Transfer film and method for manufacturing laminate having conductor pattern

Abstract

The present invention addresses the problem of providing a transfer film capable of forming a pattern having excellent resolution and suppressing a decrease in development speed. A transfer film having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer in this order, the thermoplastic resin layer containing an alkali-soluble thermoplastic resin, a plasticizer having a polymerizable group, a polymerization inhibitor, and a photodecolorizing compound, the mass ratio of the content of the photodecolorizing compound to the content of the polymerization inhibitor is 400 or less, and the photodecolorizing compound is decolored when the amount of irradiation at a wavelength of 365 nm reaches 1000 mJ / cm2 by irradiating a laminate obtained by peeling the temporary support from the transfer film with ultraviolet light containing light at a wavelength of 365 nm from the thermoplastic resin layer side. When the transmittance of the laminate at a wavelength of 365 nm before the irradiation is T0 and the transmittance of the laminate at a wavelength of 365 nm after the irradiation is T1000, the transfer film satisfies the relationship of formula (1). Formula (1): T1000 / T0 > = 4.

Description

Technical Field

[0001] This invention relates to a transfer film and a method for manufacturing a laminate with a conductor pattern. Background Technology

[0002] In display devices (such as organic electroluminescent (EL) display devices and liquid crystal display devices) with touch panels equipped with capacitive input devices, conductor patterns such as electrode patterns of sensors equivalent to visual recognition units, peripheral wiring portions, and lead-out wiring portions are provided inside the touch panel. Furthermore, wiring patterns are also formed in printed circuit board wiring processes through etching and plating.

[0003] In the formation of the aforementioned conductor pattern, a method is used where a patterned layer is formed on the conductor layer, followed by etching and plating processes. To minimize the number of steps required to obtain the desired pattern shape in the formation of this patterned layer, a widely used method is to deposit a photosensitive composition layer on any substrate using a transfer film, expose the photosensitive composition layer to a pattern, and then develop it.

[0004] As an example of the transfer film described above, Patent Document 1 discloses a transfer film having a temporary support, an intermediate layer containing a surfactant, and a photosensitive composition layer, wherein, after peeling off the temporary support, the surface free energy of the exposed surface on the side not containing the temporary support is 66.0 mJ / m². 2 the following.

[0005] Patent Document 1: International Publication No. 2023 / 210777

[0006] In the aforementioned documents, as one method of transfer film, a transfer film having a specified thermoplastic resin layer is disclosed.

[0007] Recently, there has been a demand to further improve the resolution of the resulting patterns. On the other hand, there is also a demand to ensure the development speed.

[0008] The inventors have discovered that when photodecolorizing compounds are applied to the transfer film disclosed in Document 1 above for the purpose of improving resolution, the development speed after exposure sometimes decreases, necessitating structural research. Summary of the Invention

[0009] Therefore, the objective of this invention is to provide a transfer film capable of forming patterns with excellent resolution and suppressing a decrease in development speed.

[0010] Furthermore, the objective of this invention is to provide a method for manufacturing a laminate having the conductor pattern described above in the transfer film.

[0011] The inventors, through in-depth research to solve the above-mentioned problems, discovered that the problems can be solved through the following structure.

[0012] [1] A transfer film comprising, in sequence, a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer,

[0013] The aforementioned thermoplastic resin layer comprises an alkali-soluble thermoplastic resin, a plasticizer with polymerizable groups, a polymerization inhibitor, and a light-decolorizing compound.

[0014] In the aforementioned thermoplastic resin layer, the mass ratio of the content of the aforementioned photodecolorizing compound to the content of the aforementioned polymerization inhibitor is 400 or less.

[0015] The laminate obtained by peeling the temporary support from the transfer film from the thermoplastic resin layer side is irradiated with ultraviolet light containing a wavelength of 365 nm, so that the irradiation dose at a wavelength of 365 nm reaches 1000 mJ / cm. 2 In the case where the transmittance of the above-mentioned laminate before irradiation at a wavelength of 365nm is set to T0, and the transmittance of the above-mentioned laminate after irradiation at a wavelength of 365nm is set to T1000, the above-mentioned transfer film satisfies the relationship of equation (1).

[0016] Equation (1) T1000 / T0≥4

[0017] [2] According to the transfer film described in [1], wherein,

[0018] The aforementioned photosensitive composition layer comprises an alkali-soluble thermoplastic resin, a monomer having free radical polymerizable groups, and a free radical polymerization initiator.

[0019] [3] According to the transfer film described in [1] or [2], wherein,

[0020] The content of the aforementioned photodecolorizing compound is 5.00 to 40.00% by mass relative to the total mass of the aforementioned thermoplastic resin layer.

[0021] [4] The transfer film according to any one of [1] to [3], wherein,

[0022] The thickness of the aforementioned thermoplastic resin layer is 1–15 μm.

[0023] [5] The transfer film according to any one of [1] to [4], wherein,

[0024] The above T1000 is above 65%.

[0025] [6] The transfer film according to any one of [1] to [5], wherein,

[0026] The thickness of the aforementioned intermediate layer is 0.1–3 μm.

[0027] [7] The transfer film according to any one of [1] to [6], wherein,

[0028] The aforementioned intermediate layer contains polyvinyl alcohol.

[0029] [8] The transfer film according to any one of [1] to [7], wherein,

[0030] The aforementioned intermediate layer contains a photodecolorizing compound.

[0031] [9] The transfer film according to any one of [1] to [8], wherein,

[0032] The above-mentioned photodecolorizing compound has a molar absorptivity of 8000 L·mol⁻¹·cm⁻¹ at a wavelength of 365 nm. -1 above.

[0033]

[10] The transfer film according to any one of [1] to [9], wherein,

[0034] The photosensitive composition layer after the above irradiation has a transmittance of 75% or more at a wavelength of 365 nm.

[0035]

[11] The transfer film according to any one of [1] to

[10] , wherein,

[0036] The thickness of the above-mentioned photosensitive composition layer is 2 to 20 μm.

[0037]

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

[0038] In the bonding process, the transfer film described in any one of [1] to

[11] is bonded to the metal layer of a substrate having a metal layer on its surface in such a way that the photosensitive composition layer side is in contact with the metal layer of the substrate.

[0039] In the exposure process, the photosensitive composition layer is patterned and exposed from the side opposite to the substrate side.

[0040] In the developing process, an alkaline developing solution is used to develop the above-exposed photosensitive composition layer to form a resist pattern.

[0041] The etching process in which the metal layer located in the area where the resist pattern is not provided is etched to form a conductor pattern, and the plating process in which plating is performed;

[0042] The resist stripping process involves stripping the resist pattern described above; and

[0043] In addition to the above-described plating process, a removal process is further provided to remove the metal layer exposed by the above-described resist stripping process and form a conductor pattern on the substrate.

[0044]

[13] The method for manufacturing a laminate with a conductor pattern according to

[12] includes a step of peeling off the temporary support before the exposure step described above.

[0045] Invention Effects

[0046] According to the present invention, a transfer film capable of forming patterns with excellent resolution and suppressing the decrease in the development speed of the thermoplastic resin layer can be provided.

[0047] Furthermore, according to the present invention, it is also possible to provide a method for manufacturing a laminate having the conductor pattern involved in the above-described transfer film. Attached Figure Description

[0048] Figure 1 This is a schematic diagram illustrating an example of the structure of the transfer film of the present invention. Detailed Implementation

[0049] The present invention will now be described in detail.

[0050] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0051] In this specification, the numerical range indicated by “~” represents the range included by the values ​​recorded before and after “~” as the lower and upper limits.

[0052] Furthermore, in this specification, when there are two or more components of a certain ingredient, the “content” of that component refers to the total content of these two or more components.

[0053] In this specification, within a range of values ​​described in stages, the upper or lower limit value described in a certain range can be replaced by the upper or lower limit value of other ranges of values ​​described in stages. Furthermore, within the range of values ​​described in this specification, the upper or lower limit value described in a certain range can also be replaced by the value shown in the embodiment.

[0054] In this specification, a combination of two or more preferred methods is a more preferred method.

[0055] In this specification, the term "process" includes not only independent processes, but also processes that can achieve the desired purpose of the process, even if they cannot be clearly distinguished from other processes.

[0056] In this specification, "transparent" means that the average transmittance of visible light with wavelengths of 400 to 700 nm is 80% or more, preferably 90% or more. The above-mentioned average transmittance of visible light is a value measured using a spectrophotometer, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd. can be used for measurement.

[0057] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​converted from polystyrene measured using a gel permeation chromatography (GPC) analyzer with TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard.

[0058] Unless otherwise specified, the ratio of the structural units of the polymer in this specification is a mass ratio.

[0059] Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight-average molecular weight (Mw).

[0060] Unless otherwise specified, the refractive index in this specification is the value measured using an ellipsometer at a wavelength of 550 nm.

[0061] Unless otherwise specified, the hue in this instruction manual refers to the value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0062] In this specification, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid, "(meth)acryloyl" refers to both acryloyl and methacryloyl, "(meth)acrylate" refers to both acrylate and methacrylate, and "(meth)acrylamide" refers to both acrylamide and methacrylamide.

[0063] In this specification, "alkali-soluble" means that the solubility of sodium carbonate in 100g of a 1% by mass aqueous solution is greater than 0.1g at 22°C.

[0064] In this specification, "water-soluble" means that the solubility of the resin in 100g of water at pH 7.0 with a concentration of 0.1g or more is specified. For example, "water-soluble resin" refers to a resin that meets the above solubility requirement.

[0065] In this specification, "solid component" of a composition refers to the component used to form the composition layer formed using the composition. If the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Furthermore, if it is a component forming the composition layer, even liquid components are considered solid components.

[0066] In this specification, unless otherwise specified, the designation of groups (atomic groups) without indicating whether they are substituted or unsubstituted includes both unsubstituted and substituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0067] In this specification, it is indicated that when multiple substituents and linking groups (hereinafter referred to as substituents, etc.) are shown by specific symbols, or when multiple substituents, etc. are specified simultaneously, the individual substituents, etc., may be the same as each other or different from each other. The same applies to the specification of the number of substituents, etc.

[0068] In this specification, for convenience, compounds capable of having stereoisomers are sometimes described using only one general formula or structural formula. Even in such cases, unless otherwise specified, the stereoisomers are not limited to any particular stereoisomer; any stereoisomer may be used alone or in combination.

[0069] [Transfer film]

[0070] The transfer film will be described in detail below.

[0071] The transfer film of the present invention (hereinafter also simply referred to as "transfer film") sequentially comprises a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer. The thermoplastic resin layer comprises an alkali-soluble thermoplastic resin, a plasticizer having polymerizable groups, a polymerization inhibitor, and a photodecolorizing compound. The mass ratio of the photodecolorizing compound to the polymerization inhibitor is 400 or less. The laminate obtained by peeling the temporary support from the transfer film from the thermoplastic resin layer side is irradiated with ultraviolet light containing a wavelength of 365 nm, such that the irradiation dose at a wavelength of 365 nm reaches 1000 mJ / cm². 2 In the case where the transmittance of the above-mentioned laminate before irradiation at a wavelength of 365nm is set to T0 and the transmittance of the above-mentioned laminate after irradiation at a wavelength of 365nm is set to T1000, the above-mentioned transfer film satisfies the relationship of equation (1).

[0072] Equation (1) T1000 / T0≥4

[0073] While the reason why the transfer film with the above structure can solve the problem of the present invention is not yet clear, the inventors speculate as follows.

[0074] Furthermore, based on the following deductions, the mechanisms by which the effect can be achieved are not limited. In other words, even if the effect can be achieved through mechanisms other than those described below, it is still included within the scope of this invention.

[0075] In the transfer film of the present invention, the thermoplastic resin layer contains a photodecolorizing compound, and the transfer film satisfies the relationship of formula (1), with the thermoplastic resin layer functioning as a contrast enhancement layer (CEL). Thus, the pattern light incident on the photosensitive composition layer achieves high contrast, enabling the formation of patterns with excellent resolution. Furthermore, it is speculated that by maintaining the ratio of the polymerization inhibitor to the aforementioned photodecolorizing compound in the thermoplastic resin layer within a specified range, while exhibiting the function of a CEL, the reaction of the plasticizer with polymerizable groups is suppressed, and the decrease in the development speed of the thermoplastic resin layer is also suppressed.

[0076] Hereinafter, the situation in which a pattern with excellent resolution can be formed using a transfer film will also be referred to as "excellent resolution", and the situation in which at least one of achieving even better resolution and being able to further suppress the decrease in development speed will also be referred to as "the effect of the present invention is even better".

[0077] Figure 1 This is a cross-sectional schematic diagram illustrating an example of an embodiment of the transfer film of the present invention.

[0078] Figure 1 The transfer film 10 shown has a structure in which a temporary support 12, a thermoplastic resin layer 14, an intermediate layer 16, a photosensitive composition layer 18, and a protective film 20 are sequentially stacked. Furthermore, Figure 1 The transfer film 10 shown is configured with a protective film 20, but the protective film 20 may not be configured.

[0079] [Transmittance]

[0080] The laminate obtained by peeling a temporary support from a transfer film is irradiated with ultraviolet light containing a wavelength of 365 nm from the thermoplastic resin layer side, so that the irradiation dose at a wavelength of 365 nm reaches 1000 mJ / cm. 2 In the case where the transmittance of the laminate before irradiation at a wavelength of 365nm is set to T0 and the transmittance of the laminate after irradiation at a wavelength of 365nm is set to T1000, the transfer film satisfies the relationship of equation (1).

[0081] Equation (1) T1000 / T0≥4

[0082] By satisfying the relationship in equation (1) above, the transfer film can form patterns with excellent resolution.

[0083] Specifically, the aforementioned T1000 and T0 can be measured using a laminate T (glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer), which is obtained by attaching a transfer film to glass so that it contacts the photosensitive composition layer of the transfer film, and then peeling off a temporary support. By excluding the transmittance of the glass from the transmittance measured before and after ultraviolet light irradiation of the laminate T, the T1000 and T0 of the aforementioned laminate (a laminate of thermoplastic resin layer / intermediate layer / photosensitive composition layer obtained by peeling off the temporary support from the transfer film of the present invention) can be obtained.

[0084] The light irradiating the aforementioned laminate is ultraviolet light containing a wavelength of 365 nm. As the irradiation method described above, a method can be used to irradiate light emitted by a light source using a bandpass filter with a wavelength of 365 nm. The light source is not particularly limited as long as it is capable of irradiating ultraviolet light containing a wavelength of 365 nm; examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the 150–450 nm wavelength range.

[0085] Exposure time and other parameters can be appropriately adjusted to achieve an irradiation dose of 1000 mJ / cm at a wavelength of 365 nm. 2 .

[0086] The transmittance before and after irradiation can be measured using a spectrophotometer (e.g., the UV-1800 manufactured by Shimadzu Corporation). The irradiation dose at a wavelength of 365 nm can be measured using a known illuminance meter.

[0087] From the perspective of achieving superior resolution, the transfer film preferably satisfies the relationship T1000 / T0 ≥ 10, more preferably T1000 / T0 ≥ 50, even more preferably T1000 / T0 ≥ 500, and particularly preferably T1000 / T0 ≥ 3000. Furthermore, from the perspective of suppressing planar defects, it is preferable to satisfy the relationship T1000 / T0 ≤ 10000, more preferably T1000 / T0 ≤ 5000. Additionally, the aforementioned planar defects refer to defects such as cracks and particles observed on the surface during the transfer of the transfer film.

[0088] The T1000 / T0 value can be adjusted by modifying the composition of each layer in the transfer film (especially the type and content of photodecolorizing compounds) and the layer thickness.

[0089] T0 is preferably 50% or less, more preferably 20% or less, and even more preferably 5% or less. The lower limit of T0 is 0% or more, and it is often 0.001% or more, preferably 0.01% or more.

[0090] The T1000 content is preferably 50% or more, more preferably 65% ​​or more, and even more preferably 70% or more. The upper limit of T1000 is below 100%, and it is mostly below 95%, and even more often below 90%.

[0091] The transfer film of the present invention preferably uses ultraviolet light containing light with a wavelength of 405 nm instead of ultraviolet light containing light with a wavelength of 365 nm, and the ratio of transmittance measured at a wavelength of 405 nm also satisfies the above-mentioned requirements.

[0092] That is, the laminate obtained by peeling off the temporary support is irradiated with ultraviolet light containing light with a wavelength of 405 nm, so that the irradiation dose at a wavelength of 405 nm reaches 1000 mJ / cm. 2 In the case where the transmittance of the laminate before irradiation at a wavelength of 405 nm is set to T0' and the transmittance of the laminate after irradiation at a wavelength of 405 nm is set to T1000', the transfer film preferably satisfies the relationship of equation (1).

[0093] Equation (1')T1000' / T0'≥4

[0094] The preferred methods for the values ​​of T1000' / T0', T1000', and T0' are the same as the values ​​of T1000 / T0, T1000, and T0 mentioned above.

[0095] The following is a detailed explanation of the various elements that make up the transfer film.

[0096] [Temporary support]

[0097] The transfer film has a temporary support.

[0098] The temporary support is a component that supports the thermoplastic resin layer, intermediate layer, and photosensitive composition layer, and is eventually removed by a peeling process.

[0099] The temporary support can be any structure, whether it is a single-layer or multi-layer structure.

[0100] The temporary support is preferably a flexible membrane that does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat. Examples of such membranes include polyethylene terephthalate (PET) films (e.g., biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being the most preferred. Furthermore, the temporary support is preferably free from wrinkles, deformation, and scratches.

[0101] From the perspective of enabling pattern exposure via the temporary support, high transparency of the temporary support is preferable. Specifically, the transmittance at any wavelength of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and most preferably 90% or more. The upper limit is preferably less than 100%.

[0102] From the perspective of pattern formation properties during pattern exposure via the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably low. Specifically, the haze value of the temporary support is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.1% or less. The lower limit is not particularly limited, and examples include 0.01% or more.

[0103] From the perspective of pattern formation and transparency during pattern exposure via a temporary support, the number of particles, foreign objects, and defects contained in the temporary support is preferably low. The number of particles, foreign objects, and defects with a diameter of 1 μm or larger in the temporary support is preferably 50 per 10 mm. 2 The following is more preferably 10 per 10mm 2 The following is a further preferred option: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0104] The thickness of the temporary support is preferably 5 μm or more, more preferably 6 μm or more. The upper limit is preferably 200 μm or less, and from the perspective of ease of operation and versatility, it is more preferably 150 μm or less, further preferably 50 μm or less, and especially preferably 20 μm or less.

[0105] The thickness of the temporary support was calculated as the average of any five points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

[0106] From a processability perspective, the temporary support may have a layer containing microparticles (lubricant layer) on one or both sides of the temporary support. The diameter of the microparticles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0107] To improve the adhesion between the temporary support and the thermoplastic resin layer, the surface of the temporary support in contact with the thermoplastic resin layer can be modified. Examples of surface modification treatments include UV (ultraviolet) irradiation, corona discharge, and plasma treatment.

[0108] The preferred exposure level for UV irradiation is 10–2000 mJ / cm². 2 More preferably 50–1000 mJ / cm 2 .

[0109] Examples of light sources used in UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the 150–450 nm wavelength range.

[0110] If the exposure is within the above range, the lamp output and illuminance are not subject to any special restrictions.

[0111] Examples of temporary supports include biaxially stretched polyethylene terephthalate films with a thickness of 16 μm, biaxially stretched polyethylene terephthalate films with a thickness of 12 μm, and biaxially stretched polyethylene terephthalate films with a thickness of 9 μm.

[0112] Furthermore, as temporary supports, examples include paragraphs

[0017] to

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

[0019] to

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

[0041] to

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

[0029] to

[0040] of International Publication No. 2018 / 179370, all of which are incorporated herein by reference.

[0113] Commercially available temporary support structures include, for example, Lumirror 6FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34 and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); COSMOSHINE A4100, COSMOSHINE A4160, COSMOSHINE A4300, COSMOSHINE A4360 and COSMOSHINE A8300 (all manufactured by TOYOB0CO., LTD.).

[0114] [Thermoplastic resin layer]

[0115] The transfer film has a thermoplastic resin layer.

[0116] The thermoplastic resin layer contains alkali-soluble thermoplastic resin, plasticizer with polymerizable groups, polymerization inhibitor, and light-decolorizing compound.

[0117] As described above, in the transfer film of the present invention, the thermoplastic resin layer contains a photodecolorizing compound and functions as a CEL, thereby achieving excellent resolution. Furthermore, since the transfer film has a thermoplastic resin layer containing a thermoplastic resin and a plasticizer, the following bonding process between the transfer film and the substrate is performed, improving the tracking of the transfer film to the substrate, suppressing the introduction of air bubbles between the substrate and the transfer film, and also suppressing pattern defects.

[0118] The following is a detailed description of the components that a thermoplastic resin layer can contain.

[0119] <Alkali-soluble thermoplastic resins>

[0120] Examples of alkali-soluble thermoplastic resin layers include, for example, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0121] From the perspective of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble thermoplastic resin.

[0122] Here, acrylic resin refers to a resin having at least one structural unit selected from structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0123] As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin.

[0124] The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate is preferably 30 to 100% by mass relative to the total mass of the acrylic resin, more preferably 50 to 100% by mass.

[0125] Furthermore, the alkali-soluble thermoplastic resin preferably has an acid group. Examples of acid groups include carboxyl, sulfonyl, phosphoric acid, and phosphonic acid groups, with a carboxyl group being preferred. In this case, the alkali-soluble thermoplastic resin preferably has an acid group as a repeating unit.

[0126] From the perspective of developability, alkali-soluble thermoplastic resins are more preferably alkali-soluble thermoplastic resins with an acid value of 60 mg KOH / g or higher, and even more preferably acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher.

[0127] The lower limit of the aforementioned acid value is not particularly limited, but from the perspective of superior developability, it is more preferably 120 mg KOH / g or more, further preferably 150 mg KOH / g or more, and especially preferably 170 mg KOH / g or more. The upper limit of the acid value of the alkali-soluble thermoplastic resin is not particularly limited, but it is preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, and even more preferably 200 mg KOH / g or less.

[0128] Additionally, acid value (mgKOH / g) refers to the mass [mg] of potassium hydroxide required to neutralize 1g of a sample. Acid value can be calculated, for example, from the average content of acid groups in a compound. The acid value of alkali-soluble thermoplastic resins can be adjusted simply by the types of structural units constituting the resin (e.g., the content of structural units containing acid groups).

[0129] As an acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher, it is not particularly restricted and can be appropriately selected from known resins.

[0130] For example, examples include the alkali-soluble thermoplastic resin containing carboxyl groups that is an acrylic resin with an acid value of 60 mg KOH / g or higher, as described in paragraph 0025 of Japanese Patent Application Publication No. 2011-095716; the acrylic resin containing carboxyl groups that is an acrylic resin with an acid value of 60 mg KOH / g or higher, as described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589; and the acrylic resin containing carboxyl groups that is an adhesive polymer with an acid value of 60 mg KOH / g or higher, as described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0131] The copolymerization ratio of the carboxyl-containing structural units in the above-mentioned acrylic resin containing carboxyl groups is preferably 5 to 70% by mass relative to the total mass of the acrylic resin, more preferably 20 to 60% by mass, and even more preferably 30 to 55% by mass.

[0132] From the perspective of developability and adhesion to adjacent layers, acrylic resins having structural units derived from (meth)acrylic acid are particularly preferred as alkali-soluble thermoplastic resins.

[0133] Alkali-soluble thermoplastic resins can possess reactive groups. Any group capable of addition polymerization can be considered a reactive group; examples include olefinic unsaturated groups; condensation groups such as hydroxyl and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (block) isocyanate groups.

[0134] The alkali-soluble thermoplastic resin has a weight-average molecular weight (Mw) of 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0135] The polydispersity of the alkali-soluble thermoplastic resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and especially preferably 1.0 to 3.0.

[0136] Alkali-soluble thermoplastic resins can be used alone or in combination of two or more.

[0137] From the perspective of resolution, the content of alkali-soluble thermoplastic resin relative to the total mass of the thermoplastic resin layer is preferably 20.00 to 80.00% by mass, more preferably 20.00 to 60.00% by mass, and even more preferably 35.00 to 60.00% by mass.

[0138] Plasticizers with polymerizable groups

[0139] The thermoplastic resin layer contains a plasticizer with polymerizable groups.

[0140] The molecular weight (weight-average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) of the aforementioned plasticizer is preferably less than the molecular weight of the alkali-soluble thermoplastic resin. The molecular weight (weight-average molecular weight) of the plasticizer is 200 to preferably 2,000.

[0141] Plasticizers with polymerizable groups are preferably in liquid form at 25°C (1 atmosphere).

[0142] Plasticizers with polymerizable groups preferably have a viscosity of 10,000 mPa·s or less at 25°C. While the lower limit of this viscosity is not particularly limited, it is often above 3 mPa·s. This viscosity can be measured using a known viscometer.

[0143] The polymerizable groups in the aforementioned plasticizers are preferably free radical polymerizable groups, more preferably olefinic double bonds, and even more preferably (meth)acryloyl groups. From the perspectives of compatibility, resolution, and adhesion to adjacent layers, alkali-soluble thermoplastic resins are more preferably acrylic resins, and plasticizers with polymerizable groups are compounds having (meth)acryloyl groups.

[0144] The plasticizer has one or more polymerizable groups, preferably two or more. There is no particular upper limit, but it is often six or less, and preferably four or less.

[0145] From a plasticizing perspective, plasticizers with polymerizable groups preferably have epoxy alkyl chains.

[0146] The alkylene groups in the aforementioned alkylene oxide chain can be any of the following: linear, branched, and cyclic, preferably linear or branched, and more preferably linear.

[0147] The number of carbon atoms in the aforementioned alkylene group is preferably 1 to 6, more preferably 2 or 3.

[0148] The aforementioned epoxy chain can be a polyepoxide chain linked with two or more epoxy alkyl groups.

[0149] The plasticizer having polymerizable groups preferably has at least one structure selected from ethylene oxide chains and propylene oxide chains.

[0150] Examples of plasticizers having two polymerizable groups include tricyclodecanediethanol diacrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane. More specifically, examples include tricyclodecanediethanol diacrylate (manufactured by A-DCPSHIN-NAKAMURA CHEMICAL CO.,LTD.), tricyclodecanediethanol dimethacrylate (manufactured by DCP SHIN-NAKAMURA CHEMICAL CO.,LTD.), 1,9-nonanediol diacrylate (manufactured by A-NOD-N SHIN-NAKAMURA CHEMICAL CO.,LTD.), and 1,6-hexanediol diacrylate (manufactured by A-HD-N SHIN-NAKAMURA CHEMICAL CO.,LTD.).

[0151] Examples of plasticizers having three or more polymerizable groups include dipentaerythritol (tris / tetra / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds with a glycerol tri(meth)acrylate backbone. Here, "(tris / tetra / penta / hexa)methacrylate" encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, while "(tris / tetra)meth)acrylate" encompasses both tri(meth)acrylate and tetra(meth)acrylate.

[0152] Examples of plasticizers with polymerizable groups include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), epoxy-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glyceryl triacrylates (such as A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.).

[0153] Examples of plasticizers with polymerizable groups include urethane (meth)acrylates (preferably urethane (meth)acrylates) with three or more functional groups. Examples of urethane (meth)acrylate compounds include, for example, propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate.

[0154] Examples of urethane (meth)acrylates include, for example, 8UX-015A (manufactured by TAISEI FINECHEMICAL CO., LTD.); UA-32P, U-15HA and UA-1100H (all manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.); AH-600 manufactured by KYOEISHA CHEMICAL Co., Ltd; UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0155] Furthermore, plasticizers having polymerizable groups preferably also have acid groups. Examples of acid groups include carboxylic acid groups, which can be groups derived from acid anhydrides.

[0156] Plasticizers containing acidic and polymerizable groups include, for example, ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0157] As a plasticizer having acid groups and polymerizable groups, for example, (meth)acrylate compounds having acid groups as described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 can also be used.

[0158] Plasticizers with polymerizable groups can be used alone or in combination of two or more.

[0159] From the perspectives of resolution, adhesion to adjacent layers, and developability, the content of plasticizer with polymerizable groups relative to the total mass of the thermoplastic resin layer is preferably 10.00 to 50.00% by mass, more preferably 15.00 to 36.00% by mass, and even more preferably 25.00 to 36.00% by mass.

[0160] <Polymerization inhibitors>

[0161] The thermoplastic resin layer contains a polymerization inhibitor.

[0162] As a polymerization inhibitor, known polymerization inhibitors can be used.

[0163] Specific examples of polymerization inhibitors include, for instance, phenothiazine compounds such as bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(oxyethylene)]2,4-bis[(dodecylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylphenylamino)-1,3,5-triazine and pentaerythritol tetrakis(3-ethylhexyl)-3-ethylhexylene(2 ... Hindered phenolic compounds such as 3,5-di-tert-butyl-4-hydroxyphenyl)propionate; phenoxazine compounds such as phenoxazine; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate, preferably phenothiazine compounds.

[0164] A polymerization inhibitor can be used alone or in combination of two or more.

[0165] The content of the polymerization inhibitor relative to the total mass of the thermoplastic resin layer is preferably 0.01 to 5.00% by mass, more preferably 0.03 to 0.50% by mass, and even more preferably 0.04 to 0.10% by mass.

[0166] <Photochromic compounds>

[0167] The thermoplastic resin layer contains photo-decolorizing compounds.

[0168] Photodecolorizing compounds are those that, upon exposure, exhibit reduced absorption of the exposure wavelength and increased transmittance (i.e., decolorization).

[0169] The photodecolorizing compound can be decolorized simply by exposure light used for pattern exposure. Specifically, it is preferable to decolorize with light of wavelength 190 to 500 nm, more preferably with light of wavelength 365 nm or 405 nm, and even more preferably with light of wavelength 365 nm.

[0170] The preferred molar absorptivity of the photodecolorizing compound at a wavelength of 365 nm is 5000 L·mol⁻¹. -1cm -1 The above, more preferably 8000 L·mol -1 cm -1 The above is further preferred to be 15000 L·mol -1 cm -1 The above. The upper limit of the above molar absorptivity is not particularly limited, but 40000 L·ml -1 cm -1 The following situations are common. The molar absorptivity at the wavelength of 365 nm mentioned above is the value before exposure (i.e., before decolorization). The molar absorptivity at the wavelength of 365 nm mentioned above can be measured using a spectrophotometer (e.g., the UV-3100 manufactured by Shimadzu Corporation).

[0171] The difference in molar absorptivity at 365 nm before and after decolorization of the photodecolorizing compound (the value of (molar absorptivity at 365 nm before decolorization) - (molar absorptivity at 365 nm after decolorization)) is preferably 5000 L·mol⁻¹. -1 cm -1 The above, more preferably 8000 L·mol -1 cm -1 The above is further preferred to be 10000 L·mol -1 cm -1 That's all. The upper limit is not specifically restricted, but 40000 L·mol⁻¹ is acceptable. -1 cm -1 The following situations are more common.

[0172] As photodecolorizing compounds, examples include, for instance, oxime sulfonates, oxime esters, acylphosphine oxides, diazonium salts, stilbazolium salts, and arylnitroso salts, with oxime sulfonates being preferred.

[0173] The preferred oxime sulfonate compound is one having an aromatic ring group, and more preferably a compound represented by formula (X1) or a compound represented by formula (X2).

[0174] [Chemical Formula 1]

[0175]

[0176] In equation (X1), R 1 It indicates alkyl, cycloalkyl, or aryl.

[0177] The alkyl group can be either straight-chain or branched, preferably branched. The alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 6.

[0178] The number of carbon atoms in the above-mentioned cycloalkyl group is preferably 3 to 10, more preferably 5 to 7.

[0179] The aryl group can be either monocyclic or polycyclic. The number of carbon atoms in the aryl group is preferably 6 to 12, more preferably 6 to 8.

[0180] Examples of aryl groups include phenyl and naphthyl groups, with phenyl being the most preferred.

[0181] The aforementioned alkyl, cycloalkyl, and aryl groups may have substituents. Examples of substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkyl groups (preferably with 1 to 3 carbon atoms); alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, cyano, carboxyl, hydroxyl, alkoxy, aryloxy, alkylthio, arylthio, heterocyclic, acyloxy, amino, nitro, hydrazyl, and heterocyclic groups. Furthermore, these substituents can be further substituted by the aforementioned substituents. Additionally, when the aforementioned alkyl group has a fluorine atom as a substituent, the aforementioned alkyl group may be a perfluoroalkyl group.

[0182] As a substituent, a halogen atom or a methyl group is preferred.

[0183] As R 1 Preferably, it is an alkyl group with 3 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; more preferably, it is a branched alkyl group with 3 to 6 carbon atoms, a cycloalkyl group with 5 to 7 carbon atoms, or a phenyl group; and even more preferably, it is a branched alkyl group with 3 to 6 carbon atoms or a cycloalkyl group with 5 to 7 carbon atoms.

[0184] Among them, as R 1 Preferably, it is isopropyl, tert-butyl, neopentyl or cyclohexyl, more preferably tert-butyl or cyclohexyl.

[0185] In equation (X1), R 2 It represents a monovalent organic group.

[0186] Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, and heteroaryl groups.

[0187] The alkyl group can be either straight-chain or branched, preferably branched. The alkyl group preferably has 1 to 10 carbon atoms.

[0188] The aforementioned cycloalkyl group may have a carbonyl carbon atom as a ring member atom. The number of carbon atoms in the aforementioned cycloalkyl group is preferably 3 to 20, more preferably 5 to 15.

[0189] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, adamantyl, norbornyl, and 7,7-dimethylbicyclo[2.2.1]heptanone.

[0190] The aryl group can be either monocyclic or polycyclic. The preferred number of carbon atoms in the aryl group is 6 to 10.

[0191] Examples of aryl groups include phenyl, naphthyl, and p-methylphenyl (p-toluyl), with phenyl or p-methylphenyl being preferred.

[0192] Examples of heteroaryl groups include pyrrole, indolyl, carbazolyl, furanyl, and thiophene.

[0193] The aforementioned alkyl, cycloalkyl, aryl, and heteroaryl groups may have substituents. Examples of such substituents include those derived from R... 1 The alkyl, cycloalkyl, and substituents that can be present as aryl groups are preferably alkyl or halogen atoms, more preferably methyl or halogen atoms.

[0194] Preferred substituents are branched alkyl groups, cycloalkyl groups, cycloalkyl carbonyloxy groups, cycloalkoxy carbonyl groups, 7,7-dimethylbicyclo[2.2.1]heptanone groups, and decahydroisoquinoline sulfonyl groups.

[0195] As R 2 Preferably alkyl, cycloalkyl, or aryl, more preferably aryl, and even more preferably phenyl or p-methylphenyl.

[0196] In equation (X1), R 3 ~R 6 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, or halogen atom.

[0197] By R 3 ~R 6 The definitions and preferred methods of alkyl, cycloalkyl, and aryl groups are the same as those of R mentioned above. 2 All groups in it are the same.

[0198] R 3 With R 4 R 4 With R 5 Or R 5 With R 6 They can bond together to form a ring.

[0199] The aforementioned ring can be either an alicyclic ring or an aromatic ring, preferably an aromatic ring.

[0200] The aromatic ring can be any of the aromatic hydrocarbon rings and aromatic heterocycles, preferably an aromatic hydrocarbon ring, and more preferably a benzene ring.

[0201] As R 3 ~R 6Preferably, it is a hydrogen atom, an alkyl atom, or a halogen atom (preferably a fluorine atom, a chlorine atom, or a bromine atom), and more preferably a hydrogen atom, a methyl atom, a fluorine atom, a chlorine atom, or a bromine atom.

[0202] Furthermore, R is preferred. 3 With R 4 R 4 With R 5 and R 5 With R 6 Any pair of atoms in the group can bond with each other to form a benzene ring, more preferably R. 5 With R 6 They bond together to form a benzene ring.

[0203] R 3 ~R 6 The preferred method is as follows.

[0204] (Method 1) R 3 ~R 6 At least two of them are hydrogen atoms.

[0205] (Method 2) The total number of alkyl, cycloalkyl, aryl, and halogen atoms is three or less. Preferably, it is one or less.

[0206] (Method 3) R 3 With R 4 R 4 With R 5 and R 5 With R 6 Any one of them can bond with each other to form a benzene ring.

[0207] (Method 4) Satisfies the methods of Method 1 and 2 above and / or satisfies the methods of Method 1 and 3 above.

[0208] In equation (X1), X 1 It represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

[0209] Examples of compounds represented by formula (X1) include the compounds shown below. Additionally, hereinafter, Ts represents p-toluenesulfonyl, Me represents methyl, Bu represents n-butyl, and Ph represents phenyl.

[0210] [Chemical Formula 2]

[0211]

[0212] [Chemical Formula 3]

[0213]

[0214] [Chemical Formula 4]

[0215]

[0216] In equation (X2), R 11 This represents an organic group with a monovalent valence.

[0217] By R 11 The definition and preferred method of the monovalent organic group are as shown in formula (X1) by R. 2 The 1-valent organic groups are the same as the groups exemplified.

[0218] As R 11 Preferably, the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl, phenyl, p-methylphenyl, p-chlorophenyl, pentachlorophenyl, pentafluorophenyl, o-methoxyphenyl or p-phenoxyphenyl, more preferably phenyl or p-methylphenyl.

[0219] In equation (X2), R 12 Each of these groups independently represents a hydrogen atom, alkyl group, aryl group, or halogen atom. In some cases, there are two or more R groups. 12 At least one of them represents an alkyl, aryl, or halogen atom.

[0220] The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6.

[0221] The number of carbon atoms in the aryl group is preferably 6 to 30.

[0222] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine or bromine being preferred.

[0223] The aforementioned alkyl and aryl groups may have substituents. Examples of such substituents include those derived from R in formula (X1). 1 The alkyl, cycloalkyl, and substituents that can be present in an aryl group are preferably halogen atoms, aryl, alkoxy, alkoxycarbonyl, aryloxycarbonyl, alkylthio, or amino groups. When the alkyl and aryl groups have substituents, the number of carbon atoms containing the substituents preferably satisfies the preferred range described above.

[0224] There are more than 2 R 12 They can be the same as each other, or they can be different.

[0225] As R 12 Preferably, it is an alkyl or phenyl group with 1 to 6 carbon atoms, containing hydrogen atoms.

[0226] In equation (X2), Ar 11 It represents the aromatic ring.

[0227] The aforementioned aromatic ring can be any of an aromatic hydrocarbon ring or an aromatic heterocycle. Furthermore, the aforementioned aromatic ring can be any of a monocyclic or polycyclic ring.

[0228] Examples of aromatic rings include benzene rings, naphthalene rings, furan rings, thiophene rings, and quinoline rings, with benzene rings or naphthalene rings being preferred, and naphthalene rings being more preferred.

[0229] The aromatic ring described above may have substituents. Examples of substituents include those derived from R in formula (X1). 1 The alkyl, cycloalkyl, and substituents that can be present as aryl groups are preferably alkyl or alkoxy groups.

[0230] The alkyl and alkoxy groups used as the above-mentioned substituents preferably have 1 to 30 carbon atoms, more preferably 1 to 6.

[0231] The alkyl and alkoxy groups that are the above-mentioned substituents may further have the above-mentioned substituents (preferably halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and aminocarbonyl groups).

[0232] The number of substituents that the aromatic ring may have is preferably 0 to 6, more preferably 0 to 2, and even more preferably 0.

[0233] In equation (X2), X 11 It represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

[0234] In formula (X2), n represents 1 or 2, preferably 1.

[0235] As an example of a compound represented by formula (X2), the following compound can be cited.

[0236] [Chemical Formula 5]

[0237]

[0238] [Chemical Formula 6]

[0239]

[0240] [Chemical Formula 7]

[0241]

[0242] [Chemical Formula 8]

[0243]

[0244] [Chemical Formula 9]

[0245]

[0246] Examples of oxime ester compounds include, for instance, 1,2-octanedione, 1-[4-(phenylthio)phenyl-2-(O-benzoyl oxime)] (product name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (product name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazole][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl ketone-(O-acetyl oxime) (product name: IRGACURE) OXE-03 (manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyl oxime) (product name: IRGACURE OXE-04, manufactured by BASF and product name: Lunar 6, manufactured by DKSH JAPAN KK), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (product name: TR-PBG-305, manufactured by ChangzhouTronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-2-(O-acetyl oxime) (product name: TR-PBG-326, manufactured by ChangzhouTronly New Electronic Materials Co., Ltd.) Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (Product name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

[0247] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. Furthermore, acylphosphine oxide compounds described in Japanese Patent Application Publication Nos. 55-13794 and 55-15471 can also be used.

[0248] Examples of aryl diazonium salts include 4-(N,N-dimethylamino)benzenediazotetrafluoroborate, benzenediazohexafluoroantimonate, benzenediazohexafluorophosphate, benzenediazotetrafluoroborate, and 4-chlorobenzenediazohexafluorophosphate.

[0249] Photodecolorizing compounds can be used alone or in combination of two or more.

[0250] In the thermoplastic resin layer, the mass ratio of the content of the photodecolorizing compound to the content of the polymerization inhibitor is 400 or less. When the mass ratio is greater than 400, the plasticizer with polymerizable groups in the thermoplastic resin layer reacts, resulting in deteriorated solubility in the developer and a decrease in the development speed, which is undesirable from this perspective.

[0251] From the perspective of further suppressing the decrease in development speed and further suppressing planar defects, the above-mentioned quality ratio is preferably 350 or less, more preferably 300 or less. From the perspective of better resolution, the lower limit of the above-mentioned quality ratio is preferably 1 or more, more preferably 10 or more, even more preferably 20 or more, and particularly preferably 30 or more.

[0252] From the viewpoint of further enhancing the effects of the present invention, the content of the light-decolorizing compound relative to the total mass of the thermoplastic resin layer is preferably 1.00 to 60.00% by mass, more preferably 5.00 to 40.00% by mass, and even more preferably 8.00 to 30.00% by mass.

[0253] <Other ingredients>

[0254] The thermoplastic resin layer may contain other components besides those mentioned above.

[0255] Other components include, for example, surfactants and rust inhibitors.

[0256] (surfactant)

[0257] The thermoplastic resin layer may contain surfactants.

[0258] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

[0259] As surfactants, examples include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application No. 2009-237362.

[0260] As a surfactant, fluorinated surfactants or silicone surfactants are preferred.

[0261] Examples of fluorinated surfactants include acrylic compounds that have a molecular structure containing a functional group with a fluorine atom, and whose fluorine-containing functional group is partially cleaved and the fluorine atom volatilizes when heat is applied. Examples of such fluorinated surfactants include the MEGAFACE DS series (manufactured by DIC Corporation, Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016), and MEGAFACE DS-21, etc.).

[0262] Furthermore, as a fluorinated surfactant, it can be a polymer of a fluorinated vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Fluorinated surfactants can also be block polymers.

[0263] As a fluorinated surfactant, it can be a fluorinated polymer compound comprising repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxide or propoxide).

[0264] Furthermore, as fluorinated surfactants, examples include fluorinated polymers having groups containing olefinic unsaturated double bonds on their side chains. Specifically, examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC CORPORATION).

[0265] From the perspective of improving environmental adaptability, surfactants derived from alternative materials of compounds having a straight-chain perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred as fluorinated surfactants.

[0266] Commercially available fluorinated surfactants include, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (these are DIC COR). (manufactured by DIC CORPORATION); EXP.MFS-324, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21 (manufactured by DIC CORPORATION); Fluorad FC430, FC 431 and FC171 (manufactured by Sumitomo3M Limited); SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA SOLUTIONS INC.); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS); U-120E (Uni-che m (Manufactured by Co., Ltd.)

[0267] Examples of silicone surfactants include linear polymers composed of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or ends, and polymers having repeating units with hydrophilic groups on the side chains and repeating units with groups containing siloxane bonds on the side chains. Preferably, polymers having repeating units with hydrophilic groups on the side chains and repeating units with groups containing siloxane bonds on the side chains are preferred silicone surfactants. These polymers can be either random copolymers or block copolymers.

[0268] Commercially available silicone surfactants include, for example, EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2, and EXP.S-506 (manufactured by DIC CORPORATION); DOWSIL8032ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (manufactured by Toray Silicone Co., Ltd.). Co., Ltd.); X-22-4952, -642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-1 05. KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, K P-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626 and KP-652 (the above are Shin-Etsu (manufactured by Chemical Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials Inc.); BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377 and BYK378 (manufactured by BY K Chemie).

[0269] Surfactants can be used alone or in combination of two or more.

[0270] The surfactant content is preferably 0.01 to 5.00% by mass relative to the total mass of the thermoplastic resin layer, more preferably 0.05 to 1.00% by mass.

[0271] (Rust inhibitor)

[0272] The thermoplastic resin layer preferably also contains a rust inhibitor.

[0273] As a rust inhibitor, for example, heterocyclic compounds can be mentioned. Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, bortanene compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds, with triazole compounds, benzotriazole compounds, or tetraazole compounds being preferred.

[0274] As heterocyclic compounds, the compounds described in International Publication No. 2022 / 039027 can be cited as examples.

[0275] Rust inhibitors can be used alone or in combination of two or more.

[0276] The content of the rust inhibitor relative to the total solids content of the photosensitive composition is preferably 0.01 to 5.00% by mass, more preferably 0.05 to 1.00% by mass.

[0277] Properties of thermoplastic resin layers

[0278] From the perspective of resolution and development speed, the thickness of the thermoplastic resin layer is preferably 1 to 15 μm, more preferably 3 to 15 μm, and even more preferably 8 to 13 μm.

[0279] The thickness of each layer in the transfer film can be measured using a white interferometer (NewView 7200) manufactured by Zygo Corporation.

[0280] [Intermediate layer]

[0281] The transfer film has an intermediate layer. By having an intermediate layer, the mixing of components between the thermoplastic resin layer and the photosensitive composition layer can be suppressed, and the decrease in the development speed of the thermoplastic resin layer can be suppressed.

[0282] As the intermediate layer, a water-soluble resin layer containing a water-soluble resin is preferred. Furthermore, an oxygen-barrier layer with an oxygen-barrier function, as described as a "separation layer" in Japanese Patent Application Publication No. 5-072724, can also be used as the intermediate layer. If the intermediate layer is an oxygen-barrier layer, the sensitivity during exposure is increased, the time load on the exposure machine is reduced, and thus productivity is increased, making it a preferred choice.

[0283] Regarding the oxygen barrier layer that can be used as an intermediate layer, any suitable layer can be selected from those known in the aforementioned publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0284] Water-soluble resins

[0285] Examples of water-soluble resins that include the aforementioned water-soluble resin layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0286] The lower limit for the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Furthermore, the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0287] The polydispersity of the water-soluble resin is preferably 1.0 to 10.0, more preferably 1.0 to 5.0.

[0288] From the perspective of further improving oxygen barrier properties and interlayer mixing inhibition ability, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0289] The water-soluble resin also preferably includes cellulose resin.

[0290] Water-soluble resins can be used alone or in combination of two or more.

[0291] The content of water-soluble resin relative to the total mass of the intermediate layer is preferably 50.00% by mass or more, more preferably 70.00% by mass or more, and even more preferably 80.00% by mass or more. The upper limit of the water-soluble resin content is not particularly limited, but it is often 99.90% by mass or less relative to the total mass of the intermediate layer, and preferably 99.80% by mass or less.

[0292] <Photochromic compounds>

[0293] For even better resolution, the intermediate layer preferably further contains a photodecolorizing compound. Because the intermediate layer contains a photodecolorizing compound, it also functions as a CEL, resulting in superior resolution.

[0294] Examples of photo-decolorizing compounds that can be included in the intermediate layer include the photo-decolorizing compounds contained in the aforementioned thermoplastic resin layer. Furthermore, when the intermediate layer contains a photo-decolorizing compound, the photo-decolorizing compound contained in the intermediate layer may be the same as or different from the photo-decolorizing compound contained in the thermoplastic resin layer.

[0295] Photodecolorizing compounds can be used alone or in combination of two or more.

[0296] The content of the photodecolorizing compound relative to the total mass of the intermediate layer is preferably 1.00 to 50.00% by mass, more preferably 5.00 to 20.00% by mass.

[0297] In addition to the components mentioned above, the intermediate layer may contain other known components such as surfactants.

[0298] As an example of surfactants that can be included in the intermediate layer, the surfactants that can be included in the aforementioned thermoplastic resin layer are examples.

[0299] Surfactants can be used alone or in combination of two or more.

[0300] The surfactant content relative to the total mass of the intermediate layer is preferably 0.01 to 10.00% by mass, more preferably 0.10 to 1.00% by mass.

[0301] <Properties of the intermediate layer>

[0302] The thickness of the intermediate layer is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm.

[0303] [Photosensitive composition layer]

[0304] The transfer film has a photosensitive composition layer.

[0305] From a resolution perspective, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed by exposure corresponds to the cured layer.

[0306] The negative photosensitive composition layer preferably comprises resin A, which is an alkali-soluble thermoplastic resin, a monomer having free radical polymerizable groups, and a free radical polymerization initiator.

[0307] <Alkali-soluble thermoplastic resin (Resin A)>

[0308] Examples of resin A include, for example, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0309] From the perspective of suppressing the swelling of the photosensitive composition layer caused by the alkaline developer, thereby achieving better resolution, the acid value of resin A is preferably 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g. The lower limit of the above acid value is not particularly limited, but from the perspective of achieving better developability, it is more preferably 120 mg KOH / g or more, and even more preferably 150 mg KOH / g or more.

[0310] The weight-average molecular weight of resin A is not particularly limited, but from the perspective of resolution and developability, it is preferably 500,000 or less, more preferably 100,000 or less, and even more preferably 60,000 or less. Furthermore, from the perspective of edge fuse properties and chip scattering of the transfer film, it is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. Edge fuse properties refer to the degree to which the photosensitive composition layer easily overflows from the roll end when the transfer film is rolled into a roll. Chip scattering refers to the ease with which debris scatters when the unexposed film is cut with a cutter. If such debris adheres to the upper surface of the photosensitive composition layer, it can be transferred to the mask in subsequent exposure processes, resulting in defective products.

[0311] The polydispersity of resin A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0312] From a resolution perspective, resin A preferably comprises structural units based on monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include phenyl groups, which may have substituents, and aralkyl groups, which may have substituents.

[0313] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer), preferably monomers having an aralkyl group or styrene.

[0314] Aryl groups include phenylalkyl groups that can have substituents, with benzyl groups being preferred.

[0315] Examples of monomers having an aralkyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol; and non-benzyl (meth)acrylates having a benzoalkyl group, such as phenethyl (meth)acrylate.

[0316] As a monomer having an aralkyl group, benzyl (meth)acrylate is preferred.

[0317] Resin A may have one structural unit based on a monomer with an aromatic hydrocarbon group, or it may have two or more structural units based on monomers with aromatic hydrocarbon groups.

[0318] The content of the structural units based on monomers having aromatic hydrocarbon groups is preferably 20 to 80% by mass relative to all structural units of resin A, more preferably 25 to 70% by mass, and even more preferably 30 to 65% by mass.

[0319] From the perspective of alkaline developability, resin A preferably contains structural units having acid groups. Examples of acid groups include carboxyl groups, sulfonyl groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred.

[0320] As a monomer that imparts structural units with acid groups, (meth)acrylates or (meth)acrylic acid having carboxyl groups are preferred, and (meth)acrylic acid is more preferred.

[0321] Resin A may have one type of structural unit with an acid group, or it may have two or more types of structural units with acid groups.

[0322] From the perspective of developability and resolution, the content of structural units with acid groups (preferably structural units derived from (meth)acrylic acid) is preferably 10 to 50% by mass relative to all structural units of resin A, more preferably 15 to 40% by mass.

[0323] From the perspective of resolution, resin A preferably has reactive groups, and more preferably contains structural units with reactive groups.

[0324] As a reactive group, it is preferably a free radical polymerizable group, and more preferably an olefin unsaturated group. As an olefin unsaturated group, it is more preferably allyl or (meth)acryloyloxy.

[0325] Examples of structural units with reactive groups can be given below, but are not limited to these.

[0326] [Chemical Formula 10]

[0327]

[0328] Resin A may have one structural unit with a reactive group, or it may have two or more structural units with reactive groups.

[0329] From the perspective of resolution, the content of structural units having reactive groups is preferably 5 to 70% by mass relative to all structural units of resin A, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0330] As a method for introducing reactive groups into resin A, the following methods can be used: reacting compounds such as epoxy compounds, block isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds and carboxylic anhydrides with functional groups such as hydroxyl, carboxyl, primary amino, secondary amino, acetoacetyl group and sulfonyl group.

[0331] As a preferred example of a method for introducing reactive groups into resin A, a method can be described that after synthesizing a polymer having carboxyl groups through a polymerization reaction, (meth)acryloyloxy groups are introduced into the polymer by reacting glycidyl (meth)acrylate with a portion of the carboxyl groups of the obtained polymer through a polymer reaction. By this method, a resin having (meth)acryloyloxy groups on its side chains can be obtained.

[0332] Resin A may contain structural units derived from non-acidic monomers.

[0333] Examples of non-acidic monomers include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate; vinyl acetate and other vinyl alcohol esters; and methacrylonitrile. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0334] The content of structural units derived from non-acidic monomers in resin A is preferably 0.5 to 60% by mass relative to all structural units of resin A, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass.

[0335] Resin A can have any of the following structures in its side chain: straight chain, branched chain, and alicyclic chain.

[0336] In this specification, "main chain" refers to the longest bond chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to the atomic groups that branch off from the main chain.

[0337] By using monomers containing groups having branched or alicyclic structures on their side chains, branched or alicyclic structures can be introduced into the side chains of resin A. The groups having alicyclic structures can be monocyclic or polycyclic.

[0338] Examples of monomers containing groups having a branched structure on their side chains include those described in paragraph

[0064] of International Publication No. 2021 / 166719, which are incorporated herein by reference.

[0339] Resin A can be used alone or in combination with two or more types.

[0340] The content of resin A relative to the total mass of the photosensitive composition layer is preferably 20.00 to 80.00% by mass, more preferably 30.00 to 70.00% by mass, and even more preferably 40.00 to 65.00% by mass.

[0341] In addition, the photosensitive composition layer may contain resins other than resin A mentioned above.

[0342] Other resins that can be cited include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0343] Monomers with free radical polymerizable groups

[0344] The photosensitive composition layer preferably contains monomers having free radical polymerizable groups (hereinafter also simply referred to as "free radical polymerizable monomers").

[0345] As the free radical polymerizable group mentioned above, olefinic double bonds such as vinyl, (meth)acryloyl, styrene, and maleimide are preferred, and (meth)acryloyl is more preferred.

[0346] In addition, the free radical polymerizable monomer is a compound different from the resin A mentioned above, and its molecular weight (weight average molecular weight) is preferably 200 to 2,000.

[0347] From the perspective of resolution, the preferred free radical polymerizable monomer is a multifunctional free radical polymerizable monomer having two or more free radical polymerizable groups in one molecule.

[0348] The number of free radical polymerizable groups in one molecule of the free radical polymerizable monomer is preferably 6 or less, more preferably 3 or less.

[0349] (Free radical polymerizable monomer B1)

[0350] The free radical polymerizable monomer preferably comprises a free radical polymerizable monomer B1 having an aromatic ring and two olefinic unsaturated groups.

[0351] Examples of aromatic rings include, for instance, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings, as well as their fused rings, preferably aromatic hydrocarbon rings, and more preferably benzene rings. Furthermore, the aforementioned aromatic rings may have substituents.

[0352] The free radical polymerizable monomer B1 can have only one aromatic ring or more than two aromatic rings.

[0353] From the perspective of suppressing the swelling of the photosensitive composition layer caused by the developer and achieving better resolution, the free radical polymerizable monomer B1 preferably has a bisphenol structure.

[0354] Examples of bisphenol structures include, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0355] As a free radical polymerizable monomer B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0356] The two ends of the bisphenol structure can be directly bonded to the two polymerizable groups, or they can be bonded via one or more alkene groups, preferably via one or more alkene groups. That is, the free radical polymerizable monomer B1 preferably has an epoxide-modified bisphenol structure.

[0357] The alkoxides added to both ends of the bisphenol structure are preferably ethoxide or propoxide, more preferably ethoxide. The number of alkoxides added to the bisphenol structure is not particularly limited, but preferably 4 to 16 per molecule, more preferably 6 to 14.

[0358] Regarding the free radical polymerizable monomer B1 having a bisphenol structure, it is described in paragraphs

[0072] to

[0080] of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0359] As a free radical polymerizable monomer B1, it is preferably a difunctional olefinic unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0360] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include, for instance, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), 2,2-bis(4-(methacryloyloxydodecylethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.). 2,2-Bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.).

[0361] As a free radical polymerizable monomer B1, it is also preferred to be a compound represented by the following general formula (B1).

[0362] [Chemical Formula 11]

[0363]

[0364] In general formula (B1), R1 and R2 independently represent a hydrogen atom or a methyl group, respectively. A represents C2H4. B represents C3H6. n1 and n3 are independent integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are independent integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The arrangement of the structural units -(A-0)- and -(B-0)- can be random or block. Moreover, in the case of block, either group in -(A-0)- and -(B-0)- can be located on the bisphenyl side.

[0365] In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0366] The free radical polymerizable monomer B1 can be used alone or in combination of two or more.

[0367] From the perspective of achieving better resolution, the content of the free radical polymerizable monomer B1 relative to the total mass of the photosensitive composition layer is preferably 10.00 to 70.00% by mass, more preferably 20.00 to 60.00% by mass or more, and even more preferably 25.00 to 50.00% by mass.

[0368] As a free radical polymerizable monomer, it may contain free radical polymerizable monomers other than free radical polymerizable monomer B1.

[0369] Polymerizable compounds other than the radical polymerizable monomer B1 can be appropriately selected from known compounds. For example, compounds having one olefinic unsaturated group in one molecule (monofunctional olefinic unsaturated compounds), difunctional olefinic unsaturated compounds without an aromatic ring, and olefinic unsaturated compounds with three or more functions can be cited.

[0370] Examples of monofunctional alkenyl unsaturated compounds include, for example, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0371] Examples of difunctional olefinic unsaturated compounds that do not have an aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.

[0372] Examples of alkylene glycol di(meth)acrylates include, for instance, tricyclodecanediethanol diacrylate (A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), tricyclodecanediethanol dimethacrylate (DCP, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), polyethylene glycol dimethacrylate (4G, 9G, 14G, and 23G, etc., manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), ARONIX (registered trademark) M-220 (manufactured by TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-240 (manufactured by TOAGOSEI CO., LTD.). (Manufactured by CO.,LTD.), ARONIX (registered trademark) M-270 (manufactured by TOAGOSEI CO.,LTD.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.

[0373] Examples of polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0374] Examples of urethane dimethacrylates include, for example, propylene oxide-modified urethane dimethacrylates and ethylene oxide and propylene oxide-modified urethane dimethacrylates. Commercially available examples include, for example, 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), and UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.).

[0375] Examples of olefinic unsaturated compounds with three or more functions include, for example, dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and epoxide-modified versions of these.

[0376] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized olefinic unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), ethoxylated trimethylolpropane triacrylates (such as SR454, SR499, and SR502 manufactured by TOMOE Engineering Co., LTD.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., LTD., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., and EBECRYL 135 manufactured by DAI CEL-ALLNEX LTD.), and ethoxylated glycerol triacrylates (such as SHIN-NAKAMURA...). A-GLY-9E, etc. manufactured by CHEMICAL CO., LTD., ARONIX (registered trademark) T0-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0377] Furthermore, polymerizable compounds containing acid groups (such as carboxyl groups) can be used. These acid groups can form anhydride groups. Examples of polymerizable compounds containing acid groups include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0378] As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 can be used.

[0379] Free radical polymerizable monomers can be used alone or in combination of two or more.

[0380] The total mass of the free radical polymerizable monomer relative to the photosensitive composition layer is preferably 10.00 to 70.00% by mass, more preferably 20.00 to 60.00% by mass, and even more preferably 30.00 to 50.00% by mass.

[0381] <Free radical polymerization initiators>

[0382] The photosensitive composition layer preferably contains a free radical polymerization initiator.

[0383] As a free radical polymerization initiator, a known free radical polymerization initiator can be used, preferably a photoradical polymerization initiator.

[0384] Photoradical polymerization initiators are polymerization initiators that generate free radicals by receiving activating light such as ultraviolet light, visible light and X-rays, but are preferably compounds that generate free radicals by receiving ultraviolet light.

[0385] Examples of photoradical polymerization initiators include, for instance, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having an acylphosphine oxide structure, photopolymerization initiators having an N-phenylglycine structure, and photopolymerization initiators having a bis(triaryl)imidazolium structure. Preferably, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an N-phenylglycine structure, or photopolymerization initiators having a triarylbiimidazole structure are used, and more preferably, photopolymerization initiators having a triarylbiimidazole structure are used.

[0386] As a photopolymerization initiator having a triarylbiimidazole structure, 2,4,5-triarylimidazolium dimer and its derivatives are preferred. Specifically, examples include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

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

[0031] to

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

[0064] to

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

[0388] As photoradical polymerization initiators, examples include, for instance, ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisole (p,p'-dimethoxybenzoin), TAZ-110 (manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Kagaku Co., Ltd.), 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyl oxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone-1-(o-acetyl oxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGA... CURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one (Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (Omnirad) 1173 (manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins BV), and oxime ester photopolymerization initiators (Lunar 6, DKSH Japan K.K.).(manufactured), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyl oxime) (TR-PBG-326, Changzhou Tronly New Electronic Materials CO.,LTD.) (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

[0389] Free radical polymerization initiators can be used alone or in combination of two or more.

[0390] The content of the free radical polymerization initiator relative to the total mass of the photosensitive composition layer is preferably 1.00 to 15.00% by mass, more preferably 3.00 to 10.00% by mass.

[0391] The photosensitive composition layer may contain other components besides those described above.

[0392] <Sensers>

[0393] From a resolution perspective, the photosensitive composition layer preferably also contains a sensitizer.

[0394] Examples of sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds. Dialkylaminobenzophenone compounds, anthracene compounds, stilbeneylbenzene compounds, or styrylpyridine compounds are preferred, and dialkylaminobenzophenone compounds are more preferred.

[0395] Sensitizers can be used alone or in combination of two or more.

[0396] The content of the sensitizer relative to the total mass of the photosensitive composition layer is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass.

[0397] Pigment

[0398] From the viewpoints of visual recognizability of the exposed and unexposed areas, visual recognizability of the developed pattern, and resolution, the photosensitive composition layer preferably contains a pigment (also called "pigment N") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength changes due to acid, alkali, or free radicals. While the detailed mechanism is not fully understood, the inclusion of pigment N improves adhesion to adjacent layers and results in superior resolution.

[0399] In this specification, the phrase "the maximum absorption wavelength of the pigment changes due to acid, alkali or free radical" can refer to any of the following: a pigment in a chromogenic state is decolorized by acid, alkali or free radical; a pigment in a decolorized state is chromogenic by acid, alkali or free radical; or a pigment in a chromogenic state changes to a chromogenic state of other hues.

[0400] Specifically, pigment N can be a compound that changes color from a decolorized state upon exposure, or a compound that changes color from a color-developing state upon exposure. In this case, it can be a pigment that changes color or decolorization upon exposure by generating acids, bases, or free radicals within the photosensitive composition layer, or a pigment whose color or decolorization upon exposure is caused by changes in the state (e.g., pH) within the photosensitive composition layer by acids, bases, or free radicals. Furthermore, it can also be a pigment whose color or decolorization upon direct exposure to acids, bases, or free radicals as stimuli without exposure.

[0401] From the viewpoint of visual recognizability and resolution of the exposed and unexposed portions, pigment N is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to free radicals.

[0402] When the photosensitive composition layer is a negative photosensitive composition layer, from the viewpoint of visual distinguishability and resolution of the exposed and unexposed areas, the negative photosensitive composition layer preferably contains a pigment whose maximum absorption wavelength changes through free radicals and a photoradical polymerization initiator as pigment N.

[0403] Furthermore, from the viewpoint of visual recognizability of the exposed and unexposed parts, pigment N is preferably a pigment that develops color through acid, alkali or free radicals.

[0404] Examples of chromogenic mechanisms for pigment N include the addition of a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator to a photosensitive composition layer, followed by exposure, which generates free radicals, acids, or salts from the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator, thereby causing a radical-reactive pigment, an acid-reactive pigment, or an alkali-reactive pigment (e.g., a colorless pigment) to develop color.

[0405] From the viewpoint of visual recognition of the exposed and unexposed parts, the maximum absorption wavelength of pigment N in the wavelength range of 400-780nm during color development is preferably 550nm or more, more preferably 550-700nm, and even more preferably 550-650nm.

[0406] Furthermore, pigment N may have only one maximum absorption wavelength in the wavelength range of 400–780 nm for color development, or it may have two or more maximum absorption wavelengths in the same range. When pigment N has two or more maximum absorption wavelengths in the wavelength range of 400–780 nm for color development, the maximum absorption wavelength with the highest absorbance among these two or more maximum absorption wavelengths must be 450 nm or higher.

[0407] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (at a liquid temperature of 25°C) in an atmospheric environment using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) in the range of 400–780 nm, and detecting the wavelength at which the light intensity reaches its minimum (maximum absorption wavelength).

[0408] As pigments that develop or fade color through exposure, colorless compounds can be cited as an example.

[0409] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazines, xanthene, iminonaphthoquinone, azomethyl alkaloid, and anthraquinone pigments.

[0410] From the viewpoint of visual distinguishability of the exposed and unexposed parts, colorless compound is preferred as pigment N.

[0411] Examples of colorless compounds include, for example, colorless compounds with a triarylmethane skeleton (triarylmethane pigments), colorless compounds with a spiropyran skeleton (spiropyran pigments), colorless compounds with a fluorane skeleton (fluorane pigments), colorless compounds with a diarylmethane skeleton (diarylmethane pigments), colorless compounds with a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds with an indole phthaloyl lactone skeleton (indole phthaloyl lactone pigments), and colorless compounds with a colorless auramine skeleton (colorless auramine pigments).

[0412] Preferably, the pigments are triarylmethane pigments or fluorane pigments, and more preferably, they are colorless compounds (triphenylmethane pigments) or fluorane pigments having a triphenylmethane skeleton.

[0413] From the viewpoint of visual distinguishability of the exposed and unexposed areas, it is preferable for the colorless compound to have a lactone ring, a sultine ring, or a sulfonyl ring. This allows the lactone ring, sultine ring, or sulfonyl ring of the colorless compound to react with free radicals generated by a photoradical polymerization initiator or acids generated by a photocationic polymerization initiator, thereby decolorizing the colorless compound by changing it to a closed-ring state, or changing it to an open-ring state by making it colored. Preferably, the colorless compound is a compound having a lactone ring, sultine ring, or sulfonyl ring, and the color developing from the lactone ring, sultine ring, or sulfonyl ring through ring-opening by a free radical or acid; more preferably, it is a compound having a lactone ring and the color developing from the lactone ring through ring-opening by a free radical or acid.

[0414] As pigment N, examples include the following dyes and colorless compounds.

[0415] Among pigments N, specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfonphthalein, Xylenol Blue, methyl orange, p-methyl red, Congo red, benzopurpurine 4B, α-naphthalene red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Pink #312 (manufactured by Orient Chemical Industries). Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.) (Manufactured by Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanisto-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyoctadecylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0416] Among pigments N, specific examples of colorless compounds include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6 3-Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-dimethylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylamino Fluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-dimethylaminofluorane, 3-hydropiperidinyl-6-methyl-7-anilinofluorane, 3-pyrrolidinyl-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthaloyl lactone (Phthalide), 3,3-bis(1-n-butyl-2-methylindole- 3'-yl)phthaloyl lactone, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthaloyl lactone, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthaloyl lactone, 3'-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthaloyl lactone and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0417] From the viewpoint of visual recognizability of the exposed and unexposed areas, visual recognizability of the developed pattern, and resolution, pigment N is preferably a pigment that absorbs wavelength changes maximally through free radicals, and more preferably a pigment that develops color through free radicals.

[0418] As pigment N, the preferred options are colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate.

[0419] Pigment N can be used alone or in combination with two or more pigments.

[0420] From the perspective of visual recognizability of the exposed and unexposed areas, visual recognizability of the developed pattern, and resolution, the content of pigment N relative to the total mass of the photosensitive composition layer is preferably 0.10 to 10.00% by mass, more preferably 0.10 to 5.00% by mass, and even more preferably 0.10 to 1.00% by mass.

[0421] The content of pigment N represents the amount of pigment required to achieve a chromogenic state where all pigment N contained in the total mass of the photosensitive composition layer is in its chromogenic state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for pigment N content.

[0422] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment in 100 mL of methyl ethyl ketone. Irgacure OXE01 (product name, BASF Japan Ltd.) as a photoradical polymerization initiator was added to each of the obtained solutions, and the solutions were irradiated with 365 nm light, thereby generating free radicals and setting all the pigments to their chromogenic state. Subsequently, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under ambient atmospheric conditions, and calibration curves were constructed.

[0423] Next, 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the pigment. The absorbance of the solution in which the pigment was fully developed was then measured using the same method as described above. Based on the calibration curve, the pigment content in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer.

[0424] Rust Inhibitor

[0425] The photosensitive composition layer preferably also contains a rust inhibitor. Examples of rust inhibitors that can be contained in the aforementioned thermoplastic resin layer include this type of rust inhibitor.

[0426] Rust inhibitors can be used alone or in combination of two or more.

[0427] The content of the rust inhibitor relative to the total mass of the photosensitive composition layer is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass.

[0428] <Polymerization inhibitors>

[0429] The photosensitive composition layer preferably also contains a polymerization inhibitor. Examples of polymerization inhibitors that may be included in the above-mentioned thermoplastic resin layer can be cited as examples of polymerization inhibitors.

[0430] A polymerization inhibitor can be used alone or in combination of two or more.

[0431] The content of the polymerization inhibitor relative to the total mass of the photosensitive composition layer is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass.

[0432] <surfactants>

[0433] The photosensitive composition layer preferably also contains a surfactant. Examples of surfactants that can be contained in the aforementioned thermoplastic resin layer include those mentioned above.

[0434] Surfactants can be used alone or in combination of two or more.

[0435] The content of surfactant relative to the total mass of the photosensitive composition layer is preferably 0.001 to 5.00% by mass, more preferably 0.01 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass.

[0436] <Hydrogen-donating compounds>

[0437] The photosensitive composition layer may contain a hydrogen-donating compound. The hydrogen-donating compound has the following functions: further enhancing the sensitivity of the photopolymerization initiator to activating light and inhibiting the polymerization hindrance of polymerizable compounds caused by oxygen.

[0438] Examples of hydrogen-donating compounds include, for example, amines and amino acid compounds.

[0439] Examples of amines include compounds described in, for instance, the Journal of Polymer Society, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Application Publication No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0440] In view of the superior effects of the present invention, the amine is preferably selected from at least one of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0441] Examples of amino acid compounds include, for example, N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0442] In view of the superior effects of the present invention, N-phenylglycine is preferred as the amino acid compound.

[0443] Furthermore, examples of hydrogen-donating compounds include, for instance, organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Patent Application Publication No. 6-308727.

[0444] Hydrogen-donating compounds can be used alone or in combination of two or more.

[0445] From the perspective of improving the curing speed based on the balance between polymerization growth rate and chain transfer, the content of hydrogen-donating compound relative to the total mass of the photosensitive composition layer is preferably 0.01 to 10.00% by mass, more preferably 0.01 to 8.00% by mass, and even more preferably 0.03 to 5.00% by mass.

[0446] In addition to the above-mentioned components, the photosensitive composition layer may contain known additives as needed.

[0447] Examples of additives include chain transfer agents, polymerization inhibitors, antioxidants (e.g., phenidones), plasticizers, and particles (e.g., metal oxide particles). Other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Publication No. 2000-310706 may also be cited as other components.

[0448] <Properties of the Photosensitive Composite Layer>

[0449] From the perspective of resolution, the thickness of the photosensitive composition layer is preferably 1 to 30 μm, more preferably 2 to 20 μm.

[0450] Irradiate with ultraviolet light containing wavelengths of 365 nm to achieve an irradiation dose of 1000 mJ / cm at 365 nm. 2The transmittance (hereinafter also referred to as "resist transmittance") of the subsequent photosensitive composition layer is preferably 60% or more, more preferably 75% or more, and even more preferably 85% or more. The upper limit is 100% or less.

[0451] The transmittance of the above-mentioned resist can be determined by the following method.

[0452] The laminate T, obtained by peeling off the temporary support after bonding the transfer film to the glass from the side of the thermoplastic resin layer, is irradiated with ultraviolet light containing a wavelength of 365 nm, so that the irradiation dose at a wavelength of 365 nm reaches 1000 mJ / cm. 2 This process yields a laminate T after ultraviolet light irradiation. The transmittance of the photosensitive composition layer obtained by removing the thermoplastic resin layer and intermediate layer from the irradiated laminate T using an alkaline developing solution is measured using a spectrophotometer.

[0453] Regarding the ultraviolet light irradiation method mentioned above, the same method as the method for measuring T1000 / T0 of the transfer film mentioned above can be used.

[0454] [Protective film]

[0455] Transfer films can have a protective film on the photosensitive composition layer.

[0456] As a protective film, resin films with heat resistance and solvent resistance can be used. Examples include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0457] Furthermore, as a protective film, a resin film made of the same material as the temporary support described above can be used.

[0458] The protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0459] From the perspective of mechanical strength and economy, the thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and especially preferably 15 to 30 μm.

[0460] Furthermore, in the protective film, the number of fisheyes with a diameter of 80 μm or larger contained in the protective film is preferably 5 per μm. 2 The term "fisheye" refers to a film formed when foreign matter, undissolved substances, and oxidized deteriorated substances are mixed into the film during the manufacturing process of heating and melting materials and then producing a film through methods such as mixing, extrusion, biaxial stretching, and casting coating.

[0461] The number of particles with a diameter of 3 μm or larger contained in the protective film is preferably 30 particles / mm.2 The following is more preferably 10 pieces / mm 2 The following is a further preferred option: 5 per mm 2 Therefore, it is possible to suppress defects caused by uneven transfer of particles contained in the protective film onto the photosensitive composition layer or metal layer.

[0462] From the perspective of imparting rollability, the arithmetic mean roughness Ra of the surface of the protective film and the side opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0463] From the perspective of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0464] [Manufacturing method of transfer film]

[0465] There are no particular restrictions on the manufacturing method of transfer film, and well-known methods can be cited.

[0466] As Figure 1 The manufacturing method of the transfer film 10 shown may include, for example, a method comprising the following steps: coating a thermoplastic resin layer forming composition onto the surface of a temporary support 12 to form a coating film, and then drying the coating film to form a thermoplastic resin layer 14; coating an intermediate layer forming composition to form a coating film, and then drying the coating film to form an intermediate layer 16; and coating a photosensitive composition layer forming composition onto the surface of the intermediate layer 16 to form a coating film, and then drying the coating film to form a photosensitive composition layer 18.

[0467] Through the above process, a transfer film 10 can be manufactured by sequentially stacking a temporary support 12, a thermoplastic resin layer 14, an intermediate layer 16, and a photosensitive composition layer 18.

[0468] When the transfer film 10 has a protective film 20, the protective film 20 can be pressed onto the photosensitive composition layer 18 of the transfer film 10 manufactured by the above manufacturing method.

[0469] After manufacturing the transfer film 10 by the above manufacturing method, a roll-shaped transfer film can be produced and stored by winding the transfer film 10. The roll-shaped transfer film 10 can be provided in its original form to the roll-to-roll bonding process with the substrate described later.

[0470] <Composition for forming thermoplastic resin layers and method for forming thermoplastic resin layers>

[0471] There are no particular limitations on the method for forming a thermoplastic resin layer on a temporary support, and known methods can be used. For example, it can be formed by coating a thermoplastic resin layer forming composition onto the temporary support and drying it as needed.

[0472] The composition for forming a thermoplastic resin layer preferably includes various components and solvents for forming the aforementioned thermoplastic resin layer. Furthermore, in the composition for forming a thermoplastic resin layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the aforementioned thermoplastic resin layer.

[0473] As a solvent, there are no particular limitations as long as it can dissolve or disperse all components other than the solvent, and known solvents can be used. Examples of solvents that are the same as those contained in the compositions for forming photosensitive compositions described later can be cited, and are preferably the same.

[0474] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 100 to 900 parts by mass.

[0475] The method of forming the thermoplastic resin layer is not particularly limited as long as it is a method that can form a layer containing the above-mentioned components. For example, well-known coating methods (slot coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0476] <Composition for forming an intermediate layer and method for forming an intermediate layer>

[0477] As a composition for forming an intermediate layer, it is preferable to include various components and solvents for forming the intermediate layer described above. Furthermore, in the composition for forming an intermediate layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the intermediate layer described above.

[0478] As a solvent, it is not particularly limited as long as it can dissolve or disperse all components other than the solvent. It is preferably selected from at least one of water and water-mixed organic solvents, and more preferably water or a mixture of water and water-mixed organic solvents.

[0479] Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0480] It can be used alone or in combination with two or more solvents.

[0481] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0482] The method of forming the intermediate layer composition is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0483] <Composition for forming a photosensitive composition layer and method for forming a photosensitive composition layer>

[0484] From the perspective of excellent productivity and ease of forming the above-mentioned photosensitive composition layer, the photosensitive composition layer is preferably formed by coating a composition for forming the photosensitive composition layer containing the components constituting the above-mentioned photosensitive composition layer (e.g., alkali-soluble thermoplastic resin, monomers having free radical polymerizable groups and free radical polymerization initiators, etc.) and a solvent.

[0485] As a composition for forming a photosensitive composition layer, it is preferable to include various components and solvents for forming the photosensitive composition layer described above. Furthermore, in the composition for forming a photosensitive composition layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above.

[0486] As a solvent, there are no particular limitations as long as it can dissolve or disperse all components other than the solvent itself, and known solvents can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0487] As a solvent, it is preferred to include at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, it is a mixed solvent including at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from ketone solvents and cyclic ether solvents. More preferably, it is a mixed solvent including at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0488] Examples of alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0489] Examples of solvents for alkylene glycol ether acetates include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0490] As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated into this specification.

[0491] It can be used alone or in combination with two or more solvents.

[0492] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass.

[0493] Examples of coating methods for forming photosensitive composition layers include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0494] The preferred drying method for the coating film of the photosensitive composition for forming the layer is heating drying or vacuum drying. The preferred drying temperature is 80°C or higher, more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, more preferably 120°C or lower. The drying process can also be achieved by continuously changing the temperature.

[0495] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. While there is no particular limitation on the upper limit, it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0496] Furthermore, a transfer film can be manufactured by laminating a protective film onto a photosensitive composition layer. The method for laminating the protective film onto the photosensitive composition layer is not particularly limited, and known methods can be cited.

[0497] As a device for attaching a protective film to a photosensitive composition layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0498] The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heating.

[0499] 〔use〕

[0500] The transfer film of this invention is applicable to a variety of uses. For example, it can be used for electrode protective films, insulating films, planarization films, outer coating films, hard coating films, passivation films, separators, spacers, microlenses, filters, anti-reflective films, etching resists, and plated components. More specific examples include protective or insulating films for touch panel electrodes, protective or insulating films for printed circuit boards, protective or insulating films for TFT substrates, color filters, outer coating films for color filters, etching resists and plating resists used to form wiring, and metal masks with tiny through holes used in the manufacture of OLD (Organic Light Emitting Diode) devices.

[0501] Regarding the transfer film of the present invention, it is preferably used to manufacture a laminate having a conductor pattern, and more specifically, it is preferably used for the formation of an etch resist or a plating resist for forming the conductor pattern.

[0502] [Method for manufacturing a laminate with a conductor pattern]

[0503] The method for manufacturing the laminate with the conductor pattern is not particularly limited as long as the method of the transfer film of the present invention is used, and the following method is preferred.

[0504] In the bonding process, the transfer film of the present invention described above is bonded to the metal layer of a substrate having a metal layer on its surface in such a way that the photosensitive composition layer side is in contact with the metal layer of the substrate.

[0505] In the exposure process, the photosensitive composition layer is patterned and exposed from the side opposite to the substrate side.

[0506] In the developing process, an alkaline developing solution is used to develop the above-exposed photosensitive composition layer to form a resist pattern.

[0507] Etching the metal layer in the area where the resist pattern is not provided to form a conductor pattern is performed in either the etching process or the plating process.

[0508] The resist stripping process involves stripping the resist pattern described above; and

[0509] In addition to the above-described plating process, a removal process is further provided to remove the metal layer exposed by the above-described resist stripping process and form a conductor pattern on the substrate.

[0510] The specific steps of the above manufacturing method will be described in detail below.

[0511] [Stripping process]

[0512] When the transfer film has a protective film, the above manufacturing method preferably includes a peeling step that removes the protective film from the transfer film before the lamination step. If the peeling step is performed, the surface of the photosensitive composition layer of the transfer film is exposed.

[0513] The method for peeling off the protective film is not particularly limited and can be carried out using known methods. For example, the protective film can be rolled up and then peeled off.

[0514] [Lamination process]

[0515] The bonding process is a process of bonding a transfer film in such a way that the photosensitive composition layer side is in contact with the metal layer of a substrate having a metal layer on its surface.

[0516] If a bonding process is performed, a laminate (a substrate with a photosensitive composition layer) can be obtained, which sequentially comprises a substrate, a conductive layer, a thermoplastic resin layer, an intermediate layer, a photosensitive composition layer, and a temporary support.

[0517] The substrate having the aforementioned conductive layer has a conductive layer on the substrate, and any layer can be formed as needed. That is, the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0518] Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.

[0519] Preferred substrate materials are described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference. The preferred materials for the resin substrate are cyclic olefin polymers and polyimide. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0520] From the perspective of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer selected from metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers and conductive polymer layers.

[0521] Furthermore, a single conductive layer or two or more conductive layers can be disposed on the substrate. When two or more conductive layers are disposed, conductive layers of different materials are preferred.

[0522] Preferred methods for conductive layers are described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0523] The conductive layer can also be a transparent conductive layer that can form a transparent electrode through the processes described later. As a transparent conductive layer, it is preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal wires such as metal mesh and metal nanowires.

[0524] Examples of fine metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0525] The thickness of the conductive layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more. The upper limit is preferably 10 μm or less, more preferably 2 μm or less.

[0526] In the above bonding process, it is preferable to press the conductive layer and the photosensitive composition layer in such a way that their surfaces come into contact.

[0527] There are no particular limitations on the above-mentioned lamination method, and known transfer methods and lamination methods can be used. Among them, it is preferable to overlap the surface of the photosensitive composition layer onto a substrate having conductive parts and perform pressure and heating based on rollers or the like.

[0528] The bonding process can utilize known laminators such as vacuum laminators and automatic cutting laminators.

[0529] The lamination temperature is not particularly limited, but is preferably 70 to 130°C.

[0530] [Exposure process]

[0531] The exposure process is a process of patterning the photosensitive composition layer from the side opposite to the substrate side. By performing the exposure process and the development process described later, a resist pattern protecting at least a portion of the conductive layer is formed on the conductive layer on the substrate.

[0532] In addition, here, "pattern exposure" refers to exposure in a patterned manner, that is, exposure with exposed and non-exposed areas.

[0533] The positional relationship between the exposed and unexposed areas in a pattern exposure is not particularly restricted and can be adjusted appropriately.

[0534] As the light source for pattern exposure, any light source capable of illuminating light in a wavelength range sufficient to cure the photosensitive composition layer (e.g., 365 nm or 405 nm) can be appropriately selected and used. Preferably, the dominant wavelength of the exposure light for pattern exposure is 365 nm. Furthermore, the dominant wavelength is the wavelength with the highest intensity.

[0535] As light sources, examples include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0536] The preferred exposure level is 5–200 mJ / cm. 2 More preferably 10–200 mJ / cm 2 .

[0537] Exposure methods include, for example, mask exposure, direct imaging exposure and projection exposure, with projection exposure being preferred.

[0538] Preferred methods for the light source, exposure amount, and exposure method used in the exposure are described, for example, in paragraphs

[0146] to

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

[0539] [Temporary support stripping process]

[0540] The manufacturing method described above preferably includes a temporary support peeling step. The temporary support peeling step is preferably performed between the bonding step and the exposure step, or between the exposure step and the development step described later, before the exposure step (specifically, between the bonding step and the exposure step).

[0541] The peeling method is not particularly limited and can use the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

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

[0542] [Developing process]

[0543] The developing process involves using an alkaline developing solution to develop the exposed photosensitive composition layer to form a resist pattern. When the photosensitive composition layer is a negative photosensitive composition layer, the unexposed portion of the photosensitive composition layer is removed by the alkaline developing solution to form an exposed photosensitive composition layer as a resist pattern. Furthermore, it is preferable to remove the thermoplastic resin layer and the intermediate layer through the developing process.

[0544] The alkaline developing solution is preferably an alkaline aqueous solution.

[0545] Examples of alkaline compounds that can be included in alkaline developing solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0546] Examples of development methods include paddle development, spray development, spin development, and immersion development.

[0547] As a preferred developer used in this specification, for example, the developer described in paragraph

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

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

[0548] It is also preferable to perform a rinsing process to remove residual developer from the substrate with the conductive layer after development and before moving to the next process. Water or the like can be used in the rinsing process.

[0549] After development and / or rinsing, a drying process can be performed to remove excess liquid from the substrate with the conductive layer.

[0550] In the manufacturing method of a laminate with a conductor pattern, either an etching process or a plating process is performed.

[0551] [Etching process]

[0552] The etching process is a process of etching the metal layer located in the area where the resist pattern is not provided to form a conductor pattern.

[0553] As a method for etching, known methods can be applied, such as the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Application Publication No. 2017-120435, the methods described in paragraphs

[0048] to

[0054] of Japanese Patent Application Publication No. 2010-152155, wet etching methods immersed in etching solution, and dry etching methods based on plasma etching, etc.

[0554] For wet etching, the etching solution can be appropriately selected as either acidic or alkaline depending on the object being etched.

[0555] Examples of acidic etching solutions include aqueous solutions of individual acidic components selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous solutions of acidic components mixed with salts selected from ferric chloride (III), ammonium fluoride, and potassium permanganate. The acidic component can also be a combination of multiple acidic components.

[0556] Examples of alkaline etching solutions include aqueous solutions of the alkaline component alone, selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of the alkaline component mixed with salts (such as potassium permanganate). The alkaline component can also be a combination of multiple alkaline components.

[0557] [Plating process]

[0558] The plating process is a process of plating a conductive layer on areas where no resist pattern is provided.

[0559] As a plating process, electroplating and chemical plating are examples, with electroplating being preferred from a productivity standpoint.

[0560] If a plating process is performed, a plating layer is obtained on the substrate with a conductive layer that has the same pattern shape as the area (opening of the resist pattern) where no resist pattern is provided.

[0561] When performing a plating process, the conductive layer is preferably a metal layer.

[0562] As for the metal contained in the plating layer, for example, well-known metals can be cited.

[0563] Specifically, examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals.

[0564] From the perspective of improving the conductivity of the conductor pattern, the plating layer preferably contains copper or its alloy. Furthermore, from the perspective of improving the conductivity of the conductor pattern, the plating layer preferably contains copper as the main component.

[0565] The thickness of the coating layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit is preferably 20 μm or less.

[0566] [Resist stripping process]

[0567] In the above-described method for manufacturing a laminate with a conductor pattern, a resist stripping process is included after the etching process or the plating process.

[0568] The resist stripping process is the process of removing the residual resist pattern.

[0569] The method for removing resist patterns is not particularly limited, and methods such as removal by chemical treatment are exemplified, with removal by a removal solution being preferred.

[0570] As a removal method, one example is to immerse a substrate with residual resist patterns in a removal solution at a temperature preferably 30 to 80°C, more preferably 50 to 80°C, under stirring for 1 to 30 minutes.

[0571] Examples of removal solutions include those prepared by dissolving an inorganic or organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic base components include sodium hydroxide and potassium hydroxide. Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0572] Furthermore, it can also be removed using a removal liquid and by known methods such as spraying, scrubbing, and paddle stirring.

[0573] [Removal process]

[0574] In the method for manufacturing the laminate, when a plating process is performed, a removal process is included, which removes the metal layer exposed by the resist stripping process to form a conductor pattern on the substrate.

[0575] The method for removing the conductive layer is not particularly limited, but a known etching solution is preferred.

[0576] Examples of known etching solutions include ferric chloride (III) solution, copper chloride (II) solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0577] If a removal process is performed, the conductive layer exposed on the surface is removed from the substrate, and a plated layer with a patterned shape (conductor pattern) remains, thereby obtaining a laminate with a conductor pattern.

[0578] The upper limit for the linewidth of the formed conductor pattern is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is not particularly limited, but is often greater than 1 μm.

[0579] [Other processes]

[0580] The manufacturing method of a laminate with a conductor pattern may include any steps other than those described above (other steps).

[0581] For example, the process of reducing visible light reflectivity described in paragraph

[0172] of International Publication No. 2019 / 022089, and the process of forming a new conductive layer on an insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089, can be cited, but are not limited to these processes.

[0582] <Process for reducing visible light reflectivity>

[0583] A method for manufacturing a laminate with a conductor pattern may include a process of performing a treatment to reduce the visible light reflectivity of some or all of the multiple conductive layers of a substrate.

[0584] Oxidation is an example of a process to reduce visible light reflectivity. When the substrate has a conductive layer containing copper, oxidizing the copper produces copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer.

[0585] The treatment for reducing visible light reflectivity is described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, the contents of which are incorporated into this specification.

[0586] <The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film>

[0587] The manufacturing method of the laminate with conductor pattern also preferably includes a step of forming an insulating film on the surface of the conductor pattern and a step of forming a new conductive layer on the surface of the insulating film.

[0588] The above process can form a second electrode pattern that is insulated from the first electrode pattern.

[0589] The process of forming an insulating film is not particularly limited, and well-known methods for forming permanent films can be cited. Furthermore, an insulating photosensitive material with insulating properties can be used, and an insulating film with the desired pattern can be formed by photolithography.

[0590] The process of forming a new conductive layer on an insulating film is not particularly limited. For example, a conductive photosensitive material can be used, and a new conductive layer with the desired pattern can be formed by photolithography.

[0591] The manufacturing method of the laminate with conductor patterns preferably uses a substrate having multiple conductive layers on each of its two surfaces, and forms circuits sequentially or simultaneously on the conductive layers formed on the two surfaces of the substrate. With this configuration, a laminate with conductor patterns for a touch panel formed on one surface of the substrate and a second conductor pattern formed on the other surface can be formed. Furthermore, it is also preferable to form the laminate with the conductor patterns for a touch panel having this configuration from both sides of the substrate in roll-to-roll fashion.

[0592] [Applications of laminates with conductor patterns]

[0593] The laminate with conductor patterns manufactured by the above-described manufacturing method can be applied to various devices. Examples of devices equipped with the laminate with conductor patterns manufactured by the above-described manufacturing method include display devices, printed circuit boards, semiconductor packages, and input devices (e.g., touch panels), preferably printed circuit boards or semiconductor packages. Furthermore, the aforementioned input devices can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[0594] Example

[0595] The present invention will now be described in further detail with reference to embodiments.

[0596] The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0597] In the following embodiments, unless otherwise specified, “parts” and “%” are quality bases.

[0598] Furthermore, in the following embodiments, the acid value used is the theoretical acid value.

[0599] [Manufacturing of transfer film]

[0600] The composition and components of each layer used to make the transfer film are explained below.

[0601] [Photosensitive composition layer]

[0602] The composition of each photosensitive composition layer in each transfer film described later is shown in Table 1. The values ​​for each component are relative to the total solids content (mass %).

[0603] [Table 1]

[0604]

[0605] The details of each ingredient are as follows.

[0606] <Resin>

[0607] Resins A1 to A3 are synthesized using known methods. Table 2 below shows the types and mass ratios (mass%) of each monomer used in the synthesis of resins A1 to A3, as well as their weight-average molecular weights.

[0608] In addition, the weight-average molecular weight (Mw) of the synthesized resins A1 to A3 was determined by GPC under the following conditions.

[0609] Equipment: Manufactured by TOSOH CORPORATION; TOSOH CORPORATION high-speed GPC device HLC-842OGPC (product name)

[0610] Protective tubing: Manufactured by TOSOH CORPORATION, HZ-L

[0611] Separation column: A column manufactured by TOSOH CORPORATION, consisting of three TSK gel Super HZM-N (product name) tubes connected in series.

[0612] Measurement temperature: 40℃

[0613] Eluent: THF (Tetrahydrofuran)

[0614] Flow rates: Sample pump 0.35 mL / min, Reference pump 0.175 mL / min

[0615] Injection volume: 10 μL

[0616] Detector: Differential refractometer

[0617] GPC column calibration standard solution: Standard polystyrene manufactured by TOSOH CORPORATION

[0618] [Table 2]

[0619] A1 A2 A3 St 55 40 40 MAA 25 25 25 MMA 20 5 5 MAA-GMA 30 30 Weight-average molecular weight (Mw) 25,000 25,000 18,000

[0620] The following abbreviations represent the following compounds.

[0621] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0622] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0623] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0624] MAA-GMA: A structural unit derived from methacrylic acid was added to a glycidyl methacrylate structural unit.

[0625] The acid value of resin A1 is 160 mg KOH / g. A solution containing resin A1 at a solid content concentration of 30% by mass (solvent: propylene glycol monomethyl ether acetate (PGMEA)) was prepared as the resin A1 solution.

[0626] The acid value of resin A2 is 160 mg KOH / g. A solution containing resin A2 at a solid content concentration of 30% by mass (solvent: PGMEA) was prepared as the resin A2 solution.

[0627] The acid value of resin A3 is 160 mg KOH / g. A solution containing resin A3 at a solid content concentration of 30% by mass (solvent: PGMEA) was prepared as the resin A3 solution.

[0628] The above-described resin solutions A1 to A3 are used in the preparation of the composition for forming the photosensitive composition layer, which will be described later. Furthermore, the resin content in Table 1 refers to the amount of solid components.

[0629] <Other ingredients>

[0630] The detailed information of each component other than the resin in Table 1 is as follows.

[0631] (Free radical polymerizable monomers)

[0632] BPE-500: 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane, manufactured by S HIN-NAKAMURACHEMICAL CO,LTD.

[0633] BPE-100: 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by SHIN-NAKA MURACHEMICAL CO,LTD.

[0634] M-270: Polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD.

[0635] (Polymerization initiator)

[0636] B-CIM: 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford Corporation

[0637] (Sensitizer)

[0638] ·SB-PI701: 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.

[0639] (Chain transfer agent)

[0640] Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by FUJIFILM Wako Pure Chemical Corporation

[0641] (pigment)

[0642] • LCV: Colorless crystal violet, manufactured by Tokyo Chemical Industry Co., Ltd.

[0643] (Rust inhibitor)

[0644] • CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD

[0645] (polymerization inhibitor)

[0646] • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0647] (surfactant)

[0648] EXP.S-315, manufactured by DIC CORPORATION

[0649] MEGAFACE (registered trademark) F-552, manufactured by DIC CORPORATION.

[0650] <Preparation of compositions for forming photosensitive composition layers>

[0651] After mixing the above-mentioned components as shown in Table 1, methyl ethyl ketone (MEK) was added to prepare a photosensitive composition layer forming composition with a solid component concentration of 15% by mass.

[0652] [Intermediate layer]

[0653] The composition of each intermediate layer in each transfer film described later is shown in Table 3. The values ​​for each component are relative to the total solids content (mass %).

[0654] [Table 3]

[0655]

[0656] The details of each ingredient are as follows.

[0657] (resin)

[0658] • PVA: Polyvinyl alcohol, product name "KURARAY POVALPVA-205", manufactured by Kuraray Co., Ltd.

[0659] • PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd.

[0660] • HPMC: Hydroxypropyl methylcellulose, product name "METOLOSE 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

[0661] (surfactant)

[0662] • BYK-345: Manufactured by BYK Japan KK.

[0663] (Photochromic compounds)

[0664] ·4-(N,N-dimethylamino)diazobenzenetetrafluoroborate, manufactured by FUJIFILM Wako Pure Chemical Corporation

[0665] <Preparation of the composition for forming the intermediate layer>

[0666] After mixing the components as shown in Table 3, a solvent (a mixed solvent prepared by mixing ion-exchanged water and methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) in a mixing ratio of 40 / 60 (ion-exchanged water / methanol [mass ratio]) was added, thereby preparing an intermediate layer forming composition with a solid component concentration of 5% by mass.

[0667] [Thermoplastic resin layer]

[0668] The composition of each thermoplastic resin layer in each transfer film described later is shown in Table 4. The values ​​for each component are relative to the total solids content (mass %).

[0669] [Table 4]

[0670]

[0671] The details of each ingredient are as follows.

[0672] <Resin>

[0673] The types and mass ratios (mass%) of each monomer used in the synthesis of resin A4, as well as the weight-average molecular weight, are shown in Table 5. The weight-average molecular weight was determined using the same method as that used for resins A1 to A3 described above.

[0674] [Table 5]

[0675]

[0676] The following abbreviations represent the following compounds.

[0677] BzMA: Benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0678] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0679] AA: Acrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0680] <Other ingredients>

[0681] The detailed information of each component other than the resin in Table 4 is as follows.

[0682] (Plasticizers with polymerizable groups)

[0683] • A-DCP: Tricyclodecanedimethyl diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.

[0684] ·8UX-015: Multifunctional carbamate acrylate compound, manufactured by TAISEI FINE CHEMICAL CO., LTD.

[0685] TO-2349: A polyfunctional acrylate compound with a carboxyl group, manufactured by TOAGOSEI CO., LTD.

[0686] (Rust inhibitor)

[0687] • CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD

[0688] (polymerization inhibitor)

[0689] • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0690] (Photochromic compounds)

[0691] Compound 1: A compound with the structure shown below, having a molar absorptivity of 15000 L·mol⁻¹. -1 cm -1

[0692] [Chemical Formula 12]

[0693]

[0694] -Synthesis of Compound 1-

[0695] Compound 1 was synthesized according to the following steps.

[0696] 15.0 g of 1-nitroso-2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.), 130.5 g of toluene (manufactured by FUJIFILM Wako Pure Chemical Corporation), 150 g of distilled water, and 37.7 g of sodium bisulfite (manufactured by FUJIFILM Wako Pure Chemical Corporation) were mixed and stirred at 25°C for 4 hours. The ice-cooled distilled water was filtered to obtain 13.1 g of intermediate 1-A.

[0697] 4.8 g of intermediate 1-A, 6.3 g of toluene (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 5.3 g of methyl trimethylacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 4 hours until reaching 140°C. After natural cooling, methanol was added for ice cooling, and the mixture was filtered to obtain 5.8 g of intermediate 1-B.

[0698] Intermediate 1-B, 15.1 g of toluene, and 0.77 g of p-toluenesulfonic acid monohydrate (manufactured by FUJIFILM WakoPure Chemical Corporation) were added, and the mixture was stirred at 120 °C for 2 hours. After natural cooling, distilled water and ethyl acetate were added, and the organic phase was separated to obtain a solution of intermediate 1-C.

[0699] 14.9 g of THF was mixed with 11.8 g of intermediate 1-C solution, and 4.0 g of 2M hydrochloric acid was added dropwise under ice cooling, followed by the addition of amyl nitrite (manufactured by FUJIFILM Wako Pure Chemical Corporation) (2.5 g). The mixture was heated to room temperature (25°C) and stirred for 2 hours. Water and ethyl acetate were added to the resulting reaction mixture, and the mixture was separated. After washing the organic phase with water, the mixture was dried over magnesium sulfate, filtered, and concentrated to obtain intermediate 1-D.

[0700] Intermediate 1-D was mixed with acetone (18 mL), and under ice-cooling conditions, triethylamine (manufactured by FUJIFILM WakoPure Chemical Corporation) (4.9 g) and p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.9 g) were added. The mixture was then heated to room temperature and stirred for 1 hour. Water was added to the resulting reaction mixture, followed by crystallization, filtration, and washing with water to obtain crude compound 1. Ethyl acetate and THF were added to 3.4 g of crude compound 1, and the mixture was heated to 50 °C to dissolve it. Methanol was then added, and the mixture was ice-cooled, stirred for 1 hour, filtered, and dried to obtain 2.9 g of compound 1.

[0701] Compound 2: The compound with the structure shown below was synthesized according to the method described in Japanese Patent Application Publication No. 2013-47765

[0227] . Molar absorptivity: 7900 L·mol⁻¹ -1 cm -1

[0702] [Chemical Formula 13]

[0703]

[0704] ·4-(N,N-dimethylamino)benzenediazotetrafluoroborate, molar absorptivity 10000 L·mol⁻¹ -1 cm -1

[0705] ·BAPO: A compound with the structure shown below, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, with a molar absorptivity of 9000 L·mol⁻¹. -1 cm -1

[0706] [Chemical Formula 14]

[0707]

[0708] (surfactant)

[0709] EXP.S-315, manufactured by DIC CORPORATION

[0710] <Preparation of compositions for thermoplastic resin layer formation>

[0711] After mixing the components as shown in Table 5, solvents (MEK, PGMEA) were added, thereby producing a thermoplastic resin layer forming composition with a solid component concentration of 25% by mass.

[0712] [Manufacturing of transfer film]

[0713] Each transfer film, consisting of a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer, was fabricated in the manner shown in Tables 6 to 8 below.

[0714] Specifically, as described below.

[0715] First, on a temporary support (16 μm thick, manufactured by Toray Industries, Inc., 16KS40), a thermoplastic resin layer forming composition for forming the thermoplastic resin layer shown in the table below is dried and then coated using a slit nozzle, so that the coating width is 1.0 μm and the film thickness after drying is the value recorded in Tables 6 to 8, and then passed through a drying zone at 80°C for 40 seconds, thereby forming a thermoplastic resin layer.

[0716] Next, the intermediate layer forming composition for forming the intermediate layers shown in Tables 6-8 is dried and coated onto the thermoplastic resin layer using a slit nozzle, so that the coating width is 1.0 μm and the film thickness after drying is the value recorded in Tables 6-8, and the intermediate layer is formed by passing it through a drying zone at 80°C for 40 seconds.

[0717] Furthermore, on the intermediate layer, the photosensitive composition layer forming composition used to form the photosensitive composition layer shown in Tables 6-8 is dried using a slit nozzle and then coated so that the coating width is 1.0 μm and the film thickness after drying is the value recorded in Tables 6-8. The photosensitive composition layer is then formed by passing the coating through a drying zone at 80°C for 40 seconds.

[0718] A 16μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40) is pressed onto it as a protective film to make a transfer film, and then wound into a roll.

[0719] [Determination of physical properties of transfer film]

[0720] [T1000 / T0]

[0721] The value of T1000 / T0 was determined by the following steps.

[0722] Each of the prepared transfer films was laminated onto the glass with the photosensitive composition layer side in contact with the glass, and the temporary support was peeled off, thereby obtaining a laminate T of glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer. The transmittance T0 of the laminate T at 365 nm without exposure was measured using a spectrophotometer.

[0723] Next, a high-pressure mercury lamp was used as the light source to expose the laminate T from the thermoplastic resin layer side, so that the illuminance of ultraviolet light containing 365nm light at 365nm reached 1000mJ / cm². 2 The transmittance T1000 of the exposed laminate T at 365 nm was measured using a spectrophotometer. Based on the obtained values ​​of T0 and T1000, the value of T1000 / T0 was calculated.

[0724] The aforementioned spectrophotometer used was the UV-1800 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation.

[0725] [Resist transmittance]

[0726] The transmittance of the resist was determined using the following method.

[0727] The exposed laminate T used in the above T1000 measurement was subjected to a development process to remove the thermoplastic resin layer and the intermediate layer, thereby obtaining the exposed photosensitive composition layer. The transmittance of the exposed photosensitive composition layer at 365 nm was measured using a spectrophotometer.

[0728] In addition, in the above-mentioned development process, a sodium carbonate aqueous solution at 30°C (the content of sodium carbonate was 1% by mass relative to the total mass of the sodium carbonate aqueous solution) was used as the developer, and spray development was performed for 2.0 times the shortest development time.

[0729] [evaluate]

[0730] [Resolution]

[0731] The resolution of the pattern formed by the transfer film was evaluated by following these steps.

[0732] Cu sputtering was performed on the surface of a 0.7 mm thick silicon wafer with a thickness of 200 nm to obtain a substrate with a metal layer.

[0733] The transfer films of each example were laminated onto the substrate with the photosensitive composition layer in contact with the conductor layer. The bonding process (lamination process) was performed using a heated roller at 100°C and a pressure of 0.7 MPa at a speed of 2 m / min.

[0734] Next, the temporary support was stripped, and a mask with a wiring pattern (L = 1–2 μm, 0.1 μm scale, 10 pieces) containing a line (L) / space (S) ratio of 1 / 1 (width ratio) was used. The pattern was exposed using a projection exposure apparatus with a theoretical optical resolution of 1.5 μm and a high-pressure mercury lamp as the light source. Exposure was performed using a Stouffer 41-step trapezoidal plate, and development was performed for 2.0 times the shortest development time, with the exposure set to 13 residual trapezoidal steps.

[0735] As the developer, a sodium carbonate aqueous solution at 30°C (sodium carbonate content is 1% by mass relative to the total mass of the sodium carbonate aqueous solution) is used for spray development for 2.0 times the shortest development time to remove unexposed areas and form a resist pattern on the surface of the metal layer, thereby obtaining a patterned laminate.

[0736] After the above development, the minimum L / S (μm / μm) of the smallest pattern without residue or peeling is used as the resolution of the resist. In practical use, the minimum L / S is preferably 1.4 / 1.4 (μm / μm) or less.

[0737] [Reproducibility]

[0738] The inhibitory effect (developability) on the decrease in development rate was evaluated through the following steps.

[0739] In the above-mentioned evaluation of [resolution], the development time was set to 1.5 times the shortest development time. Otherwise, patterned laminates were manufactured using the same steps. Regarding the obtained pattern, the pattern with the smallest L / S without residue or peeling obtained in the above-mentioned evaluation of [resolution] was observed, and the developability was evaluated according to the following evaluation criteria.

[0740] A: No residue was observed.

[0741] B: Residue was observed in space.

[0742] [Surface-like fault]

[0743] The bonding process was performed using the same steps as described above regarding [resolution]. Next, the surface exposed after peeling off the temporary support was examined using an optical microscope (OLYMPUS M X63 industrial inspection microscope) with a field of view of 0.25 mm². 2 The surface faults were evaluated according to the following evaluation criteria, with five random areas (1mm × 1mm) on the surface observed.

[0744] A: No particles or cracks were observed.

[0745] B: At least one of the particles and cracks was observed.

[0746] [result]

[0747] The structure and evaluation results of each transfer film are shown in Tables 6-8 below.

[0748] In the table, "photosensitive composition layer", "intermediate layer" and "thermoplastic resin layer" respectively indicate the types of layers constituting each transfer film. For example, the transfer film of Example 1 has a photosensitive composition layer 1, an intermediate layer 1 and a thermoplastic resin layer 1.

[0749] In the table, the "Photochromic Compound / Inhibitor" column indicates the mass ratio of the content of photochromic compound to the content of inhibitor in the thermoplastic resin layer.

[0750] [Table 6]

[0751]

[0752] [Table 7]

[0753]

[0754] [Table 8]

[0755]

[0756] The results shown in the table above confirm that the transfer film of the present invention can form patterns with excellent resolution and suppresses the decrease in development speed.

[0757] Based on the comparison of Examples 1 to 3, it was confirmed that when the thickness of the thermoplastic resin layer is 3 μm or more, the resolution is better, and when the thickness of the thermoplastic resin layer is 8 μm or more, the resolution is further improved.

[0758] Based on the comparisons of Examples 1-3 and 11-20, it was confirmed that when T1000 / T0 ≥ 10, the resolution is superior; when T1000 / T0 ≥ 50, the resolution is further superior; and when T1000 / T0 ≥ 500, the resolution is particularly superior. Furthermore, it was confirmed that when T1000 / T0 ≤ 5000, planar faults can be suppressed.

[0759] Comparisons of Examples 11-20 confirmed that when the mass ratio of the content of the photodecolorizing compound to the content of the polymerization inhibitor is 350 or less, planar defects can be further suppressed, and when the mass ratio is 300 or less, the decrease in development speed can be further suppressed. Furthermore, it was confirmed that when the mass ratio is 10 or more, the resolution is superior, and when the mass ratio is 30 or more, the resolution is further superior.

[0760] Comparisons of Examples 11-20 confirmed that when the content of the photodecolorizing compound relative to the total mass of the thermoplastic resin layer is 5.00% by mass or more, the resolution is superior; and when the content of the photodecolorizing compound relative to the total mass of the thermoplastic resin layer is 8.00% by mass or more, the resolution is further superior. Furthermore, it was confirmed that when the content of the photodecolorizing compound relative to the total mass of the thermoplastic resin layer is 40.00% by mass or less, surface defects can be further suppressed.

[0761] According to the comparison of Examples 11 to 20, it was confirmed that when the content of the polymerization inhibitor is 0.04% by mass or more relative to the total mass of the thermoplastic resin layer, the decrease in development speed can be further suppressed.

[0762] A comparison of Examples 11 and 18 confirmed that the resolution was superior when the intermediate layer contained a photodecolorizing compound.

[0763] [Manufacturing of laminates with conductor patterns]

[0764] The following methods were used to manufacture laminates with conductor patterns using the transfer films of various embodiments.

[0765] Cu sputtering was performed on the surface of a 0.7 mm thick silicon wafer with a thickness of 200 nm to obtain a substrate with a metal layer.

[0766] The transfer films of each example were laminated onto the substrate with the photosensitive composition layer in contact with the conductor layer. The bonding process (lamination process) was performed using a heated roller at 100°C and a pressure of 0.7 MPa at a speed of 2 m / min.

[0767] Using a mask with a specified pattern, and a projection exposure apparatus with a high-pressure mercury lamp as the light source, the pattern was exposed (exposure process) at the following exposure levels. When exposing with a 41-step trapezoidal plate manufactured by Stouffer and developing for 2.0 times the shortest development time, the exposure level was set to an exposure level with a residual trapezoidal step number of 13.

[0768] Using a 1% sodium carbonate aqueous solution at 30°C as the developer, spray development is performed for 2.0 times the shortest development time to remove unexposed areas, thereby forming a resist pattern (development process).

[0769] Electrolytic plating with copper sulfate plating solution was performed on the conductor layer in areas where no resist pattern was formed, resulting in a copper plating layer with a thickness of 2 μm (plating process). Subsequently, the resist pattern was removed using a stripping solution (resist stripping process). The conductor layer exposed by the removal of the resist pattern was etched (removal process), thereby forming a conductor pattern layer.

[0770] Furthermore, a step of peeling off the temporary support was added between the above-mentioned bonding step and the exposure step. Otherwise, a laminate with a conductor pattern was manufactured using the transfer film of Example 12 in the same way.

[0771] Symbol Explanation

[0772] 10-Transfer film, 12-Temporary support, 14-Thermoplastic resin layer, 16-Intermediate layer, 18-Photosensitive composition layer, 20-Protective film.

Claims

1. A transfer film, comprising, in sequence: Temporary support structure; Thermoplastic resin layer; Intermediate layer; and Photosensitive composition layer, The thermoplastic resin layer comprises an alkali-soluble thermoplastic resin, a plasticizer with polymerizable groups, a polymerization inhibitor, and a light-decolorizing compound. In the thermoplastic resin layer, the mass ratio of the content of the photodecolorizing compound to the content of the polymerization inhibitor is 400 or less. The laminate obtained by peeling the temporary support from the transfer film from the thermoplastic resin layer side is irradiated with ultraviolet light containing a wavelength of 365 nm, so that the irradiation dose at a wavelength of 365 nm reaches 1000 mJ / cm. 2 In the case where the transmittance of the laminate before irradiation at a wavelength of 365 nm is set to T0, and the transmittance of the laminate after irradiation at a wavelength of 365 nm is set to T1000, the transfer film satisfies the relationship of equation (1). Equation (1) T1000 / T0≥4.

2. The transfer film according to claim 1, wherein, The photosensitive composition layer comprises an alkali-soluble thermoplastic resin, a monomer having free radical polymerizable groups, and a free radical polymerization initiator.

3. The transfer film according to claim 1 or 2, wherein, The content of the photo-decolorizing compound is 5.00% to 40.00% by mass relative to the total mass of the thermoplastic resin layer.

4. The transfer film according to claim 1 or 2, wherein, The thickness of the thermoplastic resin layer is 1 μm to 15 μm.

5. The transfer film according to claim 1 or 2, wherein, The T1000 content is above 65%.

6. The transfer film according to claim 1 or 2, wherein, The thickness of the intermediate layer is 0.1 μm to 3 μm.

7. The transfer film according to claim 1 or 2, wherein, The intermediate layer contains polyvinyl alcohol.

8. The transfer film according to claim 1 or 2, wherein, The intermediate layer contains a photodecolorizing compound.

9. The transfer film according to claim 1 or 2, wherein, The photodecolorizing compound has a molar absorptivity of 8000 L·mol⁻¹ at a wavelength of 365 nm. -1 cm -1 above.

10. The transfer film according to claim 1 or 2, wherein, The irradiated photosensitive composition layer has a transmittance of over 75% at a wavelength of 365 nm.

11. The transfer film according to claim 1 or 2, wherein, The thickness of the photosensitive composition layer is 2 μm to 20 μm.

12. A method for manufacturing a laminate having a conductor pattern, comprising: In the bonding process, the transfer film according to any one of claims 1 to 11 is bonded to the metal layer of a substrate having a metal layer on its surface in such a way that the photosensitive composition layer side is in contact with the metal layer. The exposure process involves patterning the photosensitive composition layer from the side opposite to the substrate side; In the developing process, an alkaline developing solution is used to develop the exposed photosensitive composition layer to form a resist pattern; The etching process that forms a conductor pattern by etching the metal layer in the area where the resist pattern is not provided, and the plating process that performs plating. The resist stripping process involves stripping the resist pattern. and In the case of the plating process, a further removal process is provided to remove the metal layer exposed by the resist stripping process to form a conductor pattern on the substrate.

13. The method for manufacturing a laminate with a conductor pattern according to claim 12, wherein prior to the exposure step, the method includes a step of peeling off the temporary support.

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