TW202311856A - Transfer film for forming vapor deposition mask and manufacturing method of vapor deposition mask - Google Patents

Abstract

The present invention provides a transfer film for forming a deposition mask capable of forming a photoresist pattern with few defects and applications thereof. A transfer film for forming a deposition mask and applications thereof are provided, wherein the transfer film for forming a deposition mask sequentially includes: a pseudo-support; and a photosensitive layer comprising a polymer having an acid value of 30 mg KOH/g or more. An intermediate layer before the pseudo-support and the photosensitive layer can be further provided. The average thickness of the pseudo-support is 50 [mu]m or less.

Description

Transfer film for deposition mask formation and manufacturing method of deposition mask

The disclosure relates to a transfer film for forming a deposition mask and a method for manufacturing the deposition mask.

For example, a deposition mask is used as a master for a pattern formed by deposition. 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. For example, the through holes of the deposition mask are formed by photolithography (for example, refer to the following patent document 1 and the following patent document 2).

[Patent Document 1] Japanese Patent Laid-Open No. 2020-002470 [Patent Document 2] Japanese Patent Laid-Open No. 2019-214788

From the viewpoint of thickness uniformity of a photoresist layer, a method of manufacturing a deposition mask using a transfer film is being studied. For example, in the method of manufacturing a deposition mask using a transfer film, the deposition mask is manufactured through the steps of laminating, exposing, developing, and photoresist stripping of the base material used as the raw material of the deposition mask and the transfer film. In the method of depositing a mask, the transfer film forms a photoresist pattern, which protects a part of the substrate during etching.

However, in the manufacturing method of the deposition mask using a transfer film, the adhesiveness of a transfer film (especially a photosensitive layer) to a base material may be low. For example, when the adhesiveness between the base material and the transfer film is low, there is a possibility that the photoresist pattern may be chipped.

An object of an embodiment of the present disclosure is to provide a transfer film for deposition mask formation capable of forming a photoresist pattern with few defects. An object of another embodiment of the present disclosure is to provide a method of manufacturing a deposition mask using a deposition mask forming a transfer film capable of forming a resist pattern with few defects.

This disclosure includes the following aspects. <1> A transfer film for forming a deposition mask, which includes in this order: a dummy support; and a photosensitive layer containing a polymer having an acid value of 30 mgKOH/g or more. <2> The transfer film for deposition mask formation according to <1>, wherein the polymer has an acid value of 270 mgKOH/g or less. <3> The transfer film for deposition mask formation according to <1> or <2>, wherein the acid value of the photosensitive layer is 15 mg/KOH or more. <4> The transfer film for deposition mask formation as described in <1> or <2> in which the acid value of the said photosensitive layer is 135 mg/KOH or less. <5> The transfer film for deposition mask formation according to any one of <1> to <4>, which includes an intermediate layer between the dummy support and the photosensitive layer. <6> The transfer film for forming a deposition mask according to any one of <1> to <5>, wherein the average thickness of the dummy support is 50 μm or less. <7> The transfer film for deposition mask formation according to any one of <1> to <6>, wherein the haze value of the dummy support is 5% or less. <8> The transfer film for deposition mask formation according to any one of <1> to <7>, wherein the polymer has a weight average molecular weight of 10,000 or more. <9> The transfer film for deposition mask formation according to any one of <1> to <8>, wherein the polymer includes a structural unit having an aromatic ring. <10> The transfer film for deposition mask formation according to any one of <1> to <9>, wherein the photosensitive layer contains a polymerizable compound having a bisphenol A structure. <11> The transfer film for forming a deposition mask according to any one of <1> to <10>, wherein the photosensitive layer contains a compound selected from compounds having an oxime ester structure, α-hydroxyalkylbenzene At least one polymerization initiator in the group of compounds having a ketone structure, compounds having an acyl phosphine oxide structure, and compounds having a triaryl imidazole structure. <12> The transfer film for deposition mask formation according to any one of <1> to <11>, wherein the photosensitive layer contains a compound selected from dialkylaminobenzophenone compounds, pyrazoline Compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, azole compounds, benzothiazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds , at least one sensitizer selected from the group consisting of stilbene compounds, sankoujing compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. <13> The transfer film for deposition mask formation according to any one of <1> to <12>, wherein the photosensitive layer contains a polymerization inhibitor. <14> The transfer film for deposition mask formation according to any one of <1> to <13>, wherein the storage elastic coefficient of the photosensitive layer at 90° C. is 1.0×10 ⁶ Pa or less. <15> The transfer film for forming a deposition mask according to any one of <1> to <14>, wherein the complex viscosity of the photosensitive layer at 30° C. is 1.0×10 ⁴ Pa or more. <16> A method for manufacturing a deposition mask, comprising the following steps: preparing the transfer film for forming a deposition mask according to any one of <1> to <15>; preparing a transfer film having a first surface and the above-mentioned first surface The base material on the second surface opposite to the base material; the base material and the transfer film are bonded together, and the photosensitive layer and dummy layer included in the transfer film are sequentially arranged on the first surface of the base material. support body; pattern exposure of the above photosensitive layer disposed on the above substrate; after pattern exposure of the above photosensitive layer, developing treatment of the above photosensitive layer to form a photoresist pattern; after forming the above photoresist pattern, Etching the substrate to form a through hole extending from the first surface of the substrate to the second surface of the substrate; and removing the photoresist pattern after forming the through hole. <17> The method for producing a deposition mask according to <16>, wherein the surface roughness Ra of the first surface is 1.0 μm or less. <18> The method for producing a deposition mask according to any one of <16> or <17>, wherein the base material includes a metal layer having an average thickness of 30 μm or less. <19> The method of manufacturing a deposition mask according to <18>, wherein the metal layer contains iron. <20> The method for producing a deposition mask according to any one of <16> to <19>, wherein the diameter of the through hole on the second surface of the substrate is 35 μm or less. [Invention effect]

According to an embodiment of the present disclosure, a transfer film for forming a deposition mask capable of forming a photoresist pattern with few defects can be provided. According to another embodiment of the present disclosure, there is provided a method of manufacturing a deposition mask using a deposition mask capable of forming a resist pattern with few defects.

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 this disclosure, a group (atomic group) that does not describe "substituted" and "unsubstituted" includes a group (atomic group) that does not have a substituent and a group (atomic group) that has a substituent. 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, it 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. Liquid components other than the solvent are contained in the solid component.

In this disclosure, ordinal numbers (for example, "1st" and "2nd") are terms used to distinguish elements, and do not limit the number of elements and the quality of elements.

＜Transfer film for deposition mask formation＞ Hereinafter, the transfer film for deposition mask formation of this indication (it may only be called a "transfer film" hereafter.) is demonstrated. In one embodiment, the transfer film for deposition mask formation includes a dummy support and a photosensitive layer containing a polymer having an acid value of 30 mgKOH/g or more in this order. According to the embodiment described above, a transfer film for deposition mask formation capable of forming a photoresist pattern with few defects can be provided. The reason why a photoresist pattern with few defects can be formed is estimated as follows. If the photosensitive layer is arranged on the substrate by laminating the substrate and the transfer film, the polymer with an acid value of 30 mgKOH/g or more contained in the photosensitive layer and the components of the substrate (such as , metals and metal oxides) interact with each other, thereby improving the adhesion between the photosensitive layer and the substrate. For example, the acidic functional group (ie, acid group) contained in the polymer which has an acid value of 30 mgKOH/g or more contributes to the improvement of adhesiveness. If the adhesion is improved, defects (for example, chipping and peeling) of the photosensitive layer forming the photoresist pattern or the cured product of the photosensitive layer can be prevented or reduced during the manufacturing process of the deposition mask. As a result, a resist pattern with few defects can be formed.

[pseudo-support] The transfer film includes a pseudo-support. The pseudo support system is a support that supports the transfer layer and can be peeled off from the transfer layer. The transfer layer refers to a layer other than the dummy support in the transfer film, which is arranged on the object by bonding the transfer film and the object when the transfer film is used. The structure of the transfer layer may be a single-layer structure or a multi-layer structure. For example, the photosensitive layer is a transfer layer. For example, the intermediate layer mentioned later is also a transfer layer.

The structure of the pseudo-support can be a single-layer structure or a multi-layer structure.

The pseudo-support is preferably a film, more preferably a resin film. As the pseudo-support, a film that is flexible and does not undergo significant deformation, shrinkage or elongation under pressure or under pressure and heat is preferred. Examples of resin films include polyethylene terephthalate films (for example, biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene film, polyimide film and polycarbonate film. The pseudo-support is preferably polyethylene terephthalate film. It is preferable that there is no deformation such as wrinkles and scratches in the film used as a pseudo-support.

From the viewpoint of enabling pattern exposure through the dummy support, it is preferable that the dummy support has high transparency. The transmittance at 365nm is preferably 60% or more, more preferably 70% or more.

From the viewpoint of the transparency of the pseudo-support and the linearity of the pattern formed by exposure through the pseudo-support, it is preferable to reduce the haze value of the pseudo-support. The haze value of the pseudo-support is preferably 5% or less, more preferably 2% or less, still more preferably 0.5% or less, and particularly preferably 0.1% or less. The lower limit of the haze value of the pseudo-support is not limited. The lower limit of the haze value of the pseudo-support may be 0.01% or 0.001%. The haze value is measured using a haze meter (eg, haze meter NDH400 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

From the viewpoint of the pattern formation property at the time of pattern exposure through the dummy support and the transparency of the dummy support, it is preferable that the number of coarse particles, foreign matter and defects contained in the dummy support is small. The number of particles, foreign substances, and defects with a diameter of 1 μm or more in the pseudo-support is preferably 50 pieces/10mm2 ^or less, more preferably 10 pieces/10mm2 ^or less, more preferably 3 pieces/10mm2 ^or less, and 0 pieces /10mm ² is especially good.

The average thickness of the dummy support is preferably 200 μm or less, more preferably 100 μm or less, and still more preferably 50 μm or less, from the viewpoint of resolution in pattern exposure through the dummy support. The average thickness of the pseudo-support is preferably 5 μm or more, more preferably 10 μm or more. The average thickness of the pseudo-support was calculated by the arithmetic mean of the thicknesses at 5 places measured in cross-sectional observation using a scanning electron microscope (SEM).

As a preferable pseudo support, for example, a biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 μm Stretched polyethylene terephthalate film.

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

From an operational point of view, the pseudo-support may comprise a particle-containing layer. A pseudo-support may include a substrate layer and a particle-containing layer. As a base material layer, the resin film mentioned above is mentioned, for example. The particle-containing layer is preferably disposed as the outermost layer on one or both sides of the pseudo-support having a multilayer structure. The diameter of the particles contained in the particle-containing layer is preferably 0.05 μm to 0.8 μm. The average thickness of the particle-containing layer is preferably 0.05 μm to 1.0 μm. The average thickness of the particle-containing layer was calculated from the arithmetic mean of the thicknesses at five locations measured in cross-sectional observation using a scanning electron microscope (SEM).

[Photosensitive layer] The transfer film includes a photosensitive layer. The photosensitive layer may be a negative photosensitive layer. The photosensitive layer may also be a positive photosensitive layer.

(polymer) The photosensitive layer contains a polymer. Specifically, the photosensitive layer contains a polymer having an acid value of 30 mgKOH/g or more. If the acid value of the polymer is 30 mgKOH/g or more, in the method of manufacturing a deposition mask using a transfer film, the adhesion between the substrate used as a raw material for the deposition mask and the transfer film is improved, and as a result, it is possible to A photoresist pattern with few defects is formed. The acid value of the polymer is preferably at least 60 mgKOH/g, more preferably at least 120 mgKOH/g, and still more preferably at least 150 mgKOH/g. In addition, the acid value of the polymer is preferably at least 170 mgKOH/g, more preferably at least 200 mgKOH/g, and still more preferably at least 220 mgKOH/g. From the viewpoint of preventing or reducing the peeling of the photosensitive layer or the cured product of the photosensitive layer that forms the photoresist pattern in the developing process, the acid value of the polymer is preferably below 270mgKOH/g, more preferably below 250mgKOH/g Preferably, 220 mgKOH/g or less is more preferred. In addition, the acid value of the polymer is preferably at most 200 mgKOH/g, more preferably at most 190 mgKOH/g. The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value was calculated from the average content of acid groups in the compound. The acid value of a polymer is adjusted by the kind of the structural unit which comprises a polymer, and content of the structural unit containing an acid group, for example.

The weight average molecular weight of the polymer is preferably at least 10,000, more preferably at least 20,000. If the weight average molecular weight of the polymer is 10,000 or more, peeling of the photosensitive layer or the cured product of the photosensitive layer for forming the photoresist pattern during development can be prevented or reduced. From the viewpoint of resolution and developability, the weight average molecular weight of the polymer is preferably at most 500,000, more preferably at most 100,000, and still more preferably at most 80,000. The degree of dispersion of the polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0. Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography. Dispersion is the ratio of weight average molecular weight to number average molecular weight (ie, weight average molecular weight/number average molecular weight).

The polymer preferably includes a structural unit having an aromatic ring. If the polymer contains structural units having aromatic rings, the hydrophobicity of the above structural units can prevent or reduce peeling of the photosensitive layer or the cured product of the photosensitive layer forming the photoresist pattern during development. The aromatic ring may be a single ring or a condensed ring. Aromatic rings can contain one or more than two types of atoms. The number of carbon atoms in the aromatic ring is preferably 6-18, more preferably 6-12. As an aromatic ring, a benzene ring and a naphthalene ring are mentioned, for example. The aromatic ring is preferably a benzene ring.

As a structural unit which has an aromatic ring, the structural unit which has an aromatic hydrocarbon group is mentioned, for example. As an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example. The content rate of the structural unit having an aromatic hydrocarbon group in the polymer is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and 45% by mass relative to the total mass of the polymer A. More than 50% by mass is the best, and more than 50% by mass is the best. The content of the structural unit having an aromatic hydrocarbon group in the polymer is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of the polymer. Moreover, when a photosensitive layer contains several types of polymers, the content rate of the structural unit which has an aromatic hydrocarbon group was calculated|required as a mass average value.

As a monomer forming a structural unit having an aromatic hydrocarbon group, for example, a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butylene, etc.) oxystyrene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer). A monomer having an aralkyl group or styrene is preferred. When the monomer forming the structural unit having an aromatic hydrocarbon group is styrene, the content rate of the structural unit derived from styrene is preferably 20 mass % to 50 mass % relative to the total mass of the polymer, and 25 mass % to 45 mass % is more preferable, 30 mass % - 40 mass % is still more preferable, and 30 mass % - 35 mass % is especially preferable.

As an aralkyl group, a substituted or unsubstituted phenylalkyl group is mentioned, for example. Substituted or unsubstituted benzyl is preferred.

Examples of monomers having a substituted or unsubstituted benzyl group include (meth)acrylates having a substituted or unsubstituted benzyl group (for example, benzyl (meth)acrylate, (meth)acrylate ) chlorobenzyl acrylate) and vinyl monomers with substituted or unsubstituted benzyl groups (for example, vinylbenzyl chloride and vinylbenzyl alcohol). Benzyl (meth)acrylate is preferred. When the monomer forming the structural unit having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content rate of the structural unit derived from benzyl (meth)acrylate is 50% by mass to 95% by mass relative to the total mass of the polymer. The mass % is more preferable, 60 mass % - 90 mass % is more preferable, 70 mass % - 90 mass % is still more preferable, and 75 mass % - 90 mass % is especially preferable.

Examples of the monomer having a phenylalkyl group other than a substituted or unsubstituted benzyl group include phenylethyl (meth)acrylate.

The polymer containing the structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one monomer selected from the group consisting of the first monomer and the second monomer. As for each monomer, one kind or two or more kinds of monomers may be used.

It is preferable to obtain the polymer which does not contain the structural unit which has an aromatic hydrocarbon group by polymerizing a 1st monomer, and it is more preferable to obtain it by polymerizing a 1st monomer and a 2nd monomer. As for each monomer, one kind or two or more kinds of monomers may be used.

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, and maleic acid. half ester. (Meth)acrylic acid is preferred.

The content of the constituent unit derived from the first monomer in the polymer is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 15% by mass to 30 mass % is more preferable.

It is preferable that the content rate of the structural unit derived from a 1st monomer is 10 mass % - 50 mass % with respect to the gross mass of a polymer. From the viewpoint of exhibiting good developability and controlling edge melting properties, the content of the structural unit derived from the first monomer is preferably 10% by mass or more. Moreover, the content rate of the structural unit derived from a 1st monomer is 15 mass % or more with respect to the total mass of a polymer, More preferably, it is 20 mass % or more. From the viewpoint of the high resolution of the resist pattern, the bead shape of the resist pattern, and the chemical resistance of the resist pattern, the content of the constituent unit derived from the first monomer is preferably 50% by mass or less. In addition, the content of the constituent unit derived from the first monomer is preferably at most 35% by mass, more preferably at most 30% by mass, and still more preferably at most 27% by mass, based on the total mass of the polymer.

The second monomer system is a monomer that is non-acidic and has at least one ethylenically unsaturated group. As a 2nd monomer, a (meth)acrylate compound is mentioned, for example. Examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) n-butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth) ) cyclohexyl acrylate and 2-ethylhexyl (meth)acrylate. Examples of the second monomer include ester compounds of vinyl alcohol. As an ester compound of vinyl alcohol, vinyl acetate is mentioned, for example. As a 2nd monomer, (meth)acrylonitrile is mentioned, for example. Methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferable, and methyl (meth)acrylate is more preferable.

The content of the constituent unit derived from the second monomer in the polymer 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 mass % is more preferable.

From the viewpoint of suppressing deterioration of the line width and resolution when the focal position shifts during exposure, the polymer contains at least One type of constituent unit is preferable. As a preferable polymer, the copolymer containing the structural unit derived from methacrylic acid, the structural unit derived from benzyl methacrylate, and the structural unit derived from styrene is mentioned, for example. Preferable polymers include, for example, constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, constituent units derived from benzyl methacrylate, and constituent units derived from styrene. of copolymers.

The polymer contains 25% to 40% by mass of structural units having aromatic hydrocarbon groups, 20% to 35% by mass of structural units derived from the first monomer, and 30% to 45% by mass of structural units derived from the second monomer. The polymer in mass % is preferable.

The polymer is preferably a polymer containing 70% by mass to 90% by mass of structural units having an aromatic hydrocarbon group and 10% by mass to 25% by mass of structural units derived from the first monomer.

The polymer may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain. A polymer may have both a branched structure and an alicyclic structure in a side chain. The use of a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain can introduce a branched structure or an alicyclic structure into the side chain of the polymer. The alicyclic structure may be a monocyclic structure or a polycyclic structure.

Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, ( Tertiary butyl methacrylate, isopentyl (meth)acrylate, tertiary pentyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and (meth)acrylate base) tertiary octyl acrylate. Isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate are preferable, and isopropyl methacrylate or tertiary butyl methacrylate are more preferable.

Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. As a specific example of the monomer containing the group which has an alicyclic structure in a side chain, the (meth)acrylate which has the alicyclic hydrocarbon group of 5-20 carbon numbers (carbon number) is mentioned. Specific examples of monomers containing a group having an alicyclic structure in the side chain include (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl Alkyl esters, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1 (meth)acrylate -Adamantyl ester, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, (meth)acrylic acid- 3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate 2- Methyl-2-adamantyl ester, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro(meth)acrylate -4,7-methanoindene-5-yl ester, octahydro-4,7-methanoindene-1-yl methyl (meth)acrylate, 1-menthol (meth)acrylate ester, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7-(meth)acrylate ,7-Trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenzyl (meth)acrylate, 2,2,5-Trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate.

Among the (meth)acrylates mentioned above, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid -1-adamantyl ester, 2-adamantyl (meth)acrylate, fenzyl (meth)acrylate, 1-menthol (meth)acrylate or tricyclodecanyl (meth)acrylate Alkane is preferably cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or ( Tricyclodecane meth)acrylate is more preferred.

The photosensitive layer may contain one kind or two or more kinds of polymers. The content of the polymer having an acid value of 30 mgKOH/g or more is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more, based on the total mass of the photosensitive layer. The content rate of the polymer which has an acid value of 30 mgKOH/g or more may be less than 100 mass % with respect to the gross mass of a photosensitive layer. The upper limit of the content rate of the polymer which has an acid value of 30 mgKOH/g or more may be 80 mass %, 70 mass %, or 60 mass %. It is preferable that the photosensitive layer contains two kinds of polymers having an aromatic hydrocarbon group. The photosensitive layer preferably contains a polymer having an aromatic hydrocarbon group and a polymer not having an aromatic hydrocarbon group. In the latter case, the content ratio of the polymer A having an aromatic hydrocarbon group is preferably at least 50% by mass, more preferably at least 70% by mass, and still more preferably at least 80% by mass, based on the total mass of the polymer A. , more than 90% by mass is especially good.

Polymers are synthesized by adding free radical polymerization initiators (e.g., benzoyl peroxide and azoisobutyl Nitrile) and heating and stirring the resulting mixture is preferably carried out. It is also possible to synthesize|combine, dropping a part of the mixture of some raw materials to a reaction liquid. After the reaction, the concentration can be adjusted by adding a solvent. Examples of synthesis means include solution polymerization, block polymerization, suspension polymerization, and emulsion polymerization.

The glass transition temperature (Tg) of the polymer is preferably not less than 30°C and not more than 135°C. The use of a polymer having a Tg of 135° C. or lower can suppress deterioration of line width and resolution when the focal position shifts during exposure. From the above viewpoints, the Tg of the polymer is preferably 130°C or lower, more preferably 120°C or lower, and still more preferably 110°C or lower. Use of a polymer having a Tg of 30° C. or higher can improve edge melting resistance. From the above viewpoints, the Tg of the polymer is preferably 40°C or higher, more preferably 50°C or higher, still more preferably 60°C or higher, and particularly preferably 70°C or higher.

The photosensitive layer may contain polymers other than polymers having an acid value of 30 mgKOH/g or more, that is, other polymers. Examples of other polymers include acrylic resins, styrene-acrylic acid copolymers (however, limited to copolymers with a styrene content of 40% by mass or less), polyurethane, polyvinyl alcohol, polyvinyl formaldehyde, polyamide , polyester, epoxy resin, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, polysiloxane, polyethyleneimine, polyallylamine and polyalkylene glycol .

(polymeric compound) It is preferable that the photosensitive layer (preferably a negative photosensitive layer) contains a compound having a polymeric group (that is, a polymeric compound). The "polymerizable compound" refers to a compound different from the above-mentioned polymer that is polymerized by the action of a polymerization initiator.

As a polymeric group, the group which has an ethylenically unsaturated group is mentioned, for example. As a group which has an ethylenically unsaturated group, a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group are mentioned, for example. As a polymeric group, a cationic polymeric group is mentioned, for example. As a cationic polymeric group, an epoxy group and an oxetanyl group are mentioned, for example. A group having an ethylenically unsaturated group is preferable, and an acryl group or a methacryl group is more preferable.

It is preferable that a polymeric compound has a bisphenol structure from a viewpoint of reducing image development residue. 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 from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). Bisphenol A structure is preferred. As a polymeric compound which has a bisphenol structure, the ethylenically unsaturated compound B1 which has a bisphenol structure mentioned later is mentioned, for example.

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (that is, an ethylenically unsaturated compound) is preferable from the viewpoint of better photosensitivity of the photosensitive layer, and a compound having two or more ethylenically unsaturated groups is preferable. Compounds with permanent unsaturated groups (ie, polyfunctional ethylenically unsaturated compounds) are more preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group is preferable. From the standpoint of better resolving properties and exfoliation properties, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and still more preferably 2 or less. good.

From the standpoint of a better balance between photosensitivity, resolving power, and peelability of the photosensitive layer, it is preferable that the photosensitive layer contains a compound having 2 or 3 ethylenically unsaturated groups, including a compound having 2 ethylenically unsaturated groups. Compounds based on (ie, bifunctional ethylenically unsaturated compounds) are more preferred. From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and still more preferably 55% by mass or more. good. The upper limit may be 100% by mass. That is, all polymerizable compounds may be bifunctional ethylenically unsaturated compounds.

It is preferable that the photosensitive layer contains the compound (Hereinafter, it may be called "the ethylenically unsaturated compound B1.") which has an aromatic ring and two 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 photosensitive layer, from the viewpoint of better resolution, the 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, more preferably 50% by mass or more. Preferably, 55% by mass or more is more preferred, and 60% by mass or more is particularly preferred. From the viewpoint of releasability, the ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less. Preferably, 85% by mass or less is particularly preferred.

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. Aromatic heterocyclic rings and condensed rings thereof. An aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a substituent. The ethylenically unsaturated compound B1 may have one or 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 photosensitive 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. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the content described in the 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.).

The ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis) from the standpoint of line width change over time, development temperature line width change, and sensitivity.

[chemical formula 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.

The photosensitive layer may contain one kind or two or more kinds of ethylenically unsaturated compound B1. From the viewpoint of better resolution, the content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting resistance, it is preferably 70% by mass or less, and more preferably 60% by mass or less.

The photosensitive layer may contain ethylenically unsaturated compounds other than 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 urethane di(meth)acrylates 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.).

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 modified substances. "(Three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates The concept of "(three/four) (meth)acrylates" includes the concept of three (meth)acrylates and four (meth)acrylates. In one aspect, the photosensitive layer preferably includes the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and preferably includes the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. Unsaturated compounds are more preferred. Regarding the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compound, (total mass of the ethylenically unsaturated compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compound)=1: 1-5:1 is preferable, 1.2:1-4:1 is more preferable, and 1.5:1-3:1 is still more preferable. Also, in one aspect, it is preferable that the photosensitive 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 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 of the content of the ethylenically unsaturated compound in the photosensitive layer to the content of the polymer (preferably an alkali-soluble resin) is preferably 1.0 or less, more preferably 0.9 or less. Preferably, 0.5 to 0.9 is still more preferable.

It is preferable that the ethylenically unsaturated compound in a photosensitive layer contains a (meth)acrylic compound, and it is more preferable that it contains a (meth)acrylate compound from a curability and a resolution viewpoint. From the viewpoints of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive layer includes (meth)acrylic compound, and the content of acrylic compound is relative to the above-mentioned (meth)acrylic acid compound contained in the photosensitive layer. ) The total mass of the acrylic compound is more preferably 60% by mass or less.

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

The photosensitive layer may contain one kind or two or more kinds of polymerizable compounds. The content of the polymerizable compound in the photosensitive layer is preferably 10% by mass to 70% by mass relative to the total mass of the photosensitive layer, more preferably 20% by mass to 60% by mass, further preferably 20% by mass to 50% by mass. better.

-polymerization initiator- It is preferable that a photosensitive layer (preferably a negative photosensitive layer) contains a polymerization initiator. The kind of the polymerization initiator can be selected according to the form of the polymerization reaction, and examples thereof include thermal polymerization initiators and photopolymerization initiators. Moreover, a radical polymerization initiator and a cationic polymerization initiator are mentioned as a polymerization initiator.

It is preferable that a photosensitive layer (preferably a negative photosensitive layer) contains a photoinitiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound 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 photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, A photoradical polymerization initiator is preferable.

Examples of photoradical polymerization initiators include compounds having an α-aminoalkylphenone structure, compounds having an N-phenylglycine structure, compounds having an oxime ester structure, compounds having an α-hydroxyalkyl Compounds with benzophenone structure, compounds with acyl phosphine oxide structure and compounds with triaryl imidazole structure. As a preferable photoradical polymerization initiator, for example, a compound having an oxime ester structure, a compound having an α-hydroxyalkylphenone structure, a compound having an acyl phosphine oxide structure, and a compound having a triaryl imidazole structure compound.

From the viewpoints of photosensitivity, visibility of exposed parts and non-exposed parts, and resolution, the photosensitive layer (preferably a negative photosensitive layer) contains 2,4,5-triaryl imidazole dimer And at least one of the group of derivatives thereof is preferably used as a photoradical polymerization initiator. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)- 4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

As the photoradical polymerization initiator, for example, those described in paragraphs 0031 to 0042 of JP-A-2011-95716 and those described in 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 names, 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.).

As a commercially available photoradical polymerization initiator, for example, 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-acetyloxime) (trade name, IRGACURE OXE-02, manufactured by BASF Corporation), IRGACURE OXE-03 (manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methano phenyl)methyl]-1-[4-(4-portolinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-( 4-methylthiophenyl)-2-portolinylpropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy- 2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino- 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 - Ketone (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-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan K.K. manufacturing), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenyl imidazole 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.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG -305, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carba Azol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) and 3-cyclohexyl-1-(6- (2-(Benzyloxyimino)octyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

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 300nm or more, preferably 300nm-450nm, 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 paragraph 0114 to 0133 of JP-A-2014-85643 can be used. Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-three wells, 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-three wells, 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 photosensitive layer may contain one kind or two or more kinds of polymerization initiators. The content of the polymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more relative to the total mass of the photosensitive layer. good. 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 photosensitive layer.

-pigment- 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, it is preferable that the photosensitive layer contains a pigment, and the maximum absorption wavelength in the wavelength range of 400nm to 780nm during color development is included. More than 450nm, the pigment whose maximum absorption wavelength is changed by acid, alkali or free radicals (also referred to as "pigment N") is more preferable. When the photosensitive layer contains the dye N, although the detailed mechanism is unclear, the adhesion with adjacent layers (for example, a pseudo-support and an intermediate layer) is improved, resulting in better resolution.

In this disclosure, "the maximum absorption wavelength of the pigment is changed by acid, alkali or free radicals" may refer to the state in which the pigment in the color development state is decolorized by acid, alkali or free radicals, or the pigment in the 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 an acid, an alkali, or a free radical in the photosensitive layer by exposure, and these acts to change the state of color development or decolorization, or the state in the photosensitive layer ( For example, pH) is a pigment whose color development or decolorization state changes due to changes in acid, alkali or free radicals. 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 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, it is preferable that the photosensitive layer contains a dye whose maximum absorption wavelength is changed by radicals as the dye N and the photoradical polymerization initiator. good.

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 coloring 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 exemplified by adding photoradical polymerization to the photosensitive layer. Initiators, photocationic polymerization initiators (photoacid generators) or photobase generators and radicals generated by photoradical polymerization initiators, photocationic polymerization initiators, or photobase generators after exposure, A state of color development due to acid or alkali.

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

The maximum absorption wavelength of pigment N was measured in the range of 400nm to 780nm by using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in the atmospheric environment. It 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 colorless compounds, diarylmethane-based dyes, Kuchiguchi-based dyes, Kuchiyamaguchi-based dyes, iminonaphthoquinone-based dyes, and azomethine-based dyes. and anthraquinone 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 dyes. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal Rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzorubin (benzopurpurine) 4B, α-naphthyl red, nile blue (nile blue) 2B, nile blue A, methyl violet, malachite green, parafuchsin, victoria pure blue )-Naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical 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 (Hodogaya Chemical Co., Ltd. Manufactured), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, auretamine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino -4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone , 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylene Amino-5-pyrazolone.

Examples of the dye N include colorless compounds. Examples of colorless compounds include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green Lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent 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-anilinofluorescent Luminous yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl -7-stibamidofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino )-6-methoxy-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluorescent yellow precursor, 3-(N, N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-(N,N-di Ethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N, N-dibutylamino)-6-methyl-7-stibamidofluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilinyl fluorescent yellow precursor, 3-pyrrolidinyl- 6-Methyl-7-anilinofluorescent yellow precursor, 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, 3-(4-di Ethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethyl Aminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1 (3H), 9'-[9H]koukousing-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. 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.

The photosensitive layer may contain one kind or two or more kinds of pigments. 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, 0.1% by mass to 10% by mass, relative to the total mass of the photosensitive layer. 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 pattern visibility after development, and the resolution, the content of the dye N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive layer, and 0.1% by mass % to 10 mass % is more preferable, 0.1 mass % to 5 mass % is still more preferable, and 0.1 mass % to 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 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, manufactured by BASF Corporation) was added to each of the obtained solutions, and 365 nm light was irradiated to generate radicals to bring all the pigments into a colored 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 the photosensitive layer 3g in methyl ethyl ketone instead of a dye, the absorbance of the solution which color-developed all the dyes was measured by the method similar to the above. Based on the calibration curve, the content of the pigment contained in the photosensitive layer was calculated from the absorbance of the obtained solution containing the photosensitive 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 layer contains a thermally crosslinkable compound. In addition, the heat-crosslinkable compound which has an ethylenically unsaturated group mentioned later is not handled as an ethylenically unsaturated 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. Blocked isocyanate compounds react with hydroxyl and carboxyl groups, so for example, when alkali-soluble resins and/or ethylenically unsaturated compounds have at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film will decrease, which will make the photosensitive The function of the film formed by hardening the hardened layer tends to be enhanced when used as a protective film. 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 in 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 formula 2]

The photosensitive layer may contain one type or two or more types of thermally crosslinkable compounds. When the photosensitive 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, based on the total mass of the photosensitive layer.

-Other ingredients- The photosensitive layer may contain other components. Examples of other components include polymerization inhibitors, surfactants, sensitizers, and various additives. The photosensitive layer may contain one kind or two or more kinds of other components.

It is preferable that a photosensitive layer contains a polymerization inhibitor. When the photosensitive layer contains a polymerization inhibitor, it can suppress that the line width of a photoresist pattern fluctuates with the lapse of time from the end of an exposure process to the start of a next process. As a polymerization inhibitor, a radical polymerization inhibitor is mentioned, for example. Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenanthamide, or 4-methoxyphenol is preferred. Examples of other radical polymerization inhibitors include naphthylamine, copper (I) chloride, N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, and the like. In order not to impair the sensitivity of the photosensitive layer, it is preferable to use N-nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor.

The photosensitive layer may contain one type or two or more types of radical polymerization inhibitors. When the photosensitive layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor relative to the total mass of the photosensitive layer is preferably 0.001% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, 0.02 mass % - 2.0 mass % are more preferable. Also, the content of the radical polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass relative to the total mass of the polymerizable compound, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.01% by mass to 1.0% by mass. good.

The photosensitive layer may contain a surfactant. 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. Moreover, as a surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable.

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 Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Specific examples include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (the above are manufactured by BASF Corporation), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (above, manufactured by BASF Corporation), Solsperse (trade name) 20000 (above, manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (above, manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (Trade names) D-1105, D-6112, D-6112-W, D-6315 (the above are manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (the above are Nissin Chemical Co., Ltd.), etc.

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, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, 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 (the above are manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (the above are OMNOVA Solutions Inc. Ftergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by Neos Company Limited), U-120E (Uni-chem Co., Ltd.), etc.

Also, as the fluorine-based surfactant, an acrylic compound having a molecular structure containing a functional group containing a fluorine atom is preferably used, and when heat is applied, the functional group containing a fluorine atom is cut off, 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.

Furthermore, 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 fluorine-based surfactant, for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms can also be used. However, from the viewpoint of improving environmental suitability, it is preferable to use perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) as an alternative to the fluorine-based surfactant.

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 EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (manufactured by DIC Corporation). , 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 (the above are Dow Corning Todray Co., L .manufacturing) 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, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP- 341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc. above), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK333, BYK331, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (the above are manufactured by BYK Chemie), etc.

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

It is preferable that the photosensitive layer contains a sensitizer. The kind of sensitizer is not limited, and known sensitizers, dyes and pigments can be used. As preferred sensitizers, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridine compounds, Pyridone compounds, benzothiazole compounds, benzothiazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, three well compounds, thiophene compounds, naphthalene Diformimide compounds, triarylamine compounds and aminoacridine compounds.

The photosensitive layer may contain one kind or two or more kinds of sensitizers. When the photosensitive 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 hardening speed by balancing the polymerization speed and chain transfer, relative to the photosensitive The total mass of the sexual layer is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass.

The photosensitive layer may contain known additives as needed. Examples of additives include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and solvents. The photosensitive layer may contain one kind or two or more kinds of additives.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)amino Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl ) Aminomethylene-1,2,3-benzotriazole, etc.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N - Di-2-ethylhexyl)aminoethylenylcarboxybenzotriazole and the like. As carboxybenzotriazoles, commercial items such as CBT-1 (JOHOKU CHEMICAL CO., LTD., brand name) can be used, for example.

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 mass % to 3 mass % with respect to the total mass of the photosensitive 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 layer. On the other hand, it is preferable to make the said content into 3 mass % or less from a viewpoint of maintaining sensitivity and suppressing decolorization of a dye.

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

In addition, the photosensitive layer may further contain metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or Well-known additives, such as an inorganic precipitation preventive agent.

About the additive contained in a photosensitive layer, it describes in the 0165 paragraph - 0184 paragraph of Unexamined-Japanese-Patent No. 2014-85643, The content of this publication is incorporated in this specification.

The photosensitive 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, since halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, it is preferable to set the following contents.

The content of impurities in the photosensitive layer is preferably at most 80 ppm on a mass basis, more preferably at most 10 ppm, and still more preferably at most 2 ppm. 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, selection of a material with a small content of impurities as a raw material of the composition, prevention of impurities from being mixed in the photosensitive layer, and removal by washing are mentioned. 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 spectrometry, and ion chromatography.

Benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and It is preferable that the content of compounds such as hexane is small. As content of these compounds with respect to the total mass of a photosensitive layer, 100 ppm or less is preferable on a mass basis, More preferably, it is 20 ppm or less, More preferably, it is 4 ppm or less. The lower limit may be 10 ppb or more with respect to the total mass of the photosensitive layer on a mass basis, and 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 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 photosensitive layer may contain a residual monomer corresponding to each structural 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 content of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, relative to the total mass of the photosensitive layer. More preferably, it is 100 mass ppm or less. 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 synthesizing an alkali-soluble resin by making glycidyl acrylate and a carboxylic acid side chain react, 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.

The photosensitive layer may be a colored layer containing a pigment. What is necessary is just to select a pigment suitably according to desired hue, and can select from a black pigment, a 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. The particle size 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 with an electron microscope and a circle having the same area as the area of the pigment particle is considered. The number average particle diameter is calculated for any 100 particles. The above-mentioned particle size is obtained, and the average value obtained by averaging 100 obtained particle sizes is obtained.

As the pigments other than the black pigment, the white pigments described in paragraph 0015 and paragraph 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.

The surface of titania may be treated with silica, alumina, titania, zirconia, organic matter, or two or more treatments. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, delustering properties, and the like are improved. From the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of alumina treatment and zirconia treatment is preferred as the surface treatment on the surface of titanium oxide, and alumina treatment and zirconia treatment are preferred. Dealing with both is excellent.

When the photosensitive layer is a colored layer, it is also preferable that the photosensitive layer further contains color pigments other than the black pigment and the white pigment from the viewpoint of transferability. 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 layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass relative to the total mass of the photosensitive layer, more preferably more than 3% by mass and not more than 35% by mass, more than 5% by mass and 35 mass % or less is more preferable, and 10 mass % or more and 35 mass % or less are especially preferable.

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

In the manufacturing method of the photosensitive layer containing a black pigment, it is preferable to introduce a black pigment (preferably carbon black) into the photosensitive composition mentioned later in the form of a pigment dispersion liquid. 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).

The acid value of the photosensitive layer is preferably at least 15 mg/KOH, more preferably at least 40 mgKOH/g. When the acid value of a photosensitive layer is 15 mg/KOH or more, the adhesiveness of the base material used as the raw material of a deposition mask, and a transfer film will improve. The acid value of the photosensitive layer is preferably at most 200 mg/KOH, more preferably at most 150 mgKOH/g, and still more preferably at most 135 mg/KOH. If the acid value of the photosensitive layer is 200 mg/KOH or less, peeling of the photosensitive layer or the cured product of the photosensitive layer forming the photoresist pattern during the development process can be prevented or reduced. The acid value of the photosensitive layer was calculated from the average content of acid groups in the photosensitive layer.

The storage elastic coefficient of the photosensitive layer at 90°C is preferably at most 1.0×10 ⁷ Pa, more preferably at most 1.0×10 ⁶ Pa, and still more preferably at most 1.0×10 ⁵ Pa. When the storage modulus of the photosensitive layer at 90° C. is 1.0×10 ⁷ Pa or less, the adhesiveness between the base material used as a raw material of the deposition mask and the transfer film will improve. The storage elastic coefficient of the photosensitive layer at 90°C is preferably at least 1.0×10 ² Pa, more preferably at least 1.0×10 ³ Pa, and still more preferably at least 1.0×10 ⁴ Pa. When the storage modulus of elasticity of the photosensitive layer at 90° C. is 1.0×10 ² Pa or more, patternability will improve. The storage modulus of the photosensitive layer is adjusted by, for example, the composition of the photosensitive layer. The storage elastic coefficient of the photosensitive layer is adjusted by, 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.

In this disclosure, the storage modulus of elasticity uses 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) at the following measured under the conditions. (1) Temperature: 20℃～125℃ (2) Heating rate: 5°C/min (3) Frequency: 1Hz (4) Strain: 0.5%

The complex viscosity of the photosensitive layer at 30°C is preferably at least 1.0×10 ³ Pa, more preferably at least 1.0×10 ⁴ Pa, and still more preferably at least 1.0×10 ⁵ Pa. If the complex viscosity of the photosensitive layer at 30°C is 1.0×10 ³ Pa or more, peeling of the photosensitive layer or the cured product of the photosensitive layer forming the photoresist pattern during development can be prevented or reduced. The complex viscosity of the photosensitive layer at 30°C is preferably at most 1.0×10 ⁹ Pa, more preferably at most 1.0×10 ⁸ Pa, and still more preferably at most 1.0×10 ⁷ Pa. When the complex viscosity of the photosensitive layer at 30° C. is 1.0×10 ⁹ Pa or less, the adhesiveness between the base material used as the raw material of the deposition mask and the transfer film will improve.

In this disclosure, the complex viscosity uses 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. (1) Temperature: 20℃～125℃ (2) Heating rate: 5°C/min (3) Frequency: 1Hz (4) Strain: 0.5%

From the viewpoint of developability and resolution, the average thickness of the photosensitive layer is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 5 μm or less. The average thickness of the photosensitive layer is preferably at least 0.5 μm, more preferably at least 1 μm. The average thickness of the photosensitive layer was calculated by the arithmetic mean of the thickness of 5 places measured by the cross-sectional observation using the scanning electron microscope (SEM).

When the transfer layer has a multilayer structure, the ratio of the average thickness of the photosensitive layer to the average thickness of the transfer layer is preferably 10% to 50%, and 15% to 50%. 35% is more preferable, and 20% to 30% is still more preferable.

In addition, from the viewpoint of adhesiveness, the transmittance of light having a wavelength of 365 nm of the photosensitive layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

The method for producing the photosensitive layer is not limited as long as the target photosensitive layer can be obtained. For example, the photosensitive layer is prepared by preparing a photosensitive composition including an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a solvent, and coating the photosensitive composition on an object such as a pseudo-support and controlling the photosensitive composition. The coating film of the composition is dried and formed. Moreover, the photosensitive layer can also be formed by apply|coating and drying the photosensitive composition on the protective film mentioned later.

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

Examples of solvents contained in the photosensitive composition include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, Lactone solvents and mixed solvents containing two or more of these.

It is preferable that the photosensitive composition contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. 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 composition may contain one kind or two or more kinds of solvents. The content of the solvent when applying the photosensitive 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 solids in the photosensitive composition.

The preparation method of the photosensitive 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 composition. method. It is preferable to filter the photosensitive composition with a filter having a pore diameter of 0.2 μm to 30 μm before forming the photosensitive layer.

The coating method of the photosensitive 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.

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. In addition, in this specification, "drying" means removing at least a part of the solvent contained in a composition. As a drying method, natural drying, heat drying, and reduced-pressure drying are mentioned, for example. The above methods can be applied individually or in combination. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Moreover, as its upper limit, it is preferable that it is 130 degreeC or less, and it is more preferable that it is 120 degreeC or less. Drying can also be performed by changing the temperature continuously. The drying time is preferably at least 20 seconds, more preferably at least 40 seconds, and still more preferably at least 60 seconds. Also, the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

[middle layer] It is preferable that the transfer film includes an intermediate layer. The intermediate layer can suppress air bubbles from being mixed between the transfer layer and the object during bonding of the transfer film and the object, thereby improving the adhesion between the transfer layer and the object. The intermediate layer can also improve the followability of the transfer layer to objects with rough surfaces. It is preferable that an intermediate layer is arrange|positioned between a dummy support body and a photosensitive layer. That is, it is preferable that the transfer film includes a dummy support, an intermediate layer, and a photosensitive layer in this order.

The structure of the middle layer may be a single-layer structure or a multi-layer structure. As an intermediate layer, a thermoplastic resin layer and a water-soluble resin layer are mentioned, for example. When the intermediate layer includes both a thermoplastic resin layer and a water-soluble resin layer, it is preferable that the transfer film sequentially includes a dummy support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive layer. Furthermore, as the intermediate layer, for example, an oxygen barrier layer having an oxygen barrier function described in JP-A-5-72724 as a "separation layer" can also be mentioned. When 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 productivity is improved.

(thermoplastic resin layer) The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin. 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.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesiveness with an adjacent layer. The acrylic resin means having at least one kind selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylate, and constituent units derived from (meth)acrylamide. The resin that constitutes the unit. As an acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide relative to the total mass of the acrylic resin is More than 50% by mass is preferable. Among them, the total content of the constituent units derived from (meth)acrylic acid and the constituent units derived from (meth)acrylate is preferably 30% by mass to 100% by mass, and 50% by mass to 100% by mass is more preferable.

The alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo 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 of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins for use. For example, among the polymers described in paragraph 0025 of JP-A-2011-95716, an alkali-soluble resin that is a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more, JP-A-2010-237589 Among the polymers described in paragraphs 0033 to 0052 of the publication, of the carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more and the alkali-soluble resins described in paragraphs 0053 to 0068 of JP-A-2016-224162 Carboxyl-containing acrylic resin with a medium acid value of 60 mgKOH/g or more.

The copolymerization 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 acrylic resin. 30 mass % is more preferable.

As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesiveness with an adjacent layer.

Alkali-soluble resins may have reactive groups. As the reactive group, as long as it is a group capable of polymerizing, for example, a group capable of addition polymerization, polycondensation or polyaddition, ethylenically unsaturated groups; polycondensable groups such as hydroxyl groups and carboxyl groups; epoxy groups , (blocked) isocyanate groups and other polyaddition reactive 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 still more preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one type or two or more types of alkali-soluble resins. From the viewpoint of developability and adhesiveness to the adjacent layer, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, based on the total mass of the thermoplastic resin layer. Preferably, 40 mass % - 80 mass % is more preferable, 50 mass % - 70 mass % is especially preferable.

The thermoplastic resin 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 (also referred to as "pigment B"). good. The preferred aspect of the dye B is the same as the preferred aspect of the dye N except for the points described later.

From the viewpoint of visibility and resolution of exposed and non-exposed areas, dye B is preferably a dye whose maximum absorption wavelength is changed by acid or free radicals, and a dye whose maximum absorption wavelength is changed by acid for better. From the viewpoint of the visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer contains both a dye whose maximum absorption wavelength of the dye B is changed by an acid and a compound that generates an acid by light as described later. Whichever is better.

The thermoplastic resin layer may contain one kind or two or more kinds of dye B. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, and 0.2% by mass relative to the total mass of the thermoplastic resin layer. -5 mass % is more preferable, and 0.25 mass %-3.0 mass % is especially preferable. The content of the dye B means the content of the dye when all the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content 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 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, manufactured by BASF Corporation) was added to each of the obtained solutions, and 365 nm light was irradiated to generate radicals to bring all the pigments into a colored 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 for dissolving 0.1 g of the thermoplastic resin layer 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 thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer.

The thermoplastic resin layer may contain a compound (also simply referred to as "compound C") that generates acid, base, or radical by light. Compound C is preferably a compound that generates acid, base or free radicals upon exposure to active rays such as ultraviolet rays and visible rays. As the compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used. Among them, photoacid generators are preferred.

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

As the photoacid generator, it is preferable to include at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoints of sensitivity and resolution. From a viewpoint, it is more preferable to contain an oxime sulfonate compound. Moreover, as a photoacid generator, the photoacid generator which has the following structures is also preferable.

[chemical formula 3]

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

The thermoplastic resin layer may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, and examples include 2-nitrobenzylcyclohexylcarbamate, triphenylcarbinol, O-carbamoylhydroxyl Amide, O-aminoformyl oxime, {[(2,6-dinitrobenzyl)oxy]carbonyl}cyclohexylamine, bis{[(2-nitrobenzyl)oxy]carbonyl}hexyl Alkane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-portolinylethane, (4-porterolylbenzoyl)-1- Benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaaminecobalt(III) tris(triphenylmethylborate), 2-benzyl- 2-Dimethylamino-1-(4-pornolinylphenyl)butanone, 2,6-Dimethyl-3,5-diacetyl-4-(2-nitrophenyl) -1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

The thermoplastic resin layer may contain one compound C or two or more. From the viewpoint of the visibility and resolution of the exposed portion and the non-exposed portion, 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 thermoplastic resin layer. better.

It is preferable that the thermoplastic resin layer contains a plasticizer from the viewpoint of resolution, adhesiveness with an adjacent layer, and developability.

The plasticizer preferably has a molecular weight (weight average molecular weight (Mw) when it is an oligomer or a polymer) smaller than that of the alkali-soluble resin. It is preferable that the molecular weight (weight average molecular weight (Mw)) of a plasticizer is 200-2,000.

The plasticizer is not particularly limited as long as it is compatible with the alkali-soluble resin and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene group in the molecule. The diol compound is more preferable. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethoxyl structure or a polypropoxyl structure.

Moreover, it is preferable that a plasticizer contains a (meth)acrylate compound from a viewpoint of analytical property and storage stability. It is more preferable that the alkali-soluble resin is an acrylic resin and that the plasticizer contains a (meth)acrylate compound from the viewpoint of compatibility, resolution, and adhesiveness with adjacent layers. As a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound described as an ethylenically unsaturated compound contained in the said photosensitive layer is mentioned.

When the thermoplastic resin layer and the photosensitive layer are laminated in direct contact with each other in the transfer film, it is preferable that both the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound. This is because, when the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, the diffusion of components between the layers can be suppressed, and storage stability can be improved.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure from the viewpoint of adhesion to the adjacent layer. .

In addition, from the viewpoint of resolution, adhesion to adjacent layers, and developability, as a (meth)acrylate compound used as a plasticizer, there are two or more (meth)acrylic compounds in one molecule. Acyl polyfunctional (meth)acrylate compounds are preferred.

Moreover, as a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound or urethane (meth)acrylate compound which has an acidic group is also preferable.

The thermoplastic resin layer may contain one kind or two or more kinds of plasticizers. From the standpoint of resolution, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, and 10% by mass to 60% by mass relative to the total mass of the thermoplastic resin layer. % is more preferred, and 20% by mass to 50% by mass is still more preferred.

From the viewpoint of thickness uniformity, it is preferable that the thermoplastic resin layer contains a surfactant. Examples of the surfactant include those that may be included in the above-mentioned photosensitive layer, and the same is true for preferred aspects. The thermoplastic resin layer may contain one type or two or more types 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 thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. It does not specifically limit as a sensitizer, The sensitizer which may be contained in the said photosensitive layer is mentioned. The thermoplastic resin layer may contain one kind or two or more kinds of sensitizers. 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 the visibility of the exposed part and the non-exposed part, it is 0.01% by mass to 5% by mass relative to the total mass of the thermoplastic resin layer. The range of 0.05% by mass to 1% by mass is more preferable.

The thermoplastic resin layer may contain known additives as needed in addition to the above components. Moreover, about a thermoplastic resin layer, it describes in paragraph 0189 - 0193 of Unexamined-Japanese-Patent No. 2014-85643, and the content described in this publication is incorporated in this specification.

The average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesiveness with adjacent layers. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. The average thickness of the thermoplastic resin layer was calculated from the arithmetic mean of the thicknesses at five locations measured in cross-sectional observation using a scanning electron microscope (SEM).

The production method of the thermoplastic resin layer is not limited as long as the target thermoplastic resin layer can be obtained. As a method for producing a thermoplastic resin layer, for example, by preparing a thermoplastic resin composition containing the above-mentioned components and a solvent, coating the thermoplastic composition on an object such as a dummy support, and drying the coated film of the thermoplastic resin composition And the method of formation. In order to adjust the viscosity of the thermoplastic resin composition to facilitate the formation of the thermoplastic resin layer, it is preferable that the thermoplastic resin composition contains a solvent.

The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above-mentioned components contained in the thermoplastic resin layer. As a solvent contained in a thermoplastic resin composition, the solvent which can be contained in the said photosensitive composition is mentioned, and a preferable aspect is also the same. The thermoplastic resin composition may contain one kind or two or more kinds of solvents. The content of the solvent when coating the thermoplastic 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 thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the preparation method of the above-mentioned photosensitive composition and the formation method of the photosensitive layer. For example, a solution obtained by dissolving the components contained in the thermoplastic resin layer in the above-mentioned solvent is prepared in advance, and after the thermoplastic resin composition is prepared by mixing the obtained solution at a predetermined ratio, the obtained thermoplastic resin composition The thermoplastic resin layer is formed by coating on the surface of the dummy support and drying the coating film of the thermoplastic resin composition. Moreover, after forming a photosensitive layer and a water-soluble resin layer on the protective film mentioned later, you may form a thermoplastic resin layer on a water-soluble resin layer.

(water-soluble resin layer) The water-soluble resin layer preferably contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyvinyl ether-based resins, Amide resins and their copolymers and other resins. From the viewpoint of suppressing mixing of components between multiple layers, the water-soluble resin contained in the water-soluble resin layer is compatible with the polymer contained in the photosensitive layer and the thermoplastic resin (such as alkali) contained in the thermoplastic resin layer. Soluble resins) are all different resins are preferred.

From the viewpoint of oxygen barrier properties and suppression of mixing of components when applying multiple layers and when storing after coating, it is preferable that the water-soluble resin layer contains polyvinyl alcohol, including polyvinyl alcohol and polyvinylpyrrolidone. whichever is better.

The water-soluble resin layer may contain one kind or two or more kinds of water-soluble resins.

The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but from the viewpoint of oxygen barrier properties and the mixing of components when applying multiple layers and when storing after coating, relative to the content of the water-soluble resin layer The total mass is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

Moreover, the water-soluble resin layer may contain additives, such as a surfactant, as needed.

The average thickness of the water-soluble resin layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. This is because, if the thickness of the water-soluble resin layer is within the above-mentioned range, the mixing of components when applying multiple layers and when storing after coating can be suppressed without reducing the oxygen barrier property, and the water-soluble resin layer can be suppressed during development. Layer removal time increases. The average thickness of the water-soluble resin layer was calculated from the arithmetic mean of the thicknesses at five locations measured in cross-sectional observation using a scanning electron microscope (SEM).

The method for producing the water-soluble resin layer is not limited as long as the target water-soluble resin layer can be obtained. The water-soluble resin layer is prepared, for example, by preparing a water-soluble resin layer-forming composition containing a water-soluble resin and optional additives, applying it to a thermoplastic resin layer or a photosensitive layer, and coating the water-soluble resin layer-forming composition. formed by drying. In order to adjust the viscosity of the water-soluble resin layer-forming composition to facilitate the formation of the water-soluble resin layer, it is preferable that the water-soluble resin layer-forming composition contains a solvent.

As the solvent contained in the composition for forming a water-soluble resin layer, at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or a mixed solvent of water and a water-miscible organic solvent is more preferable. good. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred.

[other layers] The transfer layer may further include other layers. As another layer, a refractive index adjustment 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, it describes in paragraph 0194 - 0196 of Unexamined-Japanese-Patent No. 2014-85643 about another layer. The contents of these publications are incorporated into this specification.

From the viewpoint of irregularity followability, the total mass of polymerizable compounds (preferably ethylenically unsaturated compounds) relative to the polymer (preferably alkali-soluble resin) in the transfer layer (preferably photosensitive layer) The ratio of the total mass is preferably 0.4 or more, more preferably 0.6 or more, and still more preferably 0.8 or more. The ratio of the total mass of the polymerizable compound (preferably an ethylenically unsaturated compound) to the total mass of the polymer (preferably an alkali-soluble resin) in the transfer layer (preferably a photosensitive layer) is 1.6 or less. Preferably, 1.4 or less is more preferred, and 1.2 or less is still more preferred.

From the analytical viewpoint, the average thickness of the transfer layer is preferably 50 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. From the viewpoint of transferability, the average thickness of the transfer layer is preferably at least 0.1 μm, more preferably at least 0.5 μm, and still more preferably at least 1.0 μm. The average thickness of the transfer layer was calculated from the arithmetic mean of the thicknesses at five locations measured in cross-sectional observation using a scanning electron microscope (SEM).

[protective film] It is preferable that the transfer film includes a protective film. For example, it is preferable that the transfer film sequentially includes a dummy support, a transfer layer, and a 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 average thickness of the protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, still more preferably from 5 μm to 40 μm, and most preferably from 15 μm to 30 μm. The average thickness of the protective film was calculated by the arithmetic mean of the thicknesses at 5 places measured by cross-sectional observation using a scanning electron microscope (SEM).

From the standpoint of better resolution, the surface of the protective film facing the transfer layer (hereinafter, also simply referred to as "the surface of the protective film") has an arithmetic average roughness Ra of 0.3 μm or less, preferably 0.1 μm or less More preferably, it is more preferably 0.05 μm or less. When the Ra value of the surface of the protective film is within the above-mentioned range, the uniformity of the thickness of the transfer layer and the formed photoresist pattern improves. The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.

The Ra value of the surface of the protective film was measured by the following method. The surface profile of the optical film was obtained by measuring the surface of 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. The arithmetic mean roughness was calculated from the obtained histogram data, and the Ra value of the surface of the protective film was obtained.

The protective film is introduced into the transfer film by bonding the protective film and the transfer layer together, for example. Bonding of a protective film and a transfer layer is implemented using a well-known laminator, for example. As a laminator, a vacuum laminator and an automatic cutting laminator are mentioned, for example. It is preferable that the laminator is equipped with any heatable roller such as a rubber roller and is capable of pressurization and heating.

<Manufacturing method of deposition mask> Hereinafter, the manufacturing method of the deposition mask of the present disclosure will be described. In one embodiment, a method for manufacturing a deposition mask includes the following steps. (1) Prepare the transfer film for deposition mask formation of this disclosure (it may be called "the 1st preparation process" hereafter.). (1) Prepare the base material which has the 1st surface and the 2nd surface opposite to the 1st surface (Hereinafter, it may be called "the 1st preparation process."). (3) Bonding the base material and the transfer film, and sequentially disposing the photosensitive layer and the dummy support included in the transfer film on the first surface of the base material (hereinafter, sometimes referred to as "bonding step") ".). (4) Pattern exposure is performed on the photosensitive layer arrange|positioned on the base material (Hereinafter, it may be called "exposure process."). (5) After performing pattern exposure on the photosensitive layer, developing treatment is performed on the photosensitive layer to form a photoresist pattern (hereinafter, it may be referred to as a "development step."). (6) After the photoresist pattern is formed, the substrate is etched to form through holes extending from the first surface of the substrate to the second surface of the substrate (hereinafter, sometimes referred to as "etching step"). (7) After forming the through hole, remove the photoresist pattern (hereinafter, sometimes referred to as “removal step”).

[1st preparation step] In the first preparation step, the transfer film for deposition mask formation according to the present disclosure is prepared. The aspect of depositing the transfer film for mask formation is as already mentioned.

[2nd preparation step] In the second preparation step, a substrate having a first surface and a second surface opposite to the first surface is prepared. The second preparatory step may be performed before the first preparatory step. The second preparatory step may be carried out after the first preparatory step. The second preparatory step may be carried out simultaneously with the first preparatory step.

The structure of the substrate can be a single-layer structure or a multi-layer structure.

Preferably, the substrate includes a metal layer. The substrate can be a metal layer. 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. The metal layer preferably contains iron (Fe). A part or all of the metal layer may be an alloy. Examples of alloys include Ni—Co alloys, Fe—Ni alloys, and Fe—Ni—Co alloys. Examples of Fe—Ni alloys include invar. Examples of Fe-Ni-Co alloys include Super Invar. 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. good. 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 may contain impurities inevitably mixed in during the manufacturing process. Preferably, the metal layer is an iron alloy. The metal layer is preferably an alloy containing Fe and Ni. The metal layer is preferably an alloy containing Fe, Ni and Co. The ratio of Ni occupied in the alloy is preferably 10% by mass to 50% by mass, more preferably 30% by mass to 40% by mass, and still more preferably 32% by mass to 38% by mass. The proportion of Co contained in the alloy is preferably 0% by mass to 10% by mass, more preferably 2% by mass to 6% by mass.

From the standpoint of resolution of the through-holes in the deposition mask manufacturing process, the average thickness of the metal layer is preferably 100 μm or less, more preferably 30 μm or less, and still more preferably 25 μm or less. From the viewpoint of the rigidity of the deposition mask, the average thickness of the metal layer is preferably 5 μm or more, more preferably 10 μm or more. 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).

The metal layer may be a known metal substrate (including commercially available ones). The metal layer can be produced by known methods. The metal layer can be produced by casting, forging, sputtering or electroplating.

The substrate may include a metal layer and a substrate layer. It is preferable that the base material layer is located closer to the second surface of the base material than the metal layer. The base material layer may constitute the second surface of the base material. The structure of the substrate layer may be a single-layer structure or a multi-layer structure. As a component of a base material layer, 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 layer 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 suppressing generation of air bubbles during lamination, the surface roughness Ra of the first surface of the substrate is preferably 5.0 μm or less, more preferably 3.0 μm or less, still more preferably 1.0 μm or less. From the viewpoint of suppressing scratches due to lubricity during transportation, the surface roughness Ra of the first surface of the substrate is preferably 0.1 μm or more, more preferably 0.2 μm or more.

From the viewpoint of suppressing generation of bubbles during lamination, the surface roughness Ra of the second surface of the substrate is preferably 5.0 μm or less, more preferably 3.0 μm or less, still more preferably 1.0 μm or less. From the viewpoint of suppressing scratches due to lubricity during transportation, the surface roughness Ra of the second surface of the substrate is preferably 0.1 μm or more, more preferably 0.2 μm or more. The surface roughness Ra of the second surface of the substrate may be the same as the surface roughness Ra of the first surface of the substrate. The surface roughness Ra of the second surface of the substrate may be different from the surface roughness Ra of the first surface of the substrate.

In the present disclosure, the surface roughness Ra is measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation). First, use a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation) to obtain the surface profile of the object surface. 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 arithmetic mean roughness calculated from the obtained histogram data was used as "surface roughness Ra".

[Fitting procedure] In the bonding step, the base material and the transfer film are bonded together, and the photosensitive layer and the dummy support included in the transfer film are sequentially arranged on the first surface of the base material.

The bonding step can be implemented by a known method. In the bonding step, it is preferable to press-bond the base material and the transfer film. For example, it is preferable to bond the base material and the transfer film by laminating the base material, the transfer film, and the metal layer, and applying pressure and heat 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 transfer film includes a protective film, the attaching step is performed after removing the protective film.

[Exposure steps] In the exposure step, pattern exposure is performed on the photosensitive layer arranged on the substrate. "Exposing a photosensitive layer in a pattern" means forming an exposed part and a non-exposed part in a photosensitive layer by irradiating light to a photosensitive 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.

The exposing step preferably includes irradiating light to the photosensitive layer in a direction from the photosensitive layer toward the substrate.

It is preferable that the light used in the exposure step 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 a lens system or a mirror system, an exposure machine having 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 directly performed on the photosensitive layer, or reduction projection exposure may be performed on the photosensitive layer through a lens. The exposure step can be performed under the atmosphere, under reduced pressure, or under vacuum. The exposure step can also be performed by interposing a liquid such as water between the light source and the photosensitive layer.

The exposure step can also be carried out before or after peeling off the dummy support. When the exposure step is performed before peeling off the dummy support, the photosensitive layer can be exposed via the dummy support. In the exposure step using a photomask, the photosensitive layer may be subjected to pattern exposure with the photomask in contact with the photosensitive layer, or may be brought close to the photosensitive layer without making the photomask contact the photosensitive layer. Next, the photosensitive layer is subjected to pattern exposure. In order to prevent contamination of the photomask caused by the contact between the photomask and the photosensitive 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 photosensitive layer without peeling off the dummy support. When exposing the photosensitive layer through a dummy support, it is preferable to peel off the dummy support after the exposure step and before the image development step.

[Development procedure] In the developing step, a developing process is performed on the photosensitive layer to form a photoresist pattern. The photoresist pattern is formed by removing the exposed portion or the non-exposed portion of the photosensitive layer. When the photosensitive layer is a negative photosensitive layer, the non-exposed portion of the photosensitive layer is usually removed by developing treatment, and a photoresist pattern is formed from the exposed portion of the photosensitive layer. When the photosensitive layer is a positive-type photosensitive layer, usually, the exposed portion of the photosensitive layer is removed with a developing solution, and a photoresist pattern is formed from the non-exposed portion of the photosensitive 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.

The shape of the photoresist pattern may be determined according to the shape of the target through hole in the etching step. Examples of the shape of the opening defined by the resist pattern viewed in plan view include a circle, an ellipse, and a rectangle. The shape of the opening viewed from above is preferably a quadrilateral, more preferably a square or a rectangle. When the opening viewed from above is a polygon (for example, a quadrilateral), some or all of the plural corners of the polygon may be rounded.

The diameter of the opening defined by the photoresist pattern can be determined according to the diameter of the target through hole in the etching step. The smaller the diameter of the opening defined by the photoresist pattern becomes, the smaller the diameter of the through hole formed in the substrate during the etching step becomes. The diameter of the opening defined by the photoresist pattern is preferably 40 μm or less, more preferably 35 μm or less, and still more preferably 30 μm or less. In addition, the diameter of the opening 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 diameter of the opening is not limited. The lower limit of the diameter of the opening may be 5 μm, 1 μm or 0.1 μm.

In the present disclosure, the diameter of the opening is measured from an image obtained using a scanning electron microscope (SEM). The diameter of the opening is defined by the maximum value of a straight line connecting any two points on the contour line of the opening viewed from above. When the number of openings is two or more, the diameter of the openings is represented by the average diameter of the openings. The average diameter of the opening was calculated by the arithmetic mean of the diameters of 10 openings. However, when the number of openings is two to nine, the average diameter of the openings is calculated as the arithmetic mean of the diameters of all the openings.

When the shape of the opening viewed from above is quadrangular, the length of one side of the quadrangular opening is preferably 5 μm to 50 μm, more preferably 5 μm to 40 μm, and even more preferably 5 μm to 30 μm.

[etching step] In the etching step, the substrate is etched to form through holes extending from the first surface of the substrate to the second surface of the substrate. Through holes are formed by removing the substrate not protected by the photoresist pattern. At least one through hole is formed in the etching step. A plurality of through holes may also be formed in the etching step.

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 an aqueous solution 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.

The through hole extending from the first surface of the substrate to the second surface of the substrate has an opening on the first surface of the substrate and an opening on the second surface of the substrate. Hereinafter, the opening formed on the first surface of the substrate through the through hole may be referred to as "first opening", and the opening formed on the second surface of the substrate through the through hole may be referred to as "second opening". Examples of the shape of the through-hole (that is, the opening) viewed in 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 through-holes observed in cross-section are defined by the inner surface of the substrate. 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 surface delineating the through-hole viewed in cross-section may also be a combination of straight lines and curved lines. "Cross-section" in this paragraph refers to observing the section along the thickness direction of the deposition mask.

The diameter of the through-hole on the second surface of the substrate (that is, the diameter of the second opening) is preferably 40 μm or less, more preferably 35 μm or less, still more preferably 30 μm or less. In addition, the diameter of the second opening is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. When the diameter of the second opening is reduced, a pattern can be formed with high resolution. The lower limit of the diameter of the second opening is not limited. The lower limit of the diameter of the second opening may be 5 μm, 1 μm or 0.1 μm.

The diameter of the through-hole on the second surface of the substrate (that is, the diameter of the second opening) is preferably smaller than the diameter of the through-hole on the first surface of the substrate (that is, the diameter of the first opening). For example, in a deposition method in which a deposition mask is arranged so that the second surface of the substrate faces the object, the substance that reaches the first surface of the substrate from the vaporization source travels along the direction from the first surface of the substrate toward the second surface. It moves in the through hole and attaches to the object in the same direction. In the above method, if the diameter of the second opening is smaller than that of the first opening, the substance reaching the first surface of the base material from the vaporization source will easily enter the through hole. As a result, for example, productivity and pattern accuracy are improved.

The ratio of the diameter of the second opening to the diameter of the first opening is preferably 0.8 or less, more preferably 0.4 or less, still more preferably 0.3 or less. From the viewpoint of high resolution of the pattern, the ratio of the diameter of the second opening to the diameter of the first opening is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.15 or more. For example, it is considered that etching characteristics (for example, isotropy) cause a difference between the diameter of the first opening and the diameter of the second opening.

From the viewpoint of increasing the resolution of the pattern, the diameter of the first opening is preferably 15 μm to 100 μm, more preferably 20 μm to 50 μm, and still more preferably 20 μm to 30 μm. The lower limit of the diameter of the first opening may be 8 μm or 10 μm.

The diameter of the first opening and the diameter of the second opening were measured by following the method described above for the diameter of the opening defined by the resist pattern.

When the shape of the first opening is a quadrangle, the length of one side of the first opening is preferably 5 μm to 50 μm, more preferably 5 μm to 40 μm, and still more preferably 5 μm to 30 μm. When the shape of the second opening is a quadrangle, it is preferably 5 μm to 50 μm, more preferably 5 μm to 40 μm, and still more preferably 5 μm to 30 μm.

The diameter of the through-hole viewed in cross-section may change continuously or discontinuously along the direction from the first surface of the substrate toward the second surface of the substrate. It is preferable that the diameter of the through-hole viewed in cross-section gradually decreases along the direction from the first surface toward the second surface. "Cross-section" in this paragraph refers to observing the section along the thickness direction of the deposition mask.

[removal steps] 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-dip.

[additional steps] The manufacturing method of the deposition mask may further include other steps as required.

The method of manufacturing the deposition mask may include a pressing step after the attaching step. For example, in the pressurization step, the laminate obtained by bonding the substrate and the transfer film is pressurized. It is preferable that the laminated body to be pressurized is a laminated body which sequentially includes a base material, a photosensitive layer, and a dummy support. The laminated body to be pressed may be a laminated body including a base material and a photosensitive layer in this order. For example, if the dummy support is peeled off after the bonding step, a laminate including a substrate and a photosensitive layer in this order can be formed. In the pressurizing step, the laminate obtained by bonding the transfer film and the substrate can be pressurized using an autoclave. For example, the pressure treatment can be performed under the conditions of 50° C. to 60° C., 0.5 MPa to 0.6 MPa, and 60 minutes. By subjecting the laminate to the pressure treatment, the adhesiveness between the base material and the photosensitive layer can be improved, and the followability of the photosensitive layer to the unevenness on the surface of the base material can be improved. The pressurizing step is preferably carried out before the exposure step.

When the substrate includes a metal layer and a substrate layer, the method of manufacturing the deposition mask may include a step of removing the substrate layer included in the substrate.

Referring to FIG. 1 , FIG. 2 and FIG. 3 , the structure of the deposition mask will be described. FIG. 1 is a schematic top view showing a deposition mask of an embodiment. 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 a through hole 10H. The first surface 10F of the metal layer 10 faces the observer 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 that the contour line of the opening (specifically, the first opening 10FA in FIG. 3 ) formed on the first surface 10F of the metal layer 10 is different. The outline of the opening (specifically, the second opening 10RA in FIG. 3 ) formed in the second surface 10R of the metal layer 10 is seen from the inside. 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 has a first opening 10FA on the first surface 10F of the metal layer 10 , and has a second opening 10RA on 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 diameter of the second opening 10RA is smaller than the diameter of the first opening 10FA. The diameter of the through hole 10H gradually decreases along the direction from the first surface 10F toward the second surface 10R.

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 the first surface 10F and the second surface 10R opposite to the first surface 10F is prepared. As shown in FIG. 4( b ), a transfer film (not shown) is bonded to the metal layer 10 to arrange the photosensitive layer 20 on the first surface 10F of the metal layer 10 . As shown in FIG. 4( c ), pattern exposure is performed on the photosensitive layer 20 , and then, a development process is performed on the photosensitive layer 20 to form a photoresist pattern 21 . As shown in FIG. 4( d ), through-holes 10H are formed by etching the metal layer 10 . 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 a first opening 10FA in the first surface 10F of the metal layer 10 , and forms a second opening 10RA in the second surface 10R of the metal layer 10 .

The deposition mask obtained by the manufacturing method of the deposition mask of the present disclosure may include other constituent elements. As other constituent elements, for example, a housing can be mentioned. The frame can enhance the deposition mask or improve the operability of the deposition mask. The frame body may be disposed around the through hole in plan view, or may be disposed on the outer periphery of the deposition mask 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).

As a preferable use of the deposition mask obtained by the manufacturing method of the deposition mask of this disclosure, the manufacturing method of the pattern using a deposition method is mentioned, for example. In the deposition method, it is preferable to arrange the deposition mask on the object so that the second surface of the substrate faces the object. When the second surface of the substrate faces the object, the substance reaching the first surface of the substrate from the vaporization source easily enters the through-holes. The substance entering the through hole moves in the through hole along the direction from the first surface of the substrate toward the second surface, and adheres to the object. Patterns are formed by depositing substances passing through the through holes on the object. 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 specific application of the deposition mask, for example, a method for manufacturing an OLED (Organic Light Emitting Diode: Organic Light Emitting Diode) 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".

＜Pseudo-support 1＞ The dummy support 1 was produced by the following method.

[Preparation of Composition 1 for Particle-Containing Layer Formation] A mixture obtained by mixing the following components was filtered using a 6 μm filter (F20, manufactured by Mahle Filter Systems Japan Corp.), and then membrane degassed using 2×6 Radial Flow Super Phobic (manufactured by Polypore Co., Ltd.) . Composition 1 for forming a particle-containing layer was obtained through the above procedures.

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

[extrusion molding] The pellets of polyethylene terephthalate produced by using the citric acid chelated organic titanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst are dried so that the moisture content becomes 50 ppm or less. The pellets were charged into a hopper of a 30 mm diameter single-screw kneading extruder, melted and extruded at 280°C. After passing the melt through a filter (pore size: 2 μm), it was extruded from a die onto a 25° C. cooling roll. Specifically, the melt was brought into close contact with the cooling roll using an electrostatic application method. An unstretched film was obtained by the above procedure.

[Stretching and Coating] The cured unstretched film was sequentially biaxially stretched by the following method.

(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. Specifically, stretching was carried out under the conditions that the preheating temperature was 75° C., the stretching temperature was 90° C., the stretching ratio was 3.4 times, and the stretching speed was 1300%/sec.

(b) coating Composition 1 for forming a particle-containing layer was coated on one side of the longitudinally stretched film using a bar coater so that the thickness after film formation became 40 nm.

(c) Transverse stretch The longitudinally stretched and coated film was laterally 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 fix] The biaxially stretched film after transverse stretching was heat-set under the following conditions. Heat Fixing Temperature: 227°C Heat fixation time: 6 seconds

[hot relaxation] 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%

[coiling] After thermal relaxation, both ends of the film were trimmed, and the film was wound up at a tension of 40 kg/m after extruding (knurling) the ends of the film at a width of 10 mm. The width of the film was 1.5 m, and the roll length of the film was 6,300 m. The obtained film roll was used as a dummy support. The pseudo-support consisted of a polyester film with a thickness of 16 μm and a particle-containing layer with a thickness of 40 nm.

The haze value of the pseudo-support was 0.2%. The haze value was measured as the total haze using a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD., NDH2000). 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), the direction perpendicular to the conveying direction in the in-plane direction of the film. . The thickness of the particle-containing layer measured using a cross-sectional TEM photograph was 40 nm. The average particle diameter of the particles contained in the particle-containing layer measured using a transmission electron microscope (TEM) Model HT-7700 manufactured by Hitachi High-Technologies Corporation was 50 nm.

<Photosensitive compositions 1 to 17> Components selected as described in Table 1 and a mixed solvent of methyl ethyl ketone (SANKYO CHEMICAL Co., Ltd., 60 parts) and propylene glycol monomethyl ether acetate (SHOWA DENKO K.K., 40 parts) were mixed. About the addition amount of a mixed solvent, the quantity of a mixed solvent was adjusted so that the solid content density|concentration of the photosensitive composition might become 13 mass %. A photosensitive composition was prepared by filtering the obtained mixture using a filter made of polytetrafluoroethylene having a pore size of 2.0 μm.

[Table 1] Photosensitive composition (unit of addition amount of each component: parts by mass (solid content)) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 polymer Styrene/methacrylic acid/methyl methacrylate=52/6/42 (mass%) acid value=39, Mw=60,000 50.00 - - - - - - - - - - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/13/35 (mass%) acid value=85, Mw=60,000 - 50.00 - - - - - - - - - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/28/20 (mass%) acid value=182, Mw=60,000 - - 50.00 - - 50.00 50.00 - - - - - - - - 50.00 - Styrene/methacrylic acid/methyl methacrylate=52/34/14 (mass%) acid value=222, Mw=60,000 - - - 50.00 - - - - - - - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/39/9 (mass %) acid value=254, Mw=60,000 - - - - 50.00 - - - - - - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/28/20 (mass%) acid value=182, Mw=5,000 - - - - - - - 50.00 - - - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/28/20 (mass%) acid value=182, Mw=12,000 - - - - - - - - 50.00 - - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/28/20 (mass%) acid value=182, Mw=20,000 - - - - - - - - - 50.00 - - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/28/20 (mass%) acid value=182, Mw=70,000 - - - - - - - - - - 50.00 - - - - - - Styrene/methacrylic acid/methyl methacrylate=52/28/20 (mass%) acid value=182, Mw=100,000 - - - - - - - - - - - 50.00 - - - - - Benzyl methacrylate/methacrylic acid=78/22 (% by mass), acid value=143, Mw=40,000 - - - - - - - - - - - - 50.00 - - - - Styrene/methacrylic acid/methyl methacrylate=50/34/16 (mass%) acid value=222, Mw=35,000 - - - - - - - - - - - - - 50.00 - - - Cyclohexyl methacrylate/methacrylic acid/methyl methacrylate=52/19/29 (mass %) acid value=124, Mw=30,000 - - - - - - - - - - - - - - 50.00 - - Styrene/methacrylic acid/methyl methacrylate=52/3/45 (mass%) acid value=20, Mw=60,000 - - - - - - - - - - - - - - - - 50.00 polymeric compound BPE-500 (Shin-Nakamura Chemical Co., Ltd.) 15.50 15.50 15.50 15.50 15.50 - 15.50 15.50 15.50 15.50 15.50 15.50 15.50 15.50 15.50 36.00 15.50 Dimethacrylate of polyethylene glycol with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A 10.00 10.00 10.00 10.00 10.00 - 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 - 10.00 M-270 (TOAGOSEI CO.,LTD.) - - - - - - - - - - - - - - - 5.00 - A-TMPT (Shin-Nakamura Chemical Co., Ltd.) 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 - 5.00 SR-454 (Arkema SA company) 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 - 4.50 A-9300-CL1 (Shin-Nakamura Chemical Co., Ltd.) 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 9.77 - 9.77 DPHA (Di-Neopentylthritol Hexaacrylate) - - - - - 25.50 - - - - - - - - - - - polymerization initiator B-CIM (KUROGANE KASEI Co., Ltd.) 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 6.80 3.35 Sensitizer SB-PI 701 (Sanyo Trading Co., Ltd.) 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.60 0.35 chain transfer agent Colorless crystal violet (Tokyo Chemical Industry Co.,Ltd.) 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.30 0.55 N-Phenylglycine (Tokyo Chemical Industry Co.,Ltd.) - - - - - - - - - - - - - - - 0.12 - Colorant Bright green (Tokyo Chemical Industry Co.,Ltd.) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Rust inhibitor CBT-1 (JOHOKU CHEMICAL CO.,LTD.) - - - - - - - - - - - - - - - 0.10 - Mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole ( Mass ratio = 1:1) 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 - 0.08 polymerization inhibitor TDP-G (Kawaguchi Chemical Industry Company, Limited) - - - - - - - - - - - - - - - 0.27 - Irganox245 (BASF company) 0.20 0.20 0.20 0.20 0.20 0.20 - 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 - 0.20 N-Nitrosophenylhydroxylamine aluminum salt (FUJIFILM Wako Pure Chemical Corporation) 0.01 0.01 0.01 0.01 0.01 0.01 - 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 - 0.01 Antioxidants Phenidone (Tokyo Chemical Industry Co.,Ltd.) - - - - - - - - - - - - - - - 0.02 - Surfactant F-552 (DIC Corporation) - - - - - - - - - - - - - - - 0.30 -

<Water-soluble resin layer-forming composition 1> The composition 1 for forming a water-soluble resin layer was prepared by mixing the following components. ·Ion-exchanged water: 38.12 parts Methanol (Mitsubishi Gas Chemical Company, Inc.): 57.17 parts ・KURARAY POVAL 4-88LA (polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts ・Polyvinylpyrrolidone K-30 (NIPPON SHOKUBAI CO.,LTD.): 1.49 parts ・MEGAFACE F-444 (fluorine-based surfactant, DIC Corporation): 0.0035 parts

<Thermoplastic resin layer-forming composition 1> Composition 1 for forming a thermoplastic resin layer was prepared by mixing the following components. BzMA represents benzyl methacrylate, MAA represents methacrylic acid, and AA represents acrylic acid. Contains polymer (BzMA/MAA/AA=78/14.5/7.5 (mass %), 40 mass %), propylene glycol monomethyl ether acetate (30 mass %), and 1-methoxy-2-propanol ( 30% by mass) solution: 40.00 parts ・Polymer compound (A-DCP, Shin-Nakamura Chemical Co., Ltd.): 6.00 parts · Polymeric compound (8UX-015A, Taisei Fine Chemical Co., Ltd.): 3.00 parts ・Polymerizable compound (ARONIX TO-2349, TOAGOSEI CO.,LTD.): 1.00 parts · Surfactant (MEGAFACE F-552, DIC Corporation): 0.02 parts Additives (Phenibutan well): 0.06 parts ・Additive (CBT-1, JOHOKU CHEMICAL CO.,LTD.): 0.03 parts ・Solvent (methyl ethyl ketone): 49.9 parts

<Examples 1 to 18 and Comparative Example 1> Using a slit-shaped nozzle, after coating the photosensitive composition selected according to the description in Table 2 on the dummy support 1, the photosensitive composition was dried at 80° C. for 2 minutes, thereby forming a photosensitive composition with a surface The thickness of the photosensitive layer described in 2. A transfer film including a pseudo-support and a photosensitive layer was obtained through the above procedures.

<Examples 19-20> After coating the thermoplastic resin layer-forming composition 1 on the dummy support 1 using a slit-shaped nozzle, the thermoplastic resin layer-forming composition 1 was dried at 80° C. for 2 minutes to form a The thermoplastic resin layer with the thickness listed in Table 2. After coating the water-soluble resin layer-forming composition 1 on the thermoplastic resin layer using a slit nozzle, the water-soluble resin layer-forming composition 1 was dried at 90°C for 2 minutes to form The water-soluble resin layer having the thickness described in Table 2. Using a slit-shaped nozzle, apply the photosensitive composition selected according to the description in Table 2 on the water-soluble resin layer, and then dry the photosensitive composition at 80°C for 2 minutes, thereby forming a photosensitive composition with a surface The thickness of the photosensitive layer described in 2. A transfer film comprising a pseudo-support, a thermoplastic resin layer, a water-soluble resin layer and a photosensitive layer was obtained through the above procedures.

＜Evaluation＞ The following evaluations were implemented using each transfer film manufactured in the Example and the comparative example. Referring to Japanese Patent Laid-Open No. 2019-214788, the Invar steel substrate used in the following evaluations was produced by the following method. First, a base material composed of an iron alloy containing 36% by mass of nickel, the remainder of iron, and unavoidable impurities was prepared. Next, a rolling step, a slit step, and an annealing step were performed on the base material to obtain a base material made of steel having a thickness of 30 μm. Since the static friction coefficient of the first surface of the steel substrate is 0.61, the dynamic friction coefficient of the first surface of the steel substrate is 0.52. Since the surface roughness Ra of the first surface of the steel substrate is 0.8 μm, the surface roughness Ra of the second surface of the steel substrate is 0.9 μm. Since the steel substrate corresponds to the metal layer already described.

[patternability] (Preparation of photoresist pattern) (1) Using a vacuum laminator (MCK Co., Ltd., roll temperature: 100° C., line pressure: 1.0 MPa, line speed: 0.5 m/min), a steel substrate having a thickness of 20 μm was rolled The transfer film was bonded face to face, and the transfer layer and the dummy support were sequentially arranged on the first surface of the steel substrate. The obtained laminated body sequentially includes the steel base material, the transfer layer and the pseudo-support body. (2) Using an autoclave apparatus, pressure defoaming was performed on the laminate under the conditions of 0.6 MPa, 60° C., and 60 minutes. (3) Using an ultra-high pressure mercury lamp, the transfer layer was exposed through a photomask without peeling off the dummy support. The pattern of the mask includes a plurality of square light-shielding portions, and the length of one side of the light-shielding portion is set stepwise in units of 5 μm from 10 μm to 100 μm. (4) After peeling off the dummy support, a photoresist pattern is formed by developing. Specifically, shower image development was performed using 25 degreeC 1.0 mass % sodium carbonate aqueous solution. In image development, the image development time was set to 1.5 times the dissolution time of the non-exposed part with respect to the 1.0 mass % sodium carbonate aqueous solution of 25 degreeC. (5) Regarding the opening defined by the photoresist pattern, until the length of one side of the opening corresponding to the light-shielding portion with a side length of 30 μm in the mask becomes exactly 30 μm, the exposure conditions and development conditions were appropriately changed and the above was repeated. A series of operations from (1) to (4). Hereinafter, the condition in which an opening with a length of 30 μm on one side is formed with respect to the target opening is referred to as “standard condition”. (6) A laminate is produced by the method described in (1) to (2) above. Using an ultra-high pressure mercury lamp, the transfer layer was exposed through a photomask under standard conditions without peeling off the dummy support. The pattern of the mask includes a plurality of square light-shielding portions, and the length of one side of the light-shielding portion is set stepwise in units of 5 μm from 10 μm to 100 μm. After peeling off the dummy support, development was performed under standard conditions to form a resist pattern.

(minimum resolution) The resist pattern obtained in (6) above was observed using a scanning electron microscope. Based on the length of one side of the smallest opening properly resolved in the resist pattern, the minimum resolution was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: less than 15μm B: 15 μm or more and less than 25 μm C: 25 μm or more

(Stability of opening diameter) The resist pattern obtained in (6) above was observed using a scanning electron microscope. The length of one side of each of the 100 openings corresponding to the light-shielding portion having a side length of 30 μm in the mask was measured. From the difference between the maximum value and the minimum value (that is, [the maximum value of the length of one side] - [the minimum value of the length of one side]), the stability of the opening diameter was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: Less than 1.0 μm B: 1.0 μm or more and less than 2.0 μm C: 2.0 μm or more and less than 3.0 μm D: 3.0 μm or more

(Changes in opening diameter with time after exposure) A photoresist pattern was produced by the method described in (6) above by setting the standing time after exposure (that is, the time from the end of exposure to the start of development) to 1 hour. In addition, a photoresist pattern was produced by the method described in (6) above by setting the standing time after exposure to 24 hours. The diameter D1 of the opening formed after leaving for 1 hour and the diameter D24 of the opening formed after leaving for 24 hours were measured. Based on the change rate of the opening diameter calculated by the following formula, the change of the opening diameter with the standing time after exposure was evaluated according to the following criteria. The evaluation results are shown in Table 2. Formula: Change rate of opening diameter (%)={(|D24-D1|)/D1}×100 A: Less than 10% B: More than 10% and less than 20% C: More than 20% and less than 40% D: more than 40%

(opening defect) The resist pattern obtained in (6) above was observed using an optical microscope. The defect state of 100 openings each having a length of 20 μm on one side was observed, and the defect of the opening was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: No defect was confirmed. B: Defects were confirmed at 1 or 2 places. C: Defects were confirmed at 3 to 5 places. D: Chipping was confirmed at 6 or more places, or no photoresist pattern remained.

(Development residue) The resist pattern obtained in (6) above was observed using an optical microscope. 100 openings each having a length of 30 μm on one side were observed, and development residue was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: No development residue was confirmed. B: Development residue was confirmed at 1 or 2 places. C: Development residue was confirmed at 3 or more places.

[lamination properties] (1) Using a vacuum laminator (MCK Co., Ltd., roll temperature: 100° C., line pressure: 1.0 MPa, line speed: 0.5 m/min), a steel base material having a thickness of 20 μm was rolled The transfer film was bonded face to face, and the transfer layer and the dummy support were sequentially arranged on the first surface of the steel substrate. The obtained laminate at least sequentially includes a steel substrate, a transfer layer and a pseudo-support. (2) Using an autoclave apparatus, pressure defoaming was performed on the laminate under the conditions of 0.6 MPa, 60° C., and 60 minutes. (3) The bubbles contained in the laminate were observed using an optical microscope, and the adhesiveness was evaluated according to the following criteria. The smaller the number of air cells, the higher the adhesion. The evaluation results are shown in Table 2. A: Less than 10 B: More than 10 and less than 100 C: more than 100

[Table 2] transfer film thermoplastic resin layer Water-soluble resin layer photosensitive layer patterning Lamination Composition thickness Composition thickness Composition thickness Storage modulus of elasticity at 90°C (Pa) Complex viscosity at 30°C (Pa) Acid value (mg/KOH) minimum resolution Stability of opening diameter Variation of opening diameter with time after exposure opening defect Development residue Example 1 1 - - - - 1 10.0μm 6×10 ² 9×10 ⁴ 20 C C C C B A Example 2 2 - - - - 2 10.0μm 5×10 ³ 7×10 ⁵ 43 B B B A A A Example 3 3 - - - - 3 10.0μm 3×10 ⁴ 6×10 ⁶ 92 B B B A A A Example 4 4 - - - - 4 10.0μm 2×10 ⁵ 7×10 ⁷ 112 B B B A A A Example 5 5 - - - - 5 10.0μm 8×10 ⁵ 9×10 ⁸ 128 B B B B A B Example 6 6 - - - - 3 5.0μm 3×10 ⁴ 6×10 ⁶ 92 A A A A A A Example 7 7 - - - - 3 15.0μm 3×10 ⁴ 6×10 ⁶ 92 B B B A A A Example 8 8 - - - - 3 20.0μm 8×10 ⁴ 6×10 ⁶ 92 C C C B A A Example 9 9 - - - - 6 10.0μm 3×10 ⁴ 9×10 ⁶ 92 B C B B A A Example 10 10 - - - - 7 10.0μm 3×10 ⁴ 6×10 ⁶ 92 B C C A A A Example 11 11 - - - - 8 10.0μm 1×10 ² 8×10 ³ 92 B B B C C A Example 12 12 - - - - 9 10.0μm 8×10 ² 2×10 ⁵ 92 B B B B A A Example 13 13 - - - - 10 10.0μm 9×10 ³ 3×10 ⁶ 92 B B B A A A Example 14 14 - - - - 11 10.0μm 2×10 ⁵ 6×10 ⁷ 92 B B B A A A Example 15 15 - - - - 12 10.0μm 3×10 ⁶ 7×10 ⁸ 92 B B B A A C Example 16 16 - - - - 13 10.0μm 1×10 ⁴ 3×10 ⁵ 72 B B B A A A Example 17 17 - - - - 14 10.0μm 8×10 ³ 2×10 ⁵ 112 B B B A A A Example 18 18 - - - - 15 10.0μm 3×10 ³ 8×10 ⁴ 62 B C B B A A Example 19 19 1 6.0μm 1 1.0μm 16 2.0μm 6×10 ⁴ 4×10 ⁶ 92 A A A A A A Example 20 20 1 2.0μm 1 1.0μm 16 6.0μm 6×10 ⁴ 4×10 ⁶ 92 A A A A A A Comparative example 1 twenty one - - - - 17 10.0μm 3×10 ² 3×10 ⁴ 10 C D. C D. B A

Table 2 shows that, compared with Comparative Example 1, in Examples 1 to 20, there are fewer defects in openings. That is, compared with the comparative example 1, in Examples 1-20, the resist pattern with few chipping was formed.

<Examples 101 to 120> Using each of the transfer films of Examples 1 to 20, a deposition mask was produced by the following method. By the method described in (6) of the evaluation of the above-mentioned "patternability", a resist pattern was formed on the base material made of Invar using the transfer film. However, for exposure, a mask having a plurality of square light-shielding portions of 25 μm in length and 25 μm in width was used. Using an etchant (refer to Example 1 of JP-A-2018-178142), etch by spraying at 50°C and a spraying pressure of 0.2MPa to form a steel substrate. A plurality of through holes. The etching processing time was set to 1.2 times the minimum time until the through hole was formed. The deposition mask was obtained by removing the photoresist pattern using 4% by mass sodium hydroxide solution. In Examples 101 to 120, since the diameter of the through-hole on the first surface of the steel substrate is in the range of 23 μm to 27 μm, the diameter of the through-hole on the second surface of the steel substrate is 15 μm to 19 μm. In the range.

10: metal layer 10F: Side 1 10FA: the first opening 10H: through hole 10R: side 2 10RA: 2nd opening 20: photosensitive layer 21: Photoresist pattern 100: Deposition mask

FIG. 1 is a schematic top view showing a deposition mask of an embodiment. 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: Side 1

10H: through hole

100: Deposition mask

Claims (20)

A transfer film for deposition mask formation, which sequentially includes: pseudo-supports; and The photosensitive layer contains a polymer having an acid value of 30 mgKOH/g or more. The transfer film for deposition mask formation according to Claim 1, wherein The acid value of the said polymer is 270 mgKOH/g or less. The transfer film for deposition mask formation according to claim 1 or claim 2, wherein The acid value of the said photosensitive layer is 15 mg/KOH or more. The transfer film for deposition mask formation according to claim 1 or claim 2, wherein The acid value of the said photosensitive layer is 135 mg/KOH or less. The transfer film for forming a deposition mask according to any one of claims 1 to 4, which includes an intermediate layer between the dummy support and the photosensitive layer. The transfer film for deposition mask formation according to any one of claim 1 to claim 5, wherein The average thickness of the aforementioned pseudo-support is 50 μm or less. The transfer film for deposition mask formation according to any one of claim 1 to claim 6, wherein The haze value of the pseudo-support is 5% or less. The transfer film for deposition mask formation according to any one of claim 1 to claim 7, wherein The weight average molecular weight of the said polymer is 10,000 or more. The transfer film for deposition mask formation according to any one of claim 1 to claim 8, wherein The aforementioned polymer includes a structural unit having an aromatic ring. The transfer film for deposition mask formation according to any one of claim 1 to claim 9, wherein The aforementioned photosensitive layer contains a polymerizable compound having a bisphenol A structure. The transfer film for deposition mask formation according to any one of claim 1 to claim 10, wherein The aforementioned photosensitive layer comprises at least one selected from the group consisting of compounds having an oxime ester structure, compounds having an α-hydroxyalkylphenone structure, compounds having an acyl phosphine oxide structure, and compounds having a triaryl imidazole structure Polymerization initiator. The transfer film for deposition mask formation according to any one of claim 1 to claim 11, wherein The aforementioned photosensitive layer comprises a compound selected from dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, and oxazole compounds. Groups of compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, three well compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds at least one sensitizer from the group. The transfer film for deposition mask formation according to any one of claim 1 to claim 12, wherein The said photosensitive layer contains a polymerization inhibitor. The transfer film for forming a deposition mask according to any one of claims 1 to 13, wherein the storage elastic coefficient of the photosensitive layer at 90° C. is 1.0×10 ⁶ Pa or less. The transfer film for forming a deposition mask according to any one of claims 1 to 14, wherein the complex viscosity of the photosensitive layer at 30°C is 1.0×10 ⁴ Pa or higher. A method of manufacturing a deposition mask, comprising the steps of: Prepare the transfer film for deposition mask formation described in any one of claim 1 to claim 15; Prepare a base material having a first surface and a second surface on the opposite side of the first surface; bonding the aforementioned base material and the aforementioned transfer film, and sequentially disposing the photosensitive layer and the pseudo-support included in the aforementioned transfer film on the aforementioned first surface of the aforementioned base material; performing pattern exposure on the aforementioned photosensitive layer configured on the aforementioned substrate; After performing pattern exposure on the aforementioned photosensitive layer, performing developing treatment on the aforementioned photosensitive layer to form a photoresist pattern; After forming the aforementioned photoresist pattern, performing an etching process on the aforementioned substrate to form a through hole extending from the aforementioned first surface of the aforementioned substrate to the aforementioned second surface of the aforementioned substrate; and After the aforementioned through hole is formed, the aforementioned photoresist pattern is removed. The method for manufacturing a deposition mask as claimed in claim 16, wherein The surface roughness Ra of the first surface is 1.0 μm or less. The method for manufacturing a deposition mask according to any one of claim 16 or claim 17, wherein The aforementioned base material includes a metal layer having an average thickness of 30 μm or less. The method for manufacturing a deposition mask as claimed in claim 18, wherein The aforementioned metal layer contains iron. The method of manufacturing a deposition mask according to any one of claim 16 to claim 19, wherein The diameter of the through hole in the second surface of the base material is 35 μm or less.

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