more preferably 55% or more, and particularly preferably 60% or more. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, and particularly preferably 85% or less.

[0344] The aromatic rings present in the polymerizable compound B1 can be, for example, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings, as well as fused rings of these, preferably aromatic hydrocarbon rings, more preferably benzene rings. Furthermore, the aforementioned aromatic rings may have substituents.

[0345] Polymerizable compound B1 may have only one aromatic ring or more than two aromatic rings.

[0346] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive layer caused by the developer, it is preferable that the polymeric compound B1 has a bisphenol structure.

[0347] Examples of bisphenol structures include, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0348] As a polymeric compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymeric groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0349] The two ends of the bisphenol structure can be directly bonded to two polymerizable groups, or they can be bonded via one or more alkene oxygen groups. The alkene oxygen groups added to the two ends of the bisphenol structure are preferably ethoxy or propoxy, more preferably ethoxy. The number of alkene oxygen groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule are preferred, more preferably 6 to 14.

[0350] Regarding the polymeric compound B1 having a bisphenol structure, it is described in Japanese Patent Application Publication No. 2016-224162, paragraphs 0072 to 0080, and the contents described in that publication are incorporated into this specification.

[0351] As the polymerizable compound B1, it is preferably a difunctional olefinic unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0352] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include, for instance, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentathoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, Shin-Nakamura Chemical Co., Ltd.). 2,2-bis(4-(methacryloyloxydiethoxy)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.).

[0353] As a polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0354] [Chemical Formula 1]

[0355]

[0356] In general formula B1, R1 and R2 independently represent a hydrogen atom or a methyl group, respectively. A represents C2H4. B represents C3H6. n1 and n3 are each independently integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- can be random or block. Furthermore, in the case of blocks, both -(AO)- and -(BO)- can be on the diphenyl side.

[0357] In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0358] Polymer compound B1 can be used alone or in combination with two or more compounds.

[0359] From the viewpoint of achieving better resolution, the content of polymeric compound B1 relative to the total mass of the negative photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (the phenomenon of photosensitive resin seeping out from the ends of the transfer material), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0360] The negative photosensitive layer may contain polymeric compounds other than the polymeric compound B1 mentioned above.

[0361] Polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, compounds having one olefinic unsaturated group in one molecule (monofunctional olefinic unsaturated compounds), difunctional olefinic unsaturated compounds without an aromatic ring, and olefinic unsaturated compounds with three or more functions can be cited.

[0362] Examples of monofunctional alkenyl unsaturated compounds include, for example, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxy(meth)acrylate.

[0363] Examples of difunctional olefinic unsaturated compounds that do not have an aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.

[0364] Examples of alkylene glycol di(meth)acrylates include, for example, tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol 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 neopentyl glycol di(meth)acrylate.

[0365] Examples of polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0366] Examples of urethane dimethacrylates include, for example, propylene oxide-modified urethane dimethacrylates and ethylene oxide and propylene oxide-modified urethane dimethacrylates. Commercially available examples include 8UX-015A (manufactured by TAISEIFINE CHEMICAL CO., LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0367] Examples of olefinic unsaturated compounds with three or more functions include, for example, dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and epoxide-modified versions of these.

[0368] Here, "(tri / tetra / penta / hexa)meth)acrylate" refers to the concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" refers to the concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0369] In one embodiment, the negative photosensitive layer preferably comprises the aforementioned polymeric compound B1 and a trifunctional or higher olefinic unsaturated compound, more preferably comprising the aforementioned polymeric compound B1 and two or more trifunctional or higher olefinic unsaturated compounds. In this case, the mass ratio of the polymeric compound B1 to the trifunctional or higher olefinic unsaturated compounds is preferably (total mass of polymeric compound B1) : (total mass of trifunctional or higher olefinic unsaturated compounds) = 1 : 1 to 5 : 1, more preferably 1.2 : 1 to 4 : 1, and even more preferably 1.5 : 1 to 3 : 1.

[0370] Furthermore, in one embodiment, the negative photosensitive layer preferably comprises the aforementioned polymeric compound B1 and two or more trifunctional olefinic unsaturated compounds.

[0371] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized olefinic unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 135 manufactured by DAI-CELL-ALLNEX LTD.), ethoxylated glycerol triacrylates (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and ARONIX TO-2349 (TOAGOSEI). (Manufactured by TOAGOSEI CO., LTD.) ARONIX M-520 (Manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (Manufactured by TOAGOSEI CO., LTD.).

[0372] Furthermore, polymerizable compounds containing acid groups (such as carboxyl groups) can be used. These acid groups can form anhydride groups. Examples of polymerizable compounds containing acid groups 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.).

[0373] As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 can be used.

[0374] Polymers can be used alone or in combination with two or more compounds.

[0375] The content of the polymeric compound relative to the total mass of the negative photosensitive layer is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass.

[0376] The molecular weight (weight-average molecular weight in the case of a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0377] Polymerization initiators

[0378] When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably also contains a polymerization initiator.

[0379] Polymerization initiators can be selected based on the form of the polymerization reaction; for example, thermal polymerization initiators and photopolymerization initiators can be cited.

[0380] The polymerization initiator can be a free radical polymerization initiator or a cationic polymerization initiator.

[0381] The negative photosensitive layer preferably contains a photopolymerization initiator.

[0382] Photopolymerization initiators are compounds that initiate the polymerization of polymerizable compounds by receiving activating light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on photopolymerization initiators; any known photopolymerization initiator can be used.

[0383] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0384] Examples of photoradical polymerization initiators include, for example, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0385] Furthermore, from the viewpoint of photosensitivity, visibility of the exposed portion, and resolution of the unexposed portion, the negative photosensitive layer preferably contains at least one selected from 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium structures in the 2,4,5-triarylimidazolium dimer and its derivatives may be identical or different.

[0386] Examples of derivatives of 2,4,5-triarylimidazolium dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0387] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783 can be used.

[0388] Examples of photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p,p'-dimethoxybenzyl ester), TAZ-110 (manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0389] 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), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(o-acetyl oxime) (product name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, IGM Resins). Omnirad 907 (manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV), 2-hydroxy-1-methyl-1-phenylpropanoyl-1- ...morpholinophenyl ketone (manufactured by IGM Resins BV), 2-method Omnirad 651 (manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (manufactured by DKSH Management Ltd.), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (manufactured by IGM Resins BV, 907FF), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butane-1-one (manufactured by IGM Resins BV) 379. IGM Resins BV), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (product name: B-CIM, manufactured by Hampford Research Inc.) and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (product name: TR-PBG-305, Changzhou Tronly New Electronic Materials) (Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(o-acetyl oxime) (Product name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(o-benzoyl oxime) (Product name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

[0390] Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving activation light. Preferably, these initiators are compounds that generate acid by sensing activation light with wavelengths of 300 nm or higher, more preferably 300–450 nm, but their chemical structure is not particularly limited. Furthermore, photocationic polymerization initiators that do not directly sense activation light with wavelengths of 300 nm or higher, but are compounds that generate acid by sensing activation light with wavelengths of 300 nm or higher when used in conjunction with a sensitizer, can also be used in combination with the sensitizer and are preferably used together.

[0391] As a photocationic polymerization initiator, a photocationic polymerization initiator that produces acids with a pKa of 4 or less is preferred, a photocationic polymerization initiator that produces acids with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that produces acids with a pKa of 2 or less is particularly preferred. The lower limit of pKa is not particularly limited, but for example, -10.0 or more is preferred.

[0392] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0393] Examples of ionic photocationic polymerization initiators include, for example, onium salts such as diaryl sulfonium salts and triaryl sulfonium salts, as well as quaternary ammonium salts.

[0394] As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-085643 may be used.

[0395] Examples of nonionic photocationic polymerization initiators include trichloromethyl-symmetrical triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-symmetrical triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 can be used. Furthermore, as oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640 can be used.

[0396] The negative photosensitive layer preferably contains a photoradical polymerization initiator, more preferably contains at least one selected from 2,4,5-triarylimidazolium dimer and its derivatives.

[0397] Polymerization initiators can be used alone or in combination with two or more.

[0398] The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the negative photosensitive layer. The upper limit is not particularly limited, but it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the negative photosensitive layer.

[0399] ···pigment

[0400] From the viewpoint of visibility of the exposed and unexposed areas, the visibility of the developed pattern, and resolution, the photosensitive layer preferably contains a pigment (also called "pigment N") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength changes due to acids, alkalis, or free radicals. While the detailed mechanism of including pigment N is not yet clear, the adhesion to adjacent layers (e.g., water-soluble resin layers) is improved, resulting in superior resolution.

[0401] In this specification, "the pigment's absorption wavelength changes dramatically due to acid, alkali, or free radicals" can refer to any of the following: a pigment in a color-developing state is decolorized by acid, alkali, or free radicals; a pigment in a decolorized state is color-developed by acid, alkali, or free radicals; or a pigment in a color-developing state changes to a color-developing state of another hue.

[0402] Specifically, pigment N can be a compound that changes from an achromatic state to a chromatic state through exposure, or a compound that changes from a chromatic state to an achromatic state through exposure. In this case, it can be a pigment that changes its chromatic or achromatic state by generating acids, bases, or free radicals within the photosensitive layer through exposure, or a pigment that changes its chromatic or achromatic state by changing the state (e.g., pH) within the photosensitive layer due to acids, bases, or free radicals. Furthermore, it can also be a pigment that changes its chromatic or achromatic state directly by accepting acids, bases, or free radicals as stimuli without exposure.

[0403] From the viewpoint of visibility and resolution of the exposed and unexposed portions, pigment N is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to free radicals.

[0404] When the photosensitive layer is a negative photosensitive layer, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the negative photosensitive layer is preferably composed of both a pigment N containing a pigment whose maximum absorption wavelength changes due to free radicals and a photoradical polymerization initiator.

[0405] Furthermore, from the viewpoint of visibility of the exposed and unexposed areas, pigment N is preferably a pigment that develops color through acid, alkali or free radicals.

[0406] An example of a color-developing mechanism for pigment N can be given as follows: a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator is added to the photosensitive layer. After exposure, the free radical reactive pigment, acid reactive pigment, or alkali reactive pigment (e.g., colorless pigment) develops color due to the free radicals, acids, or bases generated by the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator.

[0407] Regarding pigment N, from the viewpoint of visibility of the exposed and unexposed portions, the maximum absorption wavelength in the wavelength range of 400–780 nm during color development is preferably 550 nm or more, more preferably 550–700 nm, and even more preferably 550–650 nm.

[0408] Furthermore, pigment N can have only one maximum absorption wavelength in the wavelength range of 400–780 nm during color development, or it can have two or more. If pigment N has two or more maximum absorption wavelengths in the wavelength range of 400–780 nm during color development, it is acceptable as long as the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is above 450 nm.

[0409] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (at a liquid temperature of 25°C) in an atmospheric environment using a UV3100 spectrophotometer (manufactured by SHIMADZU CORPORATION) in the range of 400–780 nm, and detecting the wavelength at which the light intensity reaches its minimum (maximum absorption wavelength).

[0410] As pigments that develop or decolorize upon exposure, colorless compounds can be cited as an example.

[0411] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments.

[0412] From the viewpoint of visibility of both the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0413] Examples of colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a helicopyran skeleton (helicopyran pigments), colorless compounds having a fluoran skeleton (fluoran pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a white goldamine skeleton (white goldamine pigments).

[0414] Preferably, the pigment is a triarylmethane pigment or a fluorane pigment, and more preferably, it is a colorless compound (triphenylmethane pigment) or a fluorane pigment having a triphenylmethane skeleton.

[0415] From the viewpoint of visibility of both the exposed and unexposed areas, it is preferable for the colorless compound to have a lactone ring, a sultine ring, or a sulfonyl lactone ring. This allows the lactone ring, sultine ring, or sulfonyl lactone ring of the colorless compound to react with free radicals generated by a photoradical polymerization initiator or acids generated by a photocationic polymerization initiator, thereby changing the colorless compound to a closed-ring state and thus decolorizing it, or changing the colorless compound to an open-ring state and thus developing color. Preferably, the colorless compound is one that has a lactone ring, a sultine ring, or a sulfonyl lactone ring, and that develops color due to the opening of the lactone ring, sultine ring, or sulfonyl lactone ring by a free radical or acid; more preferably, it is a compound that has a lactone ring and develops color due to the opening of the lactone ring by a free radical or acid.

[0416] As pigment N, examples include the following dyes and colorless compounds.

[0417] Specific examples of dyes in Pigment N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsin, Methyl Violet 2B, Methylquinoline Red, Bengal Rose Red, m-Amino Yellow, Bromophenol Blue, Xylenol Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzoin Purple 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Para-Fuchsin, Victoria Blue - Naphthalene Sulfonate, Victoria 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 (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Co., Ltd.), and Oil Red RR (manufactured by Orient Chemical Co., Ltd.). (manufactured by Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Co., Ltd.), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonyl rhodamine B, gold amine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0418] Specific examples of colorless compounds in pigment N include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-aniline. 3-(N,N-diethylamino)-6-methyl-7-aniline fluorane, 3-(N,N-diethylamino)-6-methyl-7-dimethylphenylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-7-methoxy-7-aminofluorane 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-dimethylphenylaminofluorane, 3-piperidinyl-6-methyl-7-anilinofluorane, 3-pyrrolidinyl-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalolide, 3,3-bis(1-n-butyl) 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalolide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalolide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalolide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthon-3-one.

[0419] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the pattern after development, and resolution, pigment N is preferably a pigment whose maximum absorption wavelength changes due to free radicals, and more preferably a pigment that develops color through free radicals.

[0420] As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0421] Pigment N can be used alone or in combination with two or more pigments.

[0422] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the content of pigment N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, relative to the total mass of the photosensitive layer.

[0423] The content of pigment N refers to the amount of pigment required for all of the pigment N contained in the total mass of the photosensitive layer to be in a colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N.

[0424] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigments in 100 mL of methyl ethyl ketone. Irgacure OXE01 (product name, BASF Japan Ltd.) was added to each of the obtained solutions as a photoradical polymerization initiator, and the solutions were irradiated with 365 nm light to generate free radicals, thus setting all pigments to a colored state. Then, under ambient atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) to create calibration curves.

[0425] Next, 3g of the photosensitive layer was dissolved in methyl ethyl ketone instead of the pigment. The absorbance of the solution in which the pigment was fully developed was then measured using the same method as described above. Based on the absorbance of the obtained solution containing the photosensitive layer, the pigment content in the photosensitive layer was calculated according to the calibration curve.

[0426] In addition, the 3g of photosensitive layer is the same as the 3g of total solids in the photosensitive composition.

[0427] ...thermal crosslinking compounds

[0428] When the photosensitive layer is a negative photosensitive layer, from the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, it is preferable to include a thermally crosslinking compound. Furthermore, in this specification, thermally crosslinking compounds having olefinically unsaturated groups (described later) are not considered polymerizable compounds, but rather thermally crosslinking compounds.

[0429] Examples of thermally crosslinking compounds include hydroxymethyl compounds and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred from the viewpoint of the strength of the cured film and the adhesion of the uncured film.

[0430] The capped isocyanate compound reacts with hydroxyl and carboxyl groups, thus, for example, in the case of resins and / or polymeric compounds having at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film decreases, and the film tends to enhance its function as a protective film when the negative photosensitive layer is cured.

[0431] In addition, capped isocyanate compounds are defined as "compounds having a structure in which isocyanate groups of isocyanate are protected (so-called masking) by capping agents".

[0432] The dissociation temperature of the capped isocyanate compound is not particularly limited, but it is preferably 100–160°C, more preferably 130–150°C.

[0433] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates, as measured by differential scanning calorimetry (DSC) using a differential scanning calorimeter".

[0434] As a 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.

[0435] Examples of end-capping agents with dissociation temperatures of 100–160°C include active methylene compounds (malonate esters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., which have a structure represented by -C (=N-OH)- in the molecule).

[0436] Among these, at least one of the oxime compounds is preferred as a capping agent with a dissociation temperature of 100 to 160°C, for example, from the viewpoint of preservation stability.

[0437] For example, from the viewpoint of improving the brittleness of the film and enhancing its adhesion to the substrate, the end-capped isocyanate compound is preferably having an isocyanurate structure.

[0438] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0439] Among the isocyanate compounds with an isocyanurate structure, compounds containing an oxime structure with an oxime compound as a capping agent are preferred from the viewpoint that it is easier to set the dissociation temperature within a preferred range and easier to reduce development residue compared to compounds without an oxime structure.

[0440] End-capped isocyanate compounds can have polymerizable groups.

[0441] As a polymerizable group, it is not particularly limited and can use known polymerizable groups, preferably free radical polymerizable groups.

[0442] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0443] Among them, the polymerizable group is preferably an olefinic unsaturated group, more preferably (meth)acryloyloxy, and even more preferably acryloyloxy.

[0444] As a capped isocyanate compound, it can be used in commercially available products.

[0445] Examples of commercially available isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and the end-capped DURANATE series (e.g., DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0446] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0447] [Chemical Formula 2]

[0448]

[0449] A single thermally crosslinking compound can be used alone, or two or more compounds can be used.

[0450] When the photosensitive layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

[0451] Other additives

[0452] In addition to the above-mentioned components, the photosensitive layer may also contain known additives as needed.

[0453] Examples of additives include free radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazoles, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and surfactants.

[0454] Each additive can be used alone or in combination with two or more.

[0455] The photosensitive layer may contain free radical polymerization inhibitors.

[0456] Examples of free radical polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenotoxazine, or 4-methoxyphenol are preferred. Other free radical polymerization inhibitors include naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive layer, aluminum nitrosophenylhydroxylamine is preferably used as the free radical polymerization inhibitor.

[0457] The preferred content of the free radical polymerization inhibitor is the same as the content of the same component in the photosensitive layer of the transfer film X2 of the second embodiment.

[0458] Examples of benzotriazoles include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0459] Examples of carboxylated benzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxylated benzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxylated benzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylene carboxylated benzotriazole. Commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD, product name) can also be used as carboxylated benzotriazoles.

[0460] The total content of benzotriazoles and carboxybenzotriazoles relative to the total mass of the photosensitive layer is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. When the content is 0.01% by mass or more, the preservation stability of the photosensitive layer is better. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of dye decolorization are better.

[0461] Furthermore, hindered phenolic compounds are preferred as free radical polymerization inhibitors, for example. Examples of hindered phenolic compounds include bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(oxyvinyl)]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-butylaniline)-1,3,5-triazine, and pentaerythritol tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0462] The photosensitive layer may contain sensitizers.

[0463] Regarding sensitizers, there are no particular limitations, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include, for instance, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthonesone compounds, thioxanthonesone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds.

[0464] Commercially available sensitizers include, for example, "SB-PI701" (4,4′-bis(diethylamino)benzophenone) manufactured by SANYO TRADING CO., LTD.

[0465] One type of sensitizer can be used alone, or two or more types can be used.

[0466] When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. However, from the viewpoint of improving the sensitivity to the light source and improving the curing speed based on the balance between polymerization rate and chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive layer.

[0467] The photosensitive layer may contain at least one selected from plasticizers and heterocyclic compounds.

[0468] As plasticizers and heterocyclic compounds, examples include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0469] The photosensitive layer preferably contains a surfactant. Examples of surfactants include those that are the same as those that may be contained in the photosensitive layer of the transfer film X2 in the second embodiment described later, and the preferred surfactants are also the same.

[0470] Furthermore, the photosensitive layer may also contain known additives such as metal oxide particles, antioxidants, rust inhibitors, dispersants, acid proliferation agents, development promoters, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.

[0471] Furthermore, as a chain transfer agent, it is also preferred to include N-phenylcarbamoylmethyl-N-hydroxymethylaniline and / or N,N-tetraethyl-4,4-diaminobenzophenone.

[0472] Regarding the additives contained in the photosensitive layer, paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-085643 are described, and the contents of that publication are incorporated into this specification.

[0473] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0474] Furthermore, from the viewpoint of superior adhesion, the transmittance of light with a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

[0475] ...impurities, etc.

[0476] The photosensitive layer may contain a specified amount of impurities.

[0477] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are easily introduced as impurities, and therefore are preferably set to the following concentrations.

[0478] The impurity content in the photosensitive layer, measured by mass, is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. Regarding the impurity content, measured by mass, it can be set to 1 ppb or more, or 0.1 ppm or more.

[0479] As a method for keeping impurities within the aforementioned range, examples include: selecting substances with low impurity content as raw materials for the composition; preventing impurities from being introduced during the fabrication of the photosensitive layer; and performing cleaning to remove them. By using this method, the amount of impurities can be kept within the aforementioned range.

[0480] Impurities can be quantified, for example, by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0481] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on a mass basis.

[0482] Based on mass standards, the lower limit relative to the total mass of the photosensitive layer can be set to 10 ppb or more, and can be set to 100 ppb or more. The content of these compounds can be suppressed using the same method as for the impurities of the aforementioned metals. Furthermore, quantification can be performed using known measurement methods.

[0483] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0484] ···pigment

[0485] The photosensitive layer can be a coloring resin layer containing pigments.

[0486] In recent years, sometimes a cover glass with a black frame-like light-shielding layer formed on the back periphery of a transparent glass substrate or the like is installed on the liquid crystal display window of electronic devices to protect the liquid crystal display window. A colored resin layer can be used to form this light-shielding layer.

[0487] As for the pigment, it can be appropriately selected according to the desired hue, and can be chosen from black pigment, white pigment, and colored pigments other than black and white. Among them, when forming a black-based pattern, black pigment is preferably selected as the pigment.

[0488] As for the black pigment, any known black pigment (organic or inorganic pigment, etc.) can be appropriately selected, provided it does not impair the effects of the present invention. From the viewpoint of optical concentration, examples of preferred black pigments include carbon black, titanium dioxide, titanium carbide, iron oxide, titanium dioxide, and lead black, with carbon black being particularly preferred. From the viewpoint of surface resistivity, carbon black in which at least a portion of its surface is coated with resin is preferred.

[0489] Regarding the particle size of the black pigment, from the viewpoint of dispersion stability, it is preferably 0.001 to 0.1 μm in terms of number average particle size, and more preferably 0.01 to 0.08 μm.

[0490] Here, particle size refers to the diameter of a circle whose area is calculated from an electron microscope image of the pigment particle and which is considered to be the same as the area of ​​the pigment particle. The number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes.

[0491] Regarding white pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 can be used. Specifically, as an inorganic pigment, the preferred white pigments are titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium dioxide or zinc oxide, and even more preferably titanium dioxide. As an inorganic pigment, rutile or anatase titanium dioxide is even more preferred, and rutile titanium dioxide is particularly preferred.

[0492] Furthermore, the surface of titanium oxide can be treated with silica, alumina, titanium dioxide, zirconium dioxide, or organic substances, or even two or more of these treatments. This inhibits the catalytic activity of titanium oxide and improves its heat resistance and fading properties.

[0493] From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of titanium oxide is preferably at least one of alumina treatment and zirconium dioxide treatment, and more preferably both alumina treatment and zirconium dioxide treatment.

[0494] Furthermore, when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, the photosensitive layer preferably further includes colored pigments other than black and white pigments. When colored pigments are included, from the viewpoint of better dispersibility, the particle size of the colored pigments is preferably 0.1 μm or less, more preferably 0.08 μm or less.

[0495] Examples of colored pigments include Victoria Blue BO (Color Index: CI 42595), Golden Amine (CI 41000), Lipid Black HB (CI 26150), Monoright Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Magenta FBB (CI Pigment Red 146), Prime Yeast Red ESB (CI Pigment Violet 19), Permanent Gem FBH (CI Pigment Red 11), and Faster Pink B Super (CI Pigment Red 81). The pigments include Mona Strahl Blue (CI Pigment Blue 15), Monoright Black B (CI Pigment Black 1), carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred.

[0496] When the photosensitive layer contains pigment, the pigment content relative to the total mass of the photosensitive layer is preferably more than 3% by mass and less than 40% by mass, more preferably more than 3% by mass and less than 35% by mass, even more preferably more than 5% by mass and less than 35% by mass, and especially preferably more than 10% by mass and less than 35% by mass.

[0497] When the photosensitive layer contains pigments other than black pigment (white pigments and colored pigments), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass relative to black pigment.

[0498] Furthermore, when the photosensitive layer contains a black pigment and the photosensitive layer is formed from a photosensitive composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.

[0499] A dispersion can be prepared by adding a pre-mixed mixture of black pigment and pigment dispersant to an organic solvent (or carrier) and then dispersing it using a disperser. Regarding the pigment dispersant, it can be selected based on the pigment and solvent; for example, a commercially available dispersant can be used. Furthermore, the carrier refers to the medium in which the pigment is dispersed when it is a pigment dispersion; it is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0500] As a dispersing machine, there are no particular limitations; for example, well-known dispersing machines such as kneaders, roller mills, grinders, supermills, dissolvers, homogenizers, and sand mixers can be cited. Furthermore, fine grinding can be achieved by utilizing friction through mechanical grinding. For information on dispersing machines and fine grinding, please refer to the "Encyclopedia of Pigments" (Kunozou Asakura, 1st edition, Asakura Publishing Co., Ltd., 2000, pp. 438, 310).

[0501] Furthermore, the thickness of the photosensitive layer is not particularly limited, and is mostly 30 μm or less. From the viewpoint of achieving better results with the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less. As a lower limit, from the viewpoint of achieving excellent film strength by curing the photosensitive layer, it is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more.

[0502] The thickness of the photosensitive layer is calculated by averaging any 5 points measured through cross-sectional observation using SEM (Scanning Electron Microscope).

[0503] Protective film

[0504] The transfer film X1 can have a protective film.

[0505] As a protective film, resin films with heat resistance and solvent resistance can be used, such as polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0506] Furthermore, as a protective film, a resin film made of the same material as the temporary support described above can also be used.

[0507] The protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0508] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and especially preferably 15 to 30 μm.

[0509] 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.

[0510] Furthermore, in the protective film, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5 per m. 2 the following.

[0511] In addition, "fisheye" refers to the phenomenon where foreign matter, undissolved substances, and oxidative degradation products are incorporated into the film when materials are manufactured by methods such as hot melting, mixing, extrusion, biaxial stretching, and casting.

[0512] The number of particles with a diameter of 3 μm or larger contained in the protective film is preferably 30 particles / mm. 2 The following is more preferably 10 pieces / mm 2 The following is a further preferred option: 5 per mm 2 the following.

[0513] Therefore, it is possible to suppress defects caused by uneven transfer of particles contained in the protective film to the photosensitive layer or conductive layer.

[0514] From the viewpoint of imparting rollability, 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 even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0515] From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface in contact with the protective film and the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0516] The arithmetic mean roughness Ra of each surface of the protective film is measured in the same manner as the arithmetic mean roughness Ra of the intermediate layer side of the temporary support described above.

[0517] •Optimal correlation of the physical properties of the temporary support, photosensitive layer and protective film

[0518] The following describes the physical properties of the transfer film X1, preferably the temporary support, the photosensitive layer, and the protective film.

[0519] The transfer film X1 preferably satisfies one or more of the following preferred methods: preferred method 1, preferred method 2, preferred method 3, preferred method 4 and preferred method 5, and more preferably satisfies all of them.

[0520] "Elongation at break of the cured film with the photosensitive layer cured" is measured by tensile testing of the cured film using an ultra-high pressure mercury lamp at 120 mJ / cm². 2 After the 20μm thick photosensitive layer is exposed and cured, it is then heated with a high-pressure mercury lamp at 400mJ / cm².2 The film is then further exposed and cured after being heated at 145°C for 30 minutes.

[0521] The method for measuring the "arithmetic mean roughness Ra of the intermediate layer side of the temporary support" is as described above.

[0522] The method for measuring the "arithmetic mean roughness Ra of the surface on the photosensitive layer side of the protective film" is carried out in the same manner as the method for measuring the "arithmetic mean roughness Ra of the intermediate layer side of the temporary support" already described.

[0523] Preferred Method 1

[0524] In the transfer film X1, the physical properties of the temporary support, the photosensitive layer and the protective film are preferably satisfied by the conditions (P1) to (P3) below.

[0525] (P1) The cured film formed by curing the photosensitive layer has an elongation at break of more than 15% at 120°C.

[0526] (P2) The arithmetic mean roughness Ra of the surface of the intermediate layer side of the temporary support is less than 50 nm.

[0527] (P3) The arithmetic mean roughness Ra of the photosensitive layer side of the protective film is less than 150 nm.

[0528] ...Preferred Method 2

[0529] The physical properties of the temporary support and photosensitive layer of the transfer film X1 preferably satisfy the following formula (1).

[0530] X×Y<1500 Equation (1)

[0531] In Equation (1), X represents the elongation at break (%) of the cured film formed by curing the photosensitive layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the intermediate layer side of the temporary support.

[0532] In the above formula (1), the value represented by X×Y is preferably 750 or less.

[0533] ...Preferred Method 3

[0534] The physical properties of the photosensitive layer of transfer film X1 preferably satisfy the following conditions (P4).

[0535] (P4) Compared to the elongation at break of the cured film formed by curing the photosensitive layer at 23°C, the elongation at break at 120°C is more than twice as high.

[0536] ...Preferred Method 4

[0537] The physical properties of the temporary support and photosensitive layer of the transfer film X1 preferably satisfy the following formula (2).

[0538] Y≤Z Equation (2)

[0539] In Equation (2), Y represents the arithmetic mean roughness Ra (nm) of the surface of the intermediate layer side of the temporary support, and Z represents the arithmetic mean roughness Ra (nm) of the surface of the photosensitive layer side of the protective film.

[0540] • Method for manufacturing transfer film X1 according to the first embodiment

[0541] The manufacturing method of the transfer film X1 in the first embodiment is not particularly limited, and known methods can be used.

[0542] As a method for manufacturing the transfer film 10, for example, a method including the following steps can be described: coating a temporary support 1 with an intermediate layer forming composition to form a coating film, and further drying the coating film to form an intermediate layer 3; and coating the intermediate layer 3 with a photosensitive composition to form a coating film, and further drying the coating film to form a photosensitive layer 5.

[0543] Furthermore, in this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. These methods can be used individually or in combination.

[0544] The transfer film 10 is manufactured by pressing the protective film 9 onto the photosensitive layer 5 of the laminate manufactured by the above manufacturing method.

[0545] As a method for manufacturing the transfer film according to the first embodiment, it is preferable to manufacture a transfer film 10 having a temporary support 1, an intermediate layer 3, a photosensitive layer 5 and a protective film 9 by a process including setting a protective film 9 to contact the surface of the photosensitive layer 5 opposite to the side having the temporary support 1.

[0546] After the transfer film 10 is manufactured using the above manufacturing method, the transfer film 10 is wound up, thereby producing and storing a roller-shaped transfer film. The roller-shaped transfer film can be provided in its original form to the roll-to-roll bonding process with the substrate described later.

[0547] Composition for forming intermediate layer and method for forming intermediate layer

[0548] The composition for forming the intermediate layer preferably includes various components and solvents for forming the intermediate layer. Furthermore, in the composition for forming the intermediate layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the intermediate layer.

[0549] As a solvent, it is not particularly limited as long as it can dissolve or disperse water-soluble resins, and is preferably selected from at least one of water and water-miscible organic solvents, more preferably water or a mixture of water and water-miscible organic solvents.

[0550] Examples of water-miscible organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0551] You can use one solvent alone, or you can use two or more solvents.

[0552] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0553] The method for forming the intermediate layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0554] The preferred drying methods for the coating film of the composition for forming the intermediate layer are heating drying and vacuum drying.

[0555] The preferred drying temperature is 80°C or higher, more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature.

[0556] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. While there is no particular limitation on the upper limit, it is preferably 600 seconds or less, more preferably 300 seconds or less.

[0557] Method for forming photosensitive compositions and photosensitive layers

[0558] From the viewpoint of superior productivity, it is desirable to use a photosensitive composition comprising the components constituting the aforementioned photosensitive layer (e.g., adhesive polymers, polymeric compounds, and polymerization initiators) and a solvent, and to form it using a coating method.

[0559] The photosensitive composition preferably includes various components and solvents that form the photosensitive layer described above. Furthermore, in the photosensitive composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive layer described above.

[0560] As a solvent, there are no particular limitations as long as it can dissolve or disperse all components other than the solvent itself; any known solvent can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixtures containing two or more of these.

[0561] As a solvent, it is preferably a solvent containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, it is a mixed solvent containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from ketone solvents and cyclic ether solvents. More preferably, it is a mixed solvent containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents.

[0562] Examples of alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0563] Examples of solvents for alkylene glycol ether acetates include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0564] As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated in this specification.

[0565] You can use one solvent alone, or you can use two or more solvents.

[0566] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass.

[0567] Examples of coating methods for photosensitive compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0568] The preferred drying methods for the coating of the photosensitive composition are heating drying and vacuum drying.

[0569] The preferred drying temperature is 80°C or higher, more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature.

[0570] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. While there is no particular limitation on the upper limit, it is preferably 600 seconds or less, more preferably 300 seconds or less.

[0571] Furthermore, by attaching the protective film to the photosensitive layer, the transfer film X1 of the first embodiment can be manufactured.

[0572] There are no particular limitations on the method of attaching the protective film to the photosensitive layer; well-known methods can be cited.

[0573] As a device for attaching a protective film to a photosensitive layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0574] The laminator is preferably equipped with any heatable roller, such as a rubber roller, which can apply pressure and heat.

[0575] The transfer film X1 of the first embodiment is preferably used in the formation of circuit wiring disposed on a support substrate such as a sheet, metal substrate, ceramic substrate, or glass in the manufacturing process film of semiconductor packaging, printed circuit board, interposer, and rewiring layer.

[0576] • Transfer film X2 of the second embodiment

[0577] Hereinafter, an example of an embodiment of the transfer film X2 of the second embodiment will be described.

[0578] Figure 2 The transfer film 20 shown in the figure has a temporary 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.

[0579] in addition, Figure 2 The transfer film 20 shown is in the form of having a protective film 21 configured, but the protective film 21 may not be configured.

[0580] and, Figure 2 The transfer film 20 shown is configured with a refractive index adjustment layer 17, but the refractive index adjustment layer 17 may not be configured.

[0581] In addition, Figure 2 In this context, each layer other than the protective film 21 that can be disposed on the temporary support 11 is called the composition layer 17.

[0582] The components constituting the transfer film X2 will now be described. Furthermore, the structures of the intermediate layer and temporary support constituting the transfer film X2 are as described above. The structure of the protective film is the same as that of the transfer film X1.

[0583] Photosensitive layer

[0584] The transfer film X2 of the second embodiment has a photosensitive layer.

[0585] By transferring a photosensitive layer onto a substrate and then exposing and developing it, a pattern can be formed on the substrate.

[0586] As the photosensitive layer, a negative photosensitive layer is preferred. Furthermore, a negative photosensitive layer is a photosensitive layer in which the solubility of the exposed portion in the developer decreases upon exposure. When the photosensitive layer is a negative photosensitive layer, the resulting pattern is equivalent to a cured layer.

[0587] The following is a detailed description of the components that can be contained in the photosensitive layer.

[0588] ...adhesive polymers

[0589] The photosensitive layer may contain an adhesive polymer.

[0590] Examples of adhesive polymers include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, polyurethane resins, epoxy acrylate resins obtained by reacting epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides.

[0591] As one of the preferred adhesive polymers, (meth)acrylic resins can be cited from the viewpoint of excellent alkali developability and film forming properties.

[0592] Furthermore, in this specification, (meth)acrylic resin refers to a resin having structural units derived from (meth)acrylic acid compounds. The content of structural units derived from (meth)acrylic acid compounds relative to all structural units of the (meth)acrylic acid resin is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0593] (Meth)acrylic resins can consist solely of structural units derived from (meth)acrylic acid compounds, or they can contain structural units derived from polymerizable monomers other than (meth)acrylic acid compounds. Specifically, the maximum content of structural units derived from (meth)acrylic acid compounds is less than 100% by mass relative to all structural units of the (meth)acrylic resin.

[0594] Examples of (meth)acrylic acid compounds include, for example, (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile.

[0595] Examples of (meth)acrylates include, for example, alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0596] Examples of (meth)acrylamides include, for example, diacetone acrylamide and other acrylamides.

[0597] The alkyl group in an alkyl (meth)acrylate can be linear or branched. Specific examples include alkyl (meth)acrylates having alkyl groups having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0598] As a (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0599] (Meth)acrylic resins can have structural units other than those derived from (meth)acrylic acid compounds.

[0600] As a polymerizable monomer that forms the above-mentioned structural unit, there are no particular restrictions as long as it is a compound other than (meth)acrylic acid compound that can copolymerize with (meth)acrylic acid compound. For example, it may have substituents at the α-position or on the aromatic ring of styrene, vinyltoluene and α-methylstyrene.

[0601] Examples include styrene compounds, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinonic acid, itaconic acid and crotonic acid.

[0602] These polymerizable monomers can be used in one or in combination of two or more.

[0603] Furthermore, from the viewpoint of improving alkaline developability, it is preferable that the (meth)acrylic resin contains structural units having acid groups. Examples of acid groups include carboxyl groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups.

[0604] The (meth)acrylic resin is more preferably a structural unit containing a carboxyl group, and even more preferably a structural unit derived from the above-mentioned (meth)acrylic acid.

[0605] From the viewpoint of superior developability, the content of acid-containing structural units (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. Furthermore, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

[0606] Furthermore, the (meth)acrylic resin is more preferably having structural units derived from the above-mentioned alkyl methacrylate.

[0607] The content of structural units derived from alkyl methacrylates in (meth)acrylic resins is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 90% by mass, relative to all structural units of (meth)acrylic resins.

[0608] As a (meth)acrylic resin, a resin having both structural units derived from (meth)acrylic acid and structural units derived from alkyl methacrylates is preferred, and a resin consisting only of structural units derived from (meth)acrylic acid and structural units derived from alkyl methacrylates is more preferred.

[0609] Furthermore, as a (meth)acrylic resin, an acrylic resin having structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from ethyl acrylate is preferred.

[0610] Furthermore, from the viewpoint of achieving better results with the present invention, the (meth)acrylic resin preferably has at least one structural unit selected from methacrylic acid and structural units selected from alkyl methacrylates, and preferably has both structural units selected from methacrylic acid and structural units selected from alkyl methacrylates.

[0611] From the viewpoint of achieving better results with the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all structural units of the (meth)acrylic resin. The upper limit is not particularly limited and can be 100% by mass or less, preferably 80% by mass or less.

[0612] Furthermore, from the viewpoint of achieving better results with the present invention, the (meth)acrylic resin preferably has at least one structural unit selected from methacrylic acid and structural units selected from alkyl methacrylates, and at least one structural unit selected from acrylic acid and structural units selected from alkyl acrylates.

[0613] From the viewpoint of achieving better results from the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate is preferably 60 / 40 to 80 / 20 by mass relative to the total content of structural units derived from acrylic acid and structural units derived from alkyl acrylate.

[0614] From the viewpoint of excellent developability of the photosensitive layer after transfer, (meth)acrylic resin is preferably one with ester groups at the ends.

[0615] Furthermore, the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. (Meth)acrylic resins with ester groups at the terminals can be synthesized using a polymerization initiator that generates free radicals containing ester groups.

[0616] Furthermore, alkali-soluble resins can be cited as another preferred type of adhesive polymer.

[0617] For example, from the viewpoint of developability, the adhesive polymer is preferably an adhesive polymer with an acid value of 60 mg KOH / g or higher.

[0618] Furthermore, from the viewpoint that a strong film can be easily formed by thermal crosslinking with the crosslinking components through heating, the adhesive polymer is more preferably a carboxyl-containing resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing resin), and even more preferably a carboxyl-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing (meth)acrylic resin).

[0619] If the adhesive polymer is a resin containing carboxyl groups, the three-dimensional crosslinking density can be increased by thermally crosslinking, for example, by adding thermally crosslinking compounds such as end-capped isocyanates. Furthermore, if the carboxyl groups of the resin are anhydrous and hydrophobic, the resistance to damp heat can be improved.

[0620] As for carboxyl-containing (meth)acrylic resins with an acid value of 60 mg KOH / g or higher, there are no particular restrictions as long as the above acid value condition is met, and appropriate selection can be made from known (meth)acrylic resins.

[0621] For example, acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher in polymers described in Japanese Patent Application Publication No. 2011-095716 (section

[0025] ) and acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher in polymers described in Japanese Patent Application Publication No. 2010-237589 (sections

[0033] to

[0052] ) are preferred.

[0622] Other preferred types of adhesive polymers include styrene-acrylic acid copolymers.

[0623] In addition, in this specification, styrene-acrylic acid copolymer refers to a resin having structural units derived from styrene compounds and structural units derived from (meth)acrylic acid compounds, wherein the total content of the structural units derived from the styrene compounds and the structural units derived from the (meth)acrylic acid compounds is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all structural units of the copolymer.

[0624] Furthermore, the content of structural units derived from styrene compounds relative to all structural units of the aforementioned copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass.

[0625] Furthermore, the content of structural units derived from the above-mentioned (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, relative to all structural units of the above-mentioned copolymer.

[0626] From the viewpoint of achieving better results with the present invention, the adhesive polymer is preferably having an aromatic ring structure, and more preferably containing structural units having an aromatic ring structure.

[0627] Examples of monomers that form structural units with aromatic ring structures include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers having aralkyl groups or styrene are preferred.

[0628] Examples of aryl alkyl groups include substituted or unsubstituted phenylalkyl groups (with benzyl removed) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0629] Examples of monomers containing phenyl alkyl groups include ethyl methacrylate (meth)acrylate.

[0630] Examples of monomers containing a benzyl group include (meth)acrylates, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; and vinyl monomers, such as vinyl benzyl chloride and benzyl alcohol. Among these, benzyl (meth)acrylate is preferred.

[0631] Furthermore, from the viewpoint of achieving better results with the present invention, the adhesive polymer is more preferably having a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0632] [Chemical Formula 3]

[0633]

[0634] From the viewpoint of achieving better results in the present invention, when the adhesive polymer contains structural units having aromatic ring structures, the content of structural units having aromatic ring structures relative to all structural units of the adhesive polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass.

[0635] Furthermore, from the viewpoint of achieving better results with the present invention, the content of the structural unit having an aromatic ring structure in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol%.

[0636] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural unit represented by the above formula (S) in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, even more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%.

[0637] Furthermore, in this specification, when the content of "structural unit" is specified in molar ratio, the term "structural unit" is synonymous with "monomer unit." Also, in this specification, the term "monomer unit" can be modified after polymerization through polymer reactions, etc. The same applies below.

[0638] From the viewpoint of achieving better results with the present invention, the adhesive polymer preferably has an aliphatic hydrocarbon ring structure. That is, the adhesive polymer preferably contains structural units having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure can be a monocyclic or polycyclic structure. More preferably, the adhesive polymer is a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings.

[0639] Examples of aliphatic hydrocarbon rings that constitute structural units with aliphatic hydrocarbon ring structures include tricyclic decane rings, cyclohexane rings, cyclopentane rings, norbornene rings, and isophorone rings.

[0640] From the viewpoint of achieving better results with this invention, a ring consisting of two or more fused aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclic [5.2.1.0]) is more preferably preferred. 2，6 [decane ring].

[0641] Examples of monomers that form structural units with aliphatic hydrocarbon ring structures include dicyclopentyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

[0642] Furthermore, from the viewpoint of achieving better results with the present invention, the adhesive polymer is more preferably having the structural unit represented by the following formula (Cy), and more preferably having the structural unit represented by the above formula (S) and the structural unit represented by the following formula (Cy).

[0643] [Chemical Formula 4]

[0644]

[0645] In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

[0646] R in equation (Cy) M Methyl is preferred.

[0647] From the viewpoint that the present invention has superior effects, R in formula (Cy) Cy Preferably, it is a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms.

[0648] Furthermore, from the viewpoint that the present invention has superior effects, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in the sample is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornene ring structure, or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.

[0649] From the viewpoint that the present invention has superior effects, R of formula (Cy) Cy The preferred aliphatic hydrocarbon ring structure is a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings, and more preferably a ring formed by the fusion of two to four aliphatic hydrocarbon rings.

[0650] Furthermore, from the viewpoint that the present invention has superior effects, R in formula (Cy) Cy Preferably, the oxygen atom of -C(=O)O- in formula (Cy) is a group that is directly bonded to the aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon cyclic group, more preferably cyclohexyl or dicyclopentyl, and even more preferably dicyclopentyl.

[0651] The adhesive polymer may have a single structural unit with an aliphatic hydrocarbon ring structure, or it may have two or more structural units.

[0652] In cases where the adhesive polymer contains structural units having an aliphatic hydrocarbon ring structure, from the viewpoint of achieving better results in this invention, the content of structural units having an aliphatic hydrocarbon ring structure relative to all structural units of the adhesive polymer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass.

[0653] Furthermore, from the viewpoint of achieving better results with the present invention, the content of structural units having aliphatic hydrocarbon ring structures in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to all structural units of the adhesive polymer.

[0654] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural unit represented by the above formula (Cy) in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to all structural units of the adhesive polymer.

[0655] From the viewpoint of achieving better results in the present invention, when the adhesive polymer contains structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures relative to all structural units of the adhesive polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass.

[0656] Furthermore, from the viewpoint of achieving better results with the present invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures in the adhesive polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the adhesive polymer.

[0657] Furthermore, from the viewpoint of achieving even better results from the present invention, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the adhesive polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the adhesive polymer.

[0658] Furthermore, from the viewpoint of achieving better results in this 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 adhesive polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2).

[0659] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0660] 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1)

[0661] 0.40≤nS / (nS+nCy)≤0.70 Formula (SCy-2)

[0662] From the viewpoint of achieving better results in this invention, the adhesive polymer is preferably a structural unit containing an acid group.

[0663] Examples of acid groups include carboxyl, sulfonic acid, phosphonic acid, and phosphate groups, with carboxyl being the most preferred.

[0664] As the structural unit having the above-mentioned acid group, the preferred structural unit is the one derived from (meth)acrylic acid as shown below, and more preferably the structural unit derived from methacrylic acid.

[0665] [Chemical Formula 5]

[0666]

[0667] Adhesive polymers may have one or more structural units with an acid group.

[0668] From the viewpoint of achieving better results in the present invention, when the adhesive polymer contains structural units with acid groups, the content of structural units with acid groups relative to all structural units of the adhesive polymer is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass.

[0669] Furthermore, from the viewpoint of achieving better results with the present invention, the content of the structural units having acid groups in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0670] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of structural units derived from (meth)acrylic acid in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0671] From the viewpoint of achieving better results with the present invention, the adhesive polymer is preferably having reactive groups, and more preferably having structural units containing reactive groups.

[0672] As a reactive group, a free radical polymerizable group is preferred, and an olefinically unsaturated group is more preferred. Furthermore, when the adhesive polymer has an olefinically unsaturated group, the adhesive polymer preferably contains structural units having olefinically unsaturated groups in their side chains.

[0673] In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to the atomic group that branches off from the main chain.

[0674] As an olefinic unsaturated group, allyl or (meth)acryloyloxy is more preferred.

[0675] Examples of structural units with reactive groups include the structural units shown below, but are not limited to these.

[0676] [Chemical Formula 6]

[0677]

[0678] Adhesive polymers may contain only one structural unit with reactive groups, or they may contain two or more such units.

[0679] From the viewpoint of achieving better results in the present invention, when the adhesive polymer contains structural units with reactive groups, the content of structural units with reactive groups relative to all structural units of the adhesive polymer is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0680] Furthermore, from the viewpoint of achieving better results with the present invention, the content of structural units having reactive groups in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%.

[0681] As a method for introducing reactive groups into adhesive polymers, one can cite the method of reacting compounds such as epoxy compounds, terminal isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds and carboxylic anhydrides with functional groups such as hydroxyl, carboxyl, primary amino, secondary amino, acetoacetyl group and sulfonic acid group.

[0682] As a preferred example of a method for introducing reactive groups into an adhesive polymer, a method can be described in which a polymer having carboxyl groups is synthesized by polymerization, and then (meth)acryloyloxy groups are introduced into the polymer by reacting glycidyl (meth)acrylate with a portion of the carboxyl groups of the obtained polymer through a polymer reaction. By this method, an adhesive polymer having (meth)acryloyloxy groups in its side chains can be obtained.

[0683] The polymerization reaction described above is preferably carried out at a temperature of 70–100°C, more preferably at a temperature of 80–90°C. The polymerization initiator used in the above polymerization reaction is preferably an azo initiator, such as, more preferably, V-601 or V-65 manufactured by FUJIFILM Wako Pure Chemical Corporation. The above polymer reaction is preferably carried out at a temperature of 80–110°C. In the above polymer reaction, an ammonium salt or other catalyst is preferably used.

[0684] From the viewpoint of achieving better results with the present invention, polymers X1 to X4 shown below are preferred as adhesive polymers. Furthermore, the content ratios (a to d) and weight-average molecular weight Mw of each structural unit shown below can be appropriately changed according to the purpose, but from the viewpoint of achieving better results with the present invention, the following structures are preferred.

[0685] (Polymer X1) a: 20–60% by mass, b: 10–50% by mass, c: 5.0–25% by mass, d: 10–50% by mass.

[0686] (Polymer X2) a: 20–60% by mass, b: 10–50% by mass, c: 5.0–25% by mass, d: 10–50% by mass.

[0687] (Polymer X3) a: 30–65% by mass, b: 1.0–20% by mass, c: 5.0–25% by mass, d: 10–50% by mass.

[0688] (Polymer X4) a: 1.0–20% by mass, b: 20–60% by mass, c: 5.0–25% by mass, d: 10–50% by mass.

[0689] [Chemical Formula 7]

[0690]

[0691] Furthermore, the adhesive polymer may contain polymers with structural units having a carboxylic anhydride structure (hereinafter also referred to as "polymer X").

[0692] The carboxylic anhydride structure can be either a chain-like carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but a cyclic carboxylic anhydride structure is preferred.

[0693] The ring in the cyclic carboxylic anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered or 6-membered ring, and even more preferably a 5-membered ring.

[0694] The structural unit having a carboxylic anhydride structure is preferably a structural unit in which a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 is directly or via a divalent linker bonded to the main chain.

[0695] [Chemical Formula 8]

[0696]

[0697] In equation P-1, R A1a Indicates substituent, n 1a R A1a They can be the same or different, Z 1a This indicates a divalent group that forms a ring containing -C(=O)-OC(=O)-, n 1a Represents integers greater than or equal to 0.

[0698] As R A1a The substituents represented, for example, include alkyl groups.

[0699] As Z 1a Preferably, it is an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.

[0700] n 1a Represents integers greater than or equal to 0. In Z... 1aIn the case of alkylene groups having 2 to 4 carbon atoms, n 1a Preferably, it is an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0.

[0701] In n 1a When representing integers greater than 2, there exist multiple R values. A1a They can be the same or different. Furthermore, there can be multiple R values. A1a They can bond together to form a ring, but it is preferable that they bond together without forming a ring.

[0702] As a structural unit having a carboxylic anhydride structure, it is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, even more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, especially preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0703] The following are specific examples of structural units having a carboxylic anhydride structure, but structural units having a carboxylic anhydride structure are not limited to these specific examples. In the structural units described below, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0704] [Chemical Formula 9]

[0705]

[0706] [Chemical Formula 10]

[0707]

[0708] The structural units with carboxylic anhydride structures in polymer X can be a single type or two or more types.

[0709] The total content of structural units having a carboxylic anhydride structure relative to all structural units of polymer X is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 35 mol%.

[0710] The photosensitive layer may contain only one polymer X, or it may contain two or more polymers X.

[0711] When the photosensitive layer contains polymer X, from the viewpoint of achieving better results according to the present invention, the content of polymer X relative to the total mass of the photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass.

[0712] From the viewpoint of achieving better results from the present invention, the weight-average molecular weight (Mw) of the adhesive polymer is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0713] The acid value of the adhesive polymer is preferably 10-200 mg KOH / g, more preferably 60-200 mg KOH / g, even more preferably 60-150 mg KOH / g, and especially preferably 70-125 mg KOH / g.

[0714] In addition, the acid value of the adhesive polymer can be measured, for example, according to the method described in JIS K0070:1992.

[0715] From the viewpoint of developability, the dispersion of the adhesive polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0716] The photosensitive layer may contain only one type of adhesive polymer, or it may contain two or more types.

[0717] From the viewpoint of achieving better results with the present invention, the content of the adhesive 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 even more preferably 30 to 70% by mass.

[0718] Polymer compounds

[0719] The photosensitive layer may contain polymeric compounds.

[0720] Polymerizable compounds are compounds having polymerizable groups. Examples of polymerizable groups include free radical polymerizable groups and cationic polymerizable groups, with free radical polymerizable groups being preferred.

[0721] The polymerizable compound is preferably a free radical polymerizable compound containing an olefinically unsaturated group (hereinafter also simply referred to as "olefinically unsaturated compound").

[0722] As an olefinic unsaturated group, (meth)acryloyloxy is preferred.

[0723] In addition, the olefinic unsaturated compounds in this specification are compounds other than the adhesive polymers mentioned above, and preferably have a molecular weight of less than 5,000.

[0724] As one of the preferred methods for polymerizable compounds, compounds represented by the following formula (M) (also simply referred to as "compound M") can be cited.

[0725] Q2 -R 1 -Q 1 Formula (M)

[0726] In formula (M), Q 1 and Q 2 Each independently represents (meth)acryloyloxy, R 1 This represents a divalent linker with a chain-like structure.

[0727] Q in equation (M) 1 and Q 2 From the perspective of ease of synthesis, Q is preferred. 1 and Q 2 They are the same functional groups.

[0728] Furthermore, from a reactive point of view, Q in equation (M) 1 and Q 2 Acryloyloxy is preferred.

[0729] As R in equation (M) 1 From the viewpoint of achieving better results in this invention, alkylene or alkoxide-containing compounds (-L) are preferred. 1 -OL 1 -) or polyalkoxyalkylene (-(L 1 -O) p -L 1 -), more preferably a hydrocarbon group or a polyalkoxyalkylene group having 2 to 20 carbon atoms, even more preferably an alkylene group having 4 to 20 carbon atoms, and especially preferably a straight-chain alkylene group having 6 to 18 carbon atoms.

[0730] The aforementioned hydrocarbon group only needs to have a chain structure in at least a portion. The portion other than the aforementioned chain structure is not particularly limited. For example, it can be any one of branched, cyclic, or straight-chain alkylene, aryl, ether bond, and combinations thereof with 1 to 5 carbon atoms. It is preferably an alkylene group or a group formed by combining 2 or more alkylene groups with 1 or more aryl groups, more preferably an alkylene group, and even more preferably a straight-chain alkylene group.

[0731] In addition, the above L 1 Each alkyl group is independently represented, preferably vinyl, propylene, or butylene, more preferably vinyl or 1,2-propylene. p represents an integer of 2 or more, preferably an integer from 2 to 10.

[0732] Furthermore, from the viewpoint of achieving better results in this invention, the link Q in compound M... 1 With Q 2 The number of atoms in the shortest connecting chain is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and particularly preferably 8 to 12.

[0733] In this manual, "Connecting Q" 1 With Q 2 "The number of atoms in the shortest link chain between Q" refers to the number of atoms in the link chain between Q and Q. 1 R 1 The atoms are connected to Q. 2 R 1 The shortest number of atoms that can be connected to another atom.

[0734] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. These ester monomers can also be used in mixtures.

[0735] From the viewpoint of achieving better results in this invention, the preferred compound among the above-mentioned compounds is at least one selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; more preferably, at least one selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate; and even more preferably, at least one selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

[0736] Furthermore, as one of the preferred types of polymerizable compounds, olefinic unsaturated compounds with more than two functions can be cited.

[0737] In this specification, "a 2 or more functional olefin unsaturated compound" refers to a compound having 2 or more olefin unsaturated groups in one molecule.

[0738] The preferred olefinic unsaturated group in an olefinic unsaturated compound is (meth)acryloyl.

[0739] As an olefinic unsaturated compound, (meth)acrylate compounds are preferred.

[0740] As a difunctional olefinic unsaturated compound, it is not particularly restricted and can be appropriately selected from known compounds.

[0741] Examples of difunctional olefinic unsaturated compounds other than compound M mentioned above include tricyclodecanediethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0742] Commercially available examples of difunctional olefinic unsaturated compounds include tricyclodecanediethanol diacrylate (product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol 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.), and 1,6-hexanediol diacrylate (product name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0743] As an olefinic unsaturated compound with more than three functions, it is not particularly restricted and can be appropriately selected from known compounds.

[0744] Examples of olefinic unsaturated compounds with more than three functions include dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate skeletons.

[0745] Here, "(tri / tetra / penta / hexa)meth)acrylate" refers to the concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" refers to the concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0746] Examples of polymerizable compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy-modified (meth)acrylate compounds (such as KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glycerol triacrylates (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0747] Other examples of polymerizable compounds include urethane (meth)acrylate compounds.

[0748] Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.

[0749] Furthermore, urethane (meth)acrylates with 3 or more functional groups can be cited as examples. As a lower limit for the number of functional groups, 6 or more functional groups are more preferred, and 8 or more functional groups are even more preferred. Additionally, as an upper limit for the number of functional groups, 20 or fewer functional groups are preferred. Examples of urethane (meth)acrylates with three or more functions include, for example, 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., as well as UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0750] As one of the preferred methods for polymerizable compounds, olefinic unsaturated compounds with acid groups can be cited.

[0751] Examples of acid groups include phosphate groups, sulfonic acid groups, and carboxyl groups.

[0752] Among these, the carboxyl group is preferred as the acid group.

[0753] Examples of olefinic unsaturated compounds with acid groups include 3- to 4-functional olefinic unsaturated compounds with acid groups (compounds with carboxyl groups introduced into the pentaerythritol triacrylate and tetraacrylate (PETA) skeleton, 80-120 mg KOH / g) and 5- to 6-functional olefinic unsaturated compounds with acid groups (compounds with carboxyl groups introduced into the dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) skeleton, 25-70 mg KOH / g).

[0754] These trifunctional or more olefinic unsaturated compounds with acid groups can be used simultaneously with difunctional olefinic unsaturated compounds with acid groups, as needed.

[0755] As an olefinic unsaturated compound having an acid group, it is preferably selected from at least one of olefinic unsaturated compounds having two or more functions having a carboxyl group and their carboxylic anhydrides.

[0756] If the olefinic unsaturated compound having an acid group is selected from at least one of olefinic unsaturated compounds with two or more functions having a carboxyl group and their carboxylic anhydrides, then the reproducibility and film strength are further improved.

[0757] There are no particular restrictions on difunctional or more olefinic unsaturated compounds with carboxyl groups, and appropriate selection can be made from known compounds.

[0758] Examples of olefinic unsaturated compounds with more than two functions, including a carboxyl 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.).

[0759] As an olefinic unsaturated compound having an acid group, the preferred choice is a polymeric compound having an acid group as described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942, and the contents described in that publication are incorporated into this specification.

[0760] Examples of olefinically unsaturated compounds include, for instance, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols, compounds obtained by reacting α,β-unsaturated carboxylic acids with compounds containing glycidyl groups, urethane monomers such as (meth)acrylate compounds having urethane bonds, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, as well as alkyl (meth)acrylates.

[0761] These can be used individually or in combination of two or more.

[0762] Examples of compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols include, for example, bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate with 2 to 14 propylene oxide groups; and polyethylene glycol polypropylene glycol with 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. Di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane)tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0763] Preferably, the compound is an olefinic unsaturated compound having a tetrahydroxymethylmethane structure or a trihydroxymethylpropane structure, more preferably a tetrahydroxymethylmethane tri(meth)acrylate, a tetrahydroxymethylmethane tetra(meth)acrylate, a trihydroxymethylpropane tri(meth)acrylate, or a di(trihydroxymethylpropane)tetraacrylate.

[0764] Examples of polymerizable compounds include caprolactone-modified olefinic compounds (e.g., KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-modified olefinic compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glycerol triacrylates (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0765] From the viewpoint of excellent developability of the transferred photosensitive layer, compounds containing ester bonds are preferred as polymerizable compounds (especially olefinically unsaturated compounds).

[0766] As an olefinic unsaturated compound containing ester bonds, it is not particularly limited as long as it contains ester bonds within the molecule. However, from the viewpoint of superior effect of the present invention, it is preferred to have an olefinic unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure, and more preferably tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate.

[0767] From the viewpoint of imparting reliability, olefinic unsaturated compounds are preferably those containing aliphatic groups having 6 to 20 carbon atoms or those having a tetrahydroxymethylmethane or trihydroxymethylpropane structures.

[0768] Examples of olefinic unsaturated compounds with an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecanediethanol di(meth)acrylate.

[0769] As one of the preferred types of polymerizable compounds, polymerizable compounds having an aliphatic hydrocarbon ring structure (preferably difunctional olefinic unsaturated compounds) can be cited.

[0770] As the aforementioned polymerizable compound, a polymerizable compound having a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings (preferably a structure selected from tricyclodecane and tricyclodecene structures) is preferred, a difunctional olefinic unsaturated compound having a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings is more preferred, and tricyclodecanediethanol di(meth)acrylate is even more preferred.

[0771] From the viewpoint of achieving better results in this invention, the preferred aliphatic hydrocarbon ring structures are cyclopentane, cyclohexane, tricyclodecane, tricyclodecene, norbornene, or isophorone.

[0772] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0773] The proportion of polymeric compounds with a molecular weight of 300 or less in the photosensitive layer is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total content of all polymeric compounds in the photosensitive layer.

[0774] As one of the preferred methods for a photosensitive layer, the photosensitive layer is preferably an olefin unsaturated compound containing two or more functions, more preferably an olefin unsaturated compound containing three or more functions, and even more preferably an olefin unsaturated compound containing three or four functions.

[0775] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is preferably a binder polymer comprising a difunctional olefinic unsaturated compound having an aliphatic hydrocarbon ring structure and an adhesive polymer containing structural units having an aliphatic hydrocarbon ring.

[0776] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably includes compounds represented by formula (M) and olefinic unsaturated compounds having acid groups, more preferably including 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate and polyfunctional olefinic unsaturated compounds having carboxylic acid groups, and even more preferably a succinic acid modified form including 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate and dipentaerythritol pentaacrylate.

[0777] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is preferably a compound represented by formula (M), an olefinic unsaturated compound having an acid group, and a thermally crosslinking compound described later, and more preferably a compound represented by formula (M), an olefinic unsaturated compound having an acid group, and a capped isocyanate compound described later.

[0778] Furthermore, as one of the preferred methods for the photosensitive layer, from the viewpoint of suppressing development residue and preventing rust, the photosensitive layer is preferably composed of a difunctional olefin unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or more olefin unsaturated compound (preferably a trifunctional or more meth)acrylate compound).

[0779] The mass ratio of the content of difunctional olefinic unsaturated compounds to difunctional or more olefinic unsaturated compounds is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.

[0780] The content of the 2-functional olefinic unsaturated compound relative to the total amount of all olefinic unsaturated compounds is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

[0781] The difunctional olefinic unsaturated compound in the photosensitive layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.

[0782] Furthermore, as one of the preferred methods for the photosensitive layer, from the viewpoint of rust prevention, the photosensitive layer is preferably a compound containing compound M and a difunctional olefinic unsaturated compound having an aliphatic hydrocarbon ring structure.

[0783] Furthermore, as one of the preferred embodiments of the photosensitive layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive layer is preferably a compound M and an olefin unsaturated compound having an acid group, more preferably a compound M, a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, and an olefin unsaturated compound having an acid group, even more preferably a compound M, a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher olefin unsaturated compound, and an olefin unsaturated compound having an acid group, and especially preferably a compound M, a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher olefin unsaturated compound, an olefin unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

[0784] Furthermore, as one of the preferred embodiments of the photosensitive layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive layer preferably comprises 1,9-nonanediol diacrylate and a polyfunctional olefin unsaturated compound having a carboxylic acid group, more preferably comprising 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate and a polyfunctional olefin unsaturated compound having a carboxylic acid group, further preferably comprising 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate and an olefin unsaturated compound having a carboxylic acid group, and especially preferably comprising 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, an olefin unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0785] The photosensitive layer may contain monofunctional olefin unsaturated compounds as olefin unsaturated compounds.

[0786] The content of the olefinic unsaturated compounds with two or more functions in the above-mentioned olefinic unsaturated compounds is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total content of all olefinic unsaturated compounds contained in the photosensitive layer.

[0787] Polymerizable compounds (especially olefinic unsaturated compounds) can be used alone or in combination with two or more compounds.

[0788] The content of polymeric compounds (especially olefinic unsaturated compounds) in the photosensitive layer is preferably 1 to 70% by mass relative to the total mass of the photosensitive layer, more preferably 5 to 70% by mass, even more preferably 5 to 60% by mass, and especially preferably 5 to 50% by mass.

[0789] Polymerization initiators

[0790] The photosensitive layer may contain a polymerization initiator.

[0791] As a polymerization initiator, a photopolymerization initiator is preferred.

[0792] As a photopolymerization initiator, it is not particularly restricted and can use known photopolymerization initiators.

[0793] Examples of photopolymerization initiators include photopolymerization initiators with oxime ester structures (hereinafter also called "oxime-based photopolymerization initiators"), photopolymerization initiators with α-aminoalkylphenyl ketone structures (hereinafter also called "α-aminoalkylphenyl ketone-based photopolymerization initiators"), photopolymerization initiators with α-hydroxyalkylphenyl ketone structures (hereinafter also called "α-hydroxyalkylphenyl ketone-based polymerization initiators"), photopolymerization initiators with acylphosphine oxide structures (hereinafter also called "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators with N-phenylglycine structures (hereinafter also called "N-phenylglycine-based photopolymerization initiators").

[0794] The photopolymerization initiator preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylbenzophenone-based photopolymerization initiators, α-hydroxyalkylbenzophenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylbenzophenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0795] Furthermore, as a photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of Japanese Patent Application Publication No. 2011-95716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Publication No. 2015-014783 may also be used.

[0796] 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], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(o-acetyl oxime) [product name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [product name: Omnirad (registered trademark) 379EG, IGM Resins] [BV Manufacturing], 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one [Product Name: Omnirad (Registered Trademark) 907, IGM Resins BV Manufacturing], 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one [Product Name: Omnirad (Registered Trademark) 127, IGM Resins BV Manufacturing], 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [Product Name: Omnirad (Registered Trademark) 369, IGM Resins BV Manufacturing], 2-Hydroxy-2-methyl-1-phenylpropane-1-one [Product Name: Omnirad (Registered Trademark) 1173, IGM Resins BV Manufacturing], 1-Hydroxycyclohexylphenyl ketone [Product Name: Omnirad (Registered Trademark) 184, IGM Resins [BV Manufacturing], 2,2-Dimethoxy-1,2-diphenylethyl-1-one [Product Name: Omnirad (Registered Trademark) 651, IGM Resins BV Manufacturing], etc., oxime esters [Product Name: Lunar (Registered Trademark) 6, DKSH MANAGEMENT LTD. Manufacturing], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (Product Name: TR-PBG-305, Changzhou Tronly NewElectronic Materials CO.,LTD. Manufacturing), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(o-acetyl oxime) (Product Name: TR-PBG-326, Changzhou Tronly NewElectronic Materials CO.,LTD. Manufacturing).Manufactured by: 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-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-morpholinopropane-1-one, manufactured by Shenzhen UV-ChemTech Ltd.), etc.

[0797] Photopolymerization initiators can be used alone or in combination with two or more.

[0798] When using two or more at the same time, it is preferable to use an oxime-based photopolymerization initiator and at least one selected from α-aminoalkylphenyl ketone-based photopolymerization initiator and α-hydroxyalkylphenyl ketone-based polymerization initiator.

[0799] 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 even more preferably 1.0% by mass or more. Furthermore, as an upper limit, it is preferably 10% by mass or less relative to the total mass of the photosensitive layer, more preferably 5% by mass or less.

[0800] Heterocyclic compounds

[0801] The photosensitive layer may contain heterocyclic compounds.

[0802] Heterocyclic compounds can have any type of heterocycle, including monocyclic and polycyclic heterocycles.

[0803] Examples of heteroatoms in heterocyclic compounds include nitrogen, oxygen, and sulfur atoms. Heterocyclic compounds preferably have at least one atom selected from nitrogen, oxygen, and sulfur atoms, and more preferably have a nitrogen atom.

[0804] Examples of heterocyclic compounds include, for example, triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, razotanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0805] In the above, the heterocyclic compound is preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, razotanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0806] The following are preferred examples of heterocyclic compounds. Examples of triazole and benzotriazole compounds include the following compounds.

[0807] [Chemical Formula 11]

[0808]

[0809] [Chemical Formula 12]

[0810]

[0811] The following compounds can be cited as examples of tetrazolium compounds.

[0812] [Chemical Formula 13]

[0813]

[0814] [Chemical Formula 14]

[0815]

[0816] The following compounds can be cited as examples of thiadiazole compounds.

[0817] [Chemical Formula 15]

[0818]

[0819] The following compounds can be cited as examples of triazine compounds.

[0820] [Chemical Formula 16]

[0821]

[0822] The following compounds can be cited as examples of cyclotannin compounds.

[0823] [Chemical Formula 17]

[0824]

[0825] The following compounds can be cited as examples of thiazole compounds.

[0826] [Chemical Formula 18]

[0827]

[0828] The following compounds can be cited as examples of benzothiazole compounds.

[0829] [Chemical Formula 19]

[0830]

[0831] The following compounds can be cited as examples of benzimidazole compounds.

[0832] [Chemical Formula 20]

[0833]

[0834] [Chemical Formula 21]

[0835]

[0836] The following compounds can be cited as examples of benzoxazole compounds.

[0837] [Chemical Formula 22]

[0838]

[0839] Heterocyclic compounds can be used alone or in combination with two or more compounds.

[0840] When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound relative to the total mass of the photosensitive layer is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, even more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass.

[0841] ...aliphatic thiols

[0842] The photosensitive layer may contain aliphatic thiols.

[0843] By incorporating aliphatic thiols in the photosensitive layer, and allowing the aliphatic thiols to undergo an olefin-thiol reaction with a free radical polymerizable compound having olefin unsaturated groups, the curing shrinkage of the resulting film is suppressed, and stress is alleviated.

[0844] As an aliphatic thiol compound, it is preferred to be a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound with two or more functions).

[0845] Of the above, from the viewpoint of the adhesion of the formed pattern (especially the adhesion after exposure), a multifunctional aliphatic thiol compound is preferred as the aliphatic thiol compound.

[0846] In this specification, "multifunctional aliphatic thiols" refers to aliphatic compounds having two or more thiol groups (also called "mercapto groups") within their molecules.

[0847] As a multifunctional aliphatic thiol compound, a low molecular weight compound with a molecular weight of 100 or more is preferred. Specifically, the molecular weight of the multifunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0848] The number of functional groups in a multifunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of the tightness of the formed pattern.

[0849] Examples of multifunctional aliphatic thiols include, for instance, trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetra(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, and trihydroxy... Methylpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethylenedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethylthiol, meso 2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0850] In the above, the multifunctional aliphatic thiol compound is preferably at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0851] Examples of monofunctional aliphatic thiols include, for example, 1-octylthiol, 1-dodecylthiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearic acid-3-mercaptopropionate.

[0852] The photosensitive layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0853] When the photosensitive layer contains aliphatic thiol compounds, the content of aliphatic thiol compounds relative to the total mass of the photosensitive layer is preferably 5% by mass or more, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass.

[0854] ...thermal crosslinking compounds

[0855] From the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, the photosensitive layer preferably contains a thermally crosslinking compound. Furthermore, in this specification, the thermally crosslinking compound having olefinic unsaturated groups described later is not treated as an olefinic unsaturated compound, but rather as a thermally crosslinking compound.

[0856] Examples of thermally crosslinking compounds include epoxy compounds, oxetane compounds, hydroxymethyl compounds, and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred from the viewpoint of the strength of the cured film and the adhesion of the uncured film.

[0857] When the capped isocyanate compound reacts with hydroxyl and carboxyl groups, and at least one of the adhesive polymers and free radical polymers having olefinic unsaturated groups has at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film tends to decrease and its function as a protective film is enhanced.

[0858] In addition, capped isocyanate compounds are defined as "compounds having a structure in which isocyanate groups of isocyanate are protected (so-called masking) by capping agents".

[0859] The dissociation temperature of the capped isocyanate compound is not particularly limited, but it is preferably 100–160°C, more preferably 130–150°C.

[0860] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates, as measured by differential scanning calorimetry (DSC) using a differential scanning calorimeter".

[0861] As a 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.

[0862] Examples of end-capping agents with dissociation temperatures of 100–160°C include active methylene compounds (malonate esters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., which have a structure represented by -C (=N-OH)- in the molecule).

[0863] Among these, at least one of the oxime compounds is preferred as a capping agent with a dissociation temperature of 100 to 160°C, for example, from the viewpoint of preservation stability.

[0864] For example, from the viewpoint of improving the brittleness of the film and enhancing its adhesion to the substrate, the end-capped isocyanate compound is preferably having an isocyanurate structure.

[0865] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0866] Among the isocyanate compounds with an isocyanurate structure, compounds containing an oxime structure with an oxime compound as a capping agent are preferred from the viewpoint that it is easier to set the dissociation temperature within a preferred range and easier to reduce development residue compared to compounds without an oxime structure.

[0867] End-capped isocyanate compounds can have polymerizable groups.

[0868] As a polymerizable group, it is not particularly limited and can use known polymerizable groups, preferably free radical polymerizable groups.

[0869] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0870] Among them, the polymerizable group is preferably an olefinic unsaturated group, more preferably (meth)acryloyloxy, and even more preferably acryloyloxy.

[0871] As a capped isocyanate compound, it can be used in commercially available products.

[0872] Examples of commercially available isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and the end-capped DURANATE series (e.g., DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0873] Thermally crosslinking compounds can be used alone or in combination with two or more compounds.

[0874] When the photosensitive layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

[0875] Surfactants

[0876] The photosensitive layer may contain surfactants.

[0877] As surfactants, examples include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Publication No. 2009-237362.

[0878] The surfactant is preferably a nonionic surfactant, a fluorinated surfactant, or a silicone surfactant. Furthermore, a nonionic surfactant is preferred.

[0879] Commercially available fluorinated surfactants include, for example, 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, etc. MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-6 31. 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 is DIC (manufactured by CORPORATION), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC INC.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions). (manufactured by NEOS Corporation), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Corporation), U-120E (UNICHEMCO., LTD.), etc.

[0880] Furthermore, acrylic compounds are preferably used as fluorinated surfactants. These compounds have a molecular structure containing functional groups with fluorine atoms, and when heated, the functional groups containing fluorine atoms are partially cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MEGAFACEDS series manufactured by DIC Corporation (Hydrogen Kagaku Nihon (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as MEGAFACE DS-21.

[0881] Furthermore, as a fluorinated surfactant, a polymer of a fluorinated vinyl ether compound having fluorinated alkyl or fluorinated alkylene ether groups and a hydrophilic vinyl ether compound is preferred.

[0882] Furthermore, as a fluorinated surfactant, block polymers can also be used.

[0883] Furthermore, as a fluorinated surfactant, a fluorinated polymer compound can preferably be used, which comprises structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethyleneoxy or propyleneoxy groups).

[0884] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with olefinically unsaturated groups in the side chains. Examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0885] From the perspective of improving environmental adaptability, compounds with straight-chain perfluoroalkyl groups having 7 or more carbon atoms are preferred as fluorinated surfactants, and are alternatives to PFOA or PFOS.

[0886] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters. Specific examples include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all manufactured by BASF), SOLSPERSE 20000 (all manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Pionin D-1105, D-6112, D-6112-W, D-6315 (all manufactured by TAKEMOTO OIL&FAT Co., Ltd.), and OLFINE. E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.) etc.

[0887] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers obtained by introducing organic groups into the side chains or ends.

[0888] 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, and Toray Silicone... SH30PA, Toray Silicone SH8400 (all manufactured by BYK-Chemie GmbH), and models 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, and KP-101. KP-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 Shin-Etsu (Manufactured by Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by MomentivePerformance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (manufactured by BYK Chemie GmbH), etc.

[0889] Surfactants can be used alone or in combination with two or more.

[0890] When the photosensitive layer contains a surfactant, the surfactant content relative to the total mass of the photosensitive layer is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass.

[0891] ...polymerization inhibitors

[0892] The photosensitive layer may contain polymerization inhibitors.

[0893] Polymerization inhibitors are compounds that have the function of delaying or inhibiting polymerization reactions. For example, known compounds that are used as polymerization inhibitors can be used as polymerization inhibitors.

[0894] Examples of polymerization inhibitors include phenothiazine compounds such as bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(oxyvinyl)]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-butylaniline)-1,3,5 Hindered phenolic compounds such as triazine and pentaerythritol tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

[0895] From the viewpoint of achieving better results with the present invention, the polymerization inhibitor is preferably selected from at least one of phenothiazine compounds, nitroso compounds or their salts, and hindered phenolic compounds, more preferably phenothiazine, 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.

[0896] Polymerization inhibitors can be used alone or in combination with two or more.

[0897] When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total mass of the photosensitive layer is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.02 to 2.0% by mass. The content of the polymerization inhibitor relative to the total mass of the polymerizable compound is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass.

[0898] ...hydrogen-donating compounds

[0899] The photosensitive layer may contain hydrogen-donating compounds.

[0900] Hydrogen-donating compounds can further enhance the sensitivity of photopolymerization initiators to activating light and inhibit the polymerization hindrance of polymerizable compounds caused by oxygen.

[0901] Examples of hydrogen-donating compounds include, for example, amines and amino acid compounds.

[0902] As amines, examples include M.R. Sander et al., "Journal of Polymer Society", Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Application Publication No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure. Compounds described in reference 33825, etc. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0903] From the viewpoint of achieving better results in this invention, the amine is preferably at least one selected from 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0904] Examples of amino acid compounds include, for example, N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0905] From the viewpoint of achieving better results in this invention, N-phenylglycine is preferred as the amino acid compound.

[0906] Furthermore, examples of hydrogen-donating compounds include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithianes) described in Japanese Patent Application Publication No. 6-308727.

[0907] Hydrogen-donating compounds can be used alone or in combination with two or more.

[0908] When the photosensitive layer contains a hydrogen-donating compound, from the viewpoint of improving the curing speed by balancing the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound relative to the total mass of the photosensitive layer is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and even more preferably 0.03 to 5.0% by mass.

[0909] ...impurities, etc.

[0910] The photosensitive layer may contain a specified amount of impurities.

[0911] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are easily introduced as impurities, and therefore are preferably set to the following concentrations.

[0912] The impurity content in the photosensitive layer, measured by mass, is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content in the photosensitive layer, measured by mass, can be set to 1 ppb or more or 0.1 ppm or more.

[0913] As a method for keeping impurities within the aforementioned range, examples include: selecting a material with low impurity content as the raw material for the photosensitive layer; preventing impurities from being introduced during the formation of the photosensitive layer; and removing impurities by washing them off. By using this method, the amount of impurities can be kept within the aforementioned range.

[0914] Impurities can be quantified, for example, by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0915] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. The content of these compounds in the photosensitive layer, on a mass basis, is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less. On a mass basis, the lower limit can be set to 10 ppb or more, and can be set to 100 ppb or more. The content of these compounds can be suppressed using the same method as for the aforementioned metal impurities. Furthermore, quantification can be performed using known measurement methods.

[0916] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0917] ...residual monomers

[0918] The photosensitive layer sometimes contains residual monomers of the structural units of the aforementioned alkali-soluble resin.

[0919] From the viewpoint of patternability and reliability, the content of residual monomers relative to the total mass of alkali-soluble resin is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more.

[0920] From the viewpoint of patternability and reliability, the residual monomer of each structural unit of the alkali-soluble resin relative to the total mass of the photosensitive layer is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0921] When synthesizing alkali-soluble resins via polymer reactions, the residual monomer content is preferably set within the above-mentioned range. For example, in the case of synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable to set the glycidyl acrylate content within the above-mentioned range.

[0922] The amount of residual monomers can be measured using known methods such as liquid chromatography and gas chromatography.

[0923] Other ingredients

[0924] The photosensitive layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of other components include, for example, colorants, antioxidants, and particles (e.g., metal oxide particles). Furthermore, examples of other additives may include those described in paragraphs

[0058] to

[0071] of Japanese Patent Application Publication No. 2000-310706.

[0925] -particle-

[0926] As particles, metal oxide particles are preferred.

[0927] The metal oxide particles also contain half-metals such as B, Si, Ge, As, Sb, and Te.

[0928] For example, from the viewpoint of the transparency of the cured film, the average primary particle size is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0929] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, in cases where the particle shape is not spherical, the longest side was used as the particle size.

[0930] When the photosensitive layer contains particles, it can contain only one type of metal and different sizes of particles, or it can contain two or more types.

[0931] When the photosensitive layer does not contain particles, or when the photosensitive layer contains particles, the particle content relative to the total mass of the photosensitive layer is preferably more than 0% by mass and less than 35% by mass, or the particle content relative to the total mass of the photosensitive composition is more preferably more than 0% by mass and less than 10% by mass, or the particle content relative to the total mass of the photosensitive layer is more preferably more than 0% by mass and less than 5% by mass, or the particle content relative to the total mass of the photosensitive layer is more preferably more than 0% by mass and less than 1% by mass, and especially preferably does not contain particles.

[0932] -Coloring agents-

[0933] The photosensitive layer may contain trace amounts of colorants (pigments, dyes, etc.), but from the viewpoint of transparency, it is preferable that it does not contain colorants.

[0934] When the photosensitive layer contains a colorant, the content of the colorant relative to the total mass of the photosensitive layer is preferably less than 1% by mass, more preferably less than 0.1% by mass.

[0935] -Antioxidants-

[0936] Examples of antioxidants include 3-pyrazolone derivatives such as 1-phenyl-3-pyrazolone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; and p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0937] From the viewpoint of achieving better results with the present invention, 3-pyrazolones are preferred as antioxidants, and 1-phenyl-3-pyrazolones are more preferred.

[0938] When the photosensitive layer contains an antioxidant, the antioxidant content relative to the total mass of the photosensitive layer is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more. The upper limit is not particularly limited, but is preferably 1% by mass or less.

[0939] The thickness of the photosensitive layer

[0940] Furthermore, the thickness of the photosensitive layer is not particularly limited, and is mostly 30 μm or less. From the viewpoint of achieving better results with the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less. As a lower limit, from the viewpoint of achieving excellent film strength by curing the photosensitive layer, it is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more.

[0941] The thickness of the photosensitive layer is calculated by averaging any 5 points measured through cross-sectional observation using SEM (Scanning Electron Microscope).

[0942] The refractive index of the photosensitive layer

[0943] The refractive index of the photosensitive layer is preferably 1.47 to 1.56, and more preferably 1.49 to 1.54.

[0944] The color of the photosensitive layer

[0945] The photosensitive layer is preferably colorless. Specifically, in the CIE1976 (L*, a*, b*) color space with total internal reflection (8° incident angle, light source: D-65 (2° field of view)), L * The preferred value is 10 to 90, a * The preferred value is -1.0 to 1.0, b * The preferred value is -1.0 to 1.0.

[0946] Furthermore, the pattern obtained by curing the photosensitive layer (the cured film of the photosensitive layer) is preferably colorless.

[0947] Specifically, in the CIE1976 (L*, a*, b*) color space, under total internal reflection (8° incident angle, light source: D-65 (2° field of view) with an incident angle of 8°, the L* of the pattern... * The preferred value is 10 to 90, and the a value of the pattern is... * The preferred value is -1.0 to 1.0, and the b value of the pattern is... * The preferred value is -1.0 to 1.0.

[0948] • Moisture permeability of the photosensitive layer

[0949] From a rust prevention perspective, the moisture permeability of the pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer is preferably 500 g / m² at a film thickness of 40 μm. 2 / 24hr or less, preferably 300g / m 2 / 24hr or less, further preferably 100g / m 2 / less than 24 hours.

[0950] In addition, moisture permeability was measured using a cured film, which was prepared by exposing the photosensitive layer to i-rays at an exposure dose of 300 mJ / cm. 2 The photosensitive layer is cured by baking at 145°C for 30 minutes after exposure.

[0951] •Refractive index adjustment layer

[0952] The transfer film X2 in the second embodiment is preferably provided with a refractive index adjustment layer.

[0953] As a refractive index adjusting layer, known refractive index adjusting layers can be used. Materials included in the refractive index adjusting layer include, for example, adhesive polymers, polymeric compounds, metal salts, and particles.

[0954] The method for controlling the refractive index of the refractive index adjustment layer is not particularly limited. For example, methods such as using a resin with a specified refractive index alone, using resin and particles, and using a composite of metal salt and resin can be cited.

[0955] As adhesive polymers and polymeric compounds, examples include the adhesive polymers and polymeric compounds described in the section on "photosensitive layer" above.

[0956] As particles, examples include metal oxide particles and metal particles.

[0957] The types of metal oxide particles are not particularly limited; well-known metal oxide particles can be cited. Metals in metal oxide particles also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0958] For example, from the viewpoint of the transparency of the cured film, the average primary particle size is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0959] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, in cases where the particle shape is not spherical, the longest side was used as the particle size.

[0960] As metal oxide particles, specifically, they are preferably selected from at least one of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof.

[0961] Among these, metal oxide particles, for example from the viewpoint of easy adjustment of refractive index, are more preferably selected from at least one of zirconium oxide particles and titanium oxide particles.

[0962] 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%-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 NISSANCHEMICAL INDUSTRIES, LTD.), and zirconia particles (Nanouse OZ-S30K, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.).

[0963] One type of particle can be used alone, or two or more types can be used simultaneously.

[0964] The particle content in the refractive index adjustment layer is preferably 1 to 95% by mass relative to the total mass of the refractive index adjustment layer, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass.

[0965] When titanium oxide is used as the metal oxide particles, the content of titanium oxide particles relative to the total mass of the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass.

[0966] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive layer.

[0967] The refractive index of the refractive index adjustment layer is preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and particularly preferably 1.65 or higher. The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or lower, more preferably 1.85 or lower, and even more preferably 1.78 or lower.

[0968] The thickness of the refractive index adjustment layer is preferably 50–500 nm, more preferably 55–110 nm, and even more preferably 60–100 nm.

[0969] The thickness of the refractive index adjustment layer was calculated as the average of five arbitrary points measured by cross-sectional observations based on scanning electron microscopy (SEM).

[0970] Method for manufacturing transfer film according to the second embodiment

[0971] The method for manufacturing the transfer film in the second embodiment is not particularly limited, and known methods can be used.

[0972] As a method for manufacturing the transfer film 20, for example, a method including the following steps can be described: coating a temporary support 11 with an intermediate layer forming composition to form a coating film, and further drying the coating film to form an intermediate layer 13; coating the intermediate layer 13 with a photosensitive composition to form a coating film, and further drying the coating film to form a photosensitive layer 15; and coating the photosensitive layer 15 with a refractive index adjusting layer forming composition to form a coating film, and further drying the coating film to form a refractive index adjusting layer 17.

[0973] The transfer film 20 is manufactured by pressing the protective film 21 onto the refractive index adjustment layer 17 of the laminate manufactured by the above manufacturing method.

[0974] As a method for manufacturing the transfer film according to the second embodiment, it is preferable to manufacture the transfer film 20 having a temporary support 11, an intermediate layer 13, a photosensitive layer 15, a refractive index adjustment layer 17 and a protective film 21 by a process including setting a protective film 21 to contact the surface of the refractive index adjustment layer 17 opposite to the side having the temporary support 11.

[0975] After the transfer film 20 is manufactured using the above manufacturing method, the transfer film 20 is wound up, thereby producing and storing a roller-shaped transfer film. The roller-shaped transfer film can be provided in its original form to the roll-to-roll bonding process with the substrate described later.

[0976] Furthermore, as a method for manufacturing the aforementioned transfer film 20, it can be formed by forming an intermediate layer 13 and a photosensitive layer 15 on a temporary support 11, separately forming a refractive index adjustment layer 17 on a protective film 21, and then attaching the refractive index adjustment layer 17 to the photosensitive layer 15.

[0977] Composition for forming intermediate layer and method for forming intermediate layer

[0978] The composition for forming the intermediate layer and the method for forming the intermediate layer are the same as those for forming the intermediate layer of the transfer film X1 in the first embodiment.

[0979] Method for forming photosensitive compositions and photosensitive layers

[0980] From the viewpoint of superior productivity, the photosensitive layer in the transfer film X2 is expected to be formed by coating and using a photosensitive composition of the components constituting the photosensitive layer (e.g., adhesive polymers, polymeric compounds, and polymerization initiators) and a solvent. Specifically, as a method for manufacturing the transfer film according to the second embodiment, it is preferable to coat a photosensitive composition onto a temporary support to form a coating film, and then dry the coating film at a predetermined temperature to form the photosensitive layer.

[0981] Organic solvents are preferred as solvents that can be included in the photosensitive composition. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-acetic acid propyl ester), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0982] Furthermore, as a solvent, organic solvents with boiling points of 180–250°C (high-boiling-point solvents) can be used as needed.

[0983] Solvents can be used alone or in combination with two or more solvents.

[0984] The total solid content of the photosensitive composition is preferably 5 to 80% by mass relative to the total mass of the photosensitive composition, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass.

[0985] That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass relative to the total mass of the photosensitive composition, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass.

[0986] Regarding the viscosity of the photosensitive composition at 25°C, from the viewpoint of coatability, it is preferably 1–50 mPa·s, more preferably 2–40 mPa·s, and even more preferably 3–30 mPa·s. Viscosity is measured using a viscometer. For example, a viscometer manufactured by TOKI SANGYO CO., LTD. (product name: VISCOMETER TV-22) is preferably used. However, the viscometer is not limited to the one described above.

[0987] Regarding the surface tension of the photosensitive composition at 25°C, from a coating point of view, it is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m. The surface tension is measured using a surface tension meter. For example, a surface tension meter manufactured by Kyowa Interface Science Co., Ltd. (product name: Automatic Surface Tensiometer CBVP-Z) is preferably used. However, the surface tension meter is not limited to the one described above.

[0988] Examples of coating methods for photosensitive compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0989] The preferred drying methods for the coating of the photosensitive composition are heating drying and vacuum drying.

[0990] The preferred drying temperature is 80°C or higher, more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature.

[0991] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. While there is no particular limitation on the upper limit, it is preferably 600 seconds or less, more preferably 300 seconds or less.

[0992] • Composition for forming refractive index adjustment layer and method for forming refractive index adjustment layer

[0993] The composition for forming the refractive index adjustment layer preferably includes various components and solvents used to form the refractive index adjustment layer. Furthermore, in the composition for forming the refractive index adjustment layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjustment layer.

[0994] As a solvent, it is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer. It is preferably selected from at least one of water and water-miscible organic solvents, and more preferably water or a mixture of water and water-miscible organic solvents.

[0995] Examples of water-miscible organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0996] One solvent can be used alone, or two or more solvents can be used.

[0997] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0998] The method for forming the refractive index adjustment layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0999] As a drying method for the coating film, heating drying and vacuum drying are preferred. As a drying temperature, 80°C or higher is preferred, more preferably 90°C or higher. Furthermore, as an upper limit, 130°C or lower is preferred, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature.

[1000] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. While there is no particular limitation on the upper limit, it is preferably 600 seconds or less, more preferably 300 seconds or less.

[1001] Furthermore, by attaching the protective film to the refractive index adjustment layer, the transfer film of the second embodiment can be manufactured.

[1002] There are no particular limitations on the method of attaching the protective film to the refractive index adjustment layer; well-known methods can be cited.

[1003] As a device for attaching a protective film to a refractive index adjustment layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[1004] The laminator is preferably equipped with any heatable roller, such as a rubber roller, which can apply pressure and heat.

[1005] •Optimal correlation of the physical properties of the temporary support, photosensitive layer and protective film

[1006] Regarding the transfer film X2 of the second embodiment, similarly to the transfer film X1 of the first embodiment, the physical properties of the temporary support, the photosensitive layer, and the protective film preferably satisfy at least one of preferred embodiment 1, preferred embodiment 2, preferred embodiment 3, preferred embodiment 4, and preferred embodiment 5, and more preferably all of them. The preferred embodiments 1, 2, 3, 4, and 5 are as described above.

[1007] [Circuit Wiring Manufacturing Method (Circuit Wiring Manufacturing Method 1)]

[1008] This invention also relates to a method for manufacturing circuit wiring.

[1009] The pattern formed by the above-described method for manufacturing the laminate of the present invention can be used as a protective pattern for the seed layer during the plating process in the manufacturing of circuit wiring using the semi-additive process (SAP).

[1010] The method for manufacturing circuit wiring of the present invention is a method for manufacturing laminates comprising the above-described method of the present invention, wherein the method for manufacturing circuit wiring comprises:

[1011] The process of forming a seed layer on a substrate to form a substrate with a seed layer (hereinafter also referred to as the "seed layer formation process").

[1012] A process (transfer film bonding process) in which a transfer film having a temporary support, an intermediate layer and a photosensitive layer is brought into contact with the substrate having a seed layer on the side opposite to the temporary support side, thereby bonding the transfer film to the substrate having a seed layer, thereby obtaining a substrate having the substrate, the seed layer, the photosensitive layer, the intermediate layer and the temporary support in sequence.

[1013] The process of peeling off the temporary support between the temporary support and the intermediate layer (temporary support peeling process);

[1014] The process of exposing the above-mentioned intermediate layer to a mask for exposure, and then performing a development process after exposure to form a pattern (pattern forming process);

[1015] The process of forming a metal plating layer by plating on the seed layer in the areas where the above-mentioned pattern is not configured (hereinafter also referred to as the "metal plating formation process");

[1016] The process of forming a protective layer on the aforementioned metal plating (hereinafter also referred to as the "protective layer forming process");

[1017] The process of removing the above pattern (hereinafter also referred to as the "pattern removal process"); and

[1018] The process of removing the exposed seed layer to obtain conductive fine lines (hereinafter also referred to as the "conductive fine line forming process"),

[1019] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2 the following.

[1020] Hereinafter, each step of the method for manufacturing circuit wiring according to the present invention will be described in detail. Furthermore, the descriptions of the constituent elements described below are sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[1021] [First Embodiment]

[1022] The first embodiment of the method for manufacturing circuit wiring sequentially includes a seed layer formation step, a transfer film lamination step, a temporary support peeling step, a pattern formation step, a metal plating layer formation step, a protective layer formation step, a pattern removal step, and a conductive fine wire formation step. The surface free energy of the surface of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 the following.

[1023] Furthermore, the transfer film lamination process, the temporary support peeling process, and the pattern forming process are the same as those in the first embodiment of the above-described method for manufacturing laminates, except that the substrate is a substrate with a seed layer. The preferred embodiments are also the same.

[1024] Seed layer formation process

[1025] The seed layer formation process is the process of forming a seed layer on a substrate.

[1026] As a substrate used in this process, the substrate described in the first embodiment of the above-described method for manufacturing laminates is an example of the substrate used in the transfer film bonding process.

[1027] Seed layer

[1028] The metals contained in the seed layer are not particularly restricted, and any known metals can be used.

[1029] Examples of the main components (so-called major metals) contained in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. Furthermore, the term "major component" refers to the metal with the highest abundance among the metals contained in the seed layer.

[1030] The thickness of the seed layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more. The upper limit is not particularly limited, but is preferably 2 μm or less.

[1031] The method for forming the seed layer is not particularly limited. For example, known methods such as sintering a coating by coating a dispersion of metal particles, sputtering, and vapor deposition can be cited.

[1032] Metal plating formation process

[1033] The metal plating formation process is a process of forming a metal plating layer on a seed layer that exists in an area where no pattern is configured, by means of a plating process.

[1034] As a plating process, electroplating and electroless plating methods can be cited. From a production point of view, electroplating is preferred.

[1035] The metal included in the metal coating is not particularly restricted, and any known metal can be used.

[1036] Metal coatings may include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals.

[1037] From the viewpoint that the conductive fine wires exhibit superior conductivity, the metal coating preferably contains copper or its alloy. Furthermore, from the viewpoint that the conductive fine wires exhibit superior conductivity, the main component of the metal coating is preferably copper.

[1038] The lower limit for the thickness of the metal coating is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm. The upper limit is also not particularly limited, but is preferably 20 μm or less.

[1039] Protective layer formation process

[1040] The protective layer lamination process is the process of forming a protective layer on a metal plating layer.

[1041] The material used as the protective layer is preferably a material that is resistant to the removal solution or etching solution during the removal process or the conductive wire forming process. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, their alloys, and resins. Among these, nickel or chromium is preferred as the material used as the protective layer.

[1042] Methods for forming the protective layer include, for example, electroless plating and electroplating, with electroplating being the preferred method.

[1043] The lower limit of the thickness of the protective layer is not particularly limited, but 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.

[1044] Pattern Removal Process

[1045] The pattern removal process is the process of removing patterns.

[1046] There are no particular limitations on the method for removing patterns, but methods that remove them by chemical treatment are possible, and methods that remove them by using a removal solution are preferred.

[1047] The preferred temperature of the removal liquid is 30–80°C, and more preferably 50–80°C.

[1048] As a preferred method for removal, one example is to immerse the substrate with the pattern to be removed in a stirred removal solution at a temperature of 50 to 80°C for 1 to 30 minutes.

[1049] Examples of removal solutions include those obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[1050] Furthermore, it can be removed using a removal liquid and by known methods such as spraying, rinsing, and immersion.

[1051] Seed layer removal process

[1052] The seed layer removal process is a process of obtaining conductive fine wires by removing the exposed seed layer.

[1053] In addition, in the seed layer removal process, the metal coating formed by the metal coating formation process is used as an etching resist to perform etching treatment on the seed layer located in the non-pattern formation area (in other words, the area not protected by the metal coating).

[1054] The method for removing the seed layer is not particularly limited, but a known etching solution is preferred.

[1055] Examples of known etching solutions include ferric chloride solution, copper chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[1056] The upper limit of the linewidth of the formed conductive fine line is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is not particularly limited, and is often 2 μm or more.

[1057] Other processes

[1058] The first embodiment of the method for manufacturing circuit wiring may include any process other than the process described above (other processes).

[1059] For example, the process of reducing visible light reflectivity described in paragraph

[0172] of International Publication No. 2019 / 022089, and the process of forming a new conductive layer on an insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089, are examples, but these processes are not limited.

[1060] <Process for reducing visible light reflectivity>

[1061] A first embodiment of the method for manufacturing circuit wiring may include a step of performing a process to reduce the visible light reflectivity of some or all of the multiple conductive layers of a substrate.

[1062] Oxidation is an example of a process to reduce visible light reflectivity. When a substrate has a conductive layer containing copper, copper is oxidized to produce copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer.

[1063] Regarding the treatment of reducing visible light reflectivity, it is described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, and the contents described in these publications are incorporated into this specification.

[1064] <The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film>

[1065] The first embodiment of the method for manufacturing circuit wiring also preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.

[1066] Through the above process, a second electrode pattern that is insulated from the first electrode pattern can be formed.

[1067] The process of forming the insulating film is not particularly limited, and methods for forming known permanent films can be cited. Furthermore, an insulating film with a desired pattern can be formed by photolithography using a photosensitive material with insulating properties.

[1068] The process of forming a new conductive layer on an insulating film is not particularly limited. For example, a new conductive layer with a desired pattern can be formed by using a conductive photosensitive material and photolithography.

[1069] [Applications of circuit wiring]

[1070] The circuit wiring manufactured by the first embodiment of the circuit wiring manufacturing method is preferably used as a circuit wiring disposed on a support substrate such as a sheet, metal substrate, ceramic substrate, or glass in the manufacturing process film of a semiconductor package, printed circuit board, or interposer rewiring layer.

[1071] [Circuit Wiring Manufacturing Method (Circuit Wiring Manufacturing Method 2)]

[1072] Furthermore, although the method for forming conductive fine line patterns on a substrate by a semi-additive process has been described in the preceding section, the method for manufacturing circuit wiring to which the method for manufacturing a laminate of the present invention is applied is not limited thereto. Other methods for manufacturing circuit wiring include the method for manufacturing a laminate of the present invention described above, wherein the method for manufacturing circuit wiring includes:

[1073] A transfer film having a temporary support, an intermediate layer, and a photosensitive layer is bonded to a conductive substrate (as described above, a substrate consisting of at least a support substrate and a conductive layer disposed on the support substrate) to obtain a substrate having the conductive substrate, the photosensitive layer, the intermediate layer, and the temporary support in sequence (wherein the conductive substrate is arranged with the conductive layer and the photosensitive layer facing each other) in a manner described in the transfer film bonding process.

[1074] The process of peeling off the temporary support between the temporary support and the intermediate layer (temporary support peeling process);

[1075] The process of exposing the aforementioned intermediate layer to a mask for exposure, followed by a development process after exposure to form a pattern (patterning process); and

[1076] An etching process (etching process) that etches the conductive layer in areas where the above pattern is not configured.

[1077] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2Below. Furthermore, the transfer film lamination process, the temporary support peeling process, and the pattern forming process are the same as in the first embodiment of the above-described method for manufacturing the laminate, except that the substrate is a substrate with a conductive layer. The preferred embodiments are also the same.

[1078] The etching process is a process of etching the conductive layer located in areas where no pattern is configured.

[1079] As a method for etching, known methods can be applied, such as the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Application Publication No. 2017-120435, the methods described in paragraphs

[0048] to

[0054] of Japanese Patent Application Publication No. 2010-152155, wet etching methods immersed in etching solution, and dry etching methods based on plasma etching, etc.

[1080] As a device equipped with circuit wiring manufactured by the above-described manufacturing method, an input device can be cited as an example, preferably a touch panel, and more preferably a capacitive touch panel. Furthermore, the above-described input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[1081] In a second embodiment of the method for manufacturing circuit wiring, it is also preferable to form circuits sequentially or simultaneously on both surfaces of the substrate. With this structure, it is possible to form touch panel circuit wiring with a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface. Furthermore, it is also preferable to form this type of touch panel circuit wiring from both sides of the substrate by roll-to-roll.

[1082] [Transfer film]

[1083] The present invention also relates to a transfer film.

[1084] The transfer film of the present invention will be described below.

[1085] The transfer film of the present invention comprises a temporary support, an intermediate layer, and a photosensitive layer, wherein,

[1086] The surface free energy of the temporary support side of the aforementioned intermediate layer is 68.0 mJ / m. 2 the following,

[1087] The arithmetic mean roughness Ra of the surface of the temporary support side of the aforementioned intermediate layer is less than 50 nm.

[1088] The above-mentioned transfer film is suitable for exposure methods after the temporary support is peeled off. It can suppress excessive adhesion between the exposed photosensitive layer and the photomask, and also has excellent resolution.

[1089] As the transfer film of the present invention, it corresponds to one embodiment of the transfer film X described above. The structure and preferred embodiment of the transfer film X are as described above.

[1090] Example

[1091] The present invention will now be described in further detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[1092] In addition, unless otherwise specified, “parts” and “%” are the quality standards.

[1093] Furthermore, in the following embodiments, the weight-average molecular weight of the resin is the weight-average molecular weight obtained based on polystyrene conversion using gel permeation chromatography (GPC). Also, the theoretical acid value was used.

[1094] [The various components of transfer film]

[1095] First, we will explain the various components used in making the transfer film.

[1096] [Intermediate layer]

[1097] Various components of the intermediate layer

[1098] The following shows the various components of the intermediate layer as illustrated in Table 4.

[1099] PVA: (Polyvinyl alcohol: Product name "KURARAY POVALPVA-205" (manufactured by Kuraray Co., Ltd.))

[1100] PVP: (Polypyrrolidone: Product name "Polyvinylpyrrolidone K-30" (manufactured by NIPPON SHOKUBAI CO., LTD.))

[1101] HPMC: (Hydroxypropyl methylcellulose: Product name "METOLOSE 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.)

[1102] PEG: (Polyethylene glycol: Product name "Polyethylene glycol 1,000" (Molecular weight: 900-1000), manufactured by FUJIFILM WakoPure Chemical Corporation)

[1103] HPC: (Hydroxypropyl cellulose: product name "HPC-SSL", manufactured by NISSO CORPORATION)

[1104] Glycerin: Product name "Glycerin" (molecular weight: 92.09), manufactured by FUJIFILM Wako Pure Chemical Corporation.

[1105] Bisphenol A: Product name "4,4'-isopropyldiol" (molecular weight: 228.29), manufactured by FUJIFILM Wako PureChemical Corporation.

[1106] Compositions for forming intermediate layers

[1107] An intermediate layer forming composition was prepared by mixing the components according to the description in Table 4 and then adding a solvent (solvent: a mixed solvent of ion-exchanged water and methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) in a mixing ratio (mass ratio) of 40 / 60).

[1108] In addition, the values ​​corresponding to each component recorded in the "Composition of the Intermediate Layer (Types and Amounts of Components (mass%))" column in Table 4 represent the content of each component relative to the total mass of the intermediate layer.

[1109] [Photosensitive layer]

[1110] Table 2 shows the composition of the photosensitive layers 1 to 4 shown in Table 4.

[1111] [Table 2]

[1112]

[1113] Various components of the photosensitive layer

[1114] The components of the photosensitive layer shown in Table 2 are as follows.

[1115] <Polymer>

[1116] Polymers P-1 and P-2 were synthesized using known methods. Furthermore, the weight-average molecular weight (Mw) of the synthesized polymers was measured by gel permeation chromatography (GPC) under the following conditions.

[1117] (GPC conditions)

[1118] Equipment: Manufactured by TOSOH CORPORATION; TOSOH CORPORATION high-speed GPC device HLC-8420GPC (product name)

[1119] Protective tubing: Manufactured by TOSOH CORPORATION, HZ-L

[1120] Separation column: A column manufactured by TOSOH CORPORATION, consisting of three TSK gel Super HZM-N (product name) tubes connected in series.

[1121] Temperature measured: 40℃

[1122] Eluent: THF (Tetrahydrofuran)

[1123] Flow rate: Sampling pump 0.35 mL / min, reference pump 0.175 mL / min

[1124] Injection volume: 10 μL

[1125] Detector: Differential refractometer

[1126] GPC column calibration standard solution: Standard polystyrene manufactured by TOSOH CORPORATION

[1127] (Polymer Synthesis)

[1128] In the following synthetic examples, the following abbreviations refer to the following compounds.

[1129] Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1130] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1131] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1132] BA: Butyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1133] PGMEA: Propylene Glycol Monomethyl Ether Acetate (manufactured by SHOWA DENKO KK)

[1134] MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[1135] V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1136] Synthesis of polymer P-1

[1137] 116.5 parts of PGMEA were placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. After 2 hours, a solution containing 52.0 parts of St, 29.0 parts of MAA, 19.0 parts of MMA, 4.0 parts of V-601, and 116.5 parts of PGMEA was added dropwise to the solution in the flask, which was maintained at 90°C ± 2°C. After the addition was complete, the solution in the flask was stirred at 90°C ± 2°C for 2 hours to obtain polymer P-1 (solid content concentration of 30.0% by mass).

[1138] Synthesis of polymer P-2

[1139] By changing the type and amount of monomers used, and other conditions, a solution containing polymer P-2 was obtained using the same method as polymer P-1. The solid content concentration of the solution containing polymer P-2 was set to 30% by mass.

[1140] The following shows the types of monomers used to synthesize each polymer, as well as the content (mass%) and weight-average molecular weight of the structural units derived from each monomer in each polymer.

[1141] In addition, resins P-1 to P-2 are all equivalent to alkali-soluble resins.

[1142] [Table 3]

[1143] St 52 20 MAA 29 25 MMA 19 30 BA 25 Weight-average molecular weight (Mw) 60,000 70,000

[1144] <Other Ingredients>

[1145] The following shows the other components contained in the photosensitive layer shown in Table 2.

[1146] (polymeric compounds)

[1147] BPE-500: 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1148] M-270: Polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD.

[1149] • A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1150] (Polymerization initiator)

[1151] B-CIM: 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, Hampford Corporation

[1152] • Irgacure OXE-02 (oxime ester photopolymerization initiator, manufactured by BASF JAPAN)

[1153] 0mnirad 907FF: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, manufactured by IGM Resins B.V.

[1154] Omnirad 379: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butane-1-one, manufactured by IGMresins BV

[1155] (Sensitizer)

[1156] SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.

[1157] (Chain transfer agent)

[1158] • Colorless crystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[1159] N,N-Tetraethyl-4,4-diaminobenzophenone: Manufactured by HODOGAYA CHEMICAL CO.,LTD.

[1160] ·N-Phenylenylmethyl-N-carbonylmethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1161] (Coloring agent)

[1162] Bright Green: Manufactured by Tokyo Chemical Industry Co., Ltd.

[1163] (Rust inhibitor)

[1164] • CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD

[1165] (Polymerization inhibitor)

[1166] • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[1167] Irganox 245: A hindered phenolic antioxidant manufactured by BASF.

[1168] (Antioxidants)

[1169] ·4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1170] (surfactant)

[1171] MEGAFACE F-552: Surfactant, manufactured by DIC Corporation.

[1172] Photosensitive Compositions 1-4

[1173] After mixing the components as described in Table 2, photosensitive compositions 1 to 4 with a solid component concentration of 25% by mass were prepared by adding methyl ethyl ketone.

[1174] Furthermore, the values ​​corresponding to each component listed in the ingredient column of Table 2 represent the parts by mass of the solid component. That is, the above values ​​refer to the amount of the mixture excluding solvents such as diluents.

[1175] [Temporary support]

[1176] The temporary supports (temporary supports A to F) in Table 4 are shown below.

[1177] Temporary support A: Lumirer 16KS40 (manufactured by TORAY INDUSTRIES, INC.)

[1178] Temporary support B: A material manufactured using the method described later.

[1179] Temporary support C: TOYOBO ESTER FILM E5000 (manufactured by TOYOBO CO., LTD.)

[1180] Temporary support D: UNIPEEL TR-1 (manufactured by UNITIKA LTD.)

[1181] Temporary support E: Therapy25WZ (manufactured by TORAY INDUSTRIES, INC.)

[1182] Temporary support F: Cosmo Shine A4300 (manufactured by TOYOBO CO., LTD.)

[1183] <Manufacturing Method of Temporary Support B>

[1184] (Preparation of particle layer forming composition 1)

[1185] The components were mixed in the manner shown below to obtain particle layer forming composition 1. After preparing particle layer forming composition 1, it was filtered through a 6 μm filter (F20, manufactured by Mahle Filter Systems Japan Corp.) and then degassed using a 2×6 RADIAL FLOW SUPERPHOBIC membrane (manufactured by Polypore International, Inc.).

[1186] • 167 parts of propylene polymer (AS-563A, manufactured by DAICL FINECHEM LTD., solids content 27.5% by mass)

[1187] • Nonionic surfactant (Naro Acty CL95, manufactured by Sanyo Chemical Industries, Ltd., 100% by weight solids) 0.7 parts

[1188] • Anionic surfactant (Rapisol A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass) 114.4 parts

[1189] • Carnauba wax dispersion (Cerozol 524, manufactured by CHUKYO YUSHI CO., LTD., solids content 30% by mass) 7 parts

[1190] • 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

[1191] • Matting agent (SNOWTEX XL, manufactured by Nissan Chemical Industries, LTD., 40% by weight solids, average particle size 50 nm) 2.8 parts

[1192] ·Water 690.2 portions

[1193] (Extrusion molding)

[1194] Particles of polyethylene terephthalate (PET) using a citric acid-chelated organotitanium complex as a polymerization catalyst, as described in Japanese Patent No. 5575671, were dried to a moisture content of less than 50 ppm and then fed into the hopper of a 30 mm diameter uniaxial compounding extruder. The PET was melted and extruded at 280°C. The melt was then passed through a filter (3 μm pore size) and extruded from a die onto a cooling roller at 25°C to obtain an unstretched film. Furthermore, an electrostatic application method was used to ensure the extruded melt adhered tightly to the cooling roller.

[1195] (Extension, coating)

[1196] The solidified, unstretched film was extruded onto a cooling roller using the above method, and then biaxially stretched sequentially using the following method to obtain a polyester film with a thickness of 16 μm and a temporary support containing a particle layer with a thickness of 40 nm.

[1197] (a) Longitudinal extension

[1198] The unstretched film is passed between two pairs of pressure rollers with different circumferential speeds and stretched longitudinally (in the conveying direction). The process is carried out with a preheating temperature of 75°C, a stretching temperature of 90°C, a stretch ratio of 3.4 times, and a stretching speed of 1300% / second.

[1199] (b) Coating

[1200] The particle-containing layer forming composition 1 was coated on one side of a longitudinally extended film using a doctor blade coater to achieve a film thickness of 40 nm after film formation.

[1201] (c) Lateral extension

[1202] The film that had undergone the above longitudinal stretching and coating was stretched laterally using a tenter frame under the following conditions.

[1203] -Lateral Extension Conditions-

[1204] Preheating temperature: 110℃

[1205] Extended temperature: 120℃

[1206] Extension ratio: 4.2x

[1207] Extension speed: 50% / second

[1208] (Heat-fixed, heat-relieving)

[1209] Next, the biaxially stretched film, after longitudinal and transverse stretching, was heat-fixed under the following conditions. Following further heat-fixing, the width of the tenter frame was shortened, and heat tempering was performed under the following conditions.

[1210] -Heat-setting conditions-

[1211] Heat setting temperature: 227℃

[1212] Heat setting time: 6 seconds

[1213] -Heat mitigation conditions-

[1214] Heat relief temperature: 190℃

[1215] Heat mitigation rate: 4%

[1216] (Roll-up)

[1217] After heat setting and heat thawing, the ends are trimmed, and the ends are extruded (knurled) to a width of 10 mm, then wound up at a tension of 40 kg / m. The width is 1.5 m, and the winding length is 6300 m. The resulting film roller is used as a temporary support B.

[1218] [Preparation of photosensitive transfer film]

[1219] [Examples 1-48, Comparative Examples 5-7]

[1220] The photosensitive transfer film, consisting of a temporary support, an intermediate layer, and a photosensitive layer, is fabricated as shown in Table 4. Specifically, it is as follows.

[1221] First, on the temporary support shown in Table 4, the intermediate layer forming composition for forming the intermediate layer shown in Table 4 is dried using a slit nozzle and then coated so that the coating width is 1.0 μm and the film thickness is the value recorded in Table 4. The intermediate layer is formed by passing it through a drying zone at 80°C for 40 seconds.

[1222] Furthermore, on the intermediate layer, after drying the photosensitive composition used to form the photosensitive layer shown in Table 4 using a slit nozzle, coating is performed so that the coating width is 1.0 μm and the film thickness is the value recorded in Table 4, and the negative photosensitive layer is formed by passing it through a drying zone at 80°C for 40 seconds.

[1223] A polyethylene film (manufactured by Tredegar Corporation, OSM-N) is pressed onto it as a protective film to make a photosensitive transfer film, and then rolled into a roll.

[1224] In addition, through the above process, for example as the transfer film used in Example 1, a transfer film with a temporary support: type A, an intermediate layer: type 1 and a photosensitive layer: type 1 was produced.

[1225] [Comparative Examples 1-4]

[1226] The photosensitive transfer films, consisting of a temporary support and a photosensitive layer, were fabricated as shown in Table 4. Furthermore, except for the absence of an intermediate layer, they were fabricated using the same method as the transfer film used in Example 1.

[1227] [Surface free energy E on the surface of the temporary support side of the intermediate layer] I Surface free energy E in the intermediate layer side of the temporary support s [Arithmetic mean roughness Ra in the surface of the temporary support side of the intermediate layer]

[1228] The temporary support for the prepared transfer film was peeled off using any method, and the surface free energy E of the intermediate layer side of the temporary support was measured. s (mJ / cm 2 The surface free energy E of the temporary support side of the intermediate layer and the intermediate layer I (mJ / cm 2 The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer. Furthermore, the measurement method is as described above.

[1229] The measurement results are shown in Table 4.

[1230] [Various reviews]

[1231] [Evaluation 1: Temporary support peelability]

[1232] A copper layer with a thickness of 200 nm was deposited on a PET substrate with a thickness of 0.1 mm by vapor deposition, thus preparing a PET substrate with a copper layer.

[1233] After the protective film of the transfer film is peeled off, it is laminated onto the PET substrate with the copper layer under the lamination conditions of roller temperature of 100°C, linear pressure of 1.0 MPa and linear speed of 4.0 m / min, so that the copper layer and the photosensitive layer are in contact.

[1234] After the temporary support was peeled off at a 180° angle, the surfaces of the temporary support and the photosensitive layer were visually observed and evaluated based on the following evaluation criteria.

[1235] The measurement results are shown in Table 4.

[1236] (Evaluation Criteria)

[1237] “A”: The temporary support can be smoothly peeled off.

[1238] "B": The temporary support can be peeled off, but it makes a sound during peeling.

[1239] “C”: During the peeling of the temporary support, the intermediate layer peels off, and the temporary support is torn and / or coalesced and destroyed.

[1240] [Evaluation 2: Mask non-adhesiveness]

[1241] After the above exposure operation, the surface of the photosensitive layer was visually observed and evaluated based on the following evaluation criteria.

[1242] The measurement results are shown in Table 4.

[1243] (Evaluation Criteria)

[1244] "A": The photosensitive layer is not attached to the mask.

[1245] "B": The photosensitive layer was not attached to the mask, but made a sound when peeled off.

[1246] “C”: The photosensitive layer is attached to the mask (the mask can be peeled off, but the photosensitive layer peels off).

[1247] [Evaluation 3: Resolution]

[1248] A copper layer with a thickness of 200 nm was deposited on a PET substrate with a thickness of 0.1 mm by vapor deposition, thus preparing a PET substrate with a copper layer.

[1249] After the protective film of the transfer film is peeled off, it is laminated onto the PET substrate with the copper layer under the lamination conditions of roller temperature of 100°C, linear pressure of 1.0 MPa and linear speed of 4.0 m / min, so that the copper layer and the photosensitive layer are in contact.

[1250] Next, a photomask with a specified line (μm) / space (μm) pattern was used, and a temporary support was brought into contact with the stripped-off mask for exposure. A high-pressure mercury lamp with i-rays (365nm) as the primary exposure wavelength was used for exposure. The exposure amount was arbitrarily set to ensure that the top shape of each pattern aligned with the mask opening.

[1251] Next, a 1% sodium carbonate aqueous solution at a liquid temperature of 25°C was used for spray development, followed by water washing, to form a specified pattern on the copper.

[1252] Next, the resolution was evaluated based on the following evaluation criteria.

[1253] The measurement results are shown in Table 4.

[1254] Additionally, the following phrase, "able to resolve patterns without residue," refers to the ability to resolve patterns without residue in the recessed areas (equivalent to the unexposed areas) of the pattern.

[1255] (Evaluation Criteria)

[1256] “AA”: L / S = 3μm / 3μm enables residue-free resolution between patterns.

[1257] “A”: L / S = 6μm / 6μm enables residue-free resolution between patterns.

[1258] “B”: L / S = 8μm / 8μm enables residue-free resolution between patterns.

[1259] “C”: L / S = 8μm / 8μm cannot be resolved.

[1260] [Overall evaluation of ratings 1-3]

[1261] Based on the evaluation results of evaluations 1 to 3, a comprehensive evaluation was conducted using the following evaluation criteria.

[1262] <Evaluation Criteria>

[1263] "AA": The resolution is rated AA, and both the mask non-adhesion and temporary support peelability are rated A.

[1264] "A": The resolution is rated A, and both the mask non-adhesion and the temporary support peelability are rated A.

[1265] "B": Resolution is rated A, and either mask non-adhesion or temporary support peelability is rated A, while the other is rated B.

[1266] "C": The resolution is rated as B, and the mask non-adhesiveness and temporary support peelability are rated as either A or B.

[1267] "D": The resolution is rated as C or the mask non-adhesion is rated as C. Additionally, the temporary support evaluation can be any evaluation.

[1268] Table 4 is shown below.

[1269] In Table 4, the “Types of Photosensitive Layers” correspond to the numbers of the photosensitive layers shown in Table 2, as described above.

[1270] Furthermore, in Table 4, "Whether a temporary support stripping process is implemented" indicates whether a temporary support stripping process is implemented. "A" indicates that a temporary support stripping process is implemented in the manufacturing method of the laminate, and "B" indicates that a temporary support stripping process is not implemented in the manufacturing method of the laminate.

[1271] Furthermore, in Comparative Examples 1 to 4 (without an intermediate layer), the surface free energy in the column “Type and Properties of Temporary Support” represents the surface free energy of the photosensitive layer side of the temporary support.

[1272]

[1273]

[1274]

[1275]

[1276] The results in Table 4 clearly show that, in the case of the manufacturing method of the laminate in the embodiment, excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed (in other words, the mask non-adhesion is excellent) and fine patterns that suppress residue in the recessed areas of the pattern can be formed (in other words, the resolution is also excellent).

[1277] On the other hand, the desired effect was not achieved in Comparative Examples 1 to 7.

[1278] As shown in Comparative Examples 1 and 3, the following results were obtained: when the photosensitive layer was directly bonded to the mask for exposure without forming an intermediate layer, the mask had poor non-adhesion.

[1279] Furthermore, as shown in Comparative Examples 3 and 4, the following results were obtained: when exposure was performed through the temporary support without forming an intermediate layer and without performing a temporary support peeling process, the resolution was poor.

[1280] Furthermore, as shown in Comparative Example 5, the following result was obtained: when an intermediate layer was formed and a temporary support stripping process was not performed, and exposure was performed through the temporary support, the resolution was poor.

[1281] Furthermore, as shown in Comparative Examples 6 and 7, the following result is obtained: the surface free energy E on the surface of the temporary support body side of the intermediate layer... I Exceeding 68.0 mJ / cm 2 In such cases, both mask non-adhesion and resolution are poor.

[1282] Furthermore, the results from Examples 1 to 6 and 9 confirmed that when the thickness of the photosensitive layer is 2.0 to 20 μm (preferably 2.0 to 10 μm), the resolution is even better.

[1283] Furthermore, the results from Examples 1, 7, 8, 10, 11, and 21-23 confirmed that when the upper limit of the content of compound X in the intermediate layer is less than 30% by mass (preferably less than 15% by mass) relative to the total mass of the intermediate layer, the resolution is even better. Furthermore, it was confirmed that when the upper limit of the content of compound X in the intermediate layer is 0.5% by mass or more relative to the total mass of the intermed...

Claims

1. A method for manufacturing a laminate, comprising: The process of bonding the transfer film to the substrate by contacting the surface of the photosensitive layer of the transfer film, which has a temporary support, an intermediate layer and a photosensitive layer, opposite to the intermediate layer side, with the substrate. The process of peeling off the temporary support between the temporary support and the intermediate layer; and The process involves exposing the exposed intermediate layer to a mask for exposure, followed by a development process to form a pattern. The surface free energy of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 the following, The surface free energy of the intermediate layer side of the temporary support is 60.0 mJ / m. 2 the following, The intermediate layer comprises polyvinyl alcohol, polyvinylpyrrolidone, and one of the following: a water-soluble cellulose derivative of compound X and a polyether. The combined content of the polyvinyl alcohol and the polyvinylpyrrolidone is 50% or more by mass relative to the total mass of the intermediate layer. The content of 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 photosensitive layer is a negative photosensitive layer. The photosensitive layer comprises an alkali-soluble resin. The content of the alkali-soluble resin is 40% or more by mass relative to the total mass of the negative photosensitive layer.

2. The method for manufacturing a laminate according to claim 1, wherein, The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is less than 50 nm.

3. The method for manufacturing a laminate according to claim 1, wherein, The surface free energy of the intermediate layer side of the temporary support is 25.0 mJ / m. 2 ~50.0mJ / m 2 .

4. The method for manufacturing a laminate according to claim 1, wherein, The content of polyvinyl alcohol is 5% to 95% by mass relative to the total mass of the intermediate layer.

5. The method for manufacturing a laminate according to claim 1, wherein, The compound X contains hydroxypropyl methylcellulose.

6. The method for manufacturing a laminate according to claim 1, wherein, The thickness of the intermediate layer is less than 3.0 μm.

7. The method for manufacturing a laminate according to claim 1, wherein, The thickness of the photosensitive layer is 2.0 μm to 20 μm.

8. A method for manufacturing a circuit wiring substrate, comprising the method for manufacturing a laminate according to any one of claims 1 to 7, wherein the method for manufacturing the circuit wiring substrate comprises: The process of forming a seed layer on a substrate to form a substrate with a seed layer; A process of bonding a transfer film having a temporary support, an intermediate layer, and a photosensitive layer to a substrate having a seed layer by contacting the surface of the photosensitive layer opposite to the intermediate layer side of the photosensitive layer with the substrate having a seed layer in sequence, thereby obtaining a substrate having the substrate, the seed layer, the photosensitive layer, the intermediate layer, and the temporary support. The process of peeling off the temporary support between the temporary support and the intermediate layer; The process of exposing the intermediate layer to a mask for exposure, and then performing a development process after exposure to form a pattern; A process of forming a metal plating layer on the seed layer in the area where the pattern is not configured; The process of forming a protective layer on the metal plating; The process of removing the pattern; and The process of removing the exposed seed layer to obtain conductive fine wires. The surface free energy of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 the following.

9. A transfer film having a temporary support, an intermediate layer, and a photosensitive layer. The surface free energy of the temporary support side of the intermediate layer is 68.0 mJ / m. 2 the following, The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is less than 50 nm. The surface free energy of the intermediate layer side of the temporary support is 60.0 mJ / m. 2 the following, The intermediate layer comprises polyvinyl alcohol, polyvinylpyrrolidone, and one of the following: a water-soluble cellulose derivative of compound X and a polyether. The combined content of the polyvinyl alcohol and the polyvinylpyrrolidone is 50% or more by mass relative to the total mass of the intermediate layer. The content of 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 photosensitive layer is a negative photosensitive layer. The photosensitive layer comprises an alkali-soluble resin. The content of the alkali-soluble resin is 40% or more by mass relative to the total mass of the negative photosensitive layer.

10. The transfer film according to claim 9, wherein, The surface free energy of the intermediate layer side of the temporary support is 25.0 mJ / m. 2 ~50.0mJ / m 2 .

11. The transfer film according to claim 9, wherein, The content of polyvinyl alcohol is 5% to 95% by mass relative to the total mass of the intermediate layer.

12. The transfer film according to claim 9, wherein, The compound X contains hydroxypropyl methylcellulose.

13. The transfer film according to claim 9 or 10, wherein, The thickness of the intermediate layer is less than 3.0 μm.

14. The transfer film according to claim 9 or 10, wherein, The thickness of the photosensitive layer is 2.0 μm to 20 μm.

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