CN115729035A - Transfer film for vapor deposition mask formation and method for manufacturing vapor deposition mask - Google Patents

Abstract

The invention provides a transfer film for forming a vapor deposition mask, which can form a resist pattern with less defect, and an application thereof. A transfer film for forming an evaporation mask, comprising in order: a temporary support; and a photosensitive layer containing a polymer having an acid value of 30mgKOH/g or more.

Description

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

Technical Field

The present invention relates to a transfer film for forming a vapor deposition mask and a method for manufacturing a vapor deposition mask.

Background

For example, an evaporation mask is used as a master for a pattern formed by an evaporation method. As a typical example of the vapor deposition method, a vacuum vapor deposition method is known. For example, in a vacuum vapor deposition method using a vapor deposition mask having a through hole, a substance vaporized from a vaporization source adheres to an object through the through hole of the vapor deposition mask disposed on the object, thereby forming a pattern. For example, through holes of a vapor deposition mask are formed by photolithography (see, for example, patent document 1 and patent document 2 below).

Patent document 1: japanese patent laid-open No. 2020-002470

Patent document 2: japanese patent laid-open publication No. 2019-214788

In view of the uniformity of the thickness of the resist layer, a method for manufacturing a vapor deposition mask using a transfer film has been studied. For example, in a method for manufacturing a vapor deposition mask using a transfer film, the vapor deposition mask is manufactured through steps of bonding a base material used as a material of the vapor deposition mask to the transfer film, exposing, developing, and removing a resist. In the method for manufacturing a vapor deposition mask, a transfer film is formed with a resist pattern, and the resist pattern protects a part of a substrate during etching.

However, in a method for manufacturing a vapor deposition mask using a transfer film, the adhesion of the transfer film (particularly, a photosensitive layer) to a substrate may be low. For example, if the adhesion between the substrate and the transfer film is low, the resist pattern may be broken.

Disclosure of Invention

An object of one embodiment of the present invention is to provide a transfer film for forming a vapor deposition mask, which can form a resist pattern with less chipping.

Another object of the present invention is to provide a method for manufacturing a vapor deposition mask using a transfer film for vapor deposition mask formation, which can form a resist pattern with less chipping.

The present invention includes the following modes.

<1> a transfer film for forming a vapor deposition mask, comprising in order: a temporary support; and a photosensitive layer containing a polymer having an acid value of 30mgKOH/g or more.

<2> the transfer film for forming a vapor deposition mask according to <1>, wherein the polymer has an acid value of 270mgKOH/g or less.

<3> the transfer film for vapor deposition mask formation according to <1> or <2>, wherein the acid value of the photosensitive layer is 15mg/KOH or more.

<4> the transfer film for vapor deposition mask formation according to <1> or <2>, wherein the acid value of the photosensitive layer is 135mg/KOH or less.

<5> the transfer film for vapor deposition mask formation according to any one of <1> to <4>, which comprises an intermediate layer between the temporary support and the photosensitive layer.

<6> the transfer film for forming a vapor deposition mask according to any one of <1> to <5>, wherein the temporary support has an average thickness of 50 μm or less.

<7> the transfer film for forming a vapor deposition mask according to any one of <1> to <6>, wherein the temporary support has a haze value of 5% or less.

<8> the transfer film for forming a vapor deposition mask according to any one of <1> to <7>, wherein the weight average molecular weight of the polymer is 10,000 or more.

<9> the transfer film for forming a vapor deposition mask according to any one of <1> to <8>, wherein the polymer contains a structural unit having an aromatic ring.

<10> the transfer film for forming a vapor deposition mask 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 vapor deposition mask according to any one of <1> to <10>, wherein the photosensitive layer contains at least one polymerization initiator selected from the group consisting of a compound having an oxime ester structure, a compound having an α -hydroxyalkylphenone structure, a compound having an acylphosphine oxide structure, and a compound having a triarylimidazole structure.

<12> the transfer film for forming a vapor deposition mask according to any one of <1> to <11>, wherein the photosensitive layer contains at least one sensitizer selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthenone (xanthone) compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

<13> the transfer film for vapor deposition mask formation according to any one of <1> to <12>, wherein the photosensitive layer contains a polymerization inhibitor.

<14>According to<1>To is that<13>The transfer film for forming a vapor deposition mask according to any of the above, wherein the storage modulus of the photosensitive layer at 90 ℃ is 1.0 × 10 ⁶ Pa or less.

<15>According to<1>To<14>The transfer film for forming a vapor deposition mask, wherein the complex viscosity of the photosensitive layer at 30 ℃ is 1.0 × 10 ⁴ Pa or above.

<16> a method for manufacturing a vapor deposition mask, comprising the steps of: preparing the transfer film for vapor deposition mask formation according to any one of <1> to <15 >; preparing a base material having a 1 st surface and a 2 nd surface opposite to the 1 st surface; laminating the base material and the transfer film, and disposing a photosensitive layer and a temporary support included in the transfer film on the 1 st surface of the base material in this order; pattern-exposing the photosensitive layer disposed on the substrate; pattern-exposing the photosensitive layer, and then developing the photosensitive layer to form a resist pattern; after the resist pattern is formed, performing etching treatment on the base material to form a through hole extending from the 1 st surface of the base material to the 2 nd surface of the base material; and removing the resist pattern after the through hole is formed.

<17> the method of manufacturing a vapor deposition mask according to <16>, wherein the surface roughness Ra of the 1 st surface is 1.0 μm or less.

<18> the method for manufacturing a vapor deposition mask according to <16> or <17>, wherein the base material includes a metal layer having an average thickness of 30 μm or less.

<19> the method for manufacturing a vapor deposition mask according to <18>, wherein the metal layer contains iron.

<20> the method for manufacturing a vapor deposition mask according to any one of <16> to <19>, wherein the diameter of the through-hole on the 2 nd surface of the base material is 35 μm or less.

Effects of the invention

According to one embodiment of the present invention, a transfer film for vapor deposition mask formation capable of forming a resist pattern with less chipping can be provided.

According to another embodiment of the present invention, a method for manufacturing a vapor deposition mask using a transfer film for vapor deposition mask formation capable of forming a resist pattern with less chipping can be provided.

Drawings

Fig. 1 is a schematic plan view showing a vapor deposition mask according to an embodiment.

Fig. 2 is an enlarged schematic plan view of a through-hole of the vapor deposition mask shown in fig. 1.

Fig. 3 is an enlarged schematic cross-sectional view of a through-hole of the vapor deposition mask shown in fig. 1.

Fig. 4 is a schematic cross-sectional view showing a method for manufacturing a vapor deposition mask according to an embodiment.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited in any way by the following embodiments. The following embodiments may be modified as appropriate within the scope of the object of the present invention.

In describing the embodiments of the present invention with reference to the drawings, description of components and symbols overlapping in the drawings may be omitted. In the drawings, the same reference numerals are used to designate the same structural elements. The ratio of sizes in the drawings does not necessarily indicate the ratio of actual sizes.

In the present invention, a numerical range represented by "to" means a range including a numerical value before "to" as a lower limit value and a numerical value after "to" as an upper limit value. In the numerical ranges recited in the present invention in stages, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in other numerical ranges recited in stages. In the numerical ranges described in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.

In the present invention, "(meth) acrylic group" means an acrylic group, a methacrylic group, or both of an acrylic group and a methacrylic group.

In the present invention, "(meth) acrylate" means acrylate, methacrylate, or both acrylate and methacrylate.

In the present invention, "(meth) acryloyl group" means an acryloyl group, a methacryloyl group, or both an acryloyl group and a methacryloyl group.

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

In the present invention, the term "step" includes not only a separate step but also a step which cannot be clearly distinguished from other steps when the intended purpose is achieved.

In the present invention, the "substituted" and "unsubstituted" groups (atomic groups) include groups (atomic groups) having no substituent and groups (atomic groups) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (i.e., unsubstituted alkyl group) but also an alkyl group having a substituent (i.e., substituted alkyl group).

In the present invention, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam unless otherwise specified. The light used for exposure may be generally an activating light (active energy ray) such as a bright line spectrum of a mercury lamp, a far ultraviolet ray typified by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, or an electron beam.

The chemical structural formula in the present invention is described as a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "mass%" means the same as "wt%" and "parts by mass" means the same as "parts by weight".

In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.

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

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

Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights converted using polystyrene as a standard substance, which are detected by a solvent THF (tetrahydrofuran) or a differential refractometer using a gel permeation spectrum (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by TOSOH CORPORATION).

In the present invention, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP: inductively Coupled Plasma) spectroscopic analyzer, unless otherwise specified.

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

In the present invention, the hue is a value measured by a colorimeter (CR-221, minolta Co., ltd.) unless otherwise specified.

In the present invention, "alkali-soluble" means that the solubility to 100g of a 1 mass% aqueous solution of sodium carbonate having a liquid temperature of 22 ℃ is 0.1g or more.

In the present invention, "water-soluble" means that the solubility to 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more.

In the present invention, "solid component" means all components except the solvent. The liquid component other than the solvent is contained in the solid component.

In the present invention, ordinal numbers (e.g., "1 st" and "2 nd") are terms used to distinguish the elements, and do not limit the number of the elements and the merits of the elements.

< transfer film for vapor deposition mask formation >

Hereinafter, a transfer film for forming a vapor deposition mask according to the present invention (hereinafter, may be simply referred to as "transfer film") will be described. In one embodiment, a transfer film for forming a vapor deposition mask includes a temporary support and a photosensitive layer containing a polymer having an acid value of 30mgKOH/g or more in this order. According to the above-described embodiments, a transfer film for vapor deposition mask formation capable of forming a resist pattern with less chipping can be provided. The reason why a resist pattern with less chipping can be formed is presumed as follows. When the photosensitive layer is disposed on the substrate by bonding the substrate and the transfer film, an interaction occurs between the polymer having an acid value of 30mgKOH/g or more contained in the photosensitive layer and a component (for example, metal or metal oxide) of the substrate, and thus the adhesion between the photosensitive layer and the substrate is improved. For example, an acidic functional group (i.e., an acid group) contained in a polymer having an acid value of 30mgKOH/g or more contributes to improvement of adhesion. When the adhesiveness is improved, defects (e.g., missing or peeling) of the photosensitive layer on which the resist pattern is formed or the cured product of the photosensitive layer can be prevented or reduced in the production process of the vapor deposition mask. As a result, a resist pattern with less chipping can be formed.

[ temporary support ]

The transfer film includes a temporary support. The temporary support is a support that supports the transfer layer and can be peeled from the transfer layer. The transfer layer is a layer other than the temporary support in the transfer film, which is disposed on the object by bonding the transfer film to 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, an intermediate layer described later is also a transfer layer.

The structure of the temporary support may be a single-layer structure or a multi-layer structure.

The temporary support is preferably a film, and more preferably a resin film. As the temporary support, a film which is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is preferable. Examples of the resin film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. The temporary support is preferably a polyethylene terephthalate film. It is preferable that the film used as a temporary support is free from deformation such as wrinkles and scratches.

The temporary support preferably has high transparency from the viewpoint of enabling pattern exposure via the temporary support. The transmittance at 365nm is preferably 60% or more, more preferably 70% or more.

From the viewpoint of transparency of the temporary support and linearity of the pattern formed by exposure through the temporary support, it is preferable to reduce the haze value of the temporary support. The haze value of the temporary 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 temporary support is not limited. The lower limit of the haze value of the temporary support may be 0.01% or 0.001%. The haze value is measured using a haze meter (e.g., a haze meter NDH400 manufactured by NIPPON DENSHOKU industies co., ltd.).

From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the number of coarse particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matter and defects having a diameter of 1 μm or more in the temporary support is preferably 50 particles/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, more preferably 3/10 mm ² The average particle size is preferably 0/10 mm ² 。

From the viewpoint of resolution in pattern exposure through the temporary support, the average thickness of the temporary support is preferably 200 μm or less, more preferably 100 μm or less, and still more preferably 50 μm or less. The average thickness of the temporary support is preferably 5 μm or more, and more preferably 10 μm or more. The average thickness of the temporary support is calculated by the arithmetic mean of the thicknesses at 5 positions measured in cross-sectional observation using a Scanning Electron Microscope (SEM).

Preferable examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of international publication No. 2012/081680, 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 by reference in the present specification.

The temporary support may contain a particle-containing layer from the viewpoint of handling properties. The temporary support may include a substrate layer and a particle-containing layer. Examples of the substrate layer include the resin films described above. The particle-containing layer is preferably disposed as the outermost layer on one side or both sides of the temporary support having a multilayer structure. The particle contained in the particle-containing layer preferably has a diameter of 0.05 μm to 0.8. Mu.m. The average thickness of the particle-containing layer is preferably 0.05 μm to 1.0. Mu.m. The average thickness of the particle-containing layer was calculated by the arithmetic mean of the thicknesses at 5 points 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 be a positive photosensitive layer.

(Polymer)

The photosensitive layer comprises a polymer. Specifically, the photosensitive layer contains a polymer having an acid value of 30mgKOH/g or more. When the acid value of the polymer is 30mgKOH/g or more, in the method for producing a vapor deposition mask using a transfer film, the adhesion between the transfer film and the substrate used as a material of the vapor deposition mask is improved, and as a result, a resist pattern with less chipping can be formed. The acid value of the polymer is preferably 60mgKOH/g or more, more preferably 120 mgKOH/g or more, and still more preferably 150mgKOH/g or more. The acid value of the polymer is preferably 170mgKOH/g or more, more preferably 200mgKOH/g or more, and still more preferably 220mgKOH/g or more. The acid value of the polymer is preferably 270mgKOH/g or less, more preferably 250 mgKOH/g or less, and even more preferably 220mgKOH/g or less, from the viewpoint of preventing or reducing peeling of the photosensitive layer forming the resist pattern or the cured product of the photosensitive layer during development. The acid value of the polymer is preferably 200mgKOH/g or less, more preferably 190mgKOH/g or less. The acid value is the mass [ mg ] of potassium hydroxide required to neutralize 1g of sample. The acid value is calculated from the average content of acid groups in the compound. The acid value of the polymer is adjusted by, for example, the type of the structural unit constituting the polymer and the content of the structural unit containing an acid group.

The weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 20,000 or more. When the weight average molecular weight of the polymer is 10,000 or more, 21085of the photosensitive layer or a cured product of the photosensitive layer in which a resist pattern is formed during development can be prevented or reduced. From the viewpoint of resolution and developability, the weight average molecular weight of the polymer is preferably 500,000 or less, more preferably 100,000 or less, and still more preferably 80,000 or less. The degree of dispersion of the polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation spectroscopy. The dispersity is the ratio of weight average molecular weight to number average molecular weight (i.e., weight average molecular weight/number average molecular weight).

The polymer preferably comprises structural units having aromatic rings. When the polymer contains a structural unit having an aromatic ring, 21085of the photosensitive layer or a cured product of the photosensitive layer which forms a resist pattern in a developing process can be prevented or reduced due to the hydrophobicity of the structural unit. The aromatic ring may be a single ring or a condensed ring. The aromatic ring may contain one or two or more atoms. The number of carbon atoms of the aromatic ring is preferably 6 to 18, more preferably 6 to 12. Examples of the aromatic ring include a benzene ring and a naphthalene ring. The aromatic ring is preferably a benzene ring.

Examples of the structural unit having an aromatic ring include structural units having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content ratio 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, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of the polymer a. The content of the structural unit having an aromatic hydrocarbon group in the polymer is preferably 95% by mass or less, and more preferably 85% by mass or less, based on the total mass of the polymer. When the photosensitive layer contains a plurality of polymers, the content of the structural unit having an aromatic hydrocarbon group is determined as a mass average value.

Examples of the monomer forming a structural unit having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Monomers having an aralkyl group or styrene are preferred. When the monomer forming the structural unit having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, further preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of the polymer.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group. Substituted or unsubstituted benzyl groups are preferred.

Examples of the monomer having a substituted or unsubstituted benzyl group include (meth) acrylates having a substituted or unsubstituted benzyl group (e.g., benzyl (meth) acrylate, chlorobenzyl (meth) acrylate) and vinyl monomers having a substituted or unsubstituted benzyl group (e.g., 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 of the structural unit derived from benzyl (meth) acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the polymer.

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

The polymer containing a 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 each monomer, one or two or more monomers may be used.

The polymer containing no structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing the first monomer, and more preferably obtained by polymerizing the first monomer and the second monomer. As each monomer, one or two or more monomers may be used.

The first monomer 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 half ester. (meth) acrylic acid is preferred.

The content of the structural unit derived from the first monomer in the polymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass, based on the total mass of the polymer.

The content of the structural unit derived from the first monomer is preferably 10 to 50% by mass based on the total mass of the polymer. The content of the structural unit derived from the first monomer is preferably 10% by mass or more from the viewpoint of exhibiting good developability and controlling edge fusibility. The content of the structural unit derived from the first monomer is preferably 15% by mass or more, and more preferably 20% by mass or more, based on the total mass of the polymer. The content of the structural unit derived from the first monomer is preferably 50 mass% or less from the viewpoints of high resolution of the resist pattern, the curl shape of the resist pattern, and chemical resistance of the resist pattern. The content of the structural unit derived from the first monomer is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 27% by mass or less, based on the total mass of the polymer.

The second monomer is a non-acidic monomer having at least 1 ethylenically unsaturated group. Examples of the second monomer include a (meth) acrylate compound. Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the second monomer include ester compounds of vinyl alcohol. As the ester compound of vinyl alcohol, for example, vinyl acetate can be cited. The second monomer is, for example, (meth) acrylonitrile. Methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferred, and methyl (meth) acrylate is more preferred.

The content of the structural unit derived from the second monomer in the polymer is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 45% by mass, based on the total mass of the polymer.

From the viewpoint of suppressing deterioration in line width and resolution when the focus position shifts during exposure, the polymer preferably contains at least one structural unit selected from a structural unit having an aralkyl group and a structural unit derived from styrene. Examples of a preferable polymer include a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene. Examples of preferable polymers include copolymers containing a structural unit derived from methacrylic acid, a structural unit derived from a preferred methyl acrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.

The polymer preferably contains 25 to 40 mass% of a structural unit having an aromatic hydrocarbon group, 20 to 35 mass% of a structural unit derived from the first monomer, and 30 to 45 mass% of a structural unit derived from the second monomer.

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

The polymer may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. The 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 branch structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain enables introduction of a branch structure or an alicyclic structure into a side chain of a polymer. The alicyclic structure may be a single ring structure or a polycyclic structure.

Specific examples of the monomer containing a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, tert-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Preferred is isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate, more preferred is isopropyl methacrylate or tert-butyl methacrylate.

Specific examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Specific examples of the monomer containing a group having an alicyclic structure in a side chain include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (carbon atoms). Specific examples of the monomer containing a group having an alicyclic structure in a side chain include (bicyclo [2.2.1] heptyl-2) acrylate, (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3,5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyladamantyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl ester, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid-2-methyl-2-adamantyl ester, (meth) acrylic acid-ethyl-2-adamantyl ester, (meth) acrylic acid-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4,7-methanoindene (meth) acrylate methyl-5-methylhydro-menthyl-3732, tricyclodecane (meth) acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate.

Among the (meth) acrylic esters described above, cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, (1-adamantyl (meth) acrylate), (2-adamantyl (meth) acrylate), (fenchyl (meth) acrylate, (1-menthyl (meth) acrylate), or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate), (2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate is more preferable.

The photosensitive layer may contain one or two or more polymers. The content of the polymer having an acid value of 30mgKOH/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 of the polymer having an acid value of 30mgKOH/g or more may be less than 100% by mass with respect to the total mass of the photosensitive layer. The upper limit of the content of the polymer having an acid value of 30mgKOH/g or more may be 80 mass%, 70 mass%, or 60 mass%. The photosensitive layer preferably 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 having no aromatic hydrocarbon group. In the latter case, the content of the polymer a having an aromatic hydrocarbon group is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more, with respect to the total mass of the polymer a.

The synthesis of the polymer is preferably performed by adding a radical polymerization initiator (e.g., benzoyl peroxide and azoisobutyronitrile) to a solution containing a monomer and a solvent (e.g., acetone, methyl ethyl ketone, and isopropyl alcohol) and heating and stirring the resulting mixture. The synthesis may be carried out while dropping a part of a mixture of a plurality of raw materials into the reaction solution. After the reaction is completed, the concentration can be adjusted by adding a solvent. Examples of the synthesis method include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

The glass transition temperature (Tg) of the polymer is preferably 30 ℃ or higher and 135 ℃ or lower. Use of a polymer having a Tg of 135 ℃ or less can suppress deterioration in line width or resolution when a focus position shifts during exposure. From the above-mentioned viewpoint, the Tg of the polymer is preferably 130 ℃ or lower, more preferably 120 ℃ or lower, and still more preferably 110 ℃ or lower. The use of a polymer having a Tg of 30 ℃ or higher can improve the edge melting resistance. From the above-mentioned viewpoint, the Tg of the polymer is preferably 40 ℃ or higher, more preferably 50 ℃ or higher, still more preferably 60 ℃ or higher, and particularly preferably 70 ℃ or higher.

The photosensitive layer may contain a polymer other than the polymer having an acid value of 30mgKOH/g or more, that is, other polymer. Examples of the other polymer include acrylic resins, styrene-acrylic copolymers (but the styrene content is not more than 40 mass%), polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamines, and polyalkylene glycols.

(polymerizable Compound)

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

Examples of the polymerizable group include groups having an ethylenically unsaturated group. Examples of the group having an ethylenically unsaturated group include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. Examples of the polymerizable group include a cationic polymerizable group. Examples of the cationically polymerizable group include an epoxy group and an oxetanyl group. Groups having an ethylenically unsaturated group are preferred, and acryloyl or methacryloyl groups are more preferred.

From the viewpoint of reducing development residue, the polymerizable compound preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2,2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane). Bisphenol a structures are preferred. Examples of the polymerizable compound having a bisphenol structure include an ethylenically unsaturated compound B1 having a bisphenol structure described later.

The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups (i.e., an ethylenically unsaturated compound), and more preferably a compound having 2 or more ethylenically unsaturated groups (i.e., a polyfunctional ethylenically unsaturated compound), from the viewpoint of more excellent photosensitivity of the photosensitive layer. As the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group is preferable. 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 even more preferably 2 or less, from the viewpoint of further excellent resolution and peelability.

The photosensitive layer preferably contains a compound having 2 or 3 ethylenically unsaturated groups, and more preferably contains a compound having 2 ethylenically unsaturated groups (i.e., a 2-functional ethylenically unsaturated compound), from the viewpoint that the photosensitive layer is more excellent in the balance of photosensitivity, resolution, and releasability. From the viewpoint of excellent peelability, the content of the 2-functional ethylenically unsaturated compound with respect to the total mass of the polymerizable compounds is preferably 20% by mass or more, more preferably more than 40% by mass, and still more preferably 55% by mass or more. The upper limit may be 100 mass%. That is, the polymerizable compounds may be all 2-functional ethylenically unsaturated compounds.

The photosensitive layer preferably contains a compound having an aromatic ring and 2 ethylenically unsaturated groups (hereinafter, sometimes referred to as "ethylenically unsaturated compound B1"). The ethylenically unsaturated compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule among the above ethylenically unsaturated compounds.

In the photosensitive layer, the proportion 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, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of more excellent resolution. From the viewpoint of peelability, the proportion 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, and particularly preferably 85% by mass or less.

Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The aromatic ring may have a substituent. The ethylenically unsaturated compound B1 may have 1 or 2 or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive layer by the developer. Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2,2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferable.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure. The bisphenol structure may have 2 polymerizable groups bonded to both ends thereof directly or through 1 or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of addition of alkyleneoxy groups to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of jp 2016-224162 a, and the contents described in this publication are incorporated in the present specification.

As the ethylenically unsaturated compound B1, a 2-functional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4- ((meth) acryloyloxyalkyl) phenyl) propane is more preferable. Examples of 2,2-bis (4- ((meth) acryloyloxyalkylpolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324m, hitachi Chemical Co., ltd. Manufactured), 2,2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (BPE-500, shift-Nakamura Chemical Co., ltd. Manufactured), 2,2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (esfa-3200 my, hitachi Chemical Co., ltd. Manufactured), 24 zxft 3924-bis (394- (methacryloyloxyethoxy) phenyl) propane (BPE-1300, n-35n-3534, n-bisphenol a, n-propylene-acrylate (napka-34, n-propylene-200, ltd. Manufactured), and naxm-n-propylene-bis (4- (methacryloyloxyethoxyethoxy) propane (FA-3534, ltd. Manufactured).

The ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis) from the viewpoints of line width variation during leaving, line width variation at development temperature, and sensitivity.

[ chemical formula 1]

In the formula (Bis), R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ B is C ₃ H ₆ ，n ₁ And n ₃ Each independently is an integer of 1 to 39, and n ₁ +n ₃ Is an integer of 2 to 40, n ₂ And n ₄ Each independently is an integer of 0 to 29, and n ₂ +n ₄ Is an integer of 0 to 30, the arrangement of the repeating units of- (A-O) -and- (B-O) -may be random, it may be a block. Further, in the case of a block, either one of- (A-O) -and- (B-O) -may be on the bisphenol structure side. In a mode, n ₁ +n ₂ +n _a +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 12. And, n ₂ +n ₄ 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 or two or more ethylenically unsaturated compounds B1. From the viewpoint of more excellent resolution, the content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10 mass% or more, and more preferably 20 mass% or more, with respect to 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 an ethylenically unsaturated compound other than the 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 thereof include a compound having 1 ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.

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

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate 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.

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. Commercially available urethane di (meth) acrylate products include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., ltd.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide-modified products thereof. "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate. In one aspect, the photosensitive layer preferably contains the above ethylenically unsaturated compound B1 and an ethylenically unsaturated compound having 3 or more functions, and more preferably contains the above ethylenically unsaturated compound B1 and two or more ethylenically unsaturated compounds having 3 or more functions. With respect to the mass ratio of the ethylenically unsaturated compound B1 to the ethylenically unsaturated compound having 3 or more functions, it is preferable (total mass of the ethylenically unsaturated compounds B1): (total mass of ethylenically unsaturated compounds having 3 or more functions) = 1: 1 to 5:1, more preferably 1.2: 1 to 4: 1, and still more preferably 1.5: 1 to 3: 1. In one embodiment, the photosensitive layer preferably contains the ethylenically unsaturated compound B1 and two or more 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the 3-or more-functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., manufactured by Ltd., KAYARAD (registered trademark) DPCA-20, manufactured by Ltd., A-9300-1CL, manufactured by Ltd.), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., manufactured by Ltd., KAYARAD RP-1040, manufactured by Ltd., shin-Nakamura Chemical Co., manufactured by Ltd., ATM-35E and A-9300, manufactured by DAICEL-ALLNEX LTD., manufactured by EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (e.g., shin-Nakamura Chemical Co., manufactured by Ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (TOAGCO., manufactured by TOAGCO., TOONEI., manufactured by Ltd., LTM 520, manufactured by LTM).

As the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of jp-a-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, alkali-soluble resin) is preferably 1.0 or less, more preferably 0.9 or less, and still more preferably 0.5 to 0.9.

The ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth) acrylic compound, and more preferably contains a (meth) acrylate compound, from the viewpoint of curability and resolution. From the viewpoint of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive layer more preferably contains a (meth) acrylic compound, and the content of the acrylic compound is 60 mass% or less with respect to the total mass of the (meth) acrylic compounds contained in the photosensitive layer.

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

The photosensitive layer may contain one or two or more polymerizable compounds. The content of the polymerizable compound in the photosensitive layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 20 to 50% by mass, based on the total mass of the photosensitive layer.

Polymerization initiators

The photosensitive layer (preferably, the negative photosensitive layer) preferably contains a polymerization initiator. The type of the polymerization initiator may be selected depending on the form of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.

The photosensitive layer (preferably, the negative photosensitive layer) preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that is polymerized by an active light such as ultraviolet light, visible light, and X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

Examples of the photo radical polymerization initiator include a compound having an α -aminoalkylphenone structure, a compound having an N-phenylglycine structure, a compound having an oxime ester structure, a compound having an a-hydroxyalkylphenone structure, a compound having an acylphosphine oxide structure, and a compound having a triarylimidazole structure. Examples of a preferable photo radical polymerization initiator include a compound having an oxime ester structure, a compound having an α -hydroxyalkylphenone structure, a compound having an acylphosphine oxide structure, and a compound having a triarylimidazole structure.

From the viewpoint of photosensitivity, visibility of exposed portions and unexposed portions, and resolution, the photosensitive layer (preferably, a negative photosensitive layer) preferably contains at least one selected from 2,4,5-triarylimidazole dimer and a derivative thereof as a photo radical polymerization initiator. In addition, 22,4,5-triarylimidazole structures in 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of 2,4,5-triarylimidazole dimer derivatives include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer.

As the photo radical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of japanese patent application laid-open No. 2011-95716 and paragraphs 0064 to 0081 of japanese patent application laid-open No. 2015-14783 can be used.

Examples of the photo-radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p '-dimethoxybenzyl) anise ester, 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 Co., ltd.), omnirad651 and 369 (trade name, manufactured by IGM Resins B.V., ltd.), and bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1,2' -biimidazole (Tokyo Industry Co., ltd.).

Commercially available products of the photo radical polymerization initiator include, for example, 1- [4- (phenylthio) phenyl ] -1,2-octanedione-2- (0-benzoyloxime) (trade name, IRGACURE (registered trade name) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (0-acetyloxime) (trade name, IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (trade name: omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: omnirad 907, IGM Resins B.V.), 2-hydroxy-1- [4- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name, 2-methylbenzoyl } -1-2-amino) -2- (4-morpholino) benzyl } -1-2- (2-methylbenzoyl) ketone (trade name, manufactured by Omnirad), 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, igm Resins b.v.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: omnirad651, igm Resins b.v., manufactured), 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, igm Resins b.v.), an oxime ester-based photopolymerization initiator (trade name: lunar 6, dksh Japan k.k.), 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbenzimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM manufactured by Hampford corporation) and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd., manufactured), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, manufactured by ltd., changzhou Tronly New electronic Materials CO), 1,2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, changzzhou Tronly New Electronic Materials CO, ltd. Manufactured) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (0-benzoyloxime) (trade name: TR-PBG-391, changzhou Tronly New Electronic Materials C0, LTD.).

The photo cation polymerization initiator (photo acid generator) is a compound that generates an acid upon receiving an activating light. The photo cation polymerization initiator is preferably a compound which generates an acid by being irradiated with an activating light having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure is not limited. The photo cation polymerization initiator that is not directly sensitive to the activation light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound that generates an acid by being sensitive to the activation light having a wavelength of 300nm or more.

As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photo cationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photo cationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of pKa is not particularly limited, but is preferably at least-10.0.

Examples of the photo cation polymerization initiator include ionic photo cation polymerization initiators and nonionic photo cation polymerization initiators. Examples of the ionic photo-cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photo-cationic polymerization initiator, the ionic photo-cationic polymerization initiators described in paragraphs 0114 to 0133 of jp 2014-85643 a can be used. Examples of the nonionic photo cation polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazine, diazomethane compound and imide sulfonate compound, compounds described in paragraphs 0083 to 0088 of jp 2011-221494 a can be used. As the oxime sulfonate compound, a compound described in paragraphs 0084 to 0088 of international publication No. 2018/179640 can be used.

The photosensitive layer may contain one or two or more 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. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, with respect to the total mass of the photosensitive layer.

Pigments-

The photosensitive layer preferably contains a dye, and more preferably contains a dye (also simply referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and having a maximum absorption wavelength that changes by an acid, an alkali, or a radical, from the viewpoint of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution. When the photosensitive layer contains the pigment N, although the detailed mechanism is not clear, the adhesion with the adjacent layers (for example, the temporary support and the intermediate layer) is improved, and the resolution is further excellent.

In the present invention, the "change in the maximum absorption wavelength of the dye by an acid, an alkali, or a radical" may mean any of a method in which the dye in a colored state is decolored by an acid, an alkali, or a radical, a method in which the dye in a decolored state is colored by an acid, an alkali, or a radical, and a method in which the dye in a colored state is changed to a colored state of another color. Specifically, the dye N may be a compound that develops color when it changes from a decolored state by exposure to light, or may be a compound that develops color when it changes from a colored state by exposure to light. In this case, the dye may be one that changes its color development or decoloration state by generating and acting on an acid, a base, or a radical in the photosensitive layer upon exposure to light, or may be one that changes its color development or decoloration state by changing its state (for example, pH) in the photosensitive layer with an acid, a base, or a radical. Further, the dye may be one which changes its color development or decoloration state by being directly stimulated by an acid, an alkali, or a radical without exposure.

Among them, the pigment N is preferably a pigment whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a pigment whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.

From the viewpoint of visibility and resolution of the exposed portion and the unexposed portion, the photosensitive layer preferably contains a dye whose maximum absorption wavelength is changed by a radical as both the dye N and the photo radical polymerization initiator.

The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, from the viewpoint of visibility of the exposed portion and the unexposed portion.

Examples of the color developing mechanism of the pigment N in the present invention include a method in which a radical reactive pigment, an acid reactive pigment, or a base reactive pigment (for example, leuco pigment) is developed by adding a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator), or a photo base generator to a photosensitive layer and exposing the resultant mixture to light, and then, a radical, an acid, or a base is generated by the photo radical polymerization initiator, the photo cation polymerization initiator, or the photo base generator.

From the viewpoint of visibility of the exposed portion and the non-exposed portion, the maximum absorption wavelength in the wavelength range of 400nm to 780nm in color development of the dye N is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm. The dye N may have only the maximum absorption wavelength in the wavelength range of 400nm to 780nm in 1 color development, or may have 2 or more. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the pigment N is determined by using a spectrophotometer under an atmospheric environment: UV3100 (manufactured by Shim adzu Corporation) by measuring the transmission spectrum of a solution containing a dye N (liquid temperature 25 ℃) in the range of 400nm to 780nm and detecting a wavelength at which the intensity of light is extremely small (maximum absorption wavelength).

Examples of the dye that develops color or decolors by exposure include colorless compounds. Examples of the dye decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. The dye N is preferably a colorless compound from the viewpoint of visibility of an exposed portion and a non-exposed portion.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolylphthalein skeleton (indolylphthalein-based dye), and a colorless compound having a leuco auramine skeleton (leuco auramine-based dye). Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.

The colorless compound preferably has a lactone ring, a sulfinyl lactone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sulfinyl lactone ring or sultone ring of the colorless compound can be reacted with a radical generated by the photo radical polymerization initiator or an acid generated by the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolor the colorless compound, or the colorless compound can be changed into an open ring state and develop color. The colorless compound is preferably a compound having a lactone ring, a sulfinolactone ring, or a sultone ring and developing a color by radical or acid ring opening, and more preferably a compound having a lactone ring and developing a color by radical or acid ring opening.

Examples of the dye N include dyes. Examples of the dye include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metanilla yellow (metanil yellow), thymolsulfonephthalein (thymol sulfonhalein), xylenol blue (xylenol blue), methyl orange, p-methyl red, congo red, benzopurpurin (benzopurpurine) 4B, α -naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parafuchsin (parafuchsin), victoria pure blue (victoria blue) -naphthalene sulfonate, victoria pure blue h (bodoya co, bodoya Chemical, ltd. Manufacture), oil blue #603 (origin Chemical Industries co., ltd., manufactured), oil pink #312 (Orient Chemical Industries co., ltd., manufactured), oil red 5B (Orient Chemical Industries co., manufactured by ltd., manufactured), oil scarlet (oil scarlet) #308 (Orient Chemical Industries co., manufactured by ltd., manufactured), oil red OG (Orient Chemical Industries co., manufactured by ltd., manufactured), oil red RR (Orient Chemical Industries co., manufactured by ltd., manufactured), oil green #502 (Orient Chemical Industries co., manufactured by ltd., manufactured), 8978 zft 8978 red (spilon red) BEH special (hodoga Chemical co., manufactured by ltd., manufactured), cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-diethylamino-p-phenylimino, 2-p-naphthylquinone, 4-carboxyaminobenzoquinone, and naphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Examples of the dye N include a colorless compound. Examples of the colorless compound include p, p' -hexamethyltriaminotriphenylmethane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy Co., ltd.), crystal violet lactone, malachite green lactone, benzoyl leuco methylene Blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluoran, 3,6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylanilino, 3- (N, N-diethylamino) -6-methyl-7-chloroanilino, 3- (N, N-diethylamino) -6-methyl-7-fluoroanilino, 4- (N, N-diethylamino) -6-diethylamino-7-fluoroanilino, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7,8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-dimethylanilinofluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalein, 3,3-bis (1-N-butyl-2-methylindol-3-yl) phthalein, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalein, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalein, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalein, and 3',6' -bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye which develops color by a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution.

As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate is preferable.

The photosensitive layer may contain one or two or more kinds of pigments. The content of the coloring matter is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, based on the total mass of the photosensitive layer, from the viewpoints of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution. The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 to 10 mass%, even more preferably 0.1 to 5 mass%, and particularly preferably 0.1 to 1 mass% with respect to the total mass of the photosensitive layer, from the viewpoints of the visibility of exposed portions and unexposed portions, the pattern visibility after development, and the resolution.

The content of the pigment N is a content of the pigment when all the pigments N contained in the photosensitive layer are brought into a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example. Two solutions were prepared by dissolving 0.001g or 0.01g of a coloring matter in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photoradical polymerization initiator (trade name, irgacure OXE01, manufactured by BASF) was added, and 365nm light was irradiated, thereby generating bovine radicals and bringing all the pigments into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV 3100, manufactured by Shimadzu Corporation) under an atmospheric environment, and a calibration curve was prepared. Next, the absorbance of the solution in which all the coloring matters were developed was measured by the same method as described above except that the photosensitive layer 3g was dissolved in methyl ethyl ketone instead of the coloring matters. The content of the pigment contained in the photosensitive layer was calculated from the absorbance of the obtained solution containing the photosensitive layer based on the calibration curve.

Thermal crosslinkable compounds

The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. The thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound but treated as a thermally crosslinkable compound.

Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among them, blocked isocyanate compounds are preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when the alkali-soluble resin and/or the ethylenically unsaturated compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film is lowered, and the function when the film obtained by curing the photosensitive layer is used as a protective film tends to be enhanced. The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, more preferably 130 to 150 ℃. The dissociation temperature of the blocked isocyanate means "the temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC 6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ], an oxime compound (a compound having a structure represented by-C (= N-OH) -in a molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime). Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ preferably contains an oxime compound, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesion to the transfer target, and the like. The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate to protect it. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the viewpoint that the dissociation temperature is more easily set in a preferable range and the development residue is easily reduced than those of compounds having no oxime structure.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferred. Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, or a styryl group, and a group having an epoxy group such as a glycidyl group. Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.

As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (manufactured by SHOWA DENKO K., supra), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation). Further, as the blocked isocyanate compound, a compound having the following structure can also be used.

[ chemical formula 2]

The photosensitive layer may contain one or two or more thermally crosslinkable compounds. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, with respect to the total mass of the photosensitive layer.

Other ingredients-

The photosensitive layer may contain other components. Examples of the other components include a polymerization inhibitor, a surfactant, a sensitizer, and various additives. The photosensitive layer may contain one or two or more other components.

The photosensitive layer preferably contains a polymerization inhibitor. When the photosensitive layer contains a polymerization inhibitor, the line width of the resist pattern can be prevented from varying with the lapse of time from the end of the exposure step to the start of the next step. Examples of the polymerization inhibitor include radical polymerization inhibitors. Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other radical polymerization inhibitors include naphthylamine, cuprous chloride, aluminum N-nitrosophenylhydroxylamine salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive layer, an aluminum salt of N-nitrosophenylhydroxylamine is preferably used as a radical polymerization inhibitor.

The photosensitive layer may contain one or two or more radical polymerization inhibitors. When the photosensitive layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.02 to 2.0% by mass, based on the total mass of the photosensitive layer. The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compounds.

The photosensitive layer may contain a surfactant. Examples of the surfactant include surfactants described in paragraphs 0017 of japanese patent No. 4502784 and paragraphs 0060 to 0071 of japanese patent application laid-open No. 2009-237362. Further, as the surfactant, a nonionic surfactant, a fluorine surfactant, or a silicone surfactant is preferable.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylated and propoxylated compounds thereof (e.g., glycerin propoxylate, glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Specific examples thereof include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (hereinafter, BASF Corporation), tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (hereinafter, BASF Corporation), solsperse (trade name) 20000 (hereinafter, lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (hereinafter, FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-1105, D-6112-W, D-6315 (hereinafter, takemoto Oil & Fat Co., ltd.), ole 1010, surfynol 104, ni400, 440 (hereinafter, lssin Chemical Co., ltd.).

As a commercially available product of the fluorine-based surfactant, for example, MEGAFACE (trade name) 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-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-41, EXP.MFS-603, MFS-177, EXP.MFS-603, and F-177R-41-LM, R-01, R-40-LM, RS-13, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation, supra), fluorad (trade name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, sur Chuan on (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc., supra), polyFox (trade name) PF636, PF656, PF6320, 6520, PF7002 (manufactured by OMVA Solutions Inc.) PF7002, ftergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by Neos Company Limited, supra), U-120E (Uni-chem Co., ltd.), and the like.

Further, the fluorine-based surfactant can also preferably use an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, and the functional group containing a fluorine atom is partially cleaved when heat is applied, thereby volatilizing the fluorine atom. Examples of such fluorine-based surfactants include MEGAFACE DS series (chemical industry journal (2016, 22/D), and History Industrial News (2016, 2, 23/D)) manufactured by DIC Corp corporation, such as MEGAFACE DS-21.

Further, as the fluorine-based surfactant, 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 is also preferably used.

As the fluorine-based surfactant, a terminal-capped polymer can also be used. The fluorine-containing surfactant can also preferably use a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy 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 (manufactured by DIC Corporation).

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 compatibility, it is preferable to use a substitute material for perfluorooctanoic acid (PFOA) or perfluorooctane sulfonic acid (PFOS) as the fluorine-based surfactant.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals thereof. <xnotran> , EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 ( DIC Corporation ), DOWSIL () 8032ADDITIVE, toray Silicone DC3PA, toray Silicone SH7PA, toray Silicone DC11PA, toray Silicone SH21PA, toray Silicone SH28PA, toray Silicone SH29PA, toray Silicone SH30PA, toray Silicone SH8400 ( Dow Corning Toray Co., ltd. ) X-22-4952, X-22-4272, X-22-6266, KF-351 5754 zxft 5754 354 3252 zxft 3252-355 3532 zxft 3532-945, 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-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 ( Shin-Etsu Chemical Co., ltd. ), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 ( Momentive Performance Materials Inc. ), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315 3425 zxft 3425 331, BYK333, BYK345, BYK347, BYK348, BYK349, </xnotran> BYK370, BYK377, BYK378 (BYK Chemie, inc., mentioned above), and the like.

The photosensitive layer may contain one or two or more surfactants. The content of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the photosensitive layer.

The photosensitive layer preferably contains a sensitizer. The type of the sensitizer is not limited, and known sensitizers, dyes, and pigments can be used. Examples of preferable sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, oxyanthrone compounds, thioxanthone (thioxanthone) compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive layer may contain one or two or more 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 a light source and improving the curing rate by the balance of the polymerization rate and the chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive layer.

The photosensitive layer may contain known additives as needed. Examples of the additive include a plasticizer, a heterocyclic compound, a benzotriazole, a carboxybenzotriazole, a pyridine (e.g., isonicotinamide), a purine base (e.g., adenine), and a solvent. The photosensitive layer may contain one or two or more additives.

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

Examples of the carboxybenzotriazole include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. As the carboxybenzotriazole, for example, a commercially available product such as CBT-1 (johaku CHEMICAL co., ltd., trade name) can be used.

The total content of the benzotriazole and carboxybenzotriazole is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive layer. From the viewpoint of imparting storage stability to the photosensitive layer, the content is preferably 0.01 mass% or more. On the other hand, from the viewpoint of suppressing discoloration of the dye while maintaining sensitivity, the content is preferably 3% by mass or less.

The photosensitive layer may include at least one selected from a plasticizer and a heterocyclic compound. 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 include a solvent. When a photosensitive layer is formed from a photosensitive composition containing a solvent, the solvent may remain in the photosensitive layer.

The photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid enhancers, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents.

Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of japanese patent application laid-open No. 2014-85643, the contents of which are incorporated in the present specification.

The photosensitive layer may contain a predetermined amount of impurities. Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the halide ions, sodium ions, and potassium ions are preferably contained in the following amounts because they are easily mixed as impurities.

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

As a method of setting the impurity within the above range, a method of selecting a raw material having a small content of the impurity as a raw material of the composition, preventing the impurity from being mixed and removing the impurity by washing when the photosensitive layer is manufactured, may be mentioned. By this method, the amount of impurities can be set within the above range.

The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

Preferably, the photosensitive layer contains a small amount of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of these compounds with respect to the total mass of the photosensitive layer is preferably 100ppm by mass or less, more preferably 20ppm by mass or less, and still more preferably 4ppm by mass or less. The lower limit may be 10ppb or more, and may be 100ppb or more, based on the total mass of the photosensitive layer. These compounds can be contained in the same manner as the impurities of the above-mentioned metals. Further, the amount can be determined by a known measurement method.

From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%.

The photosensitive layer may contain a residual monomer corresponding to each structural unit of the alkali-soluble resin. From the viewpoint of patterning property and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less, with respect to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more. From the viewpoint of patterning property and reliability, the content of the residual monomer in each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less, with respect to the total mass of the photosensitive layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the high molecular reaction is also preferably set within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range.

The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

The photosensitive layer may be a colored layer containing a pigment. The pigment may be appropriately selected depending on the desired hue, and may be selected from a black pigment, a white pigment, and a color pigment other than black and white. Among them, when forming a black pattern, it is preferable to select a black pigment as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, or the like) can be appropriately selected within a range not impairing the effects of the present invention. Among them, from the viewpoint of optical density, examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, graphite, and the like, and carbon black is particularly preferable. As the carbon black, carbon black having a surface at least a part of which is coated with a resin is preferable from the viewpoint of surface resistance. From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 to 0.1 μm, and more preferably 0.01 to 0.08 μm in number average particle diameter. The particle diameter refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the circle having the same area as the area of the pigment particle is considered, and the number average particle diameter is an average value obtained by determining the particle diameter for any 100 particles and averaging the determined 100 particle diameters.

As the pigment other than the black pigment, the white pigments described in paragraphs 0015 and 0114 of japanese patent application laid-open No. 2005-007765 can be used. Specifically, among the white pigments, the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and still more preferably titanium oxide. 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 the titanium oxide may be subjected to a silica treatment, an alumina treatment, a titania treatment, a zirconia treatment, or an organic matter treatment, or may be subjected to two or more kinds of treatments. This suppresses the catalytic activity of titanium oxide, and improves the heat resistance, light fading, and the like. From the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of the alumina treatment and the zirconia treatment is preferable as the surface treatment of the surface of the titanium oxide, and particularly both the alumina treatment and the zirconia treatment are preferable.

When the photosensitive layer is a colored layer, it is also preferable that the photosensitive layer further contains a color pigment other than the black pigment and the white pigment from the viewpoint of transferability. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. Examples of the Color pigment include victoria pure blue BO (Color Index) (c.i.: below) 42595, auramine (c.i.41000), fat black (fat black) HB (c.i.26150), mordant yellow (monolithit 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), hursbam red (permanent red) ESB (c.i. pigment violet 19), permanent red (permanent ruby) FBH (c.i. pigment red 11), sterling pink (permanent pink) B spepra (surura) (c.i. pigment red 149), mon red (red) B, c.i. pigment red 149, c.i. pigment red 215, c.i. pigment red (c.i. pigment red) c.i.7, c.i. pigment red 15, c.i. pigment red (c.i. pigment red) 15, c.i. pigment red 215, c.i. pigment red (c.i. pigment red) 15, c.i. pigment red: 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, and the like. Among them, c.i. pigment red 177 is preferable.

When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, and further … is preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, with respect to the total mass of the photosensitive layer.

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

In the method for producing a photosensitive layer containing a black pigment, the black pigment (preferably, carbon black) is preferably introduced into a photosensitive composition described later in the form of a pigment dispersion liquid. The dispersion liquid may be 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 dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle is a medium portion for dispersing the pigment when the pigment dispersion liquid is prepared, and is liquid, and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component. The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, roll mill, attritor, super mill, dissolver, homomixer, and sand mill. Further, the fine grinding may be performed by mechanical grinding and utilizing a frictional force. As for the dispersing machine and the fine pulverization, reference can be made to the description of "pigment dictionary" (manufactured by shanghan, first edition, book store, 2000, pages 438 and 310).

The acid value of the photosensitive layer is preferably 15mg/KOH or more, and more preferably 40mg KOH/g or more. When the acid value of the photosensitive layer is 15mg/KOH or more, the adhesion between the transfer film and the base material used as the material of the vapor deposition mask is improved. The acid value of the photosensitive layer is preferably 200mg/KOH or less, more preferably 150mgKOH/g or less, and still more preferably 135mg/KOH or less. If the acid value of the photosensitive layer is 200mg/KOH or less, peeling of the photosensitive layer forming the resist pattern or a cured product of the photosensitive layer during development 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 modulus of the photosensitive layer at 90 ℃ is preferably 1.0X 10 ⁷ Pa or less, more preferably 1.0X 10 ⁶ Pa or less, more preferably 1.0X 10 ⁵ Pa or less. If the storage modulus of the photosensitive layer at 90 ℃ is 1.0X 10 ⁷ Pa or less improves the adhesion between the transfer film and the base material used as the material of the vapor deposition mask. The storage modulus of the photosensitive layer at 90 ℃ is preferably 1.0X 10 ² Pa or more, more preferably 1.0X 10 ³ Pa or more, more preferably 1.0X 10 ⁴ Pa or above. If the storage modulus of the photosensitive layer at 90 ℃ is 1.0X 10 ² When Pa is larger than this, the patterning property is improved. The storage modulus of the photosensitive layer is adjusted by, for example, the composition of the photosensitive layer. The storage modulus of the photosensitive layer is adjusted by, for example, the type of polymer, the type of polymerizable compound, the ratio of the content of polymerizable compound to the content of polymer, and the type of additive.

In the present invention, the storage modulus is measured using a rheometer (for example, rheometer DHR-2 manufactured by TA Instruments), a parallel plate of 20 mm. Phi. And a Peltier plate (Gap: about 0.5 mm) under the following conditions.

(1) Temperature: 20-125 DEG C

(2) Temperature rise rate: 5 deg.C/min

(3) Frequency: 1Hz

(4) Strain: 0.5 percent

The complex viscosity of the photosensitive layer at 30 ℃ is preferably 1.0X 10 ³ Pa or more, more preferably 1.0X 10 ⁴ Pa or more, and more preferably 1.0X 10 ⁵ Pa or above. If the complex viscosity of the photosensitive layer at 30 ℃ is 1.0X 10 ³ Pa or more can prevent or reduce 21085of the photosensitive layer or the cured product of the photosensitive layer on which the resist pattern is formed in the developing process. The complex viscosity of the photosensitive layer at 30 ℃ is preferably 1.0X 10 ⁹ Pa or less, more preferably 1.0X 10 ⁸ Pa or less, more preferably 1.0X 10 ⁷ Pa or less. If the complex viscosity of the photosensitive layer at 30 ℃ is 1.0X 10 ⁹ Pa or less improves the adhesion between the transfer film and the base material used as the material of the vapor deposition mask.

In the present invention, the complex viscosity is measured using a rheometer (for example, rheometer DHR-2 manufactured by TA Instruments), a parallel plate of 20mm and a Peltier plate (Gap: about 0.5 mm) under the following conditions.

(1) Temperature: 20-125 DEG C

(2) Temperature rise rate: 5 deg.C/min

(3) Frequency: 1Hz

(4) Strain: 0.5 percent

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 0.5 μm or more, and more preferably 1 μm or more. The average thickness of the photosensitive layer was calculated by the arithmetic mean of the thicknesses at 5 points measured in cross-sectional observation using a 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%, more preferably 15% to 35%, and still more preferably 20% to 30%, from the viewpoint of resolution and concave following property.

From the viewpoint of adhesiveness, the transmittance of the photosensitive layer for light having a wavelength of 365nm 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 formed by preparing a photosensitive composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a solvent, applying the photosensitive composition on an object such as a temporary support, and drying the coating film of the photosensitive composition. The photosensitive layer may be formed by applying a photosensitive composition to a protective film described later and drying the applied photosensitive composition.

Examples of the photosensitive composition used for forming the photosensitive layer include compositions containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, any of the above components, and a solvent. In order to adjust the viscosity of the photosensitive composition so that the photosensitive layer is easily formed, the photosensitive composition preferably contains a solvent.

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

The photosensitive composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these solvents, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least three selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent is even more preferable.

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

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

As the solvent, a solvent described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and a solvent described in paragraph 0014 of japanese patent application laid-open No. 2018-177889 can be used, and these are incorporated in the present specification.

The photosensitive composition may contain one or two or more solvents. The content of the solvent in coating the photosensitive composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive composition.

The method for producing the photosensitive composition is not particularly limited, and examples thereof include a method for producing a photosensitive composition by preparing a solution in which each component is dissolved in the solvent in advance and mixing the obtained solutions at a predetermined ratio. The photosensitive composition is preferably filtered using a filter having a pore size of 0.2 to 30 μm before the photosensitive layer is formed.

The method for applying the photosensitive composition is not particularly limited, and the photosensitive composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

The coating film of the photosensitive composition is preferably dried by heating or drying under reduced pressure. In addition, in the present specification, "drying" means removing at least a part of a solvent contained in a composition. Examples of the drying method include natural drying, heat drying, and drying under reduced pressure. The above methods can be applied singly or in combination. The drying temperature is preferably 80 ℃ or higher, more preferably 90 ℃ or higher. The upper limit thereof is preferably 130 ℃ or lower, more preferably 120 ℃ or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit value is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

[ intermediate layer ]

The transfer film preferably includes an intermediate layer. The intermediate layer can suppress air bubbles from entering between the transfer layer and the object in the bonding of the transfer film and the object, and can improve the adhesion between the transfer layer and the object. The intermediate layer can also improve the following property of the transfer layer to an object having a rough surface. The intermediate layer is preferably disposed between the temporary support and the photosensitive layer. That is, the transfer film preferably includes a temporary support, an intermediate layer, and a photosensitive layer in this order.

The structure of the intermediate layer may be a single-layer structure or a multi-layer structure. Examples of the intermediate layer include a thermoplastic resin layer and a water-soluble resin layer. When the intermediate layer includes both the thermoplastic resin layer and the water-soluble resin layer, the transfer film preferably includes the temporary support, the thermoplastic resin layer, the water-soluble resin layer, and the photosensitive layer in this order. Further, as the intermediate layer, for example, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese patent laid-open No. 5-72724 can be cited. If the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, the time load of the exposure apparatus is reduced, and the productivity is improved.

(thermoplastic resin layer)

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin. Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer. The acrylic resin refers to a resin having at least one structural unit selected from a structural unit derived from (meth) acrylic acid, a structural unit derived from a (meth) acrylate ester, and a structural unit derived from a (meth) acrylic acid amide. The acrylic resin preferably contains a total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide in an amount of 50 mass% or more based on the total mass of the acrylic resin.

The total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic ester is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

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 phosphate group and a phosphonic acid group, and a carboxyl group is preferable.

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

The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins. Examples thereof include an alkali-soluble resin which is a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more among the polymers described in paragraph 0025 of Japanese patent application laid-open No. 2011-95716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more among the alkali-soluble resins described in paragraphs 0053 to 0068 of Japanese patent application laid-open No. 2016-224162.

The copolymerization ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

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 adhesion to an adjacent layer.

The alkali soluble resin may have a reactive group. The reactive group may be any group capable of polymerization, for example, a group capable of addition polymerization, condensation polymerization or polyaddition, and examples thereof include an ethylenically unsaturated group; a condensation polymerizable group such as a hydroxyl group or a carboxyl group; polyaddition-reactive groups such as epoxy groups, (blocked) isocyanate groups and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 1 ten thousand to 10 ten thousand, and further preferably 2 ten thousand to 5 ten thousand.

The thermoplastic resin layer may include one or two or more alkali-soluble resins. From the viewpoint of developability and adhesion to an adjacent layer, the content of the alkali-soluble resin is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 70 mass% with respect to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer preferably contains a coloring matter (also simply referred to as "coloring matter B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical. The preferred embodiment of the dye B is the same as that of the dye N except for the points described below.

From the viewpoint of visibility and resolution of the exposed portion and the unexposed portion, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid. From the viewpoint of visibility and resolution of the exposed portion and the unexposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength as the dye B is changed by an acid and a compound which generates an acid by light, which will be described later.

The thermoplastic resin layer may contain one or two or more kinds of the pigment B. The content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed portion and the unexposed portion. The content of the coloring matter B means the content of the coloring matter when all the coloring matter B contained in the thermoplastic resin layer is brought into a colored state. Hereinafter, a method for quantifying the content of the pigment B will be described by taking a pigment that develops color by a radical as an example. Two solutions were prepared in which 0.001g or 0.01g of a coloring matter was dissolved in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photoradical polymerization initiator (trade name, irgacure OXE01, manufactured by BASF) was added, and 365nm light was irradiated to generate radicals, thereby bringing all the dyes into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV 3100, manufactured by Shimadzu Corporation) under an atmospheric environment, and a calibration curve was prepared. Next, the absorbance of the solution in which all the coloring matters were developed was measured by the same method as described above except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the coloring matters. The amount of the coloring matter contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as "compound C"). The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an activating light such as ultraviolet light or visible light. As the compound C, a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator) can be used. Among them, a photoacid generator is preferable.

From the viewpoint of resolution, the thermoplastic resin layer contains a preferable photoacid generator. The photo acid generator may be a photo cation polymerization initiator that the photosensitive layer may contain, and is preferably the same except for the points described below.

The photoacid generator preferably contains at least one compound selected from an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[ chemical formula 3]

The thermoplastic resin layer may contain a photo radical polymerization initiator (photo radical polymerization initiator). The photo radical polymerization initiator may be a photo radical polymerization initiator that the photosensitive layer may contain, and the same is preferred.

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 thereof include 2-nitrobenzylcyclohexylcyclohexyl carbamate, triphenylmethanol, O-carbamoylhydroxyamide, 0-carbamoyloxime, { [ (2,6-dinitrobenzyl) oxy ] carbonyl } cyclohexylamine, bis { [ (2-nitrobenzyl) oxy ] carbonyl } hexane-1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammocobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2,6-dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -32 zxft Dihydropyridine, and 343862-dimethyl-5732 zxft 4232-dinitro-4234-dinitro-4232-zxft 4234-dinitro-4264-dihydropyridine.

The thermoplastic resin layer may contain one or two or more compounds C. The content of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of the exposed portion and the unexposed portion.

The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to an adjacent layer, and developability.

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

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

In addition, the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound. Examples of the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compounds described as the ethylenically unsaturated compounds contained in the photosensitive layer.

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

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound is preferably not polymerized in an exposed portion after exposure from the viewpoint of adhesion to an adjacent layer.

From the viewpoint of resolution, adhesion to an adjacent layer, and developability, the (meth) acrylate compound used as the plasticizer is preferably a polyfunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule.

Further, as the (meth) acrylate compound used as the plasticizer, a (meth) acrylate compound having an acid group or an amine ester (meth) acrylate compound is also preferable.

The thermoplastic resin layer may contain one or two or more plasticizers. From the viewpoint of resolution, adhesion to an adjacent layer, and developability, the content of the plasticizer is preferably 1 to 70 mass%, more preferably 10 to 60 mass%, and still more preferably 20 to 50 mass% with respect to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. The surfactant may be a surfactant that the photosensitive layer may contain, and the same is preferred. The thermoplastic resin layer may contain one or two or more surfactants. The content of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include sensitizers that the photosensitive layer may contain. The thermoplastic resin layer may contain one or two or more kinds of sensitizers. The content of the sensitizer can be appropriately selected according to the purpose, but is preferably in the range of 0.01 to 5 mass%, more preferably in the range of 0.05 to 1 mass%, relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to a light source and the visibility of exposed portions and non-exposed portions.

The thermoplastic resin layer may contain known additives as needed, in addition to the above components. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of japanese patent application laid-open No. 2014-85643, and the contents described in this publication are incorporated in the present specification.

The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to an adjacent layer. 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 by the arithmetic mean of the thicknesses at 5 points measured in the cross-sectional observation using a Scanning Electron Microscope (SEM).

The method for producing the thermoplastic resin layer is not limited as long as the target thermoplastic resin layer can be obtained. Examples of the method for producing the thermoplastic resin layer include a method in which a thermoplastic resin composition containing the above components and a solvent is prepared, the thermoplastic composition is applied to an object such as a temporary support, and a coating film of the thermoplastic resin composition is dried. In order to adjust the viscosity of the thermoplastic resin composition so that the thermoplastic resin layer is easily formed, the thermoplastic resin composition preferably 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. The solvent contained in the thermoplastic resin composition includes solvents that the photosensitive composition may contain, and the same is preferred. The thermoplastic resin composition may contain one or two or more solvents. The content of the solvent in coating the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the above-described method for preparing the photosensitive composition and the method for forming the photosensitive layer. For example, a thermoplastic resin layer is formed by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the solvent in advance, mixing the obtained solutions at a predetermined ratio to prepare a thermoplastic resin composition, applying the obtained thermoplastic resin composition to the surface of the temporary support, and drying the coating film of the thermoplastic resin composition. Further, after the photosensitive layer and the water-soluble resin layer are formed on the protective film described later, the thermoplastic resin layer may be formed on the water-soluble resin layer.

(Water-soluble resin layer)

The water-soluble resin layer preferably contains a water-soluble resin. Examples of the water-soluble resin include resins such as polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. From the viewpoint of suppressing the mixing of components between the plurality of layers, the water-soluble resin contained in the water-soluble resin layer is preferably a resin different from both the polymer contained in the photosensitive layer and the thermoplastic resin (for example, alkali-soluble resin) contained in the thermoplastic resin layer.

From the viewpoint of oxygen barrier properties and suppression of mixing of components during application of multiple layers and during storage after application, the water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

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

The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total mass of the water-soluble resin layer, from the viewpoints of oxygen barrier properties and mixing of components at the time of coating a plurality of layers and at the time of storage after coating.

The water-soluble resin layer may contain an additive such as a surfactant, if necessary.

The average thickness of the water-soluble resin layer is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. This is because, when the thickness of the water-soluble resin layer is within the above range, the mixing of components at the time of coating a plurality of layers and at the time of storage after coating can be suppressed without lowering the oxygen barrier property, and the increase of the removal time of the water-soluble resin layer at the time of development can be suppressed. The average thickness of the water-soluble resin layer was calculated by the arithmetic average of the thicknesses at 5 points measured in the 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 formed, for example, by preparing a water-soluble resin layer-forming composition containing a water-soluble resin and any additive, applying the composition to the thermoplastic resin layer or the photosensitive layer, and drying a coating film of the water-soluble resin layer-forming composition. In order to adjust the viscosity of the water-soluble resin layer-forming composition so as to facilitate the formation of the water-soluble resin layer, the water-soluble resin layer-forming composition preferably contains a solvent.

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

[ other layers ]

The transfer layer may also include other layers. As another layer, for example, a refractive index adjustment layer (contrast enhancement layer) can be given. The contrast enhancement layer is described in paragraph 0134 of International publication No. 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of japanese patent application laid-open No. 2014-85643. The contents of these publications are incorporated in the present specification.

From the viewpoint of the unevenness-following property, the ratio of the total mass of the polymerizable compound (preferably, ethylenically unsaturated compound) to the total mass of the polymer (preferably, alkali-soluble resin) in the transfer layer (preferably, photosensitive layer) is preferably 0.4 or more, more preferably 0.6 or more, and further preferably 0.8 or more. The U-form ratio of the total mass of the polymerizable compound (preferably, ethylenically unsaturated compound) to the total mass of the polymer (preferably, alkali-soluble resin) in the transfer layer (preferably, photosensitive layer) is 1.6 or less, more preferably 1.4 or less, and still more preferably 1.2 or less.

From the viewpoint of resolution, 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 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 1.0 μm or more. The average thickness of the transfer layer was calculated by the arithmetic mean of the thicknesses at 5 points measured in the cross-sectional observation using a Scanning Electron Microscope (SEM).

[ protective film ]

The transfer film preferably includes a protective film. For example, the transfer film preferably includes a temporary support, a transfer layer, and a protective film in this order.

Examples of the material constituting the protective film include a resin film and paper, and a resin film is preferable 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, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

The average thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm. The average thickness of the protective film was calculated by the arithmetic average of the thicknesses at 5 points measured in the cross-sectional observation using a Scanning Electron Microscope (SEM).

From the viewpoint of more excellent resolution, the arithmetic average roughness Ra of the surface of the protective film facing the transfer layer (hereinafter, also simply referred to as "the surface of the protective film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. When the Ra value of the surface of the protective film is within the above range, the uniformity of the thickness of the transfer layer and the resist pattern to be formed is improved. 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 (NewView 7300, manufactured by Zygo corporation) under the following conditions. As the measurement/analysis software, microcope application of MetropoPro ver8.3.2 was used. Next, the Surface Map screen is displayed by the analysis software, and histogram data is obtained on the Surface Map screen. The arithmetic average 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, for example, bonding the protective film to the transfer layer. The lamination of the protective film and the transfer layer is performed using, for example, a known laminator. Examples of the laminator include a vacuum laminator and an automatic cutting laminator. The laminator is preferably provided with an optional heatable roller such as a rubber roller and is a device capable of pressurization and heating.

< method for producing vapor deposition mask >

A method for manufacturing a vapor deposition mask according to the present invention will be described below. In one embodiment, a method for manufacturing a vapor deposition mask includes the following steps.

(1) A transfer film for forming a vapor deposition mask according to the present invention is prepared (hereinafter, may be referred to as "preparation step 1").

(1) A substrate having a 1 st surface and a 2 nd surface opposite to the 1 st surface is prepared (hereinafter, sometimes referred to as "1 st preparation step").

(3) The photosensitive layer and the temporary support included in the transfer film are sequentially disposed on the 1 st surface of the substrate by bonding the substrate and the transfer film (hereinafter, may be referred to as "bonding step").

(4) The photosensitive layer disposed on the substrate is subjected to pattern exposure (hereinafter, may be referred to as "exposure step").

(5) After pattern exposure of the photosensitive layer, the photosensitive layer is subjected to a development treatment to form a resist pattern (hereinafter, sometimes referred to as "development step").

(6) After the resist pattern is formed, the base material is subjected to etching treatment to form a through hole extending from the 1 st surface of the base material to the 2 nd surface of the base material (hereinafter, sometimes referred to as "etching step").

(7) After the through-hole is formed, the resist pattern is removed (hereinafter, may be referred to as a "removal process").

[ preparation Process ]

In the first preparation step 1, a transfer film for forming a vapor deposition mask according to the present invention is prepared. The method of forming the transfer film for vapor deposition mask is described as follows.

[2 nd preparation Process ]

In the 2 nd preparation step, a substrate having the 1 st surface and the 2 nd surface opposite to the 1 st surface is prepared. The 2 nd preparation process may be performed before the 1 st preparation process. The 2 nd preparation step may be performed after the 1 st preparation step. The 2 nd preparation step may be performed simultaneously with the 1 st preparation step.

The structure of the substrate may be a single layer structure or a multilayer structure.

The substrate preferably comprises a metal layer. The substrate may be a metal layer. The structure of the metal layer may be a single layer structure or a multi-layer structure. Examples of the metal element included in the metal layer include Cu, ni, fe, cr, mn, and Co. The metal layer preferably contains iron (Fe). Part or all of the metal layer may be an alloy. Examples of the alloy include Ni-Co alloy, fe-Ni alloy, and Fe-Ni-Co alloy. An invar (invar) alloy is an Fe — Ni alloy. Examples of the Fe-Ni-Co alloy include a super Invar alloy. The metal layer preferably contains at least one metal element selected from Cu, ni, fe, cr, mn, and Co, and more preferably contains at least one metal element selected from Cu, fe, and Ni. The metal layer may contain an element other than the metal element. Examples of the element other than the metal element include B, C, N, O, P, S and Cl. The metal layer may contain impurities that are inevitably mixed in during the manufacturing process. The metal layer is preferably 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 proportion of Ni in the alloy is preferably 10 to 50 mass%, more preferably 30 to 40 mass%, and still more preferably 32 to 38 mass%. The proportion of Co in the alloy is preferably 0 to 10 mass%, more preferably 2 to 6 mass%.

From the viewpoint of the resolution of the through-hole in the process of producing the vapor deposition mask, 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. The average thickness of the metal layer is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of the rigidity of the vapor deposition mask. The average thickness of the metal layer was calculated by the arithmetic mean of the thicknesses at 5 points measured in the cross-sectional observation using a Scanning Electron Microscope (SEM).

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

The substrate may include a metal layer and a substrate layer. The base material layer is preferably located closer to the 2 nd surface of the base material than the metal layer. The substrate layer may constitute the 2 nd face of the substrate. The structure of the substrate layer may be a single-layer structure or a multi-layer structure. Examples of the component of the base layer include glass and polymers. 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, and more preferably a resin film. Examples of the resin film include a polyimide film, a cycloolefin polymer film, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.

From the viewpoint of suppressing the generation of bubbles during lamination, the surface roughness Ra of the 1 st surface of the base material is preferably 5.0 μm or less, more preferably 3.0 μm or less, and further preferably 1.0 μm or less. The surface roughness Ra of the 1 st surface of the base material is preferably 0.1 μm or more, and more preferably 0.2 μm or more, from the viewpoint of suppressing scratches caused by lubricity during transportation.

From the viewpoint of suppressing the generation of bubbles during lamination, the surface roughness Ra of the 2 nd surface of the base material is preferably 5.0 μm or less, more preferably 3.0 μm or less, and further preferably 1.0 μm or less. The surface roughness Ra of the 2 nd surface of the base material is preferably 0.1 μm or more, and more preferably 0.2 μm or more, from the viewpoint of suppressing scratches caused by lubricity during transportation. The surface roughness Ra of the 2 nd surface of the base material may be the same as the surface roughness Ra of the 1 st surface of the base material. The surface roughness Ra of the 2 nd surface of the base material may be different from the surface roughness Ra of the 1 st surface of the base material.

In the present invention, the surface roughness Ra was measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation). First, a surface profile of an object surface was obtained using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation). As the measurement/analysis software, microcope Application from MetropoPro ver8.3.2 was used. Next, the measurement/analysis software was used to display the Surface Map screen, and histogram data was obtained on the Surface Map screen. The arithmetic average roughness calculated from the obtained histogram data was used as "surface roughness Ra".

[ bonding Process ]

In the bonding step, the substrate and the transfer film are bonded to each other, and the photosensitive layer and the temporary support included in the transfer film are sequentially disposed on the 1 st surface of the substrate.

The bonding step can be performed by a known method. In the bonding step, the substrate is preferably pressed against the transfer film. For example, it is preferable to laminate the base material and the transfer film by superposing the base material and the transfer film on each other 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 70 to 130 ℃. When the transfer film includes the protective film, the bonding step is performed after the protective film is removed.

[ Exposure Process ]

In the exposure step, the photosensitive layer disposed on the substrate is subjected to pattern exposure. The phrase "pattern-wise exposing the photosensitive layer" means that the photosensitive layer is irradiated with light to form an exposed portion and a non-exposed portion in the photosensitive layer. The positional relationship between the exposed portion and the non-exposed portion can be determined, for example, according to the shape of the target resist pattern.

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

The light used in the exposure step preferably includes at least one wavelength selected from 365nm and 405 nm.

Examples of the Light source include an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The exposure amount is preferably 5mJ/cm ² ～200mj/cm ² More preferably 10mJ/cm ² ～100mJ/cm ² 。

Examples of the exposure method include a contact exposure method and a non-contact exposure method. As a contact exposure method, for example, a method using a photomask can be given. Examples of the non-contact exposure system include a proximity (proximity) exposure system, a projection exposure system using a lens system or a mirror system, and a direct exposure system using an exposure laser. In the projection exposure using a lens system or a mirror system, an exposure apparatus having an appropriate number of lens apertures (NA) can be used according to the required resolution and depth of focus. In the direct exposure method, the photosensitive layer may be directly subjected to drawing, or reduced projection exposure may be performed on the photosensitive layer via a lens. The exposure step may be performed under the atmosphere, under reduced pressure, or under vacuum. The exposure step may be performed with a liquid such as water interposed between the light source and the photosensitive layer.

The exposure step may be performed before or after the temporary support is peeled. When the exposure step is performed before the temporary support is peeled off, the photosensitive layer may be exposed through the temporary support. In the exposure step using a photomask, the photosensitive layer may be pattern-exposed in a state where the photomask is brought into contact with the photosensitive layer, or the photosensitive layer may be pattern-exposed in a state where the photomask is brought into close proximity to the photosensitive layer without being brought into contact with the photosensitive layer. In order to prevent contamination of the photomask due to contact between the photomask and the photosensitive layer and to avoid the influence of foreign matter adhering to the photomask on exposure, it is preferable to perform pattern exposure on the photosensitive layer without peeling off the temporary support. When the photosensitive layer is exposed through the temporary support, the temporary support is preferably peeled off after the exposure step and before the development step.

[ developing Process ]

In the developing step, the photosensitive layer is subjected to a developing treatment to form a resist pattern. The resist 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, a non-exposed portion of the photosensitive layer is usually removed by a development treatment, and a resist pattern is formed from an exposed portion of the photosensitive layer. When the photosensitive layer is a positive photosensitive layer, an exposed portion of the photosensitive layer is usually removed with a developer to form a resist pattern from a non-exposed portion of the photosensitive layer.

The development treatment is performed using, for example, a developer. Examples of the developer include known developers (e.g., the developer described in japanese unexamined patent application, first publication No. 5-72724). As the developer, an alkaline aqueous solution type developer containing a compound having pKa =7 to 13 at a concentration of 0.05mol/L to 5mol/L is preferable. Examples of the basic compound contained in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The developer may contain a water-soluble organic solvent. The developer may contain a surfactant. Examples of a preferable developer include the developer described in paragraph 0194 of international publication No. 2015/093271.

The temperature of the developing solution is preferably 20 to 40 ℃.

Examples of the development method include a dip development (paddle development), a shower development (shower development), a shower and spin development, and a dip development. The shower development is a development method in which a developing solution is sprayed to an object by showering. A preferable development method is, for example, the development method described in paragraph 0195 of international publication No. 2015/093271.

The developer and the residue remaining after the developing step are preferably removed by a known method. Examples of the method for removing the developer and the residue include a shower treatment and an AirKnife treatment. In the spray treatment, a liquid such as water or a cleaning agent is sprayed to the object. The residue can also be removed using a brush.

The shape of the resist pattern may be determined according to the shape of a target through-hole in the etching process. Examples of the shape of the opening defined by the resist pattern in a plan view include a circle, an ellipse, and a quadrangle. The shape of the opening as viewed in plan is preferably a quadrilateral, more preferably a square or a rectangle. When the opening viewed in plan is polygonal (e.g., quadrilateral), a part or all of corners of the polygon may be rounded.

The diameter of the opening defined by the resist pattern may be determined according to the diameter of the target through-hole in the etching process. As the diameter of the opening defined by the resist pattern becomes smaller, the diameter of the through-hole formed in the substrate in the etching step becomes smaller. The diameter of the opening defined by the resist pattern is preferably 40 μm or less, more preferably 35 μm or less, and still more preferably 30 μm or less. 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 invention, 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 arbitrary 2 points on the outline of the opening as viewed in plan. When the number of openings is 2 or more, the diameter of the openings is represented by the average diameter of the openings. The average diameter of the openings is calculated by the arithmetic mean of the diameters of the 10 openings. However, when the number of openings is 2 to 9, the average diameter of the openings is calculated by the arithmetic mean of the diameters of all the openings.

When the shape of the opening is a quadrangle in a plan view, the length of one side of the quadrangle opening is preferably 5 μm to 50 μm, more preferably 5 μm to 40 μm, and still more preferably 5 μm to 30 μm.

[ etching Process ]

In the etching step, the base material is etched to form a through-hole extending from the 1 st surface of the base material to the 2 nd surface of the base material. The through-hole is formed by removing the substrate that is not protected by the resist pattern. At least 1 through hole is formed in the etching process. A plurality of through holes may be formed in the etching step.

The etching treatment may be a known method. Examples of the etching treatment include wet etching and dry etching (e.g., plasma etching). Examples of the etching treatment include methods described in paragraphs 0209 to 0210 of japanese patent application laid-open No. 2017-120435 and methods described in paragraphs 0048 to 0054 of japanese patent application laid-open No. 2010-152155.

The etching treatment is preferably wet etching. In wet etching, an etching solution is generally used. The kind of the etching solution can be selected from acidic or alkaline etching solutions according to the object to be etched. Examples of the acidic etching solution include an aqueous solution containing at least one acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of the acidic etching solution include a mixed aqueous solution of the acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride and potassium permanganate. The acidic component may be a combination of a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution containing at least one alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). The alkaline etching solution may be, for example, a mixed aqueous solution of the above-mentioned alkali component and a salt (e.g., potassium permanganate). The alkali component may be a combination of a plurality of alkali components.

The through-hole extending from the 1 st surface of the base material to the 2 nd surface of the base material has an opening on the 1 st surface of the base material and an opening on the 2 nd surface of the base material. Hereinafter, the opening formed in the 1 st surface of the base material through the through hole may be referred to as a "1 st opening", and the opening formed in the 2 nd surface of the base material through the through hole may be referred to as a "2 nd opening". Examples of the shape of the through-hole (i.e., opening) in a plan view include a circle, an ellipse, and a quadrangle. The shape of the through-hole as viewed in plan is preferably a quadrangle, more preferably a square or a rectangle. When the shape of the through-hole as viewed in plan is a polygon (e.g., a quadrangle), a part or all of corners of the polygon may be rounded. The through-holes observed in the cross-section are defined by the inner surface of the substrate. The through-going hole may be defined by 1 or more than 2 faces. The plane defining the through-hole as viewed in section may be a straight line or a curved line. The plane defining the through-hole as viewed in cross section may be a combination of a straight line and a curved line. The "cross section" in this paragraph means a cross section of the vapor deposition mask observed in the thickness direction.

The diameter of the through-hole (i.e., the diameter of the 2 nd opening) in the 2 nd surface of the base material is preferably 40 μm or less, more preferably 35 μm or less, and still more preferably 30 μm or less. The diameter of the 2 nd opening is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. If the diameter of the 2 nd opening becomes small, a pattern can be formed with high resolution. The lower limit of the diameter of the 2 nd opening is not limited. The lower limit of the diameter of the 2 nd opening may be 5 μm, 1 μm, or 0.1 μm.

The diameter of the through-hole in the 2 nd surface of the substrate (i.e., the diameter of the 2 nd opening) is preferably smaller than the diameter of the through-hole in the 1 st surface of the substrate (i.e., the diameter of the 1 st opening). For example, in a vapor deposition method in which a vapor deposition mask is disposed so that the 2 nd surface of the substrate faces the object, the substance reaching the 1 st surface of the substrate from the vapor source moves in the through-hole along the direction from the 1 st surface of the substrate to the 2 nd surface, and adheres to the object. In the above-described method, if the diameter of the 2 nd opening is smaller than the diameter of the 1 st opening, the substance reaching the 1 st surface of the substrate from the vaporization source easily enters the through-hole. As a result, productivity and pattern accuracy, for example, are improved.

The ratio of the diameter of the 2 nd opening to the diameter of the 1 st opening is preferably 0.8 or less, more preferably 0.4 or less, and still more preferably 0.3 or less. From the viewpoint of high resolution of the pattern, the ratio of the diameter of the 2 nd opening to the diameter of the 1 st 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 believed that the etching characteristics (e.g., isotropy) may create a difference between the diameter of the 1 st opening and the diameter of the 2 nd opening.

From the viewpoint of high resolution of the pattern, the diameter of the 1 st 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 1 st opening may be 8 μm or 10 μm.

The diameter of the 1 st opening and the diameter of the 2 nd opening are measured by a method in accordance with the method for measuring the diameter of the opening defined by the resist pattern described above.

When the shape of the 1 st opening is a quadrangle, the length of one side of the 1 st opening is preferably 5 to 50 μm, more preferably 5 to 40 μm, and still more preferably 5 to 30 μm. When the shape of the 2 nd opening is a quadrangle, it is preferably 5 to 50 μm, more preferably 5 to 40 μm, and still more preferably 5 to 30 μm.

The diameter of the through-hole as viewed in cross section may vary continuously or discontinuously in the direction from the 1 st face of the substrate toward the 2 nd face of the substrate. The diameter of the through-hole as viewed in cross section preferably decreases in a direction from the 1 st surface toward the 2 nd surface. The "cross section" in this paragraph means a cross section of the vapor deposition mask observed in the thickness direction.

[ removal Process ]

In the removal process, the resist pattern is removed. As a removal method, for example, a method of removing the resist pattern by chemical treatment is given. A method of removing the resist pattern using a removing liquid is preferred.

Examples of the removal solution include a removal solution containing an inorganic base component or an organic base component and water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solvent thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

The resist pattern may also be removed by immersing the laminate including the resist pattern in a removing liquid. The temperature of the removing solution is preferably 30 to 80 ℃, more preferably 50 to 80 ℃. The immersion time is preferably 1 minute to 30 minutes. In the dipping method, the removing solution may be stirred.

The resist pattern can be removed by, for example, spraying, showering, or spin-on immersion.

[ other Processes ]

The method for manufacturing a vapor deposition mask may further include other steps as necessary.

The method for manufacturing a vapor deposition mask may include a pressing step after the bonding step. For example, in the pressing step, the laminate obtained by bonding the base material and the transfer film is pressed. The pressurized laminate is preferably a laminate including a substrate, a photosensitive layer, and a temporary support in this order. The laminate to be pressed may be a laminate including a substrate and a photosensitive layer in this order. For example, when the temporary support is peeled off after the bonding step, a laminate including the substrate and the photosensitive layer in this order can be formed. In the pressing step, the laminate obtained by bonding the transfer film and the base material may be subjected to a pressing treatment in an autoclave. For example, the pressure treatment can be performed at 50 to 60 ℃ under 0.5 to 0.6MPa for 60 minutes. By subjecting the laminate to pressure treatment, the adhesion between the substrate and the photosensitive layer can be improved, and the ability of the photosensitive layer to follow the irregularities on the surface of the substrate can be improved. The pressing step is preferably performed before the exposure step.

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

The structure of the vapor deposition mask will be described with reference to fig. 1,2, and 3. Fig. 1 is a schematic plan view showing a vapor deposition mask according to an embodiment. Fig. 2 is an enlarged schematic plan view of a through-hole of the vapor deposition mask shown in fig. 1. Fig. 3 is an enlarged schematic cross-sectional view of a through-hole of the vapor deposition mask shown in fig. 1. The vapor deposition mask 100 includes a metal layer 10 having a 1 st surface 10F, a 2 nd surface 10R opposite to the 1 st surface 10F, and a through hole 10H. The 1 st surface 10F of the metal layer 10 faces the viewer who looks at fig. 1 and 2. The 1 st surface 10F of the metal layer 10 and the 2 nd surface 10R of the metal layer face in opposite directions to each other. As shown in fig. 1 and 2, the through-hole 10H is defined by a grid-like pattern formed by the metal layer 10, and the shape of the through-hole 10H is a quadrangle in plan view. In fig. 2, the reason why the outline of the through-hole 10H is doubly observed is that the outline of the opening (specifically, the 2 nd opening 10RA in fig. 3) formed on the 2 nd surface 10R of the metal layer 10 is observed inside the outline of the opening (specifically, the 1 st opening 10FA in fig. 3) formed on the 1 st surface 10F of the metal layer 10. As shown in fig. 3, the through hole 10H extends from the 1 st surface 10F of the metal layer 10 to the 2 nd surface 10R of the metal layer 10. The through-hole 10H has a 1 st opening 10FA on the 1 st surface 10F of the metal layer 10 and a 2 nd opening 10RA on the 2 nd 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 curved. The diameter of the 2 nd opening 10RA is smaller than the diameter of the 1 st opening 10 FA. The diameter of the through-hole 10H is gradually reduced in a direction from the 1 st surface 10F to the 2 nd surface 10R.

A method for manufacturing the vapor deposition mask will be described with reference to fig. 4. Fig. 4 is a schematic cross-sectional view showing a method for manufacturing a vapor deposition mask according to an embodiment. As shown in fig. 4 (a), the metal layer 10 having the 1 st surface 10F and the 2 nd surface 10R opposite to the 1 st surface 10F is prepared. As shown in fig. 4 (b), a transfer film (not shown) is bonded to the metal layer 10, and the photosensitive layer 20 is disposed on the 1 st surface 10F of the metal layer 10. As shown in fig. 4 (c), the photosensitive layer 20 is pattern-exposed, and then the photosensitive layer 20 is subjected to a developing treatment, thereby forming a resist pattern 21. As shown in fig. 4 (d), the metal layer 10 is etched to form a through hole 10H. It is considered that, in the course of the etching treatment, isotropic etching (that is, etching in a direction orthogonal 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 the through-hole 10H having the cross-sectional shape shown in fig. 4 (d). As shown in fig. 4 (e), the resist pattern 21 is removed to obtain the vapor deposition mask 100. The through-hole 10H formed in the metal layer 10 extends from the 1 st surface 10F of the metal layer 10 to the 2 nd surface 10R of the metal layer 10. The through hole 10H forms a 1 st opening 10FA on the 1 st surface 10F of the metal layer 10 and a 2 nd opening 10RA on the 2 nd surface 10R of the metal layer 10.

The vapor deposition mask obtained by the method for producing a vapor deposition mask according to the present invention may include other components. As another component, for example, a housing may be mentioned. The frame can reinforce the vapor deposition mask or improve the operability of the vapor deposition mask. The frame may be disposed around the through-hole in a plan view, or may be disposed on the outer periphery of the intermediate vapor deposition mask in a plan view. Examples of the component of the frame body include metals. Examples of the metal include an Fe-Ni alloy (e.g., invar alloy) and an Fe-Ni-Co alloy (e.g., super Invar alloy).

A preferred application of the vapor deposition mask obtained by the method for producing a vapor deposition mask according to the present invention is, for example, a method for producing a pattern by a vapor deposition method. In the vapor deposition method, the vapor deposition mask is preferably disposed on the object so that the 2 nd surface of the substrate faces the object. When the 2 nd surface of the base material faces the object, the substance reaching the 1 st surface of the base material from the vaporization source easily enters the through-hole. The substance that has entered the through-hole moves in the through-hole in a direction from the 1 st surface to the 2 nd surface of the base material, and adheres to the object. The substance passing through the through-hole is deposited on the object to form a pattern. Examples of the object to be patterned include a glass substrate and a resin film. The type of the vapor deposition method, the conditions of the vapor deposition method, and the type of the substance to be vapor deposited are determined, for example, according to the target pattern. A preferred vapor deposition method is, for example, a vacuum vapor deposition method. Specific applications of the vapor deposition mask include a method for manufacturing an OLED (Organic Light Emitting Diode).

[ examples ]

The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified.

< temporary support 1>

The temporary support 1 is produced by the following method.

[ preparation of composition 1 for Forming particle-containing layer ]

The mixture obtained by mixing the following components was filtered using a 6 μm Filter (F20, manufactured by Mahle Filter Systems Japan corp.), and then subjected to membrane degassing using 2 × 6Radial Flow Super phenolic (Polypore co., ltd.). The composition 1 for forming a particle-containing layer was obtained by the above procedure.

Acrylic polymer (AS-56FA, daicel Fine Chem Ltd., solid content: 27.5 mass%): 167 portions of

Nonionic surfactant (NAROACTY CL95, sanyo Chemical Industries, ltd., solid content: 100 mass%): 0.7 portion of

An anionic surfactant (RAPISOL a-90, nof CORPORATION, diluted with water to a solid content of 1 mass%): 114.4 portions of

Carnauba wax dispersion (Cellosol 524, chukyo YUSHI CO., ltd., solid content: 30 mass%): 7 portions of

Carbodiimide compound (CARBODILITE V-02-L2, nisshinbo Chemical inc., diluted with water to 10 mass% solid content): 20.9 portions

Matting agent (SNOWTEX XL, nissan Chemical Corporation, solid content: 40% by mass, average particle diameter: 50 nm): 2.8 parts of

Water: 690.2 parts

[ extrusion Molding ]

Pellets of polyethylene terephthalate produced using a citric acid-chelated organic titanium complex described in Japanese patent No. 5575671 as a polymerization catalyst were dried to have a water content of 50ppm or less. The pellets were put into a hopper of a uniaxial kneading extruder having a diameter of 30mm, melted at 280 ℃ and extruded. The melt was passed through a filter (pore size: 2 μm) and then extruded from a die onto a cooling roll at 25 ℃. Specifically, the melt was brought into close contact with a cooling roller by an electrostatic application method. An unstretched film was obtained by the above procedure.

[ stretching and coating ]

The cured unstretched film was subjected to sequential biaxial stretching by the following method.

(a) Longitudinal stretching

The unstretched film was stretched in the longitudinal direction (conveying direction) by passing between 2 pairs of nip rollers having different peripheral speeds. Specifically, the stretching was performed under the conditions of a preheating temperature of 75 ℃, a stretching temperature of 90 ℃, a stretching magnification of 3.4 times, and a stretching speed of 1300%/sec.

(b) Coating of

The particle-containing layer-forming composition 1 was applied to one surface of the longitudinally stretched film using a bar coater so that the thickness after film formation became 40nm.

(c) Stretching in transverse direction

The longitudinally stretched and coated film was transversely stretched using a tenter under the following conditions.

Preheating temperature: 110 deg.C

Stretching temperature: 120 deg.C

Stretching ratio: 4.2 times of

Stretching speed: 50%/second

[ Heat setting ]

The biaxially stretched film after the transverse stretching was heat-set under the following conditions.

Heat-setting temperature: 227 deg.C

Heat setting time: 6 seconds

[ thermal relaxation ]

After heat setting, the width of the tenter was reduced, and heat relaxation was performed under the following conditions.

Thermal relaxation temperature: 190 deg.C

Thermal relaxation rate: 4 percent of

[ Rolling ]

After the thermal relaxation, both ends of the film were trimmed, and after the end of the film was subjected to extrusion processing (knurling) with a width of 10mm, the film was wound up with a tension of 40 kg/m. The width of the film was 1.5m and the roll length of the film was 6, 300m. The obtained film roll was used as a temporary support. The temporary support comprises a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40nm.

The haze value of the temporary support was 0.2%. The haze value was measured as the total haze using a haze meter (NIPPON DENSHOKU industies co., ltd., NDH 2000). The heat shrinkage rate by heating at 150 ℃ for 30 minutes was 1.0% in the MD (Machine Direction) and 0.2% in the TD (Transverse Direction in the in-plane Direction of the film). The thickness of the particle-containing layer was 40nm as measured using a cross-sectional TEM photograph. The average particle diameter of the particles contained in the particle-containing layer was measured to be 50nm using a Transmission Electron Microscope (TEM) model HT-7700 manufactured by Hitachi High-Technologies Corporation.

< photosensitive compositions 1 to 17>

A mixed solvent of the components selected as described in table 1 and methyl ethyl ketone (SANKYO CHEMICAL co., ltd.,60 parts) and propylene glycol monomethyl ether acetate (SHOWA DENKO k.k.,40 parts) was mixed. The amount of the mixed solvent was adjusted so that the solid content concentration of the photosensitive composition became 13 mass%. The resultant mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 2.0 μm to prepare a photosensitive composition.

< composition 1 for Forming Water-soluble resin layer >

The following components were mixed to prepare a composition 1 for forming a water-soluble resin layer.

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 of

Polyvinylpyrrolidone K-30 (NIPPON shokubali co., ltd.): 1.49 parts

MEGAFACE F-444 (fluorosurfactant, DIC Corporation): 0.0035 portions

< composition 1 for Forming thermoplastic resin layer >

The following components were mixed to prepare a composition 1 for forming a thermoplastic resin layer. BzMA represents benzyl methacrylate, MAA represents methacrylic acid, and AA represents acrylic acid.

A solution comprising a 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 mass%): 40.00 parts

Polymerizable compound (A-DCP, shin-Nakamura Chemical Co., ltd.): 6.00 parts

Polymerizable compound (8 UX-015a, taisei Fine Chemical Co., ltd.): 3.00 parts

Polymerizable compounds (ARONIX TO-2349, toagosei CO., ltd.): 1.00 part

Surfactants (MEGAFACE F-552, DIC Corporation): 0.02 part of

Additive (phenothiazine): 0.06 part

Additives (CBT-1, JOOOKU CHEMICAL CO., LTD.): 0.03 part

Solvent (methyl ethyl ketone): 49.9 parts of

< examples 1 to 18 and comparative example 1>

After the photosensitive composition selected as described in table 2 was applied to the temporary support 1 using a slit nozzle, the photosensitive composition was dried at 80 ℃ for 2 minutes, thereby forming a photosensitive layer having a thickness described in table 2. The transfer film including the temporary support and the photosensitive layer was obtained through the above steps.

< examples 19 to 20>

After applying the composition 1 for forming a thermoplastic resin layer on the temporary support 1 using a slit nozzle, the composition 1 for forming a thermoplastic resin layer was dried at 80 ℃ for 2 minutes, thereby forming a thermoplastic resin layer having a thickness shown in table 2. After applying the water-soluble resin layer forming composition 1 to the thermoplastic resin layer using a slit nozzle, the water-soluble resin layer forming composition 1 was dried at 90 ℃ for 2 minutes, thereby forming a water-soluble resin layer having a thickness shown in table 2. After coating the photosensitive composition selected as described in table 2 on the water-soluble resin layer using a slit nozzle, the photosensitive composition was dried at 80 ℃ for 2 minutes, thereby forming a photosensitive layer having a thickness as described in table 2. The transfer film including the temporary support, the thermoplastic resin layer, the water-soluble resin layer, and the photosensitive layer was obtained through the above steps.

< evaluation >

The following evaluations were carried out using the transfer films produced in examples and comparative examples. An invar alloy substrate used for the following evaluation was produced by the following method, with reference to jp 2019-214788 a. First, a base material made of an iron alloy containing 36 mass% of nickel, the remainder of iron, and unavoidable impurities was prepared. Subsequently, the base material was subjected to a rolling step, a slit (slit) step, and an annealing step to obtain an invar alloy base material having a thickness of 30 μm. The coefficient of static friction of the 1 st surface of the invar base material was 0.61, and the coefficient of dynamic friction of the 1 st surface of the invar base material was 0.52. The surface roughness Ra of the 1 st surface of the invar alloy base material was 0.8. Mu.m, and the surface roughness Ra of the 2 nd surface of the invar alloy base material was 0.9. Mu.m. The invar base corresponds to the metal layer already described.

[ patterning Property ]

(preparation of resist Pattern)

(1) A transfer film was laminated on an invar base material having a thickness of 20 μm in a roll-to-roll manner using a vacuum laminator (MCK co., ltd., roll temperature: 100 ℃, line pressure: 1.0MPa, line speed: 0.5 m/min), and a transfer layer and a temporary support were disposed in this order on the 1 st surface of the invar base material. The obtained laminate sequentially included an invar base material, a transfer layer, and a temporary support.

(2) The laminate was subjected to pressure defoaming under conditions of 0.6MPa, 60 ℃ and 60 minutes using an autoclave apparatus.

(3) The transfer layer was exposed to light through a photomask using an ultrahigh-pressure mercury lamp without peeling off the temporary support. The photomask pattern includes a plurality of square light-shielding portions, and the length of one side of each light-shielding portion is set in a stepwise manner in units of 5 μm from 10 μm to 100 μm.

(4) After the temporary support is peeled off, a resist pattern is formed by development. Specifically, spray development was performed using a 1.0 mass% aqueous sodium carbonate solution at 25 ℃. In the development, the development time was set to 1.5 times the dissolution time of the non-exposed portion to a 1.0 mass% sodium carbonate aqueous solution at 25 ℃.

(5) The series of operations (1) to (4) above were repeated with the exposure conditions and the development conditions appropriately changed until the length of one side of the opening corresponding to the light-shielding portion having one side of 30 μm in the photomask became exactly 30 μm. Hereinafter, a condition in which an opening having a side of 30 μm in length is formed with respect to an opening of a subject is referred to as "standard condition".

(6) A laminate was produced by the method described in (1) to (2) above. The transfer layer was exposed to light under standard conditions through a photomask without peeling off the temporary support using an ultrahigh-pressure mercury lamp. The photomask pattern includes a plurality of square light-shielding portions, and the length of one side of each light-shielding portion is set in a stepwise manner in units of 5 μm in a range of 10 μm to 100 μm. After the temporary support is peeled off, development is 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. The minimum resolution was evaluated according to the following criteria, based on the length of one side of the minimum opening to be properly resolved in the resist pattern. The evaluation results are shown in table 2.

A: less than 15 μm

B:15 μm or more and less than 25 μm

C: more than 25 μm

(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 length of one side of 30 μm in the photomask was measured. The stability of the opening diameter was evaluated based on the difference between the maximum value and the minimum value (i.e., [ maximum value of length of one side ] - [ minimum value of length of one side ]) 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: more than 3.0 μm

(variation of opening diameter with standing time after Exposure)

The resist pattern was produced by the method described in (6) above with the exposure time (i.e., the time from the end of exposure to the start of development) set to 1 hour. Further, a resist pattern was produced by the method described in (6) above with the standing time after exposure set to 24 hours. The diameter D1 of the opening formed after the standing time of 1 hour and the diameter D24 of the opening formed after the standing time of 24 hours were measured. Based on the rate of change in the aperture diameter calculated according to the following equation, the change in the aperture diameter with the standing time after exposure was evaluated according to the following criteria. The evaluation results are shown in table 2.

Formula (II): rate of change in opening diameter (%) = { (| D24-D1 |)/D1 } × 100

A: less than 10 percent

B: more than 10 percent and less than 20 percent

C: more than 20 percent and less than 40 percent

D: more than 40 percent

(defect of opening)

The resist pattern obtained in (6) above was observed using an optical microscope. The state of defect of 100 openings with a side length of 20 μm 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.

C: defects were confirmed at 3 to 5.

D: no defect or no resist pattern remained at 6 or more.

(development residue)

The resist pattern obtained in (6) above was observed using an optical microscope. 100 openings having a side length of 30 μm were observed, and the development residue was evaluated according to the following criteria.

The evaluation results are shown in table 2.

A: no development residue was observed.

B: development residue was confirmed at 1 or 2.

C: development residue was confirmed at 3 or more.

[ laminating Property ]

(1) A transfer film was laminated in a roll-to-roll manner to an invar base material having a thickness of 20 μm using a vacuum laminator (MCK co., ltd., roll temperature: 100 ℃, line pressure: 1.0MPa, line speed: 0.5 m/min), and a transfer layer and a temporary support were disposed in this order on the 1 st surface of the invar base material. The obtained laminate comprises at least an invar base material, a transfer layer, and a temporary support in this order.

(2) The laminate was subjected to pressure defoaming under conditions of 0.6MPa, 60 ℃ and 60 minutes using an autoclave apparatus.

(3) Bubbles contained in the laminate were observed using an optical microscope, and adhesion was evaluated according to the following criteria. The smaller the number of bubbles, 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]

Table 2 shows that the openings were less defective in examples 1 to 20 compared to comparative example 1. That is, in examples 1 to 20, a resist pattern with less chipping was formed as compared with comparative example 1.

< examples 101 to 120>

Using the transfer films of examples 1 to 20, vapor deposition masks were produced by the following methods. By the method described in (6) of the evaluation of "patterning property", a resist pattern was formed on an invar base material using a transfer film. However, a photomask having a plurality of square light-shielding portions 25 μm long × 25 μm wide was used for exposure. An etching solution (see example 1 of jp 2018-178142 a) was sprayed by a spray method at 50 ℃ and a spray pressure of 0.2MPa to perform an etching process, thereby forming a plurality of through holes in an invar base material. The etching treatment time was 1.2 times the minimum time until the through-hole was formed. The resist pattern was removed using a 4 mass% sodium hydroxide solution to obtain a vapor deposition mask. In examples 101 to 120, the diameter of the through-hole in the 1 st surface of the invar base material was in the range of 23 μm to 27 μm, and the diameter of the through-hole in the 2 nd surface of the invar base material was in the range of 15 μm to 19 μm.

Description of the symbols

10-metal layer, 10F-1 st face, 10 FA-1 st opening, 10H-through hole, 10R-2 nd face, 10 RA-2 nd opening, 20-photosensitive layer, 21-resist pattern, 100-evaporation mask.

Claims (20)

1. A transfer film for forming a vapor deposition mask, comprising in this order:

a temporary support; and

a photosensitive layer comprising a polymer having an acid value of 30mgKOH/g or more.

2. The transfer film for forming a vapor deposition mask according to claim 1, wherein,

the acid value of the polymer is 270mgKOH/g or less.

3. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the acid value of the photosensitive layer is more than 15 mg/KOH.

4. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the acid value of the photosensitive layer is 135mg/KOH or less.

5. The transfer film for forming a vapor deposition mask according to claim 1 or 2, which comprises an intermediate layer between the temporary support and the photosensitive layer.

6. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the temporary support has an average thickness of 50 [ mu ] m or less.

7. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the temporary support has a haze value of 5% or less.

8. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the weight average molecular weight of the polymer is 10000 or more.

9. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the polymer comprises structural units having aromatic rings.

10. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the photosensitive layer contains a polymerizable compound having a bisphenol A structure.

11. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the photosensitive layer contains at least one polymerization initiator selected from a compound having an oxime ester structure, a compound having an α -hydroxyalkylphenone structure, a compound having an acylphosphine oxide structure, and a compound having a triarylimidazole structure.

12. The transfer film for forming a vapor deposition mask according to claim 1 or 2,

the photosensitive layer contains at least one sensitizer selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, oxyanthrone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

13. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the photosensitive layer contains a polymerization inhibitor.

14. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the storage modulus of the photosensitive layer at 90 ℃ is 1.0X 10 ⁶ Pa or less.

15. The transfer film for forming a vapor deposition mask according to claim 1 or 2, wherein,

the complex viscosity of the photosensitive layer at 30 ℃ is 1.0X 10 ⁴ Pa or above.

16. A method for manufacturing a vapor deposition mask, comprising the steps of:

preparing a transfer film for vapor deposition mask formation according to any one of claims 1 to 15;

preparing a base material having a 1 st surface and a 2 nd surface opposite to the 1 st surface;

bonding the base material and the transfer film, and sequentially arranging a photosensitive layer and a temporary support body included in the transfer film on the 1 st surface of the base material;

pattern-exposing the photosensitive layer disposed on the substrate;

pattern-exposing the photosensitive layer, and then developing the photosensitive layer to form a resist pattern;

after the resist pattern is formed, performing etching treatment on the base material to form a through hole extending from the 1 st surface of the base material to the 2 nd surface of the base material; and

after the through-hole is formed, the resist pattern is removed.

17. The method for manufacturing a vapor deposition mask according to claim 16, wherein,

the surface roughness Ra of the 1 st surface is 1.0 [ mu ] m or less.

18. The method for manufacturing a vapor deposition mask according to claim 16 or 17, wherein,

the substrate comprises a metal layer having an average thickness of 30 μm or less.

19. The method for manufacturing a vapor deposition mask according to claim 18, wherein,

the metal layer includes iron.

20. The method for manufacturing a vapor deposition mask according to claim 16 or 17, wherein,

the diameter of the through-hole in the 2 nd surface of the base material is 35 μm or less.

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