Wound body, method for manufacturing laminate having resin pattern, and method for manufacturing laminate having conductor pattern

Abstract

The present invention addresses the problem of providing a wound body, a method for manufacturing a laminate having a resin pattern using the wound body, and a method for manufacturing a laminate having a conductor pattern, the wound body having excellent peelability of a protective film in a transfer film unwound from the wound body and excellent laminability of an end portion. The present invention relates to a roll for a transfer film having a temporary support, a composition layer, and a protective film in this order, the composition layer comprising a photosensitive composition layer, the transfer film released from the roll being viewed in a cross-section at five different positions at intervals of 8 cm in the longitudinal direction of the transfer film, and the thickness of the transfer film being less than or equal to 10 [mu] m, and the thickness of the transfer film being less than or equal to 10 [mu] m, in the longitudinal direction of the transfer film being less than or equal to 10 [mu] m. The minimum value and the maximum value among the five positions X and the five positions Y obtained in each cross-sectional observation are within the range of-40 to 40 [mu] m.

Description

Technical Field

[0001] The present invention relates to a roll body. Specifically, the present invention relates to a roll body of a transfer film, wherein the transfer film has a support body, a composition layer, and a protective film in this order, and the composition layer includes a photosensitive composition layer.

[0002] Furthermore, the present invention also relates to a method for producing a laminate having a resin pattern and a method for producing a laminate having a conductor pattern, both of which are formed by using the wound body. Background Art

[0003] In a display device (organic electroluminescent (EL) display device and liquid crystal display device, etc.) having a touch panel such as an electrostatic capacitive input device, a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and wiring of a lead wiring portion is provided inside the touch panel. In addition, in printed circuit board wiring, etc., wiring patterns are also formed by etching and plating processes.

[0004] Generally, when forming a patterned layer, the number of steps for obtaining a desired pattern shape is small, and therefore a method of placing a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing the layer is widely used.

[0005] For example, Patent Document 1 discloses a photosensitive element (transfer film) which is composed of a support film (support), a photosensitive resin composition layer (photosensitive composition layer), and a protective film and satisfies predetermined requirements.

[0006] Patent Document 1: Japanese Patent Application Publication No. 2003-248320 Summary of the invention

[0007] The transfer film includes, for example, a temporary support, a composition layer, and a protective film in this order, and is supplied as a roll.

[0008] When a composition layer is arranged on a substrate using a transfer film, first, the transfer film is unwound from a roll, and the protective film is peeled off from the unwound transfer film to expose the composition layer (e.g., photosensitive composition layer). Then, the transfer film from which the protective film has been peeled off is attached (laminated) to the substrate so that the exposed composition layer faces the desired surface of the substrate.

[0009] In the above process, when the protective film is peeled off from the transfer film, the protective film needs to have excellent peelability. Here, if the peelability of the protective film is poor, when the protective film is peeled off from the transfer film, peeling will also occur between the temporary support and the composition layer, thereby causing the composition layer to be unable to be normally bonded to another substrate.

[0010] Furthermore, after the composition layer is transferred to the substrate, the surface properties of the laminated composition layer are required to be excellent, and in particular, the generation of wrinkles etc. is required to be suppressed at the ends of the laminated composition layer. Hereinafter, the situation where the generation of wrinkles etc. is suppressed at the ends of the laminated composition layer as described above is referred to as excellent lamination properties at the ends.

[0011] The present inventors have studied the transfer film (photosensitive element) described in Patent Document 1 as a wound body and have found that at least one of the peelability of the protective film and the lamination property of the end portions may not meet the recently required level and need to be improved. Summary of the invention

[0013] Therefore, an object of the present invention is to provide a roll body having excellent peelability of a protective film and excellent lamination properties at an end portion of a transfer film unwound from the roll body.

[0014] Furthermore, the present invention aims to provide a method for producing a laminate having a resin pattern and a method for producing a laminate having a conductor pattern, both of which are produced by using the above-mentioned wound body.

[0015] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the problems can be solved by the following configuration.

[0016] [1] A roll of a transfer film comprising a temporary support, a composition layer, and a protective film in this order, wherein the composition layer comprises a photosensitive composition layer.

[0017] The transfer film unwound from the roll was observed in cross-section at five different locations at intervals of 8 cm along the length direction of the transfer film. The minimum and maximum values ​​of the five locations X and five locations Y obtained in each cross-section observation were within the range of -40 to 40 μm.

[0018] Cross-sectional observation: The transfer film unwound from the roll is cut along the width direction of the transfer film, and one of the two exposed cross-sectional surfaces is observed in the normal direction of the cross-sectional surface.

[0019] The position of the outermost end of the temporary support in the width direction of the transfer film in the exposed cross section is set as a first position, the position of the outermost end of the protective film in the width direction of the transfer film and located on the same side as the first position is set as a second position, and the position of the second position when the outer position in the width direction of the transfer film is closer to the first position than the first position is expressed as a positive value in the width direction of the transfer film,

[0020] The position of the other end of the temporary support body located at the outermost side in the width direction of the transfer film in the exposed cross section is set as the third position, the position of the other end located at the outermost side of the protective film in the width direction of the transfer film and located on the same side as the third position is set as the fourth position, and the position of the fourth position, which is represented by a positive value in the width direction of the transfer film and is closer to the outside than the third position along the width direction of the transfer film with the third position as a reference, is set as position Y.

[0021] [2] The wound body according to [1], wherein:

[0022] The above minimum value is in the range of 0.1 to 40 μm.

[0023] [3] The wound body according to [1] or [2], wherein:

[0024] The photosensitive composition layer has a thickness of 2 to 20 μm.

[0025] [4] The wound body according to any one of [1] to [3], wherein:

[0026] The composition layer includes at least one of an intermediate layer and a thermoplastic resin layer between the temporary support and the photosensitive composition layer.

[0027] [5] The wound body according to [4], wherein:

[0028] The thickness of the intermediate layer is 0.1 to 10 μm.

[0029] [6] The wound body according to [4], wherein:

[0030] The thickness of the thermoplastic resin layer is 0.1 to 10 μm.

[0031] [7] A method for producing a laminate having a resin pattern, comprising:

[0032] An unwinding step of unwinding the transfer film from the roll described in any one of [1] to [6];

[0033] a peeling step of peeling the protective film from the transfer film to expose the surface of the composition layer;

[0034] a laminating step of laminating the transfer film to the substrate having the conductive layer so that the exposed surface of the composition layer contacts the conductive layer of the substrate having the conductive layer on the surface;

[0035] an exposure step of exposing the photosensitive composition layer contained in the composition layer; and

[0036] a development step of developing the exposed photosensitive composition layer to form a resin pattern;

[0037] The method for producing a laminate further includes a temporary support peeling step of peeling the temporary support between the bonding step and the exposure step or between the exposure step and the development step.

[0038] [8] A method for manufacturing a laminate having a conductor pattern, comprising:

[0039] An unwinding step of unwinding the transfer film from the roll described in any one of [1] to [6];

[0040] a peeling step of peeling the protective film from the transfer film to expose the surface of the composition layer;

[0041] a laminating step of laminating the transfer film to the substrate having the conductive layer so that the exposed surface of the composition layer contacts the conductive layer of the substrate having the conductive layer on the surface;

[0042] An exposure step of exposing the photosensitive composition layer contained in the composition layer;

[0043] A development step of developing the exposed photosensitive composition layer to form a resist pattern;

[0044] any one of an etching step of etching the conductive layer in a region where the resist pattern is not disposed and a plating step of plating; and

[0045] a resist pattern stripping step of stripping the resist pattern,

[0046] When the method for manufacturing the laminate having the conductor pattern has the plating treatment step, the method further comprises: a removal step of removing the conductive layer exposed by the resist pattern stripping step to form the conductor pattern on the substrate;

[0047] The method for producing a laminate having a conductor pattern further includes a temporary support peeling step of peeling the temporary support between the bonding step and the exposure step or between the exposure step and the development step.

[0048] Effects of the Invention

[0049] According to the present invention, it is possible to provide a roll body having excellent peeling properties of a protective film and excellent lamination properties at an end portion of a transfer film unwound from the roll body.

[0050] Furthermore, it is possible to provide a method for producing a laminate having a resin pattern and a method for producing a laminate having a conductor pattern, both of which are formed by using the wound body. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is a schematic diagram of the case where the transfer film is unwound from the roll.

[0052] Figure 2 Schematic diagram showing an example of the end portion of the cross section of the transfer film when the position X takes a positive value.

[0053] Figure 3 It is a schematic diagram showing an example of the end portion of the cross section of the transfer film when the position X takes a negative value.

[0054] Figure 4 This is a schematic diagram showing an example of both ends of the cross section of the transfer film when the position X and the position Y take positive values.

[0055] Figure 5 This is a schematic diagram showing an example of both ends of the cross section of the transfer film when the position X and the position Y take negative values.

[0056] Figure 6 It is a schematic diagram which shows an example of the structure of the transfer film of 1st Embodiment.

[0057] Figure 7 It is a schematic diagram which shows an example of the structure of the transfer film of 2nd Embodiment. DETAILED DESCRIPTION

[0058] Hereinafter, the present invention will be described in detail.

[0059] Although the constituent elements described below are sometimes described based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0060] The meaning of each description in this specification is shown below.

[0061] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0062] In this specification, within the numerical ranges recorded in stages, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. Furthermore, within the numerical ranges recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can also be replaced by the value shown in the embodiment.

[0063] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0064] In the present specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.

[0065] In this specification, the transmittance is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0066] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​converted to polystyrene using a standard substance, measured using a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.

[0067] In the present specification, unless otherwise specified, the ratio of the constituent units of a polymer is a mass ratio.

[0068] In the present specification, unless otherwise specifically stated, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).

[0069] In this specification, unless otherwise specified, the content of a metal element is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectrometer.

[0070] In this specification, unless otherwise specifically stated, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

[0071] In this specification, unless otherwise specifically stated, hue is a value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0072] In this specification, “(meth)acrylic acid” is a concept including both acrylic acid and methacrylic acid, and “(meth)acryloyloxy” is a concept including both acryloyloxy and methacryloyloxy.

[0073] In the present specification, the term "alkali-soluble" means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0074] In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above solubility condition.

[0075] In this specification, the "solid content" of a composition refers to the components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. In addition, if it is a component that forms a composition layer, a liquid component is also regarded as a solid component.

[0076] Unless otherwise specified, the compounds described in the present specification may include structural isomers, optical isomers, and isotopes. Furthermore, the structural isomers, optical isomers, and isotopes may include one type alone or two or more types.

[0077] In this specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -COO-) when Y in a compound represented by "XYZ" is -COO-, the compound may be any of "XO-CO-Z" and "X-CO-OZ".

[0078] [Wound body]

[0079] Hereinafter, the wound body of the present invention will be described in detail.

[0080] The roll body of the present invention is a roll body of a transfer film, wherein the transfer film has a temporary support, a composition layer, and a protective film in this order, and the composition layer includes a photosensitive composition layer.

[0081] Furthermore, in the winding body of the present invention, the transfer film unwound from the winding body is subjected to the cross-sectional observation described later at five different locations at intervals of 8 cm along the length direction of the transfer film, and the minimum and maximum values ​​of the five positions X and the five positions Y obtained in each cross-sectional observation are all within the range of -40 to 40 μm.

[0082] The above-mentioned position X and position Y are obtained by cross-sectional observation shown below.

[0083] Cross-sectional observation: The transfer film unwound from the roll is cut along the width direction of the transfer film, and one of the two exposed cross-sections is observed from the normal direction of the cross-section.

[0084] The position of the outermost end of the temporary support body in the width direction of the transfer film in the exposed cross section is set as the first position, the position of the outermost end of the protective film in the width direction of the transfer film and located on the same side as the first position is set as the second position, and the position of the second position in the width direction of the transfer film, which is represented by a positive value when it is closer to the outer side than the first position in the width direction of the transfer film with the first position as a reference, is set as position X.

[0085] Furthermore, the position of the other end of the temporary support body located at the outermost side in the width direction of the transfer film in the exposed cross section is set as the third position, the position of the other end located at the outermost side of the protective film in the width direction of the transfer film and located on the same side as the third position is set as the fourth position, and the position of the fourth position, which is represented by a positive value in the width direction of the transfer film and is closer to the outside than the third position along the width direction of the transfer film with the third position as a reference, is set as position Y.

[0086] by Figure 1 Taking the above cross-sectional observation as an example, the specific order is described. Figure 1 This is a schematic diagram of the case where the transfer film is unwound from the roll.

[0087] First, the transfer film 12 is unwound from the roll 10, and the unwound transfer film 12 is cut in the width direction. Figure 1 As shown, when the transfer film 12 is cut in the width direction, the transfer film 12 is released and cut at the cutting line CL1 extending in the width direction of the transfer film 12. In addition, the transfer film 12 is cut in the same manner at the cutting lines CL2 to CL5 each separated by a width W from the cutting line CL1. Next, as described later, one of the two cross sections exposed by the cutting is observed from the normal direction of one cross section, and the position X and the position Y of each cross section are measured. As described later, five positions X and five positions Y are measured from five cross-sectional views generated and observed by the five cutting lines CL1 to CL5.

[0088] Next, Figure 2 and Figure 3 As an example, a method for measuring position X is shown.

[0089] exist Figure 2 An example of a cut surface of a transfer film is shown in FIG. Figure 2 , a partial enlarged view of the cut surface of the transfer film 12A cut in the above-mentioned order is shown, which is equivalent to an enlarged view of one end of the transfer film 12A. Figure 2 As shown, the transfer film 12A includes a temporary support 14A, a composition layer 16A, and a protective film 18A in this order. The composition layer 16A is a layer including a photosensitive composition layer.

[0090] like Figure 2 As shown, at one end of the transfer film 12A, the protective film 18A protrudes outward from the temporary support 14A and the composition layer 16A.

[0091] exist Figure 2 , the position at the outermost end of the temporary support body 14A in the width direction of the transfer film 12A is set as the first position P1A, and the position at the outermost end of the protective film 18A in the width direction of the transfer film 12A and located on the same side as the first position P1A is set as the second position P2A, and in the width direction of the transfer film 12A, with the first position P1A as a reference, as shown by the arrow, when the position further outward than the first position P1A in the width direction of the transfer film 12A is represented by a positive value, the position X is represented by a positive value. That is, the position of the second position P2A with the first position P1A as a reference, that is, the position X is represented by a positive value.

[0092] And, in Figure 3 Another example of a cut surface of a transfer film is shown in FIG. Figure 3 FIG. 2 is a partial enlarged view of the cut surface of the transfer film 12B cut in the above order, which is equivalent to an enlarged view of one end of the transfer film 12B. Figure 3 As shown, the transfer film 12B has a temporary support 14B, a composition layer 16B, and a protective film 18B in this order. The composition layer 16B is a layer including a photosensitive composition layer.

[0093] like Figure 3 As shown, at one end of the transfer film 12B, the temporary support 14B and the composition layer 16B protrude further than the protective film 18B.

[0094] exist Figure 3 In the figure, the position at the outermost end of the temporary support body 14B in the width direction of the transfer film 12B is set as the first position P1B, and the position at the outermost end of the protective film 18B in the width direction of the transfer film 12B and located on the same side as the first position P1B is set as the second position P2B, and in the width direction of the transfer film 12B, with the first position P1B as a reference, when the position further outward than the first position P1B in the width direction of the transfer film 12B is represented by a positive value, the position X is represented by a negative value. That is, the position of the second position P2B with the first position P1B as a reference, that is, the position X is represented by a negative value.

[0095] The measurement of position Y can be performed in the same manner as the measurement of position X described above. Figure 4 and Figure 5 Provide explanation.

[0096] Then, in Figure 4An example of the two ends of the cut surface of the transfer film is shown in FIG. Figure 4 1 is an overall view of a cut surface of the transfer film 12A cut in the above-described order, and both ends of the transfer film 12A are shown. Figure 4 The meanings of 14A, 16A and 18A shown are the same as Figure 2 14A, 16A and 18A have the same meaning.

[0097] like Figure 4 As shown, at both ends of the transfer film 12A, the protective film 18A protrudes outwards more than the temporary support 14A and the composition layer 16A.

[0098] As mentioned above, position X can be determined by using Figure 2 The order of instructions is used for measurement.

[0099] And, in Figure 4 In the figure, the position of the other end of the temporary support body 14A which is located at the outermost side in the width direction of the transfer film 12A is set as the third position P3A, the position of the other end which is located at the outermost side of the protective film 18A in the width direction of the transfer film 12A and is located on the same side as the third position P3A is set as the fourth position P4A, and in the width direction of the transfer film 12A, with the third position P3A as a reference, as indicated by the arrow, when a position which is further outward than the third position P3A in the width direction of the transfer film 12A is represented by a positive value, the position Y is represented by a positive value.

[0100] The third position P3A is located on the side opposite to the first position P1A in the width direction of the transfer film 12A and corresponds to a position located at one end of the outermost side of the temporary support body 14A.

[0101] The fourth position P4A is located on the side opposite to the first position P1A in the width direction of the transfer film 12A and corresponds to a position located at one end of the outermost side of the protective film 18A.

[0102] And, in Figure 5 Another example of a cut surface of a transfer film is shown in FIG. Figure 5 1 is an overall view of a cut surface of the transfer film 12B cut in the above-described order, and both ends of the transfer film 12B are shown. Figure 5 The meanings of 14B, 16B and 18B shown are the same as Figure 3 14B, 16B and 18B have the same meaning.

[0103] like Figure 5 As shown, at both ends of the transfer film 12B, the temporary support 14B and the composition layer 16B protrude further than the protective film 18B.

[0104] As mentioned above, position X can be determined by using Figure 3 The order of instructions is used for measurement.

[0105] And, in Figure 5 In the figure, the position of the other end of the temporary support body 14B which is located at the outermost side in the width direction of the transfer film 12B is set as the third position P3B, and the position of the other end which is located at the outermost side of the protective film 18B in the width direction of the transfer film 12B and is located on the same side as the third position P3B is set as the fourth position P4B, and in the width direction of the transfer film 12B, with the third position P3B as a reference, when a position which is further outward than the third position P3B in the width direction of the transfer film 12B is represented by a positive value, the position Y is represented by a negative value.

[0106] As mentioned above Figure 2 to Figure 5 In the method shown, cross-sections of the transfer film unwound from the roll are observed at five locations, and the X value of one end of the transfer film and the Y value of the other end of the transfer film are measured. The X value of five locations and the Y value of five locations are measured.

[0107] From the 5 positions X and 5 positions Y thus obtained, the minimum value and the maximum value are selected.

[0108] As a specific method for measuring the position X and the position Y, the positions are measured by observing a cross section with a scanning electron microscope.

[0109] As described above, in the wound body of the present invention, the minimum value and the maximum value of the five positions X and the five positions Y measured in the above order are both within the range of -40 to 40 μm.

[0110] Furthermore, from the perspective of achieving a more excellent effect of the present invention, the minimum and maximum values ​​of the five positions X and the five positions Y are preferably not less than -20 μm, more preferably not less than -1 μm, and further preferably not less than 0.1 μm. That is, from the perspective of achieving a more excellent effect of the present invention, the minimum value is preferably within the range of 0.1 to 40 μm.

[0111] The minimum value and the maximum value at the five positions X and the five positions Y are not particularly limited as long as they are 40 μm or less, but are preferably 25 μm or less.

[0112] In the transfer film unwound from the roll of the present invention, the minimum and maximum values ​​at the five positions X and the five positions Y are all within the range of -40 to 40 μm. Although the mechanism by which the problems of the present invention can be solved is not clear, the present inventors presume as follows.

[0113] In addition, the mechanism of obtaining the effect is not limited to the following speculation. In other words, the case where the effect is obtained by a mechanism other than the following is also included in the scope of the present invention.

[0114] When the position X exceeds 40 μm, since the protective film 18A is in an extremely protruding state relative to the temporary support 14A, it is easy to peel off the protective film 18A when processing the roll and releasing the transfer film 12A from the roll. When releasing the transfer film 12A from the roll, rollers are used for transportation, etc., but if the protective film 18A is once peeled off, the protective film 18A is closely attached to the composition layer 16A again when passing through the roller, etc., sometimes bubbles are contained between the composition layer 16A and the protective film 18A. If such bubbles are contained, the composition layer 16A will be pressed by the bubbles, and as a result, the thickness of the composition layer 16A near the end will deviate. It is speculated that if the composition layer 16A with such a deviation in thickness is attached to the object to be attached, wrinkles will be generated at the end of the attached composition layer 16A due to the deviation of the above thickness.

[0115] Furthermore, when the position X is less than -40 μm, the protective film 18B is in a retreated state relative to the temporary support 14B, so the edge of the composition layer is exposed.

[0116] When the transfer film 12B in this state is laminated, when the protective film 18B is peeled off from the composition layer 16B using an adhesive tape or the like, the adhesive tape is likely to adhere to a portion of the composition layer 16B, so that not only the protective film 18B but also the composition layer 16B is peeled off from the temporary support 14B. That is, it is not easy to peel off only the protective film 18B.

[0117] When the position Y is 40 μm or more or less than −40 μm, the same problem as that at the position X described above will occur.

[0118] For the above reasons, it is speculated that in the roll of the present invention, in the transfer film released from the roll, the minimum and maximum values ​​at 5 positions X and 5 positions Y are both within the range of -40 to 40 μm, whereby at both ends of the protective film, the end positions of the protective film are within an appropriate range, and therefore, when the transfer film is laminated, the peelability of the protective film and the lamination of the ends are excellent.

[0119] The method for adjusting the position X and the position Y so that they are within the specified range is not particularly limited, and a known method can be cited. For example, a method of adjusting the lengths of the temporary support, the composition layer, and the protective film in the width direction and laminating them, a cutting method when slit cutting is performed on the end portions of the transfer film in the width direction including the temporary support, the composition layer, and the protective film, and a method of adjusting according to the conditions can be cited.

[0120] At one end of the cross-section of the transfer film, the relationship between the first position and the position at one end located at the outermost side of the composition layer in the width direction of the transfer film and located on the same side as the first position (hereinafter also referred to as "position Ca") is not particularly limited, but when a positive value is used to represent a position further outside in the width direction of the transfer film than the first position with the first position as a reference, the position of position Ca relative to the first position is preferably in the range of -0.5 to 0.5 μm.

[0121] Furthermore, at the other end of the cross-section of the transfer film, the relationship between the third position and the position at the outermost side of the composition layer in the width direction of the transfer film and at one end on the same side as the third position (hereinafter also referred to as "position Cb") is not particularly limited, but when the position further outside in the width direction of the transfer film than the third position is expressed as a positive value with the third position as a reference, the position of position Cb relative to the third position is preferably in the range of -0.5 to 0.5 μm.

[0122] Hereinafter, the transfer film constituting the wound body will be described. The preferred embodiments of the transfer film described below are preferred embodiments of the transfer film constituting the wound body.

[0123] [Transfer film]

[0124] The transfer film constituting the wound body of the present invention includes a temporary support, a composition layer, and a protective film in this order.

[0125] The composition layer is not particularly limited as long as it includes a photosensitive composition layer.

[0126] The photosensitive composition layer may be a negative-type photosensitive composition layer or a chemically amplified photosensitive composition layer, but is preferably a negative-type photosensitive composition layer.

[0127] Furthermore, the composition layer may be a single layer structure or a structure of two or more layers. When the composition layer includes other composition layers other than the photosensitive composition layer, examples of the other composition layers include a thermoplastic resin layer, an intermediate layer, and a refractive index adjustment layer.

[0128] The intermediate layer is preferably disposed between the temporary support and the photosensitive composition layer.

[0129] An example of the form of the transfer film constituting the wound body of the present invention is shown below, but the present invention is not limited thereto.

[0130] (1) "temporary support / photosensitive composition layer / refractive index adjusting layer / protective film"

[0131] (2) "Temporary support / photosensitive composition layer / protective film"

[0132] (3) "Temporary support / intermediate layer / photosensitive composition layer / protective film"

[0133] (4) "temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film"

[0134] In each of the above structures, the photosensitive composition layer is preferably a negative photosensitive composition layer. Furthermore, the photosensitive composition layer is also preferably a colored resin layer.

[0135] As described below, the transfer film of the present invention can be used as a transfer film for a wiring protection film or a transfer film for an etching resist.

[0136] When used as a transfer film for a wiring protection film, the structure of the transfer film is preferably, for example, the structure (1) or (2) described above. Also, when used as a transfer film for an etching resist, the structure of the transfer film is preferably, for example, the structure (2) to (4) described above.

[0137] In the composition layer of the transfer film, when it has a structure that further includes other layers on the side of the photosensitive composition layer opposite to the temporary support side, the total thickness of the other layers arranged on the side of the photosensitive composition layer opposite to the temporary support side is preferably 0.1 to 30%, more preferably 0.1 to 20%, relative to the thickness of the photosensitive composition layer.

[0138] From the viewpoint of suppressing the generation of bubbles in the laminating process described later, the maximum width of the corrugations of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 60 μm or less. In addition, the lower limit of the maximum width of the corrugations is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

[0139] The maximum width of the corrugations of the transfer film is a value measured in the following procedure.

[0140] First, cut the transfer film into a size of 20 cm in length and 20 cm in width in a direction perpendicular to the main surface, and peel off the protective film to make a test sample. Next, place the test sample on a smooth and horizontal stage so that the surface of the temporary support body is opposite to the stage. After standing still, use a laser microscope (e.g., VK-9700SP manufactured by KEYENCE CORPORATION) to scan the surface of the test sample in a 10 cm square range in the center of the test sample to obtain a three-dimensional surface image, and subtract the minimum concave height from the maximum convex height observed in the obtained three-dimensional surface image. Perform the above operation for 10 test samples, and use the arithmetic mean as the "maximum width of the corrugation of the transfer film".

[0141] The transfer film of the present invention is described below by taking an example of a specific embodiment. In addition, the transfer film of the first embodiment below has a structure that can be preferably used as a transfer film for wiring protection film, and the transfer film of the second embodiment below has a structure that can be preferably used as a transfer film for wiring protection film and a transfer film for etching resist.

[0142] [Transfer film according to the first embodiment]

[0143] Hereinafter, an example of an embodiment of the transfer film of the first embodiment will be described.

[0144] Figure 6 The transfer film 30 shown includes: a temporary support 32 ; a composition layer 38 including a photosensitive composition layer 34 and a refractive index adjusting layer 36 ; and a protective film 40 in this order.

[0145] in addition, Figure 6 The transfer film 30 shown in FIG. 1 is in a form in which the refractive index adjusting layer 36 is arranged, but the refractive index adjusting layer 36 may not be arranged.

[0146] Hereinafter, each element constituting the transfer film will be described.

[0147] Temporary support

[0148] The transfer film has a temporary support.

[0149] The temporary support is a member that supports the composition layer and is eventually removed by a peeling treatment.

[0150] The temporary support may be a single-layer structure or a multi-layer structure.

[0151] The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film that is flexible and does not significantly deform, shrink, or elongate under pressure or under pressure and heating is preferred.

[0152] Examples of the film include a polyethylene terephthalate film (eg, a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

[0153] Among them, a polyethylene terephthalate film is preferable as the temporary support.

[0154] Furthermore, it is preferred that the film used as a temporary support body has no deformation such as wrinkles or scratches.

[0155] From the aspect that can carry out pattern exposure across the temporary support, the temporary support preferably has high transparency, and the transmittance at 313nm, 365nm, 405nm and 436nm is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and most preferably 90% or more. As the preferred value of transmittance, for example, 87%, 92%, 98% etc. can be cited.

[0156] From the perspective of pattern formation when pattern exposure is performed across a temporary support and the transparency of the temporary support, it is preferred that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, further preferably 0.4% or less, and particularly preferably 0.1% or less. However, when the exposure described in the latter section is performed by peeling off the temporary support for exposure, the haze of the temporary support is not limited thereto.

[0157] Furthermore, from the viewpoint of transportability during production of the temporary support, the haze of the temporary support is preferably 0.05% or more, and more preferably 0.1% or more.

[0158] The haze is a total light haze (%) in accordance with JIS K 7136:2000, and can be measured as a total light haze using a haze meter (device name: HZ-2, manufactured by Suga Test Instruments Co., Ltd.).

[0159] As described later, when the temporary support is subjected to a surface treatment or a primer treatment, the measured value of the haze is a value obtained by measuring the temporary support after the above treatment.

[0160] From the perspective of pattern formation when pattern exposure is performed through a temporary support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter and defects contained in the temporary support is small. The number of particles, foreign matter and defects with a diameter of 1 μm or more in the temporary support is preferably 50 / 10 mm. 2 Below, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0161] The thickness of the temporary support is not particularly limited, but is preferably 5 to 300 μm, more preferably 5 to 150 μm, further preferably 5 to 50 μm, and most preferably 5 to 25 μm in view of ease of handling and versatility.

[0162] The thickness of the temporary support body was calculated as an average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0163] In order to improve the adhesion between the temporary support and the composition layer, the side of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.

[0164] When surface modification is performed by UV irradiation, the exposure amount is preferably 10 to 2000 mJ / cm 2 , more preferably 50 to 1000 mJ / cm 2 .

[0165] As the light source for UV irradiation, there can be cited low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in a wavelength band of 150 to 450 nm. As long as the light irradiation amount is within this range, the lamp output or illumination is not particularly limited.

[0166] Furthermore, from the viewpoint of adhesion with the composition layer and the like, the temporary support may be subjected to a primer treatment for forming a primer layer (containing polyvinylidene chloride resin, styrene-butadiene rubber, gelatin, or the like).

[0167] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 25 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 μm.

[0168] As a preferred method of the temporary support body, for example, the records in paragraphs

[0017] to

[0018] of Japanese Patent Gazette No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Gazette No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370 can be cited, and the contents of these gazettes are incorporated into this specification.

[0169] From the perspective of providing handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one surface or both surfaces of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

[0170] Furthermore, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0171] Examples of commercially available temporary supports include Lumirror 16KS40, Lumirror 25QS40, Lumirror 25QS60, and Lumirror 16FB40 (all manufactured by TORAY INDUSTRIES, INC.), Cosmo Shine A4100, Cosmo Shine A4160, Cosmo Shine A4300, and Cosmo Shine A8300 (all manufactured by TOYOBO CO., LTD.).

[0172] <<Photosensitive composition layer>>

[0173] The transfer film has a photosensitive composition layer.

[0174] After the photosensitive composition layer is transferred onto a transfer target, exposure and development are performed to form a pattern on the transfer target.

[0175] As the photosensitive composition layer, a negative type is preferred. In addition, a negative type photosensitive composition layer refers to a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases due to exposure. When the photosensitive composition layer is a negative type photosensitive composition layer, the pattern formed is equivalent to a cured layer.

[0176] Hereinafter, the components which can be contained in the photosensitive composition layer will be described in detail.

[0177] <Binder Polymer>

[0178] The photosensitive composition layer may contain a binder polymer.

[0179] Examples of the binder polymer 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 reaction of epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins with acid anhydrides.

[0180] As one of the preferred aspects of the binder polymer, a (meth)acrylic resin is mentioned from the viewpoint of excellent alkali developability and film-forming property.

[0181] In addition, in this specification, a (meth)acrylic resin refers to a resin having a constituent unit derived from a (meth)acrylic compound. The content of the constituent unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more relative to all the constituent units of the (meth)acrylic resin.

[0182] The (meth)acrylic resin may be composed only of constituent units derived from a (meth)acrylic compound, or may have constituent units derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of the content of constituent units derived from a (meth)acrylic compound relative to all constituent units of the (meth)acrylic resin is 100% by mass or less.

[0183] As a (meth)acrylic acid compound, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile are mentioned, for example.

[0184] Examples of the (meth)acrylate include 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, and alkyl (meth)acrylates are preferred.

[0185] Examples of (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0186] The alkyl group of the alkyl (meth)acrylate may be linear or branched. Specific examples thereof include alkyl (meth)acrylates having an alkyl group 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.

[0187] As the (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.

[0188] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.

[0189] The polymerizable monomer forming the above-mentioned constituent units is not particularly limited as long as it is a compound other than the (meth)acrylic acid compound copolymerizable with the (meth)acrylic acid compound, and examples thereof include styrene compounds which may have a substituent at the α position or on the aromatic ring, such as styrene, vinyltoluene and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid and crotonic acid.

[0190] These polymerizable monomers may be used alone or in combination of two or more.

[0191] Furthermore, from the viewpoint of further improving the alkali developability, the (meth)acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group.

[0192] Among them, the (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably contains a structural unit derived from the above-mentioned (meth)acrylic acid.

[0193] From the viewpoint of excellent developability, the content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. The upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0194] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate.

[0195] When the (meth)acrylic acid alkyl ester-derived structural unit is contained, the content of the (meth)acrylic acid alkyl ester-derived structural unit in the (meth)acrylic acid resin is preferably 1 to 90 mass %, more preferably 1 to 50 mass %, and further preferably 1 to 30 mass % based on all the structural units of the (meth)acrylic resin.

[0196] The (meth)acrylic resin is preferably a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate. A resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate is more preferred.

[0197] Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0198] Furthermore, from the viewpoint of achieving more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylates, and more preferably has both constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylates.

[0199] From the viewpoint of achieving a more excellent effect of the present invention, the total content of the constituent units derived from methacrylic acid and the constituent units derived from the alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all the constituent units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0200] Furthermore, from the viewpoint of further improving the effects of the present invention, the (meth)acrylic resin also preferably contains at least one selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from methacrylic acid alkyl esters and at least one selected from the group consisting of constituent units derived from acrylic acid and constituent units derived from acrylate alkyl esters.

[0201] From the viewpoint of further improving the effects of the present invention, the total content of the constituent units derived from methacrylic acid and the constituent units derived from the alkyl methacrylate is preferably 60 / 40 to 80 / 20 in terms of the mass ratio relative to the total content of the constituent units derived from acrylic acid and the constituent units derived from the alkyl methacrylate.

[0202] The (meth)acrylic resin preferably has an ester group at the terminal, from the viewpoint of excellent developability of the photosensitive composition layer after transfer.

[0203] The terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0204] Furthermore, another preferred embodiment of the binder polymer includes an alkali-soluble resin.

[0205] For example, from the viewpoint of developability, the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more.

[0206] Furthermore, for example, from the perspective of easily forming a strong film by thermal cross-linking with the cross-linking component by heating, the binder polymer is more preferably a resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing resin), and is further preferably a (meth) acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing (meth) acrylic resin.

[0207] If the binder polymer is a resin having a carboxyl group, the three-dimensional crosslinking density can be increased by adding a heat-crosslinkable compound such as a blocked isocyanate compound for thermal crosslinking. Furthermore, if the carboxyl group of the resin having a carboxyl group is anhydrided and hydrophobized, the wet heat resistance can be improved.

[0208] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above-mentioned acid value conditions are satisfied, and can be appropriately selected from known (meth)acrylic resins.

[0209] For example, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraph

[0025] of JP-A-2011-095716, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs

[0033] to

[0052] of JP-A-2010-237589 can be preferably used.

[0210] Another preferred embodiment of the binder polymer includes a styrene-acrylic acid copolymer.

[0211] In addition, in the present specification, a styrene-acrylic acid copolymer refers to a resin having constituent units derived from a styrene compound and constituent units derived from a (meth)acrylic acid compound, and the total content of the constituent units derived from the above-mentioned styrene compound and the constituent units derived from the above-mentioned (meth)acrylic acid compound relative to all the constituent units of the above-mentioned copolymer is preferably 30% by mass or more, more preferably 50% by mass or more.

[0212] Furthermore, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 5 to 80% by mass, based on all the structural units of the copolymer.

[0213] The content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20 to 95% by mass, based on all the structural units of the copolymer.

[0214] From the viewpoint of achieving more excellent effects of the present invention, the binder polymer preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

[0215] As the monomer forming the constituent unit having an aromatic ring structure, there can be mentioned a monomer having an aralkyl group, styrene and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred. As the aralkyl group, there can be mentioned a substituted or unsubstituted phenylalkyl group (except benzyl) and a substituted or unsubstituted benzyl group, etc., preferably a substituted or unsubstituted benzyl group.

[0216] Examples of the monomer having a phenylalkyl group include phenethyl (meth)acrylate and the like.

[0217] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride, and vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol. Among them, benzyl (meth)acrylate is preferred.

[0218] Furthermore, from the viewpoint of achieving more excellent effects of the present invention, the binder polymer more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[0219] [Chemical formula 1]

[0220]

[0221] When the binder polymer contains a constituent unit having an aromatic ring structure, from the perspective of achieving a more excellent effect of the present invention, the content of the constituent unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and further preferably 20 to 60% by mass relative to all the constituent units of the binder polymer.

[0222] Furthermore, from the viewpoint of achieving more excellent effects of the present invention, the content of the constituent units having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and further preferably 20 to 60 mol % relative to all constituent units of the binder polymer.

[0223] Furthermore, from the perspective of achieving a more excellent effect of the present invention, the content of the constituent unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, further preferably 20 to 60 mol %, and particularly preferably 20 to 50 mol %, relative to all the constituent units of the binder polymer.

[0224] In addition, in this specification, when the content of "constituent unit" is specified by molar ratio, the meaning of the above "constituent unit" is the same as the meaning of "monomer unit". In addition, in this specification, the above "monomer unit" may be modified by polymer reaction etc. after polymerization. The same applies to the following.

[0225] From the perspective of the more excellent effect of the present invention, the binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably contains a constituent unit having an aliphatic hydrocarbon ring structure. As the aliphatic hydrocarbon ring structure, it can be a monocyclic ring or a polycyclic ring. Among them, the binder polymer more preferably has a ring structure formed by condensing more than 2 aliphatic hydrocarbon rings.

[0226] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the constituent unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring.

[0227] Among them, from the viewpoint of more excellent effects of the present invention, a ring formed by condensing two or more aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2，6 ]decane ring).

[0228] Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0229] In order to achieve more excellent effects of the present invention, the binder polymer preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0230] [Chemical formula 2]

[0231]

[0232] In formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0233] R in formula (Cy) M Preferred is methyl.

[0234] From the viewpoint of further improving the effect of the present invention, R in the formula (Cy) Cy It is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0235] Furthermore, from the viewpoint of further improving the effect of the present invention, R Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, further preferably a tetrahydrodicyclopentadiene ring structure.

[0236] From the viewpoint of further improving the effect of the present invention, R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring structure in which 2 to 4 aliphatic hydrocarbon rings are condensed.

[0237] Furthermore, from the viewpoint of further improving the effect of the present invention, R in the formula (Cy) Cy It is preferably a group in which the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentyl group, and still more preferably a dicyclopentyl group.

[0238] The binder polymer may have one type of constituent unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types of constituent units having an aliphatic hydrocarbon ring structure.

[0239] When the binder polymer contains a constituent unit having an aliphatic hydrocarbon ring structure, from the perspective of achieving a more excellent effect of the present invention, the content of the constituent unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and further preferably 20 to 70% by mass relative to all the constituent units of the binder polymer.

[0240] Furthermore, from the viewpoint of achieving more excellent effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and further preferably 20 to 50 mol % relative to all structural units of the binder polymer.

[0241] Furthermore, from the perspective of achieving more excellent effects of the present invention, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and further preferably 20 to 50 mol % relative to all structural units of the binder polymer.

[0242] When the binder polymer contains constituent units having an aromatic ring structure and constituent units having an aliphatic hydrocarbon ring structure, from the perspective of achieving a more excellent effect of the present invention, the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure relative to all the constituent units of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 40 to 75% by mass.

[0243] Furthermore, in order to achieve a more excellent effect of the present invention, the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and further preferably 40 to 60 mol % relative to all the constituent units of the binder polymer.

[0244] Furthermore, from the perspective of achieving a more excellent effect of the present invention, the total content of the constituent units represented by the above formula (S) and the constituent units represented by the above formula (Cy) in the binder polymer is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and further preferably 40 to 60 mol % relative to all the constituent units of the binder polymer.

[0245] Furthermore, from the perspective of achieving a more excellent effect of the present invention, the molar amount nS of the constituent unit represented by the above formula (S) and the molar amount nCy of the constituent 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 further preferably satisfy the following formula (SCy-2).

[0246] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0247] 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1)

[0248] 0.40≤nS / (nS+nCy)≤0.70 formula (SCy-2)

[0249] From the viewpoint of achieving more excellent effects of the present invention, the binder polymer preferably contains a structural unit having an acid group.

[0250] Examples of the acid group include a carboxyl group, a sulfone group, a phosphonic acid group and a phosphoric acid group, and a carboxyl group is preferred.

[0251] As the structural unit having the acid group, the structural unit derived from (meth)acrylic acid shown below is preferred, and the structural unit derived from methacrylic acid is more preferred.

[0252] [Chemical formula 3]

[0253]

[0254] The binder polymer may have one type of structural unit having an acid group alone, or may have two or more types of structural units having an acid group.

[0255] When the binder polymer contains a structural unit having an acid group, from the perspective of achieving more excellent effects of the present invention, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass relative to all the structural units of the binder polymer.

[0256] In order to obtain more excellent effects of the present invention, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and further preferably 20 to 40 mol % based on all structural units of the binder polymer.

[0257] In order to achieve more excellent effects of the present invention, the content of the structural units derived from (meth)acrylic acid in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and further preferably 20 to 40 mol % based on all structural units of the binder polymer.

[0258] From the viewpoint of achieving more excellent effects of the present invention, the binder polymer preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0259] As the reactive group, a radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in a side chain.

[0260] In the present specification, the “main chain” refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and the “side chain” refers to an atomic group branched from the main chain.

[0261] As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferred.

[0262] Examples of the structural unit having a reactive group include the following, but are not limited thereto.

[0263] [Chemical formula 4]

[0264]

[0265] The binder polymer may have one type of constituent unit having a reactive group alone, or may have two or more types of constituent units having a reactive group.

[0266] When the binder polymer contains a constituent unit having a reactive group, from the perspective of achieving a more excellent effect of the present invention, the content of the constituent unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass relative to all the constituent units of the binder polymer.

[0267] In order to achieve more excellent effects of the present invention, the content of the constituent units having reactive groups in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and further preferably 20 to 50 mol % relative to all constituent units of the binder polymer.

[0268] As a method for introducing reactive groups into a binder polymer and a method for introducing reactive groups into a binder polymer, there can be cited a method of reacting compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds and carboxylic anhydride with functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups and sulfonic groups.

[0269] As a preferred example of a method for introducing a reactive group into a binder polymer, there can be cited a method in which a polymer having a carboxyl group is synthesized by polymerization reaction, and then glycidyl (meth)acrylate is reacted with a part of the carboxyl group of the obtained polymer by polymer reaction to introduce a (meth)acryloyloxy group into the polymer. By this method, a binder polymer having a (meth)acryloyloxy group in a side chain can be obtained.

[0270] The polymerization reaction is preferably carried out at a temperature of 70 to 100° C., more preferably at a temperature of 80 to 90° C. As the polymerization initiator used in the polymerization reaction, an azo initiator is preferred, and more preferably V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The polymer reaction is preferably carried out at a temperature of 80 to 110° C. In the polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0271] From the viewpoint of achieving more excellent effects of the present invention, the following polymers are preferred as binder polymers. The content ratio (a to d) and weight average molecular weight Mw of each structural unit shown below can be appropriately changed depending on the purpose.

[0272] [Chemical formula 5]

[0273]

[0274] In the above polymer, a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt% are preferred.

[0275] [Chemical formula 6]

[0276]

[0277] In the above polymer, a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt% are preferred.

[0278] [Chemical formula 7]

[0279]

[0280] In the above polymer, a: 30 to 65 wt%, b: 1.0 to 20 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt% are preferred.

[0281] [Chemical formula 8]

[0282]

[0283] In the above polymers, a: 1.0 to 20 wt %, b: 20 to 60 wt %, c: 5.0 to 25 wt %, and d: 10 to 50 wt %.

[0284] Furthermore, the binder polymer may include a polymer containing a structural unit (having a carboxylic acid anhydride structure) (hereinafter, also referred to as “polymer X”).

[0285] The carboxylic acid anhydride structure may be any of a chain carboxylic acid anhydride structure and a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure.

[0286] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and still more preferably a 5-membered ring.

[0287] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0288] [Chemical formula 9]

[0289]

[0290] In formula P-1, R A1a represents a substituent, n 1a RA1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a Indicates an integer greater than 0.

[0291] As R A1a Examples of the substituent represented by include an alkyl group.

[0292] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0293] n 1a represents an integer greater than 0. 1a When it represents an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

[0294] When n 1a When it represents an integer greater than 2, there are multiple R A1a They can be the same or different. Also, there are multiple R A1a They may be bonded to each other to form a ring, but preferably are not bonded to each other to form a ring.

[0295] As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is further preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0296] Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural unit, Rx represents a hydrogen atom, a methyl group, a CH2OH group or a CF3 group, and Me represents a methyl group.

[0297] [Chemical formula 10]

[0298]

[0299] [Chemical formula 11]

[0300]

[0301] The structural unit having a carboxylic acid anhydride structure in the polymer X may be a single type or two or more types.

[0302] The total content of the structural units having a carboxylic anhydride structure is preferably 0 to 60 mol %, more preferably 5 to 40 mol %, and further preferably 10 to 35 mol % based on all the structural units of the polymer X.

[0303] The photosensitive composition layer may contain only one type of polymer X, or may contain two or more types of polymer X.

[0304] When the photosensitive composition layer contains a polymer X, from the viewpoint of more excellent effects of the present invention, the content of the polymer X is preferably 0.1 to 30 mass %, more preferably 0.2 to 20 mass %, further preferably 0.5 to 20 mass %, further preferably 1 to 20 mass % relative to the total mass of the photosensitive composition layer.

[0305] From the viewpoint of achieving more excellent effects of the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, particularly preferably 15,000 to 30,000.

[0306] The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, particularly preferably 70 to 130 mgKOH / g.

[0307] The acid value of the binder polymer is a value measured according to the method described in JIS K0070: 1992. From the viewpoint of developability, the dispersion degree of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0308] The photosensitive composition layer may contain only one type of binder polymer, or may contain two or more types of binder polymers.

[0309] From the viewpoint of achieving more excellent effects of the present invention, the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass based on the total mass of the photosensitive composition layer.

[0310] <Polymerizable Compound>

[0311] The photosensitive composition layer may contain a polymerizable compound.

[0312] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cation polymerizable groups, and radical polymerizable groups are preferred.

[0313] The polymerizable compound preferably includes a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0314] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0315] In addition, the ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

[0316] One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M").

[0317] Q 2 -R 1 -Q 1 Formula (M)

[0318] In formula (M), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0319] Regarding Q in formula (M) 1 and Q 2 From the perspective of ease of synthesis, Q 1 and Q 2 The same groups are preferred.

[0320] Furthermore, from the perspective of reactivity, Q in formula (M) 1 and Q 2 An acryloyloxy group is preferred.

[0321] From the viewpoint of further improving the effect of the present invention, R in the formula (M) 1 , preferably alkylene, alkyleneoxyalkylene (-L 1 -OL l -) or polyalkyleneoxyalkylene (-(L 1 -O) p -L 1 -), more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, further preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

[0322] The above-mentioned hydrocarbon group only needs to have a chain structure in at least a part. There is no particular limitation on the part other than the above-mentioned chain structure. For example, it can be any one of a branched, cyclic or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond and a combination thereof. An alkylene group or a group composed of two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a straight-chain alkylene group is further preferred.

[0323] In addition, the above L 1 Each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and preferably an integer of 2 to 10.

[0324] Furthermore, from the viewpoint of further improving the effect of the present invention, the linker Q in the compound M 1 With Q 2 The number of atoms in the shortest connecting chain between them is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0325] In this manual, "Connecting Q 1 With Q 2 The number of atoms in the shortest chain between 1 Connected R 1 The atoms in the 2 Connected R 1 The shortest number of atoms in the chain.

[0326] 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. The above ester monomers may also be used as a mixture.

[0327] Among the above compounds, from the viewpoint of more excellent effects of the present invention, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is further preferred.

[0328] Furthermore, as one of the preferred aspects of the polymerizable compound, there is mentioned a bifunctional or higher-functional ethylenically unsaturated compound.

[0329] In the present specification, the "bifunctional or higher-functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0330] As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred.

[0331] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0332] The bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

[0333] Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, and 1,4-cyclohexanediol di(meth)acrylate.

[0334] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTER A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTER DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK ESTER A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK ESTER A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and dioxanediol diacrylate (KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd.).

[0335] The trifunctional or higher-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

[0336] Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0337] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0338] Examples of the polymerizable compound include caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), and ethoxylated glyceryl triacrylate (NK ESTER A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.).

[0339] As the polymerizable compound, a urethane (meth)acrylate compound can also be mentioned.

[0340] Examples of the urethane (meth)acrylate include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylate.

[0341] Furthermore, as the urethane (meth) acrylate, urethane (meth) acrylates having three or more functional groups may also be mentioned. As the lower limit of the number of functional groups, 6 or more functional groups are more preferred, and 8 or more functional groups are further preferred. In addition, as the upper limit of the number of functional groups, 20 or less functional groups are preferred. Examples of trifunctional or higher-functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), U-15HA (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), AH-600 (trade name) manufactured by KYOEISHA CHEMICAL CO., LTD., and UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0342] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group.

[0343] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

[0344] Among these, as the acid group, a carboxyl group is preferred.

[0345] Examples of the ethylenically unsaturated compound having an acid group include tri- to tetra-functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxyl group into a pentaerythritol tri- and tetra-acrylate (PETA) skeleton (acid value: 80 to 120 mgKOH / g)], and penta- to hexa-functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxyl group into a dipentaerythritol penta- and hexa-acrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH / g)].

[0346] These trifunctional or higher-functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, as required.

[0347] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic acid anhydrides thereof is preferred.

[0348] When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof, developability and film strength are further improved.

[0349] The bifunctional or higher functional ethylenically unsaturated compound containing a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0350] Examples of the bifunctional or higher-functional ethylenically unsaturated compound having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0351] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents described in the publication are incorporated into the present specification.

[0352] Examples of the polymerizable compound include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, urethane monomers such as (meth)acrylate compounds having a urethane bond, 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, and alkyl (meth)acrylates.

[0353] These can be used alone or in combination of two or more.

[0354] Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol include bisphenol A (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; and polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. diol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(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.

[0355] Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0356] Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated 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 (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), and ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.).

[0357] As the polymerizable compound (particularly an ethylenically unsaturated compound), a compound having an ester bond is particularly preferred from the viewpoint of excellent developability of the photosensitive composition layer after transfer.

[0358] The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the perspective of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate is more preferred.

[0359] From the viewpoint of imparting reliability, the ethylenically unsaturated compound is preferably an ethylenically unsaturated compound containing an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above-mentioned tetramethylolmethane structure or trimethylolpropane structure.

[0360] Examples of the ethylenically unsaturated compound having an aliphatic group having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0361] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).

[0362] As the above-mentioned polymerizable compound, a polymerizable compound having a ring structure formed by condensing two or more aliphatic hydrocarbon rings (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferred, a bifunctional ethylenically unsaturated compound having a ring structure formed by condensing two or more aliphatic hydrocarbon rings is more preferred, and tricyclodecane dimethanol di(meth)acrylate is further preferred.

[0363] From the viewpoint of achieving more excellent effects of the present invention, the aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure.

[0364] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, particularly preferably 300 to 2,200.

[0365] The content of polymerizable compounds having a molecular weight of 300 or less in the photosensitive composition layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all polymerizable compounds in the photosensitive composition layer.

[0366] As one preferred embodiment of the photosensitive composition layer, the photosensitive composition layer preferably contains a difunctional or higher ethylenically unsaturated compound, more preferably a trifunctional or higher ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0367] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains: a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure; and a binder polymer containing a structural unit having an aliphatic hydrocarbon ring.

[0368] Furthermore, as one of the preferred forms of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a multifunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0369] Furthermore, as one of the preferred forms of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0370] Furthermore, as one of the preferred aspects of the photosensitive composition layer, the photosensitive composition layer preferably contains a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound) from the perspective of development residue inhibition and rust resistance.

[0371] In the photosensitive composition layer, the mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the trifunctional or higher-functional ethylenically unsaturated compound is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30.

[0372] The content of the bifunctional ethylenically unsaturated compound based on the total amount of all ethylenically unsaturated compounds is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

[0373] The content of the bifunctional ethylenically unsaturated compound in the photosensitive composition layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.

[0374] Furthermore, as one of the preferred aspects of the photosensitive composition layer, the photosensitive composition layer preferably contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

[0375] Furthermore, as one of the preferred forms of the photosensitive composition layer, from the aspects of substrate adhesion, development residue inhibition and rust resistance, the photosensitive composition layer preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an ethylenically unsaturated compound having an acid group, further preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group and a carbamate (meth) acrylate compound.

[0376] Furthermore, as one of the preferred aspects of the photosensitive composition layer, from the aspects of substrate adhesion, development residue inhibition and rust resistance, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, further preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group and a urethane acrylate compound.

[0377] The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0378] The content of the difunctional or higher-functional ethylenically unsaturated compound among the ethylenically unsaturated compounds is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0379] The polymerizable compound (particularly, an ethylenically unsaturated compound) may be used alone or in combination of two or more.

[0380] The content of the polymerizable compound (especially the ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1 to 70 mass %, more preferably 5 to 70 mass %, further preferably 5 to 60 mass %, particularly preferably 5 to 50 mass % relative to the total mass of the photosensitive composition layer.

[0381] <Polymerization Initiator>

[0382] The photosensitive composition layer may contain a polymerization initiator.

[0383] As the polymerization initiator, a photopolymerization initiator is preferred.

[0384] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0385] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an “oxime-based photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, also referred to as an “α-aminoalkylphenone-based photopolymerization initiator”), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as an “α-hydroxyalkylphenone-based photopolymerization initiator”), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an “acylphosphine oxide-based photopolymerization initiator”), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an “N-phenylglycine-based photopolymerization initiator”).

[0386] The photopolymerization initiator preferably includes at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0387] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A-2011-95716 and paragraphs

[0064] to

[0081] of JP-A-2015-014783 may be used.

[0388] Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad (registered trademark) 379EG, IGM Resins BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad (registered trademark) 907, manufactured by IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad (registered trademark) 127, manufactured by IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad (registered trademark) 369, manufactured by IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad (registered trademark) 1173, manufactured by IGM Resins BV] BV company], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad (registered trademark) 184, IGM Resins BV company], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad (registered trademark) 651, IGM Resins BV company], etc. As oxime ester-based photopolymerization initiators [trade name: Lunar (registered trademark) 6, DKSH Management Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, Changzhou Tronly New Electronic Materials Co., LTD.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) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade 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.

[0389] The photopolymerization initiator may be used alone or in combination of two or more. When two or more are used, it is preferred to use at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and α-hydroxyalkylphenone-based photopolymerization initiators.

[0390] When the photosensitive composition layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the photosensitive composition layer. And, as an upper limit, it is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the photosensitive composition layer.

[0391] <Heterocyclic Compounds>

[0392] The photosensitive composition layer may contain a heterocyclic compound.

[0393] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0394] Examples of the hetero atom possessed by the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0395] Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0396] Among the above, as the heterocyclic compound, at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds and benzoxazole compounds is preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds is more preferred.

[0397] Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0398] [Chemical formula 12]

[0399]

[0400] [Chemical formula 13]

[0401]

[0402] As the tetrazole compound, the following compounds can be exemplified.

[0403] [Chemical formula 14]

[0404]

[0405] [Chemical formula 15]

[0406]

[0407] As the thiadiazole compound, the following compounds can be exemplified.

[0408] [Chemical formula 16]

[0409]

[0410] As the triazine compound, the following compounds can be exemplified.

[0411] [Chemical formula 17]

[0412]

[0413] Examples of the rhodanine compound include the following compounds.

[0414] [Chemical formula 18]

[0415]

[0416] As the thiazole compound, the following compounds can be exemplified.

[0417] [Chemical formula 19]

[0418]

[0419] As the benzothiazole compound, the following compounds can be exemplified.

[0420] [Chemical formula 20]

[0421]

[0422] As the benzimidazole compound, the following compounds can be exemplified.

[0423] [Chemical formula 21]

[0424]

[0425] [Chemical formula 22]

[0426]

[0427] As the benzoxazole compound, the following compounds can be exemplified.

[0428] [Chemical formula 23]

[0429]

[0430] The heterocyclic compound may be used alone or in combination of two or more.

[0431] When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass %, more preferably 0.10 to 10.0 mass %, further preferably 0.30 to 8.0 mass %, particularly preferably 0.50 to 5.0 mass % relative to the total mass of the photosensitive composition layer.

[0432] <Aliphatic thiol compound>

[0433] The photosensitive composition layer may contain an aliphatic thiol compound.

[0434] When the photosensitive composition layer contains an aliphatic thiol compound, an ene-thiol reaction occurs between the aliphatic thiol compound and the radical polymerizable compound having an ethylenically unsaturated group, so that cure shrinkage of the formed film is suppressed and stress is relieved.

[0435] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher-functional aliphatic thiol compound) is preferred.

[0436] Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferred from the viewpoint of the adhesiveness of the formed pattern (particularly the adhesiveness after exposure).

[0437] In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0438] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of not less than 100 is preferred. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and further preferably 150 to 1,000.

[0439] The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and even more preferably 2 to 6 functional groups, for example, from the viewpoint of the adhesion of the formed pattern.

[0440] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, ... 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3 tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether.

[0441] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of 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.

[0442] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0443] The photosensitive composition layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.

[0444] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, further preferably 5 to 30% by mass, particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive composition layer.

[0445] <Thermal crosslinking compound>

[0446] From the perspective of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive composition layer preferably contains a thermally crosslinkable compound. In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.

[0447] Examples of the heat-crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds, of which blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

[0448] The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, so for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to increase.

[0449] The blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent".

[0450] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 90 to 160°C, more preferably 100 to 150°C.

[0451] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning calorimetry) analysis using a differential scanning calorimeter."

[0452] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

[0453] Examples of the end-capping agent having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C(=N-OH)- in the molecule).

[0454] Among these, as the terminal blocking agent having a dissociation temperature of 90 to 160° C., for example, at least one selected from the group consisting of oxime compounds and pyrazole compounds is preferred from the viewpoint of storage stability.

[0455] For example, from the viewpoints of improving the brittleness of the film and improving the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0456] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to thereby protect it.

[0457] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred in that the dissociation temperature can be easily set within a preferred range and development residues can be easily reduced compared to compounds not having an oxime structure.

[0458] The blocked isocyanate compound may have a polymerizable group.

[0459] The polymerizable group is not particularly limited, and a known polymerizable group can be used, but a radical polymerizable group is preferred.

[0460] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0461] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0462] As the blocked isocyanate compound, a commercially available product can be used.

[0463] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by SHOWA DENKO KK), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) SBN-70D, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). As the blocked isocyanate compound, from the perspective of more excellent effects of the present invention, it is preferred to contain a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more (hereinafter, sometimes referred to as the first blocked isocyanate compound). The NCO value of the first blocked isocyanate compound is preferably 5.0 mmol / g or more, and more preferably 5.3 mmol / g or more.

[0464] From the perspective of achieving more excellent effects of the present invention, the upper limit of the NCO value of the first blocked isocyanate compound is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, further preferably less than 5.8 mmol / g, particularly preferably 5.7 mmol / g or less.

[0465] The NCO value of the blocked isocyanate compound in the present invention refers to the number of moles of isocyanate groups contained per 1 g of the blocked isocyanate compound and is a value calculated from the structural formula of the blocked isocyanate compound.

[0466] From the perspective of achieving a more excellent effect of the present invention, it is preferred that the first blocked isocyanate compound has a ring structure. Examples of the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring. From the perspective of achieving a more excellent effect of the present invention, an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring are preferred, and an aliphatic hydrocarbon ring is more preferred.

[0467] Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and among them, a cyclohexane ring is preferred.

[0468] Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and among them, a benzene ring is preferred.

[0469] Specific examples of the heterocyclic ring include an isocyanurate ring.

[0470] When the first blocked isocyanate compound has a ring structure, the number of rings is preferably 1 to 2, more preferably 1, from the viewpoint of more excellent effects of the present invention. When the first blocked isocyanate compound contains a condensed ring, the number of rings constituting the condensed ring is calculated, for example, the number of rings in the naphthalene ring is counted as 2.

[0471] The number of blocked isocyanate groups in the first blocked isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2, from the viewpoint of excellent strength of the formed pattern and further excellent effects of the present invention.

[0472] The first blocked isocyanate compound is preferably a blocked isocyanate compound represented by the formula Q because the effects of the present invention are more excellent.

[0473] B 1 -A 1 -L 1 -A 2 -B 2 Formula Q

[0474] In formula Q, B 1 and B 2 Each independently represents a blocked isocyanate group.

[0475] The blocked isocyanate group is not particularly limited, but from the viewpoint of the better effect of the present invention, a group in which the isocyanate group is blocked with an oxime compound is preferred, and a group in which the isocyanate group is blocked with methyl ethyl ketoxime is more preferred (specifically, a group represented by *-NH-C(=O)-ON=C(CH3)-C2H5. * represents the same as A 1 or A 2 bonding position. ).

[0476] B 1 and B 2 The same groups are preferred.

[0477] In formula Q, A 1 and A 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 10 carbon atoms is preferred.

[0478] The alkylene group may be linear, branched or cyclic, but is preferably linear.

[0479] The number of carbon atoms in the alkylene group is 1 to 10, and preferably 1 to 5, more preferably 1 to 3, and even more preferably 1, from the viewpoint of achieving a more excellent effect of the present invention.

[0480] A 1 and A 2 The same groups are preferred.

[0481] In formula Q, L 1 represents a divalent linking group.

[0482] Specific examples of the divalent linking group include divalent hydrocarbon groups.

[0483] Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group in which two or more of these groups are linked.

[0484] The divalent saturated hydrocarbon group may be linear, branched or cyclic, and is preferably cyclic from the viewpoint of achieving a better effect of the present invention. The divalent saturated hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms from the viewpoint of achieving a better effect of the present invention.

[0485] The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group).

[0486] Among them, as the divalent linking group, preferably, a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a group formed by connecting a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms and a linear alkylene group having 1 to 3 carbon atoms, a divalent aromatic hydrocarbon group which may have a substituent, or a group formed by connecting a divalent aromatic hydrocarbon group and a linear alkylene group having 1 to 3 carbon atoms, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms or a phenylene group which may have a substituent, further preferably a cyclohexylene group or a phenylene group which may have a substituent, and particularly preferably a cyclohexylene group.

[0487] The blocked isocyanate compound represented by the formula Q is particularly preferably a blocked isocyanate compound represented by the formula QA, from the viewpoint of achieving more excellent effects of the present invention.

[0488] B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0489] In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group. 1a and B 2a The preferred embodiment is the same as B in formula Q 1 and B 2 same.

[0490] In formula QA, A 1a and A 2a Each independently represents a divalent linking group. 1a and A 2a The preferred embodiment of the divalent linking group in formula Q is the same as that of A 1 and A 2 same.

[0491] In formula QA, L 1aIt represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

[0492] L 1a The number of carbon atoms in the cyclic divalent saturated hydrocarbon group is preferably 5 to 10, more preferably 5 to 8, further preferably 5 to 6, and particularly preferably 6.

[0493] L 1a The preferred embodiment of the divalent aromatic hydrocarbon group in formula Q is the same as L 1 same.

[0494] Among them, L 1a A cyclic divalent saturated hydrocarbon group is preferred, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms is more preferred, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms is further preferred, a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms is particularly preferred, and a cyclohexylene group is most preferred.

[0495] When L 1a In the case of a cyclohexylene group, the blocked isocyanate compound represented by the formula QA may be an isomer mixture of a cis-isomer and a trans-isomer (hereinafter also referred to as a "cis-trans isomer mixture").

[0496] The mass ratio of the cis isomer to the trans isomer is preferably cis isomer / trans isomer=10 / 90 to 90 / 10, more preferably cis isomer / trans isomer=40 / 60 to 60 / 40.

[0497] Although specific examples of the first blocked isocyanate compound are shown below, the first blocked isocyanate compound is not limited thereto.

[0498] [Chemical formula 24]

[0499]

[0500] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0501] When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0502] <Surfactant>

[0503] The photosensitive composition layer may contain a surfactant.

[0504] Examples of the surfactant include surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0505] As the surfactant, hydrocarbon surfactants, fluorine surfactants or silicone surfactants can be cited. From the viewpoint of improving environmental adaptability, it is preferred that the surfactant does not contain fluorine atoms. As the surfactant, hydrocarbon surfactants or silicone surfactants are preferred. And, as the surfactant, nonionic surfactants are preferred.

[0506] Examples of commercially available fluorine-based surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP. MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-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 Corporation), Fluorad FC430, FC431, FC171 (all 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 (all manufactured by AGC INC.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), FTERGENT710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS COMPANY LIMITED), U-120E (manufactured by UNICHEM CO., LTD.), etc.

[0507] In addition, as a fluorine-based surfactant, an acrylic compound can also be preferably used, which has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved and the fluorine atom is volatilized. As such a fluorine-based surfactant, MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)), such as MEGAFACE DS-21, can be cited.

[0508] Furthermore, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0509] Furthermore, as the fluorine-based surfactant, a terminal polymer can also be used.

[0510] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a constituent unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) can also be preferably used.

[0511] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain may also be used, such as MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation).

[0512] From the viewpoint of improving environmental compatibility, the fluorine-based surfactant is preferably a surfactant derived from an alternative material to a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

[0513] Examples of the hydrocarbon-based surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like. Specific examples include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all registered trademarks of BASF), Solsperse 20000 (all registered trademarks of Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (all registered trademarks of FUJIFILM WakoPure Chemical Corporation), PIONIN D-1105, D-6112, D-6112-W, D-6315 (all registered trademarks of Takemoto Oil & Fat Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (all registered trademarks of Nissin Chemical Co., Ltd.), Co., Ltd. manufacturing) etc.

[0514] Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers in which an organic group is introduced into a side chain or a terminal.

[0515] Specific examples of the silicone surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation); DOWSIL 8032ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-1 05. KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, K P-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (the above are Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (all manufactured by BYK Chemie), etc.

[0516] The surfactant may be used alone or in combination of two or more.

[0517] When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and further preferably 0.05 to 0.80 mass % relative to the total mass of the photosensitive composition layer.

[0518] <Polymerization Inhibitor>

[0519] The photosensitive composition layer may contain a polymerization inhibitor.

[0520] The polymerization inhibitor is a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0521] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate][ethylenebis(ethylene oxide)]2,4-bis[(laurylthio)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-butylanilino)-1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl ... Hindered phenol compounds such as oxazine and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propylene; 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; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; metal salt compounds such as dibutyl dithiocarbamate copper, diethyl dithiocarbamate copper, diethyl dithiocarbamate manganese and diphenyl dithiocarbamate manganese.

[0522] Among them, from the perspective of achieving a more excellent effect of the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(ethylene oxide)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt.

[0523] The polymerization inhibitor may be used alone or in combination of two or more.

[0524] When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass %, more preferably 0.01 to 3.0 mass %, and further preferably 0.02 to 2.0 mass % relative to the total mass of the photosensitive composition layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass %, more preferably 0.01 to 3.0 mass %, and further preferably 0.01 to 1.0 mass % relative to the total mass of the polymerizable compound.

[0525] <Hydrogen Donating Compound>

[0526] The photosensitive composition layer may contain a hydrogen donating compound.

[0527] The hydrogen-donating compound has the functions of further improving the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0528] Examples of the hydrogen-donating compound include amines and amino acid compounds.

[0529] Examples of the amines include compounds described in "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), JP-44-020189, JP-51-082102, JP-52-134692, JP-59-138205, JP-60-084305, JP-62-018537, JP-64-033104, and Research Disclosure No. 33825. More specifically, 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (another name: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline can be mentioned.

[0530] Among them, from the viewpoint of achieving more excellent effects of the present invention, the amine is preferably at least one selected from the group consisting of 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0531] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0532] Among them, N-phenylglycine is preferred as the amino acid compound because the effects of the present invention are more excellent.

[0533] In addition, examples of hydrogen donating compounds include organic metal compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (trithiane, etc.) described in Japanese Patent Application Laid-Open No. 6-308727.

[0534] The hydrogen-donating compound may be used alone or in combination of two or more.

[0535] When the photosensitive composition layer contains a hydrogen donating compound, the content of the hydrogen donating compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and further preferably 0.03 to 5.0 mass % relative to the total mass of the photosensitive composition layer, from the perspective of increasing the curing rate by balancing the polymerization growth rate and chain transfer.

[0536] <Impurities, etc.>

[0537] The photosensitive composition layer may contain a predetermined amount of impurities.

[0538] As specific examples of impurities, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and their ions can be cited. Among them, halide ions (chloride ions, bromide ions, iodide ions), sodium ions and potassium ions are easily mixed as impurities, so it is preferably set to the following content.

[0539] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. The content of impurities in the photosensitive composition layer can be set to 1 ppb or more or 0.1 ppm or more, based on mass. As a specific example of the content of impurities in the photosensitive composition layer, a mode in which all the above impurities are 0.6 ppm based on mass can be cited.

[0540] As methods for setting the impurities within the above range, there are: a method of selecting a raw material with a small impurity content as a raw material for the photosensitive composition layer; a method of preventing the mixing of impurities when forming the photosensitive composition layer; and a method of removing impurities by washing. By this method, the impurity amount can be set within the above range.

[0541] Impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0542] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane in the photosensitive composition layer is preferably small. As the content of these compounds in the photosensitive composition layer, it is preferably 100ppm or less, more preferably 20ppm or less, and further preferably 4ppm or less, based on the mass standard. The lower limit can be set to 10ppb or more, and can also be set to 100ppb or more, based on the mass standard. These compounds can suppress the content by the same method as the above-mentioned metal impurities. And, it can be quantified by a known measurement method.

[0543] The content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0544] <Residual Monomers>

[0545] The photosensitive composition layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble resin.

[0546] From the perspective of patterning and reliability, the residual monomer content is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 10 mass ppm or more.

[0547] From the perspective of patterning and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

[0548] The residual monomer amount of monomers when synthesizing an alkali-soluble resin by polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.

[0549] The amount of residual monomers can be measured by a known method such as liquid chromatography and gas chromatography.

[0550] <Other ingredients>

[0551] The photosensitive composition layer may contain components other than the above components (hereinafter also referred to as "other components"). Examples of other components include particles (e.g., metal oxide particles), colorants, and antioxidants. Other components include other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Laid-Open No. 2000-310706.

[0552] (particle)

[0553] As the particles, metal oxide particles are preferred.

[0554] The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb and Te.

[0555] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0556] The average primary particle size of the particles was calculated by measuring the particle sizes of 200 random particles using an electron microscope and averaging the measurement results. In addition, if the shape of the particles is not spherical, the longest side is used as the particle size.

[0557] When the photosensitive composition layer contains particles, the photosensitive composition layer may contain only one kind of particles different in metal type, size, etc., or may contain two or more kinds of particles different in metal type, size, etc.

[0558] When the photosensitive composition layer contains no particles or contains particles, it is preferred that the content of particles is greater than 0 mass % and less than 35 mass % relative to the total mass of the photosensitive composition layer, more preferably that no particles are contained or the content of particles is greater than 0 mass % and less than 10 mass % relative to the total mass of the photosensitive composition layer, further preferably that no particles are contained or the content of particles is greater than 0 mass % and less than 5 mass % relative to the total mass of the photosensitive composition layer, further preferably that no particles are contained or the content of particles is greater than 0 mass % and less than 1 mass % relative to the total mass of the photosensitive composition layer, and particularly preferably that no particles are contained.

[0559] (Colorant)

[0560] The photosensitive composition layer may contain a trace amount of a colorant (a pigment, a dye, etc.), but preferably contains substantially no colorant, for example, from the viewpoint of transparency.

[0561] When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive composition layer.

[0562] (Antioxidant)

[0563] As antioxidants, for example, 3-pyrazolidinones such as 1-phenyl-3-pyrazolidinone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidinone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone and chlorohydroquinone; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine and p-phenylenediamine.

[0564] Among them, from the viewpoint of more excellent effects of the present invention, as the antioxidant, 3-pyrazolidinones are preferred, and 1-phenyl-3-pyrazolidinone is more preferred.

[0565] When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, and further preferably 0.01 mass % or more relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 1 mass % or less.

[0566] <Thickness of Photosensitive Composition Layer>

[0567] The thickness of the photosensitive composition layer is not particularly limited, and is often less than 30 μm. From the perspective of achieving a more excellent effect of the present invention, it is preferably less than 20 μm, more preferably less than 15 μm, further preferably less than 10 μm, and particularly preferably less than 5.0 μm. From the perspective of excellent strength of a film obtained by curing the photosensitive composition layer, the lower limit is preferably greater than 0.60 μm, more preferably greater than 1.5 μm, and further preferably greater than 2.0 μm.

[0568] The thickness of the photosensitive composition layer can be calculated as an average value of arbitrary five points measured by cross-sectional observation using a scanning electron microscope (SEM), for example.

[0569] <Refractive Index of Photosensitive Composition Layer>

[0570] The refractive index of the photosensitive composition layer is preferably 1.41 to 1.59, more preferably 1.47 to 1.56.

[0571] <Color of Photosensitive Composition Layer>

[0572] The photosensitive composition layer is preferably colorless. Specifically, total reflection (incident angle 8°, light source: D-65 (2° viewing field)) is CIE1976 (L * , a * , b * ) color space, L * The value is preferably 10 to 90, a * The value is preferably -1.0 to 1.0, b * The value is preferably -1.0 to 1.0.

[0573] In addition, the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably colorless.

[0574] Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is in CIE1976 (L * , a * , b * ) color space, the pattern’s L * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0575] <Transmittance of Photosensitive Composition Layer>

[0576] The visible light transmittance per 1.0 μm film thickness of the photosensitive composition layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. As the transmittance of visible light, it is preferred that the average transmittance at a wavelength of 400 to 800 nm, the minimum transmittance at a wavelength of 400 to 800 nm, and the transmittance at a wavelength of 400 nm all satisfy the above conditions. Preferred values ​​of the transmittance include, for example, 87%, 92%, 98%, etc. The transmittance per 1 μm film thickness of the cured film of the photosensitive composition layer is also the same.

[0577] <Moisture Permeability of Photosensitive Composition Layer>

[0578] From the viewpoint of rust prevention of electrodes or wiring and the viewpoint of device reliability, the moisture permeability of the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) at a film thickness of 40 μm is preferably 500 g / m 2 / 24hr or less, more preferably 300g / m 2 / 24hr or less, more preferably 100g / m 2 / 24hr or less.

[0579] Regarding the moisture permeability, the photosensitive composition layer was exposed to i-rays at an exposure amount of 300 mJ / cm 2 After exposure, the cured film obtained by curing the photosensitive composition layer by post-baking at 145°C for 30 minutes is measured. The moisture permeability is measured according to the cup method of JIS Z0208. It is preferred that the moisture permeability is the above-mentioned under any test conditions of temperature 40°C / humidity 90%, temperature 65°C / humidity 90%, and temperature 80°C / humidity 95%. As specific preferred values, for example, 80g / m2 / 24hr, 150g / m2 / 24hr, 220g / m2 / 24hr, etc. can be cited.

[0580] <Dissolution Rate of Photosensitive Composition Layer>

[0581] From the viewpoint of suppressing the residue during development, the dissolution rate of the photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 μm / second or more, more preferably 0.10 μm / second or more, and more preferably 0.20 μm / second or more. From the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm / second or less, more preferably 4.0 μm / second or less, and further preferably 3.0 μm / second or less. As specific preferred values, for example, 1.8 μm / second, 1.0 μm / second, 0.7 μm / second, etc. can be cited. The dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass % aqueous solution of sodium carbonate is measured as follows.

[0582] The photosensitive composition layer (thickness in the range of 1.0 to 10 μm) from which the solvent is fully removed and formed on the glass substrate is spray developed at 25° C. using a 1.0 mass % sodium carbonate aqueous solution until the photosensitive composition layer is completely dissolved (up to 2 minutes). The dissolution rate of the photosensitive composition layer is obtained by dividing the thickness of the photosensitive composition layer by the time required for the photosensitive composition layer to be completely dissolved. In addition, if it is not completely dissolved within 2 minutes, it is calculated in the same manner based on the change in film thickness until that point.

[0583] The dissolution rate of the cured film of the photosensitive composition layer (with a film thickness of 1.0 to 10 μm) in a 1.0% aqueous solution of sodium carbonate is preferably 3.0 μm / second or less, more preferably 2.0 μm / second or less, further preferably 1.0 μm / second or less, and most preferably 0.2 μm / second or less. The cured film of the photosensitive composition layer is a film obtained by exposing the photosensitive composition layer to i-rays with an exposure amount of 300 mJ / cm2. As specific preferred numerical values, for example, 0.8 μm / second, 0.2 μm / second, 0.001 μm / second, etc. can be cited. For development, a 1 / 4MINJJX030PP spray nozzle manufactured by H.IKEUCHI Co., Ltd. is used, and the spray pressure of the spray is set to 0.08 MPa. Under the above conditions, the spray flow rate per unit time is set to 1,800 mL / minute.

[0584] <Swelling Rate of Photosensitive Composition Layer>

[0585] From the viewpoint of improving pattern formation, the swelling rate of the photosensitive composition layer after exposure in a 1.0 mass % sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and further preferably 30% or less. The swelling rate of the photosensitive resin layer after exposure in a 1.0 mass % sodium carbonate aqueous solution is measured as follows.

[0586] A photosensitive resin layer (with a film thickness of 1.0 to 10 μm) from which the solvent was fully removed and formed on a glass substrate was subjected to a 500 mJ / cm 2 (i-ray measurement) exposure. Each glass substrate was immersed in a 1.0 mass % sodium carbonate aqueous solution at 25°C, and the film thickness after 30 seconds was measured. Then, the ratio of the film thickness after immersion to the film thickness before immersion was calculated. As specific preferred values, for example, 4%, 13%, 25%, etc. can be cited.

[0587] <Foreign Matter in Photosensitive Composition Layer>

[0588] From the viewpoint of pattern formation, the number of foreign matters with a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10 / mm2 or less, and more preferably 5 / mm2 or less. The number of foreign matters is measured as follows. Using an optical microscope, visually observe any 5 regions (1 mm × 1 mm) on the surface of the photosensitive composition layer from the normal direction of the surface of the photosensitive composition layer, measure the number of foreign matters with a diameter of 1.0 μm or more in each region, and perform arithmetic averaging on these to calculate the number of foreign matters. As specific preferred values, for example, 0 / mm2, 1 / mm2, 4 / mm2, 8 / mm2, etc. can be cited.

[0589] <Haze of Dissolved Matter in Photosensitive Composition Layer>

[0590] From the viewpoint of suppressing the generation of agglomerates during development, the haze of a solution obtained by dissolving 1.0 cm3 of a photosensitive resin layer in 1.0 L of a 30°C aqueous solution of 1.0 mass % sodium carbonate is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and most preferably 1% or less. The haze is measured as follows. First, a 1.0 mass % sodium carbonate aqueous solution is prepared, and the liquid temperature is adjusted to 30°C. A 1.0 cm3 photosensitive resin layer is placed in 1.0 L of the sodium carbonate aqueous solution. While being careful not to mix in bubbles, stir at 30°C for 4 hours. After stirring, measure the haze of the solution after the photosensitive resin layer is dissolved. For the haze, a haze meter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD) is used, and a liquid measurement unit and a liquid measurement dedicated cell with an optical path length of 20 mm are used for measurement. Specific preferred numerical values ​​include, for example, 0.4%, 1.0%, 9%, and 24%.

[0591] <Viscosity of Photosensitive Composition Layer>

[0592] The melt viscosity of the photosensitive composition layer at a temperature near the lamination temperature (for example, at 60° C.) is preferably 1.0×10 3~1.0×10 6 Pa·s, more preferably 5.0×10 3 ~8.0×10 5 Pa·s. If the melt viscosity at 60°C is 1.0×10 3 Pa·s or more, the fluidity during lamination will not be too high, and it is difficult to contaminate the hot roller of the laminator. In addition, if the melt viscosity at 60°C is 1.0×10 6 Pa·s or less, the photosensitive composition layer has excellent followability when laminated with a substrate, bubbles are less likely to be mixed between the photosensitive composition layer and the substrate, and the adhesion with the substrate is also excellent.

[0593] The melt viscosity of the photosensitive composition layer can be measured using a melt viscosity measuring device such as Rheometer VAR-1000 (manufactured by Rheological Limited.) and Vibron DD-III (manufactured by Toyo Baldwin Co., Ltd.).

[0594] Protective film

[0595] The transfer film has a protective film (cover film).

[0596] As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0597] Furthermore, as the protective film, a resin film made of the same material as that of the temporary support body described above can be used.

[0598] Among them, as the protective film, a polyolefin film is preferred, a polypropylene film or a polyethylene film is more preferred, and a polyethylene film is further preferred.

[0599] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.

[0600] The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of relatively low cost.

[0601] 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 / m. 2 the following.

[0602] Fish eyes are formed when foreign matter, undissolved matter, oxidative degradation products, etc. of the material enter the film when the material is hot-melted and manufactured by kneading, extrusion, biaxial stretching, casting, etc.

[0603] The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles / mm 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2 the following.

[0604] Thereby, it is possible to suppress the generation of defects due to the transfer of the irregularities caused by the particles contained in the protective film to the photosensitive composition layer or the conductive layer.

[0605] From the perspective of providing windability, the arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further 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 further preferably 0.30 μm or less.

[0606] From the perspective of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further 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 further preferably 0.30 μm or less.

[0607] 《Relationship between temporary support, photosensitive composition layer and protective film》

[0608] In the first embodiment of the transfer film, it is also preferred that the cured film obtained by curing the photosensitive composition layer has an elongation at break of 15% or more at 120°C, the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the temporary support is 50 nm or less, and the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the protective film is 150 nm or less.

[0609] Furthermore, the transfer film preferably satisfies the following formula (1).

[0610] X×Y<1500 Formula (1)

[0611] Here, in formula (1), X represents the value (%) of the elongation at break of the cured film obtained by curing the photosensitive composition layer at 120°C, and Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the temporary support. The above X×Y is more preferably 750 or less. As specific numerical values ​​of the above X, 18%, 25%, 30% and 35% can be cited. As specific numerical values ​​of the above X×Y, 4nm, 8nm, 15nm and 30nm can be cited. As specific numerical values ​​of the above X×Y, 150, 200, 300, 360 and 900 can be cited.

[0612] The elongation at break at 120° C. is preferably at least twice as large as the elongation at break at 23° C. of a cured film obtained by curing the photosensitive composition layer.

[0613] The elongation at break was measured by a tensile test on the cured film obtained as follows: an ultra-high pressure mercury lamp was used at 120 mJ / cm 2 After the 20 μm-thick photosensitive composition layer was exposed and cured, a high-pressure mercury lamp was used at 400 mJ / cm 2 The cured film was further subjected to additional exposure and heated at 145° C. for 30 minutes.

[0614] Furthermore, the transfer film also preferably satisfies the following formula (2).

[0615] Y≤Z Formula (2)

[0616] Here, in formula (2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the temporary support, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the protective film.

[0617] Index of Refraction Adjustment Layer

[0618] The transfer film may have a refractive index adjusting layer.

[0619] As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include a binder polymer, a polymerizable compound, a metal salt, and particles.

[0620] The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

[0621] Examples of the binder polymer and polymerizable compound include the binder polymers and polymerizable compounds described in the above section "photosensitive composition layer".

[0622] Examples of the particles include metal oxide particles and metal particles.

[0623] The type of metal oxide particles is not particularly limited, and known metal oxide particles may be used. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0624] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0625] The average primary particle size of the particles was calculated by measuring the particle sizes of 200 random particles using an electron microscope and averaging the measurement results. In addition, if the shape of the particles is not spherical, the longest side is used as the particle size.

[0626] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles) and composite particles thereof.

[0627] Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable from the viewpoint of easy adjustment of the refractive index.

[0628] 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 NISSAN CHEMICAL INDUSTRIES, LTD.) and zirconia particles (Nanouse OZ-S30K, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.).

[0629] The particles may be used alone or in combination of two or more.

[0630] The content of the particles in the refractive index adjusting layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer.

[0631] When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer.

[0632] The refractive index of the refractive index adjusting layer is preferably higher than the refractive index of the photosensitive composition layer.

[0633] The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and further preferably 1.78 or less.

[0634] The thickness of the refractive index adjusting layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and further preferably 60 to 100 nm.

[0635] The thickness of the refractive index adjusting layer was calculated as an average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0636] 《Method for producing transfer film according to first embodiment》

[0637] The method for producing the transfer film of the first embodiment is not particularly limited, and a known method can be used.

[0638] As a method for manufacturing the above-mentioned transfer film 30, for example, there can be cited a method including the following steps: a step of coating a photosensitive composition on the surface of a temporary support body 32 to form a coating film, and then drying the coating film to form a photosensitive composition layer 34; a step of coating a refractive index adjustment layer forming composition on the surface of the photosensitive composition layer 34 to form a coating film, and then drying the coating film to form a refractive index adjustment layer 36; and a step of crimping a protective film 40 on the refractive index adjustment layer 36.

[0639] Through the above steps, the transfer film 30 including the temporary support 32 , the photosensitive composition layer 34 , the refractive index adjusting layer 36 , and the protective film 40 can be manufactured.

[0640] After the transfer film 30 is manufactured by the above manufacturing method, the roll body of the present invention is obtained by winding up the transfer film 30. The roll body of the present invention can be directly provided in this form to the step of laminating with a substrate in the roll-to-roll method described later.

[0641] Furthermore, as a method for producing the transfer film 30 , a method of forming the refractive index adjusting layer 36 on the protective film 40 and then forming the photosensitive composition layer 34 on the surface of the refractive index adjusting layer 36 may be adopted.

[0642] The transfer film 30 may be produced by forming the photosensitive composition layer 34 on the temporary support 32, forming the refractive index adjusting layer 36 on the protective film 40, and bonding the photosensitive composition layer 34 and the refractive index adjusting layer 36 together.

[0643] <Photosensitive composition and method for forming a photosensitive composition layer>

[0644] From the aspect of excellent productivity and the aspect of easy formation of the above-mentioned photosensitive composition layer, the photosensitive composition layer in the transfer film is preferably formed by a coating method using a photosensitive composition containing the components constituting the above-mentioned photosensitive composition layer (for example, a binder polymer, a polymerizable compound, and a polymerization initiator, etc.) and a solvent. As the method for manufacturing the transfer film of the first embodiment, specifically, it is preferably a method in which a photosensitive composition is coated on a temporary support to form a coating film, and the coating film is dried at a predetermined temperature to form a photosensitive composition layer.

[0645] As the solvent that can be contained in the photosensitive composition, an organic solvent is preferred. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (another name: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0646] Furthermore, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250° C. may be used as necessary.

[0647] The solvent may be used alone or in combination of two or more.

[0648] The total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition.

[0649] That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 95% by mass, relative to the total mass of the photosensitive composition.

[0650] The viscosity of the photosensitive composition at 25° C. is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and further preferably 3 to 30 mPa·s, for example, from the perspective of coating properties. The viscosity is measured using a viscometer. As a viscometer, for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0651] The surface tension of the photosensitive composition at 25° C. is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and further preferably 15 to 40 mN / m, for example, from the perspective of coating properties. The surface tension is measured using a surface tensiometer. As a surface tensiometer, for example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be preferably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0652] Examples of the method for coating the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (ie, a slit coating method).

[0653] As a drying method for the coating of the photosensitive composition, heating drying and reduced pressure drying are preferred. In addition, in this specification, "drying" means removing at least a portion of the solvent contained in the composition. As a drying method, for example, natural drying, heating drying and reduced pressure drying can be cited. The above methods can be applied alone or in combination. As a drying temperature, it is preferably above 80°C, and more preferably above 90°C. And, as its upper limit, it is preferably below 130°C, and more preferably below 120°C. It is also possible to continuously change the temperature for drying.

[0654] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and further preferably 60 seconds or longer. The upper limit is not particularly limited, but is preferably 600 seconds or shorter, and more preferably 300 seconds or shorter.

[0655] <Refractive index adjusting layer forming composition and refractive index adjusting layer forming method>

[0656] The composition for forming the refractive index adjusting layer preferably contains various components and a solvent for forming the above-mentioned refractive index adjusting layer. In addition, in the composition for forming the refractive index adjusting 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 above-mentioned refractive index adjusting layer.

[0657] The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, but is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0658] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred.

[0659] The solvent may be used alone or in combination of two or more.

[0660] The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[0661] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0662] <Protective film crimping method>

[0663] Furthermore, by bonding the protective film onto the refractive index adjusting layer, the transfer film of the first embodiment can be manufactured.

[0664] The method of laminating the protective film on the refractive index adjusting layer is not particularly limited, and a known method may be used.

[0665] As an apparatus for bonding the protective film to the refractive index adjusting layer, there may be mentioned well-known laminators such as a vacuum laminator and an automatic cutting laminator.

[0666] The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heating.

[0667] <How to cut the transfer film>

[0668] The transfer film can be cut to adjust the width and length according to the size of the laminated substrate.

[0669] As a method for cutting the transfer film, for example, various slit processes can be used. Examples of slit processes include shearing, leather cutting, longitudinal cutting, heat cutting, water jet cutting, and ultrasonic cutting, among which shearing is preferred.

[0670] When shearing is applied, it is preferred that the angle of the upper blade be small in order to reduce the absolute values ​​of the position X and the position Y.

[0671] Furthermore, by setting the gap between the upper blade and the lower blade (the lateral spacing between the upper blade and the lower blade) to a value below a certain value, the end of the protective film is not easy to retreat relative to the end of the temporary support body, thereby reducing the position X and the position Y. On the other hand, if the gap between the upper blade and the lower blade is set to a value above a certain value, the life of the upper blade and the lower blade can be extended. The overlap amount between the upper blade and the lower blade (the overlap amount between the upper blade and the lower blade in the vertical direction) can be appropriately selected.

[0672] When shearing is applied, the sharp blade may be provided on either the temporary support side or the protective film side, but is preferably provided on the temporary support side from the viewpoint of easily preventing the temporary support from peeling off during slitting.

[0673] In addition, regarding the slit processing method, reference can be made to the methods described in paragraphs

[0061] to

[0063] of Japanese Patent Application Publication No. 2017-211643, paragraph

[0054] of Japanese Patent Application Publication No. 2017-177713, and paragraphs

[0070] to

[0071] and

[0090] to

[0095] of Japanese Patent Application Publication No. 2016-061959.

[0674] When the transfer film is wound up after the slit processing, it becomes the roll body of the present invention. The tension during winding can be appropriately set within the range of, for example, 0.1 to 10 kg / 10 cm.

[0675] [Transfer film of the second embodiment]

[0676] Hereinafter, an example of an embodiment of the transfer film of the second embodiment will be described.

[0677] Figure 7 The transfer film 50 shown includes: a temporary support 52 ; a composition layer 60 including a thermoplastic resin layer 54 , an intermediate layer 56 , and a photosensitive composition layer 58 ; and a protective film 62 in this order.

[0678] and, Figure 7 The transfer film 50 shown is a form in which a thermoplastic resin layer 54 and an intermediate layer 56 are arranged, but it may be a form in which the thermoplastic resin layer 54 is not arranged, or it may be a form in which the intermediate layer 56 is not arranged. From the aspect that the effect of the present invention is more excellent, the composition layer preferably has at least one of an intermediate layer and a thermoplastic resin layer between the temporary support and the photosensitive composition layer.

[0679] Hereinafter, each element constituting the transfer film will be described.

[0680] In the transfer film of the second embodiment, the temporary support 52 and the protective film 62 may be the same as the temporary support 32 and the protective film 40 of the first embodiment, and the preferred embodiments are also the same, so the description thereof is omitted.

[0681] <<Photosensitive composition layer>>

[0682] The transfer film has a photosensitive composition layer.

[0683] In a display device (organic electroluminescent (EL) display device and liquid crystal display device, etc.) having a touch panel such as an electrostatic capacitive input device, a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and wiring of a lead wiring portion is provided inside the touch panel. Generally, when forming a patterned layer, a method of providing a negative photosensitive composition layer (photosensitive layer) on a substrate using a transfer film or the like, exposing the photosensitive layer through a mask having a desired pattern, and then developing the layer is widely used.

[0684] Therefore, the photosensitive composition layer is preferably a negative-type photosensitive composition layer. When the photosensitive composition layer is a negative-type photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0685] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a resin, a polymerizable compound and a polymerization initiator. In addition, when the photosensitive composition layer is a negative photosensitive composition layer, as described below, it is also preferred to contain an alkali-soluble resin (polymer A as an alkali-soluble resin, etc.) as part or all of the resin.

[0686] That is, in one embodiment, the photosensitive composition layer preferably contains a resin including an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[0687] Such a photosensitive composition layer (negative photosensitive composition layer) preferably contains 10 to 90% by mass of a resin, 5 to 70% by mass of a polymerizable compound, and 0.01 to 20% by mass of a polymerization initiator, based on the total mass of the photosensitive composition layer.

[0688] Hereinafter, each component will be described in sequence.

[0689] <Polymer A (resin)>

[0690] When the photosensitive composition layer is a negative photosensitive composition layer, the resin contained in the photosensitive composition layer is also particularly referred to as polymer A. The resin A is not particularly limited, and examples thereof include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, polyurethane resins, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides.

[0691] As resin A, (meth) acrylic resin is preferred. In addition, in this specification, (meth) acrylic resin refers to a resin having a constituent unit derived from a (meth) acrylic compound. The content of the constituent unit derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more relative to all the constituent units of the (meth) acrylic resin. As resin A, a polymer having a constituent unit derived from a (meth) acrylic compound and a constituent unit derived from a styrene compound is also preferred.

[0692] The polymer A is preferably an alkali-soluble resin.

[0693] From the viewpoint of achieving better resolution by suppressing swelling of the negative photosensitive composition layer by the developer, the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and further preferably less than 190 mgKOH / g.

[0694] The lower limit of the acid value of the polymer A is not particularly limited, but is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, particularly preferably 170 mgKOH / g or more, from the viewpoint of better developability.

[0695] The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample. The acid value can be calculated from the average content of acid groups in the compound, for example.

[0696] The acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.

[0697] The weight average molecular weight of the polymer A is preferably 5,000 to 500,000.

[0698] When the weight average molecular weight is 500,000 or less, it is preferred from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and further preferably 60,000 or less.

[0699] On the other hand, when the weight average molecular weight is 5,000 or more, it is preferred from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as the edge melting property and the cutting property when it is a negative photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.

[0700] Edge melting refers to the degree to which the negative photosensitive composition layer easily overflows from the end surface of the roll when the negative photosensitive resin laminate is wound into a roll. Cutting properties refer to the degree to which cuttings easily fly when the unexposed film is cut with a cutter. If the cuttings adhere to the upper surface of the negative photosensitive resin laminate, etc., they are transferred to the mask in the subsequent exposure process, etc., causing defective products.

[0701] The dispersion degree of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0702] In the present specification, the dispersion degree is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight), and the weight average molecular weight and the number average molecular weight are values ​​measured using gel permeation chromatography.

[0703] In the negative photosensitive composition layer, from the viewpoint of suppressing the line width from becoming thicker or the resolution from becoming worse when the focus position is deviated during exposure, the polymer A preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. In addition, examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.

[0704] The content of the constituent units based on the monomer having an aromatic hydrocarbon group is preferably 20% by mass or more, more preferably 30% by mass or more, relative to the total mass of the polymer A. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, when a plurality of polymers A are contained, the average value of the content of the constituent units based on the monomer having an aromatic hydrocarbon group is preferably within the above range.

[0705] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among them, monomers having an aralkyl group or styrene are preferred.

[0706] In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the structural unit based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, further preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass relative to the total mass of the polymer A. In addition, when the photosensitive resin layer contains a plurality of polymers A, the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is calculated as a weight average.

[0707] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (excluding benzyl) and substituted or unsubstituted benzyl. Among them, substituted or unsubstituted benzyl is preferred.

[0708] Examples of the monomer having a phenylalkyl group include phenethyl (meth)acrylate and the like.

[0709] As the monomer having a benzyl group, for example, (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride; for example, vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol. Among them, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the constituent unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, further preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, relative to the total mass of polymer A.

[0710] The polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one of the first monomers described below and / or at least one of the second monomers described below.

[0711] The polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

[0712] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.

[0713] The content of the structural unit based on the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass, relative to the total mass of the polymer A.

[0714] From the viewpoint of showing good developability, controlling edge melting properties, etc., the above content is preferably set to 5% by mass or more. From the viewpoint of high resolution and curling shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, the above content is preferably set to 50% by mass or less.

[0715] The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, (meth)acrylate isobutyl, (meth)acrylate tert-butyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-hydroxypropyl, (meth)acrylate cyclohexyl, (meth)acrylate 2-ethylhexyl, (meth)acrylate esters; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred.

[0716] The content of the structural unit based on the second monomer in the polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 17 to 45% by mass, relative to the total mass of the polymer A.

[0717] When the polymer A contains a structural unit based on a monomer having an aralkyl group and / or a structural unit based on styrene, it is preferred from the viewpoint of suppressing the line width from becoming thicker or the resolution from being deteriorated when the focus position is shifted during exposure. For example, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, etc. are preferred.

[0718] In one embodiment, the polymer A is preferably a polymer containing 25 to 55% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of a structural unit based on a first monomer, and 15 to 45% by mass of a structural unit based on a second monomer. In another embodiment, the polymer is preferably a polymer containing 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on the first monomer.

[0719] The polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain.

[0720] By using a monomer containing a group having a branched structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A. The group having an alicyclic structure may be monocyclic or polycyclic.

[0721] Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, tert-pentyl (meth)acrylate, sec-pentyl (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 methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

[0722] Specific examples of the monomer containing a group having an alicyclic structure in a side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, and (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2-(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate. methyl (meth)acrylate, 1-menthyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoindene-5-yl (meth)acrylate, octahydro-4,7-methanoindene-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or tricyclodecane (meth)acrylate is more preferred.

[0723] The polymer A may be used alone or in combination of two or more.

[0724] When two or more polymers are used, it is preferred to use two polymers A containing structural units based on monomers having aromatic hydrocarbon groups in a mixed manner, or to use a polymer A containing structural units based on monomers having aromatic hydrocarbon groups and a polymer A not containing structural units based on monomers having aromatic hydrocarbon groups in a mixed manner. In the latter case, the proportion of polymer A containing structural units based on monomers having aromatic hydrocarbon groups used relative to the total mass of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more.

[0725] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone and isopropanol, and heating and stirring. Sometimes, a part of the mixture is added dropwise to the reaction solution while the synthesis is carried out. Sometimes, a solvent is further added after the reaction is completed to adjust it to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization can also be used.

[0726] The glass transition temperature Tg of polymer A is preferably 30 to 135°C. By using polymer A having a Tg of 135°C or less, it is possible to suppress the thickening of the line width or the deterioration of the resolution when the focus position is shifted during exposure. From this viewpoint, the Tg of polymer A is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, from the viewpoint of improving edge melting resistance, it is preferred to use polymer A having a Tg of 30°C or more. From this viewpoint, the Tg of polymer A is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0727] The negative photosensitive composition layer may contain, as the polymer A, other resins than those described above.

[0728] Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0729] Furthermore, as the polymer A, an alkali-soluble resin described in the description of the thermoplastic resin layer to be described later can be used.

[0730] The content of polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass relative to the total mass of the negative photosensitive composition layer. From the viewpoint of controlling the development time, the content of polymer A is preferably set to 90% by mass or less. On the other hand, from the viewpoint of improving the edge melting resistance, the content of polymer A is preferably set to 10% by mass or more.

[0731] <Polymerizable Compound>

[0732] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group. In addition, in this specification, the "polymerizable compound" is a compound that is polymerized by the action of a polymerization initiator described later, and refers to a compound different from the above-mentioned polymer A.

[0733] The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group that participates in the polymerization reaction. For example, there can be mentioned groups having ethylenically unsaturated groups such as vinyl, acryloyl, methacryloyl, styryl and maleimide groups; and groups having cationic polymerizable groups such as epoxy and oxetane groups.

[0734] As the polymerizable group, a group having an ethylenically unsaturated group is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0735] From the perspective of achieving better photosensitivity of the negative photosensitive composition layer, the polymerizable compound is preferably a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compounds), and more preferably a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compounds).

[0736] Furthermore, from the viewpoint of better resolution and releasability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0737] From the perspective of achieving a better balance between the photosensitivity, resolution and peeling properties of the negative photosensitive composition layer, it is preferred to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferred to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.

[0738] From the viewpoint of excellent stripping property, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and further preferably more than 55% by mass, relative to the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited and can be 100% by mass. That is, the polymerizable compound can be all bifunctional ethylenically unsaturated compounds.

[0739] Furthermore, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0740] (Polymerizable compound B1)

[0741] It is also preferred that the negative photosensitive composition layer contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0742] Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring, aromatic heterocyclic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring, and condensed rings thereof, preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.

[0743] The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0744] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive composition layer caused by the developer, the polymerizable compound B1 preferably has a bisphenol structure.

[0745] Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), and a bisphenol A structure is preferred.

[0746] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0747] The two ends of the bisphenol structure may be directly bonded to the two polymerizable groups or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy groups added to the two ends of the bisphenol structure, ethyleneoxy groups or propyleneoxy groups are preferred, and ethyleneoxy groups are more preferred. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14, per molecule.

[0748] The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in the publication are incorporated into the present specification.

[0749] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0750] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd. 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.).

[0751] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0752] [Chemical formula 25]

[0753]

[0754] In the general formula (B1), R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be a random arrangement or a block arrangement. Furthermore, when it is a block arrangement, -(AO)- and -(BO)- may both be on the biphenyl side.

[0755] In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and further preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.

[0756] The polymerizable compound B1 may be used alone or in combination of two or more.

[0757] From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (phenomenon in which the photosensitive resin seeps out from the end of the transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0758] From the viewpoint of better resolution, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound is preferably 40% or more, more preferably 50% or more, further 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, further preferably 90% or less, and particularly preferably 85% or less.

[0759] The negative photosensitive composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.

[0760] The polymerizable compounds other than the polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds, for example, compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), bifunctional ethylenically unsaturated compounds without an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0761] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0762] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0763] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), tricyclodecane dimethanol 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.

[0764] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0765] As urethane di(meth)acrylate, for example, propylene oxide modified urethane di(meth)acrylate and ethylene oxide and propylene oxide modified urethane di(meth)acrylate can be mentioned. As commercially available products of urethane di(meth)acrylate, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) and UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) can be mentioned.

[0766] Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0767] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0768] In one embodiment, the negative photosensitive composition layer also preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is preferably (total mass of the polymerizable compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and further preferably 1.5:1 to 3:1.

[0769] Furthermore, in one embodiment, the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0770] Examples of the alkylene oxide-modified products of trifunctional or higher ethylenic unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Dai-Cell-Allnex Ltd., etc.), ethoxylated glyceryl triacrylate (Shinnakamura Chemical Co., Ltd., etc.), and ethylene oxide-modified (meth)acrylate compounds. Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0771] Furthermore, as the polymerizable compound, a polymerizable compound having an acid group (carboxyl group, etc.) can be used. The above acid group can form an acid anhydride group. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0772] As the polymerizable compound having an acid group, for example, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

[0773] The polymerizable compound may be used alone or in combination of two or more.

[0774] The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, relative to the total mass of the negative photosensitive composition layer.

[0775] The molecular weight (weight average molecular weight when having 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 further preferably 300 to 2,200.

[0776] <Polymerization Initiator>

[0777] When the photosensitive composition layer is a negative-type photosensitive composition layer, the negative-type photosensitive composition layer also preferably contains a polymerization initiator.

[0778] The polymerization initiator can be selected according to the form of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.

[0779] The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0780] The negative photosensitive composition layer preferably contains a photopolymerization initiator.

[0781] The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0782] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0783] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0784] Furthermore, from the viewpoints of photosensitivity, visibility of the exposed portion and the non-exposed portion, and resolution, the negative photosensitive composition layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof as a photoradical polymerization initiator. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different.

[0785] Examples of the derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer.

[0786] As the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 can be used.

[0787] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisil (p,p'-dimethoxybenzil), TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: 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.).

[0788] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Management Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Research Inc.) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, 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) (trade 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) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) CO., LTD.).

[0789] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid by receiving active light. As a photocationic polymerization initiator, a compound that is sensitive to active light with a wavelength of 300 nm or more (preferably 300 to 450 nm) and generates acid is preferred, but its chemical structure is not limited. In addition, as for a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more, as long as it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates acid by using it in combination with a sensitizer, it can be preferably used in combination with a sensitizer.

[0790] As the photocationic polymerization initiator, a photocationic polymerization initiator generating an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator generating an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator generating an acid with a pKa of 2 or less is particularly preferred. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.

[0791] Examples of the photocationic polymerization initiator include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0792] Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0793] As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-085643 can be used.

[0794] As nonionic photocationic polymerization initiators, for example, trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds can be cited. As trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494 can be used. And, as oximesulfonate compounds, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 can be used.

[0795] The negative photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

[0796] The polymerization initiator may be used alone or in combination of two or more.

[0797] The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, further preferably 15% by mass or less, and further preferably 10% by mass or less, relative to the total mass of the negative photosensitive composition layer.

[0798] <Pigment>

[0799] From the viewpoint of visual recognition of the exposed and non-exposed parts, visual recognition of the pattern after development and resolution, the photosensitive composition layer also preferably contains a pigment (also referred to as "pigment N") whose maximum absorption wavelength is 450 nm or more at a wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength changes by acid, alkali or free radicals. If pigment N is contained, the detailed mechanism is unclear, but the adhesion with the adjacent layer (e.g., water-soluble resin layer) is improved, thereby achieving better resolution.

[0800] In the present specification, "the maximum absorption wavelength of a pigment changes by acid, alkali or free radicals" may refer to any of the following: a pigment in a coloring state is decolorized by acid, alkali or free radicals, a pigment in a decolorized state is colorized by acid, alkali or free radicals, and a pigment in a coloring state is changed into a coloring state of another hue.

[0801] Specifically, the pigment N may be a compound that changes from a bleached state to a color by exposure, or may be a compound that changes from a coloring state to a bleached state by exposure. In this case, it may be a pigment that changes the state of coloring or bleaching by causing an acid, base, or free radical to be generated and acted in the photosensitive composition layer by exposure, or it may be a pigment that changes the state of coloring or bleaching by causing an acid, base, or free radical to change the state (e.g., pH) in the photosensitive composition layer. Furthermore, it may be a pigment that changes the state of coloring or bleaching by directly receiving an acid, base, or free radical as a stimulus without exposure.

[0802] Among them, from the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes by an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes by a radical.

[0803] From the viewpoint of visibility and resolution of the exposed and non-exposed parts, when the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains both a dye whose maximum absorption wavelength changes due to free radicals and a photoradical polymerization initiator as the dye N.

[0804] Furthermore, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by acid, alkali, or radicals.

[0805] As an example of the color development mechanism of the pigment N, the following method can be cited: a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive composition layer, and after exposure, a radical reactive pigment, an acid reactive pigment or a base reactive pigment (for example, a colorless pigment) is colored by the free radicals, acid or base generated from the photoradical polymerization initiator, the photocationic polymerization initiator or the photobase generator.

[0806] Regarding the dye N, from the viewpoint of visibility of the exposed and non-exposed parts, the maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or longer, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.

[0807] Furthermore, the pigment N may have only one maximum absorption wavelength within the wavelength range of 400 to 780 nm when developing color, or may have two or more maximum absorption wavelengths. When the pigment N has two or more maximum absorption wavelengths within the wavelength range of 400 to 780 nm when developing color, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

[0808] The maximum absorption wavelength of the pigment N was obtained by measuring the transmission spectrum of a solution containing the pigment N (liquid temperature: 25° C.) in the range of 400 to 780 nm in an atmospheric environment using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION), and detecting the wavelength (maximum absorption wavelength) at which the intensity of light is extremely small.

[0809] Examples of dyes that develop or fade color by exposure include colorless compounds.

[0810] Examples of the dye that is decolorized by exposure include colorless compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0811] From the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a colorless compound.

[0812] Preferred colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane-based pigments), colorless compounds having a spiropyran skeleton (spiropyran-based pigments), colorless compounds having a fluorane skeleton (fluorane-based pigments), colorless compounds having a diarylmethane skeleton (diarylmethane-based pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam-based pigments), colorless compounds having an indolephthalide skeleton (indolephthalide-based pigments), and colorless compounds having a colorless auramine skeleton (colorless auramine-based pigments).

[0813] Among them, triarylmethane-based dyes or fluoran-based dyes are preferred, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferred.

[0814] From the viewpoint of visual recognition of the exposure part and the non-exposure part, as a colorless compound, it is preferred to have a lactone ring, a sultine ring or a sultone ring. Thus, the lactone ring, the sultine ring or the sultone ring of the colorless compound can be reacted with the free radicals generated by the photo-radical polymerization initiator or the acid generated by the photo-cationic polymerization initiator to make the colorless compound into a closed-loop state and decolorize it, or the colorless compound is changed to an open-loop state and colorizes it. As a colorless compound, it is preferred to have a lactone ring, a sultine ring or a sultone ring and a compound that opens a lactone ring, a sultine ring or a sultone ring and colors it by a free radical or an acid, and more preferably a compound that has a lactone ring and opens a lactone ring and colors it by a free radical or an acid.

[0815] Examples of the coloring matter N include the following dyes and colorless compounds.

[0816] Specific examples of the dye in the pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymel sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzo red violet 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue-naphthalenesulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Oriont Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), and Oil Scarlet #313 (manufactured by Orient Chemical Co., Ltd.). Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Co., Ltd.), SPIRON Red BEHSPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 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.

[0817] Specific examples of the colorless compound in the dye N include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco-methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidinyl)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6 -methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, (1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0818] From the viewpoint of visibility of the exposed and non-exposed areas, and visibility and resolution of the pattern after development, the dye N is preferably a dye that changes the maximum absorption wavelength by radicals, and more preferably a dye that develops color by radicals.

[0819] As the pigment N, colorless crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate is preferred.

[0820] The dye N may be used alone or in combination of two or more.

[0821] From the viewpoint of the visibility of the exposed and non-exposed parts, the visibility and resolution of the pattern after development, the content of the pigment N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, further preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, relative to the total mass of the photosensitive composition layer.

[0822] The content of the dye N refers to the content of the dye when all the dye N contained in the total mass of the photosensitive composition layer is in a colored state. Hereinafter, a quantitative method of the content of the dye N will be described using a dye that develops color by radicals as an example.

[0823] Preparation is that pigment 0.001g and 0.01g are dissolved in the solution obtained in 100mL of methyl ethyl ketone.In each solution obtained, add the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.), and irradiate the light of 365nm, thus produce free radical and make all pigments in the color development state.Then, under the atmospheric environment, use spectrophotometer (UV3100, SHIMADZU CORPORATION manufacture) to measure the absorbance of each solution that liquid temperature is 25 ℃, and make calibration curve.

[0824] Next, the absorbance of the solution in which all the pigments are colored is measured in the same manner as above except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the pigment. The content of the pigment contained in the photosensitive composition layer is calculated from the absorbance of the solution containing the photosensitive composition layer obtained according to the calibration curve.

[0825] In addition, the photosensitive composition layer 3g is the same as the total solid content 3g in the photosensitive resin composition.

[0826] <Thermal crosslinking compound>

[0827] When the photosensitive composition layer is a negative photosensitive composition layer, it is preferred to contain a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound, but as a thermally crosslinkable compound.

[0828] Examples of the heat-crosslinkable compound include methylol compounds and blocked isocyanate compounds, of which blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

[0829] Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, when, for example, a resin and / or a polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film decreases, and the function of the film obtained by curing the negative photosensitive composition layer when used as a protective film tends to be enhanced.

[0830] The blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent".

[0831] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C.

[0832] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning calorimetry) analysis using a differential scanning calorimeter."

[0833] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0834] Examples of the end-capping agent having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C(=N-OH)- in the molecule).

[0835] Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferred from the viewpoint of storage stability.

[0836] For example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0837] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to thereby protect it.

[0838] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint of being easy to make the dissociation temperature within a preferred range and being easy to reduce development residues compared to compounds not having an oxime structure.

[0839] The blocked isocyanate compound may have a polymerizable group.

[0840] The polymerizable group is not particularly limited, and a known polymerizable group can be used, but a radical polymerizable group is preferred.

[0841] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0842] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0843] As the blocked isocyanate compound, a commercially available product can be used.

[0844] Examples of commercially available blocked 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 blocked DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0845] Furthermore, as the blocked isocyanate compound, compounds having the following structures can also be used.

[0846] [Chemical formula 26]

[0847]

[0848] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0849] When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0850] <Other additives>

[0851] The photosensitive composition layer may contain known additives as necessary in addition to the above-mentioned components.

[0852] Examples of the additive include radical inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazole), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants.

[0853] Each additive may be used alone or in combination of two or more.

[0854] The photosensitive composition layer may contain a radical polymerization inhibitor.

[0855] As the free radical inhibitor, for example, the thermal inhibitor described in paragraph 0018 of Japanese Patent Gazette No. 4502784 can be cited. Among them, phenothiazine, phenoxazine or 4-methoxyphenol are preferred. As other free radical inhibitors, naphthylamine, cuprous chloride, N-nitrosophenylhydroxylamine aluminum salt and diphenylnitrosoamine can be cited. In order not to damage the sensitivity of the photosensitive composition layer, N-nitrosophenylhydroxylamine aluminum salt is preferably used as the free radical inhibitor.

[0856] The preferred content of the radical polymerization inhibitor is the same as that in the first embodiment.

[0857] The photosensitive composition layer may contain a sensitizer.

[0858] The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. As the sensitizer, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthones, thioxanthones, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds can be cited.

[0859] The sensitizer may be used alone or in combination of two or more.

[0860] When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer.

[0861] The photosensitive composition layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.

[0862] Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0863] The photosensitive composition layer may contain benzotriazoles or carboxybenzotriazoles.

[0864] Examples of the benzotriazoles include 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.

[0865] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of the carboxybenzotriazoles include commercially available products such as CBT-1 (trade name of JOHOKU CHEMICAL CO., LTD).

[0866] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3% by mass or less, the sensitivity can be maintained and the fading of the dye can be further suppressed.

[0867] The photosensitive composition layer preferably contains a surfactant. Examples of the surfactant include the same surfactants as those in the first embodiment, and preferred aspects are also the same.

[0868] Furthermore, the photosensitive composition layer may contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-suspension agents.

[0869] Additives contained in the photosensitive composition layer are described in paragraphs 0165 to 0184 of JP-A-2014-085643, and the contents of this publication are incorporated into this specification.

[0870] The thickness of the photosensitive composition layer is usually 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 20 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm. This improves the developability of the photosensitive composition layer and can improve resolution.

[0871] Furthermore, from the viewpoint of better adhesion, the transmittance of the photosensitive composition layer to light of wavelength 365 nm is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

[0872] <Impurities, etc.>

[0873] The photosensitive composition layer may contain a predetermined amount of impurities.

[0874] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferably used.

[0875] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. The content of impurities can be 1 ppb or more, and can also be 0.1 ppm or more, based on mass.

[0876] As methods for setting the impurities within the above range, the following methods can be cited: a method of selecting a raw material with a small impurity content as a raw material of the composition; a method of preventing impurities from being mixed when preparing the photosensitive composition layer; and a method of removing impurities by washing. By this method, the impurity amount can be set within the above range.

[0877] Impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0878] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane in the photosensitive composition layer is preferably small. The content of these compounds relative to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and further preferably 4 ppm or less, based on mass.

[0879] The lower limit can be set to 10 ppb or more, or 100 ppb or more, based on the mass standard, relative to the total mass of the photosensitive composition layer. The content of these compounds can be suppressed by the same method as the above-mentioned metal impurities. Moreover, they can be quantified by known measurement methods.

[0880] From the viewpoint of improving reliability and lamination properties, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0881] <Pigment>

[0882] The photosensitive composition layer may be a colored resin layer containing a pigment.

[0883] In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the back edge of a transparent glass substrate is sometimes installed on a liquid crystal display window of an electronic device to protect the liquid crystal display window. To form such a light-shielding layer, a colored resin layer can be used.

[0884] The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white. Among them, when forming a black pattern, it is preferred to select a black pigment as the pigment.

[0885] As black pigment, as long as it is within the scope of not damaging the effect of the present invention, known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected. Among them, from the viewpoint of optical density, as black pigment, for example, carbon black, titanium carbide, iron oxide, titanium oxide and graphite, etc. can be preferably cited, and carbon black is particularly preferred. As carbon black, from the viewpoint of surface resistance, carbon black with at least a portion of the surface coated with resin is preferred.

[0886] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in terms of number average particle size.

[0887] The particle size refers to the diameter of a circle obtained by calculating the area of ​​the pigment particles from a photograph of the pigment particles taken with an electron microscope and taking into account a circle with the same area as the area of ​​the pigment particles, and the number average particle size refers to the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes calculated.

[0888] As pigments other than black pigments, white pigments described in paragraphs 0015 and 0114 of Japanese Patent Publication No. 2005-007765 can be used. Specifically, among white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred as inorganic pigments, titanium oxide or zinc oxide is more preferred, and titanium oxide is further preferred. As inorganic pigments, rutile or anatase titanium oxide is further preferred, and rutile titanium oxide is particularly preferred.

[0889] Furthermore, the surface of titanium oxide may be treated with silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide or organic matter, or two or more treatments may be applied. Thus, the catalytic activity of titanium oxide is suppressed, and heat resistance and delustering properties are improved.

[0890] From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of an aluminum oxide treatment and a zirconium oxide treatment, and particularly preferably both an aluminum oxide treatment and a zirconium oxide treatment.

[0891] Furthermore, when the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When containing a color pigment, the particle size of the color pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less from the viewpoint of better dispersibility.

[0892] Examples of color pigments include Victoria Pure Blue BO (Color Index (CI) 42595), auramine (CI41000), fat black HB (CI26150), monolight yellow GT (CI Pigment Yellow 12), permanent yellow GR (CI Pigment Yellow 17), permanent yellow HR (CI Pigment Yellow 83), permanent carmine FBB (CI Pigment Red 146), hostaperm red ESB (C.[. Pigment Violet 19), permanent ruby ​​FBH (CI Pigment Red 11), pastel pink B supura (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 83), and saturated fatty acid esters. blue) (CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and 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 them, CI Pigment Red 177 is preferred.

[0893] When the photosensitive composition layer contains a pigment, the content of the pigment is preferably greater than 3 mass % and less than 40 mass %, more preferably greater than 3 mass % and less than 35 mass %, further preferably greater than 5 mass % and less than 35 mass %, particularly preferably greater than 10 mass % and less than 35 mass %, relative to the total mass of the photosensitive composition layer.

[0894] When the photosensitive composition layer contains pigments other than the black pigment (white pigment and color pigment), the content of the pigments other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass relative to the black pigment.

[0895] When the photosensitive composition layer contains a black pigment and is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion.

[0896] The dispersion can be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser. The pigment dispersant can be selected according to the pigment and the solvent, for example, a commercially available dispersant can be used. In addition, the vehicle refers to the medium part that disperses the pigment when the pigment dispersion is prepared, which is in liquid form and includes a binder component that keeps the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0897] As the dispersant, for example, there can be mentioned carbamate dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, (partial) amine salts of polycarboxylates, ammonium salts of polycarboxylates, alkylamine salts of polycarboxylates, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, their modified products, amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups and their salts, and other oily dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid-(meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone and other water-soluble resins or water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds and phosphates, etc. The form of the dispersant can be selected from the contents described in paragraphs

[0021] to

[0065] of Japanese Patent Application Laid-Open No. 2021-012355.

[0898] As a preferred dispersant, for example, a basic polymer dispersant can be cited. As a basic polymer dispersant, for example, a polymer containing nitrogen atoms can be cited. The nitrogen atom can be contained in the main chain of the polymer, can be contained in the side chain of the polymer, or can be contained in the main chain and the side chain of the polymer. Among them, the basic polymer dispersant is preferably a polymer containing nitrogen atoms in the side chain. The surface of carbon black is usually acidic, so when using carbon black as a pigment, a basic polymer dispersant is particularly preferred as a dispersant.

[0899] As a polymer containing nitrogen atoms (preferably a polymer containing nitrogen atoms in the side chain), for example, a polymer containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group and a nitrogen-containing heterocyclic group can be cited. For example, a polymer containing a quaternary ammonium salt group is preferred. The atomic group is preferably introduced into the side chain of the polymer. For example, a polymer containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group and a nitrogen-containing heterocyclic group is preferably contained in the side chain, and a polymer containing a quaternary ammonium salt group is more preferably contained in the side chain. As a counter ion of the quaternary ammonium cation in the quaternary ammonium salt group, for example, a carboxylate ion can be cited. As the carboxylate ion, for example, aliphatic carboxylate ions and aromatic carboxylate ions can be cited.

[0900] The polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in a side chain) is preferably a polymer containing a structural unit derived from styrene and a structural unit derived from a maleimide derivative, and more preferably a copolymer of styrene and a maleimide derivative.

[0901] The maleimide derivative has a structure in which at least one hydrogen atom of maleimide is replaced by a substituent. As the maleimide derivative, for example, there can be mentioned a maleimide derivative containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group and a nitrogen-containing heterocyclic group. The maleimide derivative is preferably a maleimide derivative containing a quaternary ammonium salt group.

[0902] The dispersant may be a commercially available dispersant, and examples thereof include BYK-2012 (BYK JAPAN KK.).

[0903] In addition to the pigment, the composition may contain a dispersing aid (also referred to as a pigment dispersing aid). The dispersing aid may be selected from known dispersing aids.

[0904] As a dispersing aid, for example, a compound with an organic pigment residue can be cited. As an organic pigment, for example, phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, purple ring ketone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzisoindole, isoindoline pigments, isoindoline ketone pigments, quinophthalone pigments, naphthol pigments, shilin pigments, metal complex pigments, azo, disazo, polyazo and other azo pigments can be cited. The compound with an organic pigment residue can have an acidic substituent, a basic substituent or a neutral substituent. As an acidic substituent, for example, a sulfonic group, a carboxyl group and a phosphate group can be cited. As a basic substituent, for example, a sulfonamide group and an amino group can be cited. As a neutral substituent, for example, a phenyl group and a phthalimide alkyl group can be cited. The form of the dispersing aid can be selected from the contents described in paragraphs

[0067] to

[0084] of JP-A-2021-012355.

[0905] As a preferred dispersing aid, for example, a compound having a phthalocyanine residue can be cited. Specifically, the dispersing aid is preferably a phthalocyanine pigment derivative or a salt thereof having an acidic substituent, more preferably a phthalocyanine pigment derivative or a salt thereof having at least one acidic substituent selected from the group consisting of a sulfonic group, a carboxyl group and a phosphate group, and further preferably a phthalocyanine pigment derivative or a salt thereof having a sulfonic group. Phthalocyanine pigment derivatives are, for example, described in Japanese Unexamined Patent Publication No. 2007-226161, International Publication No. 2016 / 163351, Japanese Unexamined Patent Publication No. 2017-165820 and Japanese Patent Publication No. 5753266. These publications are incorporated into this specification by reference.

[0906] As dispersion machine, it is not particularly limited, for example, known dispersion machines such as kneader, roller mill, attritor, super mill, dissolver, homomixer and sand mill can be enumerated. In addition, it is also possible to grind mechanically and utilize friction to carry out micro-grinding. About dispersion machine and micro-grinding, it is possible to refer to the record of " pigment dictionary " (by Asakura Bangzo, first edition, Asakura Bookstore, 2000, 438 pages, 310 pages).

[0907] The thickness, refractive index, color, transmittance, foreign matter, haze of dissolved matter, viscosity, etc. of the photosensitive composition layer can be appropriately adjusted to the same range as that of the transfer film of the first embodiment.

[0908] 《Relationship between temporary support, photosensitive composition layer and protective film》

[0909] In the second embodiment, it is preferable that the relationship among the temporary support, the photosensitive composition layer, and the protective film described in the first embodiment is satisfied.

[0910] Middle Layer

[0911] The transfer film may have an intermediate layer.

[0912] In the transfer film 50, the intermediate layer 56 exists between the thermoplastic resin layer 54 and the photosensitive composition layer 58, thereby preventing the mixing of components that may occur when the thermoplastic resin layer 54 and the photosensitive composition layer 58 are formed by coating or when the thermoplastic resin layer 54 and the photosensitive composition layer 58 are stored after coating.

[0913] As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.

[0914] Furthermore, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-072724 can be used as the intermediate layer. If the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, so it is preferred.

[0915] The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above-mentioned publications, etc. Among them, an oxygen barrier layer having low oxygen permeability and dispersible or soluble in water or an alkaline aqueous solution (a 1 mass % aqueous solution of sodium carbonate at 22° C.) is preferred.

[0916] Hereinafter, each component that can be contained in the water-soluble resin layer (intermediate layer) will be described.

[0917] The water-soluble resin layer (intermediate layer) contains a resin.

[0918] The above-mentioned resin includes a water-soluble resin as a part or the whole thereof.

[0919] Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0920] Furthermore, as the water-soluble resin, a (meth)acrylic acid / vinyl compound copolymer can also be used. As the (meth)acrylic acid / vinyl compound copolymer, a (meth)acrylic acid / allyl (meth)acrylate copolymer is preferred, and a methacrylic acid / allyl methacrylate copolymer is more preferred.

[0921] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol %) is, for example, preferably 90 / 10 to 20 / 80, more preferably 80 / 20 to 30 / 70.

[0922] The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and further preferably 10,000 or more, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less.

[0923] The dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

[0924] In addition, from the perspective of further improving the interlayer mixing suppression capability of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a resin different from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side. For example, when the photosensitive composition layer 58 contains the polymer A and the thermoplastic resin layer 54 contains the thermoplastic resin (alkali-soluble resin), the resin of the water-soluble resin layer (intermediate layer) 56 is preferably a resin different from the polymer A and the thermoplastic resin (alkali-soluble resin).

[0925] From the viewpoint of further improving the oxygen barrier property and the ability to suppress interlayer mixing, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinyl pyrrolidone.

[0926] The water-soluble resin may be used alone or in combination of two or more.

[0927] The content of the water-soluble resin is not particularly limited, but from the perspective of further improving the oxygen barrier and interlayer mixing inhibition capability, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more relative to the total mass of the water-soluble resin layer (intermediate layer). In addition, the upper limit is not particularly limited, but is, for example, preferably 99.9% by mass or less, and further preferably 99.8% by mass or less.

[0928] The intermediate layer may contain known additives such as a surfactant as necessary.

[0929] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and further preferably 0.5 to 3 μm. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property will not be reduced and the interlayer mixing suppression capability is excellent. In addition, the increase in the removal time of the water-soluble resin layer (intermediate layer) during development can be further suppressed.

[0930] Furthermore, when the transfer film of the second embodiment has an intermediate layer, it is also preferable that the following relationship is satisfied regarding the interlayer adhesion.

[0931] Adhesion relationship 1: The adhesion between the intermediate layer and the photosensitive composition layer is greater than the adhesion between the photosensitive composition layer and the protective film.

[0932] Adhesion relationship 2: The adhesion between the temporary support and the intermediate layer is greater than the adhesion between the photosensitive composition layer and the protective film.

[0933] When the above-mentioned relations 1 and 2 of the adhesion are satisfied, when the protective film is peeled off from the transfer film, peeling occurs at the interface between the photosensitive composition layer and the protective film, and the transfer film can be suitably used.

[0934] Furthermore, regarding the adhesion of the intermediate layer, it is also preferable that the following relationship is satisfied.

[0935] Adhesion relationship 3: The adhesion between the intermediate layer and the photosensitive composition layer is greater than the adhesion between the temporary support and the intermediate layer.

[0936] When the adhesion relationship 3 is satisfied, the temporary support and the intermediate layer are peeled off in the temporary support peeling step described in detail later, and the intermediate layer is likely to remain on the photosensitive composition layer side. As a result, the intermediate layer is likely to function as an oxygen barrier layer or the like.

[0937] 《Thermoplastic resin layer》

[0938] The transfer film may have a thermoplastic resin layer.

[0939] The thermoplastic resin layer is usually arranged between the temporary support and the photosensitive composition layer. The transfer film has a thermoplastic resin layer, so that the followability of the transfer film to the substrate in the lamination process of the transfer film and the substrate is improved and bubbles can be suppressed from mixing between the substrate and the transfer film. As a result, the adhesion of the layer adjacent to the thermoplastic resin layer (for example, the temporary support) can be ensured.

[0940] The thermoplastic resin layer contains a resin. The above-mentioned resin includes a thermoplastic resin as part or all thereof. That is, in one embodiment, the resin of the thermoplastic resin layer is also preferably a thermoplastic resin.

[0941] <Alkali-soluble resin (thermoplastic resin)>

[0942] As the thermoplastic resin, an alkali-soluble resin is preferred.

[0943] Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0944] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion with an adjacent layer.

[0945] Here, the acrylic resin refers to a resin having at least one structural unit selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate, and a structural unit derived from (meth)acrylamide.

[0946] As for the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide is preferably 50% by mass or more based on the total mass of the acrylic resin.

[0947] Among them, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

[0948] Furthermore, the alkali-soluble resin is preferably a polymer having an acid group.

[0949] Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group and a phosphonic acid group, and a carboxyl group is preferred.

[0950] From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and is further preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more.

[0951] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0952] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins and used.

[0953] For example, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraph 0025 of JP-A-2011-095716, that is, an alkali-soluble resin, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs 0033 to 0052 of JP-A-2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the binder polymer described in paragraphs 0053 to 0068 of JP-A-2016-224162 can be cited.

[0954] The copolymerization ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

[0955] From the viewpoint of developability and adhesion to an adjacent layer, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred as the alkali-soluble resin.

[0956] The alkali-soluble resin may have a reactive group. As the reactive group, any group capable of addition polymerization may be used, and examples thereof include ethylenically unsaturated groups, polycondensable groups such as hydroxyl groups and carboxyl groups, and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0957] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and further preferably 20,000 to 50,000.

[0958] The alkali-soluble resin may be used alone or in combination of two or more.

[0959] From the viewpoint of developability and adhesion with adjacent layers, the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, further preferably 40 to 80% by mass, particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0960] <Pigment>

[0961] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B") having a maximum absorption wavelength of 450 nm or longer in the wavelength range of 400 to 780 nm when developing color and whose maximum absorption wavelength is changed by acid, base or radical.

[0962] Preferred aspects of the dye B are the same as preferred aspects of the dye N described above except for the points described later.

[0963] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid.

[0964] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the thermoplastic resin layer preferably contains, as the dye B, both a dye whose maximum absorption wavelength is changed by acid and a compound that generates acid by light as described later.

[0965] The dye B may be used alone or in combination of two or more.

[0966] From the viewpoint of visibility of the exposed and non-exposed parts, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, further preferably 0.2 to 5% by mass, and particularly preferably 0.25 to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0967] Here, the content of the pigment B refers to the content of the pigment when all the pigments B contained in the thermoplastic resin layer are in a colored state. Hereinafter, a quantitative method of the content of the pigment B will be described using a pigment that develops color by radicals as an example.

[0968] Preparation is that pigment 0.001g and 0.01g are dissolved in the solution obtained in 100mL of methyl ethyl ketone.In each solution obtained, add the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.), and irradiate the light of 365nm, thus produce free radical and make all pigments in the color development state.Then, under the atmospheric environment, use spectrophotometer (UV3100, SHIMADZU CORPORATION manufacture) to measure the absorbance of each solution that liquid temperature is 25 ℃, and make calibration curve.

[0969] Next, the absorbance of the solution containing all the pigments was measured in the same manner as above except that 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The amount of the pigment contained in the thermoplastic resin layer was calculated based on the absorbance of the obtained solution containing the thermoplastic resin layer and the calibration curve.

[0970] In addition, the thermoplastic resin layer 3g is the same as the solid content 3g of the composition.

[0971] <Compounds that generate acids, bases, or free radicals when exposed to light>

[0972] The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also referred to simply as "compound C").

[0973] As the compound C, a compound that generates an acid, a base or a radical upon exposure to active light such as ultraviolet light and visible light is preferred.

[0974] As the compound C, a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator) can be used.

[0975] (Photoacid generator)

[0976] From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator.

[0977] Examples of the photoacid generator include the photocationic polymerization initiator that the negative photosensitive composition layer may contain, and preferred aspects are the same except for the points described below.

[0978] From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.

[0979] Furthermore, as the photoacid generator, a photoacid generator having the following structure is also preferred.

[0980] [Chemical formula 27]

[0981]

[0982] (Photoradical polymerization initiator)

[0983] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0984] Examples of the photoradical polymerization initiator include the photoradical polymerization initiator that the negative photosensitive composition layer may contain, and preferred embodiments are also the same.

[0985] (Photobase Generator)

[0986] The thermoplastic resin composition may contain a photobase generator.

[0987] The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl}cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-methyl-1-morpholinoethane, and the like. The present invention also contains 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0988] The compound C may be used alone or in combination of two or more.

[0989] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the content of the compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer.

[0990] <Plasticizer>

[0991] The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to an adjacent layer, and developability.

[0992] The molecular weight of the plasticizer (weight average molecular weight when it is an oligomer or a polymer and has a molecular weight distribution) is preferably smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0993] The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyoxyethylene structure or a polyoxypropylene structure.

[0994] Furthermore, from the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution and adhesion to adjacent layers, it is more preferred that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0995] Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described as the polymerizable compound contained in the above-mentioned negative photosensitive composition layer.

[0996] In the transfer film, when the thermoplastic resin layer and the negative photosensitive composition layer are directly contacted and laminated, it is preferred that the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. The reason is that when the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound, the diffusion of components between the layers is suppressed, thereby improving the storage stability.

[0997] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferred that the (meth)acrylate compound is not polymerized even in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin layer and an adjacent layer.

[0998] The (meth)acrylate compound used as the plasticizer is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

[0999] Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferred.

[1000] The plasticizer may be used alone or in combination of two or more.

[1001] From the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70 mass %, more preferably 10 to 60 mass %, and further preferably 20 to 50 mass % relative to the total mass of the thermoplastic resin layer.

[1002] <Sensitizer>

[1003] The thermoplastic resin layer may contain a sensitizer.

[1004] The sensitizer is not particularly limited, and examples thereof include the sensitizers that can be contained in the above-mentioned negative photosensitive composition layer.

[1005] The sensitizer may be used alone or in combination of two or more.

[1006] The content of the sensitizer can be appropriately selected depending on the purpose, but is preferably 0.01 to 5 mass %, more preferably 0.05 to 1 mass % based on the total mass of the thermoplastic resin layer from the viewpoint of improving sensitivity to light sources and visibility of exposed and non-exposed areas.

[1007] <Additives, etc.>

[1008] In addition to the above components, the thermoplastic resin layer may contain known additives such as a surfactant as necessary.

[1009] The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-085643, and the contents described in the publication are incorporated into the present specification.

[1010] The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion with the adjacent layer, it is preferably 0.1 μm or more, more preferably 1 μm or more, and further preferably 2 μm or more. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 8 μm or less.

[1011] 《Method for producing transfer film according to the second embodiment》

[1012] The method for producing the transfer film of the second embodiment is not particularly limited, and a known method can be used.

[1013] As a method for manufacturing the above-mentioned transfer film 50, for example, there can be cited a method including the following steps: a step of coating a thermoplastic resin composition on the surface of a temporary support 52 to form a coating film and further drying the coating film to form a thermoplastic resin layer 54; a step of coating a water-soluble resin composition on the surface of the thermoplastic resin layer 54 to form a coating film and further drying the coating film to form an intermediate layer 56; a step of coating a photosensitive composition on the surface of the intermediate layer 56 to form a coating film and further drying the coating film to form a photosensitive composition layer 58; and a step of pressing a protective film 62 onto the photosensitive composition layer 58.

[1014] By the above-described manufacturing method, the transfer film 50 including the temporary support 52 , the thermoplastic resin layer 54 , the intermediate layer 56 , the photosensitive composition layer 58 , and the protective film 62 can be manufactured.

[1015] After the transfer film 50 is manufactured by the above manufacturing method, a roll transfer film may be produced and stored by winding up the transfer film 50. The roll transfer film can be directly provided in this form to a step of laminating the transfer film with a substrate in a roll-to-roll method described later.

[1016] Furthermore, as a method for producing the transfer film 50 , a method of forming the photosensitive composition layer 58 and the intermediate layer 56 on the protective film 62 and then forming the thermoplastic resin layer 54 on the surface of the intermediate layer 56 may be adopted.

[1017] <Photosensitive composition and method for forming a photosensitive composition layer>

[1018] From the perspective of excellent productivity and ease of forming the above-mentioned photosensitive composition layer, it is preferred to form the layer by a coating method using a photosensitive composition containing components constituting the above-mentioned photosensitive composition layer (for example, a binder polymer, a polymerizable compound, and a polymerization initiator, etc.) and a solvent.

[1019] Specifically, the method for producing the transfer film of the second embodiment is preferably a method of applying a photosensitive composition on the intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer.

[1020] As the photosensitive composition, it is preferred to contain various components and a solvent that form the above-mentioned photosensitive composition layer. In addition, 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 above-mentioned photosensitive composition layer.

[1021] As the solvent, there is no particular limitation as long as it can dissolve or disperse the components other than the solvent, and a known solvent can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these can be cited.

[1022] As the solvent, it is preferred to contain at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, it is more preferred to contain a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents, and it is further preferred to contain at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[1023] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[1024] Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[1025] As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 can be used, and these contents are incorporated into this specification.

[1026] One type of solvent may be used alone, or two or more types of solvents may be used in combination.

[1027] The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[1028] Examples of the method for coating the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (ie, a slit coating method).

[1029] As a method for drying the coating film of the photosensitive composition, heating drying and reduced pressure drying are preferred. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. And, as an upper limit, it is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by continuously changing the temperature.

[1030] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and further preferably 60 seconds or longer. The upper limit is not particularly limited, but is preferably 600 seconds or shorter, and more preferably 300 seconds or shorter.

[1031] <Thermoplastic Resin Layer-Forming Composition and Method for Forming Thermoplastic Resin Layer>

[1032] The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and a known method can be used. For example, the thermoplastic resin layer can be formed by applying a thermoplastic resin layer-forming composition on the temporary support and then drying it as needed.

[1033] The composition for forming the thermoplastic resin layer preferably contains various components and a solvent for forming the above-mentioned thermoplastic resin layer. In addition, in the composition for forming the thermoplastic resin 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 thermoplastic resin layer described above.

[1034] The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and a known solvent can be used. Examples of the solvent include the same solvents as those contained in the photosensitive composition described later, and preferred embodiments are also the same.

[1035] The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[1036] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[1037] <Water-soluble resin composition and method for forming intermediate layer (water-soluble resin layer)>

[1038] As a water-soluble resin composition, it is preferred to contain various components and a solvent that form the above-mentioned intermediate layer (water-soluble resin layer). In addition, in the water-soluble resin 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 above-mentioned water-soluble resin layer.

[1039] The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, but is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[1040] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred.

[1041] One type of solvent may be used alone, or two or more types of solvents may be used in combination.

[1042] The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[1043] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[1044] <Protective film crimping method>

[1045] Moreover, by laminating a protective film on the photosensitive composition layer, the transfer film of the second embodiment can be produced.

[1046] The method of laminating the protective film to the photosensitive composition layer is not particularly limited, and a known method may be used.

[1047] As an apparatus for bonding the protective film to the photosensitive composition layer, a known laminator such as a vacuum laminator and an automatic cutting laminator may be mentioned.

[1048] The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heating.

[1049] <How to cut the transfer film>

[1050] The transfer film can be cut to adjust the width and length according to the size of the laminated substrate.

[1051] As a method for cutting the transfer film, for example, various slit processes can be used. The slit process is as described in the transfer film of the first embodiment. After the slit process, if the transfer film is rolled up, it becomes a roll body of the present invention.

[1052] [Application of transfer film]

[1053] The transfer film constituting the winding body of the present invention can be applied to various purposes. For example, it can be applied to electrode protective films, insulating films, flattening films, outer coatings, hard coatings, passivation films, partitions, spacers, microlenses, optical filters, antireflective films, etching resists, and plated parts. As more specific examples, protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, color filters, outer coatings for color filters, etching resists for forming wiring, and plating resists can be cited.

[1054] [Method for producing a laminate having a conductor pattern]

[1055] The above-mentioned winding body can be used to produce a laminate having a conductor pattern. The method for producing the laminate having a conductor pattern is not particularly limited as long as it is a method using the above-mentioned winding body, but the method for producing the laminate having a conductor pattern of the present invention is preferably the following method.

[1056] A method for manufacturing a laminate having a conductor pattern, comprising:

[1057] An unwinding step of unwinding a transfer film from a roll of a transfer film (the roll of the present invention), wherein the transfer film has a support, a composition layer, and a protective film in this order, and the composition layer includes a photosensitive composition layer;

[1058] a peeling step of peeling the protective film from the transfer film to expose the surface of the composition layer;

[1059] a laminating step of laminating the transfer film and the substrate having the conductive layer so that the exposed surface of the composition layer contacts the conductive layer of the substrate having the conductive layer on the surface;

[1060] An exposure step of exposing the photosensitive composition layer contained in the composition layer;

[1061] A development step of developing the exposed photosensitive composition layer to form a resist pattern;

[1062] any one of an etching step and a plating step, wherein the conductive layer located in a region where the resist pattern is not disposed is subjected to any one of an etching step and a plating step; and

[1063] The resist pattern stripping step is to strip the resist pattern. The method for manufacturing a laminate having a conductor pattern further comprises:

[1064] a removal step, when there is a plating treatment step, of removing the conductive layer exposed by the resist pattern stripping step and forming a conductor pattern on the substrate,

[1065] This method for producing a laminate having a conductive pattern further includes a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step or between the exposure step and the development step.

[1066] Hereinafter, a specific procedure of a method for producing a laminate having a conductor pattern will be described.

[1067] Furthermore, possible steps of a method for producing a laminate having the above-described preferred conductor pattern will also be described.

[1068] 〔Unwinding process〕

[1069] The unwinding step is a step of unwinding the transfer film from the roll of the present invention.

[1070] The unwinding method can be implemented by a known method. The unwinding step can also be implemented by a roll-to-roll method.

[1071] [Peeling process]

[1072] The peeling step is a step of peeling the protective film from the transfer film.

[1073] When the peeling step is performed, the surface of the photosensitive composition layer of the transfer film is exposed.

[1074] The method for peeling the protective film is not particularly limited, and can be performed by a known method. For example, the protective film can be peeled while being wound into a roll.

[1075] 〔Lamination process〕

[1076] The laminating step is a step of laminating the transfer film and the substrate having a conductive layer so that the exposed surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having the conductive layer on the surface.

[1077] When the lamination step is performed, a laminate (substrate with a photosensitive composition layer) including a substrate, a conductive layer, a photosensitive composition layer, and a temporary sup...

Claims

1. A roll body, which is a roll body of a transfer film having a temporary support, a composition layer and a protective film in this order, wherein the composition layer includes a photosensitive composition layer, The transfer film unwound from the roll was observed at 5 different locations at intervals of 8 cm along the length direction of the transfer film. The minimum and maximum values ​​of the 5 locations X and 5 locations Y obtained in each cross-sectional observation were both within the range of -40 μm to 40 μm. Cross-sectional observation: The transfer film unwound from the roll is cut along the width direction of the transfer film, and one of the two exposed cross-sectional surfaces is observed in the normal direction of the cross-sectional surface. The position of the outermost end of the temporary support in the width direction of the transfer film in the exposed cross section is set as a first position, the position of the outermost end of the protective film in the width direction of the transfer film and located on the same side as the first position is set as a second position, and the position of the second position, which is closer to the outer side in the width direction of the transfer film than the first position with respect to the first position as a positive value in the width direction of the transfer film, is set as a position X, The position of the other end of the temporary support body located at the outermost side in the width direction of the transfer film in the exposed cross section is set as the third position, the position of the other end located at the outermost side of the protective film in the width direction of the transfer film and on the same side as the third position is set as the fourth position, and the position of the fourth position, which is represented by a positive value in the width direction of the transfer film and is closer to the outside than the third position along the width direction of the transfer film with the third position as a reference, is set as position Y.

2. The wound body according to claim 1, wherein The minimum value is in the range of 0.1 μm to 40 μm.

3. The wound body according to claim 1 or 2, wherein: The photosensitive composition layer has a thickness of 2 μm to 20 μm.

4. The wound body according to claim 1 or 2, wherein: The composition layer includes at least one of an intermediate layer and a thermoplastic resin layer between the temporary support and the photosensitive composition layer.

5. The wound body according to claim 4, wherein: The thickness of the intermediate layer is 0.1 μm to 10 μm.

6. The wound body according to claim 4, wherein: The thickness of the thermoplastic resin layer is 0.1 μm to 10 μm.

7. A method for producing a laminate having a resin pattern, comprising: an unwinding step of unwinding the transfer film from the roll according to any one of claims 1 to 6; a peeling step of peeling the protective film from the transfer film to expose the surface of the composition layer; a laminating step of laminating the transfer film to the substrate having the conductive layer so that the exposed surface of the composition layer contacts the conductive layer of the substrate having the conductive layer on the surface; An exposure step of exposing the photosensitive composition layer contained in the composition layer; and a developing step of developing the exposed photosensitive composition layer to form a resin pattern, The method for producing a laminate having a resin pattern further includes a temporary support peeling step of peeling off the temporary support between the bonding step and the exposure step or between the exposure step and the development step.

8. A method for manufacturing a laminate having a conductor pattern, comprising: an unwinding step of unwinding the transfer film from the roll according to any one of claims 1 to 6; a peeling step of peeling the protective film from the transfer film to expose the surface of the composition layer; a laminating step of laminating the transfer film to the substrate having the conductive layer so that the exposed surface of the composition layer contacts the conductive layer of the substrate having the conductive layer on the surface; An exposure step of exposing the photosensitive composition layer contained in the composition layer; A development step of developing the exposed photosensitive composition layer to form a resist pattern; any one of an etching step of etching the conductive layer in a region where the resist pattern is not disposed and a plating step of plating; and a resist pattern stripping step of stripping the resist pattern, When the method for manufacturing a laminate having a conductor pattern includes the plating treatment step, the method further includes: a removal step of removing the conductive layer exposed by the resist pattern stripping step, and forming a conductor pattern on the substrate; The method for producing a laminate having a conductor pattern further includes a temporary support peeling step of peeling off the temporary support between the bonding step and the exposure step or between the exposure step and the development step.

Images