TW202208988A - Method of manufacturing structure, and structure - Google Patents

Abstract

Provided are a method for manufacturing a structure, and a structure, the method comprising: a step for preparing a laminate that has a transparent base material, a light-shielding pattern 1 disposed on the transparent base material, and a negative photosensitive resin layer N that is disposed on the transparent substrate and the light-shielding pattern and is in contact with the transparent base material; a step for irradiating a portion of the negative photosensitive resin layer N with light from a surface of the transparent substrate on a side opposite from a surface on which the light-shielding pattern 1 is provided; a step for forming a resin pattern 2 on the transparent base material by developing the negative photosensitive resin layer N irradiated with light; and a step for forming a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2, wherein the obtained structure has the resin pattern 2 as a permanent film.

Description

Manufacturing method and structure of structure

The present disclosure relates to a method for manufacturing a structure and a structure.

Conductive patterns such as thin metal wires are used in various applications. Examples of the use of the conductive pattern include a touch sensor of a touch panel, an antenna, a fingerprint authentication unit, a foldable device, and a transparent FPC (Flexible printed circuit). For example, when manufacturing a semiconductor package, a printed wiring board, and a rewiring layer of an interposer, a fine conductive pattern is formed on the board. As the base material, for example, a film, a sheet, a metal substrate, a ceramic substrate, or glass is used.

As a method for forming a general conductive pattern, for example, a subtractive method and a semi-additive method are known (for example, Patent Document 1 and Patent Document 2). In the subtractive method, for example, after protecting the conductive layer on the substrate with the photoresist pattern, the conductive layer not protected by the photoresist pattern is removed by etching, whereby the conductive pattern can be formed. On the other hand, in the semi-additive method, for example, after an electroless copper plating layer called a seed layer is provided on a substrate, a photoresist pattern is further provided on the electroless copper plating layer. Next, after forming a conductive pattern by plating on the electroless copper plating layer on which the photoresist pattern is not provided, the unnecessary photoresist pattern and the electroless copper plating layer (seed layer) are removed.

[Patent Document 1] Japanese Patent Laid-Open No. 2015-225650 [Patent Document 2] Japanese Patent Laid-Open No. 2015-065376

For example, in order to reduce the resistance of the conductive pattern, a thick conductive pattern is sometimes formed. However, in the subtractive method, due to a phenomenon (for example, called "side etching") that is etched isotropically in the in-plane direction of the substrate on which the conductive layer is disposed, the conductive layer protected by the photoresist pattern Layers may also be etched by chemical liquids. Since the occurrence of side etching affects the morphology (eg, shape and size) of the conductive pattern formed by etching, it is sometimes difficult to form, for example, a rectangular conductive pattern. In the semi-additive method, there is a problem that the formation of the conductive pattern becomes unstable due to the adhesion between the seed layer and the photoresist pattern. In addition, the semi-additive method also has the same problem as the subtractive method since a part of the conductive pattern may be removed when the unnecessary seed layer is removed.

The present disclosure has been made in view of the above-mentioned circumstances. The problem to be solved by one embodiment of the present disclosure is to provide a method that reduces the occurrence of morphological abnormalities (the occurrence of tapered shapes due to cracks, peeling, defects, or side etching, or the variation in dimensions due to changes in etching. The following The same.) The manufacturing method of the structure of the pattern. Moreover, the problem to be solved by another embodiment of this disclosure is to provide a structure which has a pattern which reduces the generation|occurence|production of a morphological abnormality.

The means for solving the above-mentioned problems include the following aspects. <1> A method for producing a structure comprising the step of preparing a layered body having a transparent substrate, a light-shielding pattern 1 disposed on the transparent substrate, and a negative photosensitive resin layer N, which is disposed on the transparent base material and the light-shielding pattern 1 and in contact with the transparent base material; the negative-type photosensitive surface is from the opposite side of the transparent base material to the surface on which the light-shielding pattern 1 is provided. A step of irradiating a part of the photosensitive resin layer N with light; a step of forming a resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light; In the step of forming the pattern 3 in the area defined by the resin pattern 2, the obtained structure has the above-mentioned resin pattern 2 as a permanent film. <2> The method for producing a structure according to <1>, wherein The light-shielding pattern 1 described above contains metal. <3> The method for producing a structure according to <1> or <2>, wherein The above-mentioned pattern 3 has conductivity. <4> The method for producing the structure according to any one of <1> to <3>, wherein The above-mentioned pattern 3 is a pattern formed by a plating method. <5> The method for producing the structure according to any one of <1> to <4>, wherein The said light-shielding pattern 1 and the said pattern 3 contain the same kind of material. <6> The method for producing the structure according to any one of <1> to <5>, wherein The said negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photoinitiator. <7> The method for producing a structure according to <6>, wherein The said ethylenically unsaturated compound contains a trifunctional or more than trifunctional ethylenically unsaturated compound. <8> The method for producing a structure according to <6> or <7>, wherein The said ethylenically unsaturated compound contains the di(meth)acrylate compound which has a dicyclopentyl structure or a dicyclopentenyl structure. <9> The method for producing the structure according to any one of <1> to <5>, wherein The above-mentioned negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxyl group-containing compound, and a photocationic polymerization initiator. <10> The method for producing the structure according to any one of <1> to <9>, wherein The said negative photosensitive resin layer N contains a metal oxidation inhibitor. <11> The manufacturing method of the structure according to any one of <1> to <10>, further comprising: The step of forming a light-shielding layer on one of the surfaces of the transparent substrate; the step of forming a photoresist layer on the light-shielding layer; the steps of exposing and developing the above-mentioned photoresist layer to form a photoresist pattern; and A step of forming the above-mentioned light-shielding pattern 1 by etching the above-mentioned light-shielding layer. <12> The method for producing the structure according to any one of <1> to <11>, wherein The average thickness of the above-mentioned pattern 3 is thicker than the average thickness of the above-mentioned light-shielding pattern 1 . <13> The method for producing the structure according to any one of <1> to <12>, wherein The above-mentioned transparent substrate is a transparent film substrate. <14> The method for producing a structure according to any one of <1> to <13>, further comprising a step of performing at least one of post-exposure and post-heating on the resin pattern 2 described above. <15> The method for producing the structure according to any one of <1> to <14>, wherein The said negative photosensitive resin layer N is a layer formed with a photosensitive transfer material. <16> The method for producing the structure according to any one of <1> to <15>, wherein The obtained structure is one structure selected from the group consisting of a touch sensor, an electromagnetic wave shielding material, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. <17> A structure having: A transparent base material; a light-shielding pattern 1 disposed on the above-mentioned transparent base material; a resin pattern 2 disposed adjacent to the above-mentioned light-shielding pattern 1 on the above-mentioned transparent base material and in contact with the above-mentioned transparent base material; and a pattern 3, formed In the region defined by the light-shielding pattern 1 and the resin pattern 2, the average thickness of the light-shielding pattern 1 is 2 μm or less, the average thickness of the resin pattern 2 exceeds 2 μm, and the average thickness of the pattern 3 is larger than that of the light-shielding pattern. The average thickness of 1 is thick, and the above-mentioned structure has the above-mentioned resin pattern 2 as a permanent film. [Inventive effect]

According to one embodiment of the present disclosure, it is possible to provide a method for manufacturing a structure having a pattern that reduces the occurrence of morphological abnormalities. Furthermore, according to another embodiment of the present disclosure, it is possible to provide a structure having a pattern that reduces the occurrence of morphological abnormalities.

Hereinafter, the content of this disclosure will be described. In addition, although it demonstrates referring drawings, a code|symbol may be abbreviate|omitted. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in this specification, "(meth)acrylic acid" means both or either of acrylic acid and methacrylic acid, and "(meth)acrylate" means both or any of acrylate and methacrylate one. In addition, in this specification, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the amount of each component in the composition refers to the amount of the plurality of substances present in the composition. total. In this specification, the term "step" not only includes independent steps, but also includes in this term as long as the intended purpose of the step can be achieved even if it cannot be clearly distinguished from other steps. Regarding the labels of groups (atomic groups) in the present specification, labels that are not substituted and unsubstituted include both those having no substituent and those having a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). As long as "exposure" in this specification is not specifically limited, in addition to exposure by light, drawing by particle beams, such as an electron beam and an ion beam, is included. Moreover, as the light used for exposure, the bright-line spectrum of a mercury lamp, and active rays (active energy rays) such as extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams are usually mentioned. In addition, the chemical structural formula in this specification may be described as a simplified structural formula in which a hydrogen atom is omitted. In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In addition, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect. In addition, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin in the present disclosure are obtained by using a tube using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are product names manufactured by TOSOH Corporation). A column-based gel permeation chromatography (GPC) analyzer was used for detection by solvent THF (tetrahydrofuran) and a differential refractometer, and polystyrene was used as a standard substance to calculate the molecular weight in conversion. In the present disclosure, "alkali-solubility" refers to the property that the solubility of sodium carbonate in an aqueous solution (100 g, concentration of sodium carbonate: 1 mass %) is 0.1 g or more at a liquid temperature of 22°C. In the present disclosure, "conductive" refers to the property of current flow easily. The ease of flow of the required current is not limited as long as it is required in the purpose and use. When the electrical conductivity is represented by the volume resistivity, the volume resistivity is preferably less than 1×10 ⁶ Ωcm, and more preferably less than 1×10 ⁴ Ωcm. In this disclosure, "light" refers to electromagnetic waves including ultraviolet, visible, and infrared. The light is preferably light with a wavelength in the range of 200 nm to 1,500 nm, preferably in the range of 250 nm to 450 nm, and particularly preferably in the range of 300 nm to 410 nm. In the present disclosure, the "solid content" refers to a component obtained by removing the solvent from the total content of the object.

(Manufacturing method of structure) The manufacturing method of the structure of the present disclosure includes a step of preparing a layered body (hereinafter, sometimes referred to as a "preparation step") having a transparent substrate and a light-shielding pattern 1 arranged on the transparent substrate , and a negative photosensitive resin layer N, which is disposed on the transparent base material and the light-shielding pattern and is in contact with the transparent base material; A step of irradiating a part of the negative photosensitive resin layer N on one side with light (hereinafter, also sometimes referred to as an "exposure step"); by developing the negative photosensitive resin layer N irradiated with light, in the above The step of forming the resin pattern 2 on the transparent substrate (hereinafter, also sometimes referred to as the "development step"); and the step of forming the pattern 3 in the area delimited by the above-mentioned light-shielding pattern 1 and the above-mentioned resin pattern 2 (hereinafter, also referred to as the "development step") Sometimes referred to as "the step of forming pattern 3"), the obtained structure has the above-mentioned resin pattern 2 as a permanent film.

The reason why the manufacturing method of the structure of the present disclosure exhibits the above-mentioned effects is presumed to be as follows. As described above, the present inventors have found that the controllability of the shape and size of the pattern is sometimes insufficient in the conventional method for producing a structure (eg, subtractive and semi-additive). On the other hand, in the manufacturing method of the structure of the present disclosure, by including the above-mentioned steps, for example, it is possible to reduce the occurrence of morphological abnormalities of the pattern accompanying side etching or removal of the seed layer. Here, the manufacturing method of the structure of this invention is demonstrated with reference to (a)-(d) of FIG. (a)-(d) of FIG. 1 is a schematic cross-sectional view which shows an example of the manufacturing method of the structure of this disclosure. (a) of FIG. 1 shows an example of a preparation procedure. (b) of FIG. 1 shows an example of an exposure step. (c) of FIG. 1 shows an example of the development step. (d) of FIG. 1 shows an example of the formation process of the pattern 3 . The laminated body 100 shown in FIG.1(a) has the transparent base material 10, the light-shielding pattern 20 (light-shielding pattern 1), and the negative photosensitive resin layer 30 (negative photosensitive resin layer N). As shown in FIG.1(b), light is irradiated to the surface (that is, the to-be-exposed surface 10a) of the opposite side to the surface which opposes the light-shielding pattern 20 of the transparent base material 10. FIG. Since the ratio of the light passing through the light-shielding pattern 20 is small, the light incident on the exposed surface 10 a of the transparent base material 10 passes through the transparent base material 10 and passes through the exposure portion 30 a of the negative photosensitive resin layer 30 . As a result, the exposure part 30a of the negative photosensitive resin layer 30 is selectively exposed. As shown in FIG. 1( c ), by developing the negative photosensitive resin layer 30 , parts other than the exposed portion 30 a of the negative photosensitive resin layer 30 are removed, and the transparent substrate 10 and the light-shielding pattern are formed between the transparent substrate 10 and the light-shielding pattern. A region (ie, groove) demarcated by 20 forms a resin pattern 40 (resin pattern 2 ). As shown in FIG. 1( d ), a pattern 50 (pattern 3 ) is formed on the light-shielding pattern 20 . In (d) of FIG. 1 , the pattern 50 is formed in a region (ie, a groove) delimited by the light-shielding pattern 20 and the resin pattern 40 functioning as a mold. Through the steps as described above, the pattern 50 can be easily formed. Therefore, according to the manufacturing method of the structure of the present disclosure, a pattern (preferably a conductive pattern) in which the occurrence of abnormal morphology is reduced can be formed.

In the manufacturing method of the structure of this disclosure, the obtained structure has the resin pattern 2 mentioned above as a permanent film. In the present disclosure, a "permanent film" refers to a film (layer) that remains after an article having the above-mentioned structure (a product, including the case where the above-mentioned structure itself is an article.) is completed. As a permanent film, an insulating film, a protective film, a spacer, etc. are mentioned specifically, for example. The structure obtained by the manufacturing method of the structure of the present disclosure is, for example, one selected from the group consisting of a touch sensor, an electromagnetic wave shielding material, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film Structure is preferred.

<Preparation steps> The method for producing a layered product of the present disclosure includes a step (preparation step) of preparing a layered body, the layered body having: a transparent substrate; a light-shielding pattern 1 disposed on the transparent substrate; and a negative photosensitive resin layer N, It is arrange|positioned on the said transparent base material and the said light-shielding pattern 1, and is in contact with the said transparent base material. In the present disclosure, "preparation" refers to bringing an object into a usable state. The laminated body may be a pre-manufactured laminated body. The layered body may be the layered body produced in the preparation step. That is, the step of preparing may also include the step of manufacturing the layered body.

[Transparent substrate] The laminated body has a transparent base material. In the present disclosure, "transparent" means that the transmittance at the exposure wavelength in the above-mentioned exposure step is 50% or more. The transmittance at the exposure wavelength specified in the term "transparent" is preferably 80% or more, more preferably 90%, and particularly preferably 95%. In the present disclosure, the "transmittance of the exposure wavelength" refers to the transmittance of the wavelength included in the light reaching the object (eg, a transparent substrate) in the exposure step. For example, when a light source including a wavelength of 365 nm is used in the exposure step, the "transmittance at the exposure wavelength" refers to the transmittance at the wavelength of 365 nm. In the present disclosure, "transmittance" refers to the intensity of outgoing light and the intensity of incident light that pass through the measurement object when light is incident in a direction perpendicular to the main surface of the measurement object (that is, the thickness direction). ratio. The transmittance was measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.. In addition, it is preferable that the light transmittance of the transparent base material at a wavelength of 400 nm to 700 nm is 80% or more.

The shape of the transparent substrate is not limited. As the transparent substrate, for example, a film-like or plate-like transparent substrate is preferably used. Among them, the transparent substrate is preferably a transparent film substrate.

As a transparent base material, a resin substrate (for example, a resin film) and a glass substrate are mentioned, for example. The resin substrate is preferably a resin substrate that transmits visible light. As a preferable component of the resin substrate which transmits visible light, for example, polyamide-based resin, polyethylene terephthalate-based resin, polyethylene naphthalate-based resin, cycloolefin-based resin, polyethylene terephthalate-based resin, Amine resins and polycarbonate resins. As more preferable components of the resin substrate that transmits visible light, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), Polyimide and polycarbonate. The transparent substrate is preferably polyamide film, polyethylene terephthalate film, cyclic olefin polymer (COP), polyethylene naphthalate film, polyimide film or polycarbonate film. Polyethylene terephthalate film is more preferred.

Examples of the transparent base material include paper phenol, paper epoxy resin, glass composite, glass epoxy resin, polytetrafluoroethylene, and a rigid flexible material obtained by compounding a hard material and a soft material. The transparent substrate may also be a porous transparent substrate. The transparent substrate may also contain filler materials and additives.

The surface of the transparent substrate can be modified, for example, by alkali treatment or energy ray irradiation.

The structure of the transparent substrate may be a single-layer structure or a multi-layer structure. The transparent substrate, for example, may also include a functional layer. As a functional layer, an adhesive layer, a hard-coat layer, and a refractive index adjustment layer are mentioned, for example.

The thickness of the transparent substrate is not limited. The thickness of the transparent base material is preferably in the range of 10 μm to 200 μm, more preferably in the range of 20 μm to 120 μm, and particularly preferably in the range of 20 μm to 100 μm. The thickness of the transparent substrate was measured by the following method. The cross section in the direction perpendicular to the main surface of the transparent substrate (that is, the thickness direction) was observed using a scanning electron microscope (SEM). Based on the obtained observation image, the thickness of the transparent substrate was measured at 10 points. The average thickness of the transparent substrate was obtained by arithmetically averaging the measured values.

The total light transmittance of the transparent substrate is preferably high. The total light transmittance of the transparent substrate is preferably more than 50%, more preferably more than 80%, more preferably more than 90%, and particularly preferably more than 95%. The upper limit of the total light transmittance of the transparent substrate is not limited. The total light transmittance of the transparent substrate may be determined within the range of 100% or less. The total light transmittance was measured by the method specified in JIS K 7361-1 (1997).

[shading pattern] The laminated body has the light-shielding pattern 1 on the transparent base material. For example, as shown in FIG.1(b), when a laminated body has the light-shielding pattern 1, a part of a negative photosensitive resin layer can be selectively exposed in an exposure process. In the present disclosure, "shading" means that the transmittance at the exposure wavelength is less than 50%. The transmittance at the exposure wavelength specified in the term "shading" is preferably less than 30%, more preferably less than 10%, and particularly preferably less than 1%. In addition, it is preferable that the light transmittance of the light-shielding pattern 1 at a wavelength of 400 nm to 700 nm is less than 30%.

It is preferable that the light-shielding pattern 1 has conductivity. The light-shielding pattern 1 having conductivity can function as an electric conductor (for example, a seed layer) when plating is performed in, for example, a formation step of the pattern 3 described later. The seed layer can, for example, function as a cathode in electroplating. Among them, it is preferable that the light-shielding pattern 1 contains metal.

As a component of the light-shielding pattern 1, a metal is mentioned, for example. Examples of metals include Nb (niobium), Al (aluminum), Ni (nickel), Zn (zinc), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), Cr (chromium). ), Fe (iron), Co (cobalt), W (tungsten), Cu (copper), Sn (tin) and Mn (manganese). From the viewpoint of electrical conductivity, it is preferable that the light-shielding pattern 1 contains a metal selected from the group consisting of Nb, Al, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn At least one metal in the group is more preferably, including Cu is particularly preferred. From the viewpoint of low resistance and low cost, Cu is preferable. The light-shielding pattern 1 may contain one type of metal alone, or may contain two or more types of metals. The metal contained in the light-shielding pattern 1 may be a single metal or an alloy. It is preferable that the light-shielding pattern 1 contains Cu or a Cu alloy. When the light-shielding pattern 1 contains metal, the metal element contained in the light-shielding pattern may be the same as or different from the metal element contained in the conductive pattern described later. It is preferable that the light-shielding pattern 1 contains the same metal element as the metal element contained in the conductive pattern.

The light-shielding pattern 1 may contain elements other than metal elements. As an element other than a metal element, C (carbon), P (phosphorus), and B (boron) are mentioned, for example. Elements other than metallic elements may form alloys with metallic elements.

The shape of the light-shielding pattern 1 is not limited. The shape of the light-shielding pattern 1 may be determined according to, for example, the shape of the target conductive pattern.

The structure of the light-shielding pattern 1 may be a single-layer structure or a multi-layer structure. The composition of each layer of the light-shielding pattern 1 having a multilayer structure may be the same or different.

The thickness of the light-shielding pattern 1 is not limited. The average thickness of the light-shielding pattern 1 is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. Since the average thickness of the light-shielding pattern 1 is 3 μm or less, the formability of the light-shielding pattern can be improved. As a result, the occurrence of morphological abnormalities in the conductive pattern can be further reduced. The average thickness of the light-shielding pattern 1 is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.3 μm or more. Since the average thickness of the light-shielding pattern 1 is 0.05 μm or more, the transmittance at the exposure wavelength can be reduced. In addition, when the light-shielding pattern 1 is used as a seed layer, the productivity of the conductive pattern can be improved. The average thickness of the light-shielding pattern 1 is measured by a method in accordance with the above-mentioned measuring method of the average thickness of the transparent substrate.

The width of the light-shielding pattern 1 is not limited. In addition, the width of the light-shielding pattern 1 is the length of the light-shielding pattern 1 in the direction perpendicular to the longitudinal direction of the light-shielding pattern 1 in the surface direction of the transparent substrate. For example, if the light-shielding pattern 1 is a line-and-space pattern, the width of the light-shielding pattern 1 is the length in the short-side direction of the line pattern. Moreover, for example, if the cross-sectional shape of the transparent base material of the light-shielding pattern 1 in the plane direction is a circle or an ellipse, the width of the light-shielding pattern 1 is the smallest diameter of the circle or ellipse. The width of the light-shielding pattern 1 may be determined according to, for example, the width of the conductive pattern formed in the step of forming the pattern 3 . The average width of the light-shielding pattern 1 is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. The average width of the light-shielding pattern 1 is preferably 0.1 μm or more, and more preferably 0.5 μm or more. The average width of the light-shielding pattern 1 is the arithmetic mean of the widths of the light-shielding patterns measured at five points.

The light-shielding pattern 1 may also be in contact with the transparent substrate directly or through other layers. As another layer, an adhesive layer is mentioned, for example. For example, the laminated body may have an adhesive layer between the transparent base material and the light-shielding pattern 1 . The composition of the adhesive layer is not limited. The composition of the adhesive layer is determined according to, for example, the adhesive force between the transparent substrate and the light-shielding pattern 1, and the stability in the use environment (eg, humidity and temperature) of the conductive pattern obtained by the manufacturing method of the structure of the present disclosure. That's it. Preferably, the adhesive layer contains at least one selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn and Mn. The adhesive layer may further include at least one selected from the group consisting of C (carbon atom), O (oxygen atom), H (hydrogen atom), and N (nitrogen atom). The adhesive layer can also be a blackened layer. The blackened layer can suppress light reflection caused by the light-shielding pattern in the exposure step. When the adhesive layer functions as a blackening layer, it is preferable that the adhesive layer contains, for example, Ni-Cu alloy. The adhesive layer functioning as the blackening layer may further include at least one selected from the group consisting of C, O, H, and N. The thickness of the adhesive layer is not limited. The average thickness of the adhesive layer is preferably 3 nm to 50 nm, more preferably 3 nm to 35 nm, and particularly preferably 3 nm to 33 nm.

[Negative photosensitive resin layer N] The layered body has a negative photosensitive resin layer N which is arranged on the transparent base material and the light-shielding pattern 1 and is in contact with the transparent base material. The negative photosensitive resin layer N may be in contact with the light-shielding pattern 1 directly or via another layer. It is preferable that the negative photosensitive resin layer N is in contact with the light-shielding pattern 1 . As the negative photosensitive resin layer N, a known negative photosensitive resin layer can be used.

In one embodiment, the negative photosensitive resin layer N preferably contains the polymer A described later, the polymerizable compound B described later, and a photopolymerization initiator. The negative photosensitive resin layer N contains 10 to 90 mass % of the polymer A, 5 to 70 mass % of the polymerizable compound B, and 0.01 mass % with respect to the total mass of the negative photosensitive resin layer N. ～20% by mass of photopolymerization initiator is preferred. In one embodiment, the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.

Moreover, from the viewpoint of curability and developability, it is preferable that the negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photoacid generator. Moreover, it is preferable that the negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxyl-containing compound, and a cationic polymerization initiator from a viewpoint of the intensity|strength and durability as a permanent film of the resin pattern 2 obtained. Hereinafter, the negative photosensitive resin layer N will be specifically described.

-Alkali-soluble polymer- It is preferable that the negative photosensitive resin layer N contains an alkali-soluble polymer. In addition, in this disclosure, "alkali solubility" means that the solubility of sodium carbonate in 100 g of a 1 mass % aqueous solution at 22° C. is 0.1 g or more. From the viewpoint of developability, the alkali-soluble polymer is preferably, for example, an acid value of 60 mgKOH/g or more. In addition, from the viewpoint of easily forming a strong film by thermally crosslinking the crosslinking component by heating, the alkali-soluble polymer is, for example, a resin having a carboxyl group having an acid value of 60 mgKOH/g or more (so-called carboxyl group-containing resin) is: More preferably, an acrylic resin having a carboxyl group with an acid value of 60 mgKOH/g or more (so-called carboxyl group-containing acrylic resin) is particularly preferred. In addition, in the present disclosure, the acrylic resin refers to a resin having a structural unit derived from a (meth)acrylic compound, and the content of the structural unit is preferably 30% by mass or more, preferably 50% by mass or more, based on the total mass of the resin. for better. If the alkali-soluble polymer is a resin having a carboxyl group, the three-dimensional crosslinking density can be increased by thermally crosslinking by adding a thermally crosslinkable compound such as a block isocyanate compound, for example. Moreover, when the carboxyl group of the resin which has a carboxyl group is anhydrous and hydrophobized, the wet heat resistance can be improved.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as the conditions for the acid value are satisfied, and can be appropriately selected from known acrylic resins and used. For example, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-95716 A and 0033 to 0052 of JP 2010-237589 A can be preferably used Carboxyl group-containing acrylic resins and the like having an acid value of 60 mgKOH/g or more in the polymer described in the paragraph.

The alkali-soluble polymer is preferably an acrylic resin or a styrene-acrylic copolymer, and styrene-acrylic acid is preferred from the viewpoints of the development residue inhibiting property, the moisture permeability of the obtained cured film, and the adhesiveness of the obtained uncured film. Copolymers are more preferred. In addition, in the present disclosure, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, the above-mentioned structural unit derived from a styrene compound, the above-mentioned source The total content of the constituent units from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the total mass of the copolymer. Further, the content of the structural unit derived from the styrene compound is preferably 1 mass % or more, more preferably 5 mass % or more, and particularly preferably 5 mass % or more and 80 mass % or less, based on the total mass of the copolymer. Moreover, the content of the structural unit derived from the (meth)acrylic compound is preferably 5 mass % or more, more preferably 10 mass % or more, and 20 mass % or more and 95 mass % or less with respect to the total mass of the copolymer. Excellent. Moreover, as said (meth)acrylic compound, (meth)acrylate compound, (meth)acrylic acid, (meth)acrylamide compound, (meth)acrylonitrile etc. are mentioned. Among them, at least one compound selected from the group consisting of (meth)acrylate compounds and (meth)acrylic acid is preferable.

＜＜Polymer A＞＞ It is preferable that the negative photosensitive resin layer N contains the polymer A. The polymer A is preferably an alkali-soluble polymer. The alkali-soluble polymer includes a polymer that is easily dissolved in an alkaline substance. In addition, in this disclosure, "alkali solubility" means that the solubility of sodium carbonate in 100 g of a 1 mass % aqueous solution at 22° C. is 0.1 g or more.

The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the negative photosensitive resin layer N by the developer. Less than 190 mgKOH/g is particularly preferred. The lower limit of the acid value is not limited. From the viewpoint of more excellent developability, the acid value of the polymer A is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, further more preferably 150 mgKOH/g or more, and particularly preferably 170 mgKOH/g or more. The acid value of the polymer A can be adjusted, for example, by the kind of the structural unit which comprises the polymer A, and the content of the structural unit containing an acid group.

In the present disclosure, the acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. In the present disclosure, the unit of the acid value is described as mgKOH/g. The acid value can be calculated, for example, based on the average content of acid groups in the compound.

The weight average molecular weight (Mw) of the polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight of the polymer A is more preferably 100,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight of the polymer A is more preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more.

The degree of dispersion of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present disclosure, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing the increase of line width and the deterioration of resolution when the focal position is shifted during exposure, it is preferable that the polymer A has an aromatic hydrocarbon group-containing structural unit, and the polymer A preferably has a structural unit derived from an aromatic hydrocarbon group-containing monomer. The constituent unit is better.

As an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example.

With respect to the total mass of the polymer A, the content ratio of the structural unit derived from the aromatic hydrocarbon group-containing monomer in the polymer A is preferably 20 mass % or more, more preferably 30 mass % or more, and 40 mass % The above is more preferable, 45 mass % or more is particularly preferable, and 50 mass % or more is most preferable. The upper limit of the content ratio of the constituent unit derived from the aromatic hydrocarbon group-containing monomer is not limited. The content ratio of the constituent unit derived from the aromatic hydrocarbon group-containing monomer in the polymer A is preferably 95% by mass or less, more preferably 85% by mass or less, relative to the total mass of the polymer A. In addition, when the negative photosensitive resin layer contains a plurality of types of polymers A, the content ratio of the structural unit derived from the aromatic hydrocarbon group-containing monomer is determined as a weight average value.

Examples of the aromatic hydrocarbon group-containing monomer include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxystyrene) , acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer). The aromatic hydrocarbon group-containing monomer is preferably a monomer having an aralkyl group or styrene.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, and substituted or unsubstituted benzyl groups are preferred.

As a monomer which has a phenylalkyl group, phenylethyl (meth)acrylate is mentioned, for example.

Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group (for example, benzyl (meth)acrylate and benzyl chloride (meth)acrylate), and vinyl monomers having a benzyl group. (eg vinylbenzyl chloride and vinylbenzyl alcohol). The monomer having a benzyl group is preferably benzyl (meth)acrylate.

In one embodiment, when the constituent unit derived from the aromatic hydrocarbon group-containing monomer in the polymer A is a constituent unit derived from benzyl (meth)acrylate, the polymer A is polymerized with respect to the total mass of the polymer A. The content ratio of the constituent units derived from the benzyl (meth)acrylate monomer in the product A is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and 70% by mass to 90% by mass % is further preferred, and 75 to 90% by mass is particularly preferred.

In one embodiment, when the constituent units in polymer A derived from the aromatic hydrocarbon group-containing monomer are constituent units derived from styrene, relative to the total mass of polymer A, the source in polymer A is The content ratio of the constituent units from styrene is preferably 20% by mass to 55% by mass, more preferably 25% by mass to 45% by mass, further preferably 30% by mass to 40% by mass, and particularly preferably 30% by mass to 35% by mass .

In one embodiment, it is preferable that the polymer A having a structural unit derived from an aromatic hydrocarbon group-containing monomer is a copolymer obtained by combining an aromatic hydrocarbon group-containing monomer with a monomer selected from a group including those described below. obtained by polymerizing at least one of the group of the first monomer and the second monomer described later. The above-mentioned copolymer has: a constitutional unit derived from an aromatic hydrocarbon group-containing monomer; and at least one selected from the group consisting of a constitutional unit derived from a first monomer and a constitutional unit derived from a second monomer.

The polymer A may be a polymer which does not have a structural unit derived from an aromatic hydrocarbon group-containing monomer. The polymer A that does not have a structural unit derived from an aromatic hydrocarbon group-containing monomer is a polymer obtained by polymerizing at least one of the first monomers (excluding the aromatic hydrocarbon group-containing monomer) described later. Preferably, it is obtained by polymerizing at least one of the first monomers described later (excluding monomers containing aromatic hydrocarbon groups) and at least one of the second monomers described later (excluding monomers having aromatic hydrocarbon groups). The copolymer is better.

In one embodiment, the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and by combining at least one of the first monomers described later with at least one of the first monomers described later A copolymer obtained by polymerizing at least one of the second monomers is more preferred. The above-mentioned copolymer has a constitutional unit derived from the first monomer and a constitutional unit derived from the second monomer.

The first monomer is a monomer having a carboxyl group and a polymerizable unsaturated group in the molecule. The first monomer may also be a monomer that does not contain an aromatic hydrocarbon group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Preferably, the first monomer is (meth)acrylic acid.

Relative to the total mass of the polymer A, the content ratio of the constituent units derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 15% by mass to 40% by mass. Mass % to 30 mass % are particularly preferred.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. The second monomer may also be a monomer that does not contain an aromatic hydrocarbon group in the molecule. As a 2nd monomer, a (meth)acrylate compound, a vinyl alcohol ester compound, and (meth)acrylonitrile are mentioned, for example. In the present disclosure, "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

Examples of the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. ) n-butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate ) cyclohexyl acrylate and 2-ethylhexyl (meth)acrylate. As a (meth)acrylate compound, what has an alicyclic alkyl group, a linear alkyl group, and a branched alkyl group is mentioned.

As a vinyl alcohol ester compound, vinyl acetate is mentioned, for example.

The second monomer is preferably at least one selected from the group consisting of methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate, (methyl) ) methyl acrylate is better.

Relative to the total mass of the polymer A, the content ratio of the constituent units derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and 20% by mass. Mass % to 45 mass % are particularly preferred.

From the viewpoint of suppressing the thickening of the line width and the reduction in resolution when the focus position is deviated during exposure, the polymer A is composed of a constituent unit selected from the group consisting of a constituent unit derived from a monomer having an aralkyl group and a constituent unit derived from styrene At least one of the group is preferred. For example, the polymer A is selected from a copolymer including a constituent unit derived from methacrylic acid, a constituent unit derived from benzyl methacrylate, a constituent unit derived from styrene, and a constituent including a constituent unit derived from methacrylic acid At least one of the unit, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a copolymer derived from a structural unit derived from styrene is preferred.

In one embodiment, the polymer A contains 25% by mass to 60% by mass of a structural unit derived from an aromatic hydrocarbon group-containing monomer, and 20% by mass to 55% by mass of a structural unit derived from a first monomer , and 20 mass % - 55 mass % of polymers derived from structural units derived from the second monomer are preferred. The polymer A contains 25% by mass to 40% by mass of constitutional units derived from an aromatic hydrocarbon group-containing monomer, 20% by mass to 35% by mass of constitutional units derived from the first monomer, and 30% by mass to 45% by mass of constitutional units derived from the first monomer. The polymer of the constituent unit derived from the second monomer in % by mass is more preferable.

In one embodiment, the polymer A is a structure including 70% by mass to 90% by mass of a structural unit derived from an aromatic hydrocarbon group-containing monomer, and 10% by mass to 25% by mass of a structure derived from a first monomer Polymers of units are preferred.

The glass transition temperature (Tg) of the polymer A is preferably 30°C to 135°C. In the negative-type photosensitive resin layer, since the Tg of the polymer A is 135° C. or lower, the line width increases and the resolution decreases when the focus position is shifted during exposure can be suppressed. From the above viewpoints, the Tg of the polymer A is more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. In addition, from the viewpoint of improving the edge fuse resistance, the Tg of the polymer A is preferably 30° C. or higher. From the above viewpoints, the Tg of the polymer A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

The polymer A may be a commercial product or a synthetic product. Synthesis of polymer A, for example, by adding an appropriate amount of a radical polymerization initiator (eg, benzyl peroxide or azoisobutyronitrile) to a solvent (eg, acetone, methyl ethyl ketone, or isopropanol) ) in a solution obtained by diluting at least one of the above-mentioned monomers, followed by heating and stirring. Moreover, it may synthesize|combine while dripping a part of a mixture into a reaction liquid. After completion of the reaction, a solvent may be added to adjust to a desired concentration. As the synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The negative photosensitive resin layer N may contain one type of alkali-soluble polymer alone, or may contain two or more types of alkali-soluble polymers.

The content of the alkali-soluble polymer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and 40% by mass to 60% by mass relative to the total mass of the negative photosensitive resin layer N. Excellent. From the viewpoint of controlling the development time, the content ratio of the alkali-soluble polymer with respect to the negative photosensitive resin layer N is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the edge fuse resistance, the content ratio of the alkali-soluble polymer to the negative photosensitive resin layer N is preferably 10 mass % or more.

When the negative-type photosensitive resin layer N contains two or more alkali-soluble polymers, the negative-type photosensitive resin layer N contains two or more alkali-soluble polymers having structural units derived from an aromatic hydrocarbon group-containing monomer. Or it is preferable to include an alkali-soluble polymer having a structural unit derived from an aromatic hydrocarbon group-containing monomer and an alkali-soluble polymer having no structural unit derived from an aromatic hydrocarbon group-containing monomer. In the latter case, the content ratio of the alkali-soluble polymer having a structural unit derived from the aromatic hydrocarbon group-containing monomer is preferably 50% by mass or more, preferably 70% by mass or more, with respect to the total mass of the alkali-soluble polymer More preferably, 80 mass % or more is further preferable, and 90 mass % or more is particularly preferable.

-Polymerizable compound- It is preferable that the negative photosensitive resin layer N contains a polymerizable compound. In the present disclosure, the "polymerizable compound" refers to a compound that has a bond or a polymerizable group participating in a polymerization reaction and is polymerized under the action of a polymerization initiator described later. In addition, the polymerizable compound in the present disclosure is a compound different from the above-mentioned alkali-soluble polymer, and the molecular weight is preferably less than 5,000. As the polymerizable compound, an ethylenically unsaturated compound is preferable. From the viewpoints of the strength of the obtained cured film, substrate adhesion, development residue inhibiting property, and rust resistance, as the ethylenically unsaturated compound, it is preferable to include an ethylenically unsaturated compound having an acid group, including The compound represented by the formula (M) described later and the ethylenically unsaturated compound having an acid group are more preferable.

The above-mentioned ethylenically unsaturated compound includes a compound represented by the following formula (M) (also simply referred to as "compound M") from the viewpoints of development residue inhibition, rust prevention, and bending resistance of the obtained cured film. better. Q ² -R ¹ -Q ¹ formula (M) In formula (M), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

From the viewpoint of ease of synthesis, Q ¹ and Q ² in the formula (M) are preferably the same groups as Q ¹ and Q ² . In addition, from the viewpoint of reactivity, Q ¹ and Q ² in the formula (M) are preferably acryloxy groups. From the viewpoint of the bending resistance of the cured film obtained, R ¹ in the formula (M) is an alkylene group, an alkylene oxyalkylene group (-L ¹ -OL ¹ -), or a polyalkylene oxyalkylene group group (-(L ¹ -O) _p -L ¹ -) is preferred, hydrocarbon group or polyalkylene oxyalkylene having 2 to 20 carbon atoms is more preferred, and alkylene having 4 to 20 carbon atoms is further Preferably, a straight-chain alkyl group having 6 to 18 carbon atoms is particularly preferred. The above-mentioned hydrocarbon group may have a chain structure in at least a part, and the part other than the above-mentioned chain structure is not particularly limited. Aryl group, ether bond and any of these combinations, from the viewpoint of bending resistance of the cured film obtained, an alkylene group or a combination of two or more alkylene groups and one or more arylidene groups. The group is preferred, the alkylene group is more preferred, and the straight-chain alkylene group is particularly preferred. In addition, each of the above-mentioned L ¹ independently represents an alkylene group, preferably an ethylidene group, a propylidene group or a butylene group, and more preferably an ethylidene group or a 1,2-propylidene group. p represents an integer of 2 or more, and an integer of 2 to 10 is preferable.

In addition, from the viewpoint of the moisture permeability and bending resistance of the cured film obtained, the number of atoms of the shortest link chain between Q ¹ and Q ² in the compound M is preferably 3 to 50, and 4 1 to 40 are more preferred, 6 to 20 are further preferred, and 8 to 12 are particularly preferred. ^In the present disclosure, "the number ^of atoms in the shortest linking chain between Q1 and ^Q2 " is the shortest atom from the atom in R1 linked to ^Q1 to the atom in ^R1 linked to ^Q2 number.

Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetradene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate base) acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Acrylates, poly(ethylene glycol/propylene glycol) di(meth)acrylates, polybutylene glycol di(meth)acrylates. The above-mentioned ester monomers can also be used as mixtures. Among the above-mentioned compounds, from the viewpoint of bending resistance of the obtained cured film, those selected from the group consisting of 1,6-hexanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate At least one compound selected from the group consisting of 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferably selected from the group consisting of 1,6-hexanediol di(meth)acrylate At least one compound selected from the group of (meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is more preferably selected from At least one compound from the group comprising 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is particularly preferred.

Compound M may be used alone or in combination of two or more. From the viewpoints of the moisture permeability and bending resistance of the cured film obtained, the content of the compound M is preferably 10% by mass to 90% by mass relative to the total mass of the ethylenically unsaturated compounds in the negative photosensitive resin layer N , 15% by mass to 70% by mass is more preferable, 20% by mass to 50% by mass is further preferable, and 25% by mass to 35% by mass is particularly preferable. In addition, the ethylenically unsaturated compound in this disclosure refers to a compound having an ethylenically unsaturated group with a (weight average) molecular weight of 10,000 or less. Moreover, from the viewpoint of the moisture permeability and bending resistance of the cured film obtained, the content of the compound M is preferably 1% by mass to 30% by mass relative to the total mass of the negative photosensitive resin layer N, and is preferably 3% by mass. -25 mass % is more preferable, 5 mass % - 20 mass % are more preferable, and 6 mass % - 14.5 mass % are especially preferable.

Moreover, as an ethylenically unsaturated compound, it is preferable to contain the ethylenically unsaturated compound of bifunctional or more. In the present disclosure, the "difunctional or more ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferable. As an ethylenically unsaturated compound, a (meth)acrylate compound is preferable.

As an ethylenically unsaturated compound, from a viewpoint of the intensity|strength of the cured film after curing, for example, a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or more ethylene are contained A sexually unsaturated compound (preferably a tri- or higher functional (meth)acrylate compound) is particularly preferred.

<<Polymerizable Compound B>> It is preferable that the negative photosensitive resin layer N contains the polymerizable compound B. In addition, the polymerizable compound B is a compound different from the above-mentioned polymer A. As a bond which participates in a polymerization reaction in the polymerizable compound B, an ethylenically unsaturated bond is mentioned preferably, for example.

The polymerizable group in the polymerizable compound B is not limited as long as it is a group that participates in the polymerization reaction. Examples of the polymerizable group in the polymerizable compound B include groups containing an ethylenically unsaturated bond (for example, vinyl, acrylyl, methacryloyl, styryl, and maleidylidene) amine groups) and cationically polymerizable groups (eg, epoxy groups and oxetanyl groups). The polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter, sometimes referred to as an "ethylenically unsaturated group"), and more preferably an acrylyl group or a methacrylyl group.

From the viewpoint of better photosensitivity of the negative photosensitive resin layer N, the polymerizable compound B is preferably a compound having an ethylenically unsaturated bond, and a compound having one or more ethylenically unsaturated groups in one molecule (also That is, an ethylenically unsaturated compound) is more preferable, and a compound having two or more ethylenically unsaturated groups in one molecule (that is, a polyfunctional ethylenically unsaturated compound) is especially preferable. Further, from the viewpoint of better resolution and peelability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and particularly 2 or less good. In addition, from the viewpoints of curability and strength and durability as a permanent film of the resin pattern 2 obtained, the polymerizable compound B preferably contains a trifunctional or more ethylenically unsaturated compound, and contains a pentafunctional or more ethylenic unsaturated compound. Unsaturated compounds are more preferred.

The ethylenically unsaturated compound is preferably a (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule.

From the viewpoint of more excellent balance of photosensitivity, resolution, and releasability in the negative photosensitive resin layer N, the polymerizable compound B contains a compound selected from the group consisting of compounds having two ethylenically unsaturated groups in one molecule (also That is, at least one of the group of a 2-functional ethylenically unsaturated compound) and a compound having three ethylenically unsaturated groups in one molecule (that is, a 3-functional ethylenically unsaturated compound) is preferably included in the A compound having two ethylenically unsaturated groups in one molecule is more preferable.

In addition, from the viewpoint of strength and dimensional stability after curing, it is preferable that the polymerizable compound B contains an ethylenically unsaturated compound having an alicyclic skeleton, and includes di(meth)acrylic acid having an aliphatic cyclic skeleton. The ester compound is more preferable, and it is especially preferable to contain a di(meth)acrylate compound having a dicyclopentyl structure or a dicyclopentenyl structure. In addition, from the viewpoint of strength and dimensional stability after curing, it is preferable that the polymerizable compound B contains an ethylenically unsaturated compound having a dicyclopentyl structure or a dicyclopentenyl structure.

From the viewpoint of excellent releasability of the negative-type photosensitive resin layer N, the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B in the negative-type photosensitive resin layer N is 40 mass % or more: Preferably, more than 60 mass % is more preferable, and more than 70 mass % is especially preferable. The upper limit of the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited, and may be 100% by mass. That is, all the polymerizable compounds B contained in the negative photosensitive resin layer N may be bifunctional ethylenically unsaturated compounds.

-Polymerizable compound B1- It is preferable that the negative photosensitive resin layer N of this disclosure contains the polymerizable compound B1 which has one or more aromatic rings and two ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the polymerizable compounds B described above.

From the viewpoint of better resolution, in the negative photosensitive resin layer, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, more preferably 50% by mass or more, 55 mass % or more is more preferable, and 60 mass % or more is especially preferable. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. From the viewpoint of releasability, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass The following are excellent.

Examples of the aromatic ring in the polymerizable compound B1 include aromatic hydrocarbon rings (eg, benzene ring, naphthalene ring, and anthracene ring), aromatic heterocycles (eg, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring) ring and pyridine ring) and condensed rings of these. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. In addition, the aromatic ring may have a substituent.

It is preferable that the polymerizable compound B1 has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the negative photosensitive resin layer N by the developer. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (that is, 2,2-bis(4-hydroxyphenyl)propane), a structure derived from bisphenol F (that is, 2,2 - The bisphenol F structure of bis(4-hydroxyphenyl)methane) and the bisphenol B structure derived from bisphenol B (ie, 2,2-bis(4-hydroxyphenyl)butane). Preferably, the bisphenol structure is a bisphenol A structure.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. . Each polymerizable group may be directly bonded to the bisphenol structure. Each polymerizable group may be bonded to the bisphenol structure via one or more alkaneoxy groups. Preferably, the alkeneoxy groups added to both ends of the bisphenol structure are vinyloxy groups or propoxy groups, and more preferably vinyloxy groups. The number of alkaneoxy groups added to the bisphenol structure is not limited, but each molecule is preferably 4 to 16, more preferably 6 to 14.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese Patent Laid-Open No. 2016-224162. The contents of the above-mentioned publications are incorporated herein by reference.

The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and 2,2-bis(4-(((meth)acryloyloxypolyalkoxy)phenyl)propane is better.

Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethoxy) base)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2 -Bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyl) oxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxypentaethoxy) ) phenyl) propane (BPE-1300, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK ESTER A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

As a polymerizable compound B1, the compound represented by following general formula (I) is also mentioned, for example.

[Chemical formula 1]

In the general formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A represents C ₂ H ₄ , B represents C ₃ H ₆ , and n ₁ and n ₃ each independently represent an integer from 1 to 39. , n ₁ +n ₃ is an integer from 2 to 40, n ₂ and n ₄ are independently an integer from 0 to 29, n ₂ +n ₄ is an integer from 0 to 30, -(AO)- and -(BO) - The arrangement of the repeating units may be random or capped. In the case of capping, either -(AO) and -(BO)- may be on the biphenyl side. n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0. n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

The negative photosensitive resin layer N may contain one type of polymerizable compound B1 alone, or may contain two or more types of polymerizable compounds B1.

From the viewpoint of better resolution, the content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N is preferably 10% by mass or more, preferably 20% by mass, relative to the total mass of the negative photosensitive resin layer N. The above is better. The upper limit of the content ratio of the polymerizable compound B1 is not limited. From the viewpoints of transferability and edge fuse resistance, the content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N with respect to the total mass of the negative photosensitive resin layer N is 70% by mass or less: Preferably, 60 mass % or less is more preferable.

The negative photosensitive resin layer N may contain the polymerizable compound B1 and the polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (that is, compounds having one ethylenically unsaturated group in one molecule), 2 compounds that do not have an aromatic ring Functional ethylenically unsaturated compounds (that is, compounds having no aromatic ring in one molecule and 2 ethylenically unsaturated groups), and ethylenically unsaturated compounds of three or more functionalities (that is, having in one molecule 3 or more ethylenically unsaturated groups).

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

Examples of bifunctional ethylenically unsaturated compounds not having an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, and urethane. Di(meth)acrylate and trimethylolpropane diacrylate.

Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethyl ester Acrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol Alcohol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate and neopentyl glycol di(methyl) )Acrylate.

Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylates, dipropylene glycol diacrylates, tripropylene glycol diacrylates, and polypropylene glycol di(meth)acrylates. Acrylate.

Examples of urethane di(meth)acrylates include urethane di(meth)acrylates modified with propylene oxide, and amines modified with ethylene oxide and propylene oxide. Carbamate di(meth)acrylate. Examples of commercially available products include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.) .) .

Examples of the trifunctional or higher-functional ethylenically unsaturated compound include dipeotaerythritol (tri/tetra/penta/hexa) (meth)acrylate, neotaerythritol (tri/tetra) (meth)acrylic acid ester, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tris(meth)acrylate Meth)acrylates, glycerol tri(meth)acrylates and their alkylene oxide modifications. In the present disclosure, "(tri/tetra/penta/hexa)(meth)acrylate" includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate The concept of meth)acrylate. In the present disclosure, "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

As an alkylene oxide modified product of a trifunctional or more than trifunctional ethylenically unsaturated compound, a caprolactone modified (meth)acrylate compound (for example, KAYARAD (registered trademark) DPCA- manufactured by Nippon Kayaku Co., Ltd. 20 and Shin-Nakamura Chemical Co., Ltd. A-9300-1CL), alkylene oxide modified (meth)acrylate compound (for example, Nippon Kayaku Co., Ltd. KAYARAD RP-1040, Shin-Nakamura Chemical Co., Ltd. manufactures ATM-35E, Shin-Nakamura Chemical Co., Ltd. manufactures A-9300, and DAICEL-ALLNEX LTD. manufactures EBECRYL (registered trademark) 135), ethoxylated glycerol triacrylate (for example, Shin-Nakamura Chemical Co., Ltd. manufactures A-GLY-9E), ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX M-520 (TOAGOSEI CO., LTD.) and ARONIX M- 510 (TOAGOSEI CO., LTD.).

As the polymerizable compound B other than the polymerizable compound B1, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Laid-Open No. 2004-239942 can also be mentioned.

In one embodiment, the negative photosensitive resin layer N preferably contains the polymerizable compound B1 and a trifunctional or more ethylenically unsaturated compound, and contains the polymerizable compound B1 and two or more trifunctional or more ethylenically unsaturated compounds. Saturated compounds are more preferred. In the above-mentioned embodiment, the mass ratio of the polymerizable compound B1 to the trifunctional or higher functional ethylenically unsaturated compound ([total mass of the polymerizable compound B1]: [total weight of the trifunctional or higher functional ethylenically unsaturated compound] is 1 : 1 to 5: 1 is better, 1.2: 1 to 4: 1 is better, and 1.5: 1 to 3: 1 is particularly good.

The weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The negative photosensitive resin layer N may contain one type of polymerizable compound B alone, or two or more types of polymerizable compounds B may be contained.

With respect to the total mass of the negative photosensitive resin layer N, the content ratio of the polymerizable compound B in the negative photosensitive resin layer N is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass Preferably, 20% by mass to 50% by mass is particularly preferred.

-Multifunctional epoxy resin- From the viewpoint of strength and durability as a permanent film of the pattern 2 obtained, it is preferable that the negative photosensitive resin layer N contains a polyfunctional epoxy resin, including a polyfunctional epoxy resin, a hydroxyl group-containing compound, and a photocation. A polymerization initiator is more preferable. Examples of polyfunctional epoxy resins include epoxy compounds having at least two oxysilyl groups in one molecule, and epoxy compounds having at least two epoxy groups having an alkyl group at the β-position in one molecule. Wait.

Examples of the epoxy compound having at least two oxysilyl groups in the above-mentioned one molecule include bisphenol F-type epoxy resin (Epotohto YDF-170, manufactured by TOHTO Chemical Industry Co., Ltd.), bixylenol type or bisphenol type epoxy resin (“YX4000, manufactured by Japan Epoxy Resins Co., Ltd.”, etc.) or mixtures of these, heterocyclic epoxy resins with isocyanate skeleton, etc. (“TEPIC, Nissan Chemical Industries , LTD.”, “Araldite PT810, manufactured by Huntsman International LLC.”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin , bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (such as low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolac type epoxy resin type epoxy resin, etc.), allyl-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyl dimethanol type epoxy resin, phenol co-extended phenyl type epoxy resin, bicyclic epoxy resin Pentadiene-type epoxy resins (“HP-7200, HP-7200H; manufactured by DIC CORPORATION,” etc.), glycidylamine-type epoxy resins (diaminodiphenylmethane-type epoxy resins, diglycidyl aniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (diglycidyl phthalate, diglycidyl adipate, hexahydrophthalate bicyclic Oxypropyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3',4'-epoxy Cyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, "GT-300, GT-400, ZEHPE3150; manufactured by Daicel Corporation" etc.,), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylol ethane type epoxy resin, cyclic epoxy resin Oxypropyl phthalic acid resin, tetraglycidyl xylene glycol ethane resin, epoxy resin containing naphthyl group (biphenyl aralkyl type epoxy resin, naphthol novolac type) Epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available, "ESN-190, ESN-360; manufactured by NIPPON STEEL & SUMIKIN CHEMICAL Co., Ltd.", "HP-4032, EXA-4750, EXA- 4700; manufactured by DIC CORPORATION, etc.), by phenol compounds and diolefin compounds such as divinylbenzene or dicyclopentadiene The reaction product of the polyphenol compound and epichlorohydrin obtained by the addition reaction of Resin, 8-functional bisphenol A novolak type epoxy resin (eg EPON SU-8 manufactured by Resolution Performance Products LLC), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (eg NER-7604 manufactured by Nippon Kayaku Co., Ltd.), epoxy resin obtained by the reaction of the alcoholic hydroxyl group of bisphenol A epoxy resin with epichlorohydrin (eg NER manufactured by Nippon Kayaku Co., Ltd.) -1302), o-cresol novolak-type epoxy resins (for example, EOCN4400 manufactured by Nippon Kayaku Co., Ltd.), phenolic hydroxyl groups of resins obtained by reacting bis(methoxymethylphenyl) with phenol Biphenylphenol novolak type epoxy resin obtained by reacting with epichlorohydrin (such as NC-3000H manufactured by Nippon Kayaku Co., Ltd.), epoxy resin with cyclic phosphorus-containing structure, α-methyldiphenyl Vinyl type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azidophenyl type liquid crystal epoxy resin, double naphthyl type liquid crystal epoxy resin, 𠯤 type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP-50S, CP-50M; manufactured by Nippon Oil & Fats GmbH", etc.), cyclohexylmaleimide and Copolymerized epoxy resin of glycidyl methacrylate, bis (glycidoxy phenyl) phenylene epoxy resin, bis (glycidoxy phenyl) adamantane epoxy resin, etc. These may be used individually by 1 type, and may use 2 or more types together.

In addition to the above-mentioned epoxy compounds having at least two oxysilyl groups in one molecule, epoxy compounds containing at least two epoxy groups having an alkyl group at the β-position in one molecule can be used, including those at the β-position. Compounds of epoxy groups substituted with alkyl groups (more specifically, β-alkyl substituted glycidyl groups, etc.) are particularly preferred. In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of the two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, or may be where at least one epoxy group is a β-alkyl substituted glycidyl group.

As said oxetane compound, the oxetane compound which has at least two oxetane groups in one molecule is mentioned, for example. Specifically, for example, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy) ) methyl] ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxo) Butylmethoxy)methyl]benzene, methyl (3-methyl-3-oxetanyl)acrylate, methyl (3-ethyl-3-oxetanyl)acrylate, (3 - methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or such oligomers or polyfunctional except copolymers Compounds with oxetane groups other than oxetanes and novolak resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, resorcinol calixarene, sesquisilicon Ether compounds such as resins having hydroxyl groups such as oxanes, and copolymers of unsaturated monomers having oxetane rings and alkyl (meth)acrylates, etc. can also be used.

As the epoxy resin, any epoxy resin can be used as long as it has two or more epoxy groups in one molecule, but the epoxy equivalent of the epoxy resin is 100 g/g in order to obtain a sufficient curing rate. The equivalent to 500 g/equivalent is preferable, and the more preferable is 100 g/equivalent to 300 g/equivalent. In addition, the epoxy equivalent mentioned here means the value measured by the method based on JIS K-7236. In addition, as the type of epoxy resin, glycidyl ether type, glycidyl ester type, glycidylamine type, alicyclic type, etc. can be used, but from the viewpoint of good liquid storage stability, glycidyl ether type, The glycidyl ester type is preferred, and the glycidyl ether type is the most preferred. Furthermore, from the viewpoint of developability, the epoxy resin is preferably liquid at room temperature (25°C), and the viscosity at 25°C is more preferably 5,000 mPa·s or less, more preferably 1,000 mPa·s or less. These epoxy resins can be used alone or in combination of two or more. Specific examples of the above epoxy resins include glycidyl ether type sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, neotaerythritol polyglycidyl ether, and diglycerin. Polyglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol triglycidyl ether, neopentyl glycol diglycidyl ether, 1,4- Butylene Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Ethylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether and Polypropylene Glycol Diglycidyl ether, and, as glycidyl ester type, diglycidyl phthalate, diglycidyl tetrahydrophthalate, and diglycidyl hexahydrophthalate are exemplified. ester.

The negative photosensitive resin layer N may contain one type of polyfunctional epoxy resin alone, or may contain two or more types of polyfunctional epoxy resins. The content ratio of the polyfunctional epoxy resin in the negative photosensitive resin layer N is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 70% by mass with respect to the total mass of the negative photosensitive resin layer N. good.

-hydroxyl-containing compounds- From the viewpoint of the strength and durability of the permanent film of the obtained pattern 2, it is preferable that the negative photosensitive resin layer N contains a hydroxyl group-containing compound. As the hydroxyl group-containing compound, a polyol compound or a phenol-based compound can be appropriately used. The polyol compound contains a hydroxyl group that reacts with epoxy groups in the epoxy resin under the influence of an acid catalyst, and functions as a reactive diluent. In particular, it is preferable to contain polycaprolactone polyol. By containing polycaprolactone polyol, after coating the resin composition, the dry coating film obtained by drying the solvent content as needed will soften, so that stress during the production of the laminate can be avoided, shrinkage can be reduced, and the Cracks of the resin pattern 2 of the permanent film.

As the polyol compound, commercially available polyester polyols can be used. Specific examples include "PLACCEL 205" having a molecular weight of 530 and an OH value (also referred to as "hydroxyl value") of 210 mgKOH/g, "PLACCEL 210" having a molecular weight of 1,000 and an OH value of 110 mgKOH/g, and molecular weight "PLACCEL 220" (both product names, manufactured by Daicel Corporation) with 2,000 and OH value of 56 mgKOH/g or "Capa2054" with molecular weight of 550 and OH value of 204 mgKOH/g, molecular weight of 1,000 and OH value of 112 mgKOH/g "Capa2100", "Capa2200" with a molecular weight of 2,000 and an OH value of 56 mgKOH/g (all are product names, manufactured by Perstorp). Moreover, as a phenol type compound, for example, a phenol novolak resin, a cresol novolak resin, a polyfunctional bisphenol A novolak resin, a biphenol novolak resin, a phenol resin having a trihydroxyphenylmethane skeleton, a Phenol resins having a terpene diphenol skeleton, phenol resins using various phenols such as bisphenol A and bisphenol F as raw materials, and the like. The preferred hydroxyl value of the hydroxyl group-containing compound is preferably 90 mgKOH/g to 300 mgKOH/g, more preferably 100 mgKOH/g to 250 mgKOH/g. The hydroxyl group-containing compound may be used alone or in combination of two or more.

The negative photosensitive resin layer N may contain a single hydroxyl group-containing compound, or may contain two or more hydroxyl group-containing compounds. The content ratio of the hydroxyl group-containing compound in the negative photosensitive resin layer N is preferably 1% by mass to 35% by mass, more preferably 5% by mass to 25% by mass relative to the total mass of the negative photosensitive resin layer N .

-Photopolymerization initiator- It is preferable that the negative photosensitive resin layer N contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives actinic rays (eg, ultraviolet rays, visible rays, and X rays) to initiate polymerization of a polymerizable compound (eg, polymerizable compound B).

The polymerization initiator is not limited, and known photopolymerization initiators can be used. As a photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, From the viewpoint of curability, a photoradical polymerization initiator is preferable. Moreover, it is preferable that the negative photosensitive resin layer N contains a photocationic polymerization initiator from a viewpoint of the intensity|strength and durability as a permanent film of the resin pattern 2 obtained.

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

From the viewpoint of photosensitivity, visibility of exposed parts, visibility and resolution of unexposed parts, the negative photosensitive resin layer N as a photo-radical polymerization initiator contains a group selected from the group consisting of 2,4,5-triaryl groups At least one of the group of derivatives of imidazole dimers and 2,4,5-triarylimidazole dimers is preferred. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.

Examples of derivatives of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)- 4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

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

Examples of photo-radical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, and anisole (p,p'-dimethyl ether). oxybenzyl) and benzophenone.

Commercially available products of the photo-radical polymerization initiator include, for example, TAZ-110 (Midori Kagaku Co., Ltd.), TAZ-111 (Midori Kagaku Co., Ltd.), 1-[4-(benzene) thio)]phenyl-1,2-octanedione-2-(o-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF Corporation), 1-[9-ethyl-6 -(2-Methylbenzyl)-9H-carbazol-3-yl]ethanedione-1-(o-acetoxime) (trade name: IRGACURE OXE-02, BASF Corporation), IRGACURE OXE-03 ( BASF Corporation), IRGACURE OXE-04 (BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) Phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one ( Trade name: Omnirad 907, IGM Resins B.V. Company), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionitrile)benzyl]phenyl}-2-methylpropane-1 - Ketone (trade name: Omnirad 127, IGM Resins B.V. Company), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins B.V. Company), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins B.V. Company), 2,4,6-triphenylene Methylbenzyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (trade name: Omnirad 819) , IGM Resins B.V. Company), oxime ester photopolymerization initiator (trade name: Lunar 6, DKSH Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5' - Tetraphenyl-1,2'-biimidazole (also known as 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford Corporation) and 2 -(o-Chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo C chemical Industry Co., Ltd.).

Wherein, as a photo-radical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives of 2,4,5-triarylimidazole dimer is included is better.

The photocationic polymerization initiator (that is, the photoacid generator) is irradiated by ultraviolet rays, extreme ultraviolet rays, excimer lasers such as KrF or ArF, X-rays, electron beams, etc. to generate cations, and the cations can become polymerization initiators. starter compound. As the photocationic polymerization initiator, a compound that is sensitive to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. However, the chemical structure of the photocationic polymerization initiator is not limited. In addition, as long as the photocationic polymerization initiator that is not directly sensitive to actinic rays with a wavelength of 300 nm or more is a compound that is sensitive to actinic rays with a wavelength of 300 nm or more and generates an acid by being used in combination with a sensitizer, the It can be preferably used in combination with a sensitizer.

As a photocationic polymerization initiator, an aromatic iodonium zirconium salt or an aromatic zirconium zirconium salt can be mentioned. Specific examples of the aromatic iodonium salts include diphenyliodide tetrakis(pentafluorophenyl)borate, diphenyliodide hexafluorophosphate, diphenyliodide hexafluoroantimonate, bis(4- Nonylphenyl) iodine hexafluorophosphate, cumyl iodide tetrakis (pentafluorophenyl) borate (manufactured by Solvay, Ltd., product name Roadsil PI2074), bis(4-tertiary butane) base) iodine tris(trifluoromethanesulfonyl)methanide (manufactured by BASF, product name CGI BBI-C1) and the like. In addition, as a specific example of the aromatic zirconium salt, 4-thienyl diphenyl perylene salt hexafluoroantimonate (manufactured by San-Apro Ltd., product name CPI-101A), thienyl diphenyl hexafluoroantimonate can be preferably used Tris(pentafluoroethyl)trifluorophosphate (manufactured by San-Apro Ltd., product name CPI-210S), 4-{4-(2-chlorobenzyl)phenylthio}phenylbis( 4-Fluorophenyl) perylene hexafluoroantimonate (manufactured by ADEKA Corporation, product name SP-172), aromatic perylene salt hexafluoroantimonate containing 4-thienyldiphenyl perylene salt hexafluoroantimonate Mixture (manufactured by ACETO Corporate USA, product name CPI-6976) and triphenyl perylene tris(trifluoromethanesulfonyl) methane compound (manufactured by BASF Corporation, product name CGI TPS-C1), tris[4-(4-ethyl) Acylphenyl)sulfonylphenyl]perylium tris(trifluoromethylsulfonyl) methide (manufactured by BASF, product name GSID 26-1), tris[4-(4-acetylphenylphenyl) ) Sulfonylphenyl] peritetrakis (2,3,4,5,6-pentafluorophenyl) borate (manufactured by BASF, product name IRGACURE PAG290) and the like.

Among the above photocationic polymerization initiators, from the viewpoints of vertical rectangular processability and thermal stability, aromatic zirconium salts are preferred, and 4-{4-(2-chlorobenzyl)phenylthio}benzene bis(4-fluorophenyl) perylene hexafluoroantimonate, mixtures of aromatic perylene hexafluoroantimonates containing 4-thienyldiphenyl perylene hexafluoroantimonate, or tris[4-(4 -Acetylphenyl)sulfonylphenyl]perylium tetrakis(2,3,4,5,6-pentafluorophenyl)borate is particularly preferred.

In addition, the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and a photocationic polymerization initiator that generates a pKa of 2 or less The acid photocationic polymerization initiator is particularly preferred. There is no limit to the lower limit of pKa. The pKa of the acid generated from the photocationic polymerization initiator is preferably -10.0 or more, for example.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned.

As an ionic photocationic polymerization initiator, an onium salt compound (for example, a diaryl iodonium salt compound and a triaryl perionium salt compound) and a quaternary ammonium salt compound are mentioned, for example.

As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A No. 2014-85643 can also be mentioned.

As a nonionic photocationic polymerization initiator, a trichloromethyl mesityl compound, a diazomethane compound, an imine sulfonate compound, and an oxime sulfonate compound are mentioned, for example. Examples of the trichloromethyl mesitine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494. Moreover, as an oxime sulfonate compound, the compound described in the paragraph 0084 - 0088 of International Publication No. WO 2018/179640 can be mentioned, for example.

The negative photosensitive resin layer N may contain one type of photopolymerization initiator alone, or may contain two or more types of photopolymerization initiators.

With respect to the total mass of the negative photosensitive resin layer N, the content ratio of the photopolymerization initiator in the negative photosensitive resin layer N is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and 1.0 mass % The above are excellent. The upper limit of the content ratio of the photopolymerization initiator is not limited. With respect to the total mass of the negative photosensitive resin layer N, the content ratio of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less.

-Metal oxidation inhibitor- It is preferable that the negative photosensitive resin layer N contains a metal oxidation inhibitor. As a metal oxidation inhibitor, the compound which has an aromatic ring containing a nitrogen atom in a molecule|numerator is preferable. Furthermore, as the metal oxidation inhibitor, the aromatic ring containing the above-mentioned nitrogen atom is at least one selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and these condensed rings with other aromatic rings One ring is preferred, and the aromatic ring containing the above nitrogen atom is an imidazole ring or a condensed ring of an imidazole ring and other aromatic rings, more preferably. The above-mentioned other aromatic ring may be a monocyclic ring or a heterocyclic ring, but a monocyclic ring is preferable, a benzene ring or a naphthalene ring is more preferable, and a benzene ring is even more preferable. As preferred metal oxidation inhibitors, imidazole, benzimidazole, tetrazole, mercaptothiadiazole and benzotriazole can be preferably exemplified, and imidazole, benzimidazole and benzotriazole are more preferred. As a metal oxidation inhibitor, a commercial item can be used, For example, JOHOKU CHEMICAL CO., LTD, BT120 etc. containing a benzotriazole can also be used suitably.

Moreover, as a metal oxidation inhibitor, a benzotriazole compound or a carboxybenzotriazole compound is mentioned preferably. Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminoidene Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl) ) aminomethylene-1,2,3-benzotriazole. Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N - Di-2-ethylhexyl)aminovinylcarboxybenzotriazole. As a commercial item of a carboxybenzotriazole compound, CBT-1 (JOHOKU CHEMICAL CO., LTD) is mentioned, for example.

The negative photosensitive resin layer N may contain one metal oxidation inhibitor alone, or may contain two or more metal oxidation inhibitors. Moreover, the content of the metal oxidation inhibitor is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and 1 to 5 mass % with respect to the total mass of the negative photosensitive resin layer N. for further better.

-Any ingredient- The negative photosensitive resin layer N may contain components other than the above-mentioned components (hereinafter, sometimes referred to as "arbitrary components"). Examples of optional components include dyes, surfactants, and additives other than the above-mentioned components.

＜＜Pigment＞＞ From the viewpoints of visibility of exposed parts, visibility of unexposed parts, pattern visibility after development, and resolution, the negative photosensitive resin layer N has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development: A dye (hereinafter, sometimes referred to as "dye NC") whose maximum absorption wavelength is changed by an acid, a base, or a radical of 450 nm or more is preferable. Although the detailed mechanism is not clear, by including the dye NC in the negative photosensitive resin layer N, the adhesiveness of the layer adjacent to the negative photosensitive resin layer N is improved, and the resolution is more excellent.

In the present disclosure, the term "the maximum absorption wavelength is changed by acid, alkali or free radical" used with respect to the pigment can also refer to the state in which the pigment in the color developing state is decolorized by acid, alkali or free radical, Any of the form in which the pigment in the decolorized state is developed by acid, alkali or free radical, and the form in which the pigment in the color developed state changes to the color developed state of another hue.

Specifically, the coloring matter NC may be a compound that changes color from a decolorized state by exposure to light, or a compound that changes color from a color-developed state to light exposure and decolorizes. In the above-mentioned aspect, the dye NC may be a dye whose color development or decolorization state is changed by the action of acid, alkali or radical generated by exposure. In addition, the coloring matter NC may be a coloring matter that changes the state (eg, pH) in the negative photosensitive resin layer N by acid, alkali, or radical generated by exposure, thereby changing the color development or decolorization state. On the other hand, the pigment NC can also be directly stimulated by acid, alkali or free radical without exposure, thereby changing the color development or decolorization state.

From the viewpoints of the visibility of the exposed part and the visibility and resolution of the unexposed part, it is preferable that the dye NC is a dye whose maximum absorption wavelength is changed by acid or radicals, and the maximum absorption wavelength is changed by radicals. Pigment is better.

From the viewpoint of the visibility of the exposed part, the visibility of the unexposed part, and the resolution, the negative photosensitive resin layer N contains, as the dye NC, both a dye whose maximum absorption wavelength is changed by a radical, and a photo-radical polymerization initiator. is better.

From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, it is preferable that the coloring matter NC is a coloring matter developed by an acid, a base, or a radical.

As an example of the color-developing mechanism of the dye NC, a negative-type photosensitivity including a photoradical polymerization initiator, a photocationic polymerization initiator (that is, a photoacid generator), or a photobase generator by exposure to light is exemplified The resin layer N is a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (eg Colorless pigments) the state of color development.

From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, in the dye NC, the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 nm to 700 nm, 550 to 650 nm is particularly preferred.

In addition, the dye NC may have one or two or more maximum absorption wavelengths within the wavelength range of 400 nm to 780 nm at the time of color development. When the dye NC has two or more absorption maximum wavelengths within the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

For the maximum absorption wavelength of dye NC, in the atmosphere, use a spectrophotometer (UV3100, SHIMADZU CORPORATION) to measure the transmission spectrum of the solution containing dye NC (liquid temperature 25°C) in the range of 400nm to 780nm, and then detect by The light intensity becomes the minimum wavelength (maximum absorption wavelength) for measurement.

As a pigment|dye which develops or removes color by exposure, a colorless compound is mentioned, for example. Examples of dyes decolorized by exposure include leuco compounds, diarylmethane-based dyes, oxazine-based dyes, xanthene-based dyes, imino naphthoquinone-based dyes, Nitromethine-based dyes and anthraquinone-based dyes. From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, it is preferable that the dye NC is a colorless compound.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), and a colorless compound having a fluoran skeleton (fluoran colorless compounds with a diarylmethane skeleton (diarylmethane-based dyes), colorless compounds with a rhodamine lactamide skeleton (rhodamine lactamide-based dyes), and an indolylphthalide skeleton The colorless compound (indolylphthalide-based pigment) and the colorless compound with leuco-auramine skeleton (leuco-auramine-based pigment). The colorless compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a colorless compound (triphenylmethane-based dye) or a fluoran-based dye having a triphenylmethane skeleton.

The colorless compound preferably has a lactone ring, a sultines ring, or a sultone ring from the viewpoint of visibility of an exposed portion and visibility of an unexposed portion. By reacting a lactone ring, a sultines ring or a sultone ring contained in a colorless compound with a radical generated by a photoradical polymerization initiator, or an acid generated by a photocationic polymerization initiator, the The colorless compound becomes a ring-closed state and becomes decolorized, or the colorless compound becomes a ring-opened state and develops color. The colorless compound is preferably a compound having a lactone ring, a sultines ring or a sultone ring and the lactone ring, the sultines ring or the sultone ring is opened and colored by a free radical or an acid. Compounds in which the lactone ring is opened by free radicals or acids to develop color are more preferred.

Specific examples of the colorless compound include p,p',p''--hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone , Malachite green lactone, benzalkonium colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2- Anilino-3-methyl-6-(N-ethyl-p-tolyl)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5- Methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran, 3-( N,N-Diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylaminofluoran , 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-amino Fluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3 -(N,N-Diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoroalkane, 3-(N, N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-dimethylanilinofluoran, 3 -Piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methyl) Indol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylamino) Phenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3 -yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6 '-Bis(diphenylamino)spiroisobenzofuran-1(3H), 9'-[9H]𠮿kouxing-3-one.

As the dye NC, for example, a dye can also be mentioned. Specific examples of the dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, Kinaldine red, Bengal red, metaamine yellow, Timor sulfophthalein, dimethyl phthalate Phenol Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzopurine 4B, Alpha-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafusin, Victoria Pure Blue- Naphthalene Sulfonate, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #603 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink #312 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet #308 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red OG (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red RR (ORIENT CHEMICAL INDUSTRIES CO., LTD.) ., LTD.), Oil Green #502 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-Cresol Violet, Cresyl Red, Rhodamine B, Rhodamine 6G , sulforhodamine B, auramine, 4-p-diethylaminophenylimino-naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino-naphthoquinone, 2- Carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenylimino-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminobenzene and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

From the viewpoints of the visibility of the exposed part, the visibility of the unexposed part, the visibility of the pattern after development, and the resolution, it is preferable that the dye NC is a dye whose maximum absorption wavelength is changed by radicals. Color pigments are better.

The pigment NC is preferably colorless crystal violet, crystal violet lactone, bright green or Victoria pure blue-naphthalene sulfonate.

The negative photosensitive resin layer N may contain one type of dye alone, or may contain two or more types of dye.

From the viewpoint of the visibility of the exposed portion, the visibility of the unexposed portion, the visibility of the pattern after development, and the resolution, the content ratio of the dye with respect to the total mass of the negative photosensitive resin layer N is 0.1 mass % or more: Preferably, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.

The content ratio of the dye NC refers to the content ratio of the dye when all the dyes NC contained in the negative photosensitive resin layer N are in a color-developing state. Hereinafter, a method for quantifying the content ratio of the dye NC will be described by taking a dye developed by radicals as an example. Two solutions were prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL), respectively. IRGACURE OXE-01 (BASF) was added to each of the obtained solutions as a photo-radical polymerization initiator, and then irradiated with light of 365 nm to generate radicals, and all dyes were brought into a colored state. Next, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, SHIMADZU CORPORATION) under the atmosphere, and a calibration curve was prepared. Next, except that the negative photosensitive resin layer N (3 g) was dissolved in methyl ethyl ketone instead of the dye, the absorbance of the solution in which all the dyes were developed was measured by the same method as above. According to the absorbance of the obtained solution containing the negative photosensitive resin layer N, the content of the dye contained in the negative photosensitive resin layer N was calculated based on a calibration curve.

＜＜Surfactant＞＞ From the viewpoint of thickness uniformity, it is preferable that the negative photosensitive resin layer N contains a surfactant. As a surfactant, an anionic surfactant, a cationic surfactant, a nonionic (Nonion) surfactant, and an amphoteric surfactant are mentioned, for example, a nonionic surfactant is preferable.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkyl phenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, and polysiloxane-based nonionic surfactants and fluorine-based nonionic surfactants.

From the viewpoint of more excellent resolution, it is preferable that the negative photosensitive resin layer N contains a fluorine-based nonionic surfactant. The reason for this is considered to be because the negative photosensitive resin layer N contains a fluorine-based nonionic surfactant, thereby suppressing the penetration of the etching solution into the negative photosensitive resin layer N, thereby reducing side etching. As a commercial item of a fluorine-type nonionic surfactant, MEGAFACE (registered trademark) F-551, F-552 (DIC CORPORATION), and MEGAFACE F-554 (DIC CORPORATION) are mentioned, for example.

As the surfactant, for example, the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Patent No. 4502784, and Japanese Patent Laid-Open No. 2009 can also be mentioned. - Surfactant described in paragraphs 0060 to 0071 of Gazette No. 237362.

The negative photosensitive resin layer N may contain one type of surfactant alone, or may contain two or more types of surfactants.

With respect to the total mass of the negative photosensitive resin layer N, the content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass.

＜＜Additive＞＞ Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, resins other than the above, and solvents. The negative photosensitive resin layer N may contain one kind of additive alone, or may contain two or more kinds of additives.

The negative photosensitive resin layer N may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Patent No. 4502784. Preferably, the free-radical polymerization inhibitor is phenothiazine, phenothiae, or 4-methoxyphenol. Examples of radical polymerization inhibitors other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. In order not to impair the sensitivity of the negative photosensitive resin layer N, it is preferable to use an aluminum nitrosophenyl hydroxylamine salt as a radical polymerization inhibitor.

The ratio of the total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound relative to the total mass of the negative photosensitive resin layer N is preferably 0.01% by mass to 3% by mass, preferably 0.05% by mass % - 1 mass % is more preferable. From the viewpoint of imparting storage stability to the negative photosensitive resin layer N, it is preferable to set the ratio of the total content of each of the above components to 0.01 mass % or more. On the other hand, from the viewpoint of maintaining the sensitivity and suppressing the discoloration of the dye, the ratio of the total content of each of the above components is preferably 3 mass % or less.

The negative photosensitive resin layer N may contain a sensitizer. There is no restriction|limiting as a sensitizer, A well-known sensitizer can be used. Moreover, dyes and pigments can also be used as a sensitizer. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, and acridone. Compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazole compounds, thiophene compounds, naphthalene dicarboxylate Imine compounds, triarylamine compounds and aminoacridine compounds.

The negative photosensitive resin layer N may contain only one type of sensitizer, or may contain two or more types of sensitizers.

When the negative photosensitive resin layer N contains a sensitizer, the content ratio of the sensitizer can be appropriately selected according to the purpose, but from the viewpoints of improving the sensitivity to a light source and improving the curing speed by balancing the polymerization speed and chain transfer Considering, with respect to the total mass of the negative photosensitive resin layer N, the content ratio of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass.

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

The negative photosensitive resin layer N may contain resins other than those described above. Examples of resins other than the above include acrylic resins, styrene-acrylic copolymers (however, the styrene content is limited to copolymers with a styrene content of 40% by mass or less.), polyurethane resins, and polyvinyl alcohol , polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, Polyethyleneimine, polyallylamine and polyalkylene glycol.

The negative photosensitive resin layer N may contain a solvent. When the negative photosensitive resin layer N is formed from the photosensitive resin composition containing a solvent, the solvent may remain in the negative photosensitive resin layer N in some cases. The solvent will be described later.

As an additive, the negative photosensitive resin layer N may also contain, for example, a metal oxide particle, an antioxidant, a dispersant, an acid proliferator, a development accelerator, a conductive fiber, a thermal radical polymerization initiator, a thermal acid At least one of a generator, a UV absorber, a tackifier, a crosslinking agent, an organic precipitation inhibitor, and an inorganic precipitation inhibitor. Additives are described in, for example, paragraphs 0165 to 0184 of JP-A-2014-85643. The contents of the above-mentioned publications are incorporated herein by reference.

-Impurities, etc.- The negative photosensitive resin layer N may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among the above, halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the following contents are preferable.

The impurity content in the negative photosensitive resin layer N is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, on a mass basis. The impurity content in the negative photosensitive resin layer N may be 1 ppb or more or 0.1 ppm or more on a mass basis.

As a method of setting the impurity within the above range, a method of selecting a raw material with a small impurity content as a raw material of the negative photosensitive resin layer N, a method of preventing contamination of impurities when forming the negative photosensitive resin layer N, and A method of cleaning manufacturing equipment to remove impurities. By this method, the amount of impurities can be set within the above-mentioned range.

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

Benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylformamide in the negative photosensitive resin layer N The content of acetamide and hexane is preferably lower. As content of the said compound in a negative photosensitive resin layer N, 100 ppm or less is preferable on a mass basis, 20 ppm or less is more preferable, and 4 ppm or less is further more preferable. The content of the above-mentioned compound in the negative photosensitive resin layer N may be 10 ppb or more or 100 ppb or more on a mass basis. The content of the above-mentioned compound can be suppressed by the same method as the above-mentioned metal impurity. Moreover, it can quantify by a well-known measurement method.

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

-thickness- The thickness of the negative photosensitive resin layer N may be determined according to, for example, the thickness of the resin pattern 2 formed in the development step described later. The thickness of the negative photosensitive resin layer N may be determined, for example, within the range of 1 μm to 100 μm.

-Transmittance- In the negative photosensitive resin layer N, the transmittance of light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more, from the viewpoint of more excellent adhesion. The upper limit of transmittance is not limited. In the negative photosensitive resin layer N, the transmittance of light having a wavelength of 365 nm is preferably 99.9% or less.

The preparation step includes: the step of preparing a layered precursor having the above-mentioned transparent substrate and the light-shielding pattern 1 on the above-mentioned transparent substrate; and forming the above-mentioned negative type on the above-mentioned transparent substrate and the above-mentioned light-shielding pattern 1 The step of the photosensitive resin layer N is preferable. In the step of forming the above-mentioned negative-type photosensitive resin layer N, it is preferable to form the above-mentioned negative-type photosensitive resin layer N using a photosensitive transfer material (also referred to as a "dry film"). That is, it is preferable that the said negative photosensitive resin layer N is a layer formed with a photosensitive transfer material.

The preparation steps include: a step of preparing a transparent substrate; a step of forming a light-shielding pattern 1 on the above-mentioned transparent substrate; and a step of forming a negative photosensitive resin layer N on the above-mentioned transparent substrate and the above-mentioned light-shielding pattern 1. good. Preferably, the step of forming the light-shielding pattern 1 includes the following steps: forming a light-shielding layer on the transparent substrate; forming a photosensitive resin layer on the light-shielding layer; The step of forming a photoresist pattern by exposing and developing; and the step of removing the above-mentioned light-shielding layer not covered by the above-mentioned photoresist pattern. In the step of forming the negative-type photosensitive resin layer N, it is preferable to form the negative-type photosensitive resin layer N using a photosensitive transfer material.

The preparation step includes, for example: a step of preparing a transparent substrate; a step of forming a light-shielding pattern 1 on the transparent substrate; and forming a negative type on the transparent substrate and the light-shielding pattern 1 The step of the photosensitive resin layer N.

In addition, the preparation step includes, for example: a step of preparing a laminate precursor having a transparent base material and a light-shielding layer on the transparent base material; a step of forming the light-shielding pattern 1 from the light-shielding layer ; and the step of forming a negative photosensitive resin layer N on the above-mentioned transparent substrate and the above-mentioned light-shielding pattern 1 . The light-shielding layer is a layer that becomes the material of the light-shielding pattern 1 . As a manufacturing method of the laminated precursor which has a transparent base material and a light-shielding layer, the method of forming a light-shielding layer on a transparent base material is mentioned, for example.

In addition, the preparation step includes, for example, a step of forming a light-shielding layer on one surface of a transparent substrate; a step of forming a photoresist layer on the light-shielding layer; A step of forming a photoresist pattern by exposure and development; and a step of etching the above-mentioned light-shielding layer to form the above-mentioned light-shielding pattern 1 . There is no restriction|limiting in particular as a formation method of a photoresist layer, A well-known photoresist composition and a photosensitive transfer material can be used.

-Method for forming light-shielding pattern 1- Hereinafter, the formation method of the light-shielding pattern 1 is demonstrated. As a formation method of the light-shielding pattern 1, the method of forming a light-shielding layer on a transparent base material, and processing the said light-shielding layer into a pattern shape is mentioned, for example.

As a method of forming a light-shielding layer, sputtering and plating are mentioned, for example. In sputtering, for example, a layer (light-shielding layer) containing Cu, Ti, or Ni can be formed on a transparent substrate. Among the above metals, Cu, which has a low resistance and is inexpensive, is preferable. The composition of the layer (light-shielding layer) formed by sputtering may be Ni, Al, Nb, W, Ni-P, or Ni-B. As plating, for example, electroless plating is mentioned. As a method of electroless plating, a known method can be used. For example, in electroless copper plating, copper can be deposited on a transparent substrate by the reaction of copper ions and a reducing agent. Preferably, the catalyst used in electroless plating is a palladium-tin mixed catalyst. The primary particle size of the mixed catalyst is preferably 10 nm or less. It is preferable that the bath for electroless plating contains hypophosphorous acid as a reducing agent. As a plating, the electroplating demonstrated in the item of the following "the formation process of the pattern 3" is also mentioned, for example. The structure of the light-shielding layer may be a single-layer structure or a multilayer structure. By forming a light-shielding layer having a multilayer structure, a conductive pattern having a multilayer structure can be formed. As a formation method of each layer contained in the light-shielding layer which has a multilayer structure, electroless plating, sputtering, vapor deposition, and coupling agent coating are mentioned, for example.

As a method of processing a light-shielding layer into a pattern shape, photolithography is mentioned, for example. As the photolithography, a known photolithography can be used. For example, a photosensitive resin layer is formed on the light-shielding layer, then a photoresist pattern is formed by exposing and developing the photosensitive resin layer, and then the light-shielding layer not covered by the photoresist pattern is removed, thereby, A light-shielding pattern can be formed.

The type of the photosensitive resin layer formed on the light-shielding layer is not limited. The photosensitive resin layer may be a positive type photosensitive resin layer or a negative type photosensitive resin layer. As a negative photosensitive resin layer, the negative photosensitive resin layer demonstrated in the said "negative photosensitive resin layer N" part is mentioned, for example. As a method of forming a photosensitive resin layer, the method of using a photosensitive resin composition, and the method of using a photosensitive transfer material are mentioned, for example. As a method of using a photosensitive resin composition, the method of apply|coating a photosensitive resin composition on a photosensitive layer, and drying the photosensitive resin composition, for example is mentioned. The photosensitive resin composition is a composition containing the material of the photosensitive resin layer. As a method of using a photosensitive transfer material, the method of disposing a photosensitive resin layer on a light-shielding layer is mentioned, for example by bonding the photosensitive transfer material which has a photosensitive resin layer, and a light-shielding layer. For the method of forming the negative-type photosensitive resin layer, the following "Method for forming the negative-type photosensitive resin layer N" can be referred to.

The exposure method of the photosensitive resin layer will not be limited as long as it is a method which can form an exposed part and an unexposed part in a photosensitive resin layer. As an exposure method, a well-known method can be used. The area of the photosensitive resin layer to be exposed may be determined according to the shape of the target light-shielding pattern. For exposure conditions, refer to the "Exposure Procedure" section below.

The developing method of the photosensitive resin layer is not limited as long as it is a method which can process the photosensitive resin layer into a pattern by removing the exposed part or the unexposed part of the photosensitive resin layer. In the development of the negative photosensitive resin layer, the unexposed portion of the negative photosensitive resin layer is removed. In the development of the positive-type photosensitive resin layer, the exposed portion of the positive-type photosensitive resin layer is removed. As a development method, a well-known method can be used. For development conditions, the section "Development Steps" can be referred to below.

As a method of removing the light-shielding layer not covered by the photoresist pattern (that is, the light-shielding layer exposed to light), a known method can be used. For example, when the light-shielding layer includes metal, the light-shielding layer not covered by the photoresist pattern can be removed by etching. As etching, wet etching and dry etching are mentioned, for example. The etching is preferably wet etching. Wet etching is etching using a chemical called an etching solution. As an etching liquid, a sulfuric acid-hydrogen peroxide aqueous solution is mentioned, for example. The composition of the sulfuric acid-hydrogen peroxide aqueous solution is not limited. As a sulfuric acid-hydrogen peroxide aqueous solution, the sulfuric acid-hydrogen peroxide aqueous solution whose density|concentration of sulfuric acid is 1-10 volume% and the density|concentration of hydrogen peroxide is 1-10 volume% is mentioned, for example. The temperature of the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 20°C to 35°C. The immersion time in the sulfuric acid-hydrogen peroxide aqueous solution can be set in the range of 1 minute - 10 minutes, for example. When the light-shielding layer contains copper, the sulfuric acid-hydrogen peroxide aqueous solution can be used until the concentration of copper dissolved in the sulfuric acid-hydrogen peroxide aqueous solution reaches, for example, 50 g/L. As an etching liquid, a cupric chloride solution can also be mentioned, for example. The composition of the cupric chloride solution is not limited. As the cupric chloride solution, for example, a solution containing 20 to 35 mass % of cupric chloride and 1 to 7 mass % of chlorine can be preferably used. However, the etching conditions are not limited to those described above. For example, the temperature of the etching solution and the immersion time in the etching solution may be determined according to the composition of the light-shielding layer, the thickness of the light-shielding layer, and the type of the etching solution.

The laminated body may have an adhesive layer between the transparent base material and the light-shielding pattern 1 . For the formation of the adhesive layer, for example, the adhesive layer may be formed on the transparent substrate before the light-shielding pattern 1 is formed. As a formation method of an adhesive layer, electroless plating, sputtering, and vapor deposition are mentioned, for example. As a formation method of an adhesive layer, the method of coating, drying, and baking of the metal particle dispersion liquid in which the metal particle is dispersed can also be mentioned.

In the manufacturing method of the laminated body, the surface of the transparent substrate may be roughened by decontamination treatment as needed before forming the adhesive layer and the light-shielding pattern. Examples of the decontamination treatment liquid (oxidative roughening liquid) include chromium/sulfuric acid roughening liquid, alkali permanganic acid roughening liquid (for example, sodium permanganate roughing liquid), and sodium fluoride/chromium/sulfuric acid Coarse liquid.

-The formation method of the negative photosensitive resin layer N- Hereinafter, the formation method of the negative photosensitive resin layer N is demonstrated. As a formation method of the photosensitive resin layer N, the method of using the photosensitive resin composition, and the method of using the photosensitive transfer material are mentioned, for example.

-Photosensitive resin composition- As a method of using a photosensitive resin composition, the method of apply|coating a photosensitive resin composition on a transparent base material and a light-shielding pattern, and drying the photosensitive resin composition, is mentioned, for example.

The components of the photosensitive resin composition may be determined according to the components of the target negative photosensitive resin layer N. As a preferable component of a photosensitive resin composition, the component demonstrated in the said "negative photosensitive resin layer N" is mentioned, for example. As a photosensitive resin composition, the composition containing a polymer A, a polymerizable compound B, and a photoinitiator is mentioned, for example. In order to adjust the viscosity of the photosensitive resin composition and form a photosensitive resin layer easily, it is preferable that the photosensitive resin composition contains a solvent.

The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin composition (eg, polymer A, polymerizable compound B, and polymerization initiator), and known solvents can be used. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (for example, methanol and ethanol), ketone solvents (for example, acetone and methyl ethyl ketone), Aromatic hydrocarbon solvents (eg, toluene), aprotic polar solvents (eg, N,N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents .

Preferably, the photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent One is better. The photosensitive resin composition contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents and cyclic ether solvents are particularly preferred.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, Dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol. Monoalkyl ether acetate.

As the solvent, the solvent described in the paragraphs 0092 to 0094 of International Publication No. WO 2018/179640, and the solvent described in the paragraph 0014 of JP 2018-177889 A can also be used. The contents of these are incorporated herein by reference.

The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvents.

The content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

The preparation method of the photosensitive resin composition is not limited. As a method for preparing the photosensitive resin composition, for example, a method for preparing a photosensitive resin composition by preparing a solution obtained by dissolving each component in a solvent in advance, and mixing each of the obtained solutions in a predetermined ratio is exemplified. . The photosensitive resin composition is preferably filtered using a filter having a pore diameter of 0.2 μm to 30 μm before forming the negative photosensitive resin layer.

There is no restriction|limiting as a coating method of the photosensitive resin composition, A well-known method can be used. As a coating method, slot coating, spin coating, curtain coating, and inkjet coating are mentioned, for example.

-Photosensitive transfer material- As a method of using a photosensitive transfer material, for example, by laminating a photosensitive transfer material having a negative photosensitive resin layer N and a transparent base material having a light-shielding pattern, the transparent base material and the light-shielding pattern are attached to the transparent base material and the light-shielding pattern. A method of disposing the negative photosensitive resin layer N thereon. In the method of laminating the photosensitive transfer material having the negative photosensitive resin layer N and the transparent substrate having a light-shielding pattern, the photosensitive transfer material and the transparent substrate are superimposed and applied by means of a roller or the like. Pressure and heating are preferred. For lamination, a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used. Hereinafter, the constituent elements of the photosensitive transfer material will be described.

--Photosensitive resin layer-- The photosensitive transfer material has a negative photosensitive resin layer N. The negative-type photosensitive resin layer N is as described in the section of the above-mentioned "negative-type photosensitive resin layer N".

--Temporary support-- It is preferable that the photosensitive transfer material has a temporary support. The temporary support system is a support that can be peeled off from the photosensitive transfer material. The temporary support can support the negative photosensitive resin layer N at least. The temporary support can also be peeled off before the exposure step. In the exposure step, the temporary support may be peeled off after irradiating light without peeling off the temporary support. In the exposure step, by irradiating light without peeling off the temporary support, the influence of dust and dirt in the exposure environment can be avoided.

As a temporary support body, the temporary support body which has light transmittance can be used. In the present disclosure, "having light transmittance" means that the light transmittance of the wavelength used in pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the negative photosensitive resin layer N, in the temporary support, the light transmittance of the wavelength (preferably 365 nm) used for pattern exposure is preferably 60% or more, preferably 70% The above is better.

As a temporary support, a glass substrate, a resin film, and paper are mentioned, for example. From the viewpoints of strength, flexibility, and light transmittance, it is preferable that the temporary support is a resin film.

As a resin film, a polyethylene terephthalate film (that is, a PET film), a cellulose triacetate film, a polystyrene film, and a polycarbonate film are mentioned, for example. The resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

The thickness of the temporary support is not limited. The average thickness of the temporary support may be determined according to, for example, the strength, light transmittance, material, and flexibility required for laminating the photosensitive transfer material and the transparent substrate as the temporary support. The average thickness of the temporary support is preferably 5 μm to 100 μm. In addition, from the viewpoints of ease of handling and versatility, the average thickness of the temporary support is preferably 5 μm to 50 μm, more preferably 5 μm to 20 μm, further preferably 10 μm to 20 μm, and particularly preferably 10 μm to 16 μm.

The arithmetic mean roughness Ra of the surface on the side where the negative photosensitive resin layer N of the temporary support is arranged is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.02 μm or less. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic mean roughness Ra of the surface on the side where the negative photosensitive resin layer N of the temporary support is arranged may be determined, for example, within a range of 0 μm or more.

The arithmetic mean roughness Ra is measured by the following method. The surface profile of the object to be measured was obtained under the following conditions using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation). As measurement and analysis software, Microscope Application of MetroPro ver8.3.2 was used. Next, use the above software to display the Surface Map screen, and obtain the histogram data on the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the measurement object is obtained. In addition, when the surface of the object to be measured is in contact with the surface of the other layer, the arithmetic mean roughness Ra of the surface of the object to be measured exposed by peeling the object to be measured from the other layer may be measured.

It is preferable that the temporary support (especially the resin film) is free from deformation (eg, fine lines), damage and defects, for example. From the viewpoint of the transparency of the temporary support, it is preferable that the number of particles, foreign substances, defects, and precipitates contained in the temporary support be small. In the temporary support body, the number of particles, foreign objects and defects with a diameter of 1 μm or more is preferably 50 pieces/10mm ² or less, more preferably 10 pieces/10mm ² or less, and still more preferably 3 pieces/10mm ² or less, 0/10mm ² is particularly good.

Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of JP 2014-85643 A, paragraphs 0019 to 0026 of JP 2016-27363 A, and International Publication No. 2012/081680 It is described in paragraphs 0041 to 0057 of WO 2018/179370, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese Patent Application Laid-Open No. 2019-101405. The contents of these publications are incorporated into this specification by reference.

--cover film-- The photosensitive transfer material may have a cover film (also called a protective film). According to the coverlay film, the surface of the layer in contact with the coverlay film (for example, the negative photosensitive resin layer N) can be protected. It is preferable that the photosensitive transfer material contains a temporary support body, a negative photosensitive resin layer N, and a coverlay film in this order. It is preferable that the photosensitive transfer material has a cover film, and this cover film is in contact with the surface on the opposite side of the side where the temporary support of the negative photosensitive resin layer N is arranged.

As a coverlay film, a resin film and paper are mentioned, for example. From the viewpoint of strength and flexibility, the cover film is preferably a resin film.

As a resin film, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film are mentioned, for example. The resin film is preferably polyethylene film, polypropylene film or polyethylene terephthalate film.

The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm.

From the viewpoint of better resolution, the arithmetic mean roughness Ra of the surface on the side where the negative photosensitive resin layer N of the cover film is arranged is preferably 0.3 μm or less, more preferably 0.1 μm or less, and 0.05 μm or less. Excellent. When the arithmetic mean roughness of the surface on the side where the negative-type photosensitive resin layer N of the cover film is arranged is within the above-mentioned range, the uniformity of the thickness of the negative-type photosensitive resin layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra is not limited. It is preferable that the arithmetic mean roughness Ra of the surface on the side where the negative photosensitive resin layer N of the coverlay film is arrange|positioned is 0.001 micrometer or more. The arithmetic mean roughness Ra of the surface on the side where the negative photosensitive resin layer N is disposed of the cover film is measured by a method that follows the method for measuring the arithmetic mean roughness Ra described in the above-mentioned "Temporary Support" section.

--Thermoplastic resin layer-- The photosensitive transfer material of the present disclosure may also have a thermoplastic resin layer N. As shown in FIG. It is preferable that the photosensitive transfer material has a thermoplastic resin layer between the temporary support body and the negative photosensitive resin layer N. This is because the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the negative-type photosensitive resin layer N, so that the followability to the adherend is improved, and the transfer between the adherend and the photosensitive resin is suppressed. Incorporation of air bubbles between the printing materials, as a result, the interlayer adhesion is improved.

It is preferable that the thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.

Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, and polyester resins. , polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene dialkylene alcohol.

From the viewpoint of developability and adhesiveness with a layer adjacent to the thermoplastic resin layer, it is preferable that the alkali-soluble resin is an acrylic resin. Here, the "acrylic resin" means a group selected from the group consisting of a constitutional unit derived from (meth)acrylic acid, a constitutional unit derived from (meth)acrylate, and a constitutional unit derived from (meth)acrylate amide At least one resin of the group.

In the acrylic resin, with respect to the total mass of the acrylic resin, the total of the constitutional unit derived from (meth)acrylic acid, the constitutional unit derived from (meth)acrylate, and the constitutional unit derived from (meth)acrylic acid amide The content ratio is preferably 50% by mass or more. In the acrylic resin, with respect to the total mass of the acrylic resin, the ratio of the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylates is 30% by mass to 100% by mass. Preferably, 50 mass % - 100 mass % are more preferable.

Moreover, it is preferable that the alkali-soluble resin is a polymer having an acid group. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group are mentioned, for example, a carboxyl group is preferable.

From the viewpoint of developability, an alkali-soluble resin having an acid value of 60 mgKOH/g or more is preferable, and a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is more preferable. The upper limit of the acid value is not limited. The acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not limited, and known resins can be appropriately selected and used. Examples of carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more among polymers described in paragraph 0025 of JP-A No. 2011-95716, for example. , Carboxyl group-containing acrylic resins with an acid value of 60 mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of Japanese Patent Laid-Open No. 2010-237589, and paragraphs 0053 to 0068 of Japanese Patent Laid-Open No. 2016-224162 A carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more in the binder polymer described in .

Relative to the total mass of the carboxyl group-containing acrylic resin, the content ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12% by mass. % to 30% by mass is particularly preferred.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid from the viewpoints of developability and adhesiveness with a layer adjacent to the thermoplastic resin layer.

Alkali-soluble resins may also have reactive groups. The reactive group may be, for example, a group capable of addition polymerization. As a reactive group, an ethylenically unsaturated group, a polycondensation-polymerizable group (for example, a hydroxyl group and a carboxyl group), and a complex addition reactive group (for example, an epoxy group and a (blocked) isocyanate group) are mentioned, for example.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resin.

From the viewpoint of developability and adhesiveness with the layer adjacent to the thermoplastic resin layer, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass relative to the total mass of the thermoplastic resin layer, and 20% by mass is preferred. The content is more preferably from 90% by mass to 90% by mass, more preferably from 40% by mass to 80% by mass, and particularly preferably from 50% by mass to 70% by mass.

The thermoplastic resin layer contains a dye whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength is changed by acid, alkali, or radical (hereinafter, sometimes referred to as "dye B"): better. The preferred aspect of the dye B will be described later, and other than that, it is the same as the preferred aspect of the above-mentioned dye NC.

From the viewpoints of the visibility of the exposed part, the visibility of the unexposed part, and the resolution, it is preferable that the dye B is a dye whose maximum absorption wavelength is changed by an acid or a radical, and a dye whose maximum absorption wavelength is changed by an acid for better.

From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, and the resolution, it is preferable that the thermoplastic resin layer contains a dye whose maximum absorption wavelength of the dye B is changed by an acid, and a compound that generates an acid by light, which will be described later. good.

The thermoplastic resin layer may contain one type of pigment B alone, or two or more types of pigment B may be contained.

From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, the content ratio of the dye B is preferably 0.2 mass % or more, more preferably 0.2 mass % to 6 mass %, with respect to the total mass of the thermoplastic resin layer. , 0.2% by mass to 5% by mass is more preferable, and 0.25% by mass to 3.0% by mass is particularly preferable.

Here, the content ratio of the dye B refers to the content ratio of the dye when all the dyes B contained in the thermoplastic resin layer are in a colored state. Hereinafter, a method for quantifying the content ratio of the dye B will be described as an example of the dye developed by radicals. Two solutions were prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL), respectively. IRGACURE OXE-01 (BASF) was added to each of the obtained solutions as a photo-radical polymerization initiator, and then irradiated with light of 365 nm to generate radicals, and all dyes were brought into a colored state. Next, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, SHIMADZU CORPORATION) under the atmosphere, and a calibration curve was prepared. Next, except that the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone instead of the dye, the absorbance of the solution in which all the dyes were developed was measured by the same method as above. From the absorbance of the solution containing the obtained thermoplastic resin layer, the amount of the pigment contained in the thermoplastic resin layer was calculated based on the calibration curve.

The thermoplastic resin layer may contain a compound (hereinafter, sometimes referred to as "compound C") that generates an acid, a base, or a radical by light. Compound C is preferably a compound that generates acid, base or radical by receiving actinic rays (eg, ultraviolet rays and visible rays). As compound C, a well-known photoacid generator, a photobase generator, and a photoradical polymerization initiator (photoradical generator) are mentioned. Compound C is preferably a photoacid generator.

From the viewpoint of resolution, it is preferable that the thermoplastic resin layer contains a photoacid generator. As a photoacid generator, the photocationic polymerization initiator which can also be contained in the said negative photosensitive resin layer is mentioned, and the preferable aspect is the same except for the point mentioned later.

From the viewpoints of sensitivity and resolution, it is preferable that the photoacid generator contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoints of sensitivity, resolution and adhesion, it is preferable to include Oxime sulfonate compounds are more preferred.

Moreover, it is also preferable that the photoacid generator is a photoacid generator having the following structure.

[Chemical formula 2]

The thermoplastic resin layer may also contain a photobase generator. As the photobase generator, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-aminocarbamoyl hydroxyamide, o-aminocarbamoyl oxime, [[( 2,6-Dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexyl 1,6-diamine, 4-(methylthiobenzyl) (4-morpholinobenzyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyl) oxycarbonyl)pyrrolidine, hexamine cobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)- Butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5- Diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

The thermoplastic resin layer may also contain a photoradical polymerization initiator. As a photoradical polymerization initiator, the photoradical polymerization initiator which can also be contained in the said negative photosensitive resin layer is mentioned, for example, and a preferable aspect is also the same.

The thermoplastic resin layer may contain one compound C alone, or may contain two or more compounds C.

From the viewpoint of the visibility of the exposed portion, the visibility of the unexposed portion, and the resolution, the content of the compound C is preferably 0.1% by mass to 10% by mass, and preferably 0.5% by mass to 0.5% by mass relative to the total mass of the thermoplastic resin layer. 5 mass % is more preferable.

From the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability, it is preferable that the thermoplastic resin layer contains a plasticizer.

The molecular weight of the plasticizer (the molecular weight of the oligomer or polymer is referred to as the weight-average molecular weight (Mw). Hereinafter, the same applies in this paragraph.) is preferably smaller than that of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. It is preferable that the alkyleneoxy group contained in the plasticizer has a polyvinyloxy structure or a polypropyleneoxy structure.

From the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion with a layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

As a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound described in the said "polymerizable compound B" is mentioned, for example. In the photosensitive transfer material, when the thermoplastic resin layer and the negative photosensitive resin layer are arranged in direct contact with each other, it is preferable that the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the negative photosensitive resin layer N contain the same (meth)acrylate compound, respectively, so that the diffusion of components between layers is suppressed, and the storage stability is improved.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesiveness with a layer adjacent to the thermoplastic resin layer, the (meth)acrylate compound is even in the exposed portion after exposure. It is also preferred not to aggregate.

In one embodiment, the (meth)acrylate compound used as a plasticizer has, in one molecule, from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability A (meth)acrylate compound having two or more (meth)acryloyl groups is preferred.

In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group.

The thermoplastic resin layer may contain one type of plasticizer alone or two or more types of plasticizers.

From the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass relative to the total mass of the thermoplastic resin layer. , 10% by mass to 60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferable.

From the viewpoint of the uniformity of thickness, it is preferable that the thermoplastic resin layer contains a surfactant. As a surfactant, the surfactant which can also be contained in the said negative photosensitive resin layer N is mentioned, for example, and a preferable aspect is also the same.

The thermoplastic resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, with respect to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may also contain a sensitizer. As a sensitizer, the sensitizer which can also be contained in the said negative photosensitive resin layer is mentioned, for example.

The thermoplastic resin layer may contain one type of sensitizer alone, or may contain two or more types of sensitizers.

From the viewpoint of improving the sensitivity to the light source, the visibility of the exposed portion, and the visibility of the unexposed portion, the content of the sensitizer is preferably 0.01% by mass to 5% by mass relative to the total mass of the thermoplastic resin layer. 0.05 mass % - 1 mass % are more preferable.

In addition to the above-mentioned components, the thermoplastic resin layer may contain known additives as necessary.

In addition, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Laid-Open No. 2014-85643. The contents of the above-mentioned publications are incorporated herein by reference.

The thickness of the thermoplastic resin layer is not limited. From the viewpoint of the adhesiveness with the layer adjacent to the thermoplastic resin layer, the average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolution, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

The method for forming the thermoplastic resin layer is not limited as long as it can form a layer containing the above-mentioned components. As a formation method of a thermoplastic resin layer, the method of apply|coating a thermoplastic resin composition to the surface of a temporary support body, and drying the coating film of a thermoplastic resin composition, for example is mentioned.

As a thermoplastic resin composition, the composition containing the above-mentioned components is mentioned, for example. The thermoplastic resin composition can adjust the viscosity of the thermoplastic resin composition and easily form a thermoplastic resin layer, so it is preferable to contain a solvent.

The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. As a solvent, the solvent which can also contain the said photosensitive resin composition is mentioned, and the preferable aspect is also the same.

As a thermoplastic resin composition, 1 type of solvent may be contained independently, and 2 or more types of solvents may be contained.

The content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the preparation method of the photosensitive resin composition and the formation method of the negative photosensitive resin layer N described above. For example, a solution obtained by dissolving each component contained in the thermoplastic resin layer in a solvent is prepared in advance, and each of the obtained solutions is mixed in a predetermined ratio to prepare a thermoplastic resin composition, and then the obtained thermoplastic resin composition The thermoplastic resin layer can be formed by coating the thermoplastic resin composition on the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Moreover, after forming the negative photosensitive resin layer N on the coverlay film, you may form a thermoplastic resin layer on the surface of the negative photosensitive resin layer N.

--middle layer-- It is preferable that the photosensitive transfer material has an intermediate layer between the thermoplastic resin layer and the negative photosensitive resin layer N. According to the intermediate layer, it is possible to suppress the mixing of components when forming a plurality of layers and when storing a plurality of layers.

It is preferable that the intermediate layer is a water-soluble layer from the viewpoints of developability and suppression of the mixing of components when coating a plurality of layers and when storing a plurality of layers after coating. In the present disclosure, "water-solubility" means that the solubility in 100 g of water at a liquid temperature of 22° C. and a pH of 7.0 is 0.1 g or more.

As the intermediate layer, for example, an oxygen blocking layer having an oxygen blocking function described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724 can be mentioned. Since the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved. The oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers. The oxygen blocking layer used as the intermediate layer is preferably an oxygen blocking layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass % aqueous solution of sodium carbonate at 22°C).

It is preferable that the intermediate layer contains resin. Examples of resins contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylic acid amide-based resins, polyethylene oxide-based resins, gelatin, vinyl Base ether resins, polyamide resins and their copolymers. The resin contained in the intermediate layer is preferably a water-soluble resin.

From the viewpoint of suppressing the mixing of components between a plurality of layers, the resin contained in the intermediate layer is the polymer A contained in the negative photosensitive resin layer N and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer. Resin which is different in any of them is preferable.

The intermediate layer preferably contains polyvinyl alcohol, including polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of oxygen barrier properties and suppression of component mixing when applying multiple layers and when storing multiple layers after application. for better.

The intermediate layer may contain one type of resin alone, or may contain two or more types of resins.

From the viewpoints of oxygen barrier properties and suppression of component mixing when applying multiple layers and when storing multiple layers after application, the content ratio of the resin in the intermediate layer is 50% by mass to 50% by mass relative to the total mass of the intermediate layer. 100 mass % is preferable, 70 mass % to 100 mass % are more preferable, 80 mass % to 100 mass % are further preferable, and 90 mass % to 100 mass % are particularly preferable.

Moreover, the intermediate layer may contain an additive as needed. As an additive, a surfactant is mentioned, for example.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above-mentioned range, it is possible to suppress the mixing of components during formation and storage of a plurality of layers without reducing oxygen barrier properties, and to suppress an increase in the time required to remove the intermediate layer during development.

The method for forming the intermediate layer is not limited as long as it can form a layer containing the above-mentioned components. As a formation method of an intermediate layer, the method of apply|coating the composition for intermediate layers to the surface of a thermoplastic resin layer or a negative photosensitive resin layer N, and drying the coating film of the composition for intermediate layers, is mentioned, for example.

Examples of the composition for the intermediate layer include resins and compositions containing optional additives. The composition for an intermediate layer adjusts the viscosity of the composition for an intermediate layer, and since it is easy to form an intermediate layer, it is preferable to contain a solvent. The solvent is not limited as long as it can dissolve or disperse the resin. Preferably, the solvent is at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably, water or a mixed solvent of water and a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

Moreover, the photosensitive transfer material may have other layers, such as a refractive index adjustment layer. It does not specifically limit as a refractive index adjustment layer, A well-known refractive index adjustment layer can be used. The refractive index of the refractive index adjustment layer is preferably higher than the refractive index of the photosensitive layer from the viewpoint of suppressing the visibility of wiring. The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.70 or more. The upper limit of the refractive index of the refractive index adjustment layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less. The thickness of the refractive index adjustment layer is not particularly limited. The thickness of the refractive index adjustment layer is preferably 50 nm or more and 500 nm or less, more preferably 55 nm or more and 110 nm or less, and even more preferably 60 nm or more and 100 nm or less. The method of controlling the refractive index of the refractive index adjustment layer is not particularly limited, and examples thereof include a method of using a resin with a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, and a composite of a metal salt and a resin. method etc. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal oxide particles are specifically selected from the group consisting of zirconia particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles) and silicon dioxide particles (SiO ₂ particles) At least one of them is preferred. Among these, as the metal oxide particles, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable from the viewpoint of, for example, that it is easy to adjust the refractive index of the second resin layer to 1.6 or more. .

--The average thickness-- The average thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The average thickness of the photosensitive transfer material is measured by a method in accordance with the above-mentioned measuring method of the average thickness of the transparent substrate.

--shape-- The shape of the photosensitive transfer material is not limited. From the viewpoints of versatility and transportability, the shape of the photosensitive transfer material is preferably a roll shape. By winding up the photosensitive transfer material, the shape of the photosensitive transfer material can be made into a roll shape.

-Manufacturing method of photosensitive transfer material-- The manufacturing method of the photosensitive transfer material is not limited. As a manufacturing method of the photosensitive transfer material, for example, a method including the steps of forming a negative photosensitive resin layer N by applying a photosensitive resin composition on a temporary support body; The step of disposing a cover film on the type photosensitive resin layer N. In the above-mentioned method, the photosensitive resin composition applied on the temporary support may be dried as necessary. There is no restriction|limiting as a drying method, A well-known drying method can be used. As a method of disposing a coverlay on the negative-type photosensitive resin layer N, for example, the method of crimping the coverlay to the negative-type photosensitive resin layer N is exemplified.

<Exposure step> The manufacturing method of the structure of this disclosure includes the step (exposure step) of irradiating light from a part facing the negative photosensitive resin layer N on the side opposite to the surface on which the light shielding pattern 1 of the transparent substrate is provided. In the exposure step, light is irradiated from the surface of the transparent base material on the opposite side to the surface on which the light-shielding pattern 1 is provided. In the present disclosure, "the surface of the transparent substrate on which the light-shielding pattern 1 is provided" refers to the surface on the side of the transparent substrate having the light-shielding pattern 1 . For example, in FIG. 1( b ), “the surface of the transparent substrate on which the light-shielding pattern is provided” refers to the surface of the transparent substrate 10 in contact with the light-shielding pattern 20 , that is, the surface opposite to the exposed surface 10 a side face. For example, as shown in FIG. 1( b ), when light is irradiated to the surface of the transparent substrate on the opposite side to the surface facing the light-shielding pattern, the light-shielding pattern reaches the side of the negative photosensitive resin layer N through the light-shielding pattern. Part of the light is blocked, whereby a part of the negative photosensitive resin layer N can be selectively exposed. The solubility of the exposure part of the negative photosensitive resin layer N in a developing solution falls. Moreover, compared with the case where light is irradiated from the negative photosensitive resin layer N toward the transparent substrate, by irradiating light on the surface of the transparent substrate opposite to the surface facing the light-shielding pattern , the hardening of the negative photosensitive resin layer N located in the vicinity of the transparent base material can be accelerated. As a result, the resolution of the resin pattern can be improved in the development step described later. Also, a resin pattern having highly linear sidewalls can be formed.

The light source used in the exposure step should just be a light source that irradiates light of a wavelength capable of exposing the negative photosensitive resin layer N (for example, 365 nm or 405 nm). As a specific light source, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and LED (Light Emitting Diode: Light Emitting Diode) are mentioned, for example.

Preferably, the light irradiated in the exposure step includes wavelengths within the wavelength range of 200 nm to 1,500 nm, and more preferably includes wavelengths within the wavelength range of 250 nm to 450 nm, including wavelengths within the wavelength range of 300 nm to 410 nm. More preferably, a wavelength including 365 nm is even more preferred.

The exposure amount is preferably 5mJ/cm ² -200mJ/cm ² , more preferably 10mJ/cm ² -100mJ/cm ² .

Since a part of the negative photosensitive resin layer N can be selectively exposed by the light-shielding pattern, light can also be irradiated to all regions of the surface on the opposite side of the surface on which the light-shielding pattern 1 of the transparent substrate is provided. .

<Development step> The manufacturing method of the structure of this disclosure includes the step (development step) of forming the resin pattern 2 on the above-mentioned transparent base material by developing the above-mentioned negative photosensitive resin layer N irradiated with light. In the developing step, by developing the negative photosensitive resin layer N, the resin pattern 2 is formed in the region defined by the transparent base material and the light-shielding pattern. For example, as shown in FIG. 1( c ), in the developing step, by removing the unexposed portion of the negative photosensitive resin layer N, a shape having a shape corresponding to the shape of the exposed portion of the negative photosensitive resin layer N is formed. Resin pattern of shapes.

As a development method, a well-known method can be used. The development of the negative photosensitive resin layer N can be performed, for example, using a developer. The kind of developer is not limited as long as the unexposed part of the negative photosensitive resin layer N can be removed. As a developer, a well-known developer (for example, the developer described in Unexamined-Japanese-Patent No. 5-72724) can be used.

The developing solution is preferably an aqueous alkaline solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L. The developer may also contain a water-soluble organic solvent and/or a surfactant. As a developer, the developer described in the paragraph 0194 of International Publication No. 2015/093271 is also preferable.

The development method is not particularly limited, and may be any of spin-on immersion development, shower development, shower and spin development, and immersion development. The spray development refers to a development process in which the exposed part or the unexposed part is removed by spraying the developer to the exposed photosensitive resin layer by spraying.

After the developing step, it is preferable to spray the cleaning agent by a shower, and to remove the developing residue while wiping with a brush.

The liquid temperature of the developer is not limited. The liquid temperature of the developing solution is preferably 20°C to 40°C.

The average thickness of the resin pattern 2 is preferably larger than the average thickness of the light-shielding pattern 1 . Since the average thickness of the resin pattern 2 is larger than the average thickness of the light-shielding pattern, the thick light-shielding pattern 1 can be formed. The ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 ([the average thickness of the resin pattern 2]/[the average thickness of the light-shielding pattern 1]) is preferably 1.1 or more, more preferably 1.5 or more, and 3 The above are excellent. The ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 may be 4, 5, or 10. The average thickness of the resin pattern 2 is measured by a method in accordance with the above-mentioned measuring method of the average thickness of the transparent substrate.

The average thickness of the resin pattern 2 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably more than 2 μm. In addition, the average thickness of the resin pattern is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The upper limit of the thickness of the resin pattern 2 is not limited. The average thickness of the resin pattern may be determined, for example, within a range of 100 μm or less.

The average width of the resin pattern 2 is preferably 50 μm or less, and more preferably 5 μm or less. The average width of the resin pattern 2 is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The average width of the resin pattern 2 is measured by a method according to the method of measuring the average width of the light-shielding pattern 1 .

<Formation step of pattern 3> The manufacturing method of the structure of this disclosure includes the step of forming the pattern 3 in the region defined by the light-shielding pattern 1 and the resin pattern 2 described above (the forming step of the pattern 3 ). In the step of forming the pattern 3 , the pattern 3 is formed on the light-shielding pattern 1 . For example, as shown in FIG.1(d), in the formation process of the pattern 3, the pattern 3 is formed in the area|region defined by the light-shielding pattern 1 and the resin pattern 2. From the viewpoint of further exerting the effects of the present disclosure, it is preferable that the pattern 3 has conductivity. Moreover, it is preferable that the average thickness of the said pattern 3 is thicker than the average thickness of the said light-shielding pattern 1 from a viewpoint of pattern formability and the dimensional stability of the obtained pattern 3.

As a method of forming the pattern 3, a known method can be used. As the material of the conductive pattern 3, a conductive material suitable for the application can be used. Preferably, the material of the conductive pattern 3 contains Cu or an alloy of Cu. The Cu alloy is preferably an alloy of Cu and at least one selected from the group consisting of Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W. The pattern 3 formed using the above-mentioned material contains the above-mentioned metal element. The pattern 3 obtained in the forming step of the pattern 3 may be a conductive pattern composed of Cu. Moreover, it is preferable that the said light-shielding pattern 1 and the said pattern 3 contain the same kind of material from a viewpoint of pattern formability and the dimensional stability of the obtained pattern 3. For example, it is more preferable to contain the same metal element, and it is particularly preferable to contain the same metal or an alloy of the same metal element.

As a method of forming the pattern 3 on the light-shielding pattern 1, a well-known method can be used. The pattern 3 is preferably a pattern formed by a plating method. As the plating, known plating can be used. As plating, for example, electroplating and electroless plating are mentioned. The plating is preferably electroplating, more preferably copper electroplating.

In electroplating, for example, a light-shielding pattern 1 that can function as a seed layer is used as a cathode, and a conductive pattern 3 can be formed on the light-shielding pattern 1 by stacking metal on the light-shielding pattern 1 .

As a component of the plating solution used for electroplating, a water-soluble copper salt is mentioned, for example. As the water-soluble copper salt, a commonly used water-soluble copper salt can be used as a component of the plating solution. As the water-soluble copper salt, for example, at least one selected from the group consisting of inorganic copper salts, alkanesulfonic acid copper salts, alkanolsulfonic acid copper salts and organic acid copper salts is preferred. As an inorganic copper salt, copper sulfate, copper oxide, copper chloride, and copper carbonate are mentioned, for example. Examples of copper alkanesulfonates include copper methanesulfonate and copper propanesulfonate. Examples of copper alkanolsulfonates include copper isethionate and copper propanolsulfonate. As an organic acid copper salt, copper acetate, copper citrate, and copper tartrate are mentioned, for example.

The plating solution may also contain sulfuric acid. By containing sulfuric acid in the plating solution, the pH and sulfuric acid ion concentration of the plating solution can be adjusted.

The plating method and conditions are not limited. For example, the pattern 3 having conductivity can be formed on the light-shielding pattern 1 by supplying the transparent base material after the development step to a plating bath to which a plating solution is added. In electroplating, for example, the conductive pattern 3 can be formed by controlling the current density and the conveying speed of the transparent substrate.

The temperature of the bath used in electroplating is usually 70°C or lower, preferably 10°C to 40°C. The current density in electroplating is usually 0.1A/dm ² -100A/dm ² , preferably 0.5A/dm ² -20A/dm ² . By increasing the current density, the productivity of the conductive pattern can be improved. By reducing the current density, the uniformity of the thickness of the conductive pattern can be improved.

In the method of forming the conductive pattern 3 by plating, a plurality of metals can be continuously plated. For example, in the sexual pattern 3 formed of a metal such as copper, a reduction in visibility or aesthetics due to reflection may become a problem. As a method of reducing the reflectance of the surface of the pattern 3, for example, oxidation treatment, sulfurization treatment, nitridation treatment, chlorination treatment, blackening layer coating formation, and black plating are mentioned. For example, by performing chrome plating after copper plating, a layer containing a black material can be formed on the surface of the pattern 3 . The method for reducing the reflectance of the surface of the pattern 3 is preferably oxidation treatment or vulcanization treatment. Oxidation treatment is also preferred from the viewpoints that a more excellent anti-glare effect can be obtained, and the easiness and environmental safety of waste liquid treatment can be obtained.

After the pattern 3 is formed, a post-baking step may also be performed. In the post-baking step, by completely thermosetting the unreacted thermosetting components, it is possible to improve insulation reliability, hardening properties, or plating adhesion. The heating temperature is preferably 80°C to 240°C. The heating time is preferably 5 minutes to 120 minutes.

After the pattern 3 is formed, the surface of the pattern 3 can also be protected by a resin layer. For example, after the pattern 3 is formed, the surface of the pattern 3 can be protected by forming a resin layer on the conductive pattern. As a component of a resin layer, an acrylic resin, a polyester resin, a polyvinyl acetal resin layer, a polyimide resin, and an epoxy resin are mentioned, for example. As a formation method of a resin layer, application|coating and thermocompression bonding are mentioned, for example.

The structure of the pattern 3 may be a single-layer structure or a multi-layer structure. The composition of each layer of the pattern 3 having a multi-layer structure may be the same or different.

The thickness of the pattern 3 is not limited. The thickness of the pattern 3 may be determined, for example, depending on the application. When the pattern 3 is used as a wiring, the average thickness of the pattern 3 may be determined according to, for example, the magnitude of the current supplied to the wiring and the wiring width. From the viewpoint of electrical conductivity, the average thickness of the pattern 3 is preferably 0.5 μm or more, more preferably 1 μm or more, and particularly preferably 2 μm or more. In addition, the average thickness of the pattern 3 is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The average thickness of the pattern 3 is measured by a method in accordance with the above-mentioned measuring method of the average thickness of the transparent substrate.

The width of the pattern 3 is preferably thin. Specifically, the average width of the pattern 3 is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. By setting the average width of the pattern 3 to be 5 μm or less, the visibility of the pattern 3 in a device sensitive to visibility, such as a touch panel, can be reduced. From the viewpoint of electrical conductivity, the average width of the pattern 3 is preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The average width of the pattern 3 is measured by a method in accordance with the method for measuring the average width of the light-shielding pattern 1 described above.

The surface resistance value of the conductive pattern 3 is preferably less than 0.2Ω/□, more preferably less than 0.15Ω/□. The surface resistance value of the conductive pattern 3 was measured by the four-point probe method. When the pattern size is fine and difficult to measure, the surface resistance value of the conductive layer of the same composition and thickness can be measured.

In the step of forming the pattern 3 , the interface between the pattern 3 and the light-shielding pattern 1 may not be clearly observed. For example, when the light-shielding pattern 1 is used as a seed layer and the pattern 3 is formed by plating, the interface between the light-shielding pattern 1 and the pattern 3 may not be clearly observed. However, the inability to clearly observe the interface between the pattern 3 and the light-shielding pattern 1 does not hinder the purpose of the present disclosure.

<Post-exposure step and post-heating step> From the viewpoint of improving the strength and durability of the resin pattern 2 as a permanent film, it is preferable that the manufacturing method of the structure of the present disclosure further includes at least one of post-exposure and post-heating on the resin pattern 2 described above. The manufacturing method of the structure of the present disclosure preferably includes a post-exposure step (also referred to as a "post-exposure step") of the resin pattern 2 after the development step, and preferably includes the step of forming the pattern 3 after the above-mentioned pattern 3. More preferably, the resin pattern 2 is subjected to a post-exposure step. Moreover, the manufacturing method of the structure of the present disclosure may further include a step of heating (post-heating) the above-mentioned resin pattern 2 (also referred to as a "post-heating step") as needed. Since the resin pattern 2 is an exposure portion of the negative photosensitive resin layer N, by performing the above-mentioned post-exposure or the above-mentioned post-heating, the residual polymerization initiator, polymerizable compound, etc. are further subjected to a polymerization reaction, etc., thereby improving the The strength of the resin pattern 2 and durability such as heat resistance, light resistance, and moisture resistance.

There is no restriction|limiting in particular as a light source used for exposure in a post-exposure process, A well-known light source for exposure can be used. From the viewpoint of removability, it is preferable to use a light source containing light of the same wavelength as that in the above-described resin pattern forming step.

The exposure amount in the post-exposure step is preferably 5 mJ/cm ² to 5,000 mJ/cm ² from the viewpoint of removability, more preferably 10 mJ/cm ² to 3,000 mJ/cm ² , and 100 mJ/cm ² to 1,500 mJ/cm ² is particularly preferred.

From the viewpoint of removability, the exposure amount in the post-exposure step is preferably equal to or more than the exposure amount in the resin pattern forming step, and more preferably more than the exposure amount in the resin pattern forming step.

The manufacturing method of the structure of the present disclosure may also include a plurality of post-heating steps. The heating temperature and heating time in the post-heating step are not particularly limited, and can be appropriately selected. The method of post-heating is not specifically limited, A well-known method can be used, For example, it can be performed by the mechanism provided in an exposure apparatus and a developing apparatus, and a hotplate etc. can also be used.

<Other steps> The manufacturing method of the structure of the present disclosure may include any steps (other steps) other than those described above. There is no restriction|limiting in particular as another process, A well-known process is mentioned. In addition, as an example of the resin pattern forming step and other steps in the present disclosure, the method described in paragraphs 0035 to 0051 of JP-A 2006-23696 can also be preferably used in the present disclosure. In addition, the manufacturing method of the structure of the present disclosure may also include a step of grinding the obtained pattern, a step of cleaning the obtained pattern, and the like. In addition, the manufacturing method of the structure of the present disclosure may also include a step of arranging members according to various uses described later, and the like.

＜＜Use＞＞ The structure obtained by the manufacturing method of the structure of the present disclosure can be applied to various uses. As applications of the structure obtained by the manufacturing method of the structure of this disclosure, a touch sensor, an electromagnetic wave shielding material, an antenna, a wiring board, and a conductive heating element are mentioned, for example. Among the above-mentioned uses, the structure obtained by the manufacturing method of the structure of the present disclosure can function as a conductor, for example. In addition, among the above-mentioned uses, the structure obtained by the manufacturing method of the structure of the present disclosure can express various functions according to the characteristics of the pattern (resin pattern 2 and pattern 3, etc.) to be formed.

＜Touch sensor＞ The touch sensor of the present disclosure has a structure obtained by the manufacturing method of the structure of the present disclosure. In the touch sensor of the present disclosure, the conductive patterns (eg, the light-shielding pattern 1 and the conductive pattern 3 , the same below) of the structures can be used as transparent electrodes or frame wirings, for example. The constituent elements of the touch sensor of the present disclosure are not limited except for the structure obtained by the manufacturing method of the structure of the present disclosure. As components other than the above-described structures, components included in a known touch sensor can be used. The touch sensor is described in, for example, Patent No. 6486341 and Japanese Patent Laid-Open No. 2016-155978. The above-mentioned publications are incorporated herein by reference. The manufacturing method of the touch sensor of the present disclosure is a method of manufacturing the touch sensor having the structure obtained by the manufacturing method of the structure of the present disclosure, and is not limited.

＜Electromagnetic wave shielding material＞ The electromagnetic wave shielding material of this disclosure has a structure obtained by the manufacturing method of the structure of this disclosure. In the electromagnetic wave shielding material of the present disclosure, the pattern of the above-mentioned structure can be used as an electromagnetic wave shielding material, for example. The constituent elements of the electromagnetic wave shielding material of the present disclosure are not limited except that the structure obtained by the manufacturing method of the structure of the present disclosure is included. As components other than the above-mentioned structures, components included in known electromagnetic wave shielding materials can be used. The electromagnetic wave shielding material is described in, for example, Patent No. 6486382 and Japanese Patent Laid-Open No. 2012-163951. The above-mentioned publications are incorporated herein by reference. The manufacturing method of the electromagnetic wave shielding material of this disclosure is a method of manufacturing the electromagnetic wave shielding material which has the structure obtained by the manufacturing method of the structure of this disclosure, and is not limited.

＜Antenna＞ The antenna of the present disclosure is an antenna having the structure obtained by the manufacturing method of the structure of the present disclosure. In the antenna of the present disclosure, the pattern of the above-mentioned structure can be used as, for example, a transceiver portion or a transmission line portion. The constituent elements of the antenna of the present disclosure are not limited except that the structure obtained by the manufacturing method of the structure of the present disclosure is included. As components other than the above-described structures, components included in known antennas can be used. The antenna is described in, for example, Japanese Patent Application Laid-Open No. 2016-219999. The above-mentioned publications are incorporated herein by reference. The method of manufacturing the antenna of the present disclosure is a method of manufacturing the antenna having the structure obtained by the method of manufacturing the structure of the present disclosure, and is not limited.

<Wiring board> The wiring board of the present disclosure has a structure obtained by the manufacturing method of the structure of the present disclosure. In the wiring board of the present disclosure, the conductive pattern of the above-mentioned structure can be used, for example, as a wiring of a printed wiring board. The constituent elements of the wiring board of the present disclosure are not limited except that the structure obtained by the manufacturing method of the structure of the present disclosure is included. As components other than the above-mentioned structures, components included in a known wiring board can be used. The wiring board is described in, for example, Patent No. 5774686 and Japanese Patent Laid-Open No. 2017-204538. The above-mentioned publications are incorporated herein by reference. The manufacturing method of the wiring board of the present disclosure is a method of manufacturing a wiring board having the structure obtained by the manufacturing method of the structure of the present disclosure, and is not limited.

＜Conductive heating element＞ The conductive heating element of the present disclosure has a structure obtained by the manufacturing method of the structure of the present disclosure. In the conductive heating element of the present disclosure, the conductive pattern possessed by the above-mentioned structure can be used, for example, as a heating element. The constituent elements of the conductive heating element of the present disclosure are not limited except that the structure obtained by the manufacturing method of the structure of the present disclosure is included. As components other than the above-mentioned structure, components included in a known conductive heating element can be used. The conductive heating element is described in, for example, Japanese Laid-Open Patent Publication No. 6486382 . The above-mentioned publications are incorporated herein by reference. The method of manufacturing the conductive heating element of the present disclosure is a method of manufacturing the conductive heating element having the structure obtained by the method of manufacturing the structure of the present disclosure, and is not limited.

(struct) The structure of the present disclosure includes: a transparent substrate; a light-shielding pattern 1 disposed on the transparent substrate; a resin pattern 2 disposed adjacent to the light-shielding pattern 1 on the transparent substrate and adjacent to the transparent substrate contact; and pattern 3, formed in the area delimited by the above-mentioned light-shielding pattern 1 and the above-mentioned resin pattern 2, the average thickness of the above-mentioned light-shielding pattern 1 is 2 μm or less, the average thickness of the above-mentioned resin pattern 2 exceeds 2 μm, and the average thickness of the above-mentioned pattern 3 The average thickness is thicker than the average thickness of the said light-shielding pattern 1, and the said structure has the said resin pattern 2 as a permanent film. According to the above aspect, there is provided a structure having a conductive pattern that reduces the occurrence of morphological abnormalities. Moreover, it is preferable that the structure of this disclosure is manufactured by the manufacturing method of the structure of this disclosure.

In addition to the above-mentioned preferred aspects of the transparent substrate, the light-shielding pattern 1, the resin pattern 2, and the pattern 3 in the structure of the present disclosure, the transparent substrate and the light-shielding method in the manufacturing method of the structure of the present disclosure described above The preferred aspect of the sexual pattern 1, the resin pattern 2 and the pattern 3 is the same.

Referring to FIG. 2 , the structure A of the present disclosure will be described. FIG. 2 is a schematic cross-sectional view showing an example of the structure of the present disclosure. The structure 200 shown in FIG. 2 has a transparent substrate 11 , a pattern 21 (light-shielding pattern 1 ), a resin pattern 41 (resin pattern 2 ), and a pattern 51 (pattern 3 ). The light-shielding pattern 21 is arranged on the transparent substrate 11 . The light-shielding pattern 21 is in contact with the transparent substrate 11 . However, the light-shielding pattern 21 may be in contact with the transparent base material 11 via another layer (not shown). The resin pattern 41 is arranged adjacent to the light-shielding pattern 21 on the transparent base material 11 and is in contact with the transparent base material 11 . Moreover, the pattern 51 is arrange|positioned between the resin patterns 41 on the light-shielding pattern 21, and is arrange|positioned. [Example]

Hereinafter, the present disclosure will be described in detail by way of examples. However, the present disclosure is not limited to the following examples.

<Synthesis of tetrahydrofuran-2-yl acrylate (ATHF)> Acrylic acid (72.1 g, 1.0 mol) and hexane (72.1 g) were added to the three-necked flask, and cooled at 20°C. After adding dropwise camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (77.9 g, 1.0 mol), the mixture was stirred at 20°C ± 2°C for 1.5 hours, then the temperature was raised to 35°C and stirred for 2 hours . After spreading KYOWARD200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and KYOWARD1000 (filter material, hydrotalcite-based powder, manufactured by Kyowa Chemical Industry Co., Ltd.) on the suction filter bottle in this order , and the reaction solution was filtered to obtain a filtrate. After adding hydroquinone monomethyl ether (MEHQ, 1.2 mg) to the obtained filtrate, it was concentrated under reduced pressure at 40°C to obtain 140.8 g of tetrahydrofuran-2-yl acrylate (ATHF) as a colorless oily substance. ) (99.0% yield).

<Synthesis of polymer A-1> PGMEA (75.0 g) was added to the three-necked flask, and the temperature was raised to 90° C. under a nitrogen atmosphere. A solution containing ATHF (40.0g), AA (2.0g), EA (20.0g), MMA (22.0g), CHA (16.0g), A solution of V-601 (4.0 g) and PGMEA (75.0 g). After completion of the dropwise addition, the polymer A-1 (solid content concentration 40.0 mass %) was obtained by stirring at 90° C.±2° C. for 2 hours. The content of each structural unit in the polymer A-1 is shown in Table 1. The acid value of the polymer A-1 was 15.6 mgKOH/g. In addition, the above-mentioned abbreviations represent the following compounds, respectively. "AA": Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) "CHA": cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) "EA": Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) "MMA": methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) "PGMEA": Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.) "V-601": 2,2'-azobis(2-methylpropionic acid) dimethyl ester (manufactured by FUJIFILM Wako Pure Chemical Corporation)

<Synthesis of polymer A-2> The solution (solid content concentration: 40.0 mass %) containing polymer A-2 was obtained by the same method as polymer A-1 except having changed the usage-amount of a monomer according to the following. The weight average molecular weight of polymer A-2 was 60,000. (1) Styrene: 52.0g (2) Methacrylic acid: 29.0g (3) Methyl methacrylate: 19.0g

<Synthesis of polymer A-3> The monomers (styrene, methacrylic acid and methyl methacrylate) used in the synthesis of polymer A-1 were changed to the following monomers, except that the same method as polymer A-1 was carried out. A solution (solid content concentration: 40.0 mass %) containing the polymer A-3 was obtained. The weight average molecular weight of polymer A-3 was 40,000. (1) Benzyl methacrylate: 81.0g (2) Methacrylic acid: 19.0g

<Preparation of negative photosensitive resin composition> After mixing the components selected according to the description in Table 1, the negative photosensitive resin compositions NR1 to NR6 (solid content concentration: 25 mass %) were prepared by adding methyl ethyl ketone.

[Table 1] Negative photosensitive resin composition NR1 NR2 NR3 NR4 NR5 NR6 Polymer A-1 Styrene/methacrylic acid/methyl methacrylate=32/28/40 (mass %), Mw=40,000, acid value=182.5 mgKOH/g - 55.00 - 62.20 - - Polymer A-2 Styrene/methacrylic acid/methyl methacrylate=52/29/19 (mass %), Mw=60,000, acid value=189.0 mgKOH/g 50.00 - - - - 51.00 Polymer A-3 Benzyl methacrylate/methacrylic acid=81/19 (mass %), Mw=40,000, acid value=123.8 mgKOH/g - - 52.00 - 59.20 - BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 36.20 20.20 7.40 - 27.00 15.00 BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) - 9.80 10.00 20.00 - - Dimethacrylate of polyvinyl alcohol obtained by adding an average of 15 moles of ethylene oxide and an average of 12 moles of propylene oxide to both ends of bisphenol A, respectively - - - - - 10.00 M-270 (manufactured by TOAGOSEI CO., LTD.) 5.00 - - - - - A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) - 10.00 10.00 6.00 - 5.00 SR-454 (manufactured by ARKEMA) - - 15.00 9.00 - 5.00 SR-502 (manufactured by ARKEMA) - - - - 4.00 - A-9300-CL1 (manufactured by Shin-Nakamura Chemical Co., Ltd.) - - - - 7.80 9.77 B-CIM (manufactured by KUROGANE KASEI Co., Ltd.) 7.00 3.00 3.80 1.90 1.10 3.00 SB-PI 701 (manufactured by SANYO TRADING CO., LTD.) 0.50 0.50 0.30 0.30 0.10 0.30 Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.40 0.90 - 0.40 0.66 0.60 N-Phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.20 - 1.00 - - - Bright green (manufactured by Tokyo Chemical Industry Co., Ltd.) - 0.05 0.05 0.05 - 0.02 CBT-1 (manufactured by JOHOKU CHEMICAL CO.,LTD) 0.10 - 0.05 0.03 0.03 - 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole to 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole 1: 1 (mass ratio) mixture - 0.14 0.05 - - 0.10 TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.) 0.30 0.10 - - - - Irganox245 (manufactured by BASF) - - 0.20 0.10 0.10 0.20 N-nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation) - - 0.01 0.02 0.01 0.01 Phenidone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.01 0.01 0.01 - - - F-552 (manufactured by DIC CORPORATION) 0.29 0.30 0.13 - - - total 100 100 100 100 100 100

In addition, the unit of the numerical value of each component column in Table 1 is a mass part. In addition, the details of the abbreviations described in Table 1 are shown below. BPE-500: Ethoxylated bisphenol A dimethacrylate (10 moles of ethylene oxide added), manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-200: Ethoxylated bisphenol A dimethacrylate (4 moles of ethylene oxide added), manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated trimethylolpropane triacrylate (addition of 3 moles of ethylene oxide), manufactured by ARKEMA SR-502: Ethoxylated trimethylolpropane triacrylate (with 9 moles of ethylene oxide added), manufactured by ARKEMA A-9300-CL1: ε-caprolactone-modified tris-(2-propenyloxyethyl) isocyanate, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), manufactured by Hampford Corporation, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD. CBT-1: Rust inhibitor, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD TDP-G: Polymerization inhibitor, phenothia, manufactured by Kawaguchi Chemical Industry Co., LTD. Irganox245: Polymerization inhibitor, hindered phenolic compound, manufactured by BASF Corporation F-552: Fluorine-based surfactant, MEGAFACE F552, manufactured by DIC CORPORATION

<Preparation of positive photosensitive resin composition PR1> The solid content concentration was obtained by mixing polymer A-1, photoacid generator B-1, surfactant C-1, basic compound D-1, and PGMEA weighed according to the composition shown in Table 2 below. 10 mass % mixture. The positive photosensitive resin composition PR1 was obtained by filtering the above-mentioned mixture using a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm.

[Table 2] Positive photosensitive resin composition PR1 Polymer A-1 100 Photoacid generator B-1 3 Surfactant C-1 0.1 Basic compound D-1 1.6

In addition, the unit of the numerical value of each component column in Table 2 is a mass part. In addition, the details of each component other than the above described in Table 2 are shown below.

The photoacid generator B-1 is a compound having the following structure (the compound described in paragraph 0227 of JP-A No. 2013-47765 was synthesized according to the method described in paragraph 0227).

[Chemical formula 3]

Surfactant C-1 is a compound having the following structure.

[Chemical formula 4]

The basic compound D-1 is a compound having the following structure.

[Chemical formula 5]

<Preparation of negative photosensitive resin compositions N1 to N8> After mixing the selected components as described in Table 3 or Table 4, a 1:1 (mass ratio) mixed solvent of 1-methoxy-2-propyl acetate and methyl ethyl ketone was added to prepare a negative Type photosensitive resin compositions N1-N8 (solid content concentration: 29 mass %).

[table 3] Negative sensory resin composition N1 N2 N3 N4 N5 N6 N7 ethylenically unsaturated compounds M-1 8.41% 8.41% 8.41% 8.41% 8.41% 8.41% 8.41% M-2 - - 16.83% 16.83% - - - M-3 16.83% 16.83% - - 16.83% 16.83% 16.83% M-4 2.80% 2.80% 2.80% - 2.80% 2.80% 2.80% M-5 - - - 2.80% - - - Alkali Soluble Polymer P-1 56.32% 56.32% 56.32% 56.32% 56.32% 56.32% 62.58% photopolymerization initiator D-1 0.32% 0.32% 0.32% 0.32% 0.32% 0.32% - D-2 0.64% 0.64% 0.64% 0.64% 0.64% 0.64% - D-3 - - - - - - 7.00% Thermally Crosslinkable Compounds E-1 12.50% 12.50% 12.50% 12.50% 12.50% 12.50% - Other additives Pyridine-3-carboxylic acid (nicotinic acid) - - 0.69% - - - - 2-Aminopyridine - - - 0.69% - - - benzimidazole 0.69% - - - - - - benzotriazole - 0.69% - - - - - Pyridine - - - - 0.69% - - Pyrimidine - - - - - 0.69% - AD-1 0.10% 0.10% 0.10% 0.10% 0.10% 0.10% 0.20% AD-2 1.20% 1.20% 1.20% 1.20% 1.20% 1.20% - AD-3 0.19% 0.19% 0.19% 0.19% 0.19% 0.19% - AD-4 - - - - - - 0.50% AD-5 - - - - - - 0.40% AD-6 - - - - - - 0.30% AD-7 - - - - - - 0.69% AD-8 - - - - - - 0.29%

[Table 4] Negative photosensitive resin composition N8 Types of ingredients used Content (portions) Multifunctional epoxy resin ZFR-1492H (Epoxy resin containing bisphenol F type acid-modified ethylenically unsaturated group, manufactured by Nippon Kayaku Co., Ltd.) 90 Hydroxyl-containing compounds Phenolic resin (trade name MARUKA LYNCUR PHM-C, manufactured by Maruzen Petrochemical Co., Ltd.) 5 Cationic polymerization initiator Trade name TAG-382, manufactured by TOYO INK CO., LTD. 5

In addition, the unit of the numerical value of the content of each component in Table 3 and Table 4 is a mass part. In addition, the details of each component described in Table 3 are shown below. -ethylenically unsaturated compounds- M-1: A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) M-2: Dipionaerythritol hexaacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) M-3: A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) M-4: ARONIX TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by TOAGOSEI CO., LTD.) M-5: Urethane acrylate 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO,.LTD.)

-Alkali-soluble polymer- P-1: For the resin shown below, a structural unit derived from styrene (St) / a structural unit derived from dicyclopentyl methacrylate (DCPMA) / a structural unit derived from methacrylic acid (MAA) / The structural unit obtained by adding glycidyl methacrylate to the structural unit derived from methacrylic acid (GMA-MAA) = 41.0/15.2/23.9/19.9 (mol%), Mw = 17,000)

-Photopolymerization initiator- D-1: 1-[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (Irgacure OXE -02, made by BASF company) D-2: 2-methyl-1-(4-methylthiophenyl)-2-merolinopropan-1-one (Irgacure 907, manufactured by BASF Corporation) D-3: B-CIM (photoradical generator (photopolymerization initiator), manufactured by Hampford Corporation, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer): 0.89 mass share

-Thermal crosslinkable compound- E-1: Duranate WT32-B75P (blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Co., Ltd.): 12.50 parts

-Other ingredients- AD-1: Hydrogen-donating compound (N-phenylglycine, manufactured by JUNSEI CHEMICAL CO., LTD.) AD-2: Copolymer of styrene/maleic anhydride=4:1 (molar ratio) (AD-2, SMA EF-40, acid anhydride value 1.94 mmol/g, weight average molecular weight 10,500, manufactured by Cray Valley Corporation ) AD-3: Fluorine-based surfactant (MEGAFACE F551A, manufactured by DIC CORPORATION) AD-4: Sensitizer (4,4'-bis(diethylamino)benzophenone, SB-PI 701, manufactured by SANYO TRADING CO., LTD.) AD-5: Pigment (colorless crystal violet, manufactured by YAMADA CHEMICAL CO., LTD.) AD-6: Polymerization inhibitor (TDP-G manufactured by Kawaguchi Chemical Industry Co., LTD., Kawaguchi Chemical Industry Co., LTD.) AD-7: Rust inhibitor (Carboxybenzotriazole, CBT-1 manufactured by JOHOKU CHEMICAL CO., LTD) AD-8: Fluorine-based surfactant (MEGAFACE F552, manufactured by DIC CORPORATION)

(Example 1) <Preparation of Photosensitive Transfer Material (Dry Film) 1> As a temporary support, a PET film (lumirror 16KS40 manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm: arithmetic mean roughness Ra: 0.02 μm) was prepared. The negative photosensitive resin composition NR1 was coated on the surface of the temporary support using a slit nozzle so that the coating width was 1.0 m, and the thickness after drying was the value described in Table 5. The formed coating film of the negative photosensitive resin composition NR1 was dried at 90° C. for 100 seconds to form a photoresist layer. A photosensitive transfer material 1 was produced by crimping a polyethylene film (TAMAPOLY CO., LTD., GF-818, thickness: 19 μm) as a cover film on the surface of the formed photoresist layer. By winding the obtained photosensitive transfer material 1, the photosensitive transfer material 1 of the roll form was produced.

<Formation of the light-shielding pattern 1 (copper pattern)> On a polyethylene terephthalate (PET) film with a thickness of 100 μm, a copper layer with a thickness of 0.05 μm was formed by sputtering, thereby producing a PET film with a copper layer. After peeling off the cover film from the photosensitive transfer material 1, the photosensitive transfer material 1 is attached to the PET film with the copper layer. The bonding step was performed under the conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min. Next, the photoresist layer was exposed to light by irradiating light through a mask using a high pressure mercury lamp exposure machine (MAP-1200L manufactured by Japan Science Engineering Co., Ltd., dominant wavelength: 365 nm). After peeling off the temporary support, the photoresist layer was subjected to spray development for 30 seconds using an aqueous sodium carbonate solution with a liquid temperature of 25° C., thereby forming a resin pattern (line/space=5.5 μm/4.5 μm). The copper layer not covered with the resin pattern was etched using an etching solution (Cu-02 manufactured by KANTO CHEMICAL CO., INC.). Residual resin patterns were removed using a peeling solution (10 mass % sodium hydroxide aqueous solution). Through the above procedure, a PET film with a copper pattern (line/space=5 μm/5 μm) was produced. The copper pattern functions as the light-shielding pattern 1 . The average thickness of the light-shielding pattern 1 is shown in Table 5.

<Preparation of photosensitive transfer material 2> As a temporary support, a PET film (lumirror 16KS40 manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm: arithmetic mean roughness Ra: 0.02 μm) was prepared. The negative photosensitive resin composition N1 was coated on the surface of the temporary support using a slit nozzle so that the coating width was 1.0 m, and the thickness after drying was the value described in Table 5. The formed coating film of the negative photosensitive resin composition N1 was dried at 90° C. for 100 seconds.

Then, the photosensitive transfer material 2 was produced by press-bonding a polyethylene film (TAMAPOLY CO., LTD., GF-818, thickness: 19 μm) as a cover film. By winding the obtained photosensitive transfer material 2, the photosensitive transfer material 2 of the roll form was produced.

<Formation of pattern 3 (copper pattern)> After peeling off the cover film from the photosensitive transfer material 2, the PET film with a copper pattern and the photosensitive transfer material 2 were bonded together. The bonding step was performed under the conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min. The obtained laminated body has a PET film, a copper pattern (light-shielding pattern 1), a negative photosensitive resin layer N, and a temporary support in this order. The surface of the PET film opposite to the surface facing the copper pattern (light-shielding pattern 1) was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Japan Science Engineering Co., Ltd., dominant wavelength: 365 nm). Light. The exposure amount was set to 70 mJ/cm ² . After peeling off the temporary support, the negative photosensitive resin layer N was subjected to shower development for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25° C., thereby forming the resin pattern 2 . The space portion (ie, the groove) of the copper pattern (light-shielding pattern 1 ) is filled with the resin pattern 2 . The average thickness of the resin pattern 2 is shown in Table 2. The conductive pattern 3 is formed by depositing copper on the copper pattern (light-shielding pattern 1 ) not covered with the resin pattern 2 by electro-copper electroplating. The current density in the copper electroplating was 1.8 ASD. The treatment time in the copper electroplating was 6 minutes. The PET film after electroplating was heated at 130°C for 30 minutes. Through the above procedure, a structure having a copper pattern (line (L)/space (S)=5 μm/5 μm) was produced. Table 5 shows the average thickness of the copper pattern (pattern 3 having conductivity) deposited by electro-copper plating.

(Examples 2 to 13) The type and thickness of the base material, the thickness (average thickness) of the light-shielding pattern 1, the type of the photosensitive resin composition forming the light-shielding pattern 1, and the dry coating thickness of the photosensitive resin composition were appropriately changed as described in Table 5. (Thickness of the resist layer), the shape of the light-shielding pattern 1, the exposure method at the time of forming the photosensitive pattern 1 (including the presence or absence of peeling of the temporary support), the formation method of the negative photosensitive resin layer N, and the negative photosensitive resin layer N used. A structure having a copper pattern was produced by the same procedure as in Example 1, except for the type of photosensitive composition, the type of other layers, the thickness (average thickness) of the pattern 3, and the presence or absence of curing treatment. By prolonging the treatment time, the average thickness of copper deposited by electroplating can be increased.

In addition, in Example 2, a polyimide (PI) film having a thickness of 100 μm was used as the substrate used, and after patterning 3, a high-pressure mercury lamp exposure machine (manufactured by Japan Science Engineering Co., Ltd. was used) MAP-1200L, dominant wavelength: 365 nm), post-exposure was performed by irradiating light with an exposure amount of 1,000 mJ/cm ² .

In Example 3, as the base material used, a base material (COP/ITO) in which an indium tin oxide (ITO) film with a thickness of 0.1 μm was formed on a polycycloolefin (COP) film with a thickness of 100 μm by sputtering method On the above, a copper layer with a thickness of 0.03 μm was formed by sputtering, thereby preparing a base material with a copper layer. Moreover, in Example 3, instead of the negative photosensitive resin composition N1, N10 in which a high refractive index layer was laminated|stacked was formed on the following negative photosensitive resin composition N1. As a temporary support, a PET film (lumirror 16KS40 manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm: arithmetic mean roughness Ra: 0.02 μm) was prepared. The negative photosensitive resin composition N1 was applied on the surface of the temporary support using a slit nozzle so that the application width was 1.0 m and the thickness after drying was 3 μm. The negative photosensitive resin layer N was formed by drying the coating film of the formed negative photosensitive resin composition N1 at 90° C. for 100 seconds. Next, a coating liquid for an overcoat layer (composition N9) composed of the following formulation 201 was adjusted and applied on the negative photosensitive resin layer N using a slit nozzle so that the thickness after drying was 0.2 μm. Thickness, the solvent was removed by drying with a hot air convection dryer with a temperature gradient of 40°C to 95°C, and an overcoat layer (OC layer) was formed in direct contact with the photosensitive layer. The refractive index of the overcoat was 1.68 at a wavelength of 550 nm at 25°C. Here, formulation 201 is prepared by using a resin having an acid group and an aqueous ammonia solution, and the resin having an acid group is neutralized by an aqueous ammonia solution to prepare an aqueous resin composition containing an ammonium salt of the resin having an acid group, that is, for an outer coating coating liquid.

- Coating liquid for overcoat layer: Formulation 201 (water-based resin composition) - - Acrylic resin (ZB-015M, manufactured by FUJIFILM Wako Pure Chemical Corporation, methacrylic acid/allyl methacrylate copolymer resin, weight average molecular weight 25,000, composition ratio (molar ratio) = 20/80, solid content 5.00%, ammonia solution): 4.92 parts ・Multifunctional ethylenically unsaturated compound with carboxylic acid group (ARONIX TO-2349, TOAGOSEI CO.,LTD Manufactured): 0.04 parts ・ZrO ₂ particles (NanoUse OZ-S30M, solid content 30.5%, methanol 69.5%, refractive index 2.2, average particle size: about 12 nm, manufactured by Nissan Chemical Industries, LTD.): 4.34 parts Rust agent (benzotriazole derivative, BT-LX, manufactured by JOHOKU CHEMICAL CO., LTD): 0.03 part ・Surfactant (fluorine-based surfactant, MEGAFACE F444, manufactured by DIC CORPORATION): 0.01 part ・Distilled water: 24.83 Parts・Methanol: 65.83 parts

A photosensitive transfer material 2 was produced by press-bonding a polyethylene film (manufactured by TAMAPOLY CO., LTD., GF-818, thickness: 19 μm) as a cover film to the surface of the formed overcoat layer. By winding the obtained photosensitive transfer material 2, the photosensitive transfer material 2 of the roll form was produced.

Moreover, in Example 4, exposure was performed by the direct drawing exposure (DI exposure) method using the direct drawing exposure apparatus (Via Mechanics, Ltd. make, DE-1DH, main wavelength 405nm). In addition, in Example 7, after the substrate formed by laminating the photosensitive transfer material was fixed on a 4-inch silicon wafer with an adhesive tape, reduction projection exposure was performed using an i-ray stepper (NSR-2009i9C) manufactured by Nikon Corporation. , and further, after forming pattern 3, heating was performed at 145° C. for 20 minutes. In addition, in Examples 9 and 10, the positive photosensitive resin composition PR1 described in Table 5 was applied without using the photosensitive transfer material 1, and dried at 90° C. for 100 seconds to form Table 5. A resist layer of the thickness described in . In addition, in Examples 8 and 11, without using the photosensitive transfer material 2, the negative photosensitive resin composition described in Table 5 was applied and dried at 90° C. for 100 seconds to form the composition shown in Table 5. The negative photosensitive resin layer N of the described thickness.

In Example 12, the light-shielding pattern 1 was formed as follows. A PET film (COSMOSHINEA4300 manufactured by TOYOBO CO., LTD., thickness: 75 μm) was prepared. A printer in which the ink in the ink core of the monochrome ink jet printer PX-K100 (manufactured by Seiko Epson Corporation) was replaced with silver nano ink (DryCure Ag-J manufactured by C-INK Corporation) was prepared. This printer was subjected to a printing operation via a print driver, whereby after the wiring pattern was formed, it was heated at 60° C. for 2 minutes. A PET film with a silver wiring pattern (line/space = 50 μm/50 μm) was produced. Moreover, after the resin pattern 2 was formed, the copper pattern 3 was formed as follows. The electroless copper plating solution (ARG copper manufactured by OKUNO CHEMICAL INDUSTRIES CO., LTD.) was made into a Cu electroplating bath according to the procedure described in the installation manual, and the temperature was adjusted by adding it to a 45°C thermostat. The substrate was dipped in a plating bath, and a copper pattern was formed by electroless plating.

In Example 13, the light-shielding pattern 1 was formed as follows. After peeling the cover film from the photosensitive transfer material 1 on a polyimide (PI) film with a thickness of 100 μm, the photosensitive transfer material 1 was attached to the PET film with a copper layer. The above-mentioned bonding was performed under the conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min. Next, the resist layer was exposed to light using a maskless drawing device (DWL66+ manufactured by Heidelberger Druckmaschinen AG, dominant wavelength: 405 nm). After peeling off the temporary support, the photoresist layer was subjected to spray development for 30 seconds using an aqueous sodium carbonate solution with a liquid temperature of 25° C., thereby forming a resin pattern (line/space=15 μm/15 μm). Next, after forming a copper layer between the photoresist patterns and on the photoresist pattern by sputtering, the resin pattern and the copper layer on the resin pattern were removed using a stripping solution (10 mass % triethylamine aqueous solution). Through the above procedure, a PI film with a copper pattern (line/space=15 μm/15 μm) was produced. The copper pattern functions as the light-shielding pattern 1 . Moreover, in the image development of the resin pattern 2, it carried out similarly to Example 1 except having used 2.38 mass % of tetramethylammonium hydroxide (TMAH) aqueous solution as a developing solution.

(Comparative Example 1) Except that the light irradiation method was changed in the procedure demonstrated in the section "pattern 3 (copper pattern)", the same procedure as in Example 1 was performed to try to produce a structure having a copper pattern. Specifically, in a laminate having a PET film, a copper pattern (light-shielding pattern), a negative-type photosensitive resin layer N, and a temporary support in this order, the negative-type photosensitivity is arranged in the sum of the mask and the temporary support. After the surfaces on the opposite side of the surface of the resin layer N were in contact, the negative photosensitive resin layer N was irradiated with light through a photomask. However, in the step of irradiating light, displacement of the copper pattern (light-shielding pattern) thought to be caused by shrinkage of the PET film was observed, so it was difficult to align the position of the mask opening with the space of the copper pattern (light-shielding pattern). alignment. As a result, the resin pattern cannot be formed in the space portion of the copper pattern (light-shielding pattern).

＜Evaluation＞ [pattern formability] Any 100 fields of view of the structure having the obtained pattern 3 were observed using an optical microscope. The range of each field of view was set to 200 μm×200 μm. Based on the number of fields of view in which abnormal portions were observed in pattern 3, the formability of the conductive pattern was evaluated according to the following criteria. The abnormal part refers to the part where abnormal morphology such as cracking, peeling, and chipping is observed in pattern 3 . The evaluation results are shown in Table 5. A: The number of visual fields where abnormal parts were observed was less than 20. B: The number of fields in which abnormal parts were observed was 20 or more.

[table 5] substrate Substrate thickness (μm) Thickness of light-shielding pattern 1 (μm) Photoresist for forming light-shielding pattern 1 Temporary support stripping before exposure Exposure method when forming light-shielding pattern 1 Shape of light-shielding pattern 1 Negative photosensitive resin layer N Thickness of pattern 3 (μm) hardened Evaluation results Photoresist forming method Type of photosensitive resin composition used Photoresist layer thickness (μm) Formation method The negative photosensitive resin composition used Thickness (μm) pattern formation Example 1 PET 100 0.05 Negative dry film NR1 3 none Mask close exposure L/S=8/8 dry film N1 3 2 none A Example 2 PI 100 0.5 Negative dry film NR2 3 none Mask close exposure L/S=10/10 dry film N2 15 13 Post exposure (1,000mJ/cm ² ) A Example 3 COP/ITO 100 0.03 Negative dry film NR3 3 none Mask close exposure L/S=8/8 dry film N1 +N9 3 +0.2 2 none A Example 4 PET 50 0.01 Negative dry film NR4 3 none Unmasked exposure L/S=5/5 dry film N3 3 2 none A Example 5 PET 38 0.5 Negative dry film NR5 3 Have Mask close exposure L/S=4/4 dry film N4 2 1.5 none A Example 6 PET 16 1.0 Negative dry film NR6 10 none Mask close exposure L/S=5/5 dry film N1 3 2 none A Example 7 PET 100 0.5 Positive dry film PR1 3 none Mask Exposure (Projection Exposure) L/S=1/1 dry film N2 1 0.8 Heating (145°C, 20 minutes) A Example 8 grass 1,000 0.5 Negative dry film NR1 3 none Mask close exposure L/S=5/5 liquid N5 3 2.5 none A Example 9 PET 100 0.5 liquid (positive type) PR1 1 none Mask close exposure L/S=5/5 dry film N6 3 2.5 none A Example 10 PET 100 0.5 liquid (positive type) PR1 1 none Mask close exposure L/S=3/3 dry film N7 10 8 none A Example 11 PET 100 0.05 Negative dry film NR1 3 none Mask close exposure L/S=8/8 liquid N8 5 3 none A Example 12 PET 75 0.05 (Light-shielding pattern 1 is formed with silver nano-ink.) L/S=50/50 dry film N1 3 2 none A Example 13 PI 100 0.01 Negative dry film NR1 3 none Unmasked exposure L/S=15/15 liquid N1 30 15 Heating (100°C, 120 minutes) A

In addition, N9 in the column of the negative photosensitive composition used in Example 3 of Table 5 represents an overcoat coating liquid (composition N9). From the results described in Table 5, it was found that the methods for producing the structures of Examples 1 to 13 were able to form patterns that reduced the occurrence of morphological abnormalities as compared with the method for producing the structures of Comparative Example 1.

The entire contents of the disclosure of Japanese Patent Application No. 2020-080716 filed on April 30, 2020 are incorporated herein by reference. All documents, patent applications and technical standards described in this specification are to the same extent as the case where each document, patent application and technical standard are specifically and individually described, and are cited in this specification by reference to the same extent middle.

10,11: Transparent substrate 10a: exposed surface 20, 21: Light-shielding pattern (light-shielding pattern 1) 30: Negative photosensitive resin layer (negative photosensitive resin layer N) 30a: Exposure Department 40, 41: Resin Pattern (Resin Pattern 2) 50,51: Pattern (Pattern 3) 100: Laminate 200: Structure

(a)-(d) of FIG. 1 is a schematic cross-sectional view which shows an example of the manufacturing method of the structure of this disclosure. FIG. 2 is a schematic cross-sectional view showing an example of the structure of the present disclosure.

10: Transparent substrate

10a: exposed surface

20: Light-shielding pattern (light-shielding pattern 1)

30: Negative photosensitive resin layer (negative photosensitive resin layer N)

30a: Exposure Department

40: Resin pattern (resin pattern 2)

50: Pattern (Pattern 3)

100: Laminate

Claims (17)

A method of manufacturing a structure, comprising: A step of preparing a layered body having a transparent substrate, a light-shielding pattern 1 arranged on the transparent substrate, and a negative photosensitive resin layer N arranged on the transparent substrate and the light-shielding pattern 1 on and in contact with the aforementioned transparent substrate; A step of irradiating light from a part of the transparent substrate opposite to the surface on which the light-shielding pattern 1 is provided, which faces the negative photosensitive resin layer N; A step of forming a resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light; and In the step of forming the pattern 3 in the area defined by the light-shielding pattern 1 and the resin pattern 2, The obtained structure had the aforementioned resin pattern 2 as a permanent film. The method for manufacturing a structure as claimed in claim 1, wherein The aforementioned light-shielding pattern 1 contains metal. The method for manufacturing a structure according to claim 1 or claim 2, wherein The aforementioned pattern 3 has conductivity. The method for manufacturing a structure according to claim 1 or claim 2, wherein The aforementioned pattern 3 is a pattern formed by a plating method. The method for manufacturing a structure according to claim 1 or claim 2, wherein The said light-shielding pattern 1 and the said pattern 3 contain the same kind of material. The method for manufacturing a structure according to claim 1 or claim 2, wherein The negative photosensitive resin layer N includes an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator. The method for manufacturing a structure as claimed in claim 6, wherein The aforementioned ethylenically unsaturated compound includes a trifunctional or more functional ethylenically unsaturated compound. The method for manufacturing a structure as claimed in claim 6, wherein The aforementioned ethylenically unsaturated compound includes a di(meth)acrylate compound having a dicyclopentyl structure or a dicyclopentenyl structure. The method for manufacturing a structure according to claim 1 or claim 2, wherein The negative photosensitive resin layer N includes a polyfunctional epoxy resin, a hydroxyl group-containing compound, and a photocationic polymerization initiator. The method for manufacturing a structure according to claim 1 or claim 2, wherein The said negative photosensitive resin layer N contains a metal oxidation inhibitor. The manufacturing method of the structure described in claim 1 or claim 2, further comprising: The step of forming a light-shielding layer on one of the surfaces of the transparent substrate; the step of forming a photoresist layer on the light-shielding layer; the steps of exposing and developing the aforementioned photoresist layer to form a photoresist pattern; and A step of etching the light-shielding layer to form the light-shielding pattern 1 . The method for manufacturing a structure according to claim 1 or claim 2, wherein The average thickness of the light-shielding pattern 1 is thicker than the average thickness of the pattern 3 described above. The method for manufacturing a structure according to claim 1 or claim 2, wherein The aforementioned transparent substrate is a transparent film substrate. The method for producing a structure according to claim 1 or claim 2, further comprising the step of performing at least one of post-exposure and post-heating on the aforementioned resin pattern 2 . The method for manufacturing a structure according to claim 1 or claim 2, wherein The said negative photosensitive resin layer N is a layer formed with a photosensitive transfer material. The method for manufacturing a structure according to claim 1 or claim 2, wherein The obtained structure is one structure selected from the group consisting of a touch sensor, an electromagnetic wave shielding material, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. A structure that has: transparent substrate; The light-shielding pattern 1 is arranged on the aforementioned transparent substrate; The resin pattern 2 is disposed adjacent to the light-shielding pattern 1 on the transparent substrate and is in contact with the transparent substrate; and The pattern 3 is formed in the area defined by the light-shielding pattern 1 and the resin pattern 2, The average thickness of the light-shielding pattern 1 is 2 μm or less, The average thickness of the aforementioned resin pattern 2 exceeds 2 μm, The average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, The aforementioned structure has the aforementioned resin pattern 2 as a permanent film.

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