JP2022058739A - Photosensitive resin laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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

COPYRIGHT: (C)2022,JPO&INPIT

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 of forming a desired wiring pattern on a substrate by the following steps. That is, first, a layer made of a photosensitive resin composition is formed on a substrate, and a resist pattern is formed by pattern exposure and development on the coating film. Then, a conductor pattern is formed by etching or plating. Then, by removing the resist pattern on the substrate, a desired wiring pattern is formed on the substrate.

In the manufacture of printed wiring boards, photosensitive elements (photosensitive resin laminates) are often used. There are many known examples of a method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for the method (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 Patent Documents 1 to 3 do not satisfy the developability, the adhesiveness, etc. at the same time, and still have room for improvement.

Therefore, the problem to be solved by the present invention is to laminate a photosensitive resin on a base film, which comprises a photosensitive resin composition capable of achieving both solubility in a developing solution, that is, developability, and adhesion to a substrate, particularly a copper substrate. It is to provide the body and its manufacturing method.

The present inventor has 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 containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (D) Iron Atom;
Contains,
A photosensitive resin laminate characterized in that 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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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. body.
[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 method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (D) Iron Atom:
In the formulation manufacturing process for producing a photosensitive resin composition formulation containing
A coating / drying step of applying the photosensitive resin composition preparation solution onto the support film and drying it to form the photosensitive resin composition layer to produce the photosensitive resin laminate is included.
A method for producing a photosensitive resin laminate in which 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.
[28]
The production of the photosensitive resin laminate according to [27], wherein the content of iron atoms in the photosensitive resin composition layer is 0.5 ppm or more and 2.0 ppm or less based on the photosensitive resin composition layer. Method.
[29]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (E) Calcium Atom;
Contains,
A photosensitive resin laminate characterized in that 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.
[30]
The photosensitive resin laminate according to [29], 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.
[31]
The photosensitive resin laminate according to [29], 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.
[32]
A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (E) Calcium Atom;
In the formulation manufacturing process for producing a photosensitive resin composition formulation containing
A coating / drying step of applying the photosensitive resin composition preparation solution onto the support film and drying it to form the photosensitive resin composition layer to produce the photosensitive resin laminate is included.
A method for producing a photosensitive resin laminate in which 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.
[33]
The method for producing a photosensitive resin laminate according to [32], 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.
[34]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (F) Aluminum Atom;
Contains,
A photosensitive resin laminate characterized in that 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.
[35]
The photosensitive resin laminate according to [34], 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.
[36]
The photosensitive resin laminate according to [34], 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.
[37]
A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (F) Aluminum Atom;
In the formulation manufacturing process for producing a photosensitive resin composition formulation containing
A coating / drying step of applying the photosensitive resin composition preparation solution onto the support film and drying it to form the photosensitive resin composition layer to produce the photosensitive resin laminate is included.
A method for producing a photosensitive resin laminate in which 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.
[38]
The method for producing a photosensitive resin laminate according to [37], 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.
[39]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization initiator;
(D) Iron atom;
(E) calcium atom; and (F) aluminum atom;
Contains,
The photosensitive resin is characterized in that 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. Laminated body.
[40]
The photosensitive resin composition layer according to [39], 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. Sex resin laminate.
[41]
The photosensitive resin composition layer according to [39], 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 4 ppm or less based on the photosensitive resin composition layer. Sex resin laminate.
[42]
A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization initiator;
(D) Iron atom;
(E) calcium atom; and (F) aluminum atom;
In the formulation manufacturing process for producing a photosensitive resin composition formulation containing
A coating / drying step of applying the photosensitive resin composition preparation solution onto the support film and drying it to form the photosensitive resin composition layer to produce the photosensitive resin laminate is included.
A method for producing a photosensitive resin laminate in which 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. ..
[43]
The photosensitive resin composition layer according to [42], 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 4 ppm or less based on the photosensitive resin composition layer. A method for manufacturing a sex resin laminate.
[44]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (I) Sodium Atom;
Contains,
A photosensitive resin laminate characterized in that 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.
[45]
The photosensitive resin laminate according to [44], 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.
[46]
The photosensitive resin laminate according to [44], 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.
[47]
A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (I) Sodium Atom;
In the formulation manufacturing process for producing a photosensitive resin composition formulation containing
A coating / drying step of applying the photosensitive resin composition preparation solution onto the support film and drying it to form the photosensitive resin composition layer to produce the photosensitive resin laminate is included.
A method for producing a photosensitive resin laminate in which 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.
[48]
The method for producing a photosensitive resin laminate according to [47], 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.

According to the present invention, there is provided a laminate having a photosensitive resin composition on a base film capable of achieving both solubility in a developing solution, that is, developability, and adhesion to a substrate, particularly a copper substrate, thereby being dry. It is possible to improve the resolution of a printed wiring board formed by using a film resist.

Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be specifically described.
In addition, 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 the present embodiment, the photosensitive resin laminate comprises a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, (C) a photopolymerization initiator, and (D) an iron atom, (E) a calcium atom, and (F). It contains either an aluminum atom or an (I) sodium atom. If desired, the photosensitive resin composition may further contain other components such as (G) a photosensitizer and (H) an additive.

In particular, in the present embodiment, the photosensitive resin composition layer contains (D) an iron atom of 0.01 ppm or more and 10 ppm or less based on the photosensitive resin composition layer, or (E) a calcium atom. F) The content of any of the aluminum atoms is 0.005 ppm or more and 5 ppm or less based on the photosensitive resin composition layer, and (I) the content of the sodium atom is 1 ppm based on the photosensitive resin composition layer. It is 50 ppm or less.
By setting the contents of iron atoms, calcium atoms, and aluminum atoms in the above range, it is possible to achieve both solubility in a developing solution, that is, developability, and adhesion to a substrate, particularly a copper substrate. Good developability makes it difficult for residues to remain in the resist pattern, and good adhesion to the substrate makes it possible to form a finer resist pattern.
Hereinafter, each component will be described in order.

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

In relation to alkali solubility, the acid equivalent of (A) the alkali-soluble polymer (if the component (A) contains a plurality of copolymers, the acid equivalent for the entire mixture) is a photosensitive resin composition. It is preferably 100 or more from the viewpoint of the development resistance of the layer and the development resistance, resolution and adhesion of the resist pattern, and 900 or less from the viewpoint of the developability and peelability of the photosensitive resin composition layer. Is preferable. The acid equivalent of the alkali-soluble polymer (A) 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 1 equivalent of a carboxyl group therein.

(A) Alkali-soluble polymer (A) The alkali-soluble polymer is a polymer that is easily soluble in an alkaline substance. Specifically, a functional group (for example, a carboxyl group) that contributes to alkali solubility is dissolved in a desired alkaline substance. It is a polymer that has a sufficient amount to be used. Further, typically, the amount of the carboxyl group contained in the (A) alkali-soluble polymer is 100 to 600, preferably 250 to 450, in terms of acid equivalent. The acid equivalent refers to the mass (unit: gram) of a linear polymer having 1 equivalent of a carboxyl group in the molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary to impart developability and peelability to the alkaline aqueous solution to the photosensitive resin composition layer. 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. The weight average molecular weight is preferably 500,000 or less from the viewpoint of improving resolution and developability, the weight average molecular weight is more preferably 300,000 or less, and further 200,000 or less. preferable. On the other hand, setting the weight average molecular weight to 5,000 or more is preferable from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property of the photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, and even more preferably 20,000 or more. The edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when it is wound into a roll as a photosensitive resin laminate. The cut chip property is a phenomenon in which the chip flies when the unexposed film is cut with a cutter. When this chip adheres to the upper surface of the photosensitive resin laminate or the like, the chip is transferred to the mask in a later exposure process or the like, which causes a defective product.

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

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

The first monomer is a carboxylic acid or 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, maleic acid semi-ester and the like. In particular, (meth) acrylic acid is preferable. As used herein, (meth) acrylic refers to acrylic and / or methacrylic. The same applies hereinafter.

The second monomer is a monomer that 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, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as acetic acid. Examples include vinyl, (meth) acrylonitrile, styrene, and styrene derivatives. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. From the viewpoint of improving the resolution and adhesion of the resist pattern, styrene and benzyl (meth) acrylate are preferable.

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

(A) For the synthesis of the alkali-soluble polymer, a mixture of the first monomer and the second monomer is diluted with a solvent such as acetone, methyl ethyl ketone, or isopropanol into a solution of benzoyl peroxide and azoisobuty. It is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as butyronitrile and heating and stirring. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

(A) Alkali-soluble polymer (when a plurality of alkali-soluble polymers are mixed and used, the mixture) is a component (A), a component (B), a component (C), a component (D), The ratio of the component (G) to the total amount of the component (H) and the component (I) (hereinafter, also referred to as the total amount of the component (A) to the component (I)) is preferably in the range of 10 to 90% by mass. It is more preferably 30 to 70% by mass, still more preferably 40 to 60% by mass. It is preferable that the ratio of the component (A) to the total amount of the components (A) to (I) is 90% by mass or less from the viewpoint of controlling the development time, while the total amount of the components (A) to (I) It is preferable to make the ratio of the component (A) to 10% by mass or more from the viewpoint of improving the edge fuseability.

In particular, in the photosensitive resin composition, as the component (A), one or more components selected from the group consisting of the following (a-1) and (a-2):
(A-1) 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 ester, and methacrylic acid ester. Acrylic copolymer;
(A-2) Includes 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 esters other than benzyl methacrylate. Acrylic copolymer derived from polymerization component;
Is preferable in terms of exhibiting high resolution. As a ratio of the total amount of the component (a-1) and the component (a-2) to the total amount of the components (A) to (I), 10 to 60% by mass is high in resolution. Is preferable. From the viewpoint of resolvability, the above ratio is preferably 20% by mass or more, more preferably 30% by mass or more, and from the viewpoint of cut chip property, it is preferably 55% by mass or less, more preferably 50% by mass or less.

The polymerization component in (a-1) may be composed of only styrene and the above acrylic monomer, or may further contain other monomers. Further, the polymerization component in (a-2) may be composed of only benzyl methacrylate and the above acrylic monomer, or may further contain other monomers. Particularly preferable examples of the combination of the polymerization components are a combination of 15 to 60% by mass of styrene and 20 to 35% by mass of methacrylic acid, the rest of which is a combination of methyl methacrylate, and 30 to 50% by mass of styrene and methacrylic acid. 20-40% by mass, 10-20% by mass of 2-ethylhexyl acrylate, the rest is a combination of 2-hydroxyethyl methacrylate, 20-60% by mass of benzyl methacrylate, 10-30% by mass of styrene, the rest is methacrylic Examples of the combination of acids include a combination of 60 to 85% by mass of benzyl methacrylate, 0 to 15% by mass of 2-ethylhexyl acrylate, and a combination of methacrylic acid in the rest. It is preferable to contain a monomer having an aralkyl group or styrene as a monomer from the viewpoint of chemical resistance, adhesion, high resolution, or sewn shape of the resist pattern.

(B) A compound having an ethylenically unsaturated double bond (B) A compound containing an ethylenically unsaturated bond is a compound having a polymerizable property by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerization.

The compound having (B) an ethylenically unsaturated double bond preferably contains a compound having an acryloyl group in the molecule from the viewpoint of curability and (A) compatibility with an alkali-soluble polymer. Examples of the compound 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 and the other end is alkyl. Examples thereof include etherified or allyl etherified ones.

Examples of such a compound include phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group, or propylene oxide having an average of 2 mol (hereinafter, may be abbreviated as PO). ) Is added to polypropylene glycol and polyethylene glycol to which an average of 7 mol of ethylene oxide (hereinafter, may be abbreviated as EO) is added to nonylphenol. Propylene glycol (meth) acrylate, 4-normalnonylphenoxypentaethylene glycol, which is a (meth) acrylate of a compound obtained by adding polypropylene glycol having an average of 1 mol of propylene oxide and polyethylene glycol having an average of 5 mol of ethylene oxide added to nonylphenol. Examples include monopropylene glycol (meth) acrylate. Also included is 4-normal Nonylphenoxyoctaethylene glycol (meth) acrylate (eg, M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol having an average of 8 mol of ethylene oxide added to nonylphenol.

For example, a compound having (meth) acryloyl groups at both ends of an alkylene oxide chain, or a compound having (meth) acryloyl groups at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are randomly or blocked. be able to.

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, and octaethylene glycol di (meth). Ethylene glycol (meth) acrylicates such as acrylates, nonaethylene glycol di (meth) acrylates, decaethylene glycol di (meth) acrylates, compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain, Polypropylene glycol di (meth) acrylicate, polybutylene glycol di (meth) acrylicate and the like can be mentioned. As the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, a glycol in which an average of 12 mol of propylene oxide is added to polypropylene glycol and an average of 3 mol of ethylene oxide is added to both ends thereof. Dimethacrylate, dimethacrylate of glycol to which ethylene oxide is further added to both ends of polypropylene glycol to which an average of 18 mol of propylene oxide is added, and the like. Further, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate having both ethylene oxide and polypropylene oxide (for example, "FA-023M, FA-024M, FA-027M, product name, Hitachi" "Made by Kasei Kogyo") is preferable from the viewpoint of flexibility, resolution, adhesion and the like.

Further, a compound obtained by modifying bisphenol A with alkylene oxide and having (meth) acryloyl groups at both ends is preferable from the viewpoint of resolution and adhesion. The alkylene oxide denaturation includes ethylene oxide denaturation, propylene oxide denaturation, butylene oxide denaturation, pentylene oxide denaturation, hexylene oxide denaturation and the like. Further, from the viewpoint of resolution and adhesion, a compound obtained by modifying bisphenol A with ethylene oxide and having (meth) acryloyl groups at both ends is particularly preferable.

Examples of such a compound include 2,2-bis (4-((meth) acryloxidiethoxy) phenyl) propane (for example, NK ester BPE-200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-. Bis (4-((meth) acryloxitriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxitetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxipentaethoxy) phenyl) propane (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Industry 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-((meth)) Acryloxinonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxidecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxiddecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxidridecaethoxy) phenyl) propane, 2,2-bis (4-((Meta) acryloxitetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) ) Acryloxyhexadecaethoxy) phenyl) propane and the like 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and the like can be mentioned. Further, di (meth) cryo of polyalkylene glycol having an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide added to both ends of bisphenol A, or an average of 2 mol of propylene oxide and an average of 15 mol of propylene oxide at both ends of bisphenol A, respectively. Ethylene oxide-modified and propylene oxide-modified compounds such as di (meth) crylate of polyalkylene glycol to which ethylene oxide is added are also preferable from the viewpoint of resolution and adhesion. The number of moles of ethylene oxide with respect to 1 mol of bisphenol A in the compounds obtained by modifying these bisphenol A with alkylene oxide and having (meth) acryloyl groups at both ends is the total number of moles of ethylene oxide from the viewpoint of improving resolution, adhesion and flexibility. It is preferably 10 mol or more and 30 mol or less.

In the present embodiment, (B) the compound having more than two (meth) acryloyl groups in one molecule as the compound having an ethylenically unsaturated double bond exhibits high resolution. Preferred above. 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 exfoliation. A compound having more than two (meth) acryloyl groups in one molecule has 3 mol or more (that is, 3 or more per central skeleton) of groups capable of adding an alkylene oxide group in the molecule as a central skeleton. It is 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) acrylic acid. If the central skeleton is an alcohol, it can also be obtained by directly forming (meth) acrylic acid and (meth) acrylate. Examples of the compound that can form a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring.

Examples of such compounds include EO3 mol-modified triacrylate of trimethylolpropane, EO6 mol-modified triacrylate of trimethylolpropane, EO9 mol-modified triacrylate of trimethylolpropane, EO12 mol-modified triacrylate of trimethylolpropane, and EO3 of glycerin. Molly modified triacrylate (for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EO9 molar modified triacrylate of glycerin (for example, A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EO6 mol PO6 of glycerin. Molly modified triacrylate (A-GLY-0606PE), EO9 mol PO9 molar modified triacrylate of glycerin (A-GLY-0909PE), 4EO modified tetraacrylate of pentaerythritol (eg SR-494 manufactured by Sartmer Japan Co., Ltd.) , 35EO-modified tetraacrylate of pentaerythritol (for example, NK ester ATM-35E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), dipentaerythritol tetraacrylate, and the like. Examples of the compound having at least three methacryloyl groups include trimethacrylate, for example, ethoxylated glycerin trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, and trimethylolpropane trimethacrylate (for example, trimethylolpropane has an average of 21 mol). Trimethacrylate to which ethylene oxide has been added, and trimethylolpropane to which an average of 30 mol of ethylene oxide has been added are preferable from the viewpoints of flexibility, adhesion, and suppression of bleed-out), etc .; Tetramethacrylate, for example, trimethylolpropane. Tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate and the like; pentamethacrylate, for example, dipentaerythritol pentamethritol and the like; hexamethacrylate, for example, dipentaerythritol hexamethacrylate and the like. Among these, tetra, penta or hexamethacrylate are preferable.

Among the preferable examples of the compound having an ethylenically unsaturated double bond (B), a compound having a melting point lower than room temperature and not easily solidified at the time of storage is preferable from the viewpoint of handleability, and particularly EO3 molar modification of trimethylolpropane. 4EO-modified tetraacrylates of triacrylate and 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 having the (B) ethylenically unsaturated double bond. The content is preferably 50% by mass or more, and more preferably 60% by mass or more from the viewpoint of resolution. The content may be 100% by mass, but from the viewpoint of peelability, it may be preferably 95% by mass or less, more preferably 90% by mass or less.

In addition to the above-mentioned compounds, the component (B) may appropriately contain, for example, the following compounds. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propandi (meth) acrylate, 2,2-bis [(4-4-bis). (Meta) acryloxypolypolyoxy) phenyl] propane, 2,2-bis [(4- (meth) acryloxypolybutyleneoxy) phenyl] propane, glycerol tri (meth) acrylate, trimethyl propanetri (meth) acrylate, Polyoxypropyltrimethylol propanetri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropanetriglycidyl ether tri (meth) acrylate, β-hydroxypropyl-β'-(acryloylxi) propylphthalate, nonylphenoxy Examples thereof include polypropylene glycol (meth) acrylate, nonylphenoxypolybutylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Further, the following urethane compounds can also be mentioned. For example, hexamethylene diisocyanate, tolylene diisocyanate or diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth) acrylic group in one molecule, for example, 2-hydroxypropyl. Examples thereof include urethane compounds with acrylate and oligopropylene glycol monomethacrylate. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (for example, Blemmer PP1000 manufactured by NOF CORPORATION). Further, di or tri (meth) acrylate of isocyanuric acid ester modified with polypropylene glycol or polycaprolactone can also be mentioned. Further, for example, a urethane oligomer obtained by reacting a terminal of a urethane compound obtained as a heavy adduct of diisocyanate and a polyol with a compound having an ethylenically unsaturated double bond and a hydroxyl group can be mentioned.

Further, as the compound (B) having an ethylenically unsaturated bond, 4-normalnonylphenoxyoctaethylene glycol acrylate, 4-normalnonylphenoxytetraethylene glycol acrylate, γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl It may contain a compound having one ethylenically unsaturated bond such as -о-phthalate. It is preferable from the viewpoint of peelability and flexibility of the cured film, and it is preferable to contain γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-о-phthalate from the viewpoint of sensitivity, resolution and adhesion.
The compound having the (B) ethylenically unsaturated double bond preferably contains a hydroxyl group in the molecule. As a result, the sensitivity (productivity), resolution, and adhesion are particularly excellent.

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

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

As hexaarylbiimidazole compounds, 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'-Tetrakiss- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- (3-methoxy) Phenyl) -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) -bi Imidazole, 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'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,6-trifluorophenyl) Phenyl) -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-Methenyl Phenyl) -Bimidazo , And 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole and the like. Be done. Of these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable from the viewpoint of sensitivity and resolution.

Examples of the photopolymerization initiator that may be contained in addition to the hexaarylbiimidazole compound as the component (C) include N-aryl-α-amino acid compounds, quinones, aromatic ketones, acetophenones, and acylphosphine oxides. Examples thereof include benzoins or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acrydins, N-aryl amino 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 and the like. In particular, N-phenylglycine has a high sensitizing effect and is preferable.

Examples of quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, and the like. 2-Methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenantraquinone, 2-methyl-1,4-naphthoquinone, 2 , 3-Dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like can be mentioned.

Examples of aromatic ketones include benzophenone, Michelers' ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. be able to.

Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4). -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl- Examples thereof include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of 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 and the like. Examples of commercially available products include Lucillin TPO manufactured by BASF and Irga Cure 819 manufactured by Ciba Specialty Chemicals.

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

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

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

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

Examples of the oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. .. Examples of 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, 9- (4-acetylphenyl) acridine, 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 can be mentioned.

Examples of the ester compound of N-aryl amino acid include N-phenylglycine methyl ester, N-phenylglycine ethyl ester, N-phenylglycine n-propyl ester, N-phenylglycine isopropyl ester, and N-phenylglycine. 1-butyl ester, N-phenylglycine 2-butyl ester, N-phenylglycine tert butyl ester, N-phenylglycine pentyl ester, N-phenylglycine hexyl ester, N-phenylglycine pentyl ester, N -Examples include octyl ester of phenylglycine.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2). , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound, diallyl iodonium compound, etc. Of these, tribromomethylphenyl sulfone is particularly preferable. The content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass with respect to the total amount of the components (A) to (I) from the viewpoint of sensitivity.

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

The ratio of the photopolymerization initiator (C) to the total amount of the components (A) to (I) is preferably 0.1 to 20% by mass. It is preferable to set this ratio to 0.1% by mass or more from the viewpoint of obtaining sufficient sensitivity, more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. .. On the other hand, setting this ratio to 20% by mass or less is preferable from the viewpoint of obtaining high resolution and suppressing cohesiveness in the developing solution, and it is more preferable to set this ratio to 10% by mass or less. ..

(D) Iron Atoms In the present embodiment, 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 lower limit of the iron atom content in the photosensitive resin composition layer is 0.01 ppm or more based on the photosensitive resin composition layer.
When the iron atom content is less than the above range, poor adhesion is likely to occur due to less interaction with the metal surface of the substrate. For example, since iron ions that are stably present are trivalent, they can coordinate-bond between CuO ⁻ on the surface of the substrate and the carboxylic acid of the binder (for example, CuO ⁻ … Fe ³⁺ … COO ⁻ ). When the iron atom content is at least the above lower limit value, the interaction with the metal surface of the substrate becomes strong and the adhesion is excellent.

The content of iron atoms in the photosensitive resin composition layer may be 0.03 ppm or more, or may be 0.05 ppm or more. Further, it may be 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm or more, or 0.5 ppm or more. It may be 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. good. Further, it may 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. good. Further, it may 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 iron atom content, the better the adhesion.

On the other hand, the upper limit of the iron atom content 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, pseudo-crosslinking occurs due to the formation of coordinate-bonding bonds between the iron ions, resulting in a decrease in solubility in the developer, resulting in a decrease in development time. There will be a delay. When the iron atom content is not more than the above upper limit value, the solubility in a developing solution is appropriate and the developing time is also an appropriate time.

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. There may be. Further, it may be 1.5 ppm or less, 1.4 ppm or less, 1.3 ppm or less, 1.2 ppm or less, or 1.1 ppm or less. It may be 1.0 ppm or less. Further, it may be 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less, 0.6 ppm or less, or 0.5 ppm or less. It may be 0.4 ppm or less, 0.3 ppm or less, 0.2 ppm or less, or 0.1 ppm or less. The smaller the iron atom content, the shorter the development time can be.

The content of iron atoms in the photosensitive resin composition layer is 0.01 ppm or more and 10 ppm or less, most preferably 0.05 ppm or more and 2.0 ppm or less, based on the photosensitive resin composition layer.
By setting the iron atom content in the above range, it is possible to achieve both solubility in a developing solution, that is, 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 forming a finer resist pattern.

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

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

(E) Calcium Atom In the present embodiment, the content of calcium atom 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 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.
When the content of calcium atoms is less than the above range, poor adhesion occurs due to less interaction with the metal surface of the substrate. For example, since stable calcium ions are divalent, they can coordinate-bond between CuO ⁻ on the surface of the substrate and the carboxylic acid of the binder (for example, CuO ⁻ … Ca 2 ⁺ … COO ⁻ ). When the content of the calcium atom is at least the above lower limit value, the interaction with the metal surface of the substrate becomes strong and the adhesion is excellent.

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. There may be. Further, it may be 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm or more, or 0.5 ppm or more. It may be 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. good. Further, it may 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. good. Further, it may be 2.0 ppm or more, 3.0 ppm or more, or 4.0 ppm or more. The higher the content of calcium atoms, 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, pseudo-crosslinking occurs due to the formation of coordinate-bonding bonds between molecules of calcium ions, resulting in a decrease in solubility in a developing solution, resulting in a decrease in development time. There will be a delay. When the content of calcium atoms is not more than the above upper limit value, the solubility in a developing solution is appropriate and the developing time is also an appropriate time.

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. Further, it may be 1.5 ppm or less, 1.4 ppm or less, 1.3 ppm or less, 1.2 ppm or less, or 1.1 ppm or less. It may be 1.0 ppm or less. Further, it may be 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less, 0.6 ppm or less, or 0.5 ppm or less. It may be 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. good. The smaller the content of calcium atoms, the shorter the development time can be.

The content of calcium atoms in the photosensitive resin composition layer is 0.005 ppm or more and 5 ppm or less, most preferably 0.03 ppm or more and 1.0 ppm or less, based on the photosensitive resin composition layer.
By setting the content of calcium atoms in the above range, it is possible to achieve both solubility in a developing solution, that is, 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 forming a finer resist pattern.

The means for adjusting the content of calcium atoms in the photosensitive resin composition layer within the range of 0.005 ppm or more and 5 ppm or less is not particularly limited, but for example, the composition of the photosensitive resin composition varies with respect to each component. Adjustment is mentioned.

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

(F) Aluminum Atoms In the present embodiment, 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 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.
When the content of aluminum atoms is less than the above range, poor adhesion occurs due to less interaction with the metal surface of the substrate. For example, since stable aluminum ions are divalent, they can coordinate-bond between CuO ⁻ on the surface of the substrate and the carboxylic acid of the binder (for example, CuO ⁻ … Al 2 ⁺ … COO ⁻ ). When the content of the aluminum atom is at least the above lower limit value, the interaction with the metal surface of the substrate becomes strong and the adhesion is excellent.

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. There may be. Further, it may be 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm or more, or 0.5 ppm or more. It may be 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. good. Further, it may 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. good. Further, it may be 2.0 ppm or more, 3.0 ppm or more, or 4.0 ppm or more. The higher the content of aluminum atoms, 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, pseudo-crosslinking occurs due to the formation of coordinate-bonding bonds between molecules of aluminum ions, resulting in a decrease in solubility in a developer, resulting in a decrease in development time. There will be a delay. When the content of aluminum atoms is not more than the above upper limit value, the solubility in a developing solution is appropriate and the developing time is also an appropriate time.

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. Further, it may be 1.5 ppm or less, 1.4 ppm or less, 1.3 ppm or less, 1.2 ppm or less, or 1.1 ppm or less. It may be 1.0 ppm or less. Further, it may be 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less, 0.6 ppm or less, or 0.5 ppm or less. It may be 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. good.

The content of aluminum atoms in the photosensitive resin composition layer is 0.005 ppm or more and 5 ppm or less, most preferably 0.03 ppm or more and 1.0 ppm or less, based on the photosensitive resin composition layer.
By setting the content of aluminum atoms in the above range, it is possible to achieve both solubility in a developing solution, that is, 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 forming a finer resist pattern.

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

The content of aluminum atoms in the photosensitive resin composition layer is determined by the method described in 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 atom, calcium atom and aluminum atom may be 0.03 ppm or more, 0.04 ppm or more, 0.05 ppm or more, or 0.06 ppm or more. It may be 0.07 ppm or more, 0.08 ppm or more, 0.09 ppm or more, or 0.1 ppm or more. Further, it may be 0.1 ppm or more, 0.11 ppm or more, 0.12 ppm or more, 0.13 ppm or more, or 0.14 ppm or more. It may be 0.15 ppm or more, 0.16 ppm or more, 0.17 ppm or more, 0.18 ppm or more, or 0.19 ppm or more. It may be 0.2 ppm or more. Further, 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. It may be 0.8 ppm or more, 0.9 ppm or more, or 1.0 ppm or more. Further, it may be 1.5 ppm or more, 2.0 ppm or more, 2.5 ppm or more, 3.0 ppm or more, or 3.5 ppm or more. Well, it may be 4.0 ppm or more.

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

(I) Sodium atom In the present embodiment, the content of the sodium atom in the photosensitive resin composition layer is 1 ppm or more and 50 ppm or less with respect to the photosensitive resin composition layer.

The lower limit of the sodium atom content in the photosensitive resin composition layer is 1 ppm or more based on the photosensitive resin composition layer.
When the content of sodium atom is lower than the above range, a residue is likely to be generated between the formed wirings. Since the photosensitive resin composition contains a small amount of sodium ions, the permeability of the developing solution and the washing water is excellent, so that it is possible to develop without forming a residue even between dense 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, or 4 ppm. It may be more than or equal to 5 ppm, may be 6 ppm or more, may be 7 ppm or more, may be 8 ppm or more, may be 9 ppm or more, or may be 10 ppm or more. There may be. Further, it may 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. Further, it may be 30 ppm or more, 35 ppm or more, 40 ppm or more, or 45 ppm or more. The higher the sodium atom content, the less likely it is that a residue will form between the wires.

On the other hand, the upper limit of the sodium atom content in the photosensitive resin composition layer is 50 ppm or less based on the photosensitive resin composition layer.
When the sodium atom content exceeds the above range, the permeability of the developer and the washing water is too high, so that the formed dense wiring pattern swells and comes into contact with the adjacent wiring, so that a dense wiring pattern is obtained. I can't. When the content of sodium atoms is not more than the above upper limit, the permeability of the developer and the washing water is appropriate, and the resolution in a 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. Further, it may 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, and may be used. It may be 15 ppm or less. Further, it may be 9 ppm or less, 8 ppm or less, 7 ppm or less, 6 ppm or less, 5 ppm or less, or 4 ppm or less. It may be 3 ppm or less, or 2 ppm or less.

The content of sodium atoms in the photosensitive resin composition layer is 1 ppm or more and 50 ppm or less, preferably 1.5 ppm or more and 25 ppm or less, preferably 2 ppm or more and 10 ppm or less, based on the photosensitive resin composition layer. Is the most preferable.
By setting the content of the sodium atom in the above range, the residue between the wirings and the patterns do not come into contact with each other, so that the formability of the dense wiring pattern is excellent.

The means for adjusting the content of sodium atoms in the photosensitive resin composition layer within the range of 1 ppm or more and 50 ppm or less is not particularly limited, but for example, the composition of the photosensitive resin composition is variously adjusted for each component. Alternatively, it may be removed using an ion exchange resin, or various sodium salt compounds may be added.

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

(G) Sensitizer In the photosensitive resin composition of the present 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 absorb a large amount of light around 405 nm, which is called h-line. By using these compounds as a sensitizer, 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 sensitizer (G) is preferably 0.005 to 2% by mass with respect to the total mass of the solid content of the photosensitive resin composition. By using the above (G) sensitizer in this range, good sensitivity, resolution and adhesion can be obtained.

The (G) sensitizer in the present invention may be any one whose sensitivity is improved by combining with the (C) initiator. The functions of the (G) sensitizer include those that absorb light of the exposure wavelength and give energy or electrons to the initiator, (C) those that promote the cleavage of the initiator, and (C) the initiator generated from the initiator. Various examples include radicals or those in which growth radicals once added to a monomer and polymerized move to (G) sensitizer to regenerate radicals through new cleavage and decomposition.
Examples of the (G) sensitizer other than the pyrazoline compound, anthracene compound, triarylamine compound, and oxazole compound include N-aryl-α-amino acid compound, aromatic ketone compound substituted with an alkylamino group, and dialkylaminobenzoic acid ester. Examples thereof include compounds, pyrazoline derivatives, anthracene derivatives, triphenylamine derivatives, N-aryl amino 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 and the like. In particular, N-phenylglycine has a high sensitizing effect and is preferable.
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. And so on.
Examples of the dialkylaminobenzoic acid ester compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate and the like.

As the pyrazoline derivative, 5- (4-tert-butylphenyl) -3- (4-tert-butylstyryl) -1-phenyl-2-pyrazolin, 5- ( 4-tert-Butylphenyl) -1-phenyl-3- (4-phenylphenyl) -4,5-dihydro-1H-pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl) Phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4) -Pyrazoline) -Pyrazoline, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -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-isopropyl-phenyl) -5- (4-methoxy-phenyl) -pyrazoline, 1,5-diphenyl-3- (4-tert-butyl-phenyl) -pyrazoline, 1 , 3-Diphenyl-5- (4-tert- Butyl-Phenyl) -Pyrazolin, 1,5-Diphenyl-3- (4-Isopropyl-Phenyl) -Pyrazolin, 1,3-Diphenyl-5- (4-Isopropyl-Phenyl) -Pyrazolin, 1,5-Diphenyl-3 -(4-Meth-phenyl) -pyrazolin, 1,3-diphenyl-5- (4-methoxy-phenyl) -pyrazolin, 1-phenyl-3,5-bis (4-tert-butyl-phenyl) -pyrazolin, 1,5-Diphenyl-3- (4-tert-butyl-phenyl) -pyrazolin is preferred.
1-Phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl)- Pyrazoline is 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 preferable. Of these, 9,10-dibutoxyanthracene is more preferable from the viewpoint of sensitivity. Examples of the triarylamine compound include compounds having a triphenylamine skeleton in the molecule. As the anthracene compound, the compound represented by the following formula (2) is preferable.

In the above general formula (2), R ₁ , R ₂ and R ₃ are independently linear or branched alkyl groups having 1 to 10 carbon atoms or linear or branched chains having 1 to 4 carbon atoms. Shows an alkoxy group in the form. n4, n5 and n6 represent integers of 0 to 5 selected so that the value of n4 + n5 + n6 is 1 or more. When n4 is 2 or more, a plurality of existing _R1s may be the same or different, and when n5 is ₂ or more, a plurality of existing R2s may be the same or different, and when n6 is 2 or more. , A plurality of _R3s may be the same or different.

In the compound represented by the general formula (2), from the viewpoint of resolution and adhesion, _R2 is a linear or branched alkyl group having 1 to 10 carbon atoms, and n4 and n6 are 0. , N5 is preferably 1, _R2 is a linear or branched alkyl group having 1 to 4 carbon atoms, n4 and n6 are 0, and n5 is more preferably 1. ..

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

Examples of the ester compound of N-aryl amino acid include N-phenylglycine methyl ester, N-phenylglycine ethyl ester, N-phenylglycine n-propyl ester, N-phenylglycine isopropyl ester, and N-phenylglycine. 1-butyl ester, N-phenylglycine 2-butyl ester, N-phenylglycine tert butyl ester, N-phenylglycine pentyl ester, N-phenylglycine hexyl ester, N-phenylglycine pentyl ester, N -Examples include octyl ester of phenylglycine.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2). , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound, diallyl iodonium compound, etc. Of these, tribromomethylphenyl sulfone is particularly preferable.

(H) Additive In the present disclosure, the “(H) additive” is a component blended to give a desired function to the photosensitive resin composition, and the above-mentioned (A) component, (B) component, and the above-mentioned component (B). It includes components other than (C) component, (D) component, (E) component, (F) component, (G) component and (I) component.

(H) The additive contains carboxylbenzotriazoles from the viewpoint of preventing blushing of the substrate. It contains carboxylbenzotriazoles in an amount of 0.01 to 5% by mass based on the total amount of the components (A) to (I). The reason why the blending amount is 0.01% by mass or more is that the photosensitive resin laminate is laminated on a substrate such as a copper-clad laminate to prevent blushing of the substrate when developed after a lapse of time. It is necessary, and the blending amount is preferably 0.03% by mass or more, and more preferably 0.05% by mass or more. On the other hand, it is necessary to make this blending amount 5% by mass or less from the viewpoint of obtaining high resolution, and it is preferable to make this blending amount 3% by mass or less, and it is preferable to make it 1% by mass or less. More preferred.

Examples of the carboxylbenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and optionally substituted aminomethyl groups1. -[N, N-bis (2-ethylhexyl) aminomethyl] -5-carboxybenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4-carboxybenzotriazole, 1- [N, N-bis (isopropyl) aminomethyl] -5-carboxybenzotriazole, 1- [N-hydro-N-3- (2-ethylhexyloxy) -1-propylaminomethyl] -5-carboxybenzoriazole, 1- [N, N-bis (1-octyl) aminomethyl] -5-carboxybenzotriazole, 1- [N, N-bis (2-hydrooxypropyl) aminomethyl] -5-carboxybenzotriazole, 1- [N , N-bis (1-butyl) aminomethyl] -5-carboxylbenzotriazole and the like. Among these, 1- [N, N-bis (1-butyl) aminomethyl] -5-carboxybenzotriazole is preferable from the viewpoint of blush prevention performance. As for the substitution position of the carboxyl group, the 5-position and the 6-position may be mixed in the synthesis process, and any of them is preferable. For example, 0.5: 1.5 to 1.5: of the 5-position substituted and the 6-position substituted. Mixtures of 0.5 (mass ratio), especially 1: 1 (mass ratio), can be used. It may be simply described as "1-N-dibutylaminomethylcarboxybenzotriazole" to refer to a mixture of 5- and 6-position substituents. As the carboxylbenzotriazole, for example, the compound described in JP-A-2008-175957 can also be used. In addition, 2-mercaptobenzoimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiazylazole, 3-amino-5-mercapto-1, 2,4-Triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3-diazol-2-yl, 5-amino-1H-tetrazole and the like can also be used. ..

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

Coloring agents include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue. 20, Diamond Green (for example, Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis (4-methylphenylamino) -9,10-anthraquinone (for example, manufactured by Orient Chemical Industry Co., Ltd.), OPLAS GREEN 533), 1,4-bis (butylamino) anthraquinone (for example, manufactured by Orient Chemical Industry Co., Ltd., OIL BLUE 2N), 1,4-bis (isopropylamino) -9,10-anthraquinone (for example, Orient Chemical Industry Co., Ltd.) Manufactured by OIL BLUE 630) and the like.

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

As the colorant, for example, a leuco dye or a fluorine dye may be contained. By containing these, the exposed portion of the photosensitive resin composition layer develops color, which is preferable in terms of visibility. Further, when an inspection machine or the like reads an alignment marker for exposure, the exposed portion and the unexposed portion The larger the contrast, the easier it is to recognize, which is advantageous.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. In particular, from the viewpoint of improving the 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 (I). It is preferable to set this content to 0.1% by mass or more from the viewpoint of improving the contrast between the exposed portion and the unexposed portion, and it is more preferable to set this content to 0.2% by mass or more. It is particularly preferable to make it 4% by mass or more. On the other hand, it is preferable to make this content 10% by mass or less from the viewpoint of maintaining storage stability, more preferably 2% by mass or less, and particularly preferably 1% by mass or less. preferable.

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

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis. (4-Methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosoamine and the like can be mentioned. A nitrosophenylhydroxylamine 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, and bis (N-2-ethylhexyl) aminomethylene-1,2. , 3-Benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like. ..

Examples of the epoxy compound of bisphenol A include a compound obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal.

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

Examples of the plasticizer include phthalic acid esters such as diethylphthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, and tri-n-acetyl citrate. Examples thereof include propyl, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like. In addition, Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (all manufactured by Asahi Denka Co., Ltd.), Nieuport BP-23P, Nieuport BP-3P, Nieuport BP-5P, New Pole BPE-20T, Nieuport BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Kasei Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples thereof include compounds having a bisphenol skeleton such as 400, Nieuport DA-700 (manufactured by Nieuport Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nieuport Embroidery Co., Ltd.).

The content of the plasticizer with respect to the total amount of the components (A) to (I) is preferably 1 to 50% by mass, more preferably 1 to 30% by mass. It is preferable to make the content 1% by mass or more from the viewpoint of suppressing a delay in development time and impart flexibility to the cured film, while making the content 50% by mass or less is preferable. It is preferable from the viewpoint 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 containing the photosensitive resin composition provided on the support film.
Another embodiment provides a photosensitive resin laminate in which a photosensitive resin composition layer composed 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.

As the support film, a transparent film that transmits light emitted from an exposure light source is preferable. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, and a polymethylmethacrylate copolymer film. Examples thereof include a polystyrene film, a polyvinylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched ones can be used as needed, and those having a haze of 5 or less are preferable. The thinner the film, the more advantageous it is to improve the image forming property and the economic efficiency. However, in order to maintain the strength of the photosensitive resin laminate, a film having a thickness of 10 to 30 μm is preferably used.

An important property of the protective layer used in the photosensitive resin laminate is that the protective layer has a sufficiently smaller adhesion to the photosensitive resin composition layer than the support film and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as a protective layer. Further, for example, a film having excellent peelability shown in JP-A-59-202457 can also be used. The film thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

When polyethylene is used as the protective layer, there is a gel called fisheye on the surface of the polyethylene film, which may be transferred to the photosensitive resin composition layer. When the fish eye is transferred to the photosensitive resin composition layer, air may be entrained during laminating to form a void, which leads to a defect in the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably stretched polypropylene. As a specific example, Alfan E-200A manufactured by Oji Paper Co., Ltd. can be mentioned.

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 better the resolution, and the thicker the film strength. improves.

<Manufacturing method of photosensitive resin laminate>
A method for manufacturing a photosensitive resin laminate will be described.
The method for producing the photosensitive resin laminate according to the present embodiment is a compounding solution manufacturing step for producing the above-mentioned photosensitive resin composition formulation, and the photosensitive resin composition formulation is applied on a support film and dried to be photosensitive. It includes a coating / drying step of forming a sex resin composition layer to produce the photosensitive resin laminate.

As a method for producing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin composition layer, and if necessary, a protective layer, a known method can be adopted. For example, the photosensitive resin composition used for the photosensitive resin composition layer is mixed with a solvent for dissolving them to obtain a uniform solution (photosensitive resin composition preparation solution).

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

Then, this photosensitive resin composition preparation solution is first applied onto the support film using a bar coater or a roll coater, and then dried to form a photosensitive resin composition layer composed of the photosensitive resin composition on the support film. Laminate. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin composition layer.

<Resist pattern formation method>
Another aspect provides a method for forming a resist pattern, which comprises a step of laminating the above-mentioned photosensitive resin laminate on a substrate, exposing it, and developing it. Hereinafter, an example of a method for forming a resist pattern using the photosensitive resin laminate of the present embodiment will be described. Registration patterns include 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, and organic EL displays. Examples thereof include a resist pattern formed in wiring, PDP (plasma display panel) electrodes, and the like.

The resist pattern can be formed through the following steps.
The resist pattern forming method of the present embodiment includes a step of laminating the photosensitive resin laminate on the substrate, a step of exposing the photosensitive resin composition layer, and a step of developing the exposed photosensitive resin composition layer. ,including.
(1) Laminating Step While peeling off the protective layer of the photosensitive resin composition layer, the photosensitive resin laminate is brought into close contact with a substrate such as a copper-clad laminate or a flexible substrate using a hot roll laminator. The laminating conditions may be appropriately set under conventionally known conditions.

(2) Exposure step A mask film having a desired pattern (for example, a wiring pattern) is brought into close contact with 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 formed. It is exposed by direct drawing. It is preferable that the exposure is performed by directly drawing the drawing pattern. As the exposure wavelength, i-line, h-line, g-line, a mixture thereof and the like can be appropriately used, but the photosensitive resin composition of the present embodiment is highly exposed to i-line or h-line, particularly h-line. It is advantageous in that sensitivity and high resolution can be realized. Further, as a result, the photosensitive resin composition of the present embodiment is particularly useful for direct drawing. The exposure conditions may be appropriately set under conventionally known conditions.

(3) Development Step After exposure, the support film on the photosensitive resin composition layer is peeled off, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to form a resist pattern on the substrate. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin composition layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2 to 2% by mass and 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 of about 100 to 300 ° C. can be further performed. By carrying out this heating step, it is possible to further improve the chemical resistance. A hot air, infrared ray, or far infrared ray type heating furnace can be used for heating.

The method for forming the metal wiring of the present embodiment includes a step of forming a resist pattern by the above method, a step of forming a metal wiring (conductor pattern) using the resist pattern, and a step of peeling off the resist pattern. ..
Another aspect is a method for manufacturing a circuit board, which comprises a step of laminating, exposing, developing, and plating the above-mentioned photosensitive resin laminate on a substrate, and using the above-mentioned photosensitive resin laminate as a substrate. Provided is a method for manufacturing a circuit board, which comprises a step of laminating, exposing, developing, and etching. The circuit board can be manufactured by further etching or plating the base material on which the resist pattern is formed by the procedure as described above for the resist pattern forming method. In particular, in manufacturing a circuit board, it is advantageous from the viewpoint of productivity to perform exposure by directly drawing a drawing pattern because it is not necessary to manufacture a mask. Etching and plating can be carried out as follows.

(4) Etching step or plating step The surface of the base material 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. As the etching and plating methods, conventionally known methods can be appropriately used.

(5) Peeling step After that, the resist pattern is peeled from the substrate with an aqueous solution having a stronger alkalinity than the developing solution. The alkaline aqueous solution for peeling is also not particularly limited, but an aqueous solution of NaOH or KOH having 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 water-soluble solvent can be added to the stripping solution.
In particular, in the present embodiment, by using the diphenylpyrazolin derivative as the (G) photosensitizer, it has particularly excellent post-plating peelability.
A circuit board can be manufactured by the above procedure.

Further, in the method for manufacturing a semiconductor package of the present embodiment, a step of forming a resist pattern on a substrate for a semiconductor package as a base material by the resist pattern forming method described above, and a substrate for a semiconductor package on which the resist pattern is formed are used. Provided is a method for manufacturing a semiconductor package, which comprises a step of etching or plating. As the substrate for the semiconductor package and the configuration of the semiconductor package, any conventionally known substrate can be appropriately adopted. Further, the formation of the resist pattern and the etching or plating can be carried out by the procedures as described above.

The photosensitive resin laminate of the present embodiment is a circuit board (printed wiring board), a flexible board, a lead frame board, a COF (chip-on-film) board, a semiconductor package board, a transparent electrode for a liquid crystal panel, and a liquid crystal panel. A photosensitive resin laminate suitable for manufacturing conductor patterns such as TFT wiring, wiring for organic EL displays, and electrodes for PDPs (plasma display panels).

As described above, according to the present embodiment, it is possible to provide a photosensitive resin laminate capable of achieving both solubility in a developing solution, that is, developability, and adhesion to a substrate, particularly a copper substrate, and a method for producing the same. ..

Unless otherwise specified, the various parameters described above are measured according to the measurement method in the examples described later.

The measurement of the physical property values of the polymer and the monomer, and the method of preparing the evaluation samples of Examples and Comparative Examples will be described. Next, the evaluation method for the obtained sample and the evaluation result thereof are shown.

(1) Measurement or calculation of physical property values <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 is determined by gel permeation chromatography (GPC) manufactured by Nippon Kogaku Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex® manufactured by Showa Denko KK) (registered trademark). KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving layer solvent: tetrahydrofuran, polystyrene standard sample (using calibration curve by Showa Denko Corporation's Chromatography STANDARD SM-105) Obtained as polystyrene conversion.
Further, the degree of dispersion 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>
As used herein, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in the molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.

(2) Method for preparing evaluation samples The evaluation samples in Examples 1 to 19 and Comparative Examples 1 to 4 were prepared as follows.

<Manufacturing of photosensitive resin laminate>
The components shown in Table 1 or 2 below (however, the numbers of each component indicate the blending amount (parts by mass) as a solid content) and the solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation solution. .. The names of the components represented by abbreviations in Tables 1 and 2 are shown in Tables 3 to 6 below.
A polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) having a thickness of 16 μm was used as a support film, and this formulation was uniformly applied to the surface of the film using a bar coater, and 3 in a dryer at 95 ° C. It was dried for a minute 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 (manufactured by Tamapoli Co., Ltd., GF-818) was attached as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated, and the support film and the photosensitive film were photosensitive. A photosensitive resin laminate in which a resin composition layer and a protective layer were laminated in this order was obtained.

<Board surface preparation>
Abrasive material (Sacraund R (registered trademark # 220) manufactured by Nippon Carlit Co., Ltd.) is sprayed on a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil at a spray pressure of 0.2 MPa to surface the surface. Polished.

<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated on a copper-clad laminate preheated to 60 ° C. with 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 laminating speed was 1.5 m / min.

<Exposure>
The photosensitive resin composition prepared using the compositions 1 to 7 has an illuminance of 85 mW / cm by a direct drawing exposure machine (manufactured by Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-purple diode, main wavelength 405 ± 5 nm). The exposure was performed at ² , 60 mJ / cm ² .
The photosensitive resin compositions prepared using the compositions 8 to 15 were exposed to an exposure amount of 160 mJ / cm ² using a parallel light exposure machine (HMW-801 manufactured by ORC Manufacturing Co., Ltd.).

<Development>
After peeling off the polyethylene terephthalate film of the exposed evaluation substrate, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed for a predetermined time using an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film) to obtain a photosensitive resin. The unexposed portion of the composition layer was dissolved and removed. At this time, development was performed in twice the minimum development time to prepare a cured resist portion. The minimum development time is the shortest time required for the photosensitive resin composition layer in the unexposed portion to be completely dissolved.

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

(2) Pretreatment The obtained photosensitive resin composition layer is directly drawn from the polyethylene terephthalate film side by a drawing exposure machine (manufactured by Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-purple diode, main wavelength 405 ± 5 nm). The exposure was performed 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, 1.000 g of the exposed photosensitive resin composition layer was weighed, and the photosensitive resin was incinerated using an electric furnace.

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

<Evaluation method of developability>
After laminating the photosensitive resin composition on the substrate, the minimum development time after 15 minutes had passed was measured, and evaluation was performed according to the following criteria, and Criterion D was rejected.
A (significantly good): minimum development time less than 17 seconds B (good): minimum development time 17 seconds or more and less than 19 seconds C (allowable): minimum development time 19 seconds or more and less than 21 seconds D (defective): minimum development Time is 21 seconds or more

<Evaluation method of adhesion>
After 15 minutes have passed after laminating the photosensitive resin composition on the substrate, it was developed using the above-mentioned development conditions, the pattern was observed with an optical microscope, and the evaluation was performed according to the following criteria, and the criteria D was rejected. ..
A (significantly good): minimum contact line width of independent pattern is less than 9 μm B (good): minimum contact line width of independent pattern is 9 μm or more and less than 10 μm C (allowable): minimum contact line width of independent pattern is 10 μm or more and less than 11 μm D (defective): The minimum contact line width of the 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 contents can be read from the results in Table 7.
First, in Comparative Example 1 in which the iron atom content was smaller than 0.01 ppm, the adhesion to the substrate was poor, while in Comparative Example 2 in which the iron atom content was larger than 10 ppm, the developability was poor.

On the other hand, in Examples 1 to 13 in which the iron atom content is 0.01 ppm or more and 10 ppm or less, it can be seen that good results are 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, with respect to the calcium atom or the aluminum atom, the adhesion to the substrate is poor in Comparative Example 1 smaller than 0.005 ppm, while the content of the calcium atom or the aluminum atom is larger than 5 ppm. In Comparative Example 2, the developability was poor.

On the other hand, in Examples 1 to 13 in which the content of calcium atom or aluminum atom is 0.005 ppm or more and 5 ppm or less, good results are obtained in terms of both developability and adhesion to the substrate. I understand.
Among them, particularly good results were obtained in Examples 7 and 8 in which the content of calcium atom or aluminum atom was 0.03 ppm or more and 1.0 ppm or less.

<Evaluation method for dense wiring resolution>
The photosensitive resin compositions of Examples 14 to 19 and Comparative Examples 3 to 4 were evaluated for their dense wiring resolution.
After 15 minutes have passed after laminating the photosensitive resin composition on the substrate, it was developed using the above-mentioned development conditions, the pattern was observed with an optical microscope, and the viewpoint was divided into the residue between wirings and the contact between adjacent wirings. The evaluation was made according to the following criteria, and Criterion D was rejected.
A (significantly good): 1: 1 L / S pattern has a minimum resolution of less than 13 μm B (good): 1: 1 L / S pattern has a minimum resolution of 14 μm or more and less than 15 μm C (allowable): 1: 1 The minimum resolution of the L / S pattern is 16 μm or more and less than 17 μm D (defective): 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 to 4 are shown in Tables 10 to 11 below.

From the results of Tables 10 and 11, regarding the sodium atom, the residue between the wirings was poor in Comparative Example 3 having a sodium atom smaller than 1 ppm, while the contact between the adjacent wirings was poor in Comparative Example 4 having a sodium atom content of more than 50 ppm. ..

On the other hand, in Examples 14 to 19 in which the sodium atom content is 1 ppm or more and 50 ppm or less, it can be seen that good results are obtained in both the residue between the wirings and the contact between the adjacent wirings.

Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

The photosensitive resin composition laminate of the present invention has a circuit board (printed wiring board), a flexible substrate, a lead frame substrate, a COF (chip-on-film) substrate, and a semiconductor package substrate because of its high sensitivity and high resolution. , A transparent electrode for a liquid crystal panel, a TFT wiring for a liquid crystal panel, a wiring for an organic EL display, an electrode for a PDP (plasma display panel), and the like, which can be suitably used for manufacturing a conductor pattern.

Claims (41)

A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (D) Iron Atom;
Contains,
A photosensitive resin laminate characterized in that 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. body. 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. body. 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. body. 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. body. 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. body. 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. body. 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. body. 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. body. 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. body. 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. body. 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. body. 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 containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (E) Calcium Atom;
Contains,
A photosensitive resin laminate characterized in that 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 containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (F) Aluminum Atom;
Contains,
A photosensitive resin laminate characterized in that 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 containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization initiator;
(D) At least one of iron atom, calcium atom and aluminum atom;
Contains,
The photosensitive resin is characterized in that 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. Laminated body. 33. The photosensitive resin composition layer 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. Sex resin laminate. 33. The photosensitive resin composition layer 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. Sex resin laminate. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (I) Sodium Atom;
Contains,
A photosensitive resin laminate characterized in that 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 containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated double bond;
(C) Photopolymerization Initiator; and (J) Metal Atom;
Contains,
A photosensitive resin laminate characterized in that 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, which contains at least one of aluminum, calcium, iron, potassium, magnesium, and zinc as the metal atom.