JP2024051000A - Photosensitive resin laminate and method for manufacturing the same - Google Patents

Abstract

To provide a laminate having a photosensitive resin composition which can achieve both dissolubility to a developer, specifically, developability, and adhesion to a substrate, especially, a copper substrate on a base film.SOLUTION: A photosensitive resin laminate has a support film, and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, in which the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator, and a content of an iron atom in the photosensitive resin composition is 0.01 ppm or more and 10 ppm or less based on the photosensitive resin composition layer.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin laminate and a method for producing the same.

Printed wiring boards are generally manufactured by photolithography. Photolithography is a method for forming a desired wiring pattern on a substrate by the following steps: First, a layer made of a photosensitive resin composition is formed on the substrate, and the coating is exposed to light and developed in a pattern to form a resist pattern. Next, a conductor pattern is formed by etching or plating. After that, the resist pattern on the substrate is removed to form the desired wiring pattern on the substrate.

In the manufacture of printed wiring boards, photosensitive elements (photosensitive resin laminates) are often used. There are many known examples of methods for forming wiring patterns using these photosensitive elements, and photosensitive resin compositions suitable for such methods (Patent Documents 1 to 3).

International Publication No. 2012/101908 International Publication No. 2015/174467 International Publication No. 2015/174468

However, the photosensitive resin compositions described in the above Patent Documents 1 to 3 do not simultaneously satisfy the requirements for developability, adhesion, etc., and there is still room for improvement.

The object of the present invention is therefore to provide a photosensitive resin laminate having a base film and a photosensitive resin composition that is soluble in a developer, i.e., developable, and has good adhesion to a substrate, particularly a copper substrate, and a method for producing the same.

The present inventors have found that the above problems can be solved by the following technical means.
[1]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (D) an iron atom;
Contains
A photosensitive resin laminate, wherein the content of iron atoms in the photosensitive resin composition layer is 0.01 ppm or more and 10 ppm or less based on the photosensitive resin composition layer.
[2]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.1 ppm or more based on the photosensitive resin composition layer.
[3]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.2 ppm or more based on the photosensitive resin composition layer.
[4]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.3 ppm or more based on the photosensitive resin composition layer.
[5]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.4 ppm or more based on the photosensitive resin composition layer.
[6]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.5 ppm or more based on the photosensitive resin composition layer.
[7]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.6 ppm or more based on the photosensitive resin composition layer.
[8]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.7 ppm or more based on the photosensitive resin composition layer.
[9]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.8 ppm or more based on the photosensitive resin composition layer.
[10]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.9 ppm or more based on the photosensitive resin composition layer.
[11]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 1.0 ppm or more based on the photosensitive resin composition layer.
[12]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 2.0 ppm or more based on the photosensitive resin composition layer.
[13]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 3.0 ppm or more based on the photosensitive resin composition layer.
[14]
The photosensitive resin laminate according to any one of [1] to [13], wherein the content of iron atoms in the photosensitive resin composition layer is 5.0 ppm or less based on the photosensitive resin composition layer.
[15]
The photosensitive resin laminate according to any one of [1] to [11], wherein the content of iron atoms in the photosensitive resin composition layer is 2.0 ppm or less based on the photosensitive resin composition layer.
[16]
The photosensitive resin laminate according to any one of [1] to [11], wherein the content of iron atoms in the photosensitive resin composition layer is 1.5 ppm or less based on the photosensitive resin composition layer.
[17]
The photosensitive resin laminate according to any one of [1] to [10], wherein the content of iron atoms in the photosensitive resin composition layer is 1.0 ppm or less based on the photosensitive resin composition layer.
[18]
The photosensitive resin laminate according to any one of [1] to [9], wherein the content of iron atoms in the photosensitive resin composition layer is 0.9 ppm or less based on the photosensitive resin composition layer.
[19]
The photosensitive resin laminate according to any one of [1] to [8], wherein the content of iron atoms in the photosensitive resin composition layer is 0.8 ppm or less based on the photosensitive resin composition layer.
[20]
The photosensitive resin laminate according to any one of [1] to [7], wherein the content of iron atoms in the photosensitive resin composition layer is 0.7 ppm or less based on the photosensitive resin composition layer.
[21]
The photosensitive resin laminate according to any one of [1] to [6], wherein the content of iron atoms in the photosensitive resin composition layer is 0.6 ppm or less based on the photosensitive resin composition layer.
[22]
The photosensitive resin laminate according to any one of [1] to [5], wherein the content of iron atoms in the photosensitive resin composition layer is 0.5 ppm or less based on the photosensitive resin composition layer.
[23]
The photosensitive resin laminate according to any one of [1] to [4], wherein the content of iron atoms in the photosensitive resin composition layer is 0.4 ppm or less based on the photosensitive resin composition layer.
[24]
The photosensitive resin laminate according to any one of [1] to [3], wherein the content of iron atoms in the photosensitive resin composition layer is 0.3 ppm or less based on the photosensitive resin composition layer.
[25]
The photosensitive resin laminate according to [1] or [2], wherein the content of iron atoms in the photosensitive resin composition layer is 0.2 ppm or less based on the photosensitive resin composition layer.
[26]
The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.1 ppm or less based on the photosensitive resin composition layer.
[27]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (E) a calcium atom;
Contains
A photosensitive resin laminate, wherein the content of calcium atoms in the photosensitive resin composition layer is 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer.
[28]
The photosensitive resin laminate according to [27], wherein the content of calcium atoms in the photosensitive resin composition layer is 0.02 ppm or more and 2.5 ppm or less based on the photosensitive resin composition layer.
[29]
The photosensitive resin laminate according to [27], wherein the content of calcium atoms in the photosensitive resin composition layer is 0.03 ppm or more and 1 ppm or less based on the photosensitive resin composition layer.
[30]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (F) an aluminum atom;
Contains
A photosensitive resin laminate, wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer.
[31]
The photosensitive resin laminate according to [30], wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.02 ppm or more and 2.5 ppm or less based on the photosensitive resin composition layer.
[32]
The photosensitive resin laminate according to [30], wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.03 ppm or more and 1 ppm or less based on the photosensitive resin composition layer.
[33]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator;
(D) at least one of an iron atom, a calcium atom, and an aluminum atom;
Contains
A photosensitive resin laminate, wherein the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.02 ppm or more and 20 ppm or less based on the photosensitive resin composition layer.
[34]
The photosensitive resin laminate according to [33], wherein the total content of iron atoms, calcium atoms, and aluminum atoms in the photosensitive resin composition layer is 0.07 ppm or more and 10 ppm or less based on the photosensitive resin composition layer.
[35]
The photosensitive resin laminate according to [33], wherein the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.11 ppm or more and 5 ppm or less based on the photosensitive resin composition layer.
[36]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (I) a sodium atom;
Contains
A photosensitive resin laminate, wherein the content of sodium atoms in the photosensitive resin composition layer is 1 ppm or more and 50 ppm or less based on the photosensitive resin composition layer.
[37]
The photosensitive resin laminate according to [36], wherein the content of sodium atoms in the photosensitive resin composition layer is 1.5 ppm or more and 25 ppm or less based on the photosensitive resin composition layer.
[38]
The photosensitive resin laminate according to [36], wherein the content of sodium atoms in the photosensitive resin composition layer is 2 ppm or more and 10 ppm or less based on the photosensitive resin composition layer.
[39]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (J) a metal atom;
Contains
A photosensitive resin laminate, wherein the content of metal atoms in the photosensitive resin composition layer is 0.005 ppm or more and 70 ppm or less based on the photosensitive resin composition layer.
[40]
The photosensitive resin laminate according to [39], wherein the content of metal atoms in the photosensitive resin composition layer is 0.01 ppm or more and 5 ppm or less based on the photosensitive resin composition layer.
[41]
The photosensitive resin laminate according to [39] or [40], wherein the metal atom contains at least one of aluminum, calcium, iron, potassium, magnesium, and zinc.

According to the present invention, a laminate is provided that has a photosensitive resin composition on a base film that is soluble in a developer, i.e., developable, and has good adhesion to a substrate, particularly a copper substrate, thereby improving the resolution of a printed wiring board formed using a dry film resist.

Hereinafter, an embodiment of the present invention (hereinafter, abbreviated as "present embodiment") will be specifically described.
In this specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid. The term "(meth)acryloyl group" means an acryloyl group or a methacryloyl group. The term "(meth)acrylate" means "acrylate" or "methacrylate".

<Photosensitive resin composition>
In this embodiment, a photosensitive resin laminate including a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition includes (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, (C) a photopolymerization initiator, and (J) a metal atom. The (J) metal atom includes at least one of (D) an iron atom, (E) a calcium atom, and (F) an aluminum atom and zinc. The (J) metal atom may include (I) a sodium atom. If desired, the photosensitive resin composition may further include other components such as (G) a photosensitizer and (H) an additive.

In particular, in this embodiment, the photosensitive resin composition layer has a metal atom content of (J) 0.005 ppm or more and 70 ppm or less, preferably 0.01 ppm or more and 5 ppm or less, based on the photosensitive resin composition layer. Specifically, the iron atom content of (D) is 0.01 ppm or more and 10 ppm or less, based on the photosensitive resin composition layer. Alternatively, the content of either the calcium atom (E) or the aluminum atom (F) is 0.005 ppm or more and 5 ppm or less, based on the photosensitive resin composition layer. Alternatively, the sodium atom content of (I) is 1 ppm or more and 50 ppm or less, based on the photosensitive resin composition layer.
By setting the content of metal atoms, such as iron atoms, calcium atoms, aluminum atoms, and sodium atoms, within the above ranges, it is possible to achieve both solubility in a developer, i.e., developability, and adhesion to a substrate, particularly a copper substrate. Good developability means that residues are less likely to remain in the resist pattern, and good adhesion to the substrate means that a thinner resist pattern can be formed.
Each component will be described in turn below.

(A) Alkali-soluble polymer (A) is a polymer that can be dissolved in an alkaline substance. (A) Alkali-soluble polymer may be a single type of copolymer, a mixture of multiple types of copolymers, and/or a mixture of multiple types of homopolymers.

In relation to alkali solubility, the acid equivalent of the (A) alkali-soluble polymer (when the (A) component contains multiple types of copolymers, the acid equivalent of the entire mixture) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin composition layer, and the development resistance, resolution, and adhesion of the resist pattern. From the viewpoint of the developability and peelability of the photosensitive resin composition layer, it is preferably 900 or less. The acid equivalent of the (A) alkali-soluble polymer is more preferably 200 to 600, and even more preferably 250 to 500. The acid equivalent refers to the mass of a linear polymer having one equivalent of a carboxyl group therein.

(A) Alkali-soluble polymer (A) Alkali-soluble polymer is a polymer that is easily soluble in an alkaline substance. Specifically, it is a polymer that has a functional group (e.g., carboxyl group) that contributes to alkali solubility in an amount sufficient to dissolve in a desired alkaline substance. Typically, the amount of carboxyl group contained in (A) alkali-soluble polymer is 100 to 600 in acid equivalent, preferably 250 to 450. The acid equivalent refers to the mass (unit: grams) of a linear polymer having one equivalent of carboxyl group in its molecule. The carboxyl group in (A) alkali-soluble polymer is necessary to give the photosensitive resin composition layer developability and peelability against an alkaline aqueous solution. It is preferable to set the acid equivalent to 100 or more from the viewpoint of improving development resistance, resolution, and adhesion, and it is preferable to set the acid equivalent to 250 or more. On the other hand, it is preferable to set the acid equivalent to 600 or less from the viewpoint of improving developability and peelability, and it is preferable to set the acid equivalent to 450 or less.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. A weight average molecular weight of 300,000 or less is more preferable, and a weight average molecular weight of 200,000 or less is even more preferable. On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as the edge fuse property and cut chip property of the photosensitive resin laminate. A weight average molecular weight of 10,000 or more is more preferable, and a weight average molecular weight of 20,000 or more is even more preferable. Edge fuse property refers to the phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. Cut chip property refers to the phenomenon in which chips fly off when the unexposed film is cut with a cutter. If these chips adhere to the top surface of the photosensitive resin laminate, they can be transferred to the mask during subsequent exposure processes, resulting in defective products.

(A) The dispersity (sometimes called molecular weight distribution) of the alkali-soluble polymer may be about 1 to 6, and preferably 1 to 4. The dispersity is expressed as the ratio of the weight average molecular weight to the number average molecular weight, and is expressed as (dispersity) = (weight average molecular weight) / (number average molecular weight). The weight average molecular weight and number average molecular weight are values measured using gel permeation chromatography and converted into polystyrene equivalents.

(A) The alkali-soluble polymer is preferably a copolymer obtained from at least one type of a first monomer described below and at least one type of a second monomer described below.

The first monomer is a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. (Meth)acrylic acid is particularly preferred. In this specification, (meth)acrylic refers to acrylic and/or methacrylic. The same applies below.

The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and vinyl alcohol esters. Examples of vinyl alcohol esters include vinyl acetate, (meth)acrylonitrile, styrene, and styrene derivatives. Among these, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate are preferred. From the viewpoint of improving the resolution and adhesion of the resist pattern, styrene and benzyl (meth)acrylate are preferred.

From the viewpoint of adjusting the alkali solubility of (A) the alkali-soluble polymer, the copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60 mass% for the first monomer and 40 to 90 mass% for the second monomer. More preferably, the first monomer is 15 to 35 mass% and the second monomer is 65 to 85 mass%.

(A) The synthesis of an alkali-soluble polymer is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used.

The proportion of the alkali-soluble polymer (A) (when a mixture of multiple types of alkali-soluble polymers is used) in the total amount of components (A), (B), (C), (D), (G), (H), (I) and (J) (hereinafter sometimes referred to as the total amount of components (A) to (J)) is preferably in the range of 10 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass. It is preferable to set the proportion of component (A) to the total amount of components (A) to (J) to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the proportion of component (A) to the total amount of components (A) to (J) to 10% by mass or more from the viewpoint of improving edge fusing properties.

In particular, the photosensitive resin composition contains, as component (A), one or more components selected from the group consisting of the following (a-1) and (a-2):
(a-1) an acrylic copolymer derived from a polymerization component containing 15 to 60% by mass of styrene and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters;
(a-2) an acrylic copolymer derived from a polymerization component containing 20 to 85% by mass of benzyl methacrylate and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters other than benzyl methacrylate;
In order to achieve high resolution, it is preferable that the total amount of the components (a-1) and (a-2) in the total amount of the components (A) to (J) is 10 to 60% by mass. In order to achieve high resolution, the total amount of the components (a-1) and (a-2) in the total amount of the components (A) to (J) is preferably 10 to 60% by mass. In terms of resolution, the above-mentioned ratio is preferably 20% by mass or more, more preferably 30% by mass or more, and in terms of cut-chip properties, it is preferably 55% by mass or less, more preferably 50% by mass or less.

The polymerization components in (a-1) may consist only of styrene and the above acrylic monomers, or may further contain other monomers. The polymerization components in (a-2) may consist only of benzyl methacrylate and the above acrylic monomers, or may further contain other monomers. Particularly preferred examples of combinations of polymerization components include a combination of 15 to 60% by mass of styrene, 20 to 35% by mass of methacrylic acid, and the remainder being methyl methacrylate, a combination of 30 to 50% by mass of styrene, 20 to 40% by mass of methacrylic acid, 10 to 20% by mass of 2-ethylhexyl acrylate, and the remainder being 2-hydroxyethyl methacrylate, a combination of 20 to 60% by mass of benzyl methacrylate, 10 to 30% by mass of styrene, and the remainder being methacrylic acid, a combination of 60 to 85% by mass of benzyl methacrylate, 0 to 15% by mass of 2-ethylhexyl acrylate, and the remainder being methacrylic acid, and the like. It is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer from the viewpoints of chemical resistance, adhesion, high resolution, and foot shape of the resist pattern.

(B) Compound Having Ethylenically Unsaturated Double Bond (B) The ethylenically unsaturated bond-containing compound is a compound having polymerizability due to having an ethylenically unsaturated group in its structure. From the viewpoint of addition polymerizability, the ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

From the viewpoint of curability and compatibility with the alkali-soluble polymer (A), it is preferable that the compound having an ethylenically unsaturated double bond (B) contains a compound having an acryloyl group in the molecule. Examples of compounds having an acryloyl group in the molecule include a compound in which (meth)acrylic acid is added to one end of a polyalkylene oxide, or a compound in which (meth)acrylic acid is added to one end of a polyalkylene oxide and the other end is alkyl-etherified or allyl-etherified.

Examples of such compounds include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound in which polyethylene glycol is added to a phenyl group; 4-normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound in which polypropylene glycol to which an average of 2 moles of propylene oxide (hereinafter sometimes abbreviated as PO) has been added and polyethylene glycol to which an average of 7 moles of ethylene oxide (hereinafter sometimes abbreviated as EO) has been added are added to nonylphenol; and 4-normal nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound in which polypropylene glycol to which an average of 1 mole of propylene oxide has been added and polyethylene glycol to which an average of 5 moles of ethylene oxide has been added are added to nonylphenol. Another example is 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate (e.g., M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound in which polyethylene glycol to which an average of 8 moles of ethylene oxide has been added is added to nonylphenol.

Examples include compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, or compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which ethylene oxide chains and propylene oxide chains are bonded randomly or in blocks.

Examples of such compounds include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of a 12-mol ethylene oxide chain, such as polyethylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate. Examples of polyalkylene oxide di(meth)acrylate compounds containing ethylene oxide and propylene oxide groups include dimethacrylates of glycols in which an average of 3 moles of ethylene oxide have been added to each end of polypropylene glycol to which an average of 12 moles of propylene oxide have been added, and dimethacrylates of glycols in which an average of 15 moles of ethylene oxide have been added to each end of polypropylene glycol to which an average of 18 moles of propylene oxide have been added. Furthermore, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and di(meth)acrylates having both ethylene oxide and polypropylene oxide (for example, "FA-023M, FA-024M, FA-027M, product names, manufactured by Hitachi Chemical Co., Ltd.") are preferred in terms of flexibility, resolution, adhesion, etc.

In addition, from the viewpoint of resolution and adhesion, a compound obtained by modifying bisphenol A with an alkylene oxide and having (meth)acryloyl groups at both ends is preferred. Examples of alkylene oxide modifications include ethylene oxide modifications, propylene oxide modifications, butylene oxide modifications, pentylene oxide modifications, and hexylene oxide modifications. In addition, from the viewpoint of resolution and adhesion, a compound obtained by modifying bisphenol A with an ethylene oxide and having (meth)acryloyl groups at both ends is particularly preferred.

Examples of such compounds include 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane (e.g., NK Ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-((meth)acryloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane (e.g., NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-((meth)acryloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyheptaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyoctaethoxy)phenyl)propane, 2,2-bis(4 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propanes such as 2,2-bis(4-((meth)acryloxynonaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxydecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyundecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxydodecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytridecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetradecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypentadecaethoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxyhexadecaethoxy)phenyl)propane are mentioned. Furthermore, ethylene oxide-modified and propylene oxide-modified compounds such as di(meth)acrylate of polyalkylene glycol in which an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide are added to both ends of bisphenol A, di(meth)acrylate of polyalkylene glycol in which an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide are added to both ends of bisphenol A, and dimethacrylate of polyethylene glycol in which an average of 5 moles of EO are added to both ends of bisphenol A (e.g., BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) are also preferred from the viewpoint of resolution and adhesion. In these compounds in which bisphenol A is modified with alkylene oxide and has (meth)acryloyl groups at both ends, the number of moles of ethylene oxide per mole of bisphenol A is preferably 10 moles or more and 30 moles or less in total from the viewpoint of improving resolution, adhesion and flexibility.

In this embodiment, it is preferable to include a compound having more than two (meth)acryloyl groups in one molecule as the compound having an ethylenically unsaturated double bond (B) in order to achieve high resolution. The number of (meth)acryloyl groups in one molecule is more preferably 3 or more. The number of (meth)acryloyl groups in one molecule is preferably 6 or less, more preferably 4 or less, from the viewpoint of peelability. A compound having more than two (meth)acryloyl groups in one molecule has 3 moles or more (i.e., 3 or more per central skeleton) of a group to which an alkylene oxide group can be added in the molecule as a central skeleton, and can be obtained by forming a (meth)acrylate from an alcohol to which an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group is added, and (meth)acrylate from (meth)acrylic acid. If the central skeleton is an alcohol, it can also be obtained by directly forming a (meth)acrylate with (meth)acrylic acid. Examples of compounds that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

Such compounds include trimethylolpropane modified with 3 mol of EO, trimethylolpropane modified with 6 mol of EO, trimethylolpropane modified with 9 mol of EO, trimethylolpropane modified with 12 mol of EO, glycerin modified with 3 mol of EO (e.g., A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), glycerin modified with 9 mol of EO (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), glycerin modified with 6 mol of EO and 6 mol of PO (A-GLY Examples of the glycerin modified triacrylate with 9 mol EO and 9 mol PO (A-GLY-0909PE) include a 4 EO modified tetraacrylate of pentaerythritol (for example, SR-494 manufactured by Sartomer Japan Co., Ltd.), a 35 EO modified tetraacrylate of pentaerythritol (for example, NK Ester ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol tetraacrylate, and a 7:3 mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (for example, M-306 manufactured by Toagosei Co., Ltd.). Examples of compounds having at least three methacryloyl groups include trimethacrylates such as ethoxylated glycerin trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, and trimethylolpropane trimethacrylate (e.g., trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane are preferred in terms of flexibility, adhesion, and bleed-out suppression); tetramethacrylates such as ditrimethylolpropane tetramethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol tetramethacrylate; pentamethacrylates such as dipentaerythritol pentamethacrylate; and hexamethacrylates such as dipentaerythritol hexamethacrylate. Among these, tetra, penta, or hexamethacrylates are preferred.

Among these, preferred examples of compounds having an ethylenically unsaturated double bond (B) are those that have a melting point lower than room temperature and do not easily solidify during storage, from the viewpoint of ease of handling. In particular, EO 3-mol-modified triacrylate of trimethylolpropane and 4EO-modified tetraacrylate of pentaerythritol are preferred.

The content of the compound having more than two (meth)acryloyl groups in one molecule is preferably 50 to 100% by mass of the compound (B) having an ethylenically unsaturated double bond. From the viewpoint of resolution, the content is preferably 50% by mass or more, and more preferably 60% by mass or more. The content may be 100% by mass, but from the viewpoint of peelability, it may be preferably 95% by mass or less, and more preferably 90% by mass or less.

In addition to the compounds described above, component (B) may also contain, as appropriate, the compounds listed below. For example, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, 2,2-bis[(4-(meth)acryloxypolypropyleneoxy)phenyl]propane, 2,2-bis[(4-(meth)acryloxypolybutyleneoxy)phenyl]propane, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxypropyl trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, β-hydroxypropyl-β'-(acryloyloxy)propyl phthalate, nonylphenoxy polypropylene glycol (meth)acrylate, nonylphenoxy polybutylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. Further examples include the following urethane compounds. Examples of such compounds include urethane compounds of hexamethylene diisocyanate, tolylene diisocyanate, or diisocyanate compounds (e.g., 2,2,4-trimethylhexamethylene diisocyanate) and compounds having a hydroxyl group and a (meth)acrylic group in one molecule, such as 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate. Specific examples include reaction products of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (e.g., Blenmer PP1000, manufactured by Nippon Oil & Fats Co., Ltd.). Other examples include di- or tri(meth)acrylates of isocyanuric acid esters modified with polypropylene glycol or polycaprolactone. Other examples include urethane oligomers obtained by reacting the terminals of a urethane compound obtained as a polyaddition product of a diisocyanate and a polyol with a compound having an ethylenically unsaturated double bond and a hydroxyl group.

In addition, the compound having an ethylenically unsaturated bond (B) may contain a compound having one ethylenically unsaturated bond, such as 4-normal nonylphenoxy octaethylene glycol acrylate, 4-normal nonylphenoxy tetraethylene glycol acrylate, or γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate. This is preferable from the viewpoint of peelability and cured film flexibility, and containing γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is also preferable from the viewpoint of sensitivity, resolution, and adhesion.
The compound (B) having an ethylenically unsaturated double bond preferably contains a hydroxyl group in the molecule, which provides excellent sensitivity (productivity), resolution, and adhesion.

The ratio of the compound (B) having an ethylenically unsaturated double bond to the total amount of the components (A) to (J) is preferably 5 to 70% by mass. A ratio of 5% by mass or more is preferable from the viewpoints of sensitivity, resolution, and adhesion, and this ratio is more preferably 10% by mass or more, and even more preferably 20% by mass or more. On the other hand, a ratio of 70% by mass or less is preferable from the viewpoints of suppressing edge fuse and peeling delay of the cured resist, and this ratio is more preferably 60% by mass or less, and even more preferably 50% by mass or less.

(C) Photopolymerization Initiator From the viewpoint of obtaining high sensitivity and high resolution, the photopolymerization initiator (C) preferably contains a hexaarylbiimidazole compound.

Hexaarylbiimidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5 ,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)- Biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bi Examples of the imidazole include 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoint of sensitivity and resolution.

Examples of photopolymerization initiators that may be contained as component (C) other than the hexaarylbiimidazole compound include N-aryl-α-amino acid compounds, quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acridines, N-aryl amino acid ester compounds, and halogen compounds.

Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. N-phenylglycine is particularly preferred due to its high sensitizing effect.

Quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.

Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

Examples of acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucirin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

Examples of benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

Examples of dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

Examples of thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Examples of dialkylaminobenzoic acid esters include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

Examples of oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals.

Examples of acridines include 1,7-bis(9,9'-acridinyl)heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, and 9-(4-acetylphenyl)acridine. Examples of such acridine include lysine, 9-(4-dimethylaminophenyl)acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetylphenyl)acridine, 9-(3-dimethylaminophenyl)acridine, 9-(3-diethylaminophenyl)acridine, 9-(3-chlorophenyl)acridine, 9-(3-bromophenyl)acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, and 9-(4-pyridyl)acridine.

Examples of ester compounds of N-arylamino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds, with tribromomethylphenylsulfone being particularly preferred. From the viewpoint of sensitivity, the content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass based on the total amount of the components (A) to (J).

These photopolymerization initiators may be used alone or in combination of two or more types.

The ratio of the photopolymerization initiator (C) to the total amount of the components (A) to (J) is preferably 0.1 to 20% by mass. In order to obtain sufficient sensitivity, it is preferable to set this ratio to 0.1% by mass or more, and it is more preferable to set this ratio to 0.2% by mass or more, and it is even more preferable to set this ratio to 0.5% by mass or more. On the other hand, it is preferable to set this ratio to 20% by mass or less, from the viewpoints of obtaining high resolution and suppressing aggregation in the developer, and it is more preferable to set this ratio to 10% by mass or less.

(D) Iron Atoms In this embodiment, the photosensitive resin composition layer has an iron atom content of 0.01 ppm or more and 10 ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of iron atoms in the photosensitive resin composition layer is 0.01 ppm or more based on the photosensitive resin composition layer.
If the content of iron atoms is below the above range, poor adhesion is likely to occur due to reduced interaction with the metal surface of the substrate. For example, stably present iron ions are trivalent, so they can form coordinate bonds between ^CuO- on the substrate surface and carboxylic acid in the binder (e.g., CuO ^-... Fe3 ⁺ ...COO- ⁾ . If the content of iron atoms is equal to or greater than the above lower limit, the interaction with the metal surface of the substrate is strong, resulting in excellent adhesion.

The content of iron atoms in the photosensitive resin composition layer may be 0.03 ppm or more, or 0.05 ppm or more. It may also be 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm or more, 0.5 ppm or more, 0.6 ppm or more, 0.7 ppm or more, 0.8 ppm or more, 0.9 ppm or more, or 1.0 ppm or more. It may also be 1.1 ppm or more, 1.2 ppm or more, 1.3 ppm or more, 1.4 ppm or more, or 1.5 ppm or more. It may also be 2.0 ppm or more, 3.0 ppm or more, 4.0 ppm or more, or 5.0 ppm or more. The higher the content of iron atoms, the better the adhesion.

On the other hand, the upper limit of the content of iron atoms in the photosensitive resin composition layer is 10 ppm or less based on the photosensitive resin composition layer.
When the content of iron atoms exceeds the above range, iron ions form coordinate bonds between molecules, resulting in pseudo-crosslinking. This pseudo-crosslinking reduces the solubility in the developer, causing a delay in development time. When the content of iron atoms is equal to or less than the above upper limit, the solubility in the developer is appropriate, and the development time is also appropriate.

The content of iron atoms in the photosensitive resin composition layer may be 5.0 ppm or less, 4.0 ppm or less, 3.0 ppm or less, or 2.0 ppm or less. It may also be 1.5 ppm or less, 1.4 ppm or less, 1.3 ppm or less, 1.2 ppm or less, 1.1 ppm or less, or 1.0 ppm or less. It may also be 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less, 0.6 ppm or less, 0.5 ppm or less, 0.4 ppm or less, 0.3 ppm or less, 0.2 ppm or less, or 0.1 ppm or less. The lower the content of iron atoms, the shorter the development time can be.

The content of iron atoms in the photosensitive resin composition layer is from 0.01 ppm to 10 ppm, and most preferably from 0.05 ppm to 2.0 ppm, based on the photosensitive resin composition layer.
By setting the content of iron atoms within the above range, it is possible to achieve both solubility in a developer, i.e., developability, and adhesion to a substrate, particularly a copper substrate. Good developability has the effect of preventing residues from remaining in the resist pattern, and good adhesion to the substrate has the effect of allowing a thinner resist pattern to be formed.

The means for adjusting the content of iron atoms in the photosensitive resin composition layer to within the range of 0.01 ppm or more and 10 ppm or less is not particularly limited, but examples thereof include variously adjusting the composition of the photosensitive resin composition with respect to each component.

The content of iron atoms in the photosensitive resin composition layer is determined by the method described in the Examples.

(E) Calcium Atoms In this embodiment, the photosensitive resin composition layer has a calcium atom content of 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of calcium atoms in the photosensitive resin composition layer is 0.005 ppm or more based on the photosensitive resin composition layer.
If the content of calcium atoms is below the above range, poor adhesion occurs due to reduced interaction with the metal surface of the substrate. For example, calcium ions that exist stably are divalent, so they can form coordinate bonds between CuO ^- on the substrate surface and carboxylic acid in the binder (e.g., CuO ^- ...Ca ²⁺ ...COO ^- ). If the content of calcium atoms is equal to or greater than the above lower limit, the interaction with the metal surface of the substrate becomes strong, resulting in excellent adhesion.

The content of calcium atoms in the photosensitive resin composition layer may be 0.01 ppm or more, 0.03 ppm or more, 0.05 ppm or more, or 0.08 ppm or more. It may also be 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm or more, 0.5 ppm or more, 0.6 ppm or more, 0.7 ppm or more, 0.8 ppm or more, 0.9 ppm or more, or 1.0 ppm or more. It may also be 1.1 ppm or more, 1.2 ppm or more, 1.3 ppm or more, 1.4 ppm or more, or 1.5 ppm or more. It may also be 2.0 ppm or more, 3.0 ppm or more, or 4.0 ppm or more. The higher the calcium atom content, the better the adhesion.

On the other hand, the upper limit of the content of calcium atoms in the photosensitive resin composition layer is 5 ppm or less based on the photosensitive resin composition layer.
When the content of calcium atoms exceeds the above range, calcium ions form coordinate bonds between molecules, resulting in pseudo-crosslinking. This pseudo-crosslinking reduces the solubility in the developer, causing a delay in development time. When the content of calcium atoms is equal to or less than the above upper limit, the solubility in the developer is appropriate, and the development time is also appropriate.

The content of calcium atoms in the photosensitive resin composition layer may be 4.0 ppm or less, 3.0 ppm or less, or 2.0 ppm or less. It may also be 1.5 ppm or less, 1.4 ppm or less, 1.3 ppm or less, 1.2 ppm or less, 1.1 ppm or less, or 1.0 ppm or less. It may also be 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less, 0.6 ppm or less, 0.5 ppm or less, 0.4 ppm or less, 0.3 ppm or less, 0.2 ppm or less, 0.1 ppm or less, or 0.05 ppm or less. The lower the content of calcium atoms, the shorter the development time can be.

The content of calcium atoms in the photosensitive resin composition layer is from 0.005 ppm to 5 ppm, and most preferably from 0.03 ppm to 1.0 ppm, based on the photosensitive resin composition layer.
By setting the calcium atom content within the above range, it is possible to achieve both solubility in a developer, i.e., developability, and adhesion to a substrate, particularly a copper substrate. Good developability has the effect of preventing residues from remaining in the resist pattern, and good adhesion to the substrate has the effect of allowing a thinner resist pattern to be formed.

The means for adjusting the calcium atom content in the photosensitive resin composition layer to within the range of 0.005 ppm or more and 5 ppm or less is not particularly limited, but examples thereof include variously adjusting the composition of the photosensitive resin composition with respect to each component.

The content of calcium atoms in the photosensitive resin composition layer is determined by the method described in the Examples.

(F) Aluminum Atoms In this embodiment, the photosensitive resin composition layer has an aluminum atom content of 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of aluminum atoms in the photosensitive resin composition layer is 0.005 ppm or more based on the photosensitive resin composition layer.
If the content of aluminum atoms is below the above range, poor adhesion occurs due to reduced interaction with the metal surface of the substrate. For example, stably existing aluminum ions are trivalent, so they can form coordinate bonds between CuO ^- on the substrate surface and the carboxylic acid of the binder (e.g., CuO ^- ...Al ³⁺ ...COO ^- ). If the content of aluminum atoms is equal to or greater than the above lower limit, the interaction with the metal surface of the substrate becomes strong, resulting in excellent adhesion.

The content of aluminum atoms in the photosensitive resin composition layer may be 0.01 ppm or more, 0.03 ppm or more, 0.05 ppm or more, or 0.08 ppm or more. It may also be 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm or more, 0.5 ppm or more, 0.6 ppm or more, 0.7 ppm or more, 0.8 ppm or more, 0.9 ppm or more, or 1.0 ppm or more. It may also be 1.1 ppm or more, 1.2 ppm or more, 1.3 ppm or more, 1.4 ppm or more, or 1.5 ppm or more. It may also be 2.0 ppm or more, 3.0 ppm or more, or 4.0 ppm or more. The higher the aluminum atom content, the better the adhesion.

On the other hand, the upper limit of the content of aluminum atoms in the photosensitive resin composition layer is 5 ppm or less based on the photosensitive resin composition layer.
When the content of aluminum atoms exceeds the above range, aluminum ions form coordinate bonds between molecules, resulting in pseudo-crosslinking. This pseudo-crosslinking reduces the solubility in the developer, causing a delay in development time. When the content of aluminum atoms is equal to or less than the above upper limit, the solubility in the developer is appropriate, and the development time is also appropriate.

The content of aluminum atoms in the photosensitive resin composition layer may be 4.0 ppm or less, 3.0 ppm or less, or 2.0 ppm or less. It may also be 1.5 ppm or less, 1.4 ppm or less, 1.3 ppm or less, 1.2 ppm or less, 1.1 ppm or less, or 1.0 ppm or less. It may also be 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less, 0.6 ppm or less, 0.5 ppm or less, 0.4 ppm or less, 0.3 ppm or less, 0.2 ppm or less, 0.1 ppm or less, or 0.05 ppm or less.

The content of aluminum atoms in the photosensitive resin composition layer is from 0.005 ppm to 5 ppm, preferably from 0.02 ppm to 2.5 ppm, and most preferably from 0.03 ppm to 1.0 ppm, based on the photosensitive resin composition layer.
By setting the content of aluminum atoms within the above range, it is possible to achieve both solubility in a developer, i.e., developability, and adhesion to a substrate, particularly a copper substrate. Good developability has the effect of preventing residues from remaining in the resist pattern, and good adhesion to the substrate has the effect of allowing a thinner resist pattern to be formed.

The means for adjusting the content of aluminum atoms in the photosensitive resin composition layer to within the range of 0.005 ppm or more and 5 ppm or less is not particularly limited, but examples thereof include variously adjusting the composition of the photosensitive resin composition with respect to each component.

The content of aluminum atoms in the photosensitive resin composition layer is determined by the method described in the Examples.

The content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is preferably 0.02 ppm or more and 20 ppm or less.
The content of iron atoms, calcium atoms and aluminum atoms may be 0.03 ppm or more, 0.04 ppm or more, 0.05 ppm or more, 0.06 ppm or more, 0.07 ppm or more, 0.08 ppm or more, 0.09 ppm or more, or 0.1 ppm or more. Also, it may be 0.1 ppm or more, 0.11 ppm or more, 0.12 ppm or more, 0.13 ppm or more, 0.14 ppm or more, 0.15 ppm or more, 0.16 ppm or more, 0.17 ppm or more, 0.18 ppm or more, 0.19 ppm or more, or 0.2 ppm or more. In addition, it may be 0.3 ppm or more, 0.4 ppm or more, 0.5 ppm or more, 0.6 ppm or more, 0.7 ppm or more, 0.8 ppm or more, 0.9 ppm or more, or 1.0 ppm or more. In addition, it may be 1.5 ppm or more, 2.0 ppm or more, 2.5 ppm or more, 3.0 ppm or more, 3.5 ppm or more, or 4.0 ppm or more.

The content of iron atoms, calcium atoms, and aluminum atoms may be 15 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, or 1 ppm or less. Preferably, it is 0.11 ppm or more and 5 ppm or less.

(I) Sodium Atoms In this embodiment, the photosensitive resin composition layer has a sodium atom content of 1 ppm or more and 50 ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of sodium atoms in the photosensitive resin composition layer is 1 ppm or more based on the photosensitive resin composition layer.
If the content of sodium atoms is below the above range, residues are likely to be generated between the formed wirings. Since the photosensitive resin composition contains a small amount of sodium ions, it has excellent permeability to the developer and washing water, so that development can be performed without generating residues even between closely packed wirings.

The content of sodium atoms in the photosensitive resin composition layer may be 1 ppm or more, 1.5 ppm or more, 2 ppm or more, 3 ppm or more, 4 ppm or more, 5 ppm or more, 6 ppm or more, 7 ppm or more, 8 ppm or more, 9 ppm or more, or 10 ppm or more. It may also be 15 ppm or more, 16 ppm or more, 17 ppm or more, 18 ppm or more, 19 ppm or more, or 20 ppm or more. It may also be 30 ppm or more, 35 ppm or more, 40 ppm or more, or 45 ppm or more. The higher the content of sodium atoms, the less likely residues are to occur between the wirings.

On the other hand, the upper limit of the content of sodium atoms in the photosensitive resin composition layer is 50 ppm or less based on the photosensitive resin composition layer.
If the content of sodium atoms exceeds the above range, the permeability of the developer and washing water is too high, so that the dense wiring pattern formed swells and comes into contact with adjacent wiring, and therefore a dense wiring pattern cannot be obtained. If the content of sodium atoms is equal to or less than the above upper limit, the permeability of the developer and washing water is appropriate, and the resolution of the dense pattern is excellent.

The content of sodium atoms in the photosensitive resin composition layer may be 45 ppm or less, 40 ppm or less, 35 ppm or less, or 30 ppm or less. It may also be 25 ppm or less, 20 ppm or less, 19 ppm or less, 18 ppm or less, 17 ppm or less, 16 ppm or less, or 15 ppm or less. It may also be 9 ppm or less, 8 ppm or less, 7 ppm or less, 6 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, or 2 ppm or less.

The content of sodium atoms in the photosensitive resin composition layer is from 1 ppm to 50 ppm, preferably from 1.5 ppm to 25 ppm, and most preferably from 2 ppm to 10 ppm, based on the photosensitive resin composition layer.
By setting the content of sodium atoms within the above range, contact between the patterns and residues between the wirings is prevented, resulting in excellent formability of a dense wiring pattern.

There are no particular limitations on the means for adjusting the sodium atom content in the photosensitive resin composition layer to within the range of 1 ppm to 50 ppm, but examples of such means include adjusting the composition of the photosensitive resin composition for each component, removing the sodium atom using an ion exchange resin, or adding various sodium salt compounds.

The content of sodium atoms in the photosensitive resin composition layer is determined by the method described in the Examples.

(G) Sensitizer In the photosensitive resin composition of this embodiment, the (G) sensitizer contains at least one selected from a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound. These compounds have a high absorption of light around 405 nm, which is called the h-line. By using these compounds as sensitizers, the sensitivity and image forming properties are improved. Among them, it is more preferable that the (G) sensitizer contains at least one selected from a pyrazoline compound and an anthracene compound.

The amount of the sensitizer (G) is preferably 0.005 to 2% by mass based on the total mass of the solid content of the photosensitive resin composition. By using the sensitizer (G) in this range, good sensitivity, resolution, and adhesion can be obtained.

The sensitizer (G) in the present invention may be any sensitizer that improves sensitivity when combined with the initiator (C). The functions of the sensitizer (G) include absorbing light of the exposure wavelength and donating energy or electrons to the initiator, promoting the cleavage of the initiator (C), and transferring an initiation radical generated from the initiator (C) or a growing radical after it is once added to a monomer and polymerized to the monomer to the sensitizer (G) and regenerating a radical through new cleavage and decomposition.
Examples of the sensitizer (G) other than pyrazoline compounds, anthracene compounds, triarylamine compounds, and oxazole compounds include N-aryl-α-amino acid compounds, aromatic ketone compounds substituted with an alkylamino group, dialkylaminobenzoic acid ester compounds, pyrazoline derivatives, anthracene derivatives, triphenylamine derivatives, N-arylamino acid ester compounds, halogen compounds, and the like.

Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. N-phenylglycine is particularly preferred because of its high sensitizing effect.
Examples of the aromatic ketone compound substituted with an alkylamino group include Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.
Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives include 5-(4-tert-butylphenyl)-3-(4-tert-butylstyryl)-1-phenyl-2-pyrazoline, 5-(4-tert-butylphenyl)-1-phenyl-3-(4-phenylphenyl)-4,5-dihydro-1H-pyrazole, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, and 1-phenyl-3-(3,5-dimethoxystyryl)-5-(4-methoxyphenyl)-pyrazoline. 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3,5-bis(4-tert-butyl-phenyl)-pyrazoline 1-phenyl-3,5-bis(4-methoxy-phenyl)-pyrazoline, 1-phenyl-3-(4-methoxy-phenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-tert-butyl-phenyl)-5-(4-methoxy-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropyl-phenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-tert-butyl-phenyl)-5-(4-isopropyl-phenyl)-pyrazoline, 1-phenyl-3-(4-methoxy-phenyl)-5-(4-isopropyl-phenyl)-pyrazoline, 1-phenyl-3-(4-methoxy-phenyl)-5-(4-isopropyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropyl-phenyl)-5-(4-isopropyl-phenyl)-pyrazoline, Preferred are 1,5-diphenyl-3-(4-tert-butyl-phenyl)-pyrazoline, 1,3-diphenyl-5-(4-tert-butyl-phenyl)-pyrazoline, 1,5-diphenyl-3-(4-isopropyl-phenyl)-pyrazoline, 1,3-diphenyl-5-(4-isopropyl-phenyl)-pyrazoline, 1,5-diphenyl-3-(4-methoxy-phenyl)-pyrazoline, 1,3-diphenyl-5-(4-methoxy-phenyl)-pyrazoline, 1-phenyl-3,5-bis(4-tert-butyl-phenyl)-pyrazoline, 1,5-diphenyl-3-(4-tert-butyl-phenyl)-pyrazoline.
1-Phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline are preferred.

上記一般式（２）中、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立に、炭素数１～１０の直鎖状若しくは分岐鎖状のアルキル基又は炭素数１～４の直鎖状若しくは分岐鎖状のアルコキシ基を示す。ｎ４、ｎ５及びｎ６は、ｎ４＋ｎ５＋ｎ６の値が１以上となるように選ばれる０～５の整数を示す。なお、ｎ４が２以上の場合、複数存在するＲ_１は同一でも異なっていてもよく、ｎ５が２以上の場合、複数存在するＲ_２は同一でも異なっていてもよく、ｎ６が２以上の場合、複数存在するＲ_３は同一でも異なっていてもよい。 As the anthracene compound, anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene are preferred. Among them, 9,10-dibutoxyanthracene is more preferred from the viewpoint of sensitivity. As the triarylamine compound, a compound having a triphenylamine skeleton in the molecule can be mentioned. As the triarylamine compound, a compound represented by the following formula (2) is preferred.

In the above general formula (2), R ₁ , R ₂ and R ₃ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkoxy group having 1 to 4 carbon atoms. n4, n5 and n6 represent integers from 0 to 5 selected such that the value of n4+n5+n6 is 1 or greater. When n4 is 2 or greater, multiple R _1s may be the same or different, when n5 is 2 or greater, multiple R _2s may be the same or different, and when n6 is 2 or greater, multiple R _3s may be the same or different.

In the compound represented by formula (2), from the viewpoints of resolution and adhesion, it is preferable that _R2 is a linear or branched alkyl group having 1 to 10 carbon atoms, n4 and n6 are 0, and n5 is 1. It is more preferable that _R2 is a linear or branched alkyl group having 1 to 4 carbon atoms, n4 and n6 are 0, and n5 is 1.

Examples of oxazole compounds include compounds having an oxazole skeleton in the molecule. From the viewpoint of sensitivity, 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophene-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazol-2-yl)naphthalene-1-yl]-1,3-benzoxazole are preferred.

Examples of ester compounds of N-arylamino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds, with tribromomethylphenylsulfone being particularly preferred.

(H) Additives In the present disclosure, the term "(H) additives" refers to components that are blended in order to impart desired functions to the photosensitive resin composition, and includes components other than the above-mentioned (A), (B), (C), (D), (E), (F), (G), (I) and (J).

The (H) additive contains carboxylbenzotriazoles from the viewpoint of preventing the substrate from becoming blushed. The amount of carboxylbenzotriazoles is 0.01 to 5% by mass based on the total amount of the (A) to (J) components. The amount of 0.01% by mass or more is necessary from the viewpoint of preventing the substrate from becoming blushed when the photosensitive resin laminate is laminated onto a substrate such as a copper-clad laminate and developed after a certain period of time, and the amount of 0.03% by mass or more is preferable, and 0.05% by mass or more is more preferable. On the other hand, the amount of 5% by mass or less is necessary from the viewpoint of obtaining high resolution, and the amount of 3% by mass or less is preferable, and 1% by mass or less is even more preferable.

Examples of carboxylbenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-5-carboxylbenzotriazole, which contain an optionally substituted aminomethyl group, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-4-carboxylbenzotriazole, 1-[N,N-bis(isopropyl)aminomethyl]-5-carboxylbenzotriazole, 1-[N-hydro-N-3-(2-ethylhexyloxy)-1-propylaminomethyl]-5-carboxylbenzotriazole, 1-[N,N-bis(1-octyl)aminomethyl]-5-carboxylbenzotriazole, 1-[N,N-bis(2-hydroxypropyl)aminomethyl]-5-carboxylbenzotriazole, and 1-[N,N-bis(1-butyl)aminomethyl]-5-carboxylbenzotriazole. Among these, 1-[N,N-bis(1-butyl)aminomethyl]-5-carboxylbenzotriazole is preferred from the viewpoint of blush prevention performance. The substitution position of the carboxyl group may be a mixture of 5-position and 6-position during the synthesis process, but either of these is preferred. For example, a mixture of 5-position and 6-position substitutions at 0.5:1.5 to 1.5:0.5 (mass ratio), particularly a 1:1 (mass ratio) mixture, can be used. Sometimes the mixture is simply referred to as "1-N-dibutylaminomethylcarboxylbenzotriazole" to refer to a mixture of 5-position and 6-position substitutions. For example, compounds described in JP-A-2008-175957 can also be used as carboxylbenzotriazole. Other examples that can be used include 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3-diazol-2-yl, and 5-amino-1H-tetrazole.

Other additives that may be added as component (H) to the above-mentioned photosensitive resin composition include colorants, radical polymerization inhibitors, benzotriazoles other than carboxylbenzotriazoles, epoxy compounds of bisphenol A, plasticizers, etc.

Colorants include fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, diamond green (e.g., Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLAS GREEN 533 manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OIL BLUE manufactured by Orient Chemical Industry Co., Ltd. 630) etc.

The ratio of the colorant to the total amount of components (A) to (J) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.5 to 2% by mass, and particularly preferably 0.5 to 1% by mass.

The colorant may contain, for example, a leuco dye or a fluoran dye. By containing these, the exposed parts of the photosensitive resin composition layer develop a color, which is preferable in terms of visibility, and when an inspection machine or the like reads the alignment marker for exposure, it is advantageous that the greater the contrast between the exposed and unexposed parts, the easier it is to recognize.

Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green]. In particular, from the viewpoint of obtaining good contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass with respect to the total amount of the components (A) to (J). It is preferable to set this content to 0.1% by mass or more from the viewpoint of obtaining good contrast between the exposed and unexposed parts, and it is more preferable to set this content to 0.2% by mass or more, and it is particularly preferable to set this content to 0.4% by mass or more. On the other hand, it is preferable to set this content to 10% by mass or less from the viewpoint of maintaining storage stability, and it is more preferable to set this content to 2% by mass or less, and it is particularly preferable to set this content to 1% by mass or less.

In addition, it is preferable to use a combination of a leuco dye and a halogen compound in the photosensitive resin composition from the viewpoint of optimizing adhesion and contrast. The halogen compound can be derived from the organic halogen compound described above as component (C), and tribromomethylphenylsulfone is particularly preferable.

Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, etc. Nitrosophenylhydroxyamine aluminum salt is preferred so as not to impair the sensitivity of the photosensitive resin composition.

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

Examples of epoxy compounds of bisphenol A include compounds in which bisphenol A is modified with polypropylene glycol and the ends are epoxidized.

The total content of the radical polymerization inhibitor, benzotriazoles other than carboxylbenzotriazoles, carboxylbenzotriazoles, and bisphenol A epoxy compounds is preferably 0.001 to 3 mass%, and more preferably 0.01 to 1 mass%, based on the total amount of components (A) to (J). A content of 0.001 mass% or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while a content of 3 mass% or less is preferable from the viewpoint of maintaining the sensitivity of the photosensitive resin composition and suppressing decolorization and color development of the dye.

Examples of plasticizers include phthalate esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc. Other examples include compounds having a bisphenol skeleton such as ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (all manufactured by Asahi Denka Co., Ltd.), NEWPOL BP-23P, NEWPOL BP-3P, NEWPOL BP-5P, NEWPOL BPE-20T, NEWPOL BPE-60, NEWPOL BPE-100, NEWPOL BPE-180 (all manufactured by Sanyo Chemical Industries, Ltd.), UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, UNIOL DA-700 (all manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U Glycol, and BA-P8 Glycol (all manufactured by Nippon Nyukazai Co., Ltd.).

The content of the plasticizer relative to the total amount of the components (A) to (J) is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass. A content of 1% by mass or more is preferred from the viewpoints of suppressing delays in development time and imparting flexibility to the cured film, while a content of 50% by mass or less is preferred from the viewpoints of suppressing insufficient curing and cold flow.

<Photosensitive Resin Laminate>
The photosensitive resin laminate of the present embodiment includes a support film and a photosensitive resin composition layer including a photosensitive resin composition provided on the support film.
Another embodiment provides a photosensitive resin laminate in which a photosensitive resin composition layer made of the above-mentioned photosensitive resin composition is laminated on a support film. If necessary, the photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin composition layer opposite to the support film side.

The support film is preferably transparent and transmits the light emitted from the exposure light source. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary, and preferably have a haze of 5 or less. The thinner the film, the more advantageous it is for improving image formation and economy, but a film with a thickness of 10 to 30 μm is preferably used in order to maintain the strength of the photosensitive resin laminate.

An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive strength between the protective layer and the photosensitive resin composition layer is sufficiently smaller than that of the support film, and the protective layer can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Also, a film with excellent peelability, such as that shown in JP-A-59-202457, can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

When polyethylene is used for the protective layer, gels called fish eyes are present on the surface of the polyethylene film, and these may be transferred to the photosensitive resin composition layer. If fish eyes are transferred to the photosensitive resin composition layer, they may trap air during lamination, causing voids and leading to defects in the resist pattern. From the viewpoint of preventing fish eyes, the material for the protective layer is preferably oriented polypropylene. A specific example is Alphan E-200A manufactured by Oji Paper Co., Ltd.

The thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm; the thinner the layer, the better the resolution, and the thicker the layer, the better the film strength.

<Method for producing photosensitive resin laminate>
A method for producing the photosensitive resin laminate will be described.
The method for producing a photosensitive resin laminate of the present embodiment includes a preparation preparation step of producing the above-mentioned photosensitive resin composition preparation, and a coating/drying step of coating the photosensitive resin composition preparation on a support film and drying it to form a photosensitive resin composition layer to produce the photosensitive resin laminate.

A known method can be used to prepare a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin composition layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used in the photosensitive resin composition layer is mixed with a solvent that dissolves the photosensitive resin composition to form a homogeneous solution (photosensitive resin composition preparation).

Suitable solvents include ketones such as acetone, methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation is 500 mPa·s to 4000 mPa·s at 25°C.

The photosensitive resin composition preparation is first applied onto a support film using a bar coater or roll coater, and then dried to laminate a photosensitive resin composition layer made of the photosensitive resin composition onto the support film. Next, if necessary, a protective layer is laminated onto the photosensitive resin composition layer to produce a photosensitive resin laminate.

<Method of forming a resist pattern>
Another embodiment provides a method for forming a resist pattern, comprising laminating the above-mentioned photosensitive resin laminate on a substrate, exposing the laminate to light, and developing the laminate. An example of a method for forming a resist pattern using the photosensitive resin laminate of the present embodiment will be described below. Examples of the resist pattern include resist patterns formed in circuit boards (printed wiring boards), flexible boards, lead frame boards, COF (chip-on-film) boards, semiconductor package boards, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, wiring for organic EL displays, electrodes for PDPs (plasma display panels), and the like.

The resist pattern can be formed through the following steps.
The method for forming a resist pattern of the present embodiment includes the steps of laminating a photosensitive resin laminate onto a substrate, exposing the photosensitive resin composition layer, and developing the exposed photosensitive resin composition layer.
(1) Lamination process While peeling off the protective layer of the photosensitive resin composition layer, the photosensitive resin laminate is adhered to a substrate such as a copper-clad laminate, a flexible substrate, etc., using a hot roll laminator. The lamination conditions may be appropriately set according to conventionally known conditions.

(2) Exposure Step A mask film having a desired pattern (e.g., a wiring pattern) is attached to the support film of the photosensitive resin laminate and exposed using an active light source, or a drawing pattern corresponding to the desired pattern is exposed by direct drawing. It is preferable to perform exposure by direct drawing of a drawing pattern. As the exposure wavelength, i-line, h-line, g-line, a mixture thereof, etc. can be appropriately used. The photosensitive resin composition of this embodiment is advantageous in that high sensitivity and high resolution can be achieved in exposure with i-line or h-line, especially h-line. In addition, this makes the photosensitive resin composition of this embodiment particularly useful in direct drawing. The exposure conditions may be appropriately set according to conventionally known conditions.

(3) Development process After exposure, the support film on the photosensitive resin composition layer is peeled off, and then the unexposed areas are developed and removed using an aqueous alkaline developer to form a resist pattern on the substrate. As the aqueous alkaline solution, an aqueous _Na2CO3 or _K2CO3 solution is used. The aqueous alkaline solution is appropriately selected according to the characteristics of the photosensitive resin composition layer, but an _{aqueous Na2CO3} solution with a concentration of about 0.2 _to 2% by _mass and at a temperature of about 20 to 40°C is generally used.

A resist pattern can be obtained through each of the above steps, but in some cases, a heating step at about 100 to 300°C can also be performed. By carrying out this heating step, it is possible to further improve chemical resistance. For heating, a heating furnace using hot air, infrared rays, or far infrared rays can be used.

The method for forming metal wiring of this embodiment includes the steps of forming a resist pattern by the above-described method, forming metal wiring (conductor pattern) using the resist pattern, and peeling off the resist pattern.
Another aspect provides a method for producing a circuit board, comprising the steps of laminating the above-mentioned photosensitive resin laminate on a substrate, exposing, developing, and plating, and a method for producing a circuit board, comprising the steps of laminating the above-mentioned photosensitive resin laminate on a substrate, exposing, developing, and etching. The circuit board can be produced by further etching or plating the substrate on which a resist pattern has been formed by the procedure described above for the resist pattern formation method. In particular, in the production of a circuit board, performing exposure by direct drawing of a drawing pattern is advantageous from the viewpoint of productivity, since it is not necessary to prepare a mask. Etching and plating can be carried out as follows, respectively.

(4) Etching or plating process The surface of the substrate exposed by the above-mentioned development (for example, the copper surface in the case of a copper-clad laminate) is etched or plated to form a conductor pattern. The etching and plating methods can be any conventionally known method.

(5) Stripping Step: The resist pattern is then stripped from the substrate using an aqueous solution that is more alkaline than the developer. There are no particular limitations on the aqueous alkaline solution used for stripping, but an aqueous solution of NaOH or KOH with a concentration of about 2 to 5% by mass and a temperature of about 40 to 70° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.
In particular, in this embodiment, by using a diphenylpyrazoline derivative as the photosensitizer (G), it has particularly excellent peelability after plating.
A circuit board can be manufactured by the above-mentioned procedure.

The semiconductor package manufacturing method of this embodiment provides a semiconductor package manufacturing method including a step of forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method described above, and a step of etching or plating the semiconductor package substrate on which the resist pattern has been formed. The semiconductor package substrate and the semiconductor package can be appropriately configured as desired from any conventionally known configuration. Furthermore, the formation of the resist pattern and the etching or plating can each be performed according to the procedures described above.

The photosensitive resin laminate of this embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns such as circuit boards (printed wiring boards), flexible boards, lead frame boards, boards for COF (chip on film), boards for semiconductor packages, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, wiring for organic EL displays, and electrodes for PDPs (plasma display panels).

As described above, this embodiment can provide a photosensitive resin laminate that is compatible with solubility in a developer, i.e., developability, and adhesion to a substrate, particularly a copper substrate, and a method for producing the same.

Unless otherwise specified, the various parameters mentioned above are measured according to the measurement methods described in the examples below.

We will explain how to measure the physical properties of the polymer and monomer, and how to prepare evaluation samples for the examples and comparative examples. We will then show the evaluation methods and results for the obtained samples.

(1) Measurement or calculation of physical properties <Measurement of weight-average molecular weight or number-average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer was determined in terms of polystyrene by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: four Shodex (registered trademark) columns (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K. arranged in series, mobile phase solvent: tetrahydrofuran, using a calibration curve based on a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)).
Furthermore, the dispersity of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

<Acid equivalent>
In this specification, the acid equivalent means the mass (grams) of a polymer having one equivalent of a carboxyl group in a molecule. The acid equivalent was measured by potentiometric titration using a 0.1 mol/L aqueous sodium hydroxide solution using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

(2) Method of Preparing Evaluation Samples The evaluation samples in Examples 1 to 19 and Comparative Examples 1 to 4 were prepared as follows.

<Preparation of Photosensitive Resin Laminate>
The components shown in Tables 1 and 2 below (wherein the numbers for each component indicate the amount (parts by mass) of the solid content) and the solvent were thoroughly stirred and mixed to obtain photosensitive resin composition preparations. The names of the components shown by abbreviations in Tables 1 and 2 are shown in Tables 3 to 6 below.
A polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was used as the support film. The prepared liquid was uniformly applied to the surface of the support film using a bar coater, and dried in a dryer at 95° C. for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 μm.
Next, a 19 μm-thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer on the surface of the photosensitive resin composition layer on the side on which the polyethylene terephthalate film was not laminated, thereby obtaining a photosensitive resin laminate in which the support film, the photosensitive resin composition layer, and the protective layer were laminated in this order.

<Substrate surface preparation>
A 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was sprayed with an abrasive (Sakurandum R (registered trademark #220) manufactured by Nippon Carlit Co., Ltd.) at a spray pressure of 0.2 MPa to polish the surface.

<Lamination>
While peeling off the polyethylene film of the photosensitive resin laminate, the laminate was laminated on a copper-clad laminate preheated to 60° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.

<Exposure>
The photosensitive resin compositions prepared using compositions 1 to 7 were exposed to light at an illuminance of 85 mW/cm 2 and 60 mJ ^/ cm ² using a direct imaging exposure machine (Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, dominant wavelength 405±5 nm).
The photosensitive resin compositions prepared using compositions 8 to 15 were exposed to light at an exposure dose of 160 mJ/cm ² using a parallel light exposure machine (Oak Manufacturing Co., Ltd., HMW-801).

<Developing>
The polyethylene terephthalate film of the exposed evaluation substrate was peeled off. After that, an alkali developing machine (manufactured by Fuji Kiko, a dry film developing machine) was used to spray a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. for a predetermined time, and the unexposed portion of the photosensitive resin composition layer was dissolved and removed. At this time, development was performed for a time twice as long as the minimum development time to prepare a cured resist portion. The minimum development time refers to the shortest time required for the unexposed portion of the photosensitive resin composition layer to completely dissolve.

(3) Sample Evaluation Method <Measurement of iron atom, calcium atom, aluminum atom, and sodium atom content>
The iron content of the photosensitive resin composition layer was measured by inductively coupled plasma (ICP) emission spectrometry as described in JIS K1200-6 under the following measurement conditions.
(1) Equipment Inductively coupled plasma mass spectrometer (ICP-MS): ICPMS-2030 (Shimadzu Corporation)

(2) Pretreatment The obtained photosensitive resin composition layer was exposed from the polyethylene terephthalate film side with a direct imaging exposure machine (DE-1DH, manufactured by Via Mechanics Co., Ltd., light source: GaN blue-violet diode, dominant wavelength 405±5 nm) at an illuminance of 85 mW/cm ² and 60 mJ/cm ² .
Next, the polyethylene film and the polyethylene terephthalate film were peeled off, and 1.000 g of the exposed photosensitive resin composition layer was weighed out, and the photosensitive resin was incinerated in an electric furnace.

Next, 5 ml of an aqueous solution of nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.; an aqueous solution of special grade nitric acid and ultrapure water mixed in a 1:1 ratio) was added to the platinum crucible removed from the electric furnace to dissolve the above-mentioned ash.
Subsequently, 15 ml of ultrapure water was added to obtain an aqueous solution of the ashed product. The aqueous solution obtained by the above operation was measured by inductively coupled plasma (ICP) emission spectrometry according to JIS K1200-6 to determine the contents (ppmw) of iron atoms, calcium atoms, aluminum atoms, and sodium atoms in the photosensitive resin composition layer.

<Method for evaluating developability>
After laminating the photosensitive resin composition on the substrate, the minimum development time was measured 15 minutes later and evaluated according to the following criteria, with criterion D being failure.
A (Very good): Minimum development time is less than 17 seconds. B (Good): Minimum development time is between 17 and 19 seconds. C (Acceptable): Minimum development time is between 19 and 21 seconds. D (Poor): Minimum development time is 21 seconds or more.

<Method for evaluating adhesion>
After laminating the photosensitive resin composition on the substrate, 15 minutes later, the composition was developed under the above-mentioned developing conditions, and the pattern was observed under an optical microscope and evaluated according to the following criteria, with criterion D being failure.
A (very good): The minimum contact line width of an independent pattern is less than 9 μm. B (good): The minimum contact line width of an independent pattern is 9 μm or more and less than 10 μm. C (acceptable): The minimum contact line width of an independent pattern is 10 μm or more and less than 11 μm. D (poor): The minimum contact line width of an independent pattern is 11 μm or more.

(4) Evaluation Results The evaluation results of Examples 1 to 13 and Comparative Examples 1 and 2 are shown in Tables 7 to 9 below.

The following can be read from the results in Table 7.
First, in Comparative Example 1 in which the iron atom content was less than 0.01 ppm, the adhesion to the substrate was poor, while in Comparative Example 2 in which the iron atom content was more than 10 ppm, the developability was poor.

In contrast to this, in Examples 1 to 13 in which the content of iron atoms was 0.01 ppm or more and 10 ppm or less, good results were obtained in terms of both developability and adhesion to the substrate.
Among them, particularly good results were obtained in Examples 7 and 8, in which the iron atom content was 0.05 ppm or more and 2.0 ppm or less.

From the results of Tables 8 and 9, similarly for calcium atoms or aluminum atoms, in Comparative Example 1, where the content of calcium atoms or aluminum atoms was less than 0.005 ppm, adhesion to the substrate was poor. On the other hand, in Comparative Example 2, where the content of calcium atoms or aluminum atoms was more than 5 ppm, developability was poor.

In contrast to this, in Examples 1 to 13 in which the content of calcium atoms or aluminum atoms was 0.005 ppm or more and 5 ppm or less, good results were obtained in terms of both developability and adhesion to the substrate.
Among them, particularly good results were obtained in Examples 7 and 8, in which the content of calcium atoms or aluminum atoms was 0.03 ppm or more and 1.0 ppm or less.

<Method for evaluating dense wiring resolution>
The photosensitive resin compositions of Examples 14 to 19 and Comparative Examples 3 and 4 were evaluated for dense wiring resolution.
After laminating the photosensitive resin composition onto the substrate, 15 minutes later, the composition was developed using the above-mentioned developing conditions, and the pattern was observed under an optical microscope. Evaluation was performed based on the following criteria, divided into viewpoints of residues between wirings and contact between adjacent wirings, with criterion D being a failure.
A (Very good): The minimum resolution of the 1:1 L/S pattern is less than 13 μm. B (Good): The minimum resolution of the 1:1 L/S pattern is 14 μm or more and less than 15 μm. C (Acceptable): The minimum resolution of the 1:1 L/S pattern is 16 μm or more and less than 17 μm. D (Poor): The minimum resolution of the 1:1 L/S pattern is 18 μm or more.

(4) Evaluation Results The evaluation results of Examples 14 to 19 and Comparative Examples 3 and 4 are shown in Tables 10 and 11 below.

The results in Tables 10 and 11 show that in Comparative Example 3, where the sodium atom content was less than 1 ppm, the residue between the wirings was poor. On the other hand, in Comparative Example 4, where the sodium atom content was more than 50 ppm, the contact between adjacent wirings was poor.

In contrast, in Examples 14 to 19, in which the sodium atom content was 1 ppm or more and 50 ppm or less, good results were obtained with respect to both residues between wirings and contact between adjacent wirings.

The above describes an embodiment of the present invention, but the present invention is not limited to this and can be modified as appropriate without departing from the spirit of the invention.

The photosensitive resin composition laminate of the present invention has high sensitivity and high resolution. Therefore, the photosensitive resin composition laminate of the present invention can be suitably used for manufacturing conductor patterns in circuit boards (printed wiring boards), flexible boards, lead frame boards, boards for COF (chip-on-film), boards for semiconductor packages, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, wiring for organic EL displays, electrodes for PDPs (plasma display panels), etc.

Claims (41)

A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (D) an iron atom;
Contains
A photosensitive resin laminate, wherein the content of iron atoms in the photosensitive resin composition layer is 0.01 ppm or more and 10 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.1 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.2 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.3 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.4 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.5 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.6 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.7 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.8 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.9 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 1.0 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 2.0 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 3.0 ppm or more based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 13, wherein the content of iron atoms in the photosensitive resin composition layer is 5.0 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 11, wherein the content of iron atoms in the photosensitive resin composition layer is 2.0 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 11, wherein the content of iron atoms in the photosensitive resin composition layer is 1.5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 10, wherein the content of iron atoms in the photosensitive resin composition layer is 1.0 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 9, wherein the content of iron atoms in the photosensitive resin composition layer is 0.9 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the content of iron atoms in the photosensitive resin composition layer is 0.8 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 7, wherein the content of iron atoms in the photosensitive resin composition layer is 0.7 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 6, wherein the content of iron atoms in the photosensitive resin composition layer is 0.6 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 5, wherein the content of iron atoms in the photosensitive resin composition layer is 0.5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 4, wherein the content of iron atoms in the photosensitive resin composition layer is 0.4 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the content of iron atoms in the photosensitive resin composition layer is 0.3 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1 or 2, wherein the content of iron atoms in the photosensitive resin composition layer is 0.2 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.1 ppm or less based on the photosensitive resin composition layer. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (E) a calcium atom;
Contains
A photosensitive resin laminate, wherein the content of calcium atoms in the photosensitive resin composition layer is 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 27, wherein the content of calcium atoms in the photosensitive resin composition layer is 0.02 ppm or more and 2.5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 27, wherein the content of calcium atoms in the photosensitive resin composition layer is 0.03 ppm or more and 1 ppm or less based on the photosensitive resin composition layer. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (F) an aluminum atom;
Contains
A photosensitive resin laminate, wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 30, wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.02 ppm or more and 2.5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 30, wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.03 ppm or more and 1 ppm or less based on the photosensitive resin composition layer. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator;
(D) at least one of an iron atom, a calcium atom, and an aluminum atom;
Contains
A photosensitive resin laminate, wherein the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.02 ppm or more and 20 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 33, wherein the total content of iron atoms, calcium atoms, and aluminum atoms in the photosensitive resin composition layer is 0.07 ppm or more and 10 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 33, wherein the total content of iron atoms, calcium atoms, and aluminum atoms in the photosensitive resin composition layer is 0.11 ppm or more and 5 ppm or less based on the photosensitive resin composition layer. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (I) a sodium atom;
Contains
A photosensitive resin laminate, wherein the content of sodium atoms in the photosensitive resin composition layer is 1 ppm or more and 50 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 36, wherein the content of sodium atoms in the photosensitive resin composition layer is 1.5 ppm or more and 25 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 36, wherein the content of sodium atoms in the photosensitive resin composition layer is 2 ppm or more and 10 ppm or less based on the photosensitive resin composition layer. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer including a photosensitive resin composition formed on the support film,
The photosensitive resin composition comprises
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and (J) a metal atom;
Contains
A photosensitive resin laminate, wherein the content of metal atoms in the photosensitive resin composition layer is 0.005 ppm or more and 70 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 39, wherein the content of metal atoms in the photosensitive resin composition layer is 0.01 ppm or more and 5 ppm or less based on the photosensitive resin composition layer. The photosensitive resin laminate according to claim 39 or 40, containing at least one of aluminum, calcium, iron, potassium, magnesium, and zinc as the metal atom.