TW202136062A - Photosensitive transfer material and method for producing circuit wiring - Google Patents

Abstract

The present disclosure provides a photosensitive transfer material that has a temporary-support body and a photosensitive resin layer which includes an alkali soluble polymer, an ethylenically unsaturated bond-containing compound, and a photoinitiator, the ratio of the amount of a phenolic compound with a molecular mass of no more than 300 in the photosensitive resin layer being no higher than 300 ppm relative to the total mass of the photosensitive resin layer. The present disclosure also provides a use for the photosensitive transfer material.

Description

Photosensitive transfer material and manufacturing method of circuit wiring

This disclosure relates to a method for manufacturing a photosensitive transfer material and circuit wiring.

A display device (for example, an organic electroluminescence display device and a liquid crystal display device) equipped with a touch panel (for example, a capacitance type input device) has a patterned conductive layer inside the touch panel. Examples of the pattern-shaped conductive layer include electrode patterns and wiring (for example, peripheral wiring and lead wiring) of the sensor corresponding to the visual recognition portion.

When forming a patterned conductive layer, the number of steps for obtaining a desired pattern shape is small, and therefore a method using a photosensitive transfer material is widely used (for example, Patent Document 1). For example, a photosensitive resin layer is provided on a substrate using a photosensitive transfer material, and then the photosensitive resin layer is exposed through a mask having a desired pattern, and then developed and etched to form a pattern.的conductive layer.

[Patent Document 1] Japanese Patent Application Publication No. 2019-128445

However, in the etching process, there is a problem in that necessary parts of the object to be processed such as metals are also removed due to side etching. Undercutting refers to the phenomenon that the processing (ie, removal) of the processed object by etching treatment not only progresses in the depth direction of the processed object (that is, the thickness direction of the processed object), but also The depth direction of the object to be processed progresses in a direction orthogonal to the depth direction. The above problem is that, for example, the dimensional accuracy of the pattern obtained by the etching process will decrease. Therefore, it is required to reduce the amount of progress of undercutting (hereinafter referred to as "amount of undercutting").

In addition, in the pattern forming method using the photosensitive transfer material, the laminate obtained by bonding the photosensitive transfer material and the substrate may be left for an arbitrary period of time. As a result, the time (hereinafter, referred to as “continuous standing time after lamination”) from the time after the photosensitive transfer material and the substrate are bonded to the next processing stage (for example, exposure) may become longer. In addition, as the continuous storage time after lamination becomes longer, the amount of side erosion tends to increase.

This disclosure was completed in view of the above-mentioned circumstances. The purpose of one aspect of the present disclosure is to provide a photosensitive transfer material that reduces the amount of undercut that accompanies the continuous standing time after lamination. The purpose of another aspect of the present disclosure is to provide a method for manufacturing circuit wiring that reduces the amount of undercut that accompanies the continuous placement time after lamination.

This disclosure includes the following aspects. <1> A photosensitive transfer material comprising: a pseudo support; and a photosensitive resin layer containing an alkali-soluble polymer, an ethylenically unsaturated bond-containing compound, and a photopolymerization initiator, the above-mentioned photosensitive resin layer The content ratio of the phenolic compound having a medium molecular weight of 300 or less is 300 ppm or less with respect to the total mass of the photosensitive resin layer. <2> The photosensitive transfer material according to <1>, wherein the content of the phenolic compound is 200 ppm or less with respect to the total mass of the photosensitive resin layer. <3> The photosensitive transfer material according to <1> or <2>, wherein the content of the phenolic compound is 100 ppm or less with respect to the total mass of the photosensitive resin layer. <4> The photosensitive transfer material according to any one of <1> to <3>, wherein the phenolic compound contains a phenolic compound represented by the following formula (1).

[Chemical formula 1]

In formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a hydroxyl group or an alkoxy group having 1 to 6 carbons . <5> The photosensitive transfer material according to any one of <1> to <4>, wherein the phenolic compound contains at least one selected from the group consisting of the following phenolic compounds: 1-1) Phenolic compound represented by the following formula (1-2), phenolic compound represented by the following formula (1-3), represented by the following formula (1-4) The phenolic compound and the phenolic compound represented by the following formula (1-5).

[Chemical formula 2]

<6> A method of manufacturing circuit wiring, including: preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material described in any one of <1> to <5> in this order And the step of etching the conductive layer in the area where the resin pattern is not arranged in the laminated body. [Effects of the invention]

According to one aspect of the present disclosure, a photosensitive transfer material is provided that reduces the amount of undercut that accompanies the continuous placement time after lamination. According to another aspect of the present disclosure, there is provided a method for manufacturing circuit wiring that reduces the amount of undercut that accompanies the continuous placement time after lamination.

Hereinafter, an embodiment of the present disclosure will be described in detail. This disclosure is not limited to the following embodiments at all, and can be implemented with appropriate changes within the scope of the purpose of this disclosure. The size ratio in the drawing does not necessarily indicate the actual size ratio.

In the present disclosure, the numerical range indicated by "～" means a range that includes the numerical values described before and after "～" as the lower limit and the upper limit, respectively. In the numerical range described stepwise in this disclosure, the description of the upper limit or lower limit in a certain numerical range can be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in this disclosure, the upper limit or the lower limit described in a certain numerical range can also be replaced with the values shown in the examples.

In the present disclosure, when there are plural substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition means the total amount of the plural substances present in the composition .

In the present disclosure, the term "step" includes not only independent steps, but even when it cannot be clearly distinguished from other steps, as long as the intended purpose of the step can be achieved, it is also included in this term.

In this disclosure, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present disclosure, a combination of two or more preferred aspects is a better aspect.

In the present disclosure, groups (atomic groups) that are not described as being substituted and unsubstituted include groups having no substituents and groups having substituents. For example, the term "alkyl" includes not only an unsubstituted alkyl group (that is, an unsubstituted alkyl group), but also an alkyl group with a substituent (that is, a substituted alkyl group).

In the present disclosure, “(meth)acrylic acid” means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid.

In the present disclosure, “(meth)acryloyl group” means an acryloyl group, a methacryloyl group, or both an acryloyl group and a methacryloyl group.

In the present disclosure, “(meth)acrylate” means acrylate, methacrylate, or both acrylate and methacrylate.

In the present disclosure, "alkali solubility" means the property that the solubility in an aqueous solution of sodium carbonate (100 g, sodium carbonate concentration: 1% by mass) at a liquid temperature of 22° C. is 0.1 g or more.

In the present disclosure, the chemical structural formula is sometimes described as a structural formula in which the hydrogen atom is omitted.

In the present disclosure, unless otherwise specified, "exposure" includes not only exposure using light, but also depiction using particle beams (for example, electron beams and ion beams). As the light used for exposure, for example, active light (also called active energy ray) can be cited. Examples of the activating light include the bright line spectrum of a mercury lamp, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV (Extreme ultraviolet lithography) light), and X-rays.

In the present disclosure, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are used to detect compounds in THF (tetrahydrofuran) with a differential refractometer, and by using the column "TSKgel GMHxL", "TSKgel G4000HxL" and "TSKgel G2000HxL" (both are the trade names of TOSOH CORPORATION) gel permeation chromatography (GPC: Gel Permeation Chromatography) analyzer uses polystyrene as a standard substance to convert the molecular weight.

In the present disclosure, "solid content" means a component in which the solvent is removed from all components of the object.

＜Photosensitive transfer material＞ The photosensitive transfer material of the present disclosure has: a pseudo support; and a photosensitive resin layer containing an alkali-soluble polymer, an ethylenically unsaturated bond-containing compound, and a photopolymerization initiator. The molecular weight of the photosensitive resin layer is The content ratio of the phenolic compound of 300 or less is 300 ppm or less with respect to the total mass of the photosensitive resin layer. According to the photosensitive transfer material of the present disclosure, it is possible to reduce the amount of side erosion accompanying the elapse of the continuous standing time after lamination.

The reason why the photosensitive transfer material of the present disclosure exerts the above-mentioned effects is presumed to be as follows. When the content of low-molecular phenolic compounds in the photosensitive resin layer of the photosensitive transfer material is large, for example, if the metal and the photosensitive resin layer are bonded to a base covered by a metal (for example, copper) When the material is in contact with the photosensitive transfer material, the low-molecular phenolic compound will be concentrated in the vicinity of the metal due to the interaction with the metal. The localization of the low-molecular phenolic compound progresses with the elapse of the continuous standing time after lamination, and the reactivity of the photosensitive resin layer having photocuring properties is particularly hindered in the photosensitive resin layer. If the photosensitive resin layer with photocuring properties is exposed, the polymerization rate of the area where there are more phenolic compounds, that is, the area near the surface of the photosensitive resin layer in contact with the metal, will be reduced, thereby reducing the exposure. Adhesion between the photosensitive resin layer and the metal. As a result, it is thought that the etching process promotes the removal of the metal in contact with the cured product of the photosensitive resin layer used as the protective film, thereby increasing the amount of side etching. On the other hand, in the photosensitive transfer material of the present disclosure, the phenolic compound with a molecular weight of 300 or less in the photosensitive resin layer is 300 ppm or less, so that the photosensitive resin layer caused by the bias of low-molecular phenolic compounds can be suppressed The reduction of the polymerization rate. In addition, it is considered that the phenolic compound film having a molecular weight of 300 or less has particularly high mobility. Therefore, according to the photosensitive transfer material of the present disclosure, it is possible to reduce the amount of side erosion accompanying the elapse of the continuous standing time after lamination. Furthermore, according to the photosensitive transfer material of this disclosure, for example, it is possible to effectively reduce the amount of side etching in the etching process of copper, which is frequently used.

＜＜Elements＞＞ The photosensitive transfer material of the present disclosure has a pseudo support and a photosensitive resin layer. In the above-mentioned photosensitive transfer material, the photosensitive resin layer system may be laminated on the dummy support directly or through arbitrary layers. In the above-mentioned photosensitive transfer material, an arbitrary layer may be laminated on the surface of the photosensitive resin layer on the side opposite to the side on which the dummy support is arranged. As an arbitrary layer, the other layer mentioned later can be mentioned, for example. Hereinafter, the constituent elements of the photosensitive transfer material of the present disclosure will be specifically described.

[Pseudo support] The photosensitive transfer material of the present disclosure has a pseudo support. Pseudo support system A support that can be peeled from the photosensitive transfer material. The pseudo support system can support at least the photosensitive resin layer.

It is better for the pseudo support system to have light transmittance. Since the dummy support has translucency, when the photosensitive resin layer is exposed, the photosensitive resin layer can be exposed via the dummy support. In the present disclosure, “having translucency” means that the transmittance of light of the wavelength used for pattern exposure is 50% or more. In the pseudo support, from the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the light transmittance of the wavelength (preferably 365nm) used for pattern exposure is preferably 60% or more, and more preferably 70% or more. good. In the present disclosure, "transmittance" refers to the emitted light that passes through the layer to be measured when light is incident in the direction perpendicular to the main surface of the layer to be measured (that is, the thickness direction) The ratio of the intensity of the incident light to the intensity of the incident light. The transmittance was measured using MCPD Series manufactured by OTSUKA ELECTRONICS CO., LTD.

As a dummy support body, a glass substrate, a resin film, and paper are mentioned, for example. From the viewpoints of strength, flexibility, and light transmittance, a pseudo-support system resin film is preferable.

Examples of resin films include polyethylene terephthalate films (that is, PET films), cellulose triacetate films, polystyrene films, and polycarbonate films. A resin film-based PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness of the pseudo support is not limited. The thickness of the dummy support may be determined based on, for example, the strength, light transmittance, material of the dummy support, and flexibility required when bonding the photosensitive transfer material and the substrate. The average thickness of the pseudo support is preferably 5 μm to 100 μm. Furthermore, from the viewpoint of ease of handling and versatility, the average thickness of the pseudo support is preferably 5 μm to 50 μm, more preferably 5 μm to 20 μm, more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 16 μm.

The average thickness of the constituent elements of the photosensitive transfer material (for example, the dummy support and the photosensitive resin layer) is measured by the following method. A scanning electron microscope (SEM) was used to observe the cross section in the direction perpendicular to the main surface of the photosensitive transfer material (that is, the thickness direction). Based on the obtained observation image, the thickness of 10 target constituent elements was measured. Calculate the average thickness of the target component by averaging the measured values.

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

The arithmetic average roughness Ra is measured by the following method. A three-dimensional optical profiler (New View 7300, manufactured by Zygo Corporation) was used to obtain the surface profile of the measurement object under the following conditions. As the measurement and analysis software, MetroPro ver8.3.2. Microscope Application is used. Then, use the above software to display the Surface Map screen, and obtain the color gradation statistics on the Surface Map screen. The arithmetic average roughness Ra of the surface of the object to be measured is obtained from the obtained gradation statistics. Furthermore, when the surface of the measurement target is in contact with the surface of another layer, the arithmetic average roughness Ra of the surface of the measurement target exposed by peeling the measurement target from the other layer may be measured.

The pseudo support (especially, the resin film) is preferably free from deformation (for example, wrinkles), scratches, and defects, for example. From the viewpoints of the patterning property during pattern exposure through the dummy support and the transparency of the dummy support, it is preferable that the number of particles, foreign substances, defects, and precipitates contained in the dummy support be small. In the pseudo support, the number of particles, foreign bodies, and defects with a diameter of 1 μm or more ^{is preferably 50 pieces/10mm 2} or less, 10 pieces/10mm ² or less is more preferable, and 3 pieces/10mm ² or less is even more preferable. 0 pcs/10mm ² is particularly good.

With regard to the preferred aspect of the pseudo support, for example, in Japanese Patent Application Publication No. 2014-085643, paragraphs 0017 to 0018, Japanese Patent Application Publication No. 2016-027363, paragraphs 0019 to 0026, and International Publication No. 2012/081680 It is described in paragraphs 0041 to 0057 of No. 2018/179370, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese Patent Application Publication No. 2019-101405. The contents of these bulletins are quoted in this manual by reference.

[Photosensitive resin layer] The photosensitive transfer material of the present disclosure has an alkali-soluble polymer (hereinafter, sometimes referred to as "polymer A".) and an ethylenically unsaturated bond-containing compound (hereinafter, sometimes referred to as "polymerizable compound B"). ".) and the photosensitive resin layer of the photopolymerization initiator. The content ratio of a phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer (hereinafter, abbreviated as "phenolic compound" in some cases) is 300 ppm or less with respect to the total mass of the photosensitive resin layer. Hereinafter, the photosensitive resin layer will be specifically described.

(Polymer A) The photosensitive resin layer contains an alkali-soluble polymer (that is, polymer A). Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.

From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the acid value of polymer A is preferably 250 mgKOH/g or less, more preferably less than 230 mgKOH/g, and less than 210 mgKOH /g is especially good. The lower limit of the acid value is not limited. From the viewpoint of more excellent developability, the acid value of polymer A is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, more preferably 150 mgKOH/g or more, and particularly preferably 170 mgKOH/g or more. The acid value of the polymer A can be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group, for example.

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

The weight average molecular weight (Mw) of polymer A is preferably 5,000 to 500,000. From the viewpoint of improving the resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight of polymer A is more preferably 100,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties, edge melting properties, and chipping properties of the developed agglomerates, it is preferable to set the weight average molecular weight to 5,000 or more. The weight average molecular weight of the polymer A is more preferably 10,000 or more, more preferably 15,000 or more, and particularly preferably 20,000 or more. Edge melting property refers to the degree to which the photosensitive resin layer easily overflows from the end surface of the roll when the photosensitive transfer material is wound into a roll shape. The chipping property refers to the degree to which chips are easily splashed when the unexposed film is cut with a cutter. For example, if the chips adhere to the surface of the photosensitive transfer material, the chips are transferred to the mask in the exposure step, which may cause defective products.

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

From the viewpoint of suppressing deterioration of the line width and resolution when the focus position is shifted during exposure, it is preferable that the polymer A has a structural unit derived from a monomer having an aromatic hydrocarbon group.

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

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

Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (for example, methyl styrene, vinyl toluene, and tertiary butoxy styrene). , Acetoxy styrene, 4-vinyl benzoic acid, styrene dimer and styrene trimer). A monomer having an aromatic hydrocarbon group or a monomer having an aralkyl group or styrene is preferred.

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

As a monomer having a phenylalkyl group, for example, phenylethyl (meth)acrylate can be mentioned.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group (for example, benzyl (meth)acrylate and chlorobenzyl (meth)acrylate), and vinyl monomers having a benzyl group (For example, vinyl benzyl chloride and vinyl benzyl alcohol). Mono-system benzyl (meth)acrylate having a benzyl group is preferred.

In one embodiment, when the structural unit derived from a monomer having an aromatic hydrocarbon group in the polymer A is a structural unit derived from benzyl (meth)acrylate, the polymer A is derived from (former The content ratio of the constituent units of the benzyl acrylate monomer relative to the total mass of the polymer A is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, and 70% to 90% by mass The mass% is more preferable, and 75 mass% to 90 mass% is particularly preferable.

In one embodiment, when the structural unit derived from a monomer having an aromatic hydrocarbon group in the polymer A is a structural unit derived from styrene, the structural unit derived from styrene in the polymer A contains Relative to the total mass of polymer A, the ratio is preferably 20% to 70% by mass, more preferably 25% to 60% by mass, more preferably 30% to 60% by mass, and 30% to 55% by mass The quality% is particularly good.

In one embodiment, the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group is formed by polymerizing a monomer having an aromatic hydrocarbon group and a monomer selected from the first monomer described later and the second monomer described later A copolymer obtained from at least one of the constituent groups is preferred. The above-mentioned copolymer has a structural unit derived from a monomer having an aromatic hydrocarbon group and at least one selected from the group consisting of a structural unit derived from a first monomer and a structural unit derived from a second monomer.

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

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

The content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% to 50% by mass relative to the total mass of the polymer A, more preferably 10% to 40% by mass, 15 Mass%-30% by mass is particularly good.

The second single system is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. The second single system may also be a monomer that does not have an aromatic hydrocarbon group in the molecule. Examples of the second monomer include (meth)acrylate compounds, vinyl alcohol ester compounds, and (meth)acrylonitrile. In the present disclosure, "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

Examples of the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. ) N-butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) Cyclohexyl acrylate and 2-ethylhexyl (meth)acrylate.

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

The second single system is preferably at least one selected from the group consisting of methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate, (methyl) ) Methyl acrylate is more preferred.

The content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% to 60% by mass relative to the total mass of the polymer A, more preferably 10% to 50% by mass, 15 The mass %～45 mass% is particularly good.

From the viewpoint of suppressing the deterioration of the line width and resolution when the focus position is shifted during exposure, the polymer A contains a structural unit selected from a monomer having an aralkyl group and a structural unit derived from styrene At least one of the formed groups is preferable. For example, polymer A is selected from copolymers containing structural units derived from methacrylic acid, structural units derived from benzyl methacrylate, and structural units derived from styrene, and copolymers containing structural units derived from methacrylic acid, At least one of the group consisting of a copolymer derived from a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene is preferable.

In one embodiment, the polymer A contains 25% to 60% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 55% by mass of structural units derived from the first monomer, and A polymer derived from the constituent unit of the second monomer in an amount of 15% by mass to 55% by mass is preferable. Polymer A contains 25% to 40% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from the first monomer, and 30% to 45% by mass % Of the polymer derived from the constituent unit of the second monomer is more preferable.

In one embodiment, the polymer A contains 70% to 90% by mass of constituent units derived from a monomer having an aromatic hydrocarbon group and 10% to 25% by mass of constituent units derived from the first monomer. Polymers are preferred.

The polymer A system may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, the branched structure or the alicyclic structure can be introduced into the side chain of the polymer A. The base system having an alicyclic structure may be monocyclic or polycyclic. Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylate Base) tertiary butyl acrylate, isoamyl (meth)acrylate, tertiary amyl (meth)acrylate, second amyl (meth)acrylate, 2-octyl (meth)acrylate, (meth) ) 3-octyl acrylate and third octyl (meth)acrylate, etc. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and t-butyl methacrylate are preferred, and isopropyl methacrylate or t-butyl methacrylate are more preferred. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. In addition, (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are mentioned. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantane Ester, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate Alkyl ester, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, (methyl) )-3,5-Dimethyl-8-ethyl-1-adamantyl acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-(meth)acrylate Adamantyl ester, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methyleneinden-5-yl (meth)acrylate, octahydro-4 (meth)acrylate ,7-Methylene inden-1-yl methyl ester, (meth)acrylic acid-1-mentholyl ester, (meth)acrylic acid tricyclodecyl ester, (meth)acrylic acid-3-hydroxy-2, 6,6-Trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (methyl) (Nor) Camphenyl Acrylate, Isobornyl (Meth)acrylate, Fenchyl (Meth)acrylate, 2,2,5-Trimethylcyclohexyl (Meth)acrylate and Cyclohexyl (meth)acrylate Ester etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantane (meth)acrylate Ester, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthol (meth)acrylate or tricyclodecyl (meth)acrylate are preferred, (former Base) cyclohexyl acrylate, (nor)bornyl (meth)acrylate, isocamyl (meth)acrylate, 2-adamantyl (meth)acrylate or tricyclodecyl (meth)acrylate are Better.

The glass transition temperature (Tg) of polymer A is preferably 30°C to 180°C. In the photosensitive resin layer, since the Tg of the polymer A is 180° C. or less, it is possible to suppress the deterioration of the line width thickness and the resolution when the focus position shifts during exposure. From the above viewpoint, the Tg of polymer A is more preferably 170°C or less, and more preferably 160°C or less. In addition, from the viewpoint of improving the edge melting resistance, the Tg of the polymer A is preferably 30°C or higher. From the above viewpoint, the Tg of the polymer A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

The polymer A system may be a commercially available product or a synthetic product. The synthesis system of polymer A is preferably carried out, for example, as follows: Add an appropriate amount of radical polymerization initiator to a solution obtained by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone or isopropanol) (For example, benzoyl peroxide or azoisobutyronitrile), then, heating and stirring are performed. In addition, synthesis may be performed while dropping a part of the mixture into the reaction liquid. After the reaction, a solvent may be further added to adjust the concentration to a desired concentration. As a synthesis scheme, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

The photosensitive resin layer system may contain one kind of polymer A alone or two or more kinds of polymer A. When the photosensitive resin layer contains two or more types of polymer A, the photosensitive resin layer contains two or more types of polymer A having structural units derived from a monomer having an aromatic hydrocarbon group, or A polymer A which is a structural unit of a monomer having an aromatic hydrocarbon group and a polymer A which does not have a structural unit derived from a monomer having an aromatic hydrocarbon group are preferable. In the latter case, the content of polymer A having structural units derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, and more preferably 70% by mass or more with respect to the total mass of polymer A. Preferably, 80% by mass or more is more preferable, and 90% by mass or more is particularly preferable.

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

(Polymerizable compound B) The photosensitive resin layer contains an ethylenically unsaturated bond-containing compound (that is, polymerizable compound B). In the present disclosure, "a compound containing an ethylenically unsaturated bond" means a compound that contains an ethylenically unsaturated bond in the molecule and is polymerized by the action of a polymerization initiator described later. In addition, the polymerizable compound B is a compound different from the above-mentioned polymer A.

It is preferable that the polymerizable compound B has a polymerizable group. The polymerizable group in the polymerizable compound B is not limited as long as it is a group related to the polymerization reaction. As the polymerizable group in the polymerizable compound B, for example, a group containing an ethylenically unsaturated bond (for example, a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group Group) and cationic polymerizable group (for example, epoxy group and oxetanyl group). The polymerizable group is preferably an ethylenically unsaturated bond-containing group (hereinafter, sometimes referred to as "ethylenically unsaturated group"), and more preferably an acryloyl group or a methacryloyl group.

The polymerizable compound B is a compound having one or more ethylenically unsaturated groups in one molecule (that is, an ethylenically unsaturated compound), and it is more preferable that it has two or more ethylenically unsaturated groups in one molecule. Compounds (that is, polyfunctional ethylenically unsaturated compounds) are particularly preferred. In addition, from the viewpoint of better resolution and releasability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 The following are particularly good.

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

From the viewpoint of a more excellent balance between photosensitivity, resolution, and releasability in the photosensitive resin layer, the polymerizable compound B is selected from compounds having two ethylenically unsaturated groups in one molecule (that is, At least one of the group consisting of a bifunctional ethylenically unsaturated compound) and a compound having 3 ethylenically unsaturated groups in one molecule (that is, a trifunctional ethylenically unsaturated compound) is preferred. Among them, a compound having two ethylenically unsaturated groups is more preferred.

In the photosensitive resin layer, from the viewpoint of excellent peelability of the photosensitive resin layer, the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is preferably 60% by mass or more, and more than 70% by mass % Is more preferable, and more than 90% by mass is particularly preferable. The upper limit of the content ratio of the bifunctional ethylenically unsaturated compound with respect to the content of the polymerizable compound B is not limited, and may be 100% by mass. That is, all the polymerizable compounds B contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

-Polymerizable compound B1- The photosensitive resin layer preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule of the above-mentioned polymerizable compound B.

In the photosensitive resin layer, from the viewpoint of better resolution, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, more preferably 50% by mass or more, and 55 mass% % Or more is more preferable, and 60 mass% or more is particularly preferable. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. From the standpoint of releasability, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, more preferably 90% by mass or less, and 85 mass% % Or less is particularly good.

Examples of the aromatic ring in the polymerizable compound B1 include aromatic hydrocarbon rings (for example, benzene ring, naphthalene ring, and anthracene ring), aromatic heterocycles (for example, thiophene ring, furan ring, pyrrole ring, imidazole ring, Triazole ring and pyridine ring) and their condensed rings. The aromatic ring system is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. Furthermore, the aromatic ring system may have a substituent.

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

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the above-mentioned bisphenol structure. . Each polymerizable group may be directly bonded to the bisphenol structure. Each polymerizable group system may be bonded to the bisphenol structure via one or more alkoxylate groups. The alkoxylate group or propoxylate group added to the two ends of the bisphenol structure is preferable, and the ethoxy group is more preferable. The number of alkoxy groups added to the bisphenol structure is not limited, but it is preferably 4 to 16 per molecule, and more preferably 6 to 14 per molecule.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP 2016-224162 A. The content of the above-mentioned bulletin is quoted in this manual by reference.

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

As 2,2-bis(4-((meth)acryloxy polyalkoxy)phenyl)propane, for example, 2,2-bis(4-(methacryloxy diethoxy) Phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2 -Bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, SHIN-NAKAMURA CHEMICAL CO, LTD.), 2,2-bis(4-(methacryloxy) Dodecethoxy tetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecethoxy) Phenyl) propane (BPE-1300, SHIN-NAKAMURA CHEMICAL CO, LTD.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, SHIN- NAKAMURA CHEMICAL CO, LTD.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, SHIN-NAKAMURA CHEMICAL CO, LTD.).

As the polymerizable compound B1, a compound represented by the following general formula (I) can also be mentioned.

[Chemical formula 3]

In general formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A system represents C ₂ H ₄ , B system represents C ₃ H ₆ , n ₁ and n ₃ systems each independently represent 1 An integer of ～39, n ₁ +n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, n ₂ +n ₄ is an integer of 0 to 30, -(AO)- And the arrangement system of the repeating unit of -(BO)- can be random or block. In the case of a block, any one of -(AO)- and -(BO)- may be the biphenyl side. n ₂ +n ₄ is preferably an integer of 0-10, more preferably an integer of 0-4, more preferably an integer of 0-2, and particularly preferably 0. n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2-20, more preferably an integer of 2-16, and particularly preferably an integer of 4-12.

The photosensitive resin layer system may contain one kind alone or two or more kinds of polymerizable compound B1.

From the viewpoint of more excellent resolution, the content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more with respect to the total mass of the photosensitive resin layer, and more preferably 20% by mass or more. The upper limit of the content ratio of the polymerizable compound B1 is not limited. From the viewpoint of transferability and edge melting resistance, the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 70% by mass or less, and 60% by mass or less relative to the total mass of the photosensitive resin layer Better.

The photosensitive resin layer system may contain a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (that is, compounds having one ethylenically unsaturated group in one molecule), and bifunctional compounds that do not have an aromatic ring. Ethylene unsaturated compounds (that is, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups) and trifunctional or more ethylenically unsaturated compounds (that is, have three in one molecule The above ethylenically unsaturated group compound).

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

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

Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), tricyclodecane dimethanol dimethacrylic acid Esters (DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1,9-nonanediol diacrylate (A-NOD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1,6-hexanediol diacrylate Esters (A-HD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.

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

Examples of urethane di(meth)acrylates include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane Ester di(meth)acrylate. Examples of commercially available products include 8UX-015A (TAISEI FINE CHEMICAL CO,. LTD.), UA-32P (SHIN-NAKAMURA CHEMICAL CO, LTD.), and UA-1100H (SHIN-NAKAMURA CHEMICAL CO, LTD.) .

Examples of ethylenically unsaturated compounds having trifunctional or higher functionality include dineopentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, and neopentaerythritol (tri/tetra) (meth)acrylic acid. Ester, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri( Meth) acrylates, glycerol tri(meth)acrylates and these alkylene oxide modifications. In the present disclosure, “(three/four/five/six) (meth)acrylate” includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate The concept of meth)acrylate. In the present disclosure, “(tri/tetra)(meth)acrylate” includes the concepts of tri(meth)acrylate and tetra(meth)acrylate.

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

As the polymerizable compound B other than the polymerizable compound B1, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP 2004-239942 A can also be cited.

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

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

The photosensitive resin layer system may contain one kind alone or two or more kinds of polymerizable compounds B.

The content of the polymerizable compound B in the photosensitive resin layer is preferably 10% to 70% by mass relative to the total mass of the photosensitive resin layer, more preferably 20% to 60% by mass, and more preferably 20% to 60% by mass, relative to the total mass of the photosensitive resin layer. 50% by mass is particularly good.

(Photopolymerization initiator) The photosensitive resin layer contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives activating light (for example, ultraviolet rays, visible rays, and X-rays) to start polymerization of a polymerizable compound (for example, polymerizable compound B).

The photopolymerization initiator is not limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators, and photoradical polymerization initiators are preferred.

As the photoradical polymerization initiator, for example, a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, and an α-hydroxyalkylphenone structure The photopolymerization initiator, the photopolymerization initiator with the phosphine oxide structure and the photopolymerization initiator with the N-phenylglycine structure.

From the viewpoints of photosensitivity, visibility of exposed parts, and visibility and resolution of unexposed parts, the photosensitive resin layer contains 2,4,5-triarylimidazole dimer and 2,4, At least one of the derivatives of the 5-triarylimidazole dimer is preferably used as the photoradical polymerization initiator. Furthermore, the two 2,4,5-triarylimidazole structural systems in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.

As a derivative of 2,4,5-triarylimidazole dimer, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)- 4,5-Diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-095716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can also be cited. .

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethyl Oxybenzyl) and benzophenone.

As commercially available products of the photoradical polymerization initiator, for example, TAZ-110 (Midori Kagaku Co., Ltd.), TAZ-111 (Midori Kagaku Co., Ltd.), 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)benzene Yl]-1,2-octanedione-2-(ortho-benzoic oxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF company), 1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]ethylenedione-1-(o-acetoxime) (trade name: IRGACURE OXE-02, BASF company), IRGACURE OXE-03 (BASF company) , IRGACURE OXE-04 (BASF company), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-oralolinyl)phenyl ]-1-Butanone (trade name: Omnirad 379EG, IGM Resins BV company), 2-methyl-1-(4-methylthiophenyl)-2-porolin-1-one (trade name : Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl]phenyl}-2-methylprop-1- Ketone (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-terminal phenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-Dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethyl Benzyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV) and oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Management Ltd.).

The photocationic polymerization initiator (ie, photoacid generator) is a compound that generates acid by receiving activating light. As the photocationic polymerization initiator, a compound that generates an acid in response to activation light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, is preferred. However, the chemical structure of the photocationic polymerization initiator is not limited. In addition, with regard to the photocationic polymerization initiator that does not directly induce activation light with a wavelength of 300 nm or more, as long as it is a compound that generates an acid by simultaneously using a sensitizer to induce activation light with a wavelength of 300 nm or more, it can also be combined with the sensitizer. It is preferably used in combination with agents.

The photocationic polymerization initiator is preferably a photocationic polymerization initiator that produces an acid with a pKa of 4 or less, and a photocationic polymerization initiator that produces an acid with a pKa of 3 or less is more preferred, and it produces an acid with a pKa of 2 or less. The light cationic polymerization initiator is particularly preferred. The lower limit of pKa is not limited. It is preferable that the pKa system of the acid generated by the photocationic polymerization initiator is, for example, -10.0 or more.

Examples of the photocationic polymerization initiator include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

Examples of the ionic photocationic polymerization initiator include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonate compounds) and quaternary ammonium salt compounds.

As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP 2014-085643 A can also be cited.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-tris compounds, diazomethane compounds, imine sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-tris compound, the diazomethane compound, and the imine sulfonate compound, for example, the compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A can be cited. In addition, as the oxime sulfonate compound, for example, the compounds described in paragraphs 084 to 0088 of International Publication No. 2018/179640 can be cited.

The photosensitive resin layer preferably contains a photoradical polymerization initiator, and contains a derivative selected from the group consisting of 2,4,5-triarylimidazole dimer and 2,4,5-triarylimidazole dimer. At least one of the groups is more preferable.

The photosensitive resin layer system may contain one kind alone or two or more kinds of photopolymerization initiators.

The content ratio of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or more with respect to the total mass of the photosensitive resin layer, more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The upper limit of the content ratio of the photopolymerization initiator is not limited. The content ratio of the photopolymerization initiator relative to the total mass of the photosensitive resin layer is preferably 10% by mass or less, and more preferably 5% by mass or less.

(Phenolic compound) The content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer is 300 ppm or less with respect to the total mass of the photosensitive resin layer. When the content of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer is 300 ppm or less, it is possible to reduce the amount of side erosion that accompanies the elapse of the continuous standing time after lamination.

From the viewpoint of reducing the amount of side etching accompanying the elapse of the continuous standing time after lamination, the content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer is preferably as small as possible. Specifically, the content ratio of the phenolic compound with a molecular weight of 300 or less is preferably 200 ppm or less relative to the total mass of the photosensitive resin layer, more preferably 100 ppm or less, more preferably 50 ppm or less, and particularly 20 ppm or less. good. The content ratio of the phenolic compound having a molecular weight of 300 or less may be 15 ppm or less or 10 ppm or less with respect to the total mass of the photosensitive resin layer.

From the viewpoint of reducing the amount of side etching, the lower limit of the content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer is not limited. When setting the lower limit of the phenolic compound content ratio, the content ratio of the phenolic compound with a molecular weight of 300 or less in the photosensitive resin layer may be determined within the range of 0 ppm or more relative to the total mass of the photosensitive resin layer . The content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer may exceed 0 ppm with respect to the total mass of the photosensitive resin layer.

The content ratio of the phenolic compound with a molecular weight of 300 or less is measured by the following method. 100 mg of the photosensitive resin layer collected from the photosensitive transfer material was dissolved in 1 g of tetrahydrofuran. 1 g of ultrapure water was added to the resulting mixture, and after ultrasonic treatment for 10 minutes, it was filtered using a membrane filter with a pore size of 0.45 μm. Measure the content of phenolic compounds in the filtrate by high performance liquid chromatography (HPLC). The measurement conditions are shown below. Based on the measurement result, the content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer was determined. (1) Measuring equipment: SHIMADZU 20A (Shimadzu Corporation) (2) Column: TOSOH TSKgel ODS-80Ts (4.6mm×15cm, particle size: 5μm) (3) Temperature: 40℃ (4) Injection volume: 19μL (5) Flow rate: 1mL/min (6) Eluent: a mixture of liquid A and liquid B [liquid A/liquid B (volume ratio) = 20/80, liquid A: tetrahydrofuran, liquid B: ion exchange water (998 vol%), phosphoric acid (1 The mixture of volume %) and triethylamine (1 volume %) (ion exchange water/phosphoric acid/triethylamine (volume ratio)=998/1/1)]

The molecular weight of the phenolic compound whose content ratio is restricted in the photosensitive resin layer is 300 or less. The reason for setting the upper limit of the molecular weight to 300 is that, as described above, it is easy to cause side corrosion due to the concentration of low molecular weight phenolic compounds. The molecular weight of the phenolic compound may be 250 or less. The lower limit of the molecular weight of the phenolic compound is not limited. When setting the lower limit of the molecular weight of the phenolic compound, the molecular weight of the phenolic compound may be determined within the range of 94.11 or more. Examples of the phenolic compound having a molecular weight of 94.11 include compounds represented _{by C 6} H _{5 OH.}

The structure system containing the phenolic compound whose ratio is restricted in the photosensitive resin layer is not restricted as long as it contains an aromatic ring and the hydroxyl group bonded to the said aromatic ring. The aromatic ring system in the phenolic compound may be a monocyclic ring or a condensed ring. Substituents other than the hydroxyl group may be bonded to the aromatic ring in the phenolic compound. The number of hydroxyl groups in the phenolic compound may be one or two or more.

The phenolic compound whose content ratio is restricted in the photosensitive resin layer is preferably a phenolic compound containing a benzene ring and a hydroxyl group bonded to the above-mentioned benzene ring, and a phenolic compound represented by the following formula (1) is more preferred. good.

[Chemical formula 4]

In formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a hydroxyl group or an alkoxy group having 1 to 6 carbons . The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The alkoxy group may be a linear alkoxy group, a branched alkoxy group, or a cyclic alkoxy group.

The phenolic compound whose content ratio is restricted in the photosensitive resin layer preferably contains at least one selected from the group consisting of the following phenolic compounds: a phenolic compound represented by the following formula (1-1), The phenolic compound represented by the formula (1-2), the phenolic compound represented by the following formula (1-3), the phenolic compound represented by the following formula (1-4), and the phenolic compound represented by the following formula (1- 5) Said phenolic compound.

[Chemical formula 5]

The phenolic compound represented by formula (1-1) is 4-methoxyphenol. The phenolic compound represented by formula (1-2) is hydroquinone. The phenolic compound represented by formula (1-3) is 3,5-di-tert-butyl-4-hydroxytoluene. The phenolic compound represented by formula (1-4) is 2-tert-butyl-4,6-dimethylphenol. The phenolic compound represented by formula (1-5) is 4-tert-butylcatechol.

It is considered that most of the phenolic compounds having a molecular weight of 300 or less in the photosensitive resin layer are derived from the raw material of the photosensitive resin layer. For example, by removing the phenolic compound having a molecular weight of 300 or less contained in the raw material of the photosensitive resin layer, the content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer can be reduced. As a method of removing phenolic compounds with a molecular weight of 300 or less, for example, a method of dissolving the raw material in an organic solvent and then washing with an aqueous alkali solution, a method of recrystallizing low-molecular phenolic compounds, and reprecipitation of the raw material The method of purification and the method of using anion exchange resin. However, the method for removing phenolic compounds with a molecular weight of 300 or less is not limited to the above-mentioned method, and a known method can also be used.

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

-pigment- From the viewpoints of the visibility of the exposed part, the visibility of the unexposed part, the visibility of the pattern after development, and the resolution, the photosensitive resin layer contains the wavelength range during color development, that is, the maximum at 400nm to 780nm A dye whose absorption wavelength is 450 nm or more and whose maximum absorption wavelength changes due to acid, alkali, or radicals (hereinafter, sometimes referred to as "dye N") is preferred. The detailed mechanism is not yet clear, but the photosensitive resin layer containing the dye N can improve the adhesion to the layers adjacent to the photosensitive resin layer (for example, the dummy support and the intermediate layer) and make the resolution more excellent.

In the present disclosure, the term "maximum absorption wavelength changes due to acid, alkali, or free radicals" used for pigments can mean that the pigment in the color-developing state is decolorized due to acid, alkali or free radicals, or in the decolorized state. The state where the pigment is colored due to acid, alkali or free radicals, and the state where the pigment in the colored state changes to the state of the colored state of other hue.

Specifically, the pigment N may be a compound that changes color from a decolorized state by exposure, or may be a compound that changes color from a color-developed state by exposure. In the above aspect, the pigment N may be a pigment that changes color or decolorization under the action of acid, alkali, or free radicals generated by exposure. In addition, the pigment N may be a pigment whose color or decolorization state changes due to the following conditions: the state (for example, pH) in the photosensitive resin layer changes due to acid, alkali, or free radicals generated by exposure. On the other hand, the pigment N can also be a pigment that is directly stimulated by acid, alkali, or free radicals in a colored or decolored state without being changed by exposure.

From the viewpoint of the visibility of the exposed part and the visibility and resolution of the unexposed part, the pigment N is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and the maximum absorption wavelength occurs due to free radicals. The changed pigment is better.

From the viewpoint of the visibility of the exposed part and the visibility and resolution of the unexposed part, the photosensitive resin layer contains both a pigment whose maximum absorption wavelength changes due to radicals and a photo-radical polymerization initiator It is preferable as the dye N.

From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, the pigment N is preferably a pigment that develops color by acid, alkali, or free radicals.

As an example of the color development mechanism of the pigment N, a radical reactive pigment, an acid reactive pigment, or a base reactive pigment (such as a colorless pigment) develops color by free radicals, acids or alkalis. The free radicals , Acid or base is polymerized by photoradical polymerization by exposing the photosensitive resin layer containing photoradical polymerization initiator, photocationic polymerization initiator (ie, photoacid generator) or photobase generator The initiator, photocationic polymerization initiator or photobase generator is produced.

Among the pigment N, from the viewpoint of visibility of the exposed part and the visibility of the unexposed part, the wavelength range during color development, that is, the maximum absorption wavelength at 400 nm to 780 nm is preferably 550 nm or more, and 550 nm to 700 nm More preferably, 550-650nm is particularly preferred.

In addition, the dye N may have one or more maximum absorption wavelengths in the wavelength range during color development, that is, 400 nm to 780 nm. When the pigment N has two or more maximum absorption wavelengths in the wavelength range during color development, that is, 400 nm to 780 nm, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of pigment N is measured as follows: In an atmospheric environment, use a spectrophotometer (UV3100, Shimadzu Corporation) to measure the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in the range of 400nm to 780nm, and then, The wavelength at which the intensity of the detection light becomes the smallest (maximum absorption wavelength).

Examples of pigments that develop or decolor by exposure to light include colorless compounds. Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane-based pigments, 㗁-based pigments, Kouyamaguchi-based pigments, iminonaphthoquinone-based pigments, azomethine-based pigments, and anthraquinones. Department of pigments. From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, the pigment N-based colorless compound is preferable.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane dye), a colorless compound having a spiropyran skeleton (spiropyran dye), a colorless compound having a fluoran skeleton (fluoran Dyes), colorless compounds with a diarylmethane skeleton (diarylmethane dyes), colorless compounds with a rhodamine lactam skeleton (rhodamine lactam dyes), and an indolyl phthalolactone skeleton The colorless compound (indolylphthalolactone pigment) and the colorless compound with the leuco auramine skeleton (colorless auramine pigment). The colorless compound-based triarylmethane-based dye or the fluoran-based dye is preferable, and the colorless compound having a triphenylmethane skeleton (triphenylmethane-based dye) or the fluoran-based dye is more preferable.

From the viewpoint of the visibility of the exposed part and the visibility of the unexposed part, it is preferable that the colorless compound has a lactone ring, a sulfinolactone ring, or a sultone ring. By reacting the lactone ring, sulfinolactone ring or sultone ring contained in the colorless compound with the free radical generated by the photo-radical polymerization initiator or the acid generated by the photo-cationic polymerization initiator, it is possible to The colorless compound is turned into a closed ring state to decolor, or the colorless compound is turned into an open ring state to develop a color. The colorless compound is preferably a compound having a lactone ring, a sulfinolactone ring, or a sultone ring, and the lactone ring, sulfinolactone ring, or sultone ring is colored by free radical or acid ring opening. Compounds that have a lactone ring and the lactone ring develops color by free radical or acid ring opening are more preferable.

Specific examples of colorless compounds include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Ciba-Geigy company), crystal violet lactone, peacock Limelactone, Benzyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino -3-Methyl-6-(N-ethyl-p-tolylamino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl Group-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran, 3-(N ,N-Diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-aminofluoran, 3 -(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran , 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-( N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N- Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-aminofluoran, 3-hexahydro Pyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindole -3-yl)phthalolactone, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalolactone, 3,3-bis(p-dimethylaminophenyl) )-6-dimethylaminophthalolactone, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3- Yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3' ,6'-Bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]Kou Yamaguchi-3-one.

As the dye N, for example, a dye may also be mentioned. Specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose red, m-amine yellow, revanol blue, Phenol blue, methyl orange, p-methyl red, Congo red, benzene red violet 4B, α-naphthalene red, Nile blue 2B, Nile blue A, methyl violet, malachite green, para-magenta, Victoria brilliant blue -Naphthalene sulfonate, Victoria Brilliant Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #603 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink #312 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet #308 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red OG (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red RR (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Green #502 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodan Ming 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilinyl-4-p-diethylaminophenyliminonaphthoquinone, 2-Carboxysterylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethyl Aminophenylimino-5-pyrazolone and 1-β-naphthalene-4-p-diethylaminophenylimino-5-pyrazolone.

From the viewpoints of the visibility of the exposed part, the visibility of the unexposed part, the visibility of the pattern after development, and the resolution, the pigment N is preferably a pigment whose maximum absorption wavelength changes due to free radicals. Pigments that develop color by free radicals are better.

The pigment N-based colorless crystal violet, crystal violet lactone, brilliant green or Victoria Brilliant Blue-naphthalene sulfonate is preferred.

The photosensitive resin layer system may contain one kind alone or two or more kinds of dye N.

From the viewpoints of the visibility of the exposed part, the visibility of the unexposed part, the visibility of the pattern after development, and the resolution, the content of the pigment N is 0.1% by mass or more relative to the total mass of the photosensitive resin layer Preferably, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is still more preferable, and 0.1% by mass to 1% by mass is particularly preferable.

The content ratio of the dye N means the content ratio of the dye when all the dye N contained in the photosensitive resin layer is brought into a color-developing state. Hereinafter, a method for quantifying the content of the pigment N will be described by taking a pigment that develops color by free radicals as an example. Two solutions were prepared by dissolving the pigment (0.001 g) and the pigment (0.01 g) in methyl ethyl ketone (100 mL). After adding IRGACURE OXE-01 (BASF Corporation) as a photo-radical polymerization initiator to each of the resulting solutions, radicals are generated by irradiating 365nm light, so that all pigments become color-developing states. Next, in an atmospheric environment, a spectrophotometer (UV3100, Shimadzu Corporation) was used to measure the absorbance of each solution at a liquid temperature of 25°C to create a calibration curve. Next, instead of the dye, the photosensitive resin layer (3 g) was dissolved in methyl ethyl ketone, except that the absorbance of the solution that developed all the dyes was measured by the same method as described above. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the pigment contained in the photosensitive resin layer was calculated according to the calibration curve.

-Surfactant- From the viewpoint of thickness uniformity, the photosensitive resin layer system preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and nonionic surfactants are preferred.

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

From the viewpoint of more excellent resolution, the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant. It is considered that this is because the photosensitive resin layer contains a fluorine-based nonionic surfactant, which prevents the etching solution from penetrating into the photosensitive resin layer and reduces side etching. Examples of commercially available fluorine-based nonionic surfactants include MEGAFACE (registered trademark) F-551 (DIC Corporation), MEGAFACE F-552 (DIC Corporation), and MEGAFACE F-554 (DIC Corporation).

Moreover, as commercial products of fluorine-based surfactants, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-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, R-41, R-41-LM, R-01, R-40, R- 40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation above), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited above ), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (the above are ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (the above are manufactured by OMNOVA Solutions Inc.), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (the above are manufactured by NEOS COMPANY LIMITED), etc.

In addition, as the fluorine-based surfactant, the following acrylic compounds can also be preferably used: having a molecular structure holding a functional group containing fluorine atoms, and when heated, the part of the functional group containing the fluorine atom is cut to make the fluorine atom Volatile. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Daily (February 23, 2016)), such as MEGAFACE DS-21 .

Furthermore, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

Moreover, as a fluorine-based surfactant, a block polymer can also be used.

In addition, as the fluorine-based surfactant, it is also possible to preferably use a structural unit derived from a (meth)acrylate compound having a fluorine atom and an alkylene derived from having 2 or more (preferably 5 or more) A fluorine-containing polymer compound which is a constituent unit of a (meth)acrylate compound of an oxy group (preferably an ethoxy group or a propoxy group).

In addition, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (the above are manufactured by DIC Corporation).

As a fluorine-based surfactant, from the viewpoint of improving environmental adaptability, it is derived from compounds having a linear perfluoroalkyl group with a carbon number of 7 or more, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Surfactants instead of materials are preferred.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol two Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (the above are made by BASF), Tetronic 304, 701, 704 , 901, 904, 150R1 (the above are made by BASF), Solsperse 20000 (the above are made by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (the above are made by FUJIFILM Wako Pure Chemical Corporation), PIONIN D -6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT Co., Ltd. above), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd. above), etc.

Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chain or terminal.

Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc. above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie company above), etc.

As the surfactant, for example, the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 4502784, and JP 2009 -The surfactant described in paragraphs 0060 to 0071 of the 237362 Bulletin.

The photosensitive resin layer system may contain one kind alone or two or more kinds of surfactants.

The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass relative to the total mass of the photosensitive resin layer, and more preferably 0.01% by mass to 3% by mass.

-additive- In addition to the above-mentioned components, the photosensitive resin layer system may contain well-known additives as necessary. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, resins and solvents other than polymer A. The photosensitive resin layer system may contain one kind alone or two or more kinds of additives.

The photosensitive resin layer system may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. The free radical polymerization inhibitor is preferably phenanthrene, phenanthrene, or 4-methoxyphenol. Examples of radical polymerization inhibitors other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin layer, it is preferable to use nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor.

The photosensitive resin layer system may contain a benzotriazole compound. Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)amino Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl) ) Aminomethylene-1,2,3-benzotriazole.

The photosensitive resin layer system may contain a carboxy benzotriazole compound. As the carboxybenzotriazole compound, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N -Di-2-ethylhexyl)amino ethylene carboxy benzotriazole. As a commercial product of a carboxybenzotriazole compound, CBT-1 (JOHOKU CHEMICAL CO., LTD) is mentioned, for example.

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

The photosensitive resin layer system may contain a sensitizer. The sensitizer is not limited, and a known sensitizer can be used. Moreover, as a sensitizer, dyes and pigments can also be used. As the sensitizer, for example, a dialkylamino benzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a 9-oxathione compound, acridine Ketone compounds, azole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazole compounds, thiophene compounds, naphthalene dimethicone Amide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive resin layer system may contain one kind alone or two or more kinds of sensitizers.

When the photosensitive resin layer contains a sensitizer, the content ratio of the sensitizer can be appropriately selected according to the purpose. However, it is important to increase the sensitivity to the light source and increase the curing speed by the balance between the polymerization speed and the chain transfer. From a viewpoint, it is preferable that it is 0.01 mass%-5 mass% with respect to the total mass of the photosensitive resin layer, and it is more preferable that it is 0.05 mass%-1 mass %.

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

The photosensitive resin layer system may contain resins other than polymer A. Examples of resins other than polymer A include acrylic resins, styrene-acrylic copolymers (including those having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, and polyvinyl alcohol. Formaldehyde, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, Polyallylamine and polyalkylene glycol.

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

The photosensitive resin layer may contain, for example, metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, At least one of the group consisting of a tackifier, a crosslinking agent, an organic precipitation inhibitor, and an inorganic precipitation inhibitor is used as an additive. The additives are described in, for example, paragraphs 0165 to 0184 of JP 2014-085643 A. The content of the above-mentioned bulletin is quoted in this manual by reference.

Hereinafter, the preferred combination of the above-mentioned components will be described. In one embodiment, the photosensitive resin layer contains 10% to 90% by mass of polymer A, 5% to 70% by mass of polymerizable compound B, and 0.01% by mass relative to the total mass of the photosensitive resin layer. ~20% by mass of the photopolymerization initiator is preferred.

(thickness) The average thickness of the photosensitive resin layer is usually 0.1 μm to 300 μm. The average thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, more preferably 0.5 μm, and particularly preferably 1 μm or more. The average thickness of the photosensitive resin layer is preferably 100 μm or less, more preferably 50 μm or less, more preferably 15 μm or less, and particularly preferably 8 μm or less. When the average thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer can be improved, and the resolution can be improved.

In one embodiment, the average thickness of the photosensitive resin layer is preferably 0.1 μm to 15 μm, more preferably 0.5 μm to 5 μm, more preferably 0.5 μm to 4 μm, and particularly preferably 0.5 μm to 3 μm.

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

(Formation method) The method of forming the photosensitive resin layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. As a method of forming the photosensitive resin layer, for example, a method of applying a photosensitive resin composition on the surface of the dummy support, and then drying the coating film of the photosensitive resin composition.

Examples of the photosensitive resin composition include a composition containing polymer A, polymerizable compound B, a photopolymerization initiator, optional components, and a solvent. In order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer, the photosensitive resin composition system preferably contains a solvent.

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

The photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The photosensitive resin composition contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and selected from the group consisting of ketone solvents and cyclic ether solvents At least one of them is more preferable. It is particularly preferable that the photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent.

As the alkylene glycol ether solvent, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, Dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.

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

As the solvent, the solvent described in Paragraph 0092 to Paragraph 0094 of International Publication No. 2018/179640 and the solvent described in Paragraph 0014 of JP 2018-177889 A can also be used. These contents are quoted in this manual by reference.

The photosensitive resin composition system may contain one kind alone or two or more kinds of solvents.

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

The preparation method of the photosensitive resin composition is not limited. As a method of preparing the photosensitive resin composition, for example, the following method is exemplified: a solution in which each component is dissolved in a solvent is prepared in advance, and the obtained solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition. The photosensitive resin composition is preferably filtered with a filter having a pore diameter of 0.2 μm to 30 μm before forming the photosensitive resin layer.

The coating method of the photosensitive resin composition is not limited, and a known method can be used. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

Moreover, the photosensitive resin layer system can also be formed by coating a photosensitive resin composition on the cover film mentioned later, and drying it.

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

Based on the mass, the content of the impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. Based on the mass, the content of impurities in the photosensitive resin layer can be 1 ppb or more or 0.1 ppm or more.

As a method of restricting impurities within the above-mentioned range, a raw material with a low content of impurities is selected as the raw material of the photosensitive resin layer, the mixing of impurities is prevented when the photosensitive resin layer is formed, and the manufacturing equipment is cleaned to remove the impurities. With this method, the amount of impurities can be limited within the above range.

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

Benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide in the photosensitive resin layer And the content of hexane is less preferably. As the content of the above-mentioned compound in the photosensitive resin layer, based on the mass, it is preferably 100 ppm or less, more preferably 20 ppm or less, and more preferably 4 ppm or less. The content of the above-mentioned compound in the photosensitive resin layer can be 10 ppb or more or 100 ppb or more based on mass. The above-mentioned compound system can suppress the content by the same method as the above-mentioned metal impurity. In addition, it can be quantified by a known measurement method.

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

[Other layers] The photosensitive transfer material of the present disclosure may have layers other than the above-mentioned layers (hereinafter referred to as "other layers"). Examples of other layers include a cover film, a thermoplastic resin layer, an intermediate layer, and a contrast enhancement layer.

(Cover film) The photosensitive transfer material of this disclosure may have a cover film (also called a protective film). According to the cover film, the surface of the layer (for example, photosensitive resin layer) in contact with the cover film can be protected.

In one embodiment, it is preferable that the photosensitive transfer material includes a dummy support, a photosensitive resin layer, and a cover film in this order. In the above-mentioned photosensitive transfer material, the photosensitive resin layer system may be laminated on the dummy support directly or through arbitrary layers. In the above-mentioned photosensitive transfer material, the cover film system may be layered on the photosensitive resin layer directly or via arbitrary layers. As an arbitrary layer in the said photosensitive transfer material, a thermoplastic resin layer, an intermediate layer, and a contrast enhancement layer mentioned later are mentioned, for example. However, the arbitrary layer system is not limited to those of the above-mentioned layers.

In one embodiment, the photosensitive transfer material preferably has a cover film that is in contact with the surface of the photosensitive resin layer on the side opposite to the side where the dummy support is arranged.

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

Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. The resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

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

From the viewpoint of more excellent resolution, the arithmetic average roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is arranged is preferably 0.3μm or less, more preferably 0.1μm or less, and particularly preferably 0.05μm or less . When the arithmetic average roughness of the surface of the cover film on the side where the photosensitive resin layer is disposed is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern can be improved. The lower limit of the arithmetic average roughness Ra is not limited. The arithmetic mean roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is arranged is preferably 0.001 μm or more. The arithmetic mean roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is arranged is measured by a method based on the method for measuring the arithmetic mean roughness Ra described in the "pseudo support" section.

(Thermoplastic resin layer) The photosensitive transfer material of this disclosure may have a thermoplastic resin layer. In one embodiment, the photosensitive transfer material preferably has a thermoplastic resin layer between the dummy support and the photosensitive resin layer. This is because the photosensitive transfer material has a thermoplastic resin layer between the dummy support and the photosensitive resin layer, which can improve the followability to the substrate in the step of attaching to the substrate, thereby suppressing the mixing of air bubbles into the substrate and the photosensitive resin layer. As a result, the adhesion between the layers can be improved.

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

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

From the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer, an alkali-soluble resin-based acrylic resin is preferred. Here, "acrylic resin" means having a group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate, and a structural unit derived from (meth)acrylamide At least one resin in the group.

In acrylic resin, the ratio of total content of (meth)acrylic acid-derived structural units, (meth)acrylate-derived structural units, and (meth)acrylic acid amide-derived structural units is relative to acrylic resin It is preferable that the total mass of the product is 50% by mass or more. In acrylic resin, the ratio of the total content of (meth)acrylic acid-derived structural units and (meth)acrylate-derived structural units is 30% to 100% by mass relative to the total mass of acrylic resin. Preferably, 50% by mass to 100% by mass is more preferable.

In addition, alkali-soluble resins are preferably polymers having acid groups. As the acid group, for example, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group can be mentioned, and a carboxyl group is preferred.

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

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not limited, and it can be appropriately selected and used from known resins. Examples of carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more in polymers described in paragraph 0025 of JP 2011-095716 A, The carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of JP 2010-237589 A, and paragraphs 0053 to 0068 of JP 2016-224162 A carboxyl-containing acrylic resin with an acid value of 60mgKOH/g or more in the binder polymer.

The content ratio of the carboxyl group-containing structural unit in the carboxyl group-containing acrylic resin is preferably 5% to 50% by mass relative to the total mass of the carboxyl group-containing acrylic resin, more preferably 10% to 40% by mass, 12 Mass%-30% by mass is particularly good.

From the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer, an alkali-soluble resin type acrylic resin having structural units derived from (meth)acrylic acid is particularly preferred.

The alkali-soluble resin system may have a reactive group. The reactive group may be, for example, an addition polymerizable group. As the reactive group, for example, an ethylenically unsaturated group, a condensation polymerizable group (for example, a hydroxyl group and a carboxyl group), and an addition polymerization reactive group (for example, an epoxy group and a (blocked) isocyanate group) are mentioned.

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

The thermoplastic resin layer system may contain one kind alone or two or more kinds of alkali-soluble resins.

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

-pigment- The thermoplastic resin layer contains pigments whose maximum absorption wavelength at 400nm-780nm is 450nm or more and the maximum absorption wavelength changes due to acid, alkali, or free radicals (hereinafter, sometimes referred to as "dye B ".) is better. Except for the aspects described below, the preferred aspect of the pigment B is the same as the preferred aspect of the above-mentioned pigment N.

From the viewpoint of the visibility of the exposed part and the visibility and resolution of the unexposed part, the pigment B is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and the maximum absorption wavelength changes due to acid The pigment is better.

From the viewpoints of the visibility of the exposed part and the visibility and resolution of the unexposed part, the thermoplastic layer contains a pigment whose maximum absorption wavelength changes due to acid and a compound that generates acid by light as described later as the pigment B. Better.

The thermoplastic resin layer system may contain one kind alone or two or more kinds of dye B.

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

Here, the content ratio of the dye B means the content ratio of the dye when all the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of the pigment B will be described by taking a pigment that develops color by free radicals as an example. Two solutions were prepared by dissolving the pigment (0.001 g) and the pigment (0.01 g) in methyl ethyl ketone (100 mL). After adding IRGACURE OXE-01 (BASF Corporation) as a photo-radical polymerization initiator to each of the resulting solutions, radicals are generated by irradiating 365nm light, so that all pigments become color-developing states. Next, in an atmospheric environment, a spectrophotometer (UV3100, Shimadzu Corporation) was used to measure the absorbance of each solution at a liquid temperature of 25°C to create a calibration curve. Next, in place of the dye, the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone, and except that the absorbance of the solution that developed all the dyes was measured by the same method as described above. From the absorbance of the resulting solution containing the thermoplastic resin layer, the amount of the pigment contained in the thermoplastic resin layer is calculated according to the calibration curve.

-Compounds that generate acids, bases or free radicals by light- The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, it may be referred to as "compound C"). Compound C is preferably a compound that receives activating light (for example, ultraviolet light and visible light) to generate acid, base or free radical. As the compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be mentioned. The compound C-based photoacid generator is preferred.

〔Photoacid generator〕 From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. As a photoacid generator, the photocationic polymerization initiator which may be contained in the said photosensitive resin layer is mentioned, and the preferable aspect is also the same except the point mentioned later.

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

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

[Chemical formula 6]

〔Photobase generator〕 The thermoplastic resin layer system may contain a photobase generator. As the photobase generator, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-aminomethanyl hydroxyamide, O-aminomethanyl oxime, [ [(2,6-Dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methyl Thiobenzyl)-1-methyl-1-endolinoethane, (4-endolinylbenzyl)-1-benzyl-1-dimethylaminopropane, N- (2-Nitrobenzyloxycarbonyl)pyrrolidine, hexaaminocobalt(III) tris(triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4- Endolinophenyl)-butanone, 2,6-dimethyl-3,5-diethanyl-4-(2-nitrophenyl)-1,4-dihydroxypyridine and 2,6 -Dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydroxypyridine.

〔Initiator for photoradical polymerization〕 The thermoplastic resin layer system may contain a photoradical polymerization initiator. Examples of the photo-radical polymerization initiator include photo-radical polymerization initiators that can be contained in the above-mentioned photosensitive resin layer, and preferred aspects are also the same.

The thermoplastic resin layer system may contain one kind of compound C alone or two or more kinds of compound C.

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

(Plasticizer) From the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability, the thermoplastic resin layer preferably contains a plasticizer.

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

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

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

As a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound described in the item of the said "polymerizable compound B" can be mentioned, for example. In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive resin layer are arranged in direct contact, it is preferable that the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound respectively . This is because when the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, respectively, the diffusion of the 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, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer, the (meth)acrylate compound is used after exposure It is better not to polymerize in the part.

In one embodiment, from the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability, the (meth)acrylate compound used as a plasticizer has two in one molecule The above (meth)acrylic (meth)acrylate compounds are preferred.

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

The thermoplastic resin layer system may contain one kind alone or two or more kinds of plasticizers.

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

(Interface active agent) From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. As a surfactant, the surfactant which the said photosensitive resin layer may contain is mentioned, for example, and the preferable aspect is also the same.

The thermoplastic resin layer system may contain one kind alone or two or more kinds of surfactants.

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

(Sensitizer) The thermoplastic resin layer system may contain a sensitizer. As a sensitizer, the sensitizer which the said photosensitive resin layer may contain is mentioned, for example.

The thermoplastic resin layer system may contain one kind alone or two or more kinds of sensitizers.

From the viewpoint of the improvement of the sensitivity to the light source, the visibility of the exposed part and the visibility of the unexposed part, the content of the sensitizer is 0.01% to 5% by mass relative to the total mass of the thermoplastic resin layer. Preferably, 0.05% by mass to 1% by mass is more preferable.

(additive) In addition to the above-mentioned components, the thermoplastic resin layer system may contain well-known additives as necessary.

In addition, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP 2014-085643 A. The content of the above-mentioned bulletin is quoted in this manual by reference.

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

(Formation method) The method of forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. As a method of forming the thermoplastic resin layer, for example, a method of applying a thermoplastic resin composition on the surface of the pseudo support and drying the coating film of the thermoplastic resin composition is mentioned.

As a thermoplastic resin composition, the composition containing the said component is mentioned, for example. In order to adjust the viscosity of the thermoplastic resin composition to facilitate the formation of the thermoplastic resin layer, the thermoplastic resin composition system preferably contains a solvent.

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

The thermoplastic resin composition system may contain one kind alone or two or more kinds of solvents.

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

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer described above. For example, a solution in which the components contained in the thermoplastic resin layer are dissolved in a solvent is prepared in advance, and the resulting solutions are mixed in a predetermined ratio to prepare a thermoplastic resin composition, and then the resulting thermoplastic resin composition is applied to By drying the coating film of the thermoplastic resin composition on the surface of the pseudo support, the thermoplastic resin layer can be formed. Moreover, after forming the photosensitive resin layer on the cover film mentioned later, you may form a thermoplastic resin layer on the surface of the photosensitive resin layer.

(middle layer) The photosensitive transfer material of the present disclosure preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. According to the intermediate layer, it is possible to suppress mixing of components when forming a plurality of layers and when storing the plurality of layers.

From the viewpoints of developing properties and suppressing mixing of components when coating a plurality of layers and when storing after coating, the intermediate layer is preferably a water-soluble layer. In the present disclosure, "water-soluble" means that the solubility in 100 g of water with a liquid temperature of 22°C and pH 7.0 is 0.1 g or more.

As the intermediate layer, for example, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-072724 can be cited. Since the intermediate layer is an oxygen barrier layer, the sensitivity during exposure can be improved, thereby reducing the time load of the exposure machine, and as a result, the productivity can be improved. The oxygen barrier layer used as the intermediate layer may be appropriately selected from well-known layers. The oxygen barrier layer used as the intermediate layer shows low oxygen permeability and is preferably an oxygen barrier layer dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

It is preferable that the intermediate layer contains resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, and vinyl ether-based resins. Resins, polyamide resins and copolymers of these. The resin-based water-soluble resin contained in the intermediate layer is preferable.

From the viewpoint of suppressing the mixing of components between multiple layers, the resin system contained in the intermediate layer, the polymer A contained in the photosensitive resin layer, and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer All different resins are preferred.

From the viewpoints of oxygen barrier properties and inhibiting the mixing of ingredients when coating multiple layers and during storage after coating, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinylpyrrolidone. good.

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

From the viewpoint of oxygen barrier properties and inhibiting the mixing of components when coating multiple layers and during storage after coating, the content of the resin in the intermediate layer is 50% by mass relative to the total mass of the intermediate layer. 100% by mass is more preferred, 70% by mass to 100% by mass is more preferred, 80% by mass to 100% by mass is still more preferred, and 90% by mass to 100% by mass is particularly preferred.

In addition, the intermediate layer may contain additives as necessary. Examples of additives include surfactants.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, it is possible to suppress the mixing of components when forming and storing the multiple layers without reducing the oxygen barrier property, and it is possible to suppress the increase in the removal time of the intermediate layer during development. .

The method of forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. As a method of forming the intermediate layer, for example, a method of applying the composition for the intermediate layer to the surface of the thermoplastic resin layer or the photosensitive resin layer, and then drying the coating film of the composition for the intermediate layer.

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

Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

(Contrast enhancement layer) The photosensitive transfer material of the present disclosure may have a contrast enhancement layer. The contrast enhancement layer is described in, for example, paragraph 0134 of International Publication No. 2018/179640 and paragraphs 0194 to 0196 of JP 2014-085643 A. The contents of these bulletins are quoted in this manual by reference.

＜＜Average thickness＞＞ The average thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The average thickness of the photosensitive transfer material is measured by the following method. A scanning electron microscope (SEM) was used to observe the cross section in the direction perpendicular to the main surface of the photosensitive transfer material (that is, the thickness direction). Based on the obtained observation image, the thickness of 10 photosensitive transfer materials was measured. The average thickness of the photosensitive transfer material is obtained by averaging the measured values arithmetic.

＜＜Shape＞＞ The shape of the photosensitive transfer material of this disclosure is not limited. From the viewpoint of versatility and transportability, the photosensitive transfer material of the present disclosure preferably has a roll shape. By winding up the photosensitive transfer material, the shape of the photosensitive transfer material can be rolled.

＜＜Manufacturing method＞＞ In the method of manufacturing the photosensitive transfer material of the present disclosure, for example, the method of forming each layer described in the section of "Components" described above can be used. Hereinafter, a preferred example of the method of manufacturing the photosensitive transfer material will be described with reference to FIG. 1. However, the manufacturing method of the photosensitive transfer material is not limited to the method demonstrated below.

FIG. 1 is a schematic diagram showing an example of the structure of the photosensitive transfer material. As a method of manufacturing the photosensitive transfer material 100 shown in FIG. 1, for example, a method including the following steps: a step of forming a photosensitive resin layer 12 by coating a photosensitive resin composition on the dummy support 10 And the step of disposing the cover film 14 on the above-mentioned photosensitive resin layer 12. In the above method, the photosensitive resin composition coated on the dummy support 10 may be dried as needed. The drying method is not limited, and a known drying method can be used.

As a method of arranging the cover film 14 on the photosensitive resin layer 12, for example, a method of pressing the cover film 14 to the photosensitive resin layer 12 can be cited.

By going through the above steps, the photosensitive transfer material 100 having the dummy support 10, the photosensitive resin layer 12, and the cover film 14 can be manufactured. The produced photosensitive transfer material 100 can be wound into a roll shape. The roll-shaped photosensitive transfer material 100 can be used, for example, in a bonding step of bonding a substrate by a roll-to-roll method.

＜＜Use＞＞ The photosensitive transfer material of the present disclosure can be used, for example, for the formation of resin patterns and the formation of circuit wiring. However, the use of the photosensitive transfer material of the present disclosure is not limited to the above-mentioned use.

<The manufacturing method of resin pattern and the manufacturing method of circuit wiring> The manufacturing method of the resin pattern of this disclosure is not limited as long as it is a manufacturing method of the resin pattern using the photosensitive transfer material of this disclosure. For example, in the case of using a photosensitive transfer material including a dummy support and a photosensitive resin layer, the method for manufacturing the resin pattern of the present disclosure preferably includes the following steps in order: The step of bonding the photosensitive transfer material of the present disclosure and the substrate (preferably a conductive substrate) in such a way that the surface on the side opposite to the side of the dummy support is in contact with the substrate (hereinafter, sometimes referred to as " Laminating step".); a step of patterning the photosensitive resin layer (hereinafter, sometimes referred to as "exposure step"); and a step of developing the photosensitive resin layer to form a resin pattern (hereinafter, sometimes Called the "development step".).

The manufacturing method of the circuit wiring of this disclosure is not limited as long as it is a manufacturing method of the circuit wiring using the photosensitive transfer material of this disclosure. The manufacturing method of the circuit wiring of the present disclosure preferably includes the following steps: preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material of the present disclosure in this order; and the above-mentioned laminate The step of etching the conductive layer existing in the area where the resin pattern is not arranged in the body (hereinafter, sometimes referred to as the "etching step").

The manufacturing method of the resin pattern of the present disclosure and the manufacturing method of the circuit wiring of the present disclosure are preferably performed by a roll-to-roll method, respectively. The roll-to-roll method refers to the following method, that is, including: using a reelable and unwindable substrate as a substrate, and unwinding before any of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method The step of the substrate or the structure including the substrate (also called the "unwinding step"); and after any step, the step of winding the substrate or the structure including the substrate (also called the "winding step"), And while conveying the substrate or the structure including the substrate, at least any one of the steps (preferably all the steps or all the steps except the heating step) is performed. The unwinding method in the unwinding step and the winding method in the winding step are not limited, and a known method may be used in the manufacturing method in which the roll-to-roll method is applied.

Hereinafter, each step included in the manufacturing method of the resin pattern of the present disclosure and the manufacturing method of the circuit wiring of the present disclosure will be described. However, unless otherwise specified, the description of each step included in the manufacturing method of the resin pattern of the present disclosure can also be applied to each step included in the manufacturing method of the circuit wiring of the present disclosure.

＜＜Lamination steps＞＞ The manufacturing method of the resin pattern of the present disclosure includes making the photosensitive resin layer in the photosensitive transfer material on the side opposite to the side where the dummy support is arranged (hereinafter, sometimes referred to as "first The step of bonding the photosensitive transfer material of the present disclosure and the substrate (preferably a conductive substrate) in contact with the substrate is preferable.

In the bonding step, the first surface of the photosensitive resin layer is brought into contact with the substrate (conducting layer when a conductive layer is provided on the surface of the substrate), and it is preferable to press the photosensitive transfer material and the substrate into contact . According to the above aspect, the adhesiveness between the first surface of the photosensitive resin layer and the substrate can be improved, and therefore the formed resin pattern can be suitably used as an etching resist.

When the photosensitive transfer material has a cover film, after removing the cover film from the photosensitive transfer material, the photosensitive transfer material and the substrate may be bonded together.

In the photosensitive transfer material, when a layer other than a cover film (for example, a high refractive index layer and/or a low refractive index layer) is disposed on the first surface of the photosensitive resin layer, the layer other than the cover film What is necessary is just to bond the 1st surface of a photosensitive resin layer and a board|substrate with a layer.

The method of pressure bonding the photosensitive transfer material and the substrate is not limited, and a known transfer method and lamination method can be used. The bonding of the photosensitive transfer material and the substrate is preferably performed by overlapping the first surface of the photosensitive resin layer and the substrate, and applying pressure and heating using a mechanism such as a roller. In addition, laminators, vacuum laminators, and automatic cutting laminators that can further increase productivity can be used for bonding.

[Substrate] The substrate is not limited, and a known substrate can be used. The substrate is preferably a substrate having a conductive layer, and a substrate having a substrate and a conductive layer provided on a part or the entire surface of the substrate is more preferred. The substrate system may have any layers other than the conductive layer as needed.

As a base material, glass, silicon, and a film are mentioned, for example.

The base material is preferably transparent. In the present disclosure, “transparent” means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more.

The refractive index of the substrate is preferably 1.50 to 1.52.

As a transparent glass substrate, for example, tempered glass represented by Gorilla Glass of Corning Incorporated is mentioned. Moreover, as a transparent glass substrate, for example, the materials used in Japanese Patent Application Publication No. 2010-086684, Japanese Patent Application Publication No. 2010-152809, and Japanese Patent Application Publication No. 2010-257492 can be used.

When a film substrate is used as the substrate, it is preferable to use a film substrate with low optical strain and/or high transparency. Examples of the above-mentioned film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymers.

The base film base material constituting the substrate used in the roll-to-roll method is preferable. Moreover, when manufacturing the circuit wiring for a touch panel by a roll-to-roll method, it is preferable that a base material is a sheet-like resin composition.

Examples of the conductive layer include conductive layers used for general circuit wiring or touch panel wiring. From the viewpoint of conductivity and fine line formation, the conductive layer is selected from at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Preferably, the metal layer is more preferable, and the copper layer or the silver layer is particularly preferable.

The substrate system may have one layer alone or two or more conductive layers. The substrate with more than two conductive layers is preferably a plurality of conductive layers with different materials.

Examples of the material of the conductive layer include metals and conductive metal oxides. Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . In the present disclosure, "conductivity" means that the volume resistivity is less than 1×10 ⁶ Ωcm. The volume resistivity of the conductive metal oxide is preferably ^{less than 1×10 4 Ωcm.}

When a resin pattern is produced using a substrate having a plurality of conductive layers, it is preferable that at least one conductive layer of the plurality of conductive layers contains a conductive metal oxide.

As the conductive layer, the electrode pattern of the sensor corresponding to the visual recognition part of the electrostatic capacitance type touch panel or the wiring of the peripheral lead part are preferable.

＜＜Exposure Step＞＞ The manufacturing method of the resin pattern of the present disclosure preferably includes a step of patterning the photosensitive resin layer after the above-mentioned bonding step.

The detailed configuration and specific size of the pattern in the pattern exposure are not limited. In order to improve the display quality of a display device (such as a touch panel) having an input device with circuit wiring manufactured by the circuit wiring manufacturing method, and to reduce the area occupied by the lead wiring, at least a part of the pattern (preferably The electrode pattern of the touch panel and/or the portion where the wiring is drawn) preferably includes fine lines with a width of 20 μm or less, and more preferably includes fine lines with a width of 10 μm or less.

The light source used in the exposure may be a light source capable of irradiating light of a wavelength (for example, 365nm or 405nm) of the photosensitive resin layer. Specific light sources include, for example, ultra-high-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

Exposure amount based ^{5mJ / cm 2 ~ 200mJ / cm} 2 is ^{preferred, 10mJ / cm 2 ~ 100mJ /} cm 2 is more preferred.

In the exposure step, pattern exposure may be performed after peeling the dummy support from the photosensitive resin layer, or the dummy support may be peeled after pattern exposure via the dummy support. In order to prevent the contamination of the photosensitive resin layer caused by the contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure through a dummy support. Furthermore, the pattern exposure system may be exposure through a mask, or it may be direct exposure using an exposure mechanism such as a laser.

＜＜Development step＞＞ The manufacturing method of the resin pattern of the present disclosure preferably includes the step of developing the photosensitive resin layer to form the resin pattern after the above-mentioned exposure step.

The development system of the photosensitive resin layer can be performed using a developer. The type of the developer is not limited as long as it can remove the non-image portion (unexposed portion) of the photosensitive resin layer. As the developer, a known developer (for example, the developer described in JP 5-072724 A) can be used.

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

The development method is not particularly limited, and may be any of rotary immersion development, shower development, shower and spin development, and dip coating development. Shower development refers to a development process in which a developer is sprayed onto the photosensitive resin layer after exposure in a shower to remove unexposed areas.

After the development step, it is better to use a shower to spray a cleaning agent and wipe with a brush to remove the development residue.

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

For example, when the photosensitive transfer material includes a thermoplastic resin and an intermediate layer, in the development step, the thermoplastic resin and the intermediate layer are also removed together with the non-image portion (unexposed portion) of the photosensitive resin layer. In addition, in the development step, the thermoplastic resin layer and the intermediate layer can be removed by dissolving or dispersing in the developer.

＜＜Etching step＞＞ The manufacturing method of the circuit wiring of the present disclosure preferably includes the following steps: preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material of the present disclosure in this order; and the above-mentioned laminate The step of etching the conductive layer in the area where the resin pattern is not arranged in the body. The resin pattern is preferably a resin pattern formed by a resin pattern manufacturing method including the bonding step, the exposure step, and the development step. The said laminated system can be manufactured by the manufacturing method of the said resin pattern, for example.

In the etching step, the conductive layer is etched by using the resin pattern as an etching resist. As a method of etching treatment, a known method can be applied. As a method of etching treatment, for example, the method described in paragraphs 0209 to 0210 of JP 2017-120435 A, the method described in paragraphs 0048 to 0054 of JP 2010-152155, immersion in Wet etching method in etching solution and method using dry etching (for example, plasma etching).

The etching solution used in the wet etching method may be an acidic or alkaline etching solution that is appropriately selected according to the object to be etched.

As an acidic etching solution, for example, an aqueous solution of an acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an acidic component selected from the group consisting of iron trichloride, A mixed aqueous solution of salts in the group consisting of ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components.

As the alkaline etching solution, for example, a single alkali component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines and organic amine salts (for example, tetramethylammonium hydroxide) An aqueous solution and a mixed aqueous solution of an alkali component and a salt (for example, potassium permanganate). The alkali component may be a component obtained by combining a plurality of alkali components.

＜＜Removal steps＞＞ It is preferable that the manufacturing method of the circuit wiring of the present disclosure includes a step of removing the remaining resin pattern (hereinafter, sometimes referred to as a "removing step"). The removal step is preferably performed after the etching step.

As a method of removing the remaining resin pattern, for example, a method of removing the remaining resin pattern by a chemical treatment can be cited. The method of removing the remaining resin pattern is preferably a method of removing the remaining resin pattern using a removing liquid. As a method of using the removing liquid, for example, a substrate with a residual resin pattern may be immersed in the removing liquid under stirring at a liquid temperature of preferably 30°C to 80°C, more preferably 50°C to 80°C for 1 minute. The 30-minute method.

Examples of the removal liquid include a removal liquid obtained by dissolving an inorganic alkali component or an organic alkali component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution of these. As an inorganic base component, sodium hydroxide and potassium hydroxide are mentioned, for example. As an organic base component, a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound are mentioned, for example.

The method of using the removing liquid to remove the remaining resin pattern is not limited to the dipping method, and may be a well-known method other than the dipping method (for example, spraying method, showering method, and rotary immersion method).

＜＜Other steps＞＞ The manufacturing method of the circuit wiring of the present disclosure may include any steps other than the above-mentioned steps (hereinafter, sometimes referred to as "other steps"). Examples of the exposure step, the development step, and other steps applicable to the circuit wiring manufacturing method of the present disclosure include the steps described in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696. In addition, as other steps, the steps shown below can be cited. However, the other steps are not limited to the steps shown below.

[Cover film peeling step] In the case where the photosensitive transfer material of the present disclosure has a cover film, the method of manufacturing the resin pattern of the present disclosure preferably includes the step of peeling the cover film from the photosensitive transfer material. The method of peeling off the cover film is not limited, and a known method can be applied.

[Steps to reduce the reflectivity of visible light] The manufacturing method of the circuit wiring of the present disclosure may include a step of reducing the visible light reflectivity of a part or all of the conductive layer in the substrate.

As a treatment to reduce the visible light reflectance of the conductive layer, for example, an oxidation treatment can be cited. When the conductive layer contains copper, the copper is oxidized to become copper oxide and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer.

The treatment of reducing the visible light reflectance of the conductive layer is described in paragraphs 0017 to 0025 of JP 2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 middle. The contents of these bulletins are quoted in this manual by reference.

[Step of forming an insulating film and forming a new conductive layer on the surface of the insulating film] The method for manufacturing the circuit wiring of the present disclosure preferably includes the step of forming an insulating film on the surface of the circuit wiring and the step of forming a new conductive layer on the surface of the insulating film. Through the above steps, two electrode patterns insulated by an insulating film can be formed.

The method of forming the insulating film is not limited. In the step of forming the insulating film, for example, the insulating film can be formed by a method of forming a known permanent film. In addition, a photosensitive material having insulating properties may be used to form an insulating film of a desired pattern by a photolithography method.

In the step of forming a new conductive layer on the insulating film, for example, a photosensitive material having conductivity can be used to form a new conductive layer of a desired pattern by a photolithography method.

In the method of manufacturing circuit wiring of the present disclosure, a substrate having conductive layers on both surfaces of the base material is used, and it is also preferable to form circuits on the conductive layers sequentially or simultaneously. According to the above method, for example, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface of the base material. Furthermore, according to the circuit wiring manufacturing method of the present disclosure, it is also preferable to roll the above-mentioned circuit wiring for the touch panel on both surfaces of the base material by using a roll pair.

＜＜Use of circuit wiring＞＞ The circuit wiring system manufactured by the circuit wiring manufacturing method of this disclosure can be applied to various devices. As a device provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring of this disclosure, for example, an input device can be cited. A touch panel is preferable, and an electrostatic capacitance type touch panel is more preferable. In addition, the aforementioned input device can be applied to various display devices (for example, an organic EL display device and a liquid crystal display device).

<Manufacturing method of touch panel> The manufacturing method of the touch panel of the present disclosure is not limited as long as it is the manufacturing method of the touch panel using the photosensitive transfer material of the present disclosure.

The manufacturing method of the touch panel of the present disclosure includes the step of arranging the substrate, the conductive layer, and the resin pattern formed using the photosensitive transfer material of the present disclosure in a laminate that is not configured with the above resin pattern. It is preferable to perform an etching process on the above-mentioned conductive layer in a region to form wiring for a touch panel. The resin pattern is preferably a resin pattern formed by a resin pattern manufacturing method including the bonding step, the exposure step, and the development step. The said laminated system can be manufactured by the manufacturing method of the said resin pattern, for example.

Regarding the aspect of each step in the manufacturing method of the touch panel of the present disclosure, as described in the item of "the manufacturing method of resin pattern and the manufacturing method of circuit wiring", the preferable aspect is also the same. Regarding the manufacturing method of the touch panel of this disclosure, in addition to forming the wiring for the touch panel by the above-mentioned method, what is necessary is just to refer to the manufacturing method of a well-known touch panel. In addition, the manufacturing method of the touch panel of the present disclosure may include any steps other than the above-mentioned steps.

According to the manufacturing method of the touch panel of the present disclosure, a touch panel having at least wiring for the touch panel can be manufactured. The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.

As a detection method of a touch panel, a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method are mentioned, for example. The detection method is preferably the electrostatic capacitance method.

As the type of touch panel, there may be a so-called in-cell type (for example, the structure described in Figures 5, 6, 7 and 8 of JP 2012-517051 A) and the so-called on-screen type ( For example, the configuration described in Figure 19 of JP 2013-168125 A, the configuration described in Figures 1 and 5 of JP 2012-089102 A), OGS (One Glass Solution) Type, TOL (Touch-on-Lens) type (for example, the structure described in Figure 2 of JP 2013-054727 A), various external types (for example, GG, G1/G2, GFF, GF2, GF1, and G1F) and other configurations (for example, the configuration described in Figure 6 of JP 2013-164871 A). [Example]

Hereinafter, the present disclosure will be described in detail through embodiments. However, the present disclosure is not limited to those of the following examples.

＜Synthesis of polymer A-1＞ Propylene glycol 1-monomethyl ether (75.0 g, FUJIFILM Wako Pure Chemical Corporation) was placed in a three-necked flask, and the temperature of the liquid was raised to 90°C in a nitrogen environment. Will contain styrene (32.0g), methacrylic acid (28.0g), methyl methacrylate (40.0g), 2,2'-azobis(isobutyronitrile) (0.8g, FUJIFILM Wako Pure Chemical Corporation) And a solution of propylene glycol 1-monomethyl ether (75.0 g, FUJIFILM Wako Pure Chemical Corporation) was added dropwise to the liquid in a three-necked flask maintained at 90°C ± 2°C over 2 hours. After the dropping, the mixed solution was stirred at 90°C±2°C for 2 hours to obtain a solution containing polymer A-1 (solid content concentration: 40.0% by mass). The weight average molecular weight of polymer A-1 is 40,000.

＜Synthesis of polymer A-2＞ Except for changing the usage amount of the monomers as described below, a solution containing polymer A-2 (solid content concentration: 40.0% by mass) was obtained in the same manner as the polymer A-1. The weight average molecular weight of polymer A-2 is 60,000. (1) Styrene: 52.0g (2) Methacrylic acid: 29.0g (3) Methyl methacrylate: 19.0g

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

<Synthesis of bifunctional methacrylate> Bisphenol A (22.83g, 0.1mol), toluene (30g) as a solvent, and triethylamine (0.3g) as a catalyst are added to the pressure resistance of 500mL In the reaction vessel. After replacing the inside of the pressure-resistant reaction vessel with nitrogen, the nitrogen pressure was adjusted to 0.2 kg/cm ² , and the mixture was heated to 80° C. while stirring. While introducing ethylene oxide (132.15g, 3.0mol) and propylene oxide (23.24g, 0.4mol) in order to maintain ^{a pressure of about 2kg/cm 2} , the temperature was raised to 150°C. After the mixture was kept at 150°C for 1 hour, it was cooled. The mixture was neutralized with oxalic acid, and then ion-exchanged water (50 g) was added to the mixture and stirred, and then the mixture was allowed to stand, thereby separating the organic layer, and extracting the several layers. After washing the obtained organic layer 3 times with ion-exchanged water (50 g), the pressure was reduced to 30 Torr at 50° C., and the solvent was removed, thereby obtaining a glycol (105.1 g). Add diol (100.0g, 0.044mol), methacrylic acid (11.5g), 70% by mass methanesulfonic acid aqueous solution (0.9g), hydroquinone (0.2g) and toluene (200mL) to the volume of 1L In a three-necked flask, then, esterification was performed under reflux of toluene for 8 hours. The water produced in the reaction is removed by the Dean-Stark device. After the reaction, the temperature of the mixture was cooled to room temperature, and the obtained organic layer was washed once with a 5% sodium hydroxide aqueous solution (50 g), and then washed with ion-exchanged water (50 g) three times. Hydroquinone monomethyl ether (0.09g) was added to the organic layer, and the pressure was reduced to 30 Torr at 50°C, and the solvent was removed to obtain ethylene oxide with an average of 15 mol added to both ends of bisphenol A. Dimethacrylate (90.0g) of polyethylene glycol containing an alkane and an average of 2 moles of propylene oxide.

<Examples 1 to 6 and Comparative Example 1> According to the following steps, a photosensitive transfer material is produced.

(Preparation of photosensitive resin composition) After mixing the selected components according to the description in Table 1, methyl ethyl ketone was added to prepare a photosensitive resin composition (solid content concentration: 25% by mass). The numerical values corresponding to the components described in Table 1 indicate the parts by mass of the solid content. In Examples 1 to 6, a raw material for removing low-molecular phenolic compounds by the method described later was used.

(Removal of phenolic compounds) According to the following steps, the low-molecular phenolic compounds in the raw materials are removed.

-Polymer A- After adding 250g of acetone to the solution containing the polymer corresponding to polymer A in Table 1 (250g), adding dropwise to the mixed solution containing ethyl acetate (250g) and heptane (2,250g), proceed By filtering, a white solid polymer was obtained. After removing the solvent by drying the polymer by blowing air at 50°C, it was re-dissolved in propylene glycol 1-monomethyl ether (FUJIFILM Wako Pure Chemical Corporation) to obtain a solution containing the target polymer (solid content concentration: 40.0% by mass) ).

-Polymerizable compound B- The compound (50 g) corresponding to the polymerizable compound B in Table 1 was dissolved in ethyl acetate (200 g), and then a 0.2% by mass aqueous sodium hydroxide solution (100 g) was added and stirred for 5 minutes. After stirring, the mixture was allowed to stand, thereby separating the organic layer, and extracting the organic layer. After washing the obtained organic layer 3 times with ion-exchange water (100g), "Irganox245" (BASF Corporation, 0.02g) was added, and the solvent was removed by reducing the pressure to 30 Torr at 50°C.

[Table 1] Ingredients [unit of value: parts by mass] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Polymer A Polymer A-1 - 55.00 - 62.20 - - - Polymer A-2 50.00 - - - - 51.00 25.00 Polymer A-3 - - 52.00 - 59.20 - 25.00 Polymeric compound B SR-480 (ARKEMA KK Japan) 36.20 20.20 7.40 - 27.00 15.00 16.00 BPE-200 (SHIN-NAKAMURA CHEMICAL CO, LTD.) - 9.80 - 20.00 - 10.00 - 2-functional methacrylate - - 10.00 - - - 10.00 M-270 (TOAGOSEI CO., LTD.) 5.00 - - - - - - A-TMPT (SHIN-NAKAMURA CHEMICAL CO, LTD.) - 10.00 10.00 6.00 - 5.00 - SR-454 (ARKEMA KK Japan) - - 15.00 9.00 - 5.00 - SR-502 (ARKEMA KK Japan) - - - - 4.00 - - A-9300-CL1 (SHIN-NAKAMURA CHEMICAL CO, LTD.) - - - - 7.80 9.77 18.37 Photopolymerization initiator 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.) 7.00 3.00 3.80 1.90 1.10 3.00 4.00 Sensitizer 4,4'-bis(diethylamine)benzophenone (Tokyo Chemical Industry Co., Ltd.) 0.50 0.50 0.30 0.30 0.10 0.30 0.30 Chain transfer agent Colorless Crystal Violet (Tokyo Chemical Industry Co., Ltd.) 0.40 0.90 - 0.40 0.66 0.60 0.50 N-Phenylglycine (Tokyo Chemical Industry Co., Ltd.) 0.20 - 1.00 - - - 0.50 Coloring agent (pigment) Bright Green (Tokyo Chemical Industry Co., Ltd.) - 0.05 0.05 0.05 - 0.02 0.02 Rust inhibitor CBT-1 (JOHOKU CHEMICAL CO.,LTD) 0.10 - 0.05 0.03 0.03 - 0.10 Mixture of two benzotriazole compounds - 0.14 0.05 - - 0.10 0.10 Polymerization inhibitor TDP-G (Kawaguchi Chemical Industry Co., LTD.) 0.30 0.10 - - - - - Irganox245 (BASF company) - - 0.20 0.10 0.10 0.20 0.10 N-nitrosophenylhydroxylamine aluminum salt (FUJIFILM Wako Pure Chemical Corporation) - - 0.01 0.02 0.01 0.01 0.01 Antioxidants Fenidone (Tokyo Chemical Industry Co., Ltd.) 0.01 0.01 0.01 - - - - Surfactant F-552 (DIC Corporation) 0.29 0.30 0.13 - - - -

In Table 1, "-" means that the usage amount is 0 parts by mass.

In Table 1, "2-functional methacrylate" refers to polyethylene glycol with an average of 15 mol of ethylene oxide and an average of 2 mol of propylene oxide added to both ends of bisphenol A. Dimethacrylate.

In Table 1, "a mixture of two benzotriazole compounds" means 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n Butylaminomethyl)-6-carboxybenzotriazole mixture. The mass ratio of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole to 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole The system is 1:1.

(Production of photosensitive transfer material) As a pseudo support, a PET film (TORAY INDUSTRIES, INC., Lumirror 16KS40, thickness: 16 μm, arithmetic average roughness Ra: 0.02 μm) was prepared. The photosensitive resin composition was applied on the surface of the dummy support using a slit-shaped nozzle so that the application width became 1.0 m and the thickness after drying became 8.0 μm. The formed coating film of the photosensitive resin composition was dried at 90° C. for 100 seconds, thereby forming a photosensitive resin layer. A polyethylene film (TAMAPOLY CO., LTD., GF-818, thickness: 19μm) was crimped on the surface of the formed photosensitive resin layer as a cover film to produce a photosensitive transfer material. The obtained photosensitive transfer material is rolled to produce a roll-shaped photosensitive transfer material.

＜Quantification of phenolic compounds＞ 100 mg of the photosensitive resin layer collected from the photosensitive transfer material was dissolved in 1 g of tetrahydrofuran. 1 g of ultrapure water was added to the resulting mixture, and after ultrasonic treatment for 10 minutes, it was filtered using a membrane filter with a pore size of 0.45 μm. The content ratio of phenolic compounds in the filtrate was measured by high performance liquid chromatography (HPLC). The measurement conditions are shown below. Based on the measurement result, the content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer was determined. The measurement results are shown in Table 2. (1) Measuring equipment: SHIMADZU 20A (Shimadzu Corporation) (2) Column: TOSOH TSKgel ODS-80Ts (4.6mm×15cm, particle size: 5μm) (3) Temperature: 40℃ (4) Injection volume: 19μL (5) Flow rate: 1mL/min (6) Eluent: a mixture of liquid A and liquid B [liquid A/liquid B (volume ratio) = 20/80, liquid A: tetrahydrofuran, liquid B: ion exchange water (998 vol%), phosphoric acid (1 The mixture of volume %) and triethylamine (1 volume %) (ion exchange water/phosphoric acid/triethylamine (volume ratio)=998/1/1)]

＜Evaluation of the amount of side erosion＞ (The amount of side erosion after 3 hours of continuous placement (A)) A copper layer with a thickness of 500 nm was formed on a PET film with a thickness of 188 μm by a sputtering method, thereby fabricating a PET substrate with a copper layer. Under the following lamination conditions, the photosensitive transfer material was laminated on the PET substrate with a copper layer, and then it was allowed to stand for 3 hours. (1) The temperature of the crimping roller: 120℃ (2) Line pressure: 1.0MPa (3) Linear speed: 0.5m/min

After 3 hours, without peeling off the dummy support, the photosensitive resin layer was exposed through a mask (Duty ratio=1:1) for forming a line and space pattern with a line width of 10 μm. An ultra-high pressure mercury lamp is used as the light source for exposure. The exposure amount was adjusted within a range where the line width of the resin pattern formed by development became 10 μm.

The dummy support was peeled off from the surface of the photosensitive resin layer, and the photosensitive resin layer was developed. Specifically, shower development was performed for 30 seconds using a 1.0% by mass sodium carbonate aqueous solution at 25°C.

The copper layer was etched using a copper etching solution (Kanto Chemical Co., Inc., Cu-02). Specifically, shower etching was performed at 27°C for 40 seconds.

The remaining resin pattern was peeled off with a peeling solution (Kanto Chemical Co., Inc., KP-301). The line width of the obtained copper pattern was measured using an optical microscope. As the undercut amount (A), the target value of the line width, that is, the difference between 10 μm and the measured value of the line width was evaluated. The evaluation results are shown in Table 2.

(The amount of side erosion after 3 days of continuous placement (B)) Except that the continuous storage time was changed from 3 hours to 3 days, the amount of side erosion (B) was evaluated by the same procedure as the above-mentioned evaluation method of "the amount of side erosion after 3 hours of continuous storage". The evaluation results are shown in Table 2.

(The amount of change) Calculate the difference between the amount of side erosion (A) after continuous storage for 3 hours and the amount of side erosion (B) after continuous storage for 3 days (that is, the value obtained from (B)-(A). Below, Sometimes called "variation".). The evaluation results are shown in Table 2. The amount of change that can be actually used is 0.5μm or less.

＜Evaluation of peelability＞ The photosensitive transfer material wound into a roll was stored at 25°C for 3 months. Next, after the photosensitive transfer material was fed, the cover film was peeled off from the photosensitive transfer material. The condition of the peeling cover film was observed with the naked eye, and the peelability was evaluated based on the following criteria. The evaluation results are shown in Table 2. A: Only the cover film is normally peeled off from the photosensitive transfer material. B: Peeling occurred between the dummy support and the photosensitive resin layer.

[Table 2] The content ratio of phenolic compounds with a molecular weight of 300 or less [ppm] Amount of side erosion [μm] Peelability BHT HQ IA MEHQ TBC total (A) Continuous storage time: 3 hours (B) Continuous placement time: 3 days (B)-(A) Example 1 0 1 0 10 2 13 1.0 1.1 0.1 A Example 2 0 0 0 12 7 19 1.1 1.2 0.1 A Example 3 3 0 0 5 0 8 0.9 1.0 0.1 A Example 4 0 2 0 5 2 9 0.8 1.0 0.2 A Example 5 0 2 0 9 0 11 1.0 1.1 0.1 A Example 6 0 50 0 189 8 247 1.1 1.5 0.4 A Comparative example 1 0 0 2 325 5 332 1.2 2.0 0.8 B

The following abbreviations in Table 2 respectively have the following meanings. "BHT": 3,5-di-tert-butyl-4-hydroxytoluene (molecular weight: 220) "HQ": Hydroquinone (Molecular Weight: 110) "IA": 2-tert-butyl-4,6-dimethylphenol (molecular weight: 178) "MEHQ": 4-Methoxyphenol (Molecular Weight: 124) "TBC": 4-tertiary butylcatechol (molecular weight: 166)

Table 2 shows the following results. The amount of change in Examples 1 to 6 (that is, the difference between the amount of side erosion (A) after continuous storage for 3 hours and the amount of side erosion (B) after continuous storage for 3 days) is smaller than that of Comparative Example 1. Therefore, the amount of side erosion accompanying the elapse of the continuous standing time after lamination of Examples 1 to 6 is smaller than that of Comparative Example 1.

The entire disclosure of Japanese Patent Application No. 2020-034792 filed on March 2, 2020 is incorporated in this specification by reference. All the documents, patent applications, and technical standards described in this specification can be cited in this specification by reference to the same extent as the cases where each document, patent application, and technical standards are specifically and separately described by reference.

10: Pseudo support 12: Photosensitive resin layer 14: Cover film 100: photosensitive transfer material

FIG. 1 is a schematic diagram showing an example of the structure of the photosensitive transfer material.

10: Pseudo support

12: Photosensitive resin layer

14: Cover film

100: photosensitive transfer material

Claims (6)

A photosensitive transfer material, which has: Pseudo support; and A photosensitive resin layer containing alkali-soluble polymer, ethylenically unsaturated bond-containing compound and photopolymerization initiator, The content ratio of the phenolic compound having a molecular weight of 300 or less in the photosensitive resin layer is 300 ppm or less with respect to the total mass of the photosensitive resin layer. The photosensitive transfer material according to claim 1, wherein The content rate of the said phenolic compound is 200 ppm or less with respect to the total mass of the said photosensitive resin layer. The photosensitive transfer material according to claim 1 or 2, wherein The content rate of the said phenolic compound is 100 ppm or less with respect to the total mass of the said photosensitive resin layer. The photosensitive transfer material according to claim 1 or 2, wherein the phenolic compound contains a phenolic compound represented by the following formula (1),

In formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a hydroxyl group or an alkoxy group having 1 to 6 carbons . The photosensitive transfer material according to claim 1 or claim 2, wherein the aforementioned phenolic compound contains at least one selected from the group consisting of the following phenolic compounds: a phenol represented by the following formula (1-1) Compound, phenolic compound represented by the following formula (1-2), phenolic compound represented by the following formula (1-3), phenolic compound represented by the following formula (1-4), and The phenolic compound represented by the formula (1-5),

. A method for manufacturing circuit wiring includes: The step of preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material described in any one of claims 1 to 5 in sequence; and The step of etching the conductive layer in the region where the resin pattern is not arranged in the laminate.

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