Photosensitive transfer material and method for producing the same

Abstract

To provide a photosensitive transfer material which is excellent in the pattern shape of a pattern obtained by temporary support peeling exposure, and a method for producing the same.SOLUTION: There are provided a photosensitive transfer material for temporary support peeling exposure which has a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, wherein the number of projections with a height of 0.5 μm or more and less than 10 μm on a surface in contact with the thermoplastic resin layer of the temporary support is 1×102 pieces / mm2 or more and less than 5×106 pieces / mm2, the thermoplastic resin layer contains a copolyester resin, the average thickness of the thermoplastic resin layer is 1 μm to 10 μm, and peeling force between the thermoplastic resin layer and the intermediate layer is 50 mN / cm or less; and a method for producing the same.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive transfer material and a method for producing the same. [Background technology]

[0002] Because the number of steps required to obtain a desired pattern is small, a method is widely used in which a photosensitive resin layer is placed on a substrate of choice using a photosensitive transfer material, the photosensitive resin layer is exposed to light through a mask, and then developed.

[0003] Conventional photosensitive transfer materials include those described in Patent Documents 1 to 3. Patent Document 1 describes a pattern-forming material having a cushion layer and a photosensitive layer in this order on a support, wherein the photosensitive layer contains a fluorescent brightening agent as a sensitizer, and when the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the average thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 50 mJ / cm. 2 The present invention describes a pattern forming material characterized by:

[0004] Patent document 2 describes a transfer material that includes, in this order, a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer, and that has a surface roughness Ra of 2 nm or more of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer.

[0005] Patent Document 3 describes a transfer film for producing a deposition mask, which includes, in this order, a temporary support and a transfer layer having an average thickness of 50 μm or less. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-178459 [Patent Document 2] International Publication No. 2022 / 138468 [Patent Document 3] Japanese Patent Publication No. 2022-168819 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of one embodiment of the present invention is to provide a photosensitive transfer material that provides an excellent pattern shape when exposed to light after peeling off the temporary support, and a method for producing the same. [Means for solving the problem]

[0008] The means for solving the above problems include the following aspects. <1> A film having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, wherein the number of protrusions having a height of 0.5 μm or more and less than 10 μm on the surface of the temporary support in contact with the thermoplastic resin layer is 1×10 2 pieces / mm 2 5x10 or more 6 pieces / mm 2 a photosensitive transfer material for temporary support peeling exposure, wherein the thermoplastic resin layer contains a copolymer polyester resin, the thermoplastic resin layer has an average thickness of 1 μm to 10 μm, and the peel strength between the thermoplastic resin layer and the intermediate layer is 50 mN / cm or less. <2> The thermoplastic resin layer and the intermediate layer are in contact with each other. <1> The photosensitive transfer material according to claim 1. <3> The intermediate layer contains a water-soluble resin. <1> or <2> The photosensitive transfer material according to claim 1. <4> The thermoplastic resin layer has an average thickness of 1 μm to 5 μm. <1> ~ <3> 10. The photosensitive transfer material according to any one of the above items. <5> The glass transition temperature of the copolymer polyester resin is 30°C or higher and 80°C or lower. <1> ~ <4> 10. The photosensitive transfer material according to any one of the above items. <6> The thermoplastic resin layer contains a surfactant having a silicon atom. <1> ~ <5> 10. The photosensitive transfer material according to any one of the above items. <7> The intermediate layer contains a surfactant having a silicon atom. <1> ~ <6> 10. The photosensitive transfer material according to any one of the above items. <8> The thermoplastic resin layer contains a plasticizer. <1> ~ <7> 10. The photosensitive transfer material according to any one of the above items. <9> The thermoplastic resin layer contains a polyester-based plasticizer. <1> ~ <8> 10. The photosensitive transfer material according to any one of the above items. <10> The method comprises, in this order, a step of forming a thermoplastic resin layer containing a copolymer polyester resin on one surface of a temporary support by coating to a thickness of 1 μm to 10 μm, a step of forming the intermediate layer on the surface opposite to the surface of the thermoplastic resin layer that contacts the temporary support by coating, and a step of forming the photosensitive resin layer on the surface of the intermediate layer that contacts the thermoplastic resin layer by coating. <1> ~ <9> 10. A method for producing a photosensitive transfer material according to any one of the above items. [Effects of the Invention]

[0009] According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material that provides an excellent pattern shape when the temporary support is peeled off and exposed, and a method for producing the same. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic diagram illustrating an example of the configuration of a photosensitive transfer material according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In this specification, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, For example, the measurement can be performed using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by a gel permeation chromatography (GPC) analyzer using a TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and converted using polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, "(meth)acryloyloxy group" is a concept that encompasses both acryloyloxy group and methacryloyloxy group, "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0012] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions. As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and 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-mentioned solubility conditions. In this specification, the "solid content" of a composition refers to 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 excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content. In this specification, the average thickness of the temporary support, thermoplastic resin layer, intermediate layer, photosensitive resin layer, etc. is measured by cross-sectional observation using an SEM (scanning electron microscope), and the average thickness is calculated as the average value of any five points. In this specification, the dielectric loss tangent of the substrate at 24 GHz is measured by the resonator method. As a device for measuring the dielectric loss tangent, a 24 GHz split cylinder resonator manufactured by Kanto Electronics Application Development Co., Ltd. or a device of the same level can be used.

[0013] (Photosensitive transfer material) The photosensitive transfer material according to the present disclosure has a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, and the number of protrusions having a height of 0.5 μm or more and less than 10 μm on the surface of the temporary support in contact with the thermoplastic resin layer is 1×10 2 pieces / mm 2 5x10 or more 6 pieces / mm 2 the thermoplastic resin layer contains a copolymer polyester resin, the thermoplastic resin layer has an average thickness of 1 μm to 10 μm, and the peel strength between the thermoplastic resin layer and the intermediate layer is 50 mN / cm or less.

[0014] In photosensitive transfer materials used in a method in which a temporary support is peeled off and exposed, if an inexpensive film with many surface protrusions is used as the temporary support, the protrusions can cause surface roughness, including concave shapes, on the surface of the photosensitive resin layer, even though the temporary support is peeled off and exposed, which can adversely affect the exposure light and make the material unsuitable for forming fine patterns. In contrast to this, the inventors have discovered that by using the above-mentioned structure including a thermoplastic resin and an intermediate layer, and by peeling off the thermoplastic resin layer when the temporary support is peeled off, the influence of the surface protrusions of the temporary support can be suppressed, and even when a temporary support with many surface protrusions is used, roughness of the surface of the photosensitive resin layer can be suppressed, making it possible to form a fine pattern. Furthermore, after detailed investigations, the inventors have found that the roughness of the surface of the photosensitive resin layer is also caused by surface roughness caused by moisture absorption by the thermoplastic resin layer and intermediate layer.Based on this finding, the inventors have discovered that by using a thermoplastic resin layer with a film thickness of 1 μm to 10 μm, thinner than conventional, and a specific composition, and an intermediate layer between the temporary support and the photosensitive resin layer, the roughness of the surfaces of the thermoplastic resin layer and intermediate layer caused by moisture absorption by the thermoplastic resin layer and intermediate layer is suppressed, and the roughness of the surface of the photosensitive resin layer corresponding to the roughness of the surface of the intermediate layer is suppressed, making it possible to form fine patterns.

[0015] The photosensitive transfer material may have a protective film on the surface of the photosensitive resin layer opposite to the intermediate layer side. Fig. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material according to the present disclosure. The photosensitive transfer material 10 shown in Fig. 1 has, in this order, a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive resin layer 17, and a protective film 19. Although the photosensitive transfer material 10 shown in Fig. 1 has the protective film 19 disposed therein, the protective film 19 need not be disposed.

[0016] <Protrusion amount of temporary support> The number of protrusions having a height of 0.5 μm or more and less than 10 μm on the surface of the temporary support in contact with the thermoplastic resin layer is 1×10 2 pieces / mm 2 5x10 or more6 pieces / mm 2 The photosensitive transfer material according to the present disclosure has the above-described configuration, and thus it is possible to suppress roughness of the surface of the photosensitive resin layer and form a fine pattern even when a temporary support having many surface protrusions is used.

[0017] In the present disclosure, the amount of protrusions having a height of 0.5 μm or more and less than 10 μm on the surface of the temporary support in contact with the thermoplastic resin layer is measured using a three-dimensional optical profiler (for example, New View 7300, manufactured by Zygo). First, the temporary support is peeled off from the photosensitive transfer material. The surface profile of the intermediate layer side surface of the temporary support is obtained. The Microscope Application of MetroPro ver. 8.3.2 is used as the measurement and analysis software. Next, the Surface Map screen is displayed using the measurement and analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the amount of protrusions with a height of 0.5 μm or more and less than 10 μm is obtained. 1 mm 2 Observe 10 locations and take the average as the amount of protrusions.

[0018] <Peeling Force Between Thermoplastic Resin Layer and Intermediate Layer> The peeling force between the thermoplastic resin layer and the intermediate layer is 50 mN / cm or less. When the peeling force is 50 mN / cm or less, the thermoplastic resin layer is peeled off together with the temporary support when the temporary support is peeled off, thereby suppressing the influence of the surface protrusions of the temporary support. From the viewpoint of the pattern shape, the peel force between the thermoplastic resin layer and the intermediate layer is preferably 5 mN / cm to 50 mN / cm, more preferably 10 mN / cm to 40 mN / cm, even more preferably 10 mN / cm to 20 mN / cm, and particularly preferably 10 mN / cm to 15 mN / cm.

[0019] In the present disclosure, the peel strength between the thermoplastic resin layer and the intermediate layer is measured by the following method. A 5 nm thick nickel-chromium (8 / 2) layer and a 200 nm thick copper layer are formed in this order on a 25 μm thick polyimide substrate by vapor deposition to prepare a polyimide substrate with a copper layer. The photosensitive transfer material was cut into a size of 30 mm × 100 mm, and if a protective film was present, the protective film was peeled off. Using a roll laminator, the photosensitive transfer material and a polyimide substrate with a copper layer were bonded together under conditions of a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called lamination speed) of 1 m / min, and a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were arranged in this order on the surface of the polyimide substrate with the copper layer to obtain a laminate for evaluation. The obtained laminate is subjected to autoclave treatment under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The treated laminate is attached to a 0.7 mm thick glass using double-sided tape. A 180° peel test is performed on the laminate attached to the glass using a Tensilon (model number: Tensilon universal testing machine manufactured by A&D Co., Ltd.) to peel off the temporary support at a peel speed of 300 mm / min, and the peel strength is measured.

[0020] The configuration of the photosensitive transfer material other than that described above will be described in detail below.

[0021] <Temporary support> The temporary support is a member that supports the photosensitive resin layer and the like, and is removed by a peeling treatment before exposure.

[0022] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film, polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. The resin film may be a stretched film or a non-stretched film, but is preferably a stretched film, and more preferably a biaxially stretched film. Among these, a polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferable that the film used as the temporary support is free from deformation such as wrinkles, scratches, and the like.

[0023] The average thickness of the temporary support is not particularly limited, but is preferably 5.0 μm to 200.0 μm, and from the viewpoint of ease of handling and versatility, is more preferably 5.0 μm to 150.0 μm, even more preferably 5.0 μm to 50.0 μm, and particularly preferably 5.0 μm to 25.0 μm.

[0024] To improve the handling properties, 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 side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 μm to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm.

[0025] From the viewpoint of the releasability and resolution of the temporary support, the surface free energy of the surface of the intermediate layer side of the temporary support is 66.0 mJ / m 2 Preferably less than 63.0 mJ / m 2 More preferably, it is 60.0 mJ / m or less. 2 It is more preferable that: From the viewpoint of adhesion of the coating film, the lower limit of the surface free energy is 35 mJ / m 2 It is preferable that the concentration is 40 mJ / m or more. 2 More preferably, it is 45 mJ / m or more. 2 More preferably, it is equal to or greater than this.

[0026] In one embodiment, the temporary support may be one consisting of only a substrate; a laminate comprising a substrate and a particle-containing layer disposed on one surface of the substrate; or a laminate comprising a substrate and particle-containing layers disposed on both surfaces of the substrate.

[0027] Examples of the substrate constituting the temporary support include the above-mentioned resin film, glass, paper, and the like. The substrate constituting the temporary support is preferably a resin film from the viewpoints of strength, flexibility, and light transmittance. The resin film is preferably a polyethylene terephthalate film, more preferably a biaxially stretched polyethylene terephthalate film.

[0028] When a particle-containing layer is disposed on one or both surfaces of the substrate, the particle-containing layer may be one layer or two or more layers.

[0029] The particle-containing layer can be formed, for example, by applying a composition for the particle-containing layer onto a substrate and drying the composition. Alternatively, the particle-containing layer can be disposed by co-extrusion when forming a resin film.

[0030] The particle-containing layer composition preferably contains a binder polymer and particles. The type of binder polymer is not particularly limited and can be appropriately selected depending on the purpose. Examples of binder polymers include acrylic resins, urethane resins, olefin resins, styrene-butadiene resins, ester resins, vinyl chloride resins, and vinylidene chloride resins. When the particle-containing layer is disposed by co-extrusion, polyethylene terephthalate is preferably used as the binder polymer.

[0031] The particle-containing layer may contain one type of binder polymer and one type of particles, or two or more types of binder polymer and particles.

[0032] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose. The content of particles in the particle-containing layer can be appropriately adjusted by the amount of particles added to the composition for the particle-containing layer. In this specification, the particles contained in the particle-containing layer are referred to as "added particles."

[0033] The additive particles are to be distinguished from impurities unexpectedly mixed in during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support. The additive particles are preferably particles that do not melt at 200°C.

[0034] Whether or not the temporary support contains additive particles can be determined, for example, by the following method: Additive particles usually have uniform shape and distribution, and therefore can be determined by observation with an optical microscope.

[0035] Examples of the additive particles include inorganic particles and organic particles. Examples of inorganic particles include particles of inorganic oxides such as silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina). Examples of organic particles include particles of polymers such as acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene. When the temporary support has a particle-containing layer, the additive particles contained in the particle-containing layer are preferably inorganic oxide particles.

[0036] The average particle size of the added particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured by cutting a slice having an average thickness of 100 nm with an ultramicrotome and using a TEM (transmission electron microscope).

[0037] In the photosensitive transfer material according to the present disclosure, the thermal deformation rate of the temporary support is 1.0% or less, preferably 0.5% or less. The lower limit of the thermal deformation rate is not particularly limited, and is preferably 0%. By making the thermal deformation rate of the temporary support 1.0% or less, deformation of the substrate to be bonded to the photosensitive transfer material is suppressed.

[0038] In the present disclosure, the thermal deformation rate is measured by the following method. On the main surface of the temporary support, a direction parallel to one of two pairs of opposing sides is defined as direction A, and a direction perpendicular to direction A is defined as direction B. A test piece cut to a length of 30 mm in the A direction and a length of 4 mm in the B direction, and another test piece cut to a length of 30 mm in the B direction and a length of 4 mm in the A direction are prepared. Using two test pieces, the following measurements are carried out. As the measuring device, a thermal expansion coefficient measuring device (for example, product name "TMA450EM" manufactured by TA Instruments) is used. The measurement conditions are as follows. Measurement mode: tension mode, Grip distance: 16 mm Set load: Change from 0.05N to 0.48N at 6.00N / min. Each test piece is heated from 25°C to 100°C at a temperature increase rate of 20°C / min, and the elongation of each test piece is measured five times, and the average value is calculated. The larger average value of the elongation percentage of the two test pieces is used as the thermal deformation percentage.

[0039] Methods for reducing the thermal deformation rate of the temporary support include, for example, increasing the average thickness of the temporary support, and incorporating particles into the temporary support to increase the number of particles contained in the temporary support.

[0040] In the photosensitive transfer material according to the present disclosure, the haze of the temporary support is preferably greater than 2.0%, from the viewpoint of suppressing deformation of the substrate to which the photosensitive transfer material is attached.

[0041] From the above viewpoint, the haze of the temporary support is more preferably 2.5% or more. The upper limit of the haze is not particularly limited, and is, for example, 10%.

[0042] When forming a pattern using the photosensitive transfer material according to the present disclosure, it is preferable to peel off the temporary support after laminating the photosensitive transfer material to a substrate and before exposure. If the temporary support is peeled off before exposure, it is not necessary to consider the influence of high haze on the temporary support on exposure.

[0043] In the present disclosure, haze is measured using a haze meter in accordance with JIS K7136: 2000. For example, the haze meter used is a product named "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd.

[0044] In addition, in the photosensitive transfer material according to the present disclosure, from the viewpoint of suppressing deformation of the substrate to be bonded to the photosensitive transfer material, the total number of particles having a diameter of 5 μm or more and aggregates having a diameter of 5 μm or more contained in the temporary support is 30 particles / mm 2 More is preferable.

[0045] From the above viewpoint, the total number of particles and aggregates is 40 / mm 2 The upper limit of the total number is not particularly limited, and is, for example, 50 pieces / mm 2 is.

[0046] The particles and aggregates referred to here mean those having areas where a difference in polarization from the surrounding areas can be observed when the temporary support is observed under a polarizing microscope. Examples of particles and aggregates include carbonized resins formed during the production of the substrate and catalysts used in the production of the substrate. In addition, when a particle-containing layer such as that described above is provided, the added particles contained in the particle-containing layer also fall under the category of the above particles.

[0047] In the present disclosure, the total number of particles and aggregates contained in the temporary support is measured by the following method.

[0048] First, the temporary support is observed with a polarizing microscope (product name "BX60" with a "U-POT" filter and a "U-AN360" filter inserted to form a simple polarizing microscope, 10x objective lens, manufactured by Olympus Corporation), and areas where polarization is disturbed are identified as foreign matter (particles or aggregates). The identified foreign matter is observed with an incident-light laser microscope (product name "Confocal Laser Microscope VL2000D", manufactured by Lasertec Corporation). In addition, the diameter of the foreign matter is measured with an optical microscope (product name "BX60", 100x objective lens, manufactured by Olympus Corporation), and an observation area of ​​1 mm is identified. 2 Count the number of foreign particles with a diameter of 5 μm or more contained in the sample. If the foreign particle contains a void, measure the diameter including the void. If the foreign particle is not circular, measure the longest diameter.

[0049] When forming a pattern using the photosensitive transfer material according to the present disclosure, it is preferable to peel off the temporary support after laminating the photosensitive transfer material and the substrate before exposure. If the temporary support is peeled off before exposure, it is not necessary to consider the influence on exposure of the large amount of particles and aggregates contained in the temporary support.

[0050] In addition, in the photosensitive transfer material according to the present disclosure, from the viewpoint of suppressing deformation of the substrate to be bonded to the photosensitive transfer material, the temporary support is 13.5 mm when measured by an incident-light laser microscope. 2 It is preferable that the total area ratio of the optically abnormal region when observed over an area of ​​100 ppm or more is greater than 300 ppm.

[0051] From the above viewpoint, the total area ratio of the optically abnormal region is more preferably 350 ppm or more. The upper limit of the total area ratio is not particularly limited, and is, for example, 500 ppm.

[0052] In the present disclosure, the area of ​​the optically abnormal region means the area of ​​the optically abnormal region observed in a region extending from the center position of the average thickness of the temporary support to 2 μm in one direction or the other in the thickness direction.

[0053] In the present disclosure, an optically abnormal region is a region whose optical properties differ from those of the main region of the temporary support (the resin constituting the temporary support) (specifically, a region whose reflectance or refractive index differs from that of the main region, or in which optical phenomena such as scattering and diffraction occur more strongly than in the main region). When the temporary support contains, for example, particles, the optically abnormal region may include both a light-shielding portion caused by the particles and an optically abnormal region other than the particles (for example, an abnormal refractive index region having a refractive index different from that of the particles and the main region of the temporary support). Examples of optically abnormal regions include a region with orientation and / or crystallinity different from that of the main region of the temporary support, an air region, a region of gas other than air, a void region where gas is almost absent, etc.

[0054] In the present disclosure, the total area of ​​the optically abnormal region is measured in the following manner.

[0055] A polarizing filter (OLS4000-QWP) is inserted above the objective lens of an incident-light laser microscope (OLS-4100, manufactured by Olympus). Next, a temporary support cut to 30 mm x 30 mm is horizontally suction-fixed onto the stage of the laser microscope using a porous suction plate (65F-HG, manufactured by Universal Giken) and a vacuum pump. The suction-fixed temporary support is observed under conditions of a 50x objective lens and a laser light intensity of 60 (laser wavelength: 405 nm). At this time, the measurement area is defined as an area up to 2 μm in one direction or the other in the thickness direction from the center position of the average thickness of the temporary support, and measurements are taken at 200 measurement points in a measurement area of ​​259 μm x 260 μm. Therefore, the total measurement area is 0.259 mm x 0.26 mm x 200 = 13.5 mm. 2 This becomes:

[0056] The difference in light intensity between the pixel with the maximum light intensity and the pixel with the minimum light intensity in the measured image is divided into 4096 gradations (the maximum light intensity value is 4095 and the minimum light intensity value is 0). A histogram (horizontal axis: light intensity gradation (minimum value 0, maximum value 4095), vertical axis: number of pixels) is created, graphing the light intensity distribution of the pixels in the image. The measured image is binarized using a gradation 400 gradations above the value of the larger of the two base values ​​in the created histogram as the threshold, and the areas of pixels with a light intensity greater than the threshold are added together, with this total area being the total area of ​​the optical anomalous region. The ratio of the total area of ​​the optical anomalous region to the measured area is calculated.

[0057] From the viewpoint of improving adhesion to the intermediate layer, the surface of the temporary support that comes into contact with the intermediate layer may be subjected to a surface treatment such as ultraviolet irradiation, corona discharge, plasma treatment, etc. When the surface treatment is performed by ultraviolet irradiation, the exposure dose is 10 mJ / cm. 2 ~2,000mJ / cm 2 and preferably 50 mJ / cm 2 ~1,000mJ / cm 2 It is more preferable that:

[0058] Examples of light sources for ultraviolet irradiation include light sources that emit light in the 150 nm to 450 nm wavelength band (e.g., 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)). There are no particular limitations on the output and illuminance.

[0059] The intermediate layer is preferably in contact with the surface of the temporary support. From the viewpoint of transferring the irregularities of the temporary support to the intermediate layer, the surface roughness Rmax of the temporary support on the intermediate layer side is preferably 0.5 μm or less, and more preferably 0.01 μm to 0.5 μm.

[0060] The surface roughness Rmax of the intermediate layer side surface of the temporary support is measured by the following method. In the present disclosure, the surface roughness Rmax is measured using a three-dimensional optical profiler (for example, New View 7300, manufactured by Zygo). First, the temporary support is peeled off from the photosensitive transfer material. A surface profile of the intermediate layer side surface of the temporary support is obtained. MetroPro ver. 8.3.2 Microscope Application is used as the measurement and analysis software. Next, the Surface Map screen is displayed using the measurement and analysis software, and histogram data is obtained on the Surface Map screen. The surface roughness Rmax is obtained from the obtained histogram data. The surface roughness Rmax corresponds to the maximum height of the roughness curve over the reference length.

[0061] The temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning used films and then chipping them, and then using the chips as raw materials to form films. Specific examples of recycled products include the Ecouse series from Toray Industries, Inc.

[0062] <Thermoplastic resin layer> The photosensitive transfer material has a thermoplastic resin layer between the temporary support and the intermediate layer. The thermoplastic resin layer contains a copolymer polyester resin, and the average thickness of the thermoplastic resin layer is 1 μm to 10 μm. The thermoplastic resin layer has an average thickness of 1 μm to 10 μm, which is thinner than conventional ones, and contains a copolymer polyester resin, which suppresses roughness of the surfaces of the thermoplastic resin layer and intermediate layer due to moisture absorption by the thermoplastic resin layer, and also suppresses roughness of the surface of the photosensitive resin layer corresponding to the roughness of the surface of the intermediate layer, resulting in an excellent pattern shape of the pattern obtained by peeling off the temporary support and exposing.

[0063] The copolymer polyester resin is a polycondensation product of either a polycarboxylic acid component or a polyhydric alcohol component of a polyester resin, or a combination of two or more of both components. The copolymer polyester resin is not particularly limited, and known copolymer polyester resins can be used.

[0064] Examples of polycarboxylic acid components include alicyclic dicarboxylic acids such as terephthalic acid and their substituted derivatives. While not particularly limited, examples include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, or lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms), and polycarboxylic acids having a sodium sulfonate group. These polycarboxylic acid components can be used alone or in combination of two or more.

[0065] Examples of polyhydric alcohol components include aliphatic diols such as ethylene glycol and diethylene glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. Examples of polyhydric alcohol components include, but are not limited to, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosanedecanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polyethylene glycol, polypropylene glycol, polybutanediol, and polytetramethylene ether glycol. These polyhydric alcohol components can be used alone or in combination of two or more.

[0066] From the viewpoints of pattern shape and surface roughness, the glass transition temperature (Tg) of the copolymer polyester resin is preferably 20°C or higher and 100°C or lower, more preferably 30°C or higher and 80°C or lower, and particularly preferably 40°C or higher and 70°C or lower. Furthermore, from the viewpoints of pattern shape and surface roughness, the glass transition temperature (Tg) of the thermoplastic resin in the thermoplastic resin layer is preferably 20°C or higher and 100°C or lower, more preferably 30°C or higher and 80°C or lower, and particularly preferably 40°C or higher and 70°C or lower. In the present disclosure, the glass transition temperature of a resin can be measured using differential scanning calorimetry (DSC). The specific measurement method is in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature used in this specification is the extrapolated glass transition onset temperature (hereinafter sometimes referred to as Tig). When two or more thermoplastic resins are contained, the number average molecular weight and glass transition temperature of the thermoplastic resins both mean weighted average values.

[0067] From the viewpoint of pattern shape and surface roughness, the weight average molecular weight of the copolymer polyester resin is preferably 3,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000.

[0068] The thermoplastic resin layer may contain one or more copolymer polyester resins. The content of the copolymer polyester resin in the thermoplastic resin layer is preferably 10% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, and even more preferably 50% by mass to 100% by mass.

[0069] The thermoplastic resin layer may contain a thermoplastic resin other than the copolymer polyester resin. Examples of thermoplastic resins other than copolymer polyester resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, non-copolymer polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols. Among these, from the viewpoint of developability and transferability, the thermoplastic resin is preferably an acrylic resin. Here, the acrylic resin refers to a resin having at least one structural unit selected from the group consisting of structural units formed from (meth)acrylic acid, structural units formed from (meth)acrylic acid esters, and structural units formed from (meth)acrylic acid amides, and the content of the structural units is preferably 50% by mass or more relative to the total amount of the resin.

[0070] From the viewpoint of developability, the copolymer polyester resin and the thermoplastic resin preferably have an acid group.

[0071] From the viewpoint of resolution, developability, etc., the weight average molecular weight (Mw) of the thermoplastic resin is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000, and even more preferably from 30,000 to 60,000. The dispersity (Mw / Mn) of the thermoplastic resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0072] From the viewpoint of resolution, developability, and the like, the acid value of the thermoplastic resin is preferably 60 mgKOH / g to 220 mgKOH / g, more preferably 120 mgKOH / g to 200 mgKOH / g, and even more preferably 150 mgKOH / g to 190 mgKOH / g.

[0073] The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of the pattern shape and surface roughness.

[0074] The plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.

[0075] The plasticizer is not particularly limited as long as it is a compound that is compatible with the thermoplastic resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound, and the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure. Among these, the plasticizer is preferably a polyester-based plasticizer from the viewpoints of compatibility with the copolymer polyester resin, pattern shape, and surface roughness.

[0076] From the viewpoint of lamination properties, the content of the plasticizer relative to the total mass of the thermoplastic resin layer is preferably 15% by mass to 60% by mass, more preferably 25% by mass to 50% by mass, and even more preferably 35% by mass to 40% by mass.

[0077] The thermoplastic resin layer may contain one or more surfactants. The surfactant preferably includes at least one selected from the group consisting of nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants. Furthermore, from the viewpoint of improving the adhesion between the intermediate layer and the adjacent layer (photosensitive resin layer, thermoplastic resin layer, etc.) (hereinafter also referred to as "interlayer adhesion"), silicone surfactants are preferred. From the viewpoints of the releasability, resolution, oxygen blocking ability, defect suppression, interlayer adhesion, etc. of the temporary support, the content of the silicone surfactant relative to the total mass of the surfactants is preferably 60 mass% or more, preferably 80 mass% or more, preferably 95 mass% or more, and may be 100 mass%. Examples of silicone surfactants include linear polymers consisting of siloxane bonds, and modified siloxane polymers in which an organic group has been introduced into at least one of the side chains and the terminals.

[0078] In particular, from the viewpoints of peelability between the thermoplastic resin layer and the intermediate layer, pattern shape, and surface roughness, it is preferable that the intermediate layer contains a surfactant having a silicon atom, and it is more preferable that the intermediate layer contains a silicone-based surfactant.

[0079] From the viewpoints of temporary support releasability, resolution, oxygen blocking ability, etc., the content of the surfactant relative to the total mass of the thermoplastic resin layer is preferably 0.01 mass% to 3 mass%, more preferably 0.02 mass% to 1 mass%, and even more preferably 0.03 mass% to 0.3 mass%.

[0080] The thermoplastic resin layer may contain additives such as colorants, dyes, acid generators, flame retardants, antioxidants, rust inhibitors, and dispersants.

[0081] The average thickness of the thermoplastic resin layer is 1 μm to 10 μm, and from the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, pattern shape, and surface roughness, it is preferably 1 μm to 8 μm, more preferably 1 μm to 5 μm, and particularly preferably 1 μm to 3 μm.

[0082] <Middle class> The photosensitive transfer material according to the present disclosure has an intermediate layer between the temporary support and the photosensitive resin layer. From the viewpoint of the pattern shape and surface roughness, it is preferable that the thermoplastic resin layer and the intermediate layer are in contact with each other. The intermediate layer preferably has oxygen blocking ability. When the intermediate layer has oxygen blocking ability, the sensitivity during exposure is improved, the time load on the exposure machine can be reduced, and productivity can be improved. In addition, when the photosensitive resin layer in the photosensitive transfer material is a negative photosensitive resin layer containing a radical polymerizable compound, there is also the advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure.

[0083] From the viewpoints of pattern shape and surface roughness, the intermediate layer preferably contains a water-soluble resin. Examples of the water-soluble resin include polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose compounds, (meth)acrylamide, polyether compounds, gelatin, vinyl ether compounds, polyamides, phenolic compounds, and copolymers thereof.

[0084] From the viewpoints of the releasability of the temporary support, resolution, oxygen blocking ability, and defect suppression in the pattern (hereinafter also simply referred to as "defect suppression"), the intermediate layer preferably contains at least one of polyvinyl alcohol and polyvinylpyrrolidone, more preferably contains polyvinyl alcohol, and even more preferably contains polyvinyl alcohol and polyvinylpyrrolidone.

[0085] When the intermediate layer contains polyvinyl alcohol, from the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., the content of polyvinyl alcohol relative to the total mass of the intermediate layer is preferably 5% by mass to 95% by mass, more preferably 15% by mass to 90% by mass, even more preferably 25% by mass to 80% by mass, particularly preferably 50% by mass to 75% by mass, and most preferably 55% by mass to 70% by mass. When the intermediate layer contains polyvinylpyrrolidone, from the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., the content of polyvinylpyrrolidone relative to the total mass of the intermediate layer is preferably 20% by mass to 98% by mass, more preferably 23% by mass to 90% by mass, even more preferably 25% by mass to 75% by mass, and particularly preferably 25% by mass to 50% by mass. When the intermediate layer contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., the sum of the contents of polyvinyl alcohol and polyvinylpyrrolidone relative to the total mass of the intermediate layer is preferably 50% by mass to 99% by mass, more preferably 70% by mass to 99% by mass, and even more preferably 75% by mass to 99% by mass.

[0086] From the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., the intermediate layer preferably contains one or more compounds X selected from the group consisting of water-soluble cellulose compounds, polyether compounds, phenol compounds, and polyhydric alcohol compounds. Examples of the water-soluble cellulose compound include hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose. Examples of the polyether compound include polyethylene glycol and polypropylene glycol. Examples of phenol compounds include bisphenol A and bisphenol S. Examples of polyhydric alcohol compounds include glycerin, diglycerin, and diethylene glycol. From the viewpoints of releasability, resolution, oxygen blocking ability, defect suppression, etc. of the temporary support, among the above, the intermediate layer preferably contains one or more compounds X selected from the group consisting of hydroxypropyl methylcellulose, polyethylene glycol, bisphenol A, and glycerin, more preferably one or more compounds X selected from the group consisting of hydroxypropyl methylcellulose and polyethylene glycol, and even more preferably hydroxypropyl methylcellulose.

[0087] From the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., when the intermediate layer contains compound X, the sum of the contents of compound X relative to the total mass of the intermediate layer is preferably 0.1% by mass to 36% by mass, more preferably 0.5% by mass to 20% by mass, and even more preferably 1% by mass to 15% by mass.

[0088] From the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, and the like, the intermediate layer preferably contains at least one of polyvinyl alcohol and polyvinylpyrrolidone, and compound X, more preferably contains polyvinyl alcohol and compound X, and even more preferably contains polyvinyl alcohol, polyvinylpyrrolidone, and compound X. When the intermediate layer has the above-mentioned composition, compound X is likely to be unevenly distributed on the surface of the intermediate layer facing the temporary support, and the formation of a weak boundary layer (WBL) due to mixing of the intermediate layer with the photosensitive resin layer can be suppressed. As a result, the surface free energy of the intermediate layer facing the temporary support is adjusted to an appropriate value, and the releasability of the temporary support and the resolution can be further improved.

[0089] From the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., the weight average molecular weight (Mw) of the water-soluble resin is preferably 5,000 to 200,000, more preferably 7,000 to 100,000, and even more preferably 7,000 to 50,000. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5, from the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, and the like.

[0090] From the viewpoints of releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, etc., the content of the water-soluble resin relative to the total mass of the intermediate layer is preferably 60 mass% or more, more preferably 80 mass% or more, even more preferably 95 mass% or more, and may be 100 mass%.

[0091] The intermediate layer may contain a surfactant, and may contain two or more types of surfactants. The preferred embodiments of the surfactant are the same as those explained in the thermoplastic resin layer, and therefore will not be described here. In particular, from the viewpoints of peelability between the thermoplastic resin layer and the intermediate layer, pattern shape, and surface roughness, it is preferable that the intermediate layer contains a surfactant having a silicon atom, and it is more preferable that the intermediate layer contains a silicone-based surfactant. From the viewpoints of the releasability of the temporary support, resolution, oxygen blocking ability, defect suppression, interlayer adhesion, etc., the content of the surfactant relative to the total mass of the intermediate layer is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 7% by mass, and even more preferably 1% by mass to 5% by mass.

[0092] The intermediate layer may contain a water-insoluble resin, such as a polyester resin or a (meth)acrylic resin. When the intermediate layer contains a water-insoluble resin, the content of the water-insoluble resin relative to the total mass of the intermediate layer is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0093] The intermediate layer may contain additives such as colorants, flame retardants, antioxidants, anti-rust agents, dispersants, and the like.

[0094] From the viewpoints of pattern shape, surface roughness, and resolution, the average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 3 μm, and particularly preferably 0.5 μm to 2 μm.

[0095] <Photosensitive resin layer> The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, but in the photosensitive transfer material according to the present disclosure, it is preferably a negative photosensitive resin layer. The negative photosensitive resin layer is a photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure. When the photosensitive resin layer is a negative photosensitive resin layer, the formed pattern corresponds to a cured layer.

[0096] The photosensitive resin layer preferably contains a polymer (binder polymer). The photosensitive resin layer may contain one or more polymers, and the polymer is preferably an alkali-soluble resin. The polymer may contain a structural unit formed by a monomer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphate group, and a phosphonate group. Examples of the monomer having an acid group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, and maleic anhydride. The polymer may contain a structural unit formed from a monomer having no acid group, such as a (meth)acrylic acid ester, a vinyl alcohol ester compound, (meth)acrylonitrile, or an aromatic vinyl compound. Examples of (meth)acrylic acid esters include 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, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate. An example of the vinyl alcohol ester compound is vinyl acetate. Examples of the aromatic vinyl compound include styrene and styrene derivatives. The non-acidic monomer is preferably one or more monomers selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, a styrene derivative, and benzyl (meth)acrylate.

[0097] From the viewpoint of resolution, the alkali-soluble resin preferably contains at least one of a structural unit derived from styrene and a structural unit derived from a styrene derivative. Specific examples of the styrene derivative include vinyltoluene, p-methylstyrene, and p-chlorostyrene.

[0098] The copolymerization ratio of the styrene-derived structural units and the styrene derivative-derived structural units in the alkali-soluble resin is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 15% by mass to 40% by mass, relative to the total mass of the alkali-soluble resin.

[0099] From the viewpoint of adhesion, the alkali-soluble resin preferably contains a structural unit derived from a (meth)acrylic acid ester. When the alkali-soluble resin contains at least one of a styrene-derived structural unit and a styrene derivative-derived structural unit, and a (meth)acrylic acid ester-derived structural unit, when the content of the styrene-derived structural unit and the styrene derivative-derived structural unit is taken as 1, from the viewpoint of achieving both resolution and adhesion, the content of the (meth)acrylic acid ester-derived structural unit is preferably 0.3 to 2.5, more preferably 0.5 to 2.0, and even more preferably 0.7 to 1.7.

[0100] From the viewpoint of resolution, developability, etc., the weight average molecular weight (Mw) of the polymer is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000, and even more preferably from 30,000 to 60,000. The dispersity (Mw / Mn) of the polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0101] From the viewpoint of resolution, developability, etc., the acid value of the polymer is preferably 60 mgKOH / g to 220 mgKOH / g, more preferably 120 mgKOH / g to 200 mgKOH / g, and even more preferably 150 mgKOH / g to 190 mgKOH / g.

[0102] 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 determined, for example, according to the method described in JIS K0070:1992. The acid value of the polymer can be adjusted by changing the type of constituent unit and the content of the constituent unit containing an acid group.

[0103] From the viewpoints of resolution, developability, etc., the content of the polymer relative to the total mass of the photosensitive resin layer is preferably 30% by mass to 70% by mass, more preferably 40% by mass to 60% by mass, and even more preferably 45% by mass to 57% by mass.

[0104] The photosensitive resin layer may contain one or more polymerizable compounds. The polymerizable compound is not limited, and known polymerizable compounds can be used. The polymerizable compound is preferably an ethylenically unsaturated compound. The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups. The ethylenically unsaturated group is preferably a (meth)acryloyl group, and the ethylenically unsaturated compound is preferably a (meth)acrylate compound. As the ethylenically unsaturated compound, an ethylenically unsaturated compound having a bisphenol structure can also be suitably used. Examples of ethylenically unsaturated compounds having a bisphenol structure include alkylene oxide-modified bisphenol A di(meth)acrylates. Examples of alkylene oxide-modified bisphenol A di(meth)acrylates include ethylene glycol dimethacrylates in which an average of 5 moles of ethylene oxide have been added to both ends of bisphenol A, ethylene glycol dimethacrylates in which an average of 2 moles of ethylene oxide have been added to both ends of bisphenol A, ethylene glycol dimethacrylates in which an average of 5 moles of ethylene oxide have been added to both ends of bisphenol A, alkylene glycol dimethacrylates in which an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide have been added to both ends of bisphenol A, and alkylene glycol dimethacrylates in which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide have been added to both ends of bisphenol A. Specific examples of alkylene oxide-modified bisphenol A di(meth)acrylates include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, and the like.

[0105] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200. When the polymerizable compound is a compound having a molecular weight distribution (for example, a polymer), the weight-average molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0106] The content of the polymerizable compound is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the photosensitive resin layer.

[0107] From the viewpoints of resolution, oxygen blocking ability, etc., the photosensitive resin layer preferably contains one or more of the above surfactants. Preferred aspects of the surfactants are as explained for the intermediate layer, and therefore will not be explained here. From the viewpoints of resolution, oxygen blocking ability, etc., the content of the surfactant relative to the total mass of the photosensitive resin layer is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, and even more preferably 0.2% by mass to 1% by mass.

[0108] The photosensitive resin layer may contain one or more polymerization initiators, such as conventionally known radical polymerization initiators and cationic polymerization initiators.

[0109] The content of the polymerization initiator relative to the total mass of the photosensitive resin layer is not particularly limited, and can be set to 1% by mass to 10% by mass.

[0110] The photosensitive resin layer may contain additives such as colorants, sensitizers, chain transfer agents (e.g., N-phenylcarbamoylmethyl-N-carboxymethylaniline, N,N-tetraethyl-4,4-diaminobenzophenone), polymerization inhibitors, plasticizers, flame retardants, antioxidants, anti-rust agents, dispersants, and thermally crosslinkable compounds (e.g., methylol compounds, blocked isocyanate compounds).

[0111] The average thickness of the photosensitive resin layer is preferably 0.5 μm to 30 μm, more preferably 1 μm to 10 μm, and particularly preferably 1 μm to 5 μm, from the viewpoints of pattern shape, surface roughness, and resolution.

[0112] The melt viscosity of the photosensitive resin layer at 25°C is set to 1.0 x 10 from the viewpoints of transferability, crack resistance, surface stability after peeling off the temporary support, and resolution. 6 Pa·s~1.0×10 9 Pa·s is preferred, and 2.0×10 6 Pa·s~5.0×10 8 Pa·s is more preferable, and 4.0×10 6 Pa·s~1.0×10 8 It is particularly preferred that the viscosity is Pa·s.

[0113] In this disclosure, the melt viscosity is measured using a rheometer (for example, an Anton Paar MCR302 rheometer) with 12 mm diameter parallel plates and a Peltier plate (gap: approximately 0.8 mm) under the following conditions: The melt viscosity specified in this disclosure is the melt viscosity at 25°C. (1) Temperature: 20℃~125℃ (2) Temperature increase rate: 3°C / min (3) Frequency: 0.1Hz (4) Distortion: 0.02%

[0114] <Protective film> The photosensitive transfer material may have a protective film on the surface of the photosensitive resin layer opposite to the intermediate layer side. The protective film may be a resin film. Examples of the resin film include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Among these, from the viewpoint of heat resistance, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0115] The average thickness of the protective film is not particularly limited, but from the viewpoint of mechanical strength etc., it is preferably 1.0 μm to 100.0 μm, more preferably 5.0 μm to 50.0 μm, and even more preferably 5.0 μm to 40.0 μm.

[0116] <Applications of photosensitive transfer materials> The photosensitive transfer material according to the present disclosure is preferably used to form circuit wiring arranged on a support substrate such as a sheet, metal substrate, ceramic substrate, or glass in a manufacturing process film for a semiconductor package, a printed circuit board, a flexible printed wiring board, or an interposer rewiring layer.

[0117] <Method for producing photosensitive transfer material> The method for producing a photosensitive transfer material according to the present disclosure is not particularly limited, but preferably includes, in this order, a step of forming a thermoplastic resin layer containing a copolymer polyester resin by coating on one side of a temporary support to a thickness of 1 μm to 10 μm (hereinafter referred to as the thermoplastic resin layer forming step), a step of forming the intermediate layer by coating on the side of the thermoplastic resin layer opposite to the side that contacts the temporary support (hereinafter referred to as the intermediate layer forming step), and a step of forming the photosensitive resin layer by coating on the side of the intermediate layer opposite to the side that contacts the thermoplastic resin layer (hereinafter referred to as the photosensitive resin layer forming step). The method for producing a photosensitive transfer material according to the present disclosure may also include a step of providing a protective film on the surface of the photosensitive resin layer (hereinafter referred to as a protective film disposing step). In this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and reduced-pressure drying. The above-mentioned methods can be applied alone or in combination.

[0118] <<Thermoplastic resin layer formation process>> The thermoplastic resin layer-forming composition used in the thermoplastic resin layer-forming step can be prepared by dissolving or dispersing the materials to be contained in the thermoplastic resin layer in a solvent. Examples of the solvent include the above-mentioned water-soluble solvents, alkylene glycol ethers, alkylene glycol ether acetates, ketone solvents (methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), ether solvents (diethyl ether, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, and lactone solvents. Examples of methods for applying the thermoplastic resin layer-forming composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating). The drying temperature can be set to 80° C. to 130° C. The drying temperature means the temperature of the environment in which the thermoplastic resin layer-forming composition is dried. The drying time can be set to 20 to 600 seconds.

[0119] <<Intermediate layer formation process>> The composition for forming an intermediate layer used in the intermediate layer forming step can be prepared by dissolving or dispersing the materials (surfactants, etc.) to be contained in the intermediate layer in a solvent. Examples of the solvent include water and the above-mentioned water-soluble solvents. The coating method, drying temperature, and drying time of the composition for forming the intermediate layer are the same as those in the thermoplastic resin layer forming step, and therefore, the description thereof will be omitted here.

[0120] <<Photosensitive resin layer formation process>> The photosensitive resin layer forming composition used in the photosensitive layer forming step can be prepared by dissolving or dispersing the materials to be contained in the photosensitive resin layer in a solvent. Examples of the solvent include the above-mentioned water-soluble solvents, alkylene glycol ethers, alkylene glycol ether acetates, ketone solvents (methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), ether solvents (diethyl ether, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, and lactone solvents. The coating method, drying temperature, and drying time of the photosensitive resin layer-forming composition are the same as those in the thermoplastic resin layer-forming step, and therefore, the description thereof will be omitted here.

[0121] <<Protective film placement process>> The protective film disposing step can include laminating a protective film on the surface of the photosensitive resin layer. The protective film can be attached using a known laminator such as a vacuum laminator, an auto-cut laminator, etc. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0122] (Method of manufacturing laminate) The method for manufacturing a laminate according to the present disclosure is not particularly limited except for peeling off the temporary support before exposure. However, it is preferable for the method to include, in this order, a step of laminating the photosensitive transfer material according to the present disclosure to a substrate (hereinafter also referred to as a "photosensitive transfer material laminating step"), a step of peeling off the temporary support (hereinafter also referred to as a "temporary support peeling step"), and a step of performing an exposure process after peeling off the temporary support, and further performing a development process after exposure to form a pattern (hereinafter also referred to as a "pattern formation step"). It is more preferable for the method to include, in this order, a step of laminating the photosensitive transfer material according to the present disclosure to a substrate so that the surface of the photosensitive resin layer opposite the intermediate layer side of the photosensitive transfer material according to the present disclosure contacts the substrate, a step of peeling off the temporary support, and a step of performing an exposure process after peeling off the temporary support, and further performing a development process after exposure to form a pattern. The preferred embodiments of the photosensitive transfer material used in the method for producing a laminate according to the present disclosure are as described above, and therefore will not be described here.

[0123] Hereinafter, the method for producing a laminate according to the present disclosure will be described in detail for each step. Note that the following description of the constituent elements may be based on a representative embodiment of the method for producing a laminate according to the present disclosure, but the present disclosure is not limited to such an embodiment.

[0124] <Photosensitive transfer material lamination process> The photosensitive transfer material lamination process involves laminating a photosensitive transfer material having a temporary support, an intermediate layer, and a photosensitive resin layer to a substrate so that the surface of the photosensitive resin layer opposite the intermediate layer side of the photosensitive transfer material is in contact with the substrate. The photosensitive transfer material may have a thermoplastic resin layer between the temporary support and the intermediate layer. The photosensitive transfer material may have a protective film on the surface of the photosensitive resin layer opposite to the intermediate layer side. When the photosensitive transfer material has a protective film, the protective film is peeled off before the lamination step.

[0125] The method for laminating the photosensitive transfer material and the substrate is not particularly limited, and known transfer methods and lamination methods can be used. Among these, it is preferred to laminate the photosensitive transfer material and the substrate by a method in which the surface of the photosensitive resin layer of the photosensitive transfer material opposite to the intermediate layer side is placed on the substrate, and pressure and heat are applied using a roll or the like. For lamination, known laminators such as a vacuum laminator, an auto-cut laminator, etc. The laminator is preferably equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat. The lamination temperature is not particularly limited, and can be set to, for example, 70°C to 130°C.

[0126] The substrate is preferably a conductive substrate (wiring substrate) having a support substrate and a conductive layer disposed on the support substrate.

[0127] Examples of the support substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the support substrate is described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference. When the support substrate is a resin substrate, the material of the resin substrate is preferably a substrate containing cycloolefin polymer, polyethylene terephthalate, or polyimide. The average thickness of the support substrate is not particularly limited, and can be set to 5.0 μm to 200.0 μm.

[0128] From the viewpoints of conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Furthermore, the support substrate may have one or more conductive layers disposed thereon. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0129] The conductive substrate is preferably a substrate having at least one of a transparent electrode and a wiring line, and the conductive substrate having such a configuration can be suitably used as a substrate for a touch panel. The transparent electrode can function favorably as an electrode for a touch panel, and is preferably made of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a metal mesh or a metal nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among these, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0130] The material of the lead wiring is preferably metal. Examples of metals that are materials for the lead wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, alloys of two or more of these metal elements, etc. As the material for the lead wiring, copper, molybdenum, aluminum, or titanium is preferred, and copper is particularly preferred.

[0131] The substrate may be a substrate incorporating elements that interconnect semiconductor elements. An example of an element for interconnecting semiconductor elements is an element having a wiring pattern formed on a silicon substrate for interconnecting semiconductor elements.

[0132] The substrate may have a seed layer on its surface. Examples of materials constituting the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The average thickness of the seed layer is not particularly limited and can be 50 nm to 2 μm. The method for forming the seed layer is not particularly limited and includes a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering the coating film, a sputtering method, a vapor deposition method, and the like.

[0133] From the viewpoint of reducing transmission loss, the dielectric loss tangent of the substrate at 24 GHz is preferably 0.05 or less, and more preferably 0.03 or less.

[0134] <Temporary support peeling process> The method for peeling off the temporary support is not particularly limited, and can be carried out based on a known method. For example, a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.

[0135] <Pattern formation process> In the pattern forming step, after the temporary support is peeled off, an exposure treatment is carried out, and further, after the exposure, a development treatment is carried out to form a pattern. In one embodiment, the pattern is formed by bringing the exposed intermediate layer or thermoplastic resin into contact with a mask, performing an exposure process, and then performing a development process.

[0136] In the exposure treatment, the photosensitive resin layer of the laminate is exposed to light in a pattern. Here, patternwise exposure means exposure that generates exposed and unexposed areas in the photosensitive resin layer.

[0137] Furthermore, when the photosensitive resin layer is a negative photosensitive resin layer, the exposure light source can be appropriately selected and used as long as it can irradiate light at least in a wavelength range that can harden the photosensitive resin layer (for example, 365 nm or 405 nm). In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity. Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is not particularly limited and is 5 mJ / cm 2 ~200mJ / cm 2 It can be said that:

[0138] After the exposure process and before the development process, it is preferable to remove the mask used in the exposure process.

[0139] The development process is a process in which the photosensitive resin layer that has been exposed to light in a pattern obtained by the exposure process is developed to form a pattern. The photosensitive resin layer can be developed using a developer. For example, when the photosensitive resin layer is a negative photosensitive resin layer, the unexposed areas of the photosensitive resin layer are removed by development using an alkaline developer, and a pattern is formed by the photosensitive resin layer remaining in the exposed areas.

[0140] In the development process, an alkaline aqueous solution is preferably used as the developer. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0141] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0142] <Other processes> When the photosensitive transfer material has a protective film, the method for producing a laminate according to the present disclosure may include a step of peeling off the protective film before bonding to the substrate. The method for peeling off the protective film is not particularly limited, and can be carried out by a conventionally known method.

[0143] The method for manufacturing a laminate according to the present disclosure may include at least one of a step of exposing the formed pattern to light (hereinafter also referred to as a "post-exposure step") and a step of heating the formed pattern (hereinafter also referred to as a "post-bake step"). When the method for producing a laminate according to the present disclosure includes both a post-exposure step and a post-bake step, it is preferable to carry out the post-bake step after the post-exposure step. The post-exposure exposure was 100 mJ / cm 2 ~5,000mJ / cm 2 is preferred, and 200 mJ / cm 2 ~3,000mJ / cm 2 is more preferred. The post-baking temperature is preferably 80° C. to 250° C., more preferably 90° C. to 160° C. The post-baking time is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.

[0144] (Method of manufacturing a circuit wiring board) The method for manufacturing a circuit wiring board according to the present disclosure is not particularly limited, but preferably includes, in this order: a step of manufacturing a laminate by the above-described method for manufacturing a laminate according to the present disclosure; a step of plating an area where no pattern is formed to form a conductive pattern (hereinafter also referred to as a "conductive pattern forming step"); and a step of removing the pattern (hereinafter also referred to as a "pattern removing step"). The method for manufacturing a circuit wiring board according to the present disclosure may include a step of forming a protective layer on the surface of the plating layer after the conductive pattern forming step and before the pattern removing step (hereinafter also referred to as the "protective layer forming step"). When the substrate has a seed layer on its surface, the method for manufacturing a circuit wiring board according to the present disclosure may include a step of removing the seed layer (hereinafter also referred to as a "seed layer removing step"). The process for producing a laminate by the laminate production method according to the present disclosure has been described above, and therefore will not be described here.

[0145] The circuit wiring board may be a semiconductor package. When the circuit wiring board is a semiconductor package, the manufacturing method for the circuit wiring board can include, after the seed layer removal step, a step of forming a solder resist layer having openings on the surface of the substrate using solder resist (hereinafter also referred to as the "solder resist layer formation step"), a step of forming bump electrodes in the openings (hereinafter also referred to as the "bump electrode formation step"), and a step of mounting a semiconductor element to be connected to the bump electrode (hereinafter also referred to as the "semiconductor element mounting step").

[0146] <Conductor pattern formation process> The method for manufacturing a circuit wiring board includes a step of forming a conductive pattern by plating an area of ​​the laminate where no pattern has been formed by the method for manufacturing a laminate according to the present disclosure. The plating method includes electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity.

[0147] The metal used for plating is not particularly limited, and known metals can be used. Usable metals include copper, chromium, lead, nickel, gold, silver, tin, zinc, and alloys of these metals. From the viewpoint of electrical conductivity, copper or its alloys are preferred.

[0148] The average thickness of the plating layer formed by plating is not particularly limited, and can be set to 0.1 μm to 20.0 μm.

[0149] <Pattern removal process> The method for removing the pattern is not particularly limited, but includes a method of removing the pattern by chemical treatment, and a method of removing the pattern using a remover is preferred. Examples of the removal liquid include removal liquids obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, a mixed solution of these, or the like. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

[0150] The temperature of the removal liquid is preferably 30 to 80°C, and more preferably 50 to 80°C. A preferred embodiment of the removal method is a method in which the laminate having the pattern to be removed is immersed in a stirring removal liquid at a liquid temperature of 50°C to 80°C for 1 minute to 30 minutes. Alternatively, the pattern may be removed by a known method such as a spray method, a shower method, or a puddle method using a remover.

[0151] <Protective layer formation process> The method for manufacturing a circuit wiring board according to the present disclosure may include a step of forming a protective layer on the surface of the plating layer after the conductive pattern forming step and before the pattern removing step. The material constituting the protective layer is preferably a material that is insoluble in the removal solution or etching solution used in the pattern removal step or seed layer removal step. Examples of materials constituting the protective layer include nickel, chromium, tin, zinc, magnesium, gold, silver, alloys thereof, and resins. The material constituting the protective layer is preferably nickel or chromium.

[0152] Methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0153] The average thickness of the protective layer is not particularly limited, and can be set to 0.3 μm to 3.0 μm.

[0154] <Seed layer removal process> When the substrate has a seed layer on its surface, the method for manufacturing a circuit wiring board according to the present disclosure may include a step of removing the seed layer. The seed layer removal step is a step of removing the exposed seed layer to obtain conductive thin wires.

[0155] The method for removing the seed layer is not particularly limited, and may be a method using a known etching solution. Examples of the etching solution include a ferric chloride solution, a cupric chloride solution, an ammonia alkali solution, a sulfuric acid-hydrogen peroxide mixture, and a phosphoric acid-hydrogen peroxide mixture.

[0156] <Solder resist layer formation process> The method for manufacturing a circuit wiring board according to the present disclosure can include a step of forming a solder resist layer having openings using a solder resist on the surface of the substrate from which the seed layer has been removed. The opening preferably exposes a conductive pattern formed on the surface of the substrate. As the solder resist, conventionally known materials can be used, such as azide-cyclized polyisoprene resins, azide-phenol resins, and chloromethyl polystyrene resins. The average thickness of the solder resist layer is not particularly limited, and can be set to 5 μm to 50 μm. The method for forming the solder resist layer is not particularly limited, and can be performed by a conventionally known method.

[0157] <Bump electrode formation process> The method for manufacturing a circuit wiring board according to the present disclosure includes forming bump electrodes in openings in the solder resist layer, and the bump electrodes are preferably connected to the conductor patterns exposed in the openings.

[0158] <Semiconductor element mounting process> The method for manufacturing a circuit wiring board according to the present disclosure can include a step of mounting a semiconductor element to be connected to the bump electrode. The semiconductor to be mounted preferably has electrodes, which are preferably connected to bump electrodes. After the semiconductor is mounted, it is preferable to seal the semiconductor with a conventionally known sealing material.

[0159] <Circuit wiring board> The circuit wiring board according to the present disclosure is a circuit wiring board manufactured by the above-described method for manufacturing a circuit wiring board.

[0160] <Semiconductor package> A semiconductor package according to the present disclosure includes the circuit wiring board.

[0161] <Printed wiring board manufacturing method> The photosensitive transfer material according to the present disclosure can be used in the manufacture of printed wiring boards. The method for producing a printed wiring board includes a step of subjecting the substrate having the pattern in the method for producing a laminate described above to at least one treatment selected from the group consisting of etching and plating. Here, the etching or plating of the substrate can be performed by etching or plating the surface of the substrate by a known method using the developed pattern as a mask. Furthermore, before etching or plating, a process of removing residual films may be carried out using resin etching with a chemical solution containing a permanganate component, resin ashing with plasma, or the like.

[0162] Examples of the etching solution used for etching include a cupric chloride solution, a ferric chloride solution, and an alkaline etching solution. Examples of plating include copper plating, solder plating, nickel plating, and gold plating.

[0163] After etching or plating, the pattern can be removed, for example, with an aqueous solution that is more strongly alkaline than the aqueous solution used for development. Examples of such strongly alkaline solutions include a 1% to 10% by mass aqueous solution of sodium hydroxide and a 1% to 10% by mass aqueous solution of potassium hydroxide. Examples of removal methods include immersion and spraying. The printed wiring board on which the pattern is formed may be a multilayer printed wiring board and may have small-diameter through-holes.

[0164] When plating is performed on a substrate having a conductive layer, etc., it is necessary to remove the conductive layer other than the pattern. Examples of this removal method include a method in which the pattern is peeled off and then lightly etched, and a method in which solder plating or the like is performed following the plating, and then the pattern is peeled off to mask the wiring portion with solder, and then the substrate is treated with an etching solution that can etch only the conductive layer in the portion not masked with solder.

[0165] <Deposition mask> The photosensitive transfer material of the present disclosure can be particularly suitably used for microfabrication of metal substrates for deposition masks having fine irregularities on the surface. The method for producing a deposition mask includes a step of etching the substrate having the pattern in the method for producing a laminate described above. Here, the etching of the substrate can be performed by etching the surface of the substrate by a known method using the developed pattern as a mask. After etching, the pattern can be peeled off with, for example, an aqueous solution that is more alkaline than the aqueous solution used for development. Examples of such an aqueous solution include a 1% to 10% by weight sodium hydroxide solution and a 1% to 10% by weight potassium hydroxide solution. Examples of peeling methods include immersion and spraying. [Example]

[0166] The present disclosure will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are by mass. In the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene, and the acid value is the theoretical acid value.

[0167] The temporary supports used in the examples and comparative examples are shown in Table 1.

[0168] [Table 1]

[0169] The temporary support A1 is manufactured by Toyobo Co., Ltd., and the temporary support A2 is manufactured by Mitsubishi Chemical Corporation.

[0170] [Preparation of Thermoplastic Resin Layer-Forming Composition] Table 2 shows the compositions C1 to C6 for forming a thermoplastic resin layer.

[0171] [Table 2]

[0172] Details of the abbreviations listed in Table 2 are shown below. Vylon BX-1001: Copolymer polyester resin, Tg -18°C, manufactured by Toyobo Co., Ltd. Vylon GK-800: Copolymer polyester resin, Tg 50°C, manufactured by Toyobo Co., Ltd. Vylon 802: Copolymer polyester resin, Tg 60°C, manufactured by Toyobo Co., Ltd. D620: Polyester plasticizer, manufactured by Mitsubishi Chemical Corporation Evaflex EV45X: Ethylene-vinyl acetate copolymer, manufactured by Dow Mitsui Polychemicals Co., Ltd. Phenothiazinepril: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd. CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. F-552 30% MEK solution: 30% methyl ethyl ketone solution of fluorosurfactant, Megafac (registered trademark) F-552, manufactured by DIC Corporation EXP-S-315 30% MEK solution: 30% methyl ethyl ketone solution of silicone surfactant, manufactured by DIC Corporation MMPGAc: 1-Methoxy-2-propyl acetate MEK: Methyl ethyl ketone

[0173] [Preparation of intermediate layer-forming composition] Table 3 shows the compositions P1 and P2 for forming the intermediate layer.

[0174] [Table 3]

[0175] Details of the abbreviations listed in Table 3 are shown below. PVA: Polyvinyl alcohol, Kuraray Poval PVA 4-88LA manufactured by Kuraray Co., Ltd. PVP: Polyvinylpyrrolidone, Polyvinylpyrrolidone K-30 manufactured by Nippon Shokubai Co., Ltd. HPMC: Hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH-03 F-444: Fluorine-based surfactant, Megafac (registered trademark) F-444, manufactured by DIC Corporation BYK-348: Silicone surfactant, manufactured by BYK Japan MeOH: Methanol

[0176] [Preparation of Photosensitive Resin Layer-Forming Composition] Table 4 shows the compositions R1 and R2 for forming a photosensitive resin layer.

[0177] [Table 4]

[0178] Details of the abbreviations in Table 4 other than those mentioned above are shown below. Polymer 1: Resin having the following structure, Mw=60,000, solid content=30% by mass

[0179] [ka]

[0180] In the above resins, the numbers in the parentheses to the right of the brackets indicate the mass ratio.

[0181] BPE-500: 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. Aronix M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. B-IMD: (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, B-CIM manufactured by Kurogane Kasei Co., Ltd. EAB-F: 4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd. Phenothiazine: Kawaguchi Chemical Co., Ltd. Phenidone 1% MEK solution: A methyl ethyl ketone solution containing 1% phenidone by mass Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. LCV: Leuco Crystal Violet, a radical-induced coloring dye, manufactured by Tokyo Chemical Industry Co., Ltd. EXP-S-506 30% MEK solution: 30% methyl ethyl ketone solution of silicone surfactant, manufactured by DIC Corporation MFG: 1-methoxy-2-propanol

[0182] Example 1 (Production of photosensitive transfer materials) A photosensitive transfer material of Example 1 having a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a protective film in this order was produced by the following procedure.

[0183] Composition C1 was prepared containing the components listed in the "thermoplastic resin layer" column of Table 5. Composition C1 was applied onto temporary support A1 using a slit nozzle, and then dried at 80°C for 2 minutes to form a thermoplastic resin layer. The film thickness (i.e., average thickness) of the thermoplastic resin layer is as shown in Table 5.

[0184] Composition P1 was prepared containing the components listed in the "Intermediate Layer" column of Table 5. Composition P1 was applied onto the thermoplastic resin layer using a slit nozzle, and then dried at 90°C for 2 minutes to form an intermediate layer. The film thickness (i.e., average thickness) of the intermediate layer is as shown in Table 5.

[0185] Composition R1 was prepared containing the components listed in the "Photosensitive Resin Layer" column of Table 5. Composition R1 was applied onto the intermediate layer using a slit nozzle, and then dried at 80°C for 2 minutes to form a photosensitive resin layer. The film thickness (i.e., average thickness) of the photosensitive resin layer is as shown in Table 5.

[0186] Finally, a protective film (trade name: Alphan (registered trademark) E200C3, thickness: 18 μm, polypropylene film, manufactured by Oji F-Tex Co., Ltd.) was attached to the exposed surface of the photosensitive resin layer by thermal lamination.

[0187] In this way, the photosensitive transfer material of Example 1 was obtained.

[0188] <Examples 2 to 7 and Comparative Examples 1 to 5> The same operations as in Example 1 were carried out, except that the compositions of temporary support A1, composition C1, composition P1, and composition R1 were changed to the compositions shown in Table 5, and the film thickness of each layer was changed to the film thickness shown in Table 5, to obtain each of the photosensitive transfer materials (photosensitive transfer materials for temporary support peeling exposure) of Examples 2 to 7 and Comparative Examples 1 to 5.

[0189] <Comparative Example 6> Comparative Example 6 was prepared by carrying out the same operations as in Example 3, except that the photosensitive transfer material of Example 3 was used and the temporary support was peeled off immediately before development in the evaluation described below.

[0190] <Comparative Example 7> Comparative Example 7 was prepared by carrying out the same operations as in Example 1, except that the compositions of temporary support A1, composition C1, composition P1, and composition R1 were changed to the compositions shown in Table 5, the film thickness of each layer was changed to the film thickness shown in Table 5, and the temporary support was peeled off immediately before development in the evaluation described below.

[0191] (evaluation) The photosensitive transfer materials of Examples 1 to 7 and Comparative Examples 1 to 7 were used to carry out the following evaluations.

[0192] 1. Peelability between the thermoplastic resin layer and the intermediate layer 1-1. Production of laminate for evaluation A 5 nm thick nickel-chromium (8 / 2) layer and a 200 nm thick copper layer were formed in this order on a 25 μm thick polyimide substrate by vapor deposition to prepare a polyimide substrate with a copper layer. The photosensitive transfer material was cut into a size of 30 mm x 100 mm, and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material and a polyimide substrate with a copper layer were bonded together under conditions of a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called lamination speed) of 1 m / min, and a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were arranged in this order on the surface of the polyimide substrate with a copper layer. As a result, a laminate for evaluation was obtained.

[0193] 1-2.Evaluation test The obtained laminate was subjected to autoclave treatment under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The treated laminate was attached to a 0.7 mm thick glass using double-sided tape. A 180° peel test was performed on the laminate attached to the glass at a peel speed of 300 mm / min using a Tensilon (model number: Tensilon universal testing machine manufactured by A&D Corporation) to peel off the temporary support, and the peel force was measured. In addition, the laminate after the peel test was observed to confirm the peel interface. The peelability between the thermoplastic resin layer and the intermediate layer was then evaluated according to the following evaluation criteria. In the following evaluation criteria, "5," "4," and "3" are practically acceptable levels, with "5" being the most preferable.

[0194] -Evaluation criteria- 5: Peeling occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength was 15 mN / cm or less. 4: Peeling occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength was in the range of more than 15 mN / cm and 25 mN / cm or less. 3: Peeling occurs between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength is in the range of more than 25 mN / cm and 50 mN / cm or less. 2: Peeling occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength exceeded 50 mN / cm. 1: Peeling occurs between layers other than between the thermoplastic resin layer and the intermediate layer.

[0195] The results of confirming the peel interface (in the table, this is indicated as "peeling interface when the temporary support is peeled off") are shown in Table 3. In the table, "between thermoplastic resin layer / intermediate layer" means that peeling occurred between the thermoplastic resin layer and the intermediate layer, "between temporary support / thermoplastic resin layer" means that peeling occurred between the temporary support and the thermoplastic resin layer, and "between temporary support / intermediate layer" means that peeling occurred between the temporary support and the intermediate layer. In addition, when peeling occurred between the thermoplastic resin layer and the intermediate layer, the measured peel force (in the table, indicated as "Peel force between thermoplastic resin layer / intermediate layer (mN / cm)") and the evaluation results of the peelability between the thermoplastic resin layer and the intermediate layer (in the table, indicated as "Peelability between thermoplastic resin layer / intermediate layer") are shown in Table 5.

[0196] 2.Pattern shape 2-1. Production of laminate for evaluation A polyimide substrate with a copper layer was obtained in the same manner as in "1-1. Production of laminate for evaluation" in "1. Peelability between thermoplastic resin layer and intermediate layer" above. The photosensitive transfer material was cut into a size of 90 mm x 90 mm, and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material and a polyimide substrate with a copper layer were bonded together under conditions of a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called lamination speed) of 1 m / min, and a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were arranged in this order on the surface of the polyimide substrate with a copper layer. As a result, a laminate for evaluation was obtained.

[0197] 2-2.Evaluation test The resulting laminate was autoclaved under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The temporary support was peeled off from the treated laminate, and an exposure mask was attached to the surface exposed by the peeling (i.e., the exposed surface of the thermoplastic resin layer or intermediate layer). A glass mask with a line-and-space pattern with a line width of 3.0 to 50 μm was used as the exposure mask. Using a high-pressure mercury lamp exposure machine (model: MAP-1200L, dominant wavelength: 365 nm, manufactured by Dai-Nippon Kaken Co., Ltd.), the transfer layer after the operation of peeling off the temporary support was irradiated with light from the exposure mask side. The exposure dose was adjusted so that the width of the resist pattern obtained after development in the portion corresponding to the 20 μm pattern of the exposure mask would be the pattern width of the mask (i.e., 20 μm).

[0198] Next, a development process was carried out. A 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 28°C was used as the developer. The development time was twice the minimum development time. The "minimum development time" refers to the shortest time required for the unexposed portions of the photosensitive resin layer to be completely dissolved by development. The development method was shower development. Specifically, the shortest time required for the unexposed portions of the photosensitive resin layer to be completely dissolved by shower development was first determined, and then shower development was carried out on the pattern-exposed photosensitive resin layer for twice the minimum development time. After development, an air knife treatment was carried out to remove the developer, followed by shower treatment with pure water at a liquid temperature of 25°C for 30 seconds, and then further air knife treatment. As a result, a laminate substrate having a resist pattern was obtained. The obtained laminate substrate having a resist pattern was observed at 1 mm depth using a scanning electron microscope (SEM). 2 The area of ​​the pattern was observed to confirm the shape of the resolved 20 μm pattern. The resolution was then evaluated according to the following evaluation criteria. In the following evaluation criteria, "5," "4," and "3" are practically acceptable levels, with "5" being the most preferable.

[0199] -Evaluation criteria- 5: The total number of chips and gouges on the pattern wall is one or less. 4: The total number of chips and gouges on the pattern wall is 2 or more and 5 or less. 3: The total number of chips and gouges on the pattern wall is 6 or more and 10 or less. 2: The total number of chips and gouges on the pattern wall is 11 or more and 20 or less. 1: The total number of chips and gouges on the pattern wall is 21 or more.

[0200] 3. Surface roughness 3-1. Production of laminate for evaluation A laminate for evaluation was obtained in the same manner as in "2. Pattern Shape" "2-1. Production of laminate for evaluation" above.

[0201] 3-2.Evaluation test The resulting laminate was autoclaved under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The temporary support was peeled off from the treated laminate, and the surface exposed by the peeling (i.e., the exposed surface of the thermoplastic resin layer or intermediate layer) was irradiated with light without a mask using a high-pressure mercury lamp exposure machine (model number: MAP-1200L, dominant wavelength: 365 nm, manufactured by Dai-Nippon Science Research Co., Ltd.). The exposure dose was adjusted to the same exposure dose as that used in the evaluation of "2. Pattern shape."

[0202] Next, development processing was carried out in the same manner as in "2. Pattern Shape" "2-2. Evaluation Test". As a result of the above, a laminate substrate having a cured resist film was obtained. The surface shape of the obtained laminate substrate having a cured resist film was confirmed. Then, surface roughness was evaluated according to the following evaluation criteria. In the following evaluation criteria, "3" and "2" are practically acceptable levels, with "3" being the most preferable.

[0203] -Evaluation criteria- 3: The gloss can be seen with the naked eye, and no irregularities can be seen even with an optical microscope at 50x magnification. 2: The gloss can be seen with the naked eye, but unevenness can be seen with an optical microscope at 50x magnification. 1: Cloudiness is visible on the surface with the naked eye.

[0204] [Table 5]

[0205] The results in Table 5 show that the photosensitive transfer materials of Examples 1 to 7 are superior to Comparative Examples 1 to 7 in the pattern shapes of the patterns obtained by temporary support peeling exposure. [Explanation of symbols]

[0206] 10: Photosensitive transfer material, 11: Temporary support, 12: Transfer layer, 13: Thermoplastic resin layer, 15: Intermediate layer, 17: Photosensitive resin layer, 19: Protective film

Claims

1. a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order; The number of protrusions having a height of 0.5 μm or more and less than 10 μm on the surface of the temporary support in contact with the thermoplastic resin layer is 1×10 ２ pieces / mm ２ 5x10 or more ６ pieces / mm ２ is less than the thermoplastic resin layer contains a copolymer polyester resin, The average thickness of the thermoplastic resin layer is 1 μm to 10 μm, The peel strength between the thermoplastic resin layer and the intermediate layer is 50 mN / cm or less. Photosensitive transfer material for temporary support peeling exposure.

2. 2. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer and the intermediate layer are in contact with each other.

3. 3. The photosensitive transfer material according to claim 1, wherein the intermediate layer contains a water-soluble resin.

4. 3. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer has an average thickness of 1 μm to 5 μm.

5. 3. The photosensitive transfer material according to claim 1, wherein the copolymer polyester resin has a glass transition temperature of 30° C. or higher and 80° C. or lower.

6. 3. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer contains a surfactant having a silicon atom.

7. 3. The photosensitive transfer material according to claim 1, wherein the intermediate layer contains a surfactant having a silicon atom.

8. 3. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer contains a plasticizer.

9. 3. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer contains a polyester-based plasticizer.

10. a step of forming a thermoplastic resin layer containing a copolymer polyester resin on one surface of a temporary support by coating to a film thickness of 1 μm to 10 μm; forming the intermediate layer by coating on a surface of the thermoplastic resin layer opposite to a surface that comes into contact with the temporary support; and forming the photosensitive resin layer by coating on the surface of the intermediate layer opposite to the surface in contact with the thermoplastic resin layer.

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