TW202325543A - Photosensitive transfer material for forming vapor deposition mask and method for manufacturing vapor deposition mask - Google Patents

Abstract

An object of the present invention is to provide a photosensitive transfer material for producing a vapor deposition mask excellent in resolution and to provide a method for producing a vapor deposition mask excellent in resolution. A photosensitive transfer material for forming a vapor deposition mask and a method for forming a vapor deposition mask using the photosensitive transfer material for forming a vapor deposition mask are provided. The photosensitive transfer material for forming a vapor deposition mask has a temporary support and a transfer layer having at least a photosensitive resin layer in order, and the number of foreign matters with a diameter of 1.0[mu]m to 10.0[mu]m per unit volume in the temporary support is 50 pieces/mm3 or less.

Description

Photosensitive transfer material for producing deposition mask and method for producing deposition mask

The disclosure relates to a photosensitive transfer material for manufacturing a deposition mask and a method for manufacturing a deposition mask.

The deposition method using a deposition mask is used, for example, in the manufacture of OLEDs (Organic Light Emitting Diode: Organic Light Emitting Diode). The deposition mask is used as a master for the pattern formed by the deposition method. A vacuum deposition method is known as a representative example of the deposition method. For example, in a vacuum deposition method using a deposition mask having through holes, a substance vaporized from a vaporization source passes through the through holes of the deposition mask disposed on the object and adheres to the object to form a pattern.

A method for forming a metal pattern is described in Patent Document 1, which includes the steps of preparing a laminate having a positive-type photosensitive resin layer formed of a photosensitive transfer material on a substrate; The step of exposing and developing the layer to form a tapered resin pattern; and the step of forming a tapered metal pattern corresponding to the shape of the above-mentioned resin pattern. The transmittance is below 50%.

[Patent Document 1] Japanese Patent Laid-Open No. 2021-172879

Increased resolution (eg, minimization of pattern size) of patterns formed using deposition masks, for example, can contribute to increased pixel density in display devices including OLEDs.

An object of one embodiment of the present disclosure is to provide a photosensitive transfer material for producing a deposition mask with excellent resolution. The purpose of another embodiment of the present disclosure is to provide a method for manufacturing a deposition mask with excellent resolution.

This disclosure includes the following aspects. <1> A photosensitive transfer material for producing a deposition mask, which sequentially has a temporary support and a transfer layer having at least a photosensitive resin layer, wherein the temporary support has a diameter per unit volume of 1.0 μm to 10.0 μm The number of foreign objects is 50/mm ³ or less. <2> The photosensitive transfer material for producing a deposition mask according to <1>, wherein the L ^* value of the surface of the temporary support opposite to the transfer layer side measured by the SCE method is Below 1.5. <3> The photosensitive transfer material for deposition mask production according to <1> or <2>, wherein the temporary support has a thickness of 16 μm or less. <4> The photosensitive transfer material for deposition mask production according to any one of <1> to <3>, wherein the melt viscosity of the transfer layer at 25°C is 1.0×10 ⁵ Pa·s～ 1.0×10 ⁸ Pa·s. <5> The photosensitive transfer material for deposition mask production according to any one of <1> to <4>, wherein the photosensitive resin layer has a thickness of 4.8 μm or less. <6> The photosensitive transfer material for deposition mask production according to any one of <1> to <5>, wherein the transfer layer has an intermediate layer and the photosensitive resin in this order from the temporary support side layer. <7> The photosensitive transfer material for deposition mask production according to <5>, wherein the intermediate layer contains a water-soluble resin. <8> The photosensitive transfer material for deposition mask production according to <7>, wherein the water-soluble resin contains polyvinyl alcohol. <9> The photosensitive transfer material for deposition mask production according to <7> or <8>, wherein the water-soluble resin contains polyvinylpyrrolidone. <10> The photosensitive transfer material for deposition mask production according to any one of <7> to <9>, wherein the water-soluble resin contains a hydroxyalkylcellulose compound. <11> A method of manufacturing a deposition mask, which includes the following steps in sequence: preparing a metal layer having a first surface and a second surface at a position opposite to the first surface; The photosensitive transfer material sequentially includes the above-mentioned temporary support and the above-mentioned transfer layer having at least a photosensitive resin layer. and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 pieces/mm ³ or less; pattern exposure is performed on the above-mentioned transfer layer; and a development treatment is performed on the above-mentioned transfer layer. photoresist pattern; etching the metal layer not covered by the photoresist pattern to form a through hole extending from the first surface of the metal layer to the second surface of the metal layer; and removing the photoresist pattern . <12> The method for manufacturing a deposition mask according to <11>, wherein the roughness Rmax of the first surface of the metal layer is 0.5 μm to 5.0 μm. [Invention effect]

According to one embodiment of the present disclosure, a photosensitive transfer material for producing a deposition mask with excellent resolution is provided. According to another embodiment of the present disclosure, a method for manufacturing a deposition mask with excellent resolution is provided.

Embodiments of the present disclosure will be described in detail below. This disclosure is not limited by the following embodiments. The following embodiments can be appropriately modified within the scope of the purpose of the present disclosure.

When describing embodiments of the present disclosure with reference to the drawings, descriptions of constituent elements and symbols that overlap in the drawings may be omitted. Components represented by the same symbols in the drawings refer to the same components. The ratio of dimensions in the drawings does not necessarily mean the ratio of actual dimensions.

In the present disclosure, a numerical range represented by "-" means a range including the numerical value before "-" as the lower limit and the numerical value before "-" as the upper limit. In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of other numerical ranges described stepwise. Moreover, in the numerical range described in this indication, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in an Example.

In the present disclosure, a "(meth)acryl group" means an acryl group, a methacryl group, or both of an acryl group and a methacryl group.

In this disclosure, "(meth)acrylate" means acrylate, methacrylate, or both of acrylate and methacrylate.

In the present disclosure, "(meth)acryl" means acryl, methacryl, or both of acryl and methacryl.

In this disclosure, the amount of each component in the composition refers to the amount of the corresponding plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. total amount.

In the present disclosure, the term "step" not only includes independent steps, but also includes steps that cannot be clearly distinguished from other steps when the intended purpose can be achieved.

In the present disclosure, unsubstituted and unsubstituted groups (atomic groups) include groups (atomic groups) without substituents and groups (atomic groups) having substituents. For example, "alkyl" includes not only an alkyl group without a substituent (ie, an unsubstituted alkyl group), but also an alkyl group with a substituent (ie, a substituted alkyl group).

In this disclosure, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, the light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other active rays (active energy rays). .

The chemical structural formulas in this disclosure may be described as simplified structural formulas in which hydrogen atoms are omitted.

In the present disclosure, "mass %" has the same meaning as "weight %", and "mass part" has the same meaning as "weight part".

In this disclosure, a combination of two or more preferred aspects is a more preferred aspect.

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

In the present disclosure, the average transmittance of visible light is a value measured using a spectrophotometer, for example, can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this disclosure are gels using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by TOSOH CORPORATION). The permeation chromatography (GPC) analysis device uses the solvent THF (tetrahydrofuran) and a differential refractometer for detection, and uses polystyrene as a standard substance to convert the molecular weight.

In this disclosure, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectroscopic analyzer.

In this disclosure, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

In this disclosure, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

In the present disclosure, "alkali solubility" means that the solubility to 100 g of a 1 mass % aqueous solution of sodium carbonate at a liquid temperature of 22° C. is 0.1 g or more.

In the present disclosure, "water solubility" means that the solubility to 100 g of water of pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more.

In the present disclosure, "solid content" refers to all components except the solvent.

<Photosensitive transfer material for deposition mask production> The photosensitive transfer material for deposition mask production of this disclosure (hereinafter, also simply referred to as "photosensitive transfer material of this disclosure" or "photosensitive transfer material". ) sequentially has a temporary support and a transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 pieces/mm ³ or less.

The photosensitive transfer material for producing a deposition mask according to the present disclosure can suppress the above-mentioned foreign matter from masking exposure by reducing the number of foreign matter with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support to 50 pieces/mm ³ or less. Even if the light exposure barrier is a pattern with a width or a small size such as a thin line, it is possible to form a pattern by suppressing the occurrence of defects, and it is possible to provide a photosensitive transfer material for deposition mask production with excellent resolution.

The photosensitive transfer material disclosed herein has a temporary support and a transfer layer having at least a photosensitive resin layer, and preferably sequentially has a temporary support, a transfer layer including at least a photosensitive resin layer, and a protective film. Moreover, the photosensitive transfer material of this indication may have another layer between a temporary support body and a photosensitive resin layer, between a photosensitive resin layer and a protective film, etc. Moreover, it is preferable that the photosensitive transfer material of this disclosure has an intermediate layer and the said photosensitive resin layer in order from the said temporary support body side. It is preferable that the photosensitive transfer material of this indication is a roll-form photosensitive transfer material from a viewpoint of exhibiting the effect in this indication further.

In the photosensitive transfer material for producing a deposition mask according to the present disclosure, the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 pieces/mm ³ or less. From the viewpoint of the linearity of the obtained pattern, 10 pieces/mm ³ or less is preferable, 5 pieces/mm ³ or less is more preferable, 2 pieces/mm ³ or less is still more preferable, and 1 piece/mm ³ or less is particularly preferable. good. The "foreign matter" in this disclosure refers to those capable of shielding exposure light, and examples include particles such as dust and dust existing on the surface and inside of the temporary support, aggregates of components contained in the temporary support, coarse powder, and the like. In addition, the above-mentioned foreign matter may be other than spherical, for example, amorphous particles, aggregates of particles, etc., and the "diameter of foreign matter" in this disclosure means that it is observed from the thickness direction of the temporary support in the measurement method described later. The absolute maximum length of the foreign body.

The method of measuring the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support in the present disclosure is as follows. Observe the area of 1 cm ² of the temporary support body through the transmission observation of an optical microscope from its thickness direction, count the number of foreign objects with a diameter of 1.0 μm to 10.0 μm, divide the obtained number by the thickness of the temporary support body, and divide It is the number of foreign matter per unit volume as a temporary support.

From the viewpoint of the resolution and the linearity of the obtained pattern, the surface of the above-mentioned temporary support on the side opposite to the above-mentioned transfer layer side measured by the SCE (Specular Component Exclude: regular reflection light is excluded.) method The L ^* value is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.2 or less, and particularly preferably 0.9 or less.

In the present disclosure, the L ^* value of the surface to be measured (for example, the surface of the temporary support opposite to the transfer layer side) is measured by the following method. The temporary support is peeled off from the photosensitive transfer material. Using a spectrophotometer (CM-700d, manufactured by Konica Minolta, Inc.), L ^* values were measured at 3 cm intervals in total at 10 locations along the width direction of the measurement object surface. As a light source for the spectrophotometer, a D65 light source was used. Arithmetic average the L ^* values of 10 points measured by the SCE method, and use the obtained value as the L ^* value of the surface to be measured based on the SCE method.

In the photosensitive transfer material disclosed herein, from the viewpoint of adhesion and resolution, the melt viscosity of the transfer layer at 25°C is preferably 5.0×10 ⁴ Pa·s to 5.0×10 ⁸ Pa·s, 1.0×10 ⁵ Pa·s to 1.0×10 ⁸ Pa·s is more preferable, and 5.0×10 ⁵ Pa·s to 1.0×10 ⁷ Pa·s is particularly preferable. In the present disclosure, "the melt viscosity of the transfer layer" is specified by the melt viscosity of the layer located farthest from the temporary support among the one or more layers constituting the transfer layer. For example, when the transfer layer has a multilayer structure, the melt viscosity of the layer located farthest from the temporary support among the plurality of layers contained in the transfer layer is called "the melt viscosity of the transfer layer". When the printing layer has a single-layer structure, the melt viscosity of a single transfer layer is referred to as "the melt viscosity of the transfer layer". The melt viscosity of the transfer layer is adjusted, for example, according to the composition of the transfer layer. The melt viscosity of the transfer layer is adjusted according to, for example, the type of polymer, the type of polymerizable compound, the ratio of the content of the polymerizable compound to the content of the polymer, and the type of additive. For example, when the ratio of the content of the polymerizable compound to the content of the polymer increases, the melt viscosity decreases, and when the ratio of the content of the polymerizable compound to the content of the polymer decreases, the melt viscosity increases.

In this disclosure, the melt viscosity is measured using a rheometer (for example, rheometer DHR-2 manufactured by TA Instruments), a parallel plate of 20 mmΦ, and a peltier plate (Gap: about 0.5 mm) under the following conditions down to measure. The melt viscosity specified in this disclosure is the melt viscosity at 25°C. (1) Temperature: 20℃～125℃ (2) Heating rate: 5°C/min (3) Frequency: 1Hz (4) Strain: 0.5%

Although an example of the aspect of the photosensitive transfer material of this indication is shown below, it is not limited to this. (1) "Temporary support body/photosensitive resin layer/refractive index adjustment layer/protective film" (2) "Temporary support body/photosensitive resin layer/protective film" (3) "Temporary support body/intermediate layer/photosensitive resin layer/protective film" (4) "Temporary support body/buffer layer/intermediate layer/photosensitive resin layer/protective film" In addition, in each of the above configurations, the photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and the negative photosensitive resin layer is preferred. Moreover, it is also preferable that a photosensitive resin layer is a colored resin layer. Among them, as the composition of the photosensitive transfer material, for example, the constitutions of (2) to (4) above are preferable, the constitutions of (3) or (4) above are preferable, and the constitutions of (4) above are Excellent.

In the case where the photosensitive transfer material further has another layer on the side opposite to the temporary support side of the photosensitive resin layer, it is arranged on the side opposite to the temporary support side of the photosensitive resin layer. The total thickness of other layers is preferably 0.1% to 30% with respect to the layer thickness of the photosensitive resin layer, more preferably 0.1% to 20%.

Hereinafter, an example of a specific embodiment is given, and the photosensitive transfer material of this disclosure is demonstrated.

Hereinafter, each element which comprises a photosensitive transfer material is demonstrated.

〔Temporary support body〕 The photosensitive transfer material disclosed herein has a temporary support. The temporary support system supports the laminated body including the transfer layer and can be peeled off.

It is preferable that a temporary support body has translucency from a viewpoint which can perform exposure of the photosensitive resin layer via a temporary support body at the time of pattern exposure to a photosensitive resin layer. In addition, in this specification, "having translucency" means that the transmittance of the light of the wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of the light of the wavelength (more preferably a wavelength of 365 nm) used in the pattern exposure of the temporary support is preferably 60% or more, and more preferably 70% or more. good. In addition, the transmittance of the layer included in the photosensitive transfer material is the ratio of the intensity of the outgoing light emitted through the layer to the intensity of the incident light when light is incident in a direction (thickness direction) perpendicular to the main surface of the layer. Ratio, measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

As a material which comprises a temporary support body, a glass substrate, a resin film, and paper are mentioned, for example, A resin film is preferable from a viewpoint of strength, flexibility, and translucency. Examples of the resin film include a polyethylene terephthalate (PET:polyethylene terephthalate) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a PET film is preferred, and a biaxially stretched PET film is more preferred.

The thickness (layer thickness) of the temporary support is not particularly limited, and it can be obtained from the strength as the support, the flexibility required for bonding with the circuit wiring forming substrate, and the transparency required in the initial exposure step. From the point of view of light, it can be selected according to the material. The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, more preferably in the range of 10 μm to 20 μm, and more preferably in the range of 10 μm to 16 μm from the viewpoint of ease of handling and versatility. The range is excellent. In addition, from the viewpoint of defect suppression, resolution, and linearity of the photoresist pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, still more preferably 20 μm or less, and especially 16 μm or less. good.

Also, it is preferable that the film used as a temporary support has no deformation such as wrinkles, scratches, or defects. It is preferable that the number of fine particles, foreign substances, defects, precipitates, etc. contained in the temporary support is small from the viewpoint of the pattern formability at the time of pattern exposure through the temporary support and the transparency of the temporary support. The number of particles, foreign substances or defects with a diameter of 1 μm or more is preferably 50 particles/10mm2 ^or less, more preferably 10 particles/10mm2 ^or less, more preferably 3 particles/10mm2 ^or less, and 0 particles/ ^10mm2 is especially good.

It is preferable that the haze of a temporary support body is small from the viewpoint of the defect suppression property of a photoresist pattern, resolution, and the transparency of a temporary support body. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, still more preferably less than 1.0%, and particularly preferably 0.5% or less. The haze value in this disclosure is measured by a method in accordance with JIS K 7105:1981 using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.).

From the viewpoint of imparting workability, a layer (lubricant layer) containing fine particles may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be set to, for example, 0.05 μm to 0.8 μm. In addition, the layer thickness of the lubricant layer can be set to, for example, 0.05 μm to 1.0 μm.

From the viewpoint of transportability, defect suppression of photoresist patterns, and resolution, the arithmetic average roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is equal to the above-mentioned roughness Ra of the temporary support. The arithmetic mean roughness Ra or more of the surface on the photosensitive resin layer side is preferable. From the viewpoint of conveyability, defect suppression of the photoresist pattern, and resolution, the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer is preferably 100 nm or less. It is more preferably 50 nm or less, further preferably 20 nm or less, and particularly preferably 10 nm or less. From the standpoint of releasability of the temporary support, defect suppression of the photoresist pattern, and resolution, the arithmetic mean roughness Ra of the surface of the temporary support on the side of the photosensitive resin layer is preferably 100 nm or less, preferably 50 nm. Less than or equal to 20 nm is more preferred, and 10 nm or less is particularly preferred. In addition, from the viewpoint of transportability, defect suppression of photoresist patterns, and resolution, the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side-in the temporary support The value of the arithmetic mean roughness Ra of the surface on the side of the photosensitive resin layer is preferably from 0 nm to 10 nm, more preferably from 0 nm to 5 nm.

The arithmetic mean roughness Ra of the surface of the temporary support body or a protective film in this indication shall be measured by the following method. The surface profile of the film was obtained by measuring the surface of the temporary support or the protective film using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation) under the following conditions. As measurement/analysis software, Microscope Application of MetroPro ver8.3.2 was used. Then, use the above-mentioned analysis software to display the Surface Map screen, and obtain the histogram data in the Surface Map screen. Calculate the arithmetic average roughness from the obtained histogram data, and obtain the Ra value of the surface of the temporary support or protective film. When a temporary support body or a protective film is bonded to a photosensitive resin layer etc., what is necessary is just to measure the Ra value of the surface of the peeled one side from a temporary support body or a protective film from a photosensitive resin layer.

When the rolled-up laminate is re-transported by the roll-to-roll method, from the standpoint of the peeling inhibition of the temporary support caused by the bonding of the upper and lower laminates and the laminate, the temporary The peeling force of the support, specifically, the peeling force between the temporary support and the photosensitive resin layer or buffer layer is preferably 0.5 mN/mm or more, more preferably 0.5 mN/mm to 2.0 mN/mm.

The peeling force of the temporary support body in this indication shall be measured as follows. On a polyethylene terephthalate (PET) film with a thickness of 100 μm, a copper layer with a thickness of 200 nm was fabricated by sputtering to produce a PET substrate with a copper layer. Peel off the protective film from the produced photosensitive transfer material, and laminate it on the above-mentioned copper layer under the lamination conditions of lamination roller temperature 100°C, line pressure 0.6MPa, line speed (lamination speed) 1.0m/min on the PET substrate. Next, after attaching a tape (PRINTACK manufactured by Nitto Denko Corporation) to the surface of the temporary support, the laminate having at least the temporary support and the photosensitive resin layer on the PET substrate with the copper layer was cut into 70 mm × 10 mm. Production samples. The PET substrate side of the above sample was fixed on a sample stand. Conducted between the photosensitive resin layer or buffer layer and the temporary support by stretching the tape at 5.5 mm/sec in the direction of 180 degrees using a tensile compression tester (manufactured by IMADA SEISAKUSHO CO., LTD., SV-55) Peel off, and measure the force required for peeling (peeling force) and adhesion.

As a preferred embodiment of the temporary support, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019-0026 of JP-A-2016-27363, and paragraph 0041 of International Publication No. 2012/081680 Paragraphs 0057 to 0057, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese Patent Laid-Open No. 2019-101405 are described, and the contents of these publications are incorporated in this specification.

〔Photosensitive resin layer〕 The photosensitive transfer material disclosed herein has a photosensitive resin layer. The photosensitive resin layer can be a positive photosensitive resin layer or a negative photosensitive resin layer, and the negative photosensitive resin layer is preferred. The negative photosensitive resin layer preferably includes an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. Based on the total mass of the above-mentioned photosensitive resin layer, the alkali-soluble resin: 10% to 90% by mass; ethylene Permanent unsaturated compound: 5% by mass to 70% by mass; and photopolymerization initiator: more preferably 0.01% by mass to 20% by mass. The positive photosensitive resin layer is not limited, and known positive photosensitive resin layers can be used. The positive photosensitive resin layer preferably contains an acid-decomposable resin, that is, a polymer having a constituent unit of an acid group protected by an acid-decomposable group, and a photoacid generator. Moreover, it is preferable that the positive photosensitive resin layer contains the resin which has the structural unit which has a phenolic hydroxyl group, and a quinone diazide compound. Furthermore, the positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer including a polymer having a structural unit having an acid group protected by an acid decomposable group and a photoacid generator.

Hereinafter, each component will be demonstrated in order. In addition, when simply calling it a "photosensitive resin layer", it means both a positive photosensitive resin layer and a negative photosensitive resin layer.

"Polymeric Compounds" It is preferable that the negative photosensitive resin layer contains a polymerizable compound. In addition, in this specification, a "polymerizable compound" means the compound different from the said alkali-soluble resin which polymerizes by the action|action of the photoinitiator mentioned later.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group that participates in the polymerization reaction, and examples thereof include vinyl, acryl, methacryl, styryl, and maleic A group having an ethylenically unsaturated group, such as an imide group; and a group having a cationic polymerizable group, such as an epoxy group and an oxetanyl group. As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryl group or a methacryl group is more preferable. Moreover, as a polymeric compound, it is preferable to contain an ethylenic unsaturated compound, and it is more preferable to contain a (meth)acrylate compound.

From the viewpoint of resolution and pattern formation, the photosensitive resin layer preferably contains a bifunctional or higher polymerizable compound (polyfunctional polymerizable compound), and more preferably contains a trifunctional or higher polymerizable compound. Here, a bifunctional or more polymerizable compound refers to a compound having two or more polymerizable groups in one molecule. Moreover, from the viewpoint of excellent resolution and peelability, it is preferable that the number of polymerizable groups that the polymerizable compound has in one molecule is 6 or less.

From the standpoint of a better balance of photosensitivity, resolving power, and releasability of the photosensitive resin layer, it is preferable that the negative photosensitive resin layer contains a bifunctional or trifunctional ethylenically unsaturated compound, and a bifunctional ethylenically unsaturated compound compound is more preferred. From the viewpoint of excellent releasability, the content of bifunctional or trifunctional ethylenically unsaturated compounds in the negative photosensitive resin layer is preferably 60% by mass or more, and more than 70% by mass relative to the total content of ethylenically unsaturated compounds. The mass % is more preferable, and 90 mass % or more is further more preferable. The upper limit is not particularly limited, and may be 100% by mass. That is, all the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

From the viewpoint of resolution and pattern formation, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure. As a polymeric compound which has a polyalkylene oxide structure, polyalkylene glycol di(meth)acrylate etc. which are mentioned later are mentioned preferably.

-Ethylenically unsaturated compound B1- It is preferable that the negative photosensitive resin layer contains the ethylenically unsaturated compound B1 which has an aromatic ring and 2 ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned ethylenically unsaturated compounds.

In the negative photosensitive resin layer, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound is preferably 40% by mass or more, and 50% by mass from the viewpoint of better resolution. % or more is more preferable, 55 mass % or more is more preferable, and 60 mass % or more is especially preferable. The upper limit is not particularly limited, but from the viewpoint of releasability, it is preferably at most 99% by mass, more preferably at most 95% by mass, still more preferably at most 90% by mass, and most preferably at most 85% by mass.

Examples of the aromatic ring possessed by the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings. As the aromatic heterocycle and such condensed rings, an aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. In addition, the above-mentioned aromatic ring may have a substituent. The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

It is preferable that ethylenic unsaturated compound B1 has a bisphenol structure from a viewpoint of improving resolution by suppressing the swelling of the negative photosensitive resin layer by a developing solution. As the bisphenol structure, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl) phenyl)methane) and bisphenol B structure from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), bisphenol A structure is better.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a bisphenol structure and two polymerizable groups (preferably (meth)acryl groups) bonded to both ends of the bisphenol structure. compound. Both ends of the bisphenol structure may be directly bonded to two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. As the alkoxyl group added to both ends of the bisphenol structure, ethoxyl or propoxyl is preferred, and ethoxyl is more preferred. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14. About the ethylenically unsaturated compound B1 which has a bisphenol structure, it describes in paragraph 0072-0080 of Unexamined-Japanese-Patent No. 2016-224162, and the content described in this publication is incorporated in this specification.

As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl) Propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy) yl)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2, 2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methyl Acryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadeca Ethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane ( BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[chemical 1]

In the formula (Bis), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ are independently an integer of 1 to 39, And n ₁ +n ₃ is an integer of 2 to 40, n ₂ and n ₄ are independently an integer of 0 to 29, and n ₂ +n ₄ is an integer of 0 to 30, -(AO)- and -(BO )-The arrangement of repeating units can be random or block. Also, in the case of a block, either of -(AO)- and -(BO)- may be on the side of the bisphenol structure. In one aspect, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2-20, more preferably an integer of 2-16, and more preferably an integer of 4-12. Also, n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0.

Ethylenically unsaturated compound B1 may be used individually by 1 type, and may use 2 or more types together. From the standpoint of better resolution, the content of the ethylenically unsaturated compound B1 in the negative photosensitive resin layer is preferably 10% by mass or more, 20% by mass or more, based on the total mass of the negative photosensitive resin layer. for better. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (a phenomenon in which components in the negative photosensitive resin layer bleed out from the end of the photosensitive transfer material), it is preferably 70% by mass or less , 60% by mass or less is better.

The negative photosensitive resin layer may contain ethylenically unsaturated compounds other than the above-mentioned ethylenically unsaturated compound B1. The ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited, and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds. compound.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethylsuccinate, polyethylene glycol Alcohol 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, urethane di(meth)acrylate, and urethane di(meth)acrylate. base) acrylate and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol Dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 , 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl Glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Acrylate. Examples of the urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co. , Ltd. manufacturing).

Examples of ethylenically unsaturated compounds having a trifunctional or higher function include diperythritol (tri/tetra/penta/hexa)(meth)acrylate, neopentylthritol (tri/tetra)(meth)acrylic acid ester, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate Meth)acrylate, glycerol tri(meth)acrylate, and their alkylene oxide modifications. Among them, "(three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates. The concept of acrylate, "(three/tetra) (meth)acrylate" includes the concepts of tri(meth)acrylate and tetra(meth)acrylate. In one aspect, the negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and includes the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher functional compounds. Ethylenically unsaturated compounds are more preferred. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compound is (the total mass of the ethylenically unsaturated compound B1): (the total mass of the trifunctional or higher ethylenically unsaturated compound ) = 1:1 to 5:1 is more preferable, 1.2:1 to 4:1 is more preferable, and 1.5:1 to 3:1 is still more preferable. Moreover, in one aspect, it is preferable that the negative photosensitive resin layer contains the above-mentioned ethylenically unsaturated compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. , A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura ATM-35E and A-9300 manufactured by Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glycerin triacrylate (Shin-Nakamura Chemical Co., Ltd. A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX M-510 (manufactured by TOAGOSEI CO. , LTD. Manufacturing).

Moreover, as an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, the ethylenically unsaturated compound which has an acid group as described in paragraph 0025-0030 of Unexamined-Japanese-Patent No. 2004-239942 can be used.

From the viewpoint of resolution and linearity, the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound in the negative photosensitive resin layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, 0.9 or less More preferably, 0.5 or more and 0.9 or less are particularly preferable. Moreover, it is preferable that the ethylenically unsaturated compound in a negative photosensitive resin layer contains a (meth)acrylic compound from a viewpoint of curability and resolution. In addition, the ethylenically unsaturated compound in the negative photosensitive resin layer contains a (meth)acrylic compound from the viewpoints of curability, resolution, and linearity, and the content of the acrylic compound is higher than that of the negative photosensitive resin layer. It is more preferable that the total mass of the above-mentioned (meth)acrylic acid compounds contained in the above-mentioned (meth)acrylic acid compound is 60 mass % or less.

The molecular weight (weight average molecular weight (Mw) when there is a distribution) of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200. good.

One type of ethylenically unsaturated compound may be used alone, or two or more types may be used in combination. The content of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and 20% by mass to the total mass of the negative photosensitive resin layer. It is still more preferable that mass % - 50 mass %.

"Photopolymerization Initiator" It is preferable that the negative photosensitive resin layer contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates the polymerization of ethylenically unsaturated compounds upon exposure to active rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. As a photoinitiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example. Among them, it is preferable that the negative photosensitive resin layer is a photoradical polymerization initiator from the viewpoint of resolution and pattern formation properties.

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

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

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl Base) Anisyl, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 and 369 (trade name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl - 1,2'-Bimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone -1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF Corporation), IRGACURE OXE-03 (manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4 -Methylphenyl)methyl]-1-[4-(4-Perolinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1 -(4-methylthiophenyl)-2-pornolinylpropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2- Hydroxy-2-methylpropanyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamine 1-(4-Perolinylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one ( Trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethyl -1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (trade name: Lunar 6, DKSH Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-di Phenylimidazole dimer (trade name: B-CIM, manufactured by Hampford Co.) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co. , Ltd. manufacturing).

Photocationic polymerization initiators (photoacid generators) are compounds that generate acids when exposed to active light. As the photocationic polymerization initiator, a compound that generates acid in response to active light with a wavelength of 300 nm or more, preferably 300-450 nm, is preferred, but its chemical structure is not limited. Also, as for the photocationic polymerization initiator that is not directly responsive to active light with a wavelength of 300 nm or more, as long as it is a compound that generates an acid in response to active light with a wavelength of 300 nm or more by using in combination with a sensitizer, it can also be used with a sensitizer. Sensitive agents are preferably used in combination. As a photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less The photocatalytic polymerization initiator of acid is especially preferred. The lower limit of pKa is not particularly specified, but 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, such as a diaryl iodonium salt and a triaryl permeicium salt, and a quaternary ammonium salt are mentioned, for example. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can be used.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-trisulfones, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be used as the trichloromethyl-s-trisulfones, diazomethane compounds, and imidesulfonate compounds. In addition, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be used.

The negative photosensitive resin layer may contain one kind of photopolymerization initiator alone, or may contain two or more kinds thereof. The content of the photopolymerization initiator in the negative photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the negative photosensitive resin layer, It is still more preferable that it is 1.0 mass % or more. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the negative photosensitive resin layer.

《Alkali-soluble resin》 It is preferable that the negative photosensitive resin layer contains alkali-soluble resin. In addition, in this specification, "alkali solubility" means that the solubility with respect to 100 g of 1 mass % aqueous solutions of sodium carbonate at liquid temperature 22 degreeC is 0.1 g or more. Although it does not specifically limit as alkali-soluble resin, For example, the well-known alkali-soluble resin used for an etching resist (etching resist) is mentioned preferably. Moreover, it is preferable that an alkali-soluble resin is a binder polymer. As the alkali-soluble resin, an alkali-soluble resin having an acidic group is preferable. Among them, the polymer A described later is preferable as the alkali-soluble resin.

-Polymer A- It is preferable to contain polymer A as an alkali-soluble resin. From the standpoint of better resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and less than 200 mgKOH/g. It is further preferably 190 mgKOH/g. The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, and still more preferably 150 mgKOH/g or more. More than 170mgKOH/g is particularly preferred.

In addition, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of samples, and in this specification, the unit is described as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of the polymer A may be adjusted by the type of the structural unit constituting the polymer A and the content of the acid group-containing structural unit.

The weight average molecular weight 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 is more preferably 100,000 or less, still 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 and the properties of the unexposed film such as edge melting and chipping properties, it is preferable to set the weight average molecular weight to 5,000 or more. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge melting property refers to the ease with which the photosensitive resin layer protrudes from the end surface of the roll when the photosensitive transfer material is wound up into a roll. The chipping property refers to the ease of scattering of chips when the unexposed film is cut with a cutter. If this swarf adheres to the upper surface of the photosensitive resin layer, etc., it will be transferred to the mask in the subsequent exposure process etc., and will become a cause of defective products. The degree of dispersion of the polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and still more preferably from 1.0 to 3.0. In this disclosure, molecular weight is a value measured using gel permeation chromatography. Also, 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).

It is preferable that the negative photosensitive resin layer contains a monomer component having an aromatic hydrocarbon group as the polymer A from the viewpoint of suppressing deterioration of line width and resolution when the focal position shifts during exposure. Moreover, as such an aromatic hydrocarbon group, the substituted or unsubstituted phenyl group, or the substituted or unsubstituted aralkyl group is mentioned, for example. The content ratio of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably at least 20% by mass, more preferably at least 30% by mass, and even more preferably at least 40% by mass, based on the total mass of all the monomer components. Good, more than 45% by mass is particularly good, and more than 50% by mass is the best. The upper limit is not particularly limited, but is preferably at most 95% by mass, more preferably at most 85% by mass. In addition, the content rate of the monomer component which has an aromatic hydrocarbon group when containing several types of polymer A was calculated|required as a weight average.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (such as methylstyrene, vinyltoluene, tertiary butoxybenzene, etc.) ethylene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, monomers having aralkyl groups or styrene are preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content ratio of the styrene monomer component is 20% by mass to 50% by mass based on the total mass of all the monomer components. % is more preferable, 25 mass % - 45 mass % is more preferable, 30 mass % - 40 mass % is still more preferable, 30 mass % - 35 mass % is especially preferable.

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

Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

As a monomer having a benzyl group, there can be mentioned (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, benzyl chloride (meth)acrylate, etc.; vinyl monomers having a benzyl group, Examples include vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth)acrylate is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth)acrylate, the content ratio of the benzyl (meth)acrylate monomer component is calculated as the total of all monomer components Based on the mass, 50% by mass to 95% by mass is more preferred, 60% by mass to 90% by mass is more preferred, 70% by mass to 90% by mass is still more preferred, and 75% by mass to 90% by mass is particularly preferred.

Polymer A containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one first monomer described below and/or at least one second monomer described below .

Polymer A that does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one first monomer described later, by making at least one first monomer and at least one second monomer described later It is better to obtain by copolymerization.

The first monomer system is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half esters etc. Among these, (meth)acrylic acid is preferable. The content ratio of 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, more preferably 15% by mass to 30% by mass, based on the total mass of all monomer components. Mass % is further more preferable.

The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components. From the viewpoint of developing good developability and controlling edge melting properties, the copolymerization ratio is preferably at least 10% by mass, more preferably at least 15% by mass, and still more preferably at least 20% by mass. From the viewpoint of the high resolution of the photoresist pattern and the shape of the hem portion, and further from the viewpoint of the chemical resistance of the photoresist pattern, it is preferable to set the above-mentioned copolymerization ratio to 50% by mass or less. From a viewpoint, 35 mass % or less is more preferable, 30 mass % or less is further more preferable, and 27 mass % or less is especially preferable.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, Butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ring (meth)acrylate (Meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferable, and methyl (meth)acrylate is particularly preferable. The content ratio of 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, more preferably 20% by mass to 45% by mass, based on the total mass of all monomer components. Mass % is further more preferable.

From the viewpoint of suppressing deterioration of the line width and resolution when the focal position shifts during exposure, it is preferable to contain an aralkyl-containing monomer and/or styrene as a monomer. For example, copolymers containing methacrylic acid, benzyl methacrylate, and styrene, and copolymers containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferred. In one aspect, the polymer A contains 25% to 40% by mass of monomer components having aromatic hydrocarbon groups, 20% to 35% by mass of the first monomer component, and 30% to 45% by mass of the second monomer component. The polymer in mass % is preferable. Also, in another aspect, a polymer comprising 70% to 90% by mass of the monomer component having an aromatic hydrocarbon group and 10% to 25% by mass of the first monomer component is preferable.

Polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. By using a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in the side chain include, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, Tertiary butyl (meth)acrylate, isopentyl (meth)acrylate, tertiary pentyl (meth)acrylate, isopentyl (meth)acrylate, 2-octyl (meth)acrylate, (meth)acrylate base) 3-octyl acrylate, tertiary octyl (meth)acrylate. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate are preferred, and isopropyl methacrylate or tertiary butyl methacrylate is better. As a monomer containing a group having an alicyclic structure in the side chain, a monomer having a monocyclic aliphatic hydrocarbon group, a monomer having a polycyclic aliphatic hydrocarbon group, and a monomer having a carbon number (carbon (meth)acrylate of alicyclic hydrocarbon group with 5 to 20 atoms. As more specific examples, (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2- Adamantyl ester, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, (meth)acrylate- 3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1- Adamantyl ester, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (meth)acrylate base) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoindene (meth)acrylate- 5-yl ester, octahydro-4,7-inden-1-ylmethyl (meth)acrylate, 1-menthol (meth)acrylate, tricyclodecane (meth)acrylate, (Meth)acrylate-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylate-3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] Heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenzyl (meth)acrylate, 2,2,5-(meth)acrylate Trimethylcyclohexyl, cyclohexyl (meth)acrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate-1 - adamantyl ester, 2-adamantyl (meth)acrylate, fenzyl (meth)acrylate, 1-menthol (meth)acrylate or tricyclodecane (meth)acrylate as Preferably, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or (methyl) ) tricyclodecane acrylate is particularly preferred.

Polymer A may be used alone or in combination of two or more. When two or more types are used in combination, two polymers A containing monomer components having aromatic hydrocarbon groups are used in combination, or polymer A containing monomer components having aromatic hydrocarbon groups is used in combination with a polymer A containing no monomer components having aromatic hydrocarbon groups. Polymer A of the body composition is preferred. In the latter case, the proportion of the polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more to the entire polymer A. Preferably, more than 90% by mass is more preferred.

Polymer A is synthesized by adding an appropriate amount of benzoyl peroxide, azo It is preferable to heat and stir a radical polymerization initiator such as isobutyronitrile. In some cases, the synthesis may be performed while dropping a part of the mixture into the reaction liquid. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis method, in addition to solution polymerization, block polymerization, suspension polymerization, or emulsion polymerization can be used.

The glass transition temperature Tg of the polymer A is preferably not less than 30°C and not more than 135°C. By using the polymer A which has Tg of 135 degreeC or less for a photosensitive resin layer, the deterioration of the line width thickness and resolution at the time of shifting focus position at the time of exposure can be suppressed. From this viewpoint, 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. Moreover, it is preferable to use the polymer A which has Tg of 30 degreeC or more from a viewpoint of edge melting resistance improvement. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, most preferably 70°C or higher.

Also, from the viewpoint of sensitivity and resolution, it is preferable that the photosensitive resin layer (preferably negative photosensitive resin layer) comprises a polymer having a crosslinking group, and the polymer having a crosslinking group is included as Alkali-soluble resins are more preferred. As a polymer having a cross-linking group, a polymer having a polymerizable group is preferred from the viewpoints of developability, sensitivity, and resolution, and a polymer having an ethylenically unsaturated group is more preferable. An acrylic resin having an unsaturated group is further preferred, and an acrylic resin containing a structural unit having an ethylenically unsaturated group is particularly preferred. The polymerizable group is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples include vinyl, acryl, methacryl, styryl, and maleimide groups that have A group having an ethylenically unsaturated group; and a group having a cationic polymerizable group such as an epoxy group and an oxetanyl group. Moreover, as a polymer which has a crosslinkable group, polymer A which has a crosslinkable group is preferable from the viewpoint of developability, sensitivity, and resolution.

The negative photosensitive resin layer may contain resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic acid copolymers (with a styrene content of 40% by mass or more), polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide Resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycols.

Alkali-soluble resins may be used alone or in combination of two or more. The ratio of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, further preferably 40% by mass to 60% by mass %. From the viewpoint of controlling the development time, it is preferable to set the ratio of the alkali-soluble resin to the negative photosensitive resin layer to be 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, it is preferable to set the ratio of the alkali-soluble resin to the negative photosensitive resin layer to be 10% by mass or more.

"Compounds with Unshared Electron Pairs" It is preferable that the said photosensitive resin layer contains the compound which has an unshared electron pair from a viewpoint of the adhesiveness with a conductive layer. As a compound having an unshared electron pair, a compound containing at least a nitrogen atom, an oxygen atom, or a sulfur atom is preferable from the viewpoint of adhesion to the conductive layer, and a heterocyclic compound, a thiol compound, or a disulfide compound It is more preferred, a heterocyclic compound is further preferred, and a nitrogen-containing heterocyclic compound is particularly preferred.

The heterocyclic ring possessed by the heterocyclic compound may be any of monocyclic and polycyclic heterocyclic rings. As a hetero atom which a heterocyclic compound has, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

Examples of heterocyclic compounds include preferably triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazole compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzothiazole compounds, and imidazole compounds, benzoxazole compounds or pyrimidine compounds. Among the above, from the viewpoint of adhesion to the conductive layer, the heterocyclic compound is selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, trioxane compounds, rhodan At least one compound in the group of ningen compound, thiazole compound, benzimidazole compound and benzoxazole compound is preferably selected from the group consisting of triazole compound, benzotriazole compound, tetrazole compound, thiadiazole compound, At least one compound selected from the group of thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds is more preferable, and at least one compound selected from the group including triazole compounds and tetrazole compounds is further Preferably, triazole compounds are particularly preferred.

Preferred specific examples of heterocyclic compounds are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[Chem 2]

[Chem 3]

As the tetrazole compound, the following compounds can be exemplified.

[chemical 4]

[chemical 5]

As the thiadiazole compound, the following compounds can be illustrated.

[chemical 6]

As the trisulfide compound, the following compounds can be exemplified.

[chemical 7]

As the rhodanine compound, the following compounds can be exemplified.

[chemical 8]

As the thiazole compound, the following compounds can be exemplified.

[chemical 9]

As the benzothiazole compound, the following compounds can be exemplified.

[chemical 10]

As the benzimidazole compound, the following compounds can be exemplified.

[chemical 11]

[chemical 12]

As the benzoxazole compound, the following compounds can be exemplified.

[chemical 13]

As the thiol compound, preferably an aliphatic thiol compound is used. As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a difunctional or more functional aliphatic thiol compound) can be preferably used. Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, neopentylitol Tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-tris-2,4,6-(1H,3H,5H )-triketone, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3- mercaptopropionate), neopentylthritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipenteoerythritol hexa (3-mercaptopropionate), ethyl Diol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylene Methyldithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and bis(mercaptoethyl)ether. Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl- 3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate and stearyl-3-mercaptopropionate.

Examples of disulfide compounds include 2-(4'-porphyrinyldithio)benzothiazole, 2,2'-benzothiazolyl disulfide, bis(2-benzamidophenyl base) disulfide, 1,1-thiobis(2-naphthol), bis(2,4,5-trichlorophenyl) disulfide, 4,4'-dithioporline, tetra Ethylthiuram disulfide, dibenzyl disulfide, bis(2,4-dinitrophenyl) disulfide, 4,4'-diaminodiphenyl disulfide, diallyl disulfide, di-tertiary butyl disulfide, bis(6-hydroxy-2-naphthyl) disulfide, dicyclohexyl disulfide, o-isobutyryl thiamine disulfide, diphenyl disulfide.

Also, from the viewpoint of adhesion to the conductive layer, the molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50-500, still more preferably 50-200, and especially 50-115. good.

The photosensitive resin layer may contain one kind of compound having an unshared electron pair alone, or two or more kinds thereof. From the viewpoint of the adhesion to the conductive layer, the content of the compound having an unshared electron pair is preferably 0.01% by mass to 20% by mass, and 0.1% by mass to 10% by mass relative to the total mass of the photosensitive resin layer. More preferably, 0.3 mass % - 8 mass % is still more preferable, and 0.5 mass % - 5 mass % is especially preferable.

"pigment" From the viewpoint of visibility of exposed and non-exposed areas, pattern visibility and resolution after development, it is preferable that the photosensitive resin layer contains a pigment, and the maximum absorption wavelength in the wavelength range of 400nm to 780nm for color development is included. A dye whose maximum absorption wavelength is changed by acid, alkali or free radicals (also referred to as "dye N" for short) is more preferable. When the dye N is contained, although the detailed mechanism is not clear, the adhesiveness with the adjacent layer (for example, a temporary support body and a 1st resin layer) improves, and resolution is more excellent.

In this specification, "the maximum absorption wavelength of a pigment is changed by acid, alkali or free radical" may refer to a state in which a pigment in a colored state is decolorized by an acid, alkali or free radical, or a pigment in a decolorized state. Either of the state in which the color is developed by acid, alkali or free radicals, and the state in which the pigment in the color-developed state changes to a color-developed state of another hue. Specifically, the dye N may be a compound that develops color by changing from a decolorized state by exposure, or may be a compound that decolorizes by changing from a color-developed state by exposure. In this case, it may be a dye that generates acid, alkali, or free radicals in the photosensitive resin layer by exposure, and these acts to change the state of color development or decolorization, or it may be a pigment in the photosensitive resin layer. A pigment whose state (such as pH) is changed by changes in acid, alkali or free radicals to develop or decolorize. In addition, it may be a pigment whose state of color development or decolorization is changed by being directly stimulated by an acid, an alkali, or a free radical without exposure to light.

Among them, from the viewpoint of the visibility and resolution of the exposed part and the non-exposed part, dye N is preferably a dye whose maximum absorption wavelength is changed by acid or free radicals, and the maximum absorption wavelength is generated by free radicals. Varying pigments are more preferred. From the viewpoint of the visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive resin layer contains a dye whose maximum absorption wavelength is changed by radicals as both the dye N and the photoradical polymerization initiator. better. Moreover, it is preferable that dye N is a dye which develops color by acid, alkali, or a radical from the viewpoint of the visibility of an exposure part and a non-exposure part.

As an example of the color development mechanism of the dye N in this disclosure, a radical reactive dye, an acid reactive dye, or an alkali reactive dye (for example, a leuco dye) can be mentioned by adding photoradicals to the photosensitive resin layer. Free radicals generated by photoradical polymerization initiators, photocationic polymerization initiators, or photobase generators after polymerization initiators, photocationic polymerization initiators (photoacid generators) or photobase generators and exposed to light , Acid or Alkaline color development.

From the viewpoint of the visibility of the exposed part and the non-exposed part, the maximum absorption wavelength in the wavelength range of 400nm to 780nm during color development of the dye N is preferably 550nm or more, more preferably 550nm to 700nm, and 550nm to 650nm. Further better.

The maximum absorption wavelength of the pigment N was measured by using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in the atmospheric environment, and the transmission spectrum of the solution (liquid temperature 25°C) containing the pigment N was measured in the range of 400nm to 780nm and detected at the above wavelength The intensity of light within the range is obtained at an extremely small wavelength (maximum absorption wavelength).

As a coloring matter which develops or decolorizes by exposure, a colorless compound is mentioned, for example. Examples of dyes that decolorize by exposure include leuco compounds, diarylmethane-based dyes, 㗁𠯤-based dyes, Kuchi Yamaguchi-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthracene-based dyes. Quinone pigments. As the dye N, a colorless compound is preferable from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane dye), a colorless compound having a spiropyran skeleton (spiropyran dye), and a colorless compound having a fluorescent yellow parent skeleton ( Fluorescent yellow parent system pigment), colorless compound with diarylmethane skeleton (diarylmethane pigment), colorless compound with rhodamine lactam skeleton (rhodamine lactamide pigment), indolyl A colorless compound with a phthalide skeleton (indolylphthalide pigment) and a colorless compound with a colorless aureamine skeleton (colorless aureamine pigment). Among them, triarylmethane-based pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds (triphenylmethane-based pigments) with triphenylmethane skeletons or fluorescent yellow parent system pigments are more preferred.

As a colorless compound, it is preferable to have a lactone ring, a sultone ring, or a sultone ring from the viewpoint of the visibility of an exposed part and a non-exposed part. Thereby, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with the free radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator Decolorize a colorless compound by closing its ring, or develop a color by opening its ring. As a colorless compound, a compound having a lactone ring, a sultone ring or a sultone ring and the lactone ring, a sultone ring or a sultone ring is colored by free radicals or acid ring opening is preferable , a compound that has a lactone ring and the lactone ring is opened by free radicals or acid to develop color is more preferred.

Examples of the dye N include the following dyes and leuco compounds. Among dyes N, specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, and quinaldine. quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red , Congo red, benzopurpurine 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, parafuchsin , victoria pure blue (manufactured by Orient Chemical Industries Co., Ltd.), Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industries Co., Ltd.), oil scarlet (oil scarlet) #308 (manufactured by Orient Chemical Industries Co., Ltd.), oil red OG (manufactured by Orient Chemical Industries Co., Ltd.), oil red RR (manufactured by Orient Chemical Industries Co., Ltd.), oil green #502 (manufactured by Orient Chemical Industries Co., Ltd.), spilon red (manufactured by Orient Chemical Industries Co., Ltd.), BEH special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulfo-rhodamine B, auretamine, 4-p-diethylaminophenylimine Gennaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amine Base-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4- p-Diethylaminophenylimino-5-pyrazolone.

Among the dye N, specific examples of the colorless compound include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy) , crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoride Bright yellow precursor, 2-anilino-3-methyl-6-(N-ethyl-p-toluidyl) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N, N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6- Methyl-7-anilino fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilino fluorescent yellow precursor, 3-(N,N-diethyl Amino)-6-methyl-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chloro fluorescent yellow precursor, 3-(N ,N-diethylamino)-6-methoxy-7-aminofluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorescence Yellow precursor, 3-(N,N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-(N,N-diethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent Yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-stibamido fluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilino fluorescent yellow Parent, 3-pyrrolidinyl-6-methyl-7-anilinofluorescent yellow parent, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3, 3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide Esters, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino ) Spiroisobenzofuran-1(3H), 9'-[9H]koustar-3-one.

From the viewpoint of the visibility of the exposed area and the non-exposed area, the visibility of the pattern after development, and the resolution, the pigment N is preferably a pigment whose maximum absorption wavelength is changed by free radicals, and the color of the dye N is changed by free radicals. The pigment of color is better. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate are preferable.

One kind of pigment may be used alone, or two or more kinds may be used. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the visibility of the pattern after development, and the resolution, the content of the pigment is preferably 0.1% by mass or more relative to the total mass of the photosensitive resin layer, and 0.1% by mass to 0.1% by mass. 10 mass % is more preferable, 0.1 mass % - 5 mass % is still more preferable, and 0.1 mass % - 1 mass % is especially preferable. Also, from the viewpoint of the visibility of the exposed portion and the non-exposed portion, the visibility of the pattern after development, and the resolution, the content of the dye N is preferably 0.1 mass % or more with respect to the total mass of the photosensitive resin layer, and 0.1 Mass % - 10 mass % is more preferable, 0.1 mass % - 5 mass % is still more preferable, and 0.1 mass % - 1 mass % is especially preferable.

The content of the dye N means the content of the dye when all the dye N included in the photosensitive resin layer is in a color-developed state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example. Two solutions were prepared by dissolving 0.001 g or 0.01 g of the pigment in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (trade name, Irgacure OXE01, BASF Japan Ltd.) was added to each of the obtained solutions, and 365 nm light was irradiated to generate radicals to bring all the pigments into a color-developed state. Thereafter, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve was prepared. Next, except having dissolved 3 g of photosensitive resin layers in methyl ethyl ketone instead of a dye, the absorbance of the solution which color-developed all dyes was measured by the method similar to the above. According to the calibration curve, the content of the pigment contained in the photosensitive resin layer is calculated from the absorbance of the obtained solution containing the photosensitive resin layer.

《Heat-crosslinkable compound》 From the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained, it is preferable that the photosensitive resin layer contains a thermally crosslinkable compound. In addition, in this specification, the heat-crosslinkable compound which has an ethylenically unsaturated group mentioned later is not handled as a polymeric compound, but is handled as a heat-crosslinkable compound. Examples of the heat-crosslinkable compound include a methylol compound and a block (block) isocyanate compound. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. The blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group. Therefore, for example, when the resin and/or polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the formed film will decrease, thereby hardening the photosensitive resin layer. The function of the resulting film when used as a protective film tends to be enhanced. In addition, the blocked isocyanate compound means "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent."

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C. The dissociation temperature of blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of blocked isocyanate when measured by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments Inc. (model number: DSC6200) can be preferably used. However, the differential scanning calorimeter is not limited to this.

As an end-capping agent with a dissociation temperature of 100°C to 160°C, active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, etc. , Di2-ethylhexyl malonate, etc.)], oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime and cyclohexanone oxime, etc. have -C (=N- OH) - the compound of the structure represented). Among these, it is preferable to include an oxime compound as a blocking agent having a dissociation temperature of 100° C. to 160° C., for example, from the viewpoint of storage stability.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesive force with the transfer target. A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compared with compounds not having an oxime structure, it is easier to set the dissociation temperature within a preferable range, and it is easier to reduce developing residues. A compound having an oxime structure using an oxime compound as a blocking agent is preferred.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and radically polymerizable groups are preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

As a blocked isocyanate compound, a commercial item can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.) , Duranate series of blocked type (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Moreover, the compound of the following structures can also be used as a blocked isocyanate compound.

[chemical 14]

A heat-crosslinkable compound may be used individually by 1 type, and may use 2 or more types. When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, relative to the total mass of the photosensitive resin layer. good.

"Polymer with a constituent unit having an acid group protected by an acid-decomposable group" The positive photosensitive resin layer includes a polymer (hereinafter, sometimes referred to as "polymer X") having a structural unit (hereinafter, sometimes referred to as "structural unit A") having an acid group protected by an acid-decomposable group. .) is better. The positive photosensitive resin layer may contain a single polymer X, or may contain two or more polymers X.

In polymer X, the acid group protected by the acid decomposable group is converted into an acid group through a deprotection reaction by the action of a catalytic amount of acidic substance (for example, acid) generated by exposure. By generating an acid group in the polymer X, the solubility of the positive-type photosensitive resin layer to a developing solution increases.

Polymer X is preferably an addition polymerization type polymer, more preferably a polymer having a constituent unit derived from (meth)acrylic acid or its ester.

-Constituent unit having an acid group protected by an acid decomposable group- The polymer X preferably has a structural unit (constituent unit A) having an acid group protected by an acid-decomposable group. When polymer X has structural unit A, the sensitivity of a positive photosensitive resin layer can be improved.

The acid group is not limited, and known acid groups can be used. The acidic group is preferably a carboxyl group or a phenolic hydroxyl group.

As the acid-decomposable group, for example, a group that is relatively easily decomposed by an acid and a group that is relatively difficult to decompose by an acid are mentioned. Examples of groups that are relatively easily decomposed by acids include acetal-type protecting groups (for example, 1-alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl). Examples of groups that are relatively difficult to decompose with acids include tertiary alkyl groups (for example, tertiary butyl groups) and tertiary alkoxycarbonyl groups (for example, tertiary butoxycarbonyl groups). Among the above, the acid-decomposable group is preferably an acetal-type protecting group.

From the viewpoint of suppressing variations in the line width of the resist pattern, the molecular weight of the acid-decomposable group is preferably 300 or less.

From the viewpoint of sensitivity and resolution, the constituent unit A is preferably a constituent unit represented by the following formula A1, a constituent unit represented by the formula A2, or a constituent unit represented by the formula A3, and the constituent unit represented by the formula A3 is better. The structural unit represented by formula A3 is a structural unit having a carboxyl group protected by an acetal-type acid-decomposable group.

[chemical 15]

In formula A1, R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, R ¹³ represents an alkyl group or an aryl group, and R ¹¹ Or R ¹² and R ¹³ can be connected to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, X ¹ represents a single bond or a divalent linking group, R ¹⁵ represents a substituent, and n represents an integer of 0-4.

In formula A2, R ²¹ and R ²² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl or aryl group, R ²³ represents an alkyl group or an aryl group, R ²¹ Or R ²² and R ²³ can be connected to form a cyclic ether, and R ²⁴ independently represent hydroxyl, halogen atom, alkyl, alkoxy, alkenyl, aryl, aralkyl, alkoxycarbonyl, hydroxyalkyl , arylcarbonyl, aryloxycarbonyl or cycloalkyl, m represents an integer of 0-3.

In formula A3, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl or an aryl group, at least one of R ³¹ and R ³² is an alkyl or aryl group, R ³³ represents an alkyl or aryl group, R ³¹ Or R ³² and R ³³ can be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an aryl group.

In formula A3, when R ³¹ or R ³² is an alkyl group, an alkyl group with 1 to 10 carbon atoms is preferred. In formula A3, when R ³¹ or R ³² is aryl, phenyl is preferred. In formula A3, R ³¹ and R ³² are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons, which is preferred. In formula A3, R ³³ is preferably an alkyl group with 1 to 10 carbons, more preferably an alkyl group with 1 to 6 carbons. In formula A3, the alkyl and aryl groups represented by R ³¹ to R ³³ may have substituents. In formula A3, it is preferable that R ³¹ or R ³² and R ³³ are linked to form a cyclic ether. The number of ring members of the above-mentioned cyclic ether is preferably 5 or 6, more preferably 5. In formula A3, X ⁰ is preferably a single bond. The aryl group may have a substituent. In Formula A3, R ³⁴ is preferably a hydrogen atom from the viewpoint of further lowering the glass transition temperature (Tg) of the polymer X.

The content of the structural unit in which ^R34 is a hydrogen atom in the formula A3 is preferably 20% by mass or more relative to the total mass of the structural unit A contained in the polymer X. The content of the constituent unit in which R ³⁴ in the formula A3 in the constituent unit A is a hydrogen atom can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method based on ¹³ C-nuclear magnetic resonance (NMR) measurement.

For preferred aspects of Formula A1 to Formula A3, refer to paragraphs 0044 to 0058 of International Publication No. 2018/179640.

In Formula A1 to Formula A3, from the viewpoint of sensitivity, the acid-decomposable group is preferably a group having a ring structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, and a group having a tetrahydrofuran ring structure A group is further preferred, and a tetrahydrofuryl group is particularly preferred.

The polymer X may have a single type of structural unit A, or may have two or more types of structural unit A.

The content of the constituent unit A is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass, based on the total mass of the polymer X. When the content of the structural unit A is within the above range, the resolution is further improved. When the polymer X contains two or more structural units A, the above-mentioned content of the structural units A means the total content of the two or more structural units A. The content of the constituent unit A can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

-Constituent units with acid groups- The polymer X may contain a structural unit (hereinafter also referred to as "structural unit B") having an acid group.

The structural unit B is a structural unit having an acid group not protected by an acid decomposable group, that is, an acid group not having a protecting group. When the polymer X has the structural unit B, the sensitivity at the time of pattern formation becomes favorable. Moreover, since it dissolves easily in the alkaline developing solution in the developing process after exposure, shortening of developing time can be aimed at.

The acid group in the structural unit B refers to a proton-dissociating group with a pKa of 12 or less. From the viewpoint of improving the sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Also, the pKa of the acid group is preferably -5 or more.

Examples of acid groups include carboxyl groups, sulfonamide groups, phosphonic acid groups, sulfonic acid groups, phenolic hydroxyl groups, and sulfonyl imide groups. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, more preferably a carboxyl group.

The polymer X may have a single type of structural unit B, or may have two or more types of structural unit B.

The content of the constituent unit B is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and particularly preferably 0.1% by mass to 5% by mass, based on the total mass of the polymer X. When content of structural unit B exists in the said range, resolution becomes more favorable. When the polymer X has two or more structural units B, the above-mentioned content of the structural unit B means the total content of the two or more structural units B. The content of the constituent unit B can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

-Other constituent units- It is preferable that the polymer X has another structural unit (hereinafter, may be referred to as "structural unit C") other than the above-described structural unit A and structural unit B. Various properties of the polymer X can be adjusted by preparing at least one of the type and content of the constituent unit C. Since the polymer X has the constituent unit C, the glass transition temperature, acid value, and hydrophilicity and hydrophobicity of the polymer X can be easily adjusted.

Examples of monomers forming the constituent unit C include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic Acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and unsaturated dicarboxylic anhydrides.

From the viewpoint of adhesion to the substrate, the monomer forming the constituent unit C is preferably an alkyl (meth)acrylate, and the alkyl (meth)acrylate having an alkyl group having 4 to 12 carbons is better. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate and (meth)acrylate ) 2-ethylhexyl acrylate.

As the constituent unit C, styrene, α-methylstyrene, acetyloxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, Ethyl Vinyl Benzoate, Methyl (Meth)acrylate, Ethyl (Meth)acrylate, n-Propyl (Meth)acrylate, Isopropyl (Meth)acrylate, n-Butyl (Meth)acrylate, 2-Ethylhexyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, Benzyl (meth)acrylate, Cyclopentyl (meth)acrylate , a constituent unit of cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile or ethylene glycol monoacetyl acetate mono(meth)acrylate. As the structural unit C, structural units derived from the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 may also be mentioned.

From an analytical point of view, it is preferable that the structural unit C includes a structural unit having a basic group. As a basic group, the group which has a nitrogen atom is mentioned, for example. Examples of the group having a nitrogen atom include aliphatic amine groups, aromatic amine groups, and nitrogen-containing heteroaromatic ring groups. The basic group is preferably an aliphatic amine group.

The aliphatic amine group may be any of a primary amine group, a secondary amine group, and a tertiary amine group, but a secondary amine group or a tertiary amine group is preferable from an analytical viewpoint.

Examples of monomers that form constituent units having a basic group include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2-(dimethylamine methacrylate) base) ethyl ester, 2,2,6,6-tetramethyl-4-piperidinyl acrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 2,2, 6,6-Tetramethyl-4-piperidinate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)acrylate base) ethyl ester, N-(3-dimethylamino)propyl methacrylate, N-(3-dimethylamino)propyl methacrylate, N-(3-diethylamino)methacrylate ) propyl ester, N-(3-diethylamino)propyl acrylate, 2-(diisopropylamino)ethyl methacrylate, 2-portolinoethyl methacrylate, 2-acrylic acid Porphyrinyl ethyl ester, N-[3-(dimethylamino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine , 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1,2,4-triazole. Among the above, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate is preferable.

Also, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable from the viewpoint of improving electrical characteristics. Examples of monomers forming these structural units include styrene, α-methylstyrene, dicyclopentyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate esters, isocamphoryl (meth)acrylate and benzyl (meth)acrylate. Among the above, cyclohexyl (meth)acrylate is preferable.

The polymer X may have a single type of structural unit C, or may have two or more types of structural unit C.

The content of the constituent unit C is preferably at most 90% by mass, more preferably at most 85% by mass, and particularly preferably at most 80% by mass, based on the total mass of the polymer X. The content of the constituent unit C is preferably at least 10% by mass, more preferably at least 20% by mass, based on the total mass of the polymer X. When the content of the constituent unit C is within the above range, the resolution and the adhesiveness with the substrate are further improved. When the polymer X has two or more structural units C, the above-mentioned content of the structural units C means the total content of the two or more structural units C. The content of the constituent unit C can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

Preferred examples of the polymer X are shown below. However, the polymer X is not limited to the following examples. In addition, in order to obtain preferable physical properties, the ratio and weight average molecular weight of each constituent unit in the polymer X shown below can be appropriately selected, respectively.

[chemical 16]

-Glass transition temperature- The glass transition temperature (Tg) of the polymer X is preferably 90°C or lower, more preferably 20°C to 60°C, and most preferably 30°C to 50°C. When the positive-type photosensitive resin layer is formed using a transfer material described later, the transferability of the positive-type photosensitive resin layer can be improved because the glass transition temperature of the polymer X is within the above-mentioned range.

As a method of adjusting the Tg of the polymer X within the above-mentioned range, for example, a method using the FOX formula is mentioned. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted according to the Tg of the homopolymer of each structural unit in the target polymer X and the mass fraction of each structural unit.

Hereinafter, the FOX formula will be described using a copolymer having a first structural unit and a second structural unit as an example. When the glass transition temperature of the homopolymer of the first structural unit is set as Tg1, the mass fraction of the first structural unit in the copolymer is set as W1, and the glass transition temperature of the homopolymer of the second structural unit is set as Tg2, When the mass fraction of the second structural unit in the copolymer is W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit can be estimated according to the following formula. FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)

Moreover, Tg of a polymer can also be adjusted by adjusting the weight average molecular weight of a polymer.

-acid value- From an analytical point of view, the acid value of the polymer X is preferably 0 mgKOH/g to 50 mgKOH/g, more preferably 0 mgKOH/g to 20 mgKOH/g, and most preferably 0 mgKOH/g to 10 mgKOH/g.

The acid value of the polymer indicates the mass of potassium hydroxide required to neutralize the acidic component in 1 g of the polymer. A specific measurement method will be described below. First, a measurement sample is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water=9/1). Using a potentiometric titration device (for example, trade name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.), the resulting solution was subjected to neutralization titration at 25°C with a 0.1 mol/L sodium hydroxide aqueous solution. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated by the following formula. A=56.11×Vs×0.1×f/w A: acid value (mgKOH/g) Vs: the amount of 0.1mol/L sodium hydroxide aqueous solution required for titration (mL) f: Titration of 0.1mol/L sodium hydroxide aqueous solution w: Mass of the measurement sample (g) (solid content conversion)

-Weight average molecular weight- The weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of polystyrene equivalent weight average molecular weight. When the positive photosensitive resin layer is formed using a transfer material described later, the positive photosensitive resin layer can be transferred at low temperature (for example, 130° C. or lower) because the weight average molecular weight of the polymer X is 60,000 or less.

The weight average molecular weight of the polymer X is preferably from 2,000 to 60,000, more preferably from 3,000 to 50,000.

The ratio (degree of dispersion) of the number average molecular weight to the weight average molecular weight of the polymer X is preferably from 1.0 to 5.0, more preferably from 1.05 to 3.5.

The weight average molecular weight of Polymer X is measured by GPC (Gel Permeation Chromatography). As the measuring device, various commercially available devices can be used. Hereinafter, the measurement method of the weight average molecular weight of the polymer X by GPC is demonstrated concretely. As a measuring device, HLC (registered trademark)-8220GPC (manufactured by TOSOH CORPORATION) was used. As the column, TSKgel (registered trademark) Super HZM-M (4.6mmID×15cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6mmID×15cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6mmID×15cm, manufactured by TOSOH CORPORATION) were used ) and Super HZ2000 (4.6mmID x 15cm, manufactured by TOSOH CORPORATION) are connected in series, one each. As an eluent, THF (tetrahydrofuran) was used. Regarding the measurement conditions, the sample concentration was set to 0.2% by mass, the flow rate was set to 0.35 mL/min, the sample injection volume was set to 10 μL, and the measurement temperature was set to 40° C. As a detector, a differential refractive index (RI) detector is used. The calibration curve uses "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A- 2500" and "A-1000" for any one of the 7 samples.

-content- From the viewpoint of high resolution, the content of the polymer X is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 98% by mass, based on the total mass of the positive photosensitive resin layer.

-Manufacturing method- The method for producing the polymer X is not limited, and known methods can be used. For example, in an organic solvent, it is possible to polymerize by using a monomer for forming the constituent unit A and, if necessary, a monomer for forming the constituent unit B and a monomer for forming the constituent unit C using a polymerization initiator to make Polymer X. In addition, the polymer X can also be produced by a so-called polymer reaction.

"Other Polymers" When the positive photosensitive resin layer includes a polymer having a constituent unit having an acid group protected by an acid decomposable group, in addition to the polymer having a constituent unit having an acid group protected by an acid decomposable group, it may also contain A polymer that does not have a structural unit having an acid group protected by an acid-decomposable group (hereinafter, may be referred to as "other polymers").

As another polymer, polyhydroxystyrene is mentioned, for example. Examples of commercially available polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F manufactured by Sartomer Company, Inc., and ARUFON manufactured by TOAGOSEI CO., LTD. UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080, and Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 manufactured by BASF Corporation.

The positive photosensitive resin layer may contain one kind of other polymer alone, or may contain two or more kinds of other polymers.

When the positive photosensitive resin layer contains other polymers, the content of the other polymers is preferably at most 50% by mass, more preferably at most 30% by mass, and most preferably at most 20% by mass, based on the total mass of the polymer components. .

In the present disclosure, "polymer component" is a general term for all polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains polymer X and other polymers, polymer X and other polymers are collectively referred to as "polymer components". In addition, compounds corresponding to crosslinking agents, dispersants, and surfactants described later are not included in the polymer component even if they are polymer compounds.

The content of the polymer component is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 98% by mass, relative to the total mass of the positive photosensitive resin layer.

"Alkali-soluble resin (positive type)" The positive photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinonediazide compound, and particularly preferably contains a resin having a constituent unit having a phenolic hydroxyl group and a quinonediazide compound.

As an alkali-soluble resin, the resin which has a hydroxyl group, a carboxyl group, or a sulfonic acid group in a main chain or a side chain is mentioned, for example. Examples of alkali-soluble resins include polyamide resins, polyhydroxystyrene, derivatives of polyhydroxystyrene, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, carboxyl group-containing (meth)acrylic resins and novolac resins. Preferable alkali-soluble resins include, for example, polycondensates of m-/p-mixed cresol and formaldehyde, and polycondensates of phenol, cresol, and formaldehyde.

Alkali-soluble resins can have phenolic hydroxyl groups (-Ar-OH), carboxyl groups (-CO ₂ H), sulfonic acid groups (-SO ₃ H), phosphoric acid groups (-OPO ₃ H), sulfonamide groups (-SO ₂ NH-R) or substituted sulfonamide-based acid groups (eg, activated imide, -SO ₂ NHCOR, -SO ₂ NHSO ₂ R, and -CONHSO ₂ R). Here, Ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

The novolac resin is obtained, for example, by condensing a phenolic compound and an aldehyde compound in the presence of an acid catalyst. Examples of phenolic compounds include o-, m-, or p-cresol, 2,5-, 3,5-, or 3,4-xylenol, 2,3,5-trimethyl Phenol, 2-tertiary butyl-5-methylphenol and tertiary butylhydroquinone. Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde, and glyoxal) and aromatic aldehydes (for example, benzaldehyde and salicylaldehyde). Examples of the acid catalyst include inorganic acids (eg, hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (eg, oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (eg, zinc acetate). The condensation reaction can be performed according to a conventional method. The condensation reaction is performed, for example, at a temperature in the range of 60° C. to 120° C. for 2 hours to 30 hours. The condensation reaction can be carried out in a suitable solvent.

Among them, as the alkali-soluble resin, a resin having a constituent unit having a phenolic hydroxyl group, such as a novolak resin, is preferable.

From the viewpoint of pattern formation, the weight average molecular weight of the alkali-soluble resin is preferably 5.0×10 ² to 2.0×10 ⁵ . From the viewpoint of pattern formation, the number average molecular weight of the alkali-soluble resin is preferably 2.0×10 ² to 1.0×10 ⁵ .

For example, an alkyl group having 3 to 8 carbon atoms such as the polycondensate of tertiary butylphenol and formaldehyde and the polycondensate of octylphenol and formaldehyde described in US Patent No. 4123279 can be used in combination as a substituent. Polycondensation of phenol and formaldehyde. Condensates of phenol and formaldehyde having an alkyl group with a carbon number of 3 to 8 as a substituent such as tertiary butylphenol formaldehyde resin and octylphenol formaldehyde resin described in US Patent No. 4123279 can also be used together. .

The positive photosensitive resin layer may contain one kind alone or two or more kinds of alkali-soluble resins. The content of the alkali-soluble resin is preferably 30% by mass to 99.9% by mass, more preferably 40% by mass to 99.5% by mass, and most preferably 70% by mass to 99% by mass, based on the total mass of the positive photosensitive resin layer.

"Photoacid Generator" The positive photosensitive resin layer preferably contains a photoacid generator as a photosensitive compound. A photoacid generator is a compound capable of generating an acid upon irradiation with active light rays (eg, ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams).

As the photoacid generator, a compound that generates acid by sensing active light with a wavelength of 300 nm or more, preferably with a wavelength of 300 nm to 450 nm is preferred. In addition, as for the photoacid generator that does not directly respond to active light with a wavelength of 300 nm or more, as long as it is a compound that generates an acid in response to active light with a wavelength of 300 nm or more by using it in combination with a sensitizer, it can also be combined with the sensitizer. It is better to use in combination.

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a photoacid generator that generates an acid with a pKa of 2 or less is Excellent. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. The pKa of the acid derived from the photoacid generator is preferably -10.0 or more, for example.

As a photoacid generator, an ionic photoacid generator and a nonionic photoacid generator are mentioned, for example.

As an ionic photoacid generator, an onium salt compound is mentioned, for example. Examples of the onium salt compound include diaryl onium salt compounds, triaryl permedium salt compounds, and quaternary ammonium salt compounds. The ionic photoacid generator is preferably an onium salt compound, and particularly preferably at least one of a triarylconium salt compound and a diaryliodonium salt compound.

As the ionic photoacid generator, those described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

Examples of nonionic photoacid generators include trichloromethyl-s-trisulphonate compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. It is preferable that the nonionic photoacid generator is an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion to a substrate.

Specific examples of the trichloromethyl-s-trisulfone compound, the diazomethane compound, and the imidosulfonate compound include those described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-221494. compound.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.

From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, more preferably oxime sulfonate compounds.

As a preferable example of a photoacid generator, the photoacid generator which has the following structure is mentioned.

[chemical 17]

As a photoacid generator which has absorption in wavelength 405nm, ADEKA ARKLS (trademark) SP-601 (made by ADEKA CORPORATION) is mentioned, for example.

From the viewpoint of heat resistance and dimensional stability, it is preferable that the positive photosensitive resin layer contains a quinonediazide compound as an acid generator (preferably a photoacid generator). The quinonediazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group and a quinonediazidesulfonyl halide to a condensation reaction in the presence of a dehydrohalogenating agent.

Examples of quinonediazide compounds include 1,2-benzoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinone diazide, Azide-5-sulfonate, 1,2-naphthoquinonediazide-6-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide -5-sulfonate, 2,1-naphthoquinonediazide-6-sulfonate, sulfonate of other quinonediazide derivatives, 1,2-benzoquinonediazide-4-sulfonate Chlorine, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonic acid Acyl chloride, 2,1-naphthoquinonediazide-4-sulfonyl chloride, 2,1-naphthoquinonediazide-5-sulfonyl chloride and 2,1-naphthoquinonediazide-6-sulfonate Acid chloride.

The positive photosensitive resin layer may contain a single photoacid generator, or may contain two or more photoacid generators. From the viewpoint of sensitivity and resolution, the content of the photoacid generator is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, relative to the total mass of the positive photosensitive resin layer.

"Other Ingredients" The photosensitive resin layer may have components other than the above.

-Surfactant- From the viewpoint of thickness uniformity, it is preferable that the photosensitive resin layer 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 the surfactant include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include MEGAFACE (trade names) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F- 143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS- 90, R-94, RS-72-K, DS-21 (the above are manufactured by DIC Corporation), Fluorad (trade name) FC430, FC431, FC171 (the above are manufactured by Sumitomo 3M Limited), Surflon (trade name) S-382 , SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. above), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G , 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by Neos Corporation), etc. In addition, as the fluorine-based surfactant, an acrylic compound can preferably be used. The acrylic compound has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cut, thereby Fluorine atoms evaporate. Examples of such fluorine-based surfactants include MEGAFACE (trade name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), For example MEGAFACE (trade name) DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. As the fluorine-based surfactant, a blocked polymer can also be used. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a unit derived from a (meth)acrylate compound having two or more (preferably It is a constituent unit of (meth)acrylate compound having 5 or more) alkoxyl groups (preferably ethoxyl groups, propoxyl groups). As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Examples thereof include MEGAFACE (trade name) RS-101, RS-102, RS-718K, RS-72-K (the above are manufactured by DIC Corporation) and the like.

As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerin ethoxylate, etc.) base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic ( Brand name) 304, 701, 704, 901, 904, 150R1 (the above are manufactured by BASF Corporation), Solsperse (trade name) 20000 (the above are manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 ( The above are manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-6112, D-6112-W, D-6315 (the above are manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400 , 440 (manufactured by Nissin Chemical Co., Ltd. above), etc. In addition, in recent years, the environmental suitability of compounds having a straight-chain perfluoroalkyl group with 7 or more carbon atoms has become a concern, so the interface using alternative materials such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) is used Active agents are preferred.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals. Specific examples of silicone-based surfactants include DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd. above) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF -640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (the above are Shin-Etsu Chemical Co.,Ltd. Manufactured by Momentive Performance Materials Inc.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie), etc.

The photosensitive resin layer may contain one kind of surfactant alone, or may contain two or more kinds. The content of the surfactant is preferably 0.001 mass % to 10 mass % with respect to the total mass of the photosensitive resin layer, more preferably 0.01 mass % to 3 mass %.

-additive- The photosensitive resin layer may contain known additives as needed in addition to the above components. Examples of additives include polymerization inhibitors, sensitizers, plasticizers, alkoxysilane compounds, and solvents. The photosensitive resin layer may contain each additive individually by 1 type, and may contain 2 or more types. In addition, examples of additives include metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, etc. agent and organic or inorganic precipitation preventive agent. The preferred aspects of these additives are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and these contents are incorporated into this specification by referring to them.

The photosensitive resin layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferable. Examples of polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiophene, phenothiophene, or 4-methoxyphenol are preferred. Examples of other polymerization inhibitors include naphthylamine, copper (I) chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, and the like. In order not to impair the sensitivity of the photosensitive resin composition, it is preferable to use nitrosophenylhydroxylamine aluminum salt as a polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01 mass % to 3 mass % with respect to the total mass of the photosensitive resin layer, more preferably 0.05 mass % to 1 mass %. It is preferable to make the said content into 0.01 mass % or more from a viewpoint of providing storage stability to a photosensitive resin composition. On the other hand, from the viewpoint of maintaining sensitivity, it is preferable to make the said content into 3 mass % or less.

The photosensitive resin layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone (xanthone) compounds, thioxanthone (thioxanthone) compounds, Pyridone compound, oxazole compound, benzoxazole compound, thiazole compound, benzothiazole compound, triazole compound (for example, 1,2,4-triazole), stilbene compound, trioxazole compound, thiophene compound, naphthalenedi Formimide compounds, triarylamine compounds and aminoacridine compounds.

The photosensitive resin layer may contain one kind of sensitizer alone, or may contain two or more kinds. When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and increasing the curing speed by balancing the polymerization speed and chain transfer, relative to The total mass of the photosensitive resin layer is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass.

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

The photosensitive resin layer (preferably a positive photosensitive resin layer) may contain an alkoxysilane compound. Examples of alkoxysilane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ -Glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-Chloropropyltrialkoxysilane, γ-Mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane and Vinyltrialkoxysilane.

Among the above, the alkoxysilane compound is preferably a trialkoxysilane compound, γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane Silane is more preferable, γ-glycidoxypropyltrialkoxysilane is still more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable.

The photosensitive resin layer may contain a single alkoxysilane compound, or may contain two or more alkoxysilane compounds. From the viewpoint of adhesion to the substrate and etching resistance, the content of the alkoxysilane compound is preferably 0.1% by mass to 50% by mass, and 0.5% by mass to 40% by mass relative to the total mass of the photosensitive resin layer. More preferably, 1.0% by mass to 30% by mass is particularly preferred.

The photosensitive resin layer may contain a solvent. When forming a photosensitive resin layer from the photosensitive resin composition containing a solvent, a solvent may remain in a photosensitive resin layer.

"Impurities etc" The photosensitive resin layer 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, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so the following contents are preferable.

The content of impurities in the photosensitive resin layer is preferably at most 80 ppm, more preferably at most 10 ppm, and still more preferably at most 2 ppm, on a mass basis. The content of impurities may be 1 ppb or more on a mass basis, and may be 0.1 ppm or more.

As a method of keeping the impurities within the above-mentioned range, there may be mentioned selection of those with a small content of impurities as raw materials of the composition, prevention of impurities from being mixed in the photosensitive resin layer, and removal by washing. By this method, the amount of impurities can be set within the above-mentioned range.

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

Benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide in the photosensitive resin layer It is better to have less content of compounds such as hexane and hexane. The content of these compounds with respect to the total mass of the photosensitive resin layer is preferably at most 100 ppm on a mass basis, more preferably at most 20 ppm, and still more preferably at most 4 ppm. The lower limit may be 10 ppb or more with respect to the total mass of the photosensitive resin layer on a mass basis, or may be 100 ppb or more. The content of these compounds can be suppressed by the same method as the impurity of the above-mentioned metals. In addition, it can be quantified by a known measurement method.

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

"The Leftovers" The photosensitive resin layer may contain residual monomers corresponding to each constituent unit of the above-mentioned alkali-soluble resin. From the viewpoint of patternability and reliability, the residual monomer content is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, more preferably 500 mass ppm or less, relative to the total mass of the alkali-soluble resin . The lower limit is not particularly limited, but is preferably at least 1 mass ppm, more preferably at least 10 mass ppm. From the viewpoint of patternability and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and 100 mass ppm with respect to the total mass of the photosensitive resin layer. It is still more preferably below mass ppm. The lower limit is not particularly limited, but is preferably at least 0.1 mass ppm, more preferably at least 1 mass ppm.

It is also preferable to set the residual monomer amount of the monomer in the case of synthesizing the alkali-soluble resin by polymer reaction within the above-mentioned range. For example, when an alkali-soluble resin is synthesize|combined by reacting glycidyl acrylate and a carboxylic acid side chain, it is preferable to make content of glycidyl acrylate into the said range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

"Physical Properties, etc." The layer thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, still more preferably 0.5 μm to 50 μm, still more preferably 0.5 μm to 15 μm, and most preferably 0.5 μm to 10 μm , 0.5 μm ~ 8 μm is the best. Thereby, the developability of a photosensitive resin layer improves and resolution can be improved. Also, from the analytical viewpoint, the layer thickness (thickness) of the photosensitive resin layer is preferably 10 μm or less, more preferably 4.8 μm or less, still more preferably 3.0 μm or less, and particularly preferably 0.5 μm to 3.0 μm. . The layer thickness of each layer of the photosensitive transfer material is obtained by observing the cross-section of the photosensitive transfer material in the direction perpendicular to the main surface with a scanning electron microscope (SEM: Scanning Electron Microscope) and based on the obtained observation image The thickness of each layer was measured at 10 points or more, and the average value was calculated and measured.

Moreover, from a viewpoint of more excellent adhesiveness, the light transmittance of the wavelength 365nm of a photosensitive resin layer is 10% or more, Preferably it is 30% or more, More preferably, it is 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

"Formation Method" The method for forming the photosensitive resin layer is not particularly limited as long as it can form a layer containing the above-mentioned components. As a method for forming the photosensitive resin layer, for example, in the case of a negative photosensitive resin layer, it is possible to prepare a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, and the like. A method in which a photosensitive resin composition is applied to the surface of a temporary support, etc., and the coating film of the photosensitive resin composition is dried.

As a photosensitive resin composition used for formation of a photosensitive resin layer, the composition containing alkali-soluble resin, a polymerizable compound, a photoinitiator, the said arbitrary component, and a solvent is mentioned, for example. In order to easily form a photosensitive resin layer by adjusting the viscosity of the photosensitive resin composition, it is preferable that the photosensitive resin composition contains a solvent.

-Solvent- The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, polymerizable compound, photopolymerization initiator, and any of the above-mentioned components, and known solvents can be used. Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic Hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and solvents including these A mixture of two or more solvents. When making a photosensitive transfer material with a temporary support, buffer layer, intermediate layer, photosensitive resin layer and protective film, the photosensitive resin composition contains a solvent selected from alkylene glycol ethers and alkylene glycols At least one of the group of ether acetate solvents is preferred. Among them, at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents The mixed solvent is more preferably at least one of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent and a cyclic ether solvent. Further better.

Examples of alkylene glycol ether solvents 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 alkylene glycol ether acetate solvents 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 solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of Japanese Patent Laid-Open No. 2018-177889 can be used, and these contents are incorporated in this specification.

The photosensitive resin composition may contain one kind of solvent alone, or may contain two or more kinds of solvents. The content of the solvent when coating the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solids in the photosensitive resin composition.

The preparation method of the photosensitive resin composition is not particularly limited. For example, a solution obtained by dissolving each component in the above-mentioned solvent is prepared in advance and the obtained solution is mixed at a predetermined ratio to prepare a photosensitive resin. Method of composition. From the viewpoint of particle removability, it is preferable to filter the photosensitive resin composition using a filter before forming the photosensitive resin layer, more preferably a filter with a pore size of 0.2 μm to 10 μm, and a filter with a pore size of 0.2 μm It is more preferable to perform filtration with a filter of ∼7 μm, and it is particularly preferable to perform filtration with a filter with a pore diameter of 0.2 μm to 5 μm. The material and shape of the filter are not particularly limited, and known ones can be used. Moreover, it is preferable to carry out the above-mentioned filtration once or more, and it is also preferable to carry out a plurality of times.

The coating method of the photosensitive resin composition is not particularly limited, and it may be coated by a known method. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating. Moreover, the photosensitive resin layer can be formed by apply|coating and drying a photosensitive resin composition on the protective film mentioned later.

Moreover, it is preferable that the photosensitive transfer material in this indication has another layer between the said temporary support body and the said photosensitive resin layer from the viewpoint of resolving property and the peelability of a temporary support body. As another layer, an intermediate layer, a buffer layer, a protective film, etc. are mentioned preferably. Among them, as the above-mentioned transfer layer, it is preferable to have an intermediate layer, and it is more preferable to have a buffer layer and an intermediate layer.

〔middle layer〕 When the photosensitive transfer material has a buffer layer described later between the temporary support body and the photosensitive resin layer, it is preferable to have an intermediate layer between the buffer layer and the photosensitive resin layer. According to the intermediate layer, it is possible to suppress mixing of components when forming a plurality of layers and during storage.

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

The intermediate layer includes, for example, an oxygen barrier layer having an oxygen barrier function described in JP-A-5-72724 as a "separation layer". Since the intermediate layer is an oxygen barrier 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 barrier layer used as the intermediate layer may be appropriately selected from known layers. The oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (a 1 mass % aqueous solution of sodium carbonate at 22° C.). Moreover, it is preferable that the intermediate layer contains an inorganic layered compound from the viewpoint of oxygen barrier property, resolution property, and pattern formation property. As an inorganic layered compound, it is a particle having a thin plate shape, for example, mica compounds such as natural mica and synthetic mica, talc represented by the formula: 3MgO·4SiO·H ₂ O, taeniolite, montmorillonite, Soapstone, lithium bentonite, zirconium phosphate, etc. Examples of mica compounds include the formula: A(B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂ [wherein A is any one of K, Na, and Ca, and B and C is any one of Fe(II), Fe(III), Mn, Al, Mg, and V, and D is Si or Al. ] Represented natural mica, synthetic mica and other mica groups.

In the mica group, examples of natural mica include muscovite, sodium mica, phlogopite, biotite, and phlogopite. Examples of synthetic mica include non-swellable micas such as fluorphlogopite KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilica KMg _2.5 Si ₄ O ₁₀ ) F ₂ and NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li taeniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Na or Li hectorite (Na, Li) of montmorillonite series (Na, Li) _1/8 Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ and other swelling mica, etc. In addition, synthetic bentonite group (smectite) is also useful.

As for the shape of the inorganic layered compound, from the viewpoint of diffusion control, the thinner the thickness, the better, and the larger the planar size, as long as it does not hinder the smoothness of the coated surface or the transmittance of active light rays, the better. Therefore, the aspect ratio is preferably at least 20, more preferably at least 100, and most preferably at least 200. The aspect ratio is the ratio of the major diameter of a particle to the thickness, and can be measured, for example, from a projection image obtained from a micrograph of a particle. The larger the aspect ratio, the greater the effect obtained.

The particle diameter of the inorganic layered compound is preferably from 0.3 μm to 20 μm in average major diameter, more preferably from 0.5 μm to 10 μm, particularly preferably from 1 μm to 5 μm. The average thickness of the particles is preferably at most 0.1 μm, more preferably at most 0.05 μm, particularly preferably at most 0.01 μm. Specifically, for example, in the case of swelling synthetic mica, which is a representative compound, the thickness is about 1 nm to 50 nm, and the surface size (major axis) is about 1 μm to 20 μm.

From the viewpoints of oxygen barrier properties, resolving properties, and pattern forming properties, the content of the layered inorganic compound is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, relative to the total mass of the intermediate layer. good.

It is preferable that the intermediate layer contains resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, and vinyl ether resins. 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 multiple layers, the resin contained in the intermediate layer is the same as the polymer A contained in the negative photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the buffer layer. Resins in which any of them are different are preferable.

Moreover, it is preferable that an intermediate layer contains a water-soluble compound, and it is more preferable that it contains a water-soluble resin from a viewpoint of oxygen barrier property, developability, resolving property, and pattern formability. The water-soluble compound is not particularly limited, but it is selected from oxides including water-soluble cellulose derivatives, polyols, and polyols from the viewpoint of oxygen barrier properties, developability, resolution, and pattern formation properties. One or more compounds in the group of adducts, polyethers, phenol derivatives and amide compounds are preferred, selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl At least one water-soluble resin in the group of methylcellulose is more preferable. Examples of water-soluble resins include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, and vinyl ethers. resins, polyamide resins, and copolymers thereof. Among them, from the viewpoints of oxygen barrier properties, developability, resolving power, and pattern forming properties, the water-soluble resin preferably contains polyvinyl alcohol, more preferably contains polyvinyl alcohol and a water-soluble cellulose derivative, and contains polyvinyl alcohol. Alcohol and hydroxypropyl cellulose are further preferred, and polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose are particularly preferred. The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73 mol% to 99 mol% from the viewpoints of oxygen barrier properties, developability, resolving properties, and pattern forming properties. Moreover, it is preferable that polyvinyl alcohol contains ethylene as a monomer unit from a viewpoint of oxygen barrier property, developability, resolution property, and pattern formability.

The content of the polyvinyl alcohol is 10% by mass to 95% by mass relative to the total mass of the intermediate layer from the viewpoint of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution and sensitivity. It is more preferable, 30 mass % - 90 mass % is more preferable, and 50 mass % - 75 mass % is especially preferable.

In addition, from the viewpoint of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolving power and sensitivity, it is preferable that the above-mentioned water-soluble resin includes water-soluble cellulose derivatives, including hydroxyalkyl fiber More preferably, it is a vegetarian compound, and it is especially preferable to contain hydroxypropyl cellulose. The content of the hydroxypropyl cellulose is 0.005% by mass to 20% by mass relative to the total mass of the intermediate layer from the viewpoint of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolving power, and sensitivity. The mass % is more preferable, 0.01 mass % - 10 mass % is more preferable, 0.1 mass % - 5 mass % is still more preferable, and 0.5 mass % - 3 mass % is especially preferable.

In addition, it is preferable that the water-soluble resin contains polyvinylpyrrolidone from the viewpoint of oxygen barrier property, developability, defect suppression property of the obtained photoresist pattern, resolution and sensitivity. The content of the polyvinylpyrrolidone is 1% by mass to 60% by mass relative to the total mass of the intermediate layer from the viewpoint of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution and sensitivity. The mass % is more preferable, 10 mass % - 50 mass % is more preferable, 20 mass % - 45 mass % is still more preferable, and 25 mass % - 40 mass % is especially preferable.

The intermediate layer may contain one kind of resin alone or two or more kinds of resins.

From the viewpoint of oxygen barrier properties and suppression of mixing of components when applying multiple layers and when storing after coating, the content ratio of the water-soluble compound in the intermediate layer is 50% by mass to 100% by mass relative to the total mass of the intermediate layer % is more preferable, 70 mass % - 100 mass % is more preferable, 80 mass % - 100 mass % is more preferable, and 90 mass % - 100 mass % is especially preferable.

Also, the intermediate layer may contain additives 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 range, the oxygen barrier property is not reduced, and the mixing of components when forming multiple layers and during storage can be suppressed, and the increase in the removal time of the intermediate layer during development can be suppressed. .

The formation method of the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method of forming the intermediate layer, for example, a method of drying the coating film of the intermediate layer composition after coating the intermediate layer composition on the surface of the buffer layer or the photosensitive resin layer is mentioned.

As an intermediate layer composition, the composition containing resin and arbitrary additives is mentioned, for example. In order to adjust the viscosity of the intermediate layer composition to easily form the intermediate layer, it is preferable that the intermediate layer composition contains a solvent. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.

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.

〔The buffer layer〕 The photosensitive transfer material disclosed herein preferably has a buffer layer. The photosensitive transfer material preferably has a buffer layer between the temporary support and the photosensitive resin layer or intermediate layer. This is because, since the photosensitive transfer material has a buffer layer between the temporary support body and the photosensitive resin layer or the intermediate layer, the followability to the adherend is improved and the adhesion between the adherend and the photosensitive transfer material is improved. The mixing of air bubbles is suppressed, and as a result, the adhesion between layers is improved.

The buffer layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. As the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used for the buffer layer, the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used for the above-mentioned photosensitive resin layer can be preferably used.

Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, epoxy resins, polycondensate resins, and polystyrene resins. Aldehyde resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.

The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesiveness to the layer adjacent to the buffer layer. Here, "acrylic resin" refers to a group having a constituent unit derived from (meth)acrylic acid, a constituent unit derived from (meth)acrylate, and a constituent unit derived from (meth)acrylamide. At least one resin in the group.

In the acrylic resin, the ratio of the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide relative to the content of the acrylic resin The total mass is preferably 50% by mass or more. In the acrylic resin, the ratio of the total content of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate is preferably 30% by mass to 100% by mass based on the total mass of the acrylic resin , 50% by mass to 100% by mass is more preferable.

Also, it is preferable that the alkali-soluble resin is a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

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

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

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 the total mass of the carboxyl group-containing acrylic resin. % 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 viewpoint of developability and adhesiveness to the layer adjacent to the buffer layer.

Alkali-soluble resins may have reactive groups. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include ethylenically unsaturated groups, polycondensable groups (for example, hydroxyl groups and carboxyl groups), and polyaddition reactive groups (for example, epoxy groups and (blocked) isocyanate groups).

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 most preferably 20,000 to 50,000.

The buffer layer may contain alone or two or more alkali-soluble resins.

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

The buffer layer contains a pigment whose maximum absorption wavelength is 450nm or more in the wavelength range of 400nm to 780nm during color development, and the maximum absorption wavelength is changed by acid, alkali or free radicals (hereinafter, sometimes referred to as "dye B"). is better. A preferred aspect of the dye B is the same as that of the aforementioned preferred aspect of the dye N except for the points described later.

From the viewpoint of the visibility of the exposed area, the visibility of the non-exposed area, and the resolution, the pigment B is preferably a pigment whose maximum absorption wavelength is changed by an acid or a free radical, and the maximum absorption wavelength is generated by an acid. Varying pigments are more preferred.

From the viewpoint of the visibility of the exposed part, the visibility of the non-exposed part, and the resolution, the buffer layer contains a dye whose maximum absorption wavelength is changed by acid as the dye B and a compound that generates an acid by light described later. is better.

The buffer layer may contain one kind or two or more kinds of pigment B alone.

From the viewpoint of the visibility of the exposed area and the visibility of the non-exposed area, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, based on the total mass of the buffer layer. 0.2 mass % - 5 mass % is more preferable, and 0.25 mass % - 3.0 mass % is especially preferable.

Here, the content ratio of the dye B refers to the content ratio of the dye when all the dye B contained in the buffer layer is in a colored state. Hereinafter, a method for quantifying the content ratio of the dye B will be described by taking a dye that develops color by radicals as an example. Two solutions were prepared by dissolving a dye (0.001 g) and a dye (0.01 g) in methyl ethyl ketone (100 mL), respectively. After adding IRGACURE OXE-01 (BASF Corporation) as a photoradical polymerization initiator to each of the obtained solutions, radicals were generated by irradiating light of 365 nm, and all the pigments were brought into a color-developed state. Next, under the atmospheric environment, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was prepared. Next, except for dissolving the buffer layer (0.1 g) in methyl ethyl ketone instead of the dye, the absorbance of the solution in which all the dye was developed was measured by the same method as above. According to the calibration curve, the amount of the pigment contained in the buffer layer was calculated from the absorbance of the obtained solution containing the buffer layer.

The buffer 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 free radicals upon exposure to active light (for example, ultraviolet light and visible light). Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

From an analytical point of view, it is preferable that the buffer layer contains a photoacid generator. As a photoacid generator, the photocationic polymerization initiator which can be contained in the above-mentioned photosensitive resin layer is mentioned, and a preferable aspect is the same except the point mentioned later.

From the viewpoints of sensitivity and resolution, it is preferable that the photoacid generator comprises at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds. , It is more preferable to contain an oxime sulfonate compound.

Moreover, it is also preferable that a photoacid generator is a photoacid generator which has the following structures.

[chemical 18]

The buffer layer may contain a photobase generator. As the photobase generating agent, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxyamide, O-carbamoyl oxime, [[(2 ,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthio Benzoyl)-1-methyl-1-pornolinylethane, (4-pornoylbenzoyl)-1-benzyl-1-dimethylaminopropane, N-( 2-nitrobenzyloxycarbonyl)pyrrolidine, hexaaminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4- (Phenylphenyl) butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl Diacetyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

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

The buffer layer may contain one kind or two or more kinds of Compound C alone.

From the viewpoint of the visibility of the exposed area, the visibility of the non-exposed area, and the resolution, the content of the compound C is preferably 0.1% by mass to 10% by mass, and 0.5% by mass to 5% by mass relative to the total mass of the buffer layer. Quality % is better.

It is preferable that a buffer layer contains a plasticizer from a viewpoint of resolution, the adhesiveness of the layer adjacent to a buffer layer, and developability.

The molecular weight of the plasticizer (the molecular weight of the oligomer or polymer refers to 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 200-2,000.

The plasticizer is not limited as long as it is a compound 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, more preferably a polyalkylene glycol compound. It is preferable that the alkyleneoxy group contained in the plasticizer has a polyethoxyl structure or a polypropoxyl structure.

It is preferable that a plasticizer contains a (meth)acrylate compound from a viewpoint of analytical property and storage stability. From the viewpoint of compatibility, resolution, and adhesiveness to the layer adjacent to the buffer layer, it is more preferable that the alkali-soluble resin is an acrylic resin and that the plasticizer contains a (meth)acrylate compound.

As a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound described in the said ethylenically unsaturated compound is mentioned, for example. When the buffer layer and the photosensitive resin layer are arranged in direct contact with each other in the photosensitive transfer material, it is preferable that the buffer layer and the photosensitive resin layer each contain the same (meth)acrylate compound. This is because, when the buffer layer and the photosensitive resin layer each contain the same (meth)acrylate compound, interlayer component diffusion is suppressed and storage stability improves.

When the buffer layer contains a (meth)acrylate compound as a plasticizer, the (meth)acrylate compound does not polymerize at the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the buffer layer. better.

In a certain embodiment, the (meth)acrylate compound used as a plasticizer has two The above (meth)acryl (meth)acrylate compounds are preferred.

In a certain embodiment, it is preferable that the (meth)acrylate compound used as a plasticizer is a (meth)acrylate compound or a urethane (meth)acrylate compound which has an acid group.

The buffer layer may contain alone or two or more plasticizers.

From the viewpoint of resolution, adhesion to the layer adjacent to the buffer layer, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass relative to the total mass of the buffer layer, and 10% by mass -60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferred.

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

The buffer layer may contain one kind alone or two or more kinds of surfactants.

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, relative to the total mass of the buffer layer.

The buffer layer may contain a sensitizer. As a sensitizer, the sensitizer which can be contained in the above-mentioned negative photosensitive resin layer is mentioned, for example.

The buffer layer may contain one kind or two or more kinds of sensitizers alone.

From the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part, and the visibility of the non-exposed part, the content ratio of the sensitizer is preferably 0.01 mass % to 5 mass % with respect to the total mass of the buffer layer, and 0.05 Mass % - 1 mass % is more preferable.

The buffer layer may contain known additives as necessary in addition to the above components.

Moreover, about a buffer layer, it describes in paragraph 0189 - 0193 of Unexamined-Japanese-Patent No. 2014-85643. The contents of the above publications are incorporated into this specification by referring to them.

The thickness of the buffer layer is not limited. From the viewpoint of adhesiveness to the layer adjacent to the buffer layer, the average thickness of the buffer layer is preferably 1 μm or more, more preferably 2 μm or more. The upper limit of the average thickness of the buffer layer is not limited. From the viewpoint of developability and resolution, the average thickness of the buffer 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 buffer layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method of forming a buffer layer, for example, a method of applying a composition for forming a buffer layer on the surface of a temporary support and drying the coating film of the composition for forming a buffer layer is exemplified.

As a composition for buffer layer formation, the composition containing the said component is mentioned, for example. In order to easily form a buffer layer by adjusting the viscosity of the buffer layer-forming composition, it is preferable that the buffer layer-forming composition contains a solvent.

The solvent contained in the buffer layer forming composition is not limited as long as it can dissolve or disperse the components contained in the buffer layer. Examples of the solvent include solvents that may be contained in the above-mentioned photosensitive resin composition, and the same is true for preferred aspects.

The composition for forming a buffer layer may contain one kind or two or more kinds of solvents alone.

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

The preparation of the buffer layer forming composition and the formation of the buffer layer may be carried out in accordance with the above-mentioned preparation method of the photosensitive resin composition and the formation method of the negative photosensitive resin layer. For example, after preparing a composition for forming a buffer layer by preparing a solution in which each component contained in the buffer layer is dissolved in a solvent and mixing the obtained solutions in a predetermined ratio, the resulting buffer layer is formed The buffer layer can be formed by applying the composition to the surface of the temporary support and drying the coating film of the buffer layer forming composition. Moreover, after forming a photosensitive resin layer on a protective film, you may form a buffer layer on the surface of a photosensitive resin layer.

〔Protective film〕 It is preferable that the photosensitive transfer material has a protective film. In addition, a protective film is not contained in the said transfer layer. It is preferable that the photosensitive resin layer is in direct contact with the protective film.

Examples of the material constituting the protective film include resin films and paper, and resin films are preferred from the viewpoint of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, polyethylene film, polypropylene film or polyethylene terephthalate film is preferred.

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm. The arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is the above-mentioned photosensitivity in the protective film from the viewpoint of transportability, defect suppression of the photoresist pattern, and resolution. The arithmetic mean roughness Ra of the surface on the side of the resin layer is preferably at most, and it is more preferably smaller than the arithmetic mean roughness Ra of the surface on the side of the photosensitive resin layer in the protective film. The arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer is preferably 300 nm or less, more preferably 100 nm or less, and 70 nm or less from the viewpoint of conveyance and take-up properties. More preferably, the thickness of 50 nm or less is particularly preferable. Also, from the standpoint of better resolution, the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side in the protective film is preferably 300 nm or less, more preferably 100 nm or less, still more preferably 70 nm or less, Below 50nm is especially good. This is considered to be because the uniformity of the layer thickness of the photosensitive resin layer and the formed resist pattern improves when the Ra value of the surface of a protective film exists in the said range. The lower limit of the Ra value of the surface of the protective film is not particularly limited, but both sides are preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more. Moreover, it is preferable that the peeling force of a protective film is smaller than the peeling force of a temporary support body.

The photosensitive transfer material may include layers (hereinafter also referred to as "other layers") other than the above-mentioned layers. As another layer, a contrast enhancement layer (contrast enhancement layer) is mentioned, for example. Regarding the contrast enhancement layer, it is described in paragraph 0134 of International Publication No. 2018/179640. Moreover, about another layer, it describes in paragraphs 0194-0196 of Unexamined-Japanese-Patent No. 2014-85643. The contents of these publications are incorporated into this specification.

The total thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and most preferably 20 μm to 40 μm. The total thickness of the photosensitive transfer material is measured by the method according to the method of measuring the thickness of each layer described above. From the viewpoint of further exerting the effects of the present disclosure, the total thickness of the layers in the photosensitive transfer material other than the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 8 μm or less. More preferably, 2 μm or more and 8 μm or less are particularly preferred. Also, from the viewpoint of further exerting the effects of the present disclosure, the total thickness of the photosensitive resin layer, intermediate layer, and buffer layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, and 8 μm or less More preferably, it is more than 2 μm and 8 μm or less.

[Manufacturing method of photosensitive transfer material] The method of manufacturing the photosensitive transfer material disclosed herein is not particularly limited, and known manufacturing methods such as known methods for forming each layer can be used.

As a method for producing the above-mentioned photosensitive transfer material, for example, a method including a step of coating an intermediate layer composition on the surface of a temporary support and drying the coating film of the intermediate layer composition to form an intermediate layer ; and after coating the photosensitive resin composition on the surface of the intermediate layer, drying the coating film of the photosensitive resin composition to form a photosensitive resin layer.

A photosensitive transfer material is produced by crimping a protective film on the photosensitive resin layer of the laminate produced by the above production method. As the method for producing the photosensitive transfer material of the present disclosure, a temporary support, an intermediate The photosensitive transfer material of layer, photosensitive resin layer and protective film is preferable. After the photosensitive transfer material is produced by the above-mentioned production method, the photosensitive transfer material in roll form can be produced and stored by winding up the photosensitive transfer material. The roll-form photosensitive transfer material can be directly supplied to the process of bonding with the board|substrate of the roll-to-roll system mentioned later in this form.

The photosensitive transfer material of the present disclosure can be preferably used in various applications that require precise microfabrication based on photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a film, or electroforming mainly involving electroplating may be performed. Moreover, the cured film obtained by patterning can be used as a permanent film, for example, can be used as an interlayer insulating film, a wiring protection film, a wiring protection film which has a refractive index matching layer, etc. In addition, the photosensitive transfer material of the present disclosure can be suitably used for semiconductor packages, printed circuit boards, various wiring formation applications of sensor substrates, conductive films such as touch panels, electromagnetic wave shielding materials, and film heaters, Liquid crystal sealing materials, formation of structures in the field of micromechanics or microelectronics, etc.

Moreover, the photosensitive transfer material of this indication can also mention the aspect in which the photosensitive resin layer is the colored resin layer containing a pigment preferably. As the use of the colored resin layer, in addition to the above, it is suitable for forming a liquid crystal display device (LCD) and a solid-state imaging device [for example, CCD (charge-coupled device: charge-coupled device) and CMOS (complementary metal oxide semiconductor: complementary metal Oxide Semiconductor)] used in colored pixels or black matrices such as color filters. About the aspects other than the pigment in the colored resin layer, it is the same as the above-mentioned aspect.

＜Pigment＞ The photosensitive resin layer may be a colored resin layer containing a pigment. In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the back peripheral portion of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window of an electronic device in order to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer can be used. As a pigment, what is necessary is just to select suitably according to desired hue, and can select from black pigment, white pigment, and color pigments other than black and white. Among them, when forming a black-based pattern, it is preferable to select a black pigment as the pigment.

Known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as the black pigment within a range that does not impair the effects of the present disclosure. Among them, from the viewpoint of optical density, examples of the black pigment include preferably carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, and carbon black is particularly preferred. As the carbon black, carbon black whose surface is at least partially covered with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle size of the black pigment is preferably from 0.001 μm to 0.1 μm, more preferably from 0.01 μm to 0.08 μm, as a number average particle size. Here, the particle diameter refers to the diameter of a circle when the area of the pigment particle is calculated from the photo image of the pigment particle taken by an electron microscope and a circle having the same area as the area of the pigment particle is considered, and the number average particle diameter refers to an arbitrary 100 The average value obtained by obtaining the above-mentioned particle diameter for each particle and averaging the obtained particle diameters of 100 particles.

As the pigments other than the black pigment, the white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment. Specifically, among white pigments, as inorganic pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred, titanium oxide or zinc oxide Titanium oxide is more preferable, and titanium oxide is still more preferable. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable. In addition, the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or organic matter, or two or more treatments may be performed. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, light fading properties, and the like are improved. From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, at least one of alumina treatment and zirconia treatment is preferred as the surface treatment on the surface of titanium oxide. Zirconia is particularly preferred for handling both.

Moreover, when the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains color pigments other than a black pigment and a white pigment from a transferable viewpoint. When a color pigment is included, the particle size of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. Examples of color pigments include Victoria Pure Blue BO (Color Index (Color Index) (hereinafter C.I.) 42595), Auretamine (C.I. 41000), Fat Black (fat black) HB (C.I. 26150), Monolette Yellow (monolight yellow) GT (C.I. Pigment Yellow 12), permanent yellow (permanent yellow) GR (C.I. Pigment Yellow 17), permanent yellow HR (C.I. Pigment Yellow 83), permanent carmine (permanent carmine) FBB (C.I. Pigment Red 146) , Hestaperm red (hostaperm red) ESB (C.I. Pigment Violet 19), permanent ruby red (permanent ruby) FBH (C.I. Pigment Red 11), Fastel pink (pastel pink) B Supura (supura) (C.I. Pigment Red 81), monastral fast blue (C.I. Pigment Blue 15), Monolette Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. Pigment Red 97, C.I. Pigment Red 122 , C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is preferred.

When the photosensitive resin layer contains a pigment, the content of the pigment relative to the total mass of the photosensitive resin layer is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, It is more preferably more than 5 mass % and 35 mass % or less, and it is especially preferable that it is 10 mass % or more and 35 mass % or less.

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

In addition, when the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed of a photosensitive resin composition, it is preferable that the black pigment (preferably carbon black) be introduced into the photosensitive resin composition in the form of a pigment dispersion . The dispersion liquid may be one prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing it with a disperser. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used. In addition, the medium refers to the part of the medium that disperses the pigment when the pigment dispersion is prepared. It is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component. .

The dispersing machine is not particularly limited, and examples thereof include a kneader, a roll mill, an attritor, a super mill, a dissolver, a homo mixer, and a sand Known dispersing machines such as sand mills. In addition, mechanical grinding can also be used to perform fine pulverization using frictional force. Regarding the dispersing machine and fine pulverization, you can refer to the records in "Dictionary of Pigments" (by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

<Manufacturing method of deposition mask> The manufacturing method of the deposition mask of this disclosure is the method of using the photosensitive transfer material for deposition mask manufacture of this disclosure. Also, it is preferable that the manufacturing method of the deposition mask of the present disclosure includes the following steps in sequence: preparing a metal layer having a first surface and a second surface at a position opposite to the above-mentioned first surface (hereinafter also referred to as "preparation") step"); attaching the photosensitive transfer material to the metal layer, and sequentially disposing the transfer layer and the temporary support on the first surface of the metal layer (hereinafter, also referred to as "bonding step" .), the photosensitive transfer material sequentially includes the above-mentioned temporary support and the above-mentioned transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the above-mentioned temporary support 50 pieces/mm ³ or less; pattern exposure of the above-mentioned transfer layer (hereinafter, also referred to as "exposure step"); development of the above-mentioned transfer layer to form a photoresist pattern (hereinafter, also referred to as "developing step") step"); performing etching on the metal layer not covered by the photoresist pattern to form a through hole extending from the first surface of the metal layer to the second surface of the metal layer (hereinafter also referred to as "etching step".); and removing the above photoresist pattern (hereinafter, also referred to as "removal step".).

Hereinafter, the details of each step in the manufacturing method of the deposition mask of the present disclosure will be described.

(preparation steps) In the preparatory step, a metal layer having a first surface and a second surface opposite to the first surface is prepared. The metal layer may be a known metal substrate (including commercially available ones). The metal layer can also be produced by known methods (for example, casting method, forging method, sputtering method, and electroplating method).

The structure of the metal layer can be a single-layer structure or a multi-layer structure. As a metal element contained in a metal layer, Cu, Ni, Fe, Cr, Mn, and Co are mentioned, for example. A part or all of the metal layer may be an alloy. Examples of alloys include Ni—Co alloys and Fe—Ni alloys. It is preferable that the metal layer comprises at least one metal element selected from the group comprising Cu, Ni, Fe, Cr, Mn and Co, and it is more preferable to comprise at least one metal element selected from the group comprising Cu, Fe and Ni. Preferably, Fe is further preferably contained, and Fe and Ni are particularly preferably contained. The metal layer may contain elements other than metal elements. Examples of elements other than metal elements include B, C, N, O, P, S, and Cl. The metal layer can also be a metal substrate. Among them, the metal in the metal layer can preferably include nickel, Ni-Co alloy, Fe-Ni alloy, copper, etc., and the alloy containing nickel of 30 mass % or more and 45 mass % or less is preferred, and 36 mass % of The metal mainly composed of an alloy of nickel and 64% by mass of iron, that is, steel, is more preferable. When the metal in the metal layer is Invar, the thermal expansion coefficient of the metal pattern is, for example, about 1.2×10 ⁻⁶ /°C. Moreover, as a metal in a metal layer, Fe-Ni-Co alloy (for example, Super Invar) can also be mentioned, for example.

From the viewpoint of adhesion and resolution, the roughness Rmax of the first surface of the metal layer is preferably 0.5 μm to 5.0 μm, more preferably 0.60 μm to 4.0 μm, and most preferably 0.75 μm to 3.0 μm. Roughness Rmax of the second surface of the metal layer may be 0.5 μm to 5.0 μm. The roughness Rmax of the first surface of the metal layer may be the same as or different from the roughness Rmax of the second surface of the metal layer.

In the present disclosure, the roughness Rmax of the object surface is measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation). First, the surface profile of the object face is obtained. As measurement/analysis software, Microscope Application of MetroPro ver8.3.2 was used. Then, use the measurement/analysis software to display the Surface Map screen, and obtain the histogram data in the Surface Map screen. The roughness Rmax of the target surface is obtained from the obtained histogram data. In addition, the roughness Rmax of the target surface corresponds to the maximum height of the roughness curve at the reference length.

In the preparatory step, the metal layer can be prepared in a state arranged on the base material. In other words, in the preparatory step, a laminate including a substrate, a metal layer having a second surface facing the substrate and a first surface opposite to the second surface can be prepared in this order. As a component of a base material, glass and a polymer are mentioned, for example. Examples of the polymer include polyimide, cycloolefin polymer, polyethylene, polypropylene, polyethylene terephthalate, cellulose triacetate, polystyrene, and polycarbonate. The substrate is preferably a glass substrate or a resin film, more preferably a resin film. Examples of resin films include polyimide films, cycloolefin polymer films, polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Ester film.

From the viewpoint of resolution of the through holes, the average thickness of the metal layer is preferably 30 μm to 500 μm, more preferably 40 μm to 400 μm, and still more preferably 50 μm to 300 μm. The average thickness of the metal layer was calculated from the arithmetic mean of the thicknesses at five locations measured in cross-sectional observation using a scanning electron microscope (SEM).

(Bonding step) In the bonding step, a photosensitive transfer material is bonded to the metal layer, and a transfer layer and a temporary support are sequentially arranged on the first surface of the metal layer. The printing material sequentially includes the above-mentioned temporary support and the above-mentioned transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the above-mentioned temporary support is 50 pieces/mm ³ or less . In addition, the preferred aspect of the photosensitive transfer material is the same as the preferred aspect of the photosensitive transfer material for deposition mask production of the present disclosure described above.

Bonding of a photosensitive transfer material and a metal layer can be implemented by a well-known method. In the bonding step, it is preferable to press-bond the photosensitive transfer material and the metal layer. For example, it is preferable to bond the photosensitive transfer material and the metal layer by laminating the photosensitive transfer material and the metal layer and applying pressure and heating using a mechanism such as a roller. In the bonding step, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of improving productivity can be used. The lamination temperature is preferably, for example, 70°C to 130°C. When the photosensitive transfer material includes a protective film, the attaching step is performed after removing the protective film.

(pressurization step) After bonding the photosensitive transfer material and the metal layer, a pressurization step may be implemented. For example, a laminate obtained by bonding a photosensitive transfer material and a metal layer can be pressed. It is preferable that the laminate to be pressed is a laminate including a metal layer, a transfer layer and a temporary support in this order. The laminate to be pressed may also be a laminate including a metal layer and a transfer layer in this order. For example, if the temporary support is peeled off after the bonding step, a laminate including a metal layer and a transfer layer in this order can be formed. In the pressurization step, the laminate obtained by bonding the photosensitive transfer material and the metal layer can be pressurized using an autoclave. For example, pressure treatment at 50° C., 0.5 MPa, and 60 minutes can be performed. By applying pressure to the laminate, the adhesiveness between the transfer layer and the metal layer can be improved, and the followability of the transfer layer to the irregularities on the surface of the metal layer can be improved. The pressurizing step is preferably carried out before the exposure step.

(exposure steps) In the exposing step, pattern exposure is performed on the transfer layer. "Exposing a pattern to a transfer layer" means forming an exposed portion and a non-exposed portion on a transfer layer by irradiating light to the transfer layer. The positional relationship between the exposed portion and the non-exposed portion can be determined according to the shape of the target photoresist pattern, for example.

It is preferable that the light for pattern-exposing the transfer layer is irradiated to the transfer layer in a direction from the transfer layer toward the metal layer. It is preferable that the light for pattern-exposing the transfer layer contains at least one wavelength selected from the group including 365 nm and 405 nm.

As a light source, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and LED(Light Emitting Diode: Light Emitting Diode) are mentioned, for example.

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

As an exposure method, a contact exposure method and a non-contact exposure method are mentioned, for example. As a contact exposure method, the method using a photomask is mentioned, for example. Examples of the non-contact exposure method include a proximity exposure method, a lens-based or mirror-based projection exposure method, and a direct exposure method using an exposure laser. In the projection exposure of the lens system or mirror system, an exposure machine with an appropriate number of lens openings (NA) can be used according to the required resolution and depth of focus. In the direct exposure method, drawing may be performed directly on the transfer layer, or reduction projection exposure may be performed on the transfer layer via a lens. The exposure step can be performed under the atmosphere, under reduced pressure, or under vacuum. The exposure step may also be performed by interposing a liquid such as water between the light source and the transfer layer.

The exposure step may be performed before or after the temporary support is peeled off, but it is preferably performed before the temporary support is peeled from the viewpoint of further exhibiting the effects of the present disclosure. When the exposure step is performed before peeling off the temporary support, the transfer layer may be exposed via the temporary support. In the exposure step using a photomask, the transfer layer may be subjected to pattern exposure with the photomask in contact with the transfer layer, or may be brought close to the transfer layer without making the photomask contact the transfer layer Next, pattern exposure is performed on the transfer layer. In order to prevent contamination of the photomask caused by contact between the photomask and the transfer layer and to avoid the impact on exposure caused by foreign matter attached to the photomask, it is better to perform pattern exposure on the transfer layer without peeling off the temporary support. When pattern-exposing the transfer layer via a temporary support, it is preferable to peel off the temporary support after the exposure step and before the development step.

(temporary support stripping step) The manufacturing method of the deposition mask disclosed in the present disclosure preferably includes a step of stripping the temporary support between the temporary support and the transfer layer. Also, it is preferable to perform the temporary support peeling step after the exposure step and before the image development step. The method for peeling the temporary support is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.

(developing step) In the development step, a development treatment is performed on the transfer layer to form a photoresist pattern. It is considered that the resolution of the photoresist pattern formed through the developing step affects the resolution of the through-hole formed through the etching step described later, and furthermore, the resolution of the through-hole affects the resolution of the pattern formed using the deposition mask.

The photoresist pattern is formed by removing the exposed portion or the non-exposed portion of the transfer layer. When the transfer layer includes a negative photosensitive resin layer, usually the non-exposed portion of the transfer layer is removed by developing, and a photoresist pattern is formed from the exposed portion of the transfer layer. When the transfer layer includes a positive photosensitive resin layer, the exposed portion of the transfer layer is usually removed by a developer, and a photoresist pattern is formed from the non-exposed portion of the transfer layer.

The development treatment is performed using, for example, a developer. As a developing solution, a well-known developing solution (for example, the developing solution described in Unexamined-Japanese-Patent No. 5-72724) is mentioned, for example. As the developing solution, an alkali aqueous developing solution containing a compound with pKa=7-13 at a concentration of 0.05 mol/L-5 mol/L is preferable. Examples of the basic compound contained in the alkaline aqueous developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, Tetraethylammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide). The developer may contain a water-soluble organic solvent. The developer may contain a surfactant. As a preferable developing solution, the developing solution described in paragraph 0194 of International Publication No. 2015/093271 can be mentioned, for example.

The temperature of the developer is preferably 20°C to 40°C.

Examples of image development methods include spin-on-dip immersion development (puddle development), shower development (shower development), shower and spin development, and immersion development. Shower development refers to a development method in which a developer is sprayed onto an object by spraying. As a preferable image development method, the image development method described in paragraph 0195 of International Publication No. 2015/093271 is mentioned, for example.

It is preferable to remove the remaining developer and residue after the developing step by a known method. As a method of removing a developing solution and residues, for example, shower processing and Air Knife (air knife) processing are mentioned. In the shower process, a liquid such as water or a cleaning agent is sprayed on an object by showering. Residue can also be removed with a brush.

(etching step) In the etching step, the metal layer not covered by the photoresist pattern is etched to form a through hole extending from the first surface of the metal layer to the second surface of the metal layer.

Etching treatment can be a known method. Examples of the etching process include wet etching and dry etching (for example, plasma etching). Examples of the etching treatment include the methods described in paragraphs 0209 to 0210 of JP-A-2017-120435 and the methods described in paragraphs 0048-0054 of JP-A-2010-152155.

The etching treatment is preferably wet etching. In wet etching, etchant is generally used. The type of etching solution can be selected from acidic or alkaline etching solution according to the etching object. Examples of the acidic etching solution include aqueous solutions containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. As an acidic etchant, for example, a mixed aqueous solution of the above-mentioned acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate can also be mentioned. An acidic component may be a combination of several acidic components. Examples of alkaline etching solutions include those containing at least one alkali component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.). aqueous solution. As an alkaline etching solution, the mixed aqueous solution of the said alkali component and a salt (for example, potassium permanganate) can also be mentioned, for example. The base component may be a combination of a plurality of base components. Among them, it is preferable that the etching solution used in the above-mentioned etching process contains ferric chloride from the viewpoint of further exhibiting the effects of the present disclosure. In addition, the solubility of the photoresist pattern in a 45° C. solution containing 40% by mass of ferric chloride is preferably 1 μm/min or less, more preferably 0.5 μm/min or less. In addition, the lower limit is 0 μm/min.

The metal layer in the deposition mask manufactured in the deposition mask manufacturing method disclosed herein has a through hole extending from the first surface to the second surface. The metal layer may have a plurality of through holes. The depth of the through hole corresponds to the thickness of the metal layer. The through-holes are usually delimited by the inner surface of the metal layer. A through hole may be defined by one or two or more planes. The surface delineating the through-hole viewed in cross-section may be a straight line or a curved line. The number, shape and arrangement of the through holes are determined according to the target pattern, for example. The through hole extending from the first surface to the second surface has an opening on the first surface and an opening on the second surface. The diameter of the opening formed on the first surface corresponds to the diameter of the through hole on the first surface described later, and the diameter of the opening formed on the second surface corresponds to the diameter of the through hole on the second surface described later. Examples of the shape of the through-hole (specifically, the opening) viewed in a plan view include a circle, an ellipse, and a rectangle. The shape of the through-hole viewed from above is preferably a quadrangle, more preferably a square or a rectangle. When the shape of the through-hole viewed from above is a polygon (for example, a quadrilateral), some or all of the plural corners of the polygon may be rounded.

The average diameter of the through-holes on the second surface of the metal layer (hereinafter, sometimes referred to as "average diameter of the through-holes D2") is smaller than the average diameter of the through-holes on the first surface of the metal layer (hereinafter, sometimes referred to as is the "average diameter D1 of the through hole".). In other words, the average diameter D1 of the through holes is larger than the average diameter D2 of the through holes. For example, if the average diameter D1 of the through-hole is larger than the average diameter D2 of the through-hole, the substance reaching the first surface of the metal layer from the vaporization source will easily enter the through-hole through the opening formed on the first surface of the metal layer. As a result, for example, productivity and pattern accuracy are improved. The ratio of the average diameter D2 of the through-holes to the average diameter D1 of the through-holes (that is, D2/D1) is preferably 0.8 or less, more preferably 0.4 or less, and still more preferably 0.3 or less. From the viewpoint of high-resolution patterns, the ratio of the average diameter D2 of the through-holes to the average diameter D1 of the through-holes (that is, D2/D1) is preferably at least 0.01, more preferably at least 0.1, and at least 0.15. for further improvement.

The average diameter of the through-holes on the second surface of the metal layer (that is, the average diameter D2 of the through-holes) is 25 μm or less. When the average diameter D2 of the through holes is 25 μm or less, it is possible to form a pattern with high resolution. From the viewpoint of high-resolution patterns, the average diameter D2 of the through-holes is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The lower limit of the average diameter D2 of the through holes is not limited. The average diameter D2 of the through holes may also be 5 μm, 1 μm or 0.1 μm.

The average diameter D1 of the through holes is not limited as long as the relationship "average diameter D2 of the through holes" < "average diameter D1 of the through holes" is satisfied. The average diameter D1 of the through holes is preferably 15 μm to 100 μm, more preferably 20 μm to 50 μm, and still more preferably 20 μm to 30 μm, from the viewpoint of high resolution of the pattern. The lower limit of the average diameter D1 of the through holes may be 8 μm or 10 μm.

In the present disclosure, the average diameter of the through-holes is calculated by the arithmetic mean of the diameters of 10 through-holes measured from images obtained using a scanning electron microscope (SEM). In the present disclosure, the diameter of the through hole is defined by the maximum value of a straight line connecting any two points on the contour line of the through hole (specifically, the opening) viewed in plan view. The average diameter D2 of the through-holes is smaller than the average diameter D1 of the through-holes. Therefore, when the first surface of the metal layer is viewed from above, it may be observed inside the outline of the opening formed on the first surface of the metal layer. The outline of the opening on the second side of . The average diameter D1 of the through holes and the average diameter D2 of the through holes can be calculated based on the above observations.

The diameter of the through holes may change continuously or discontinuously along the direction from the first surface toward the second surface as long as the relationship of "average diameter D2 of through holes" < "average diameter D1 of through holes" is satisfied. It is preferable that the diameter of the through hole gradually decreases along the direction from the first surface toward the second surface.

(removal step) In the removing step, the photoresist pattern is removed. As a removal method, the method of removing a photoresist pattern using a chemical process is mentioned, for example. The method of using a remover to remove the photoresist pattern is preferred.

Examples of the removal liquid include those containing an inorganic base component or an organic base component, and water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solvent thereof. As an inorganic base component, sodium hydroxide and potassium hydroxide are mentioned, for example. As an organic base component, a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound are mentioned, for example.

The photoresist pattern can also be removed by immersing the laminate including the photoresist pattern in a removal solution. The temperature of the removal solution is preferably 30°C to 80°C, more preferably 50°C to 80°C. The immersion time is preferably 1 minute to 30 minutes. In the dipping method, the removal solution may be stirred.

The photoresist pattern can be removed, for example, by spraying, showering, or spin-on-dipping using a remover.

(additional steps) The manufacturing method of the deposition mask disclosed in the present disclosure may further include other steps as required. When the metal layer of the deposition mask is formed on the substrate, the method for manufacturing the deposition mask of the present disclosure may include a step of removing the substrate.

Referring to FIG. 4, the manufacturing method of the deposition mask is described. Fig. 4 is a schematic cross-sectional view showing a method of manufacturing a deposition mask according to an embodiment. As shown in FIG. 4( a ), the metal layer 10 having a first surface 10F and a second surface 10R located opposite to the first surface 10F is prepared. As shown in FIG. 4( b ), a photosensitive transfer material (not shown) is bonded to the metal layer 10 to arrange the transfer layer 20 on the first surface 10F of the metal layer 10 . The average thickness of the transfer layer 20 is 50 μm or less. As shown in FIG. 4( c ), the photoresist pattern 21 is formed by performing pattern exposure on the transfer layer 20 and then performing a development treatment on the transfer layer 20 . As shown in FIG. 4( d ), the through hole 10H is formed by etching the metal layer 10 not covered by the photoresist pattern 21 . It is considered that during the etching process, isotropic etching (that is, etching in a direction perpendicular to the depth direction of the metal layer 10 in addition to etching in the depth direction of the metal layer 10) occurs to form a Through-hole 10H having a cross-sectional shape shown in FIG. 4( d ). As shown in FIG. 4( e ), the deposition mask 100 is obtained by removing the photoresist pattern 21 . The through hole 10H formed in the metal layer 10 extends from the first surface 10F of the metal layer 10 to the second surface 10R of the metal layer 10 . The through hole 10H forms an opening 10FA in the first surface 10F of the metal layer 10 , and forms an opening 10RA in the second surface 10R of the metal layer 10 .

The deposition mask manufactured by the method of manufacturing the deposition mask of the present disclosure may include components other than the metal layer as needed. As a component other than a metal layer, a frame body is mentioned, for example. The frame can enhance the deposition mask or improve the operability of the deposition mask. The frame body may be arranged around the through hole in plan view, or may be arranged on the outer periphery of the metal layer in plan view. As a component of a frame body, metal is mentioned, for example. Examples of metals include Fe—Ni alloys (for example, Invar) and Fe—Ni—Co alloys (for example, super Invar).

Referring to FIG. 1 , FIG. 2 and FIG. 3 , the structure of the deposition mask manufactured by the method of manufacturing the deposition mask disclosed herein will be described. FIG. 1 is a schematic top view showing an embodiment of a deposition mask. FIG. 2 is an enlarged schematic plan view of a through-hole of the deposition mask shown in FIG. 1 . FIG. 3 is an enlarged schematic cross-sectional view of a through-hole of the deposition mask shown in FIG. 1 . The deposition mask 100 includes a metal layer 10 having a first surface 10F, a second surface 10R opposite to the first surface 10F, and through holes 10H. The first surface of the metal layer 10 faces the viewer looking at FIGS. 1 and 2 . The first surface 10F of the metal layer 10 and the second surface 10R of the metal layer face directions opposite to each other. As shown in FIGS. 1 and 2 , the through-holes 10H are defined by a grid-like pattern formed by the metal layer 10 , and the shape of the through-holes 10H as viewed from above is quadrangular. In FIG. 2 , the reason why the contour line of the through-hole 10H is double observed is because the contour line of the opening formed on the first surface 10F of the metal layer 10 (specifically, the opening 10FA in FIG. 3 ) is observed inside the contour line. The outline of the opening (specifically, the opening 10RA in FIG. 3 ) formed on the second surface 10R of the metal layer 10 . As shown in FIG. 3 , the through hole 10H extends from the first surface 10F of the metal layer 10 to the second surface 10R of the metal layer 10 . The through hole 10H forms an opening 10FA in the first surface 10F of the metal layer 10 , and forms an opening 10RA in the second surface 10R of the metal layer 10 . The through hole 10H is defined by the inner surface of the metal layer 10 , and the inner surface of the metal layer 10 defining the through hole 10H is a curved line. The average diameter of the through-holes 10H on the second surface 10R of the metal layer 10 is smaller than the average diameter of the through-holes 10H on the first surface 10F of the metal layer 10 . The diameter of the through hole 10H gradually decreases along the direction from the first surface 10F toward the second surface 10R.

The deposition mask manufactured by the method of manufacturing a deposition mask of the present disclosure is preferably suitable for a method of manufacturing a pattern using a deposition method. In the deposition method, it is preferable to arrange the deposition mask on the object so that the second surface of the metal layer faces the object. When the second surface of the metal layer faces the object, the substance reaching the first surface of the metal layer from the vaporization source easily enters the through hole. The substance entering the through hole moves in the through hole along the direction from the first surface of the metal layer toward the second surface and adheres to the object. The substance passing through the through hole is deposited on the object to form a pattern. Examples of objects to be patterned include glass substrates and resin films. The type of deposition method, the conditions of the deposition method, and the type of deposited substance can be determined according to the target pattern, for example. As a preferable deposition method, a vacuum deposition method is mentioned, for example. As a preferred application of the deposition mask manufactured by the method of manufacturing the deposition mask disclosed herein, for example, a method of manufacturing an OLED can be mentioned. [Example]

Hereinafter, the present disclosure will be described in detail using examples. However, the present disclosure is not limited to the following examples. In the following description, unless otherwise specified, "%" means "mass %", and "part" means "mass part".

＜Manufacture of Temporary Support 1＞ A temporary support including a polyester film with a thickness of 16 μm and a particle-containing layer with a thickness of 40 nm was produced by the following procedure.

(containing particle layer forming composition 1) Particle-containing layer-forming composition 1 was obtained by mixing the components in the following formulation. After preparing the particle-containing layer-forming composition 1, it was filtered with a 6 μm filter (F20, manufactured by MAHLE Japan Ltd.), and then membrane degassed using 2×6 Radial Flow Super Phobic (manufactured by Polypore Co., Ltd.).

Acrylic polymer (AS-563A, manufactured by Daicel FineChem Ltd., solid content 27.5% by mass): 167 parts by mass ・Nonionic surfactant (NAROACTY CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content: 100% by mass): 0.7 parts by mass ・Anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass): 114.4 parts by mass Carnauba wax dispersion (Selosol 524, manufactured by CHUKYO YUSHI CO., LTD., solid content 30% by mass): 7 parts by mass Carbodiimide compound (CARBODILITE V-02-L2, manufactured by Nisshinbo Chemical Inc., diluted with water to a solid content of 10% by mass): 20.9 parts Matting agent (SNOWTEX XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle diameter 50nm): 2.8 parts by mass Water: 690.2 parts by mass

(extrusion molding) Dry the particles of polyethylene terephthalate with the citric acid chelated organic titanium complex as the polymerization catalyst described in Japanese Patent No. 5575671 until the moisture content is below 50ppm, and then put them into a uniaxial mixer with a diameter of 30mm. In the hopper of the kneading extruder, melt and extrude at 280°C. This molten body (melt) was passed through a filter (pore size: 2 μm), and extruded from a die onto a cooling roll at 25° C. to obtain an unstretched film. In addition, the extruded melt was brought into close contact with the cooling roll by electrostatic application.

(stretching and coating) The cured unstretched film was sequentially biaxially stretched by the following method to obtain a temporary support comprising a polyester film with a thickness of 16 μm and a particle-containing layer with a thickness of 40 nm.

(a) Longitudinal stretch The unstretched film was stretched in the longitudinal direction (transportation direction) by passing between two pairs of nip rolls having different peripheral speeds. In addition, the preheating temperature was set to 75° C., the stretching temperature was set to 90° C., the stretching ratio was set to 3.4 times, and the stretching speed was set to 1300%/sec.

(b) coating The particle-containing layer-forming composition 1 was coated with a bar coater on one side of the longitudinally stretched film so as to have a thickness of 40 nm after film formation.

(c) Transverse stretch The above-mentioned longitudinally stretched and coated film was transversely stretched under the following conditions using a tenter. Preheating temperature: 110°C Stretching temperature: 120°C Stretch ratio: 4.2 times Stretching speed: 50%/sec

(heat fixation and heat relaxation) The biaxially stretched film after completion|finish of longitudinal stretching and lateral stretching was heat-fixed under the following conditions. Heat Fixing Temperature: 227°C Heat fixation time: 6 seconds

After heat setting, the width of the tenter was narrowed, and thermal relaxation was performed under the following conditions. Thermal relaxation temperature: 190°C Thermal relaxation rate: 4%

(coiled) After heat setting and heat relaxation, both ends were trimmed, and the end was extruded (knurled) at a width of 10 mm, and then coiled at a tension of 40 kg/m. In addition, the width is 1.5m, and the roll length is 6300m. The obtained film roll was used as the temporary support body 1. The haze value of the temporary support body 1 was 0.2. In addition, a haze value was measured as a total light haze value using a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD., NDH2000). Also, the thermal shrinkage rate based on heating at 150°C for 30 minutes is 1.0% on the MD (Machine Direction) side, and 0.2% on the TD (Transverse Direction) side on the film surface. . Also, the film thickness of the particle-containing layer was measured from a cross-sectional TEM photograph, and it was 40 nm. Using a transmission electron microscope (TEM) model HT-7700 manufactured by Hitachi High-Technologies, the average particle diameter of the particles contained in the particle-containing layer was measured by the above method and found to be 50 nm.

＜Temporary Support 2＞ As the temporary support body 2, the following were used. Temporary support 2: polyester film, 16QS62 manufactured by TORAY INDUSTRIES, INC., thickness 16 μm

＜Manufacture of Temporary Support 3＞ In the production method of the temporary support body 1, except that the particle-containing layer-forming composition 1 is changed to the particle-containing layer-forming composition 2 shown below, it is produced in the same manner as the production method of the temporary support body 1 Take out the temporary support body 3.

(Contains particle total formation composition 2) ・Acrylic polymer (AS-563A, Daicel Miraizu Ltd., solid content: 27.5% by mass): 167 parts by mass ・Nonionic surfactant (NAROACTY CL95, Sanyo Chemical Industries, Ltd., solid content: 100% by mass): 0.7 parts by mass ・Anionic surfactant (RAPISOL A-90, NOF CORPORATION, water dilution with a solid content concentration of 1% by mass): 55.7 parts by mass ・Carnauba wax dispersion (Selosol 524, CHUKYO YUSHI CO., LTD., solid content: 30% by mass): 7 parts by mass Carbodiimide compound (CARBODILITE V-02-L2, Nisshinbo Chemical Inc., diluted with water at a solid content concentration of 10% by mass): 20.9 parts by mass Matting agent (SNOWTEX XL, Nissan Chemical Corporation, solid content: 40% by mass, average particle diameter: 50nm): 2.8 parts by mass Matting agent (AEROSIL OX50, NIPPON AEROSIL CO., LTD., solid content: 10% by mass, water dispersion, median particle size: 0.2 μm): 3.5 parts by mass Water: 743 parts by mass

<Manufacture of Temporary Support 4> The temporary support body 4 was produced similarly to the manufacturing method of the temporary support body 1 except having changed the thickness of the temporary support body into 25 micrometers.

<Manufacture of Temporary Support 5> As the temporary support body 5, the following were used. Temporary support 5: Polyethylene terephthalate film, A1517 manufactured by Toyobo Co., Ltd., thickness 16 μm

<Example 1> (Manufacture of photosensitive transfer materials) The photosensitive transfer material including the temporary support 1, buffer layer, intermediate layer, photosensitive resin layer, and protective film in sequence was manufactured by the following sequence. The transfer layer 1 has a buffer layer, an intermediate layer, and a photosensitive resin layer, and the photosensitive resin layer is a negative photosensitive resin layer.

Composition A containing the components described in the "buffer layer" column of Table 1 was prepared. After the composition A was coated on the temporary support 1 using a slit nozzle, the composition A was dried at 80° C. for 2 minutes to form a buffer layer. Table 1 shows the layer thickness of the buffer layer.

Composition B containing the components listed in the "intermediate layer" column of Table 1 was prepared. After the composition B was coated on the buffer layer using a slit nozzle, the composition B was dried at 90° C. for 2 minutes to form an intermediate layer. Table 1 shows the layer thickness of the intermediate layer.

Composition C containing the components described in the "photosensitive resin layer" column of Table 1 was prepared. After the composition C was applied on the intermediate layer using a slit nozzle, the composition C was dried at 80° C. for 2 minutes to form a photosensitive resin layer. Table 1 describes the layer thickness of the photosensitive resin layer.

Finally, a protective film (16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm) was provided on the photosensitive resin layer to obtain a photosensitive transfer material 1 .

Subsequently, a deposition mask was manufactured using the obtained photosensitive transfer material 1 by the following procedure. An Invar substrate was prepared as a metal layer having a first surface and a second surface opposite to the first surface. The first surface and the second surface face opposite directions. The roughness Rmax of the first surface of the Invar substrate was 0.80 μm. The roughness Rmax of the second surface of the Invar substrate was 0.90 μm. The average thickness of the Invar substrate was 50 μm. The protective film was peeled off from the transfer layer 1 . Using a roll laminator, the photosensitive transfer material is bonded to the steel substrate at a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed of 4 m/min (lamination speed). A transfer layer 1 (that is, a photosensitive resin layer, an intermediate layer, and a buffer layer) and a temporary support body 1 are sequentially arranged on the first surface of the . The first surface of the Invar substrate is in contact with the photosensitive resin layer.

The exposure mask is brought into close contact with the exposed surface of the transfer layer. The exposure mask has a plurality of square light shielding parts. The size of each light-shielding portion was changed in units of 5 μm within the range of length 5 μm×width 5 μm to length 100 μm×width 100 μm. The transfer layer was irradiated with light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Japan Science Engineering Co., Ltd., dominant wavelength: 365 nm). The exposure amount is adjusted so that the pattern shape of the photoresist obtained after development reproduces the pattern shape of the photomask.

After peeling the temporary support body 1 from the transfer layer 1, it developed using 28 degreeC 1.0 mass % sodium carbonate aqueous solution as a developing solution, and obtained the resist pattern. Specifically, in image development, shower processing was performed for 30 seconds to perform Air Knife (air knife) processing to remove the developing solution, and then shower processing was performed with pure water for 30 seconds to further perform air knife processing.

Using an etchant containing ferric chloride, an etching process was performed on the steel layer not covered by the photoresist pattern at 45° C. for 60 seconds to form a through hole on the steel substrate. The through hole extends from the first surface of the Invar substrate toward the second surface of the Invar substrate. The deposition mask was obtained by removing the photoresist pattern using 4% by mass sodium hydroxide solution. In the obtained deposition mask, the average diameter of the through-holes on the first surface of the Invar substrate was 28.0 μm, and the average diameter of the through-holes on the second surface of the Invar substrate was 7.0 μm.

<Examples 2 to 21 and Comparative Example 1> In the production of the photosensitive transfer material, the type of the temporary support and the structure of the transfer layer were changed according to the descriptions in Tables 1 to 5, and the photosensitive transfer material was manufactured in accordance with the procedure of Example 1. Materials and deposition masks.

<Measurement of the number of objects of foreign matter> The temporary support body was peeled from the obtained photosensitive transfer material. Observe the area of 1 ^cm2 of the peeled temporary support through the transmission observation of an optical microscope from its thickness direction, count the number of foreign objects with a diameter of 1.0 μm to 10.0 μm, and divide the obtained number by the temporary support. The thickness is used as the number of foreign objects per unit volume of the temporary support.

＜Evaluation＞ The following items were evaluated using each photosensitive transfer material or deposition mask produced in Examples and Comparative Examples.

(analytical) In the obtained deposition mask, the obtained hole pattern was observed with an optical microscope, and the smallest size among the pattern sizes analyzed by the size of the deposition mask was taken as the resolution. The smaller the minimum pattern size for resolution, the better the resolution.

(linearity) Observing the resist pattern with the smallest analytical line width among the obtained resist patterns with a scanning electron microscope (SEM), the maximum and minimum values of the line width (hereinafter referred to as "line width") were measured within a length of 100 μm. change value".). The linearity of the resist pattern was evaluated based on the variation value of the line width according to the following criteria. A: The fluctuation value of the line width is less than 0.4 μm. B: The variation value of the line width is 0.4 μm or more and less than 0.7 μm. C: The fluctuation value of the line width is 0.7 μm or more and less than 1.0 μm. D: The fluctuation value of the line width is 1.0 μm or more and less than 1.5 μm. E: The variation value of the line width is 1.5 μm or more.

(Lamination properties) After laminating the obtained photosensitive transfer material on a metal substrate with a surface roughness Rmax of 0.5 μm to 5.0 μm, the laminated laminate was observed from the side of the temporary support with an optical microscope. The number of bubbles in the area of ^25mm2 . A: Less than 10 B: More than 10 and less than 20 C: More than 20

The evaluation results are summarized in Table 4 and Table 5.

[Table 1] transfer layer 1 Transfer layer 2 Transfer layer 3 Transfer layer 4 Transfer layer 5 Transfer layer 6 The buffer layer Layer thickness (μm) 6.0 - - - 6.0 6.0 Alkali soluble resin Compound B1 39.8 - - - 39.8 39.8 polymeric compound A-DCP 5.8 - - - 5.8 5.8 8UX-015A 2.9 - - - 2.9 2.9 TO-2349 1.3 - - - 1.3 1.3 additive Prill 0.69 - - - 0.69 0.69 CBT-1 0.04 - - - 0.04 0.04 Surfactant F-552 0.05 - - - 0.05 0.05 solvent MEK 49.4 - - - 49.4 49.4 Total (parts by mass) 100.0 - - - 100.0 100.0 middle layer Layer thickness (μm) 1.0 1.0 - - 1.0 1.0 water soluble resin PVA 2.7 2.7 - - 2.7 2.7 pvp 1.3 1.3 - - 1.3 1.3 HPMC - 0.041 - - - - Surfactant F-444 0.004 0.004 - - 0.004 0.004 solvent MeOH 70 70 - - 70 70 pure water 26 26 - - 26 26 Total (parts by mass) 100.0 100.0 - - 100.0 100.0 Photosensitive resin layer Layer thickness (μm) 2.0 3.0 3.0 6.0 2.0 2.0 M/B 1.0 1.0 1.0 1.0 0.72 0.72 Adhesive Compound B1 - - - - - - Compound B2 - - - - 23.2 - Compound B3 19.9 19.9 19.9 19.9 - 23.2 Compound B4 - - - - - - Compound B5 - - - - - - polymeric compound BPE-500 5.4 5.4 5.4 5.4 - 5.0 BPE-100 - - - - 5.0 - ARONIX M-270 0.59 0.59 0.59 0.59 0.45 0.45 Photopolymerization initiator B-IMD 0.89 0.89 0.89 0.89 0.89 0.89 Sensitizer EAB-F 0.04 0.04 0.04 0.04 0.04 0.04 polymerization inhibitor phenothiophene 0.03 0.03 0.03 0.03 0.03 0.03 Phenidone 1% MEK solution 0.14 0.14 0.14 0.14 0.14 0.14 chain transfer agent Compound A 0.02 0.02 0.02 0.02 0.02 0.02 Reagent LCV 0.05 0.05 0.05 0.05 0.05 0.05 Rust inhibitor CBT-1 0.01 0.01 0.01 0.01 0.01 0.01 Surfactant F-552 0.14 0.14 0.14 0.14 0.14 0.14 solvent MMPGAc 21.51 21.51 21.51 21.51 18.70 18.70 MEK 46.52 46.52 46.52 46.52 46.52 46.52 MFG 2.23 2.23 2.23 2.23 2.23 2.23 MeOH 2.61 2.61 2.61 2.61 2.61 2.61 Total (parts by mass) 100.0 100.0 100.0 100.0 100.0 100.0 Melt viscosity of transfer layer at 25°C (Pa) 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 9.0×10 ⁵ 3.0×10 ⁷

[Table 2] Transfer layer 7 Transfer layer 8 Transfer layer 9 transfer layer 10 transfer layer 11 transfer layer 12 The buffer layer Layer thickness (μm) 6.0 6.0 6.0 6.0 6.0 6.0 Alkali soluble resin Compound B1 39.8 39.8 39.8 39.8 39.8 39.8 polymeric compound A-DCP 5.8 5.8 5.8 5.8 5.8 5.8 8UX-015A 2.9 2.9 2.9 2.9 2.9 2.9 TO-2349 1.3 1.3 1.3 1.3 1.3 1.3 additive Prill 0.69 0.69 0.69 0.69 0.69 0.69 CBT-1 0.04 0.04 0.04 0.04 0.04 0.04 Surfactant F-552 0.05 0.05 0.05 0.05 0.05 0.05 solvent MEK 49.4 49.4 49.4 49.4 49.4 49.4 Total (parts by mass) 100.0 100.0 100.0 100.0 100.0 100.0 middle layer Layer thickness (μm) 1.0 1.0 1.0 1.0 1.0 1.0 water soluble resin PVA 2.7 2.7 2.7 2.7 2.7 2.7 pvp 1.3 1.3 1.3 1.3 1.3 1.3 HPMC - - - - - - Surfactant F-444 0.004 0.004 0.004 0.004 0.004 0.004 solvent MeOH 70 70 70 70 70 70 pure water 26 26 26 26 26 26 Total (parts by mass) 100.0 100.0 100.0 100.0 100.0 100.0 Photosensitive resin layer Layer thickness (μm) 2.0 2.0 2.0 2.0 2.0 2.0 M/B 1.00 1.00 1.00 1.00 0.82 1.00 Adhesive Compound B1 - - - 19.9 - - Compound B2 - - - - 21.9 24.9 Compound B3 24.9 - - - - - Compound B4 - - 19.9 - - - Compound B5 - 19.9 - - - - polymeric compound BPE-500 4.00 5.4 5.4 5.4 - - BPE-100 - - - - 4.9 4.04 ARONIX M-270 0.45 0.59 0.59 0.59 0.54 0.45 Photopolymerization initiator B-IMD 0.89 0.89 0.89 0.89 0.89 0.89 Sensitizer EAB-F 0.04 0.04 0.04 0.04 0.04 0.04 polymerization inhibitor phenothiophene 0.03 0.03 0.03 0.03 0.03 0.03 Phenidone 1% MEK solution 0.14 0.14 0.14 0.14 0.14 0.14 chain transfer agent Compound A 0.02 0.02 0.02 0.02 0.02 0.02 Reagent LCV 0.05 0.05 0.05 0.05 0.05 0.05 Rust inhibitor CBT-1 0.01 0.01 0.01 0.01 0.01 0.01 Surfactant F-552 0.14 0.14 0.14 0.14 0.14 0.14 solvent MMPGAc 18.00 21.51 21.51 21.51 21.51 21.51 MEK 46.52 46.52 46.52 46.52 46.52 46.52 MFG 2.23 2.23 2.23 2.23 2.23 2.23 MeOH 2.61 2.61 2.61 2.61 2.61 2.61 Total (parts by mass) 100.0 100.1 100.1 100.1 101.5 103.6 Melt viscosity of transfer layer at 25°C (Pa) 2.4×10 ⁸ 6.5×10 ⁸ 2.0×10 ⁵ 4.0×10 ⁷ 0.9×10 ⁵ 0.9×10 ⁷

[table 3] transfer layer 13 transfer layer 14 transfer layer 15 transfer layer 16 transfer layer 17 transfer layer 18 The buffer layer Layer thickness (μm) 6.0 6.0 6.0 6.0 6.0 6.0 Alkali soluble resin Compound B1 39.8 39.8 39.8 39.8 39.8 39.8 polymeric compound A-DCP 5.8 5.8 5.8 5.8 5.8 5.8 8UX-015A 2.9 2.9 2.9 2.9 2.9 2.9 TO-2349 1.3 1.3 1.3 1.3 1.3 1.3 additive Prill 0.69 0.69 0.69 0.69 0.69 0.69 CBT-1 0.04 0.04 0.04 0.04 0.04 0.04 Surfactant F-552 0.05 0.05 0.05 0.05 0.05 0.05 solvent MEK 49.4 49.4 49.4 49.4 49.4 49.4 Total (parts by mass) 100.0 100.0 100.0 100.0 100.0 100.0 middle layer Layer thickness (μm) 1.0 1.0 0.5 2.0 1.0 1.0 water soluble resin PVA 2.7 2.7 2.7 2.7 3.7 0.7 pvp 1.3 1.3 1.3 1.3 0.3 3.3 HPMC - - - - - - Surfactant F-444 0.004 0.004 0.004 0.004 0.004 0.004 solvent MeOH 70 70 70 70 70 70 pure water 26 26 26 26 26 26 Total (parts by mass) 100.0 100.0 100.0 100.0 100.0 100.0 Photosensitive resin layer Layer thickness (μm) 4.8 8.0 2.0 2.0 2.0 2.0 M/B 1.00 1.00 1.0 1.0 1.0 1.0 Adhesive Compound B1 - - - - - - Compound B2 - - - - - - Compound B3 19.9 19.9 19.9 19.9 19.9 19.9 Compound B4 - - - - - - Compound B5 - - - - - - polymeric compound BPE-500 5.4 5.4 5.4 5.4 5.4 5.4 BPE-100 - - - - - - ARONIX M-270 0.59 0.59 0.59 0.59 0.59 0.59 Photopolymerization initiator B-IMD 0.89 0.89 0.89 0.89 0.89 0.89 Sensitizer EAB-F 0.04 0.04 0.04 0.04 0.04 0.04 polymerization inhibitor phenothiophene 0.03 0.03 0.03 0.03 0.03 0.03 Phenidone 1% MEK solution 0.14 0.14 0.14 0.14 0.14 0.14 chain transfer agent Compound A 0.02 0.02 0.02 0.02 0.02 0.02 Reagent LCV 0.05 0.05 0.05 0.05 0.05 0.05 Rust inhibitor CBT-1 0.01 0.01 0.01 0.01 0.01 0.01 Surfactant F-552 0.14 0.14 0.14 0.14 0.14 0.14 solvent MMPGAc 21.51 21.51 21.51 21.51 21.51 21.51 MEK 46.52 46.52 46.52 46.52 46.52 46.52 MFG 2.23 2.23 2.23 2.23 2.23 2.23 MeOH 2.61 2.61 2.61 2.61 2.61 2.61 Total (parts by mass) 100.1 100.1 100.0 100.0 100.0 100.0 Melt viscosity of transfer layer at 25°C (Pa) 3.0×10 ⁶ 4.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶

The following abbreviations shown in Tables 1 to 3 have the following meanings, respectively. "M/B": The ratio of the total mass of the polymerizable compound to the total mass of the polymer "Compound B1": benzyl methacrylate (BzMA) / methacrylic acid (MAA) / acrylic acid (AA) = 78/14.5/7.5 (mass ratio), Mw: 12,500, acid value: 187mgKOH/g, glass transition temperature : 75°C, solid content: 30% by mass "A-DCP": Tricyclodecane dimethanol diacrylate, NK Ester A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd. "8UX-015A": UV hardening urethane acrylate, 8UX-015A manufactured by Taisei Fine Chemical Co., Ltd. "TO-2349": ARONIX TO-2349 manufactured by TOAGOSEI CO., LTD. "Prill": powder of prill, manufactured by FUJIFILM Wako Pure Chemical Corporation "CBT-1": carboxybenzotriazole, CBT-1 manufactured by JOHOKU CHEMICAL CO., LTD. "F-552": Fluorine-based surfactant, MEGAFACE F-552 manufactured by DIC Corporation, solid content: 30% by mass (methyl ethyl ketone solution) "MEK": methyl ethyl ketone "PVA": Polyvinyl alcohol, PVA205 manufactured by KURARAY CO., LTD. "PVP": Polyvinylpyrrolidone, K-30 manufactured by NIPPON SHOKUBAI CO.,LTD. "HPMC": hydroxypropyl cellulose, METOLOSE 60SH-03 manufactured by Shin-Etsu Chemical Co., Ltd. "F-444": MEGAFACE F-444 manufactured by DIC Corporation, fluorine-based surfactant "MeOH": Methanol "Compound B2": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)/methacrylic acid-glycidyl methacrylate (GMA-MAA)=47.7/1.3/19/ 32, Mw: 20,000, acid value: 124mgKOH/g, glass transition temperature: 76°C, solid content: 30% by mass Moreover, "methacrylic acid-glycidyl methacrylate" shows the structural unit which made the epoxy group of glycidyl methacrylate and the carboxyl group derived from the structural unit of methacrylic acid react. "Compound B3": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA) = 52/19/29, Mw: 50,000, acid value: 148mgKOH/g, glass transition temperature: 131°C , solid content: 30% by mass "Compound B4": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)=45/19/36, Mw: 47,000, acid value: 183mgKOH/g, glass transition temperature: 122°C , solid content: 30% by mass "Compound B5": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA) = 57/11/32, Mw: 49,000, acid value: 163 mgKOH/g, glass transition temperature: 140°C , solid content: 30% by mass "BPE-500": (2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd. "ARONIX M-270": Polypropylene glycol diacrylate, ARONIX M-270 manufactured by TOAGOSEI CO.,LTD. "B-IMD": (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, B-CIM manufactured by KUROGANE KASEI Co., Ltd. "EAB-F": 4,4'-bis(diethylamino)benzophenone obtained from Sanyo Trading Co., Ltd. "Phenothiophene": Manufactured by FUJIFILM Wako Pure Chemical Corporation "Phenidone 1% MEK solution": Methyl ethyl ketone solution containing 1% by mass of phenidone "Compound A": N-phenylaminoformylmethyl-N-carboxymethylaniline, manufactured by FUJIFILM Wako Pure Chemical Corporation "LCV": Colorless crystal violet, a pigment that develops color by free radicals, manufactured by Tokyo Chemical Industry Co., Ltd. "CBT-1": carboxybenzotriazole, CBT-1 manufactured by JOHOKU CHEMICAL CO., LTD. "MMPGAc": 1-methoxy-2-propyl acetate "MFG": 1-methoxy-2-propanol

[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Types of transfer layer transfer layer 1 transfer layer 1 transfer layer 1 transfer layer 1 Transfer layer 2 Transfer layer 3 Transfer layer 4 Transfer layer 5 Transfer layer 6 Transfer layer 7 Transfer layer 8 Layer thickness of transfer layer 9μm 9μm 9μm 9μm 4μm 3μm 6μm 9μm 9μm 9μm 9μm Melt viscosity of transfer layer at 25°C (Pa) 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 9.0×10 ⁵ 3.0×10 ⁷ 2.4×10 ⁸ 6.5×10 ⁸ temporary support type Temporary Support 1 Temporary support body 2 Temporary support body 3 Temporary support body 4 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 thickness 16μm 16μm 16μm 25μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm Haze 0.2 0.5 0.5 0.9 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Number of foreign objects (pieces/mm ³ ) 0 1 1 3 0 0 0 0 0 0 0 L ^* value 0.6 0.8 1.6 1.0 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Evaluation results analytical 10μm 10μm 15μm 20μm 5μm 5μm 15μm 10μm 10μm 15μm 20μm Linearity A A C B A B B A A A B Lamination A A A A C C B A B B C

[table 5] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Comparative example 1 Types of transfer layer Transfer layer 9 transfer layer 10 transfer layer 11 transfer layer 12 transfer layer 13 transfer layer 14 transfer layer 15 transfer layer 16 transfer layer 17 transfer layer 18 transfer layer 1 Layer thickness of transfer layer 9μm 9μm 9μm 9μm 11.8μm 15μm 8.5μm 10μm 9μm 9μm 9μm Melt viscosity of transfer layer at 25°C (Pa) 2.0×10 ⁵ 4.0×10 ⁷ 0.9×10 ⁵ 0.9×10 ⁷ 3.0×10 ⁶ 4.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ 2.0×10 ⁶ temporary support type Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary Support 1 Temporary support body 5 thickness 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm Haze 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Number of foreign objects (pieces/mm ³ ) 0 0 0 0 0 0 0 0 0 0 105 L ^* value 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.8 Evaluation results analytical 10μm 15μm 15μm 10μm 15μm 20μm 10μm 15μm 25μm 25μm 35μm Linearity A B B A A B A B C C D. Lamination A A A A A A B A A A A

Table 4 and Table 5 show that the resolution of the deposition mask manufactured by the method of manufacturing the deposition mask of the embodiment is better than that of the deposition mask manufactured by the method of manufacturing the deposition mask of the comparative example.

10: metal layer 10F: the first side of the metal layer 10FA: the opening formed on the first surface of the metal layer 10H: through hole 10R: The second side of the metal layer 10RA: Openings formed on the second side of the metal layer 20: transfer layer 21: Photoresist pattern 100: Deposition mask

FIG. 1 is a schematic top view showing an embodiment of a deposition mask manufactured by the method for manufacturing a deposition mask of the present disclosure. FIG. 2 is an enlarged schematic plan view of a through-hole of the deposition mask shown in FIG. 1 . FIG. 3 is an enlarged schematic cross-sectional view of a through-hole of the deposition mask shown in FIG. 1 . Fig. 4 is a schematic cross-sectional view showing a method of manufacturing a deposition mask according to an embodiment.

10: metal layer

10F: the first side of the metal layer

10H: through hole

100: Deposition mask

Claims (12)

A photosensitive transfer material for producing a deposition mask, which sequentially has a temporary support and a transfer layer having at least a photosensitive resin layer, foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support The number of pieces is 50 pieces/mm ³ or less. The photosensitive transfer material for deposition mask production according to claim 1, wherein the L ^* value of the surface of the temporary support opposite to the transfer layer side measured by SCE is 1.5 or less. The photosensitive transfer material for deposition mask production as described in Claim 1, wherein The thickness of the said temporary support body is 16 micrometers or less. The photosensitive transfer material for producing a deposition mask according to Claim 1, wherein the melt viscosity of the transfer layer at 25°C is 1.0×10 ⁵ Pa·s˜1.0×10 ⁸ Pa·s. The photosensitive transfer material for deposition mask production as described in Claim 1, wherein The thickness of the said photosensitive resin layer is 4.8 micrometers or less. The photosensitive transfer material for deposition mask production according to any one of claims 1 to 5, wherein The transfer layer has an intermediate layer and the photosensitive resin layer in this order from the temporary support side. The photosensitive transfer material for producing a deposition mask as described in Claim 6, wherein The aforementioned intermediate layer contains a water-soluble resin. The photosensitive transfer material for deposition mask production as described in Claim 7, wherein The aforementioned water-soluble resin contains polyvinyl alcohol. The photosensitive transfer material for deposition mask production as described in Claim 7, wherein The aforementioned water-soluble resin contains polyvinylpyrrolidone. The photosensitive transfer material for deposition mask production as described in Claim 7, wherein The aforementioned water-soluble resin contains a hydroxyalkylcellulose compound. A method for manufacturing a deposition mask, which sequentially includes the following steps: preparing a metal layer having a first surface and a second surface at a position opposite to the first surface; attaching a photosensitive transfer material to the metal layer Then, a transfer layer and a temporary support are sequentially disposed on the first surface of the metal layer, the photosensitive transfer material sequentially includes the temporary support and the transfer layer having at least a photosensitive resin layer and the The number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 pieces/mm ³ or less; pattern exposure is performed on the transfer layer; development treatment is performed on the transfer layer to form a photoresist pattern ; Etching the metal layer not covered by the photoresist pattern to form a through hole extending from the first surface of the metal layer to the second surface of the metal layer; and removing the photoresist pattern. The method for manufacturing a deposition mask as claimed in claim 11, wherein Roughness Rmax of the first surface of the metal layer is 0.5 μm to 5.0 μm.