JP7308014B2 - Photosensitive resin composition and photosensitive resin laminate - Google Patents

Description

The present invention relates to a photosensitive resin composition and the like.

2. Description of the Related Art Printed wiring boards and the like are used in electronic devices such as personal computers and mobile phones to mount parts, semiconductors, and the like. Conventionally, as a resist for manufacturing printed wiring boards, etc., a photosensitive resin laminate obtained by laminating a photosensitive resin layer on a support film and further laminating a protective film on the photosensitive resin layer as necessary, A so-called dry film photoresist (hereinafter also referred to as DF) is used. At present, the photosensitive resin layer is generally of an alkali development type using a weak alkaline aqueous solution as a developer. In order to manufacture a printed wiring board or the like using DF, for example, the following steps are taken. If the DF has a protective film, first remove the protective film. Thereafter, the DF is laminated on a permanent circuit fabrication substrate such as a copper-clad laminate or a flexible substrate using a laminator or the like, and exposed through a wiring pattern mask film or the like. Next, if necessary, the support film is peeled off, the uncured portion (for example, the unexposed portion in the negative type) of the photosensitive resin layer is dissolved or dispersed with a developer, and a cured resist pattern (hereinafter simply referred to as (also called a resist pattern) is formed.
The process of forming a circuit after forming a resist pattern is roughly divided into two methods. The first method is to remove the substrate surface not covered by the resist pattern (for example, the copper surface of a copper-clad laminate) by etching, and then remove the resist pattern portion with an aqueous alkaline solution stronger than the developer (etching method). is. In the second method, after the substrate surface is plated with copper, solder, nickel, tin, etc., the resist pattern portion is removed in the same manner as in the first method, and the exposed substrate surface (for example, It is a method (plating method) of etching the copper surface of the copper-clad laminate. Cupric chloride, ferric chloride, cuprammonium complex solution, etc. are used for etching. In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and density of printed wiring boards are progressing. There is a demand for a high-performance DF that provides performance and the like. As a material for achieving such high resolution, Patent Document 1 describes a photosensitive resin composition in which resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerization initiator. .

JP 2010-249884 A

However, in recent years, along with the reduction in size and weight of electronic devices such as mobile phones and tablets, there is an increasing demand for finer wiring spacing on printed wiring boards. In order to meet such demands for miniaturization, demands for high adhesion to DF, high resolution, good line width reproducibility, etc. are becoming more and more severe. Furthermore, in order to achieve high resolution, the number of cases where the development conditions are made severe for the purpose of eliminating resist residue on the substrate surface is increasing, making it extremely difficult to achieve high adhesion of DF. From this point of view, the technique described in Patent Document 1 still has room for improvement.
Therefore, the present invention provides a photosensitive resin composition that exhibits excellent adhesion and resolution even under severe development conditions such as overdevelopment, overwashing, and a high temperature developer, a method for forming a resist pattern using the composition, and a wiring board. An object is to provide a manufacturing method.

The present inventor has conducted extensive research and repeated experiments to solve the above problems. As a result, the inventors have found that the following technical means can solve the problem.
That is, the present invention is as follows.
[1]
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond;
(C) a photoinitiator; and (D) an inhibitor;
A photosensitive resin composition comprising
The (A) alkali-soluble polymer has an I/O value of 0.200 to 0.560. % by mass or more, and the (D) inhibitor contains a phenol derivative,
Substances other than the (A) alkali-soluble polymer and the (B) ethylenically unsaturated bond-containing compound contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
A photosensitive resin composition, wherein the ratio of the mass of components other than (A) and (B) to the mass of the compound (B) having an ethylenically unsaturated bond is 0.190 or less.
[2] The photosensitive resin composition according to [1], wherein the ratio of the mass of the alkali-soluble polymer (A-1) to the mass of the compound having an ethylenically unsaturated bond (B) is 0.500 or more. .
[3] The (A-1) alkali-soluble polymer contains structural units derived from (meth)acrylic acid, based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition according to [1] or [2], containing 21% by mass to 29% by mass.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128° C. or less.
[5] The ratio of the mass of the alkali-soluble polymer (A) to the mass of the compound having an ethylenically unsaturated bond (B) is 5.0 or less, according to any one of [1] to [4]. A photosensitive resin composition.
[6]
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator;
(D) an inhibitor;
A photosensitive resin composition comprising
The (A) alkali-soluble polymer has an I/O value of 0.200 to 0.560. including mass % or more,
The (A-1) alkali-soluble polymer contains 21% by mass of structural units derived from (meth)acrylic acid, based on the total weight of all monomer components constituting the (A-1) alkali-soluble polymer. Contains ~29% by mass,
The (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128° C. or less, and the (D) inhibitor contains a phenol derivative,
Substances other than the (A) alkali-soluble polymer and the (B) ethylenically unsaturated bond-containing compound contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
The ratio of the mass of the components other than (A) and (B) to the mass of the (B) compound having an ethylenically unsaturated bond is 0.190 or less,
The ratio of the mass of the (A-1) alkali-soluble polymer to the mass of the (B) compound having an ethylenically unsaturated bond is 0.500 or more, and the (B) compound having an ethylenically unsaturated bond The ratio of the mass of the alkali-soluble polymer (A) to the mass of the photosensitive resin composition is 5.0 or less.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the (C) photopolymerization initiator contains hexaarylbiimidazole.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (C) photopolymerization initiator contains a pyrazoline compound.
[9] The photosensitive resin composition according to any one of [1] to [8], wherein the (C) photopolymerization initiator contains an anthracene compound.
[10] The photosensitive resin composition according to any one of [1] to [9], wherein the (C) photopolymerization initiator contains aromatic ketones.
[11] Any one of [1] to [10], wherein the (C) photopolymerization initiator contains at least one selected from acridines, N-arylamino acids or ester compounds thereof, halogen compounds, and coumarin compounds. The photosensitive resin composition according to .
[12] The photosensitive resin composition according to any one of [1] to [11], further comprising a leuco dye.
[13] The photosensitive resin composition according to [12], wherein the content of the leuco dye is 0.05% by mass to 10% by mass with respect to the total solid mass in the photosensitive resin composition.
[14] The content of the (A) alkali-soluble polymer is 30% by mass or more relative to the total solid mass of the photosensitive resin composition, according to any one of [1] to [13]. A photosensitive resin composition.
[15] The photosensitive resin composition according to [14], wherein the content of (A) the alkali-soluble polymer is 40% by mass or more relative to the total solid mass in the photosensitive resin composition.
[16] The photosensitive resin composition according to any one of [1] to [15], wherein (D) the inhibitor contains a hindered phenol.
[17] The photosensitive resin composition according to any one of [1] to [16], wherein (D) the inhibitor contains p-methoxyphenol.
[18] The photosensitive resin composition according to any one of [1] to [17], wherein the inhibitor (D) contains 2,6-di-tert-butyl-p-cresol.
[19] Any one of [1] to [18], wherein the (D) inhibitor contains triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate The photosensitive resin composition described.
[20] The photosensitive resin composition according to any one of [1] to [19], wherein the inhibitor (D) contains 4,4'-butylidenebis(3-methyl-6-tert-butylphenol).
[21] The photosensitive resin composition according to any one of [1] to [20], wherein the inhibitor (D) contains catechol.
[22] The photosensitive resin composition according to any one of [1] to [21], wherein the inhibitor (D) contains tert-butylcatechol.
[23] The photosensitive resin composition according to any one of [1] to [22], wherein the inhibitor (D) contains 2,5-di-tert-butylhydroquinone.
[24] The photosensitive resin composition according to any one of [1] to [23], wherein the inhibitor (D) contains biphenol.
[25] The photosensitive resin composition according to any one of [1] to [24], wherein the inhibitor (D) has two or more phenolic nuclei.
[26] The (A-1) alkali-soluble polymer is a (meth)acrylic acid alkyl ester (alkyl The photosensitive resin composition according to any one of [1] to [25], containing 1% by mass to 20% by mass of structural units derived from (4 or more carbon atoms).
[27] The (B) compound having an ethylenically unsaturated bond includes a (meth)acrylate compound having 6 or more ethylenically unsaturated bonds, and the photosensitive according to any one of [1] to [26]. Resin composition.
[28] A photosensitive resin laminate comprising a support layer and a photosensitive resin layer composed of the photosensitive resin composition according to any one of [1] to [27] laminated on the support layer.
[29]
The following steps:
Lamination step of laminating the photosensitive resin laminate according to [28] on a substrate;
an exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate; and a developing step of developing and removing an unexposed portion of the photosensitive resin layer;
A method of forming a resist pattern, comprising:
[30]
The following steps:
Lamination step of laminating the photosensitive resin laminate according to [28] on a substrate;
an exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate;
a developing step of developing the photosensitive resin layer after exposure to obtain a substrate on which a resist pattern is formed;
A conductive pattern forming step of etching or plating the substrate on which the resist pattern is formed; and a stripping step of stripping the resist pattern;
A wiring board manufacturing method comprising:

The present invention provides a photosensitive resin composition and a photosensitive resin laminate that exhibit good adhesion and resolution even under severe development conditions such as overdevelopment, overwashing, and a high temperature developer, and the photosensitive resin composition. It is possible to provide a method for forming a resist pattern and a method for forming a conductor pattern using a flexible resin laminate. As a result, even with the increasing density of wiring, when forming a pattern by etching or plating, the reproducibility of the mask line width is good, and problems such as short circuits, chipping, disconnection, and plating defects are eliminated. It is possible to form a high-definition circuit that does not exist.

Exemplary forms for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist of the present invention. In addition, unless otherwise specified, the various measured values in this specification are according to the method described in the [Examples] section of the present disclosure or the equivalent method understood by those skilled in the art. measured by

[Photosensitive resin composition]
In the present embodiment, the photosensitive composition includes (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; In the resin composition, the alkali-soluble polymer (A) has an I/O value of 0.200 to 0.560. It contains 5% by mass or more as a standard, and (D) the inhibitor contains a phenol derivative, and the substance other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content ( When it is a component other than A) and (B), the ratio of the mass of the component other than (A) and (B) to the mass of the compound having an ethylenically unsaturated bond (B) ([(A) and ( The mass of components other than B)/[the mass of the compound having an ethylenically unsaturated bond (B)]) is 0.190 or less. Components other than (A) and (B) refer to substances obtained by removing (A) an alkali-soluble polymer and (B) a compound having an ethylenically unsaturated bond from the solid content.
Each component will be described in order below.

<(A) Alkali-soluble polymer>
In the present disclosure, the (A) alkali-soluble polymer having an I/O value of 0.200 to 0.560 is contained at 5% by mass or more of the total solid content (A-1).
The I/O value, also called (inorganic value)/(organic value), is a value that treats the polarity of various organic compounds in an organic concept, and is one of the functional group contribution methods for setting parameters for each functional group. is one. As the I / O value, in detail, non-patent literature (organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, 1-16 (1954); Area, Vol. 11, No. 10, paragraphs 719-725 (1957); Fragrance Journal, No. 34, paragraphs 97-111 (1979); Fragrance Journal, No. 50, paragraphs 79-82 (1981). ));
The concept of the I/O value is based on the direct relationship between organic groups that represent covalent bonding and inorganic groups that represent ionic bonding, and all organic compounds are labeled as the organic axis and the inorganic axis. Each point on the coordinates is positioned and shown. The closer the I/O value is to 0, the more nonpolar (hydrophobic and organic) the organic compound is, and the larger the I/O value is, the more polar (hydrophilic and inorganic) the organic compound is. show.

(A-1) The I/O value of the alkali-soluble polymer is 0.200 to 0.560. When the I/O value is 0.200 to 0.560, adhesion and resolution are excellent even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. From the same point of view, the I/O value is preferably 0.550 or less, more preferably 0.520 or less, more preferably 0.510 or less, still more preferably 0.500 or less, and more preferably 0.490 or less. , 0.480 or less is particularly preferred, and 0.470 or less is most preferred. From the same point of view, the I/O value is preferably 0.250 or more, preferably 0.300 or more, preferably 0.350 or more, more preferably 0.400 or more, more preferably 0.410 or more, and 0.410 or more. 420 or more is more preferable, 0.430 or more is more preferable, 0.440 or more is particularly preferable, and 0.450 or more is most preferable. By lowering the I/O value and making it hydrophobic, high adhesion and high resolution can be achieved even under severe development conditions. , it is thought that the I/O value needs to be higher than a certain level because the development conditions become more severe as a result.

From the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature, (A-1) contains 5% by mass or more of the total solid content of an alkali-soluble polymer. , preferably 8% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, more preferably 25% by mass or more, particularly preferably 30% by mass % or more, particularly preferably 35 mass % or more, most preferably 40 mass % or more.

(A-1) The glass transition temperature Tg of the alkali-soluble polymer is preferably 128° C. or lower. Tg is calculated by the method described in the examples below. By using (A-1) an alkali-soluble polymer having a Tg of 128°C or less in the photosensitive resin composition, adhesion can be achieved even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. Excellent image quality and resolution. From this point of view, the Tg of the alkali-soluble polymer (A-1) is preferably 125° C. or lower, more preferably 120° C. or lower, even more preferably 115° C. or lower, and 110° C. or lower. is more preferable, 105° C. or less is particularly preferable, and 100° C. or less is most preferable. Further, it is preferable that the Tg of the (A-1) alkali-soluble polymer is 30° C. or higher from the viewpoint of improving the edge fuse resistance. From this point of view, the Tg of the (A-1) alkali-soluble polymer is more preferably 40° C. or higher, still more preferably 50° C. or higher, and particularly preferably 60° C. or higher.

A photosensitive resin composition that exhibits excellent adhesion and resolution in normal development is not necessarily a photosensitive resin composition that exhibits excellent adhesion and resolution even under severe development conditions. In the present embodiment, from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature, (A-1) an aromatic carbonized polymer is used as the alkali-soluble polymer. It is preferable that the structural unit of the monomer component having a hydrogen group is contained in an amount of 52% by mass or more. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. is a monomer having a substituted or unsubstituted benzyl group (e.g., benzyl (meth)acrylate), styrene derivatives (e.g., styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid , styrene dimers, and styrene trimers), more preferably styrene derivatives, and particularly preferably styrene. (A-1) The content of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer is preferably 52% by mass or more, based on the total mass of all monomer components, and 55% by mass. % or more, more preferably 57 mass % or more, particularly preferably 58 mass % or more, and most preferably 60 mass % or more. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 80% by mass or less. (A-1) The content of the styrene derivative in the alkali-soluble polymer is preferably 52% by mass or more, more preferably 55% by mass or more, based on the total mass of all monomer components. It is more preferably 57% by mass or more, particularly preferably 58% by mass or more, and most preferably 60% by mass or more. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
The (A-1) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group comprises a monomer having an aromatic hydrocarbon group, at least one first monomer described later, and / Or it is preferably obtained by polymerizing at least one of the second monomers described below.

The (A) alkali-soluble polymer that does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and the first monomer More preferably, it is obtained by copolymerizing at least one of the monomers and at least one of the second monomers described below.
A 1st monomer is a monomer which has a carboxyl group in a molecule|numerator. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature.
In the present specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, and "(meth)acrylate ” means “acrylate” or “methacrylate”.

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature, and is preferably 15% by mass or more. is more preferably 18% by mass or more, more preferably 21% by mass or more, particularly preferably 23% by mass or more, and particularly preferably 24% by mass or more. The copolymerization ratio of 50% by mass or less is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature, and is preferably 35% by mass or less. is more preferably 30% by mass or less, more preferably 29% by mass or less, particularly preferably 27% by mass or less, and most preferably 26% by mass or less.
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. , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and other (meth)acrylates; vinyl acetate esters of vinyl alcohol such as; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred.

As the second monomer, (A-1) the alkali-soluble polymer contains 1 to 20% by mass of structural units derived from a (meth)acrylic acid alkyl ester (alkyl having 4 or more carbon atoms), It is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. From this point of view, it is more preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 15% by mass or less, and even more preferably 10% by mass or less. It is particularly preferably 8% by mass or less, most preferably 6% by mass or less.

(A-1) The acid equivalent of the alkali-soluble polymer is not particularly limited as long as the above I/O value and the copolymerization ratio of the first monomer are within the above numerical ranges, and are appropriately selected according to the purpose. Although it can be selected, it is preferably 100-600, more preferably 250-450, for example. The acid equivalent refers to the mass (unit: gram) of a polymer having one equivalent of carboxyl groups in its molecule. The acid equivalent is preferably 100 or more, more preferably 250 or more, from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. . From the same point of view, the acid equivalent is preferably 600 or less, more preferably 450 or less. In the present disclosure, the acid equivalent is a value measured by potentiometric titration using a potentiometric titrator with a 0.1 mol/L NaOH aqueous solution.

(A-1) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. ,000 or less, more preferably 60,000 or less, more preferably 50,000 or less, particularly preferably 40,000 or less, and 30,000 or less. is most preferred. From the same point of view, the weight average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and particularly preferably 17,000 or more. preferable. (A-1) The dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and 1.0 to 4.0. is more preferable, and 1.0 to 3.0 is particularly preferable.
(A) The alkali-soluble polymer can be used singly or in combination of two or more.

(A) Alkali-soluble polymer is synthesized by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, adding benzoyl peroxide, azoisobutyronitrile, or the like. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator and heating and stirring. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
(A) The ratio of the alkali-soluble polymer to the total solid mass of the photosensitive resin composition may be 10% by mass or more, may be 20% by mass or more, or may be 25% by mass or more. may be 30% by mass or more, may be 35% by mass or more, may be 40% by mass or more, may be 45% by mass or more, or may be 50% by mass or more; may be 55% by mass or more, or 60% by mass or more. Further, it may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less. good.
It is preferable from the viewpoint of controlling the developing time that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition is 10% by mass or more.

<(B) a compound having an ethylenically unsaturated double bond>
(B) The compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth)acryloyl group in the molecule from the viewpoint of curability and (A) compatibility with the alkali-soluble polymer. (B) The number of ethylenically unsaturated bonds in the compound may be 1 or more.
As the (B) compound having one ethylenically unsaturated bond, for example, a compound obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide, or a (meth)acrylic acid to one end of a polyalkylene oxide Compounds in which an acid is added and the other terminal is alkyl-etherified or allyl-etherified, phthalic acid-based compounds, and the like can be mentioned, and they are preferable from the viewpoint of releasability and cured film flexibility. In addition to the above viewpoints, it is preferable that the (B) compound having one ethylenically unsaturated bond is a methacrylate compound from the viewpoints of sensitivity, resolution, and adhesion.
Examples of such compounds include
phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group;
4-Normal nonylphenoxyheptaethylene glycol, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol with an average of 2 mol of propylene oxide and polyethylene glycol with an average of 7 mol of ethylene oxide added to nonylphenol; dipropylene glycol (meth)acrylates,
4-Normal nonylphenoxypentaethylene glycol, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol with an average of 1 mol of propylene oxide and polyethylene glycol with an average of 5 mol of ethylene oxide added to nonylphenol, monopropylene glycol (Meth) acrylate, and 4-Normal nonylphenoxyoctaethylene glycol (meth) acrylate (for example, manufactured by Toagosei Co., Ltd., M- 114) and the like.
In addition, when a phthalic acid compound such as γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is contained, in addition to the above aspects, sensitivity, resolution, and adhesion are particularly improved. preferable.

Examples of compounds having two ethylenically unsaturated bonds in the molecule include compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, or alkylene in which an ethylene oxide chain and a propylene oxide chain are randomly or block-bonded. Examples include compounds having (meth)acryloyl groups at both ends of the oxide chain.
Examples of such compounds include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, Polyethylene glycol (meth)acrylates such as meth)acrylates, nonaethylene glycol di(meth)acrylates, decaethylene glycol di(meth)acrylates, and compounds having (meth)acryloyl groups at both ends of 12 moles of ethylene oxide chain In addition to
Polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate 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, an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide is added. Glycol Dimethacrylate, Polypropylene Glycol Added with an Average of 18 mol of Propylene Oxide, with an Average of 15 mol of ethylene oxide further added to both ends of the glycol dimethacrylate, FA-023M, FA-024M, FA-027M (Product (manufactured by Hitachi Chemical Co., Ltd.). These are preferable from the viewpoint of flexibility, resolution, adhesion and the like.
As another example of a compound having two ethylenically unsaturated bonds in the molecule, a compound having (meth)acryloyl groups at both ends by modifying bisphenol A with alkylene oxide improves resolution and adhesion. is preferable from the viewpoint of

｛式中、Ｒ１及びＲ２は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ１及びｎ３は各々独立に１～３９の整数であり、かつｎ１＋ｎ３は２～４０の整数であり、ｎ２及びｎ４は各々独立に０～２９の整数であり、かつｎ２＋ｎ４は０～３０の整数であり、－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－の繰り返し単位の配列は、ランダムであってもブロックであってもよい。そして、ブロックの場合、－（Ａ－Ｏ）－と－（Ｂ－Ｏ）－とのいずれがビスフェニル基側でもよい。｝
で表される化合物を使用することができる。 Specifically, the following general formula (I):

{Wherein, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n1 and n3 each independently represent from 1 to 39 an integer, and n1+n3 is an integer of 2 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30, -(AO)- and - The arrangement of the repeating units of (BO)- may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group. }
A compound represented by can be used.

For example, dimethacrylate of polyethylene glycol obtained by adding an average of 5 mol each of ethylene oxide to both ends of bisphenol A, and polyethylene glycol obtained by adding an average of 2 mol each of ethylene oxide to both ends of bisphenol A. Polyethylene glycol dimethacrylate obtained by adding an average of 1 mol each of ethylene oxide to each end of bisphenol A is preferred from the viewpoint of resolution and adhesion.
A compound in which the aromatic ring in the general formula (I) has a heteroatom and/or a substituent may also be used.

Examples of heteroatoms include halogen atoms, and substituents include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and phenacyl groups. , amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group , a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having an alkyl group having 1 to 10 carbon atoms, an acyl group having an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocyclic ring, or these An aryl group substituted with a substituent and the like can be mentioned. These substituents form a condensed ring, or hydrogen atoms in these substituents may be substituted with heteroatoms such as halogen atoms. When the aromatic ring in general formula (I) has multiple substituents, the multiple substituents may be the same or different.

A compound having 3 or more ethylenically unsaturated bonds in the molecule has 3 mol or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and an ethyleneoxy group, a propyleneoxy group, It is obtained by converting an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group into a (meth)acrylate. In this case, examples of compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings. These compounds include tri(meth)acrylates such as ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate (e.g. Trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane are preferable from the viewpoint of flexibility, adhesion, and suppression of bleeding out), etc.; Tetra(meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol tetra(meth)acrylate; penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate; ) acrylates; hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylates;
Pentaerythritol tetra(meth)acrylate is preferred as the tetra(meth)acrylate. The pentaerythritol tetra(meth)acrylate may be a tetra(meth)acrylate in which a total of 1 to 40 mol of alkylene oxide is added to the four terminals of pentaerythritol.
As the hexa(meth)acrylate, hexa(meth)acrylate in which a total of 1 to 40 mol of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 20 mol of ε to the six ends of dipentaerythritol. - Hexa(meth)acrylates to which caprolactone is added are preferred.

The (meth)acrylate compounds described above can be used individually or in combination. The photosensitive resin composition may also contain other compounds as (B) the compound having an ethylenically unsaturated bond. Other compounds include (meth)acrylates having urethane bonds, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyhydric alcohols, and α,β-unsaturated carboxylic acids with glycidyl group-containing compounds. and 1,6-hexanediol di(meth)acrylate and the like.

As the compound having an ethylenically unsaturated bond (B), a (meth)acrylate compound having two or more ethylenically unsaturated bonds is included in the compound having an ethylenically unsaturated bond (B) in an amount of 75% by mass or more. is preferred. Containing 75% by mass or more is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. more preferably 81% by mass or more, more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 93% by mass or more.
As the (B) compound having an ethylenically unsaturated bond, it is preferable that 75% by mass or more of a methacrylate compound is contained in (B) the compound having an ethylenically unsaturated bond. Containing 75% by mass or more is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. more preferably 81% by mass or more, more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 93% by mass or more.

The (B) compound having an ethylenically unsaturated bond contains a (meth)acrylate compound having 3 or more ethylenically unsaturated bonds. It is preferable from the viewpoint of excellent adhesion and resolution even under such developing conditions. From the same point of view, the (meth)acrylate compound having 3 or more ethylenically unsaturated bonds is preferably a (meth)acrylate compound having 3 ethylenically unsaturated bonds, and has 4 ethylenically unsaturated bonds ( A meth)acrylate compound is more preferable, a (meth)acrylate compound having 5 ethylenically unsaturated bonds is more preferable, and a (meth)acrylate compound having 6 or more ethylenically unsaturated bonds is particularly preferable.
From the same viewpoint, the (meth)acrylate compound having 3 or more ethylenically unsaturated bonds is preferably a methacrylate compound having 3 or more ethylenically unsaturated bonds, and a methacrylate having 4 ethylenically unsaturated bonds. A compound is more preferable, a methacrylate compound having 5 ethylenically unsaturated bonds is more preferable, and a methacrylate compound having 6 or more ethylenically unsaturated bonds is particularly preferable.
The content of the (meth)acrylate compound having 3 or more ethylenically unsaturated bonds is, from the same viewpoint, preferably 5% by mass or more in the compound having an ethylenically unsaturated bond (B), and 10 mass. % or more, more preferably 15 mass % or more, more preferably 20 mass % or more, particularly preferably 30 mass % or more, most preferably 40 mass % or more.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid mass of the photosensitive resin composition may be 5% by mass or more, 10% by mass or more, or 20% by mass. % or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass % or more, or 50% by mass or more. Moreover, it may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.
A ratio of 5% by mass or more is preferable from the viewpoint of sensitivity, resolution and adhesion. This ratio is more preferably 20% by mass or more, and even more preferably 30% 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 hardened resist. It is more preferable to make this ratio 50% by mass or less.

<(C) Photoinitiator>
(C) A photopolymerization initiator is a compound that polymerizes a monomer by light. The photosensitive resin composition contains (C) a compound generally known in this technical field as a photopolymerization initiator.
The total content of (C) the photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, and still more preferably 0.1% by mass. % to 7% by weight, particularly preferably 0.1% to 6% by weight. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and the light is sufficiently transmitted to the bottom of the resist, resulting in good high resolution. It is preferably 20% by mass or less from the viewpoint of obtaining.
(C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkylketals, thioxanthones, dialkylaminobenzoates, and oxime esters. , acridines (e.g., 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, and 9-(m-methylphenyl)acridine are preferred in terms of sensitivity, resolution, and adhesion) Further, hexaarylbiimidazoles, pyrazoline compounds, anthracene compounds (e.g., 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9,10-diphenylanthracene improve sensitivity, resolution, and adhesion. in terms of sensitivity), coumarin compounds (for example, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion), N-arylamino acids or their ester compounds (for example, N-phenylglycine is preferred in terms of sensitivity and resolution). preferred from the viewpoint of image quality and adhesion), and halogen compounds (eg, tribromomethylphenylsulfone). These can be used individually by 1 type or in combination of 2 or more types. Other, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzo Ilu-diphenyl-phosphine oxide and triphenylphosphine oxide may also be used.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. be able to. These can be used individually by 1 type or in combination of 2 or more types. Among these, 4,4′-bis(diethylamino)benzophenone is particularly preferable from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass. It is within the range of % by mass.
Examples of hexaarylbiimidazoles include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2′,5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) -4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl )-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2′-bis-(2-fluorophenyl)-4,4′ , 5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,3-difluoromethylphenyl)-4,4′,5,5′-tetrakis-(3- methoxyphenyl)-biimidazole, 2,2′-bis-(2,4-difluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′- Bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 ,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,3,4-trifluorophenyl)-4,4′,5,5′- Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)- Biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis -(2,4,5-trifluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,4,6-trifluorophenyl) fluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,3,4,5-tetrafluorophenyl)-4,4 ',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'- Tetrakis-(3-methoxyphenyl)-biimidazole and 2,2′-bis-(2,3,4,5,6-pentafluorophenyl)-4,4′,5,5′-tetrakis-(3 -Methoxyphenyl)-biimidazole and the like, and these can be used singly or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

In the present embodiment, a hexaarylbisimidazole compound can be added to the photosensitive resin composition, and the content thereof is preferably It is in the range of 0.05% to 7% by mass, more preferably 0.1% to 6% by mass, still more preferably 1% to 5% by mass.

From the viewpoint of peeling properties, sensitivity, resolution, and adhesion of the photosensitive resin layer, the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer.
Examples of pyrazoline compounds include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl) Phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl- Phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropyl Phenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-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, etc. It is preferably mentioned from the viewpoint of. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.
In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling properties and / or sensitivity of the photosensitive resin layer. , more preferably in the range of 0.1% by mass to 3% by mass.

<(D) phenol derivative>
In this embodiment, the photosensitive resin composition preferably contains (D) an inhibitor, and (D) the inhibitor contains a phenol derivative.
(D) Since the inhibitor contains a phenol derivative, adhesion and resolution are very excellent even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature.
Phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis(4-methyl-6-tert-butylphenol) , 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di -tert-butylhydroquinone, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-t-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3 -(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4- hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di -t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol ), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol (for example Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.), tribenzylphenol (for example, TBP, manufactured by Kawaguchi Chemical Industry Co., Ltd., phenol having 1 to 3 benzyl groups), and biphenol are preferred. (D) Since the inhibitor is a phenol derivative, it is preferable from the viewpoint of extremely excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. to p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate, 4,4' -butylidenebis(3-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2,5-di-tert-butylhydroquinone, biphenol are more preferred. From the same point of view, hindered phenol is preferable as the phenol derivative. From the same point of view, the inhibitor (D) preferably has two or more phenolic nuclei.

The ratio of (D) inhibitor to the total solid mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more from the viewpoint of extremely excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. 005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, this ratio is preferably 10% by mass or less, more preferably 8% by mass or less, and 5% by mass or less in terms of less sensitivity reduction and improved resolution. is more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less.

In the present embodiment, a more preferable form of the photosensitive resin composition is that (A-1) the alkali-soluble polymer has an I/O value of 0.200 to 0.500, and a structural unit derived from (meth)acrylic acid. 21 to 29% by mass, and the (B) compound having an ethylenically unsaturated bond includes a (meth) acrylate compound having 3 or more ethylenically unsaturated bonds, and the developer is overdeveloped and overwashed with water. It is preferable from the viewpoint of extremely excellent adhesion and resolution even under extremely severe development conditions such as a high temperature.

In the present embodiment, a particularly preferred form of the photosensitive resin composition is (A-1) an alkali-soluble polymer having an I/O value of 0.200 to 0.500 and a structural unit derived from (meth)acrylic acid. 21 to 29% by mass, further containing (D) an inhibitor, and (D) the inhibitor being a phenol derivative, under extremely severe development conditions such as overdevelopment and overwashing with a high developer temperature. is also preferable from the viewpoint of extremely excellent adhesion and resolution.

<Additive>
The photosensitive resin composition may optionally contain additives such as dyes, plasticizers, antioxidants and stabilizers. For example, additives listed in JP-A-2013-156369 may be used.
(Dyes and coloring substances)
In the present embodiment, the photosensitive resin composition may optionally further contain at least one selected from the group consisting of dyes (eg, leuco dyes, fluorane dyes, etc.) and coloring substances.
Coloring substances include, for example, fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, victoria blue, malachite green (e.g. Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20 and Diamond Green (for example, AIZEN (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid content of the photosensitive resin composition is 100% by mass. The content of 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, setting the content to 1% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition.
The photosensitive resin composition is preferable in terms of visibility because the exposed portion develops color by containing a dye, and when an inspection machine or the like reads the alignment marker for exposure, the exposed portion and the unexposed portion The larger the contrast, the easier it is to recognize, which is advantageous. Preferred dyes from this point of view include leuco dyes and fluoran dyes.

Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green]. In particular, leuco crystal violet is preferably used as the leuco dye from the viewpoint of good contrast. The content of the leuco dye in the photosensitive resin composition is preferably 0.05% by mass to 10% by mass with respect to the total solid mass of the photosensitive resin composition. A content of 0.05% by mass or more is preferable from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. This content is more preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, and particularly preferably 0.2% by mass or more. On the other hand, it is preferable that the content is 10% by mass or less from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature. From this point of view, the content is more preferably 2% by mass or less, more preferably 1% by mass or less, more preferably 0.6% by mass or less, and 0.5% by mass or less. is even more preferable, 0.4% by mass or less is particularly preferable, and 0.35% by mass or less is most preferable.
Moreover, it is preferable to use the leuco dye and the halogen compound described above in (C) the photopolymerization initiator in combination in the photosensitive resin composition from the viewpoint of optimizing adhesion and contrast. When the leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is 0.01 mass when the total solid mass of the photosensitive resin composition is 100 mass%. % to 3% by mass is preferable from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.

(Other additives)
The photosensitive resin composition further contains at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles, in order to improve thermal stability and storage stability. good too.
Examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. A nitrosophenylhydroxyamine aluminum salt is preferred so as not to impair the sensitivity of the photosensitive resin composition.
Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.
Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like.

The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably from 0.01% by mass to 100% by mass of the total solid content of the photosensitive resin composition. It is 3 mass %, more preferably 0.05 mass % to 1 mass %. The content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, setting the content to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

In the present embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Epoxy compounds of bisphenol A include, for example, compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the ends.
In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalates (e.g., diethylflate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl triethyl citrate, -n-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like. In addition, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol Paul BPE-20T, Nieupol BPE-60, Nieupol BPE-100, Nieupol BPE-180 (manufactured by Sanyo Kasei Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA- 400, Uniol DA-700 (manufactured by NOF Corporation), BA-P4U glycol, and BA-P8 glycol (manufactured by Nippon Nyukazai Co., Ltd.).
When the photosensitive resin composition contains a plasticizer, the content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass with respect to the total solid mass of the photosensitive resin composition. and more preferably 1% by mass to 30% by mass. The content of 1% by mass or more is preferable from the viewpoint of suppressing the development time delay and imparting flexibility to the cured film. On the other hand, setting the content to 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.

However, from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment, overwashing, and a high developer temperature, the content of the plasticizer in the photosensitive resin composition is 10 mass. % or less is preferable, 5 mass % or less is more preferable, 2 mass % or less is still more preferable, 1 mass % or less is particularly preferable, and 0 mass % is most preferable.

In the present embodiment, substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition are When the component is (B) the mass of the compound having an ethylenically unsaturated bond, the ratio of the mass of the component other than (A) and (B) ([mass of the component other than (A) and (B) ]/[The mass of the compound having an ethylenically unsaturated bond]] is preferably 0.190 or less.When this value is 0.190 or less, a crosslinked structure is formed. (B) With respect to the content of the compound having an ethylenically unsaturated bond, the content of the component that is not incorporated into the crosslinked structure can be reduced. It is preferable from the viewpoint of excellent adhesion and resolution even under severe development conditions.From the same viewpoint, it is more preferably 0.185 or less, further preferably 0.180 or less, and 0.175 or less. It is particularly preferably 0.170 or less, and may be 0.165 or less, or may be 0.160 or less.
There is no lower limit, but this value may be 0.005 or more, 0.010 or more, 0.030 or more, or 0.050 or more. may

In the present embodiment, the ratio of the mass of the alkali-soluble polymer (A-1) to the mass of the compound having an ethylenically unsaturated bond (B) contained in the solid content of the photosensitive resin composition ([(A -1) Mass of alkali-soluble polymer]/[mass of compound having ethylenically unsaturated bond]) is preferably 0.500 or more. When it is 0.500 or more, it means that the content of the alkali-soluble polymer (A-1) with an I / O value of 0.200 to 0.560 is high, and the hydrophobicity of the photosensitive resin composition is increased. (B) The content of the compound having an ethylenically unsaturated bond is relatively small, so that curing shrinkage when the photosensitive resin composition is cured can be suppressed, and as a result, overdevelopment and It is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overwashing and high developer temperature. From the same viewpoint, it is more preferably 0.550 or more, more preferably 0.580 or more, still more preferably 0.600 or more, still more preferably 0.620 or more, and 0 0.650 or greater is particularly preferred, 0.680 or greater is particularly preferred, and 0.700 or greater is most preferred. Although the upper limit is not particularly limited, this value may be 3.0 or less, 2.5 or less, 2.0 or less, or 1.5 or less. .

In the present embodiment, the ratio ([( A) content of alkali-soluble polymer]/[content of compound having ethylenically unsaturated bond]) is preferably 5.00 or less. It is preferably 5.00 or less from the viewpoint of the flexibility of the cured film, more preferably 4.00 or less from the same viewpoint, more preferably 3.00 or less, and 2.00 or less. It is more preferably 1.800 or less, particularly preferably 1.600 or less. Although the lower limit is not particularly limited, this value may be 0.200 or more, 0.300 or more, or 0.500 or more.

[solvent]
The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation liquid for producing a photosensitive resin laminate. Examples of solvents include ketones, alcohols, and the like. The ketones are represented by methyl ethyl ketone (MEK) and acetone. Said alcohols are represented by methanol, ethanol and isopropanol. The solvent is used in an amount such that the viscosity at 25 ° C. of the photosensitive resin composition preparation applied on the support layer is 500 mPa s to 4,000 mPa s in the production of the photosensitive resin laminate. It is preferably added to the resin composition.

<Photosensitive resin laminate>
In this embodiment, a photosensitive resin laminate having a support and a photosensitive resin layer composed of the above photosensitive resin composition laminated on the support can be provided. If desired, the photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite to the support side.
Although the support is not particularly limited, a transparent support that transmits light emitted from the exposure light source is preferred. Examples of such supports include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films are included. These films may be stretched as necessary.
The support film preferably has a haze of 5% or less, more preferably 2% or less, even more preferably 1.5% or less, and particularly 1.0% or less, from the viewpoint of suppressing light scattering during exposure. preferable. From the same point of view, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. As for the thickness of the film, the thinner the film, the more advantageous it is in terms of improving the image forming property and economic efficiency.

Further, the support film may have a single-layer structure, or may have a multi-layer structure in which resin layers formed from a plurality of compositions are laminated. In the case of multilayer structures, there may be an antistatic layer. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one surface A, and on the other surface B, (1) fine particles in the same manner as on surface A (2) contains a smaller amount of fine particles than the surface A, (3) contains finer particles than the surface A, and (4) does not contain fine particles. In the case of structures (2), (3), and (4), it is preferable to form a photosensitive resin layer on the surface B side. At this time, it is preferable from the viewpoint of film slipperiness and the like that a resin layer containing fine particles is provided on the surface A side. The fine particles are, for example, inorganic fine particles or organic fine particles, and include lubricants, lubricants, agglomerates of additives, foreign substances mixed in raw materials, foreign substances mixed in manufacturing processes, and the like. At this time, the size of the fine particles is preferably less than 5 μm, more preferably less than 3 μm, even more preferably less than 2 μm, and particularly preferably less than 1.5 μm, from the viewpoint of improving resolution and resist pattern precision. The support film is FB-40 (manufactured by Toray Industries, Inc.), QS65 (manufactured by Toray Industries, Inc.), and QS66 (manufactured by Toray Industries, Inc.) from the viewpoint of improving resolution and resist pattern accuracy as a polyethylene terephthalate film. , QS67 (manufactured by Toray Industries, Inc.) and QS68 (manufactured by Toray Industries, Inc.) are preferred, FB-40 and QS68 are more preferred, and QS68 is even more preferred.

An important characteristic of the protective layer used in the photosensitive resin layered body is that the protective layer has a smaller adhesive force to the photosensitive resin layer than the support and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferable. For example, a film having excellent releasability described in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.
A gel called fish eye may be present on the surface of the polyethylene film. When a polyethylene film having fisheyes is used as the protective layer, the fisheyes may be transferred to the photosensitive resin layer. If the fisheye is transferred to the photosensitive resin layer, air may be entrapped during lamination to form voids, leading to defects in the resist pattern. From the viewpoint of preventing fish eyes, oriented polypropylene is preferable as the material for the protective layer. A specific example is Alphan E-200A manufactured by Oji Paper Co., Ltd.

In this embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thickness of the photosensitive resin layer can be selected depending on the application because the smaller the thickness, the better the resolution of the resist pattern, while the larger the thickness, the higher the strength of the cured film.
A known method may be used as a method for sequentially laminating a support, a photosensitive resin layer, and, if desired, a protective layer to produce a photosensitive resin laminate.
For example, the above photosensitive resin composition prepared solution is prepared, then coated on a support using a bar coater or roll coater and dried, and a photosensitive resin composed of the photosensitive resin composition prepared solution is applied on the support. Laminate the layers. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Method of forming resist pattern>
Next, an example of a method of manufacturing a resist pattern using the photosensitive resin laminate of this embodiment will be described. The method includes a laminating step of laminating a photosensitive resin laminate on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and a developing step of developing and removing the unexposed portion of the photosensitive resin layer. can include Examples of resist patterns include printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, flexible substrates, lead frame substrates, COF (chip-on-film) substrates, semiconductor package substrates, transparent electrodes for liquid crystals, and TFTs for liquid crystals. wiring, touch panel wiring, and PDP (plasma display panel) electrode patterns. As an example, a method for manufacturing a printed wiring board will be described as follows.

A printed wiring board is manufactured through the following steps.
(1) Lamination step First, in the lamination step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed onto the substrate surface by a laminator to laminate. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).
In this embodiment, the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as required. The heating temperature during lamination is generally 40°C to 160°C. Further, by performing the thermocompression bonding at the time of lamination two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. During thermocompression bonding, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rolls several times. Moreover, you may press-bond using a vacuum laminator.
(2) Exposure step In this step, a mask film having a desired wiring pattern is brought into close contact with the support layer and an exposure method is performed using an active light source, an exposure method by direct drawing of a drawing pattern that is the desired wiring pattern, or The photosensitive resin layer is exposed by an exposure method in which an image of the photomask is projected through a lens.
(3) Development process In this process, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed area is developed and removed using an alkaline aqueous developer, thereby forming a resist pattern on the substrate. Form.
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 properties of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20°C to about 40°C is preferable.

A resist pattern can be obtained through the above steps (1) to (3). These steps may optionally be followed by a further heating step at about 100°C to about 300°C. By carrying out this heating step, the chemical resistance can be further improved. For heating, a heating furnace using hot air, infrared rays, or far infrared rays can be used. Also, this heating process may be performed after the exposure process.

(4) Etching step or plating step A substrate surface exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern.
(5) Stripping Step After that, the resist pattern is stripped from the substrate with an aqueous solution having stronger alkalinity than the developer. The alkaline aqueous solution for stripping is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70°C is preferable. A small amount of water-soluble solvent can also be added to the stripping solution.
The photosensitive resin laminate of this embodiment includes a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, a wiring for touch panel, and an electrode for PDP. It is a photosensitive resin laminate suitable for manufacturing conductor patterns such as.
Unless otherwise specified, the various parameters described above are measured according to the measurement methods in Examples described later or equivalent methods understood by those skilled in the art.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, this embodiment is not limited to the following examples unless it deviates from the gist thereof. Physical properties in the examples were measured by the following methods.
Measurement of polymer physical property values, calculation of the glass transition temperature of the polymer, and preparation of samples for evaluation of Examples and Comparative Examples will be described. In addition, evaluation methods and evaluation results for the obtained samples are shown.

｛式中、Ｗ_ｉは、各々のアルカリ可溶性高分子の固形重量であり、Ｔｇ_ｉは、各々のアルカリ可溶性高分子のＦｏｘ式で求められるガラス転移温度であり、Ｗ_{ｔｏｔａｌ}は、各々のアルカリ可溶性高分子の合計固形重量であり、かつｎは、感光性樹脂組成物に含まれるアルカリ可溶性高分子の種類の数である｝ (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 JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Co., Ltd. ( KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (Showa Denko Co., Ltd. Shodex STANDARD SM-105) using a calibration curve) Calculated as polystyrene equivalent.
Furthermore, the polymer dispersity 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 carboxyl groups in the molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by potentiometric titration using a 0.1 mol/L sodium hydroxide aqueous solution.
<Glass transition temperature Tg>
The glass transition temperature Tg of the alkali-soluble polymer is a value determined by the Fox formula. When determining the glass transition temperature Tg, the glass transition temperature of a homopolymer composed of comonomers forming the corresponding alkali-soluble polymer is used as the glass transition temperature of the homopolymer, as described in the non-patent literature (Brandrup, J. Immergut, EH edited "Polymer Handbook, Third edition, John Wiley & sons, 1989, p.209 Chapter VI "Glass transition temperatures of polymers"") shall be used. Table 1 shows the glass transition temperatures of homopolymers composed of comonomers used in the calculations in Examples.
When the alkali-soluble polymer is composed of two or more polymers, the value obtained by the following formula is the glass transition temperature of the alkali-soluble polymer.

{Wherein, W _i is the solid weight of each alkali-soluble polymer, Tg _i is the glass transition temperature of each alkali-soluble polymer determined by the Fox formula, and W _total is each alkali-soluble is the total solid weight of the polymer, and n is the number of types of alkali-soluble polymer contained in the photosensitive resin composition}

(2) Method for producing evaluation samples Evaluation samples were produced as follows.
<Preparation of photosensitive resin laminate>
The components shown in Table 1 below (wherein the number of each component indicates the amount (parts by mass) of the solid content) and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition preparation. rice field. The names of the components represented by abbreviations in Table 1 are shown in Table 2 below. A polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was used as a support film. After drying for a minute, a photosensitive resin composition layer was formed. The dry thickness of the photosensitive resin composition layer was 20 μm.
Next, on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated, a 19 μm thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) is laminated as a protective layer to form a photosensitive resin. A laminate was obtained.
<Substrate surface preparation>
As a substrate for evaluating image quality, a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was sprayed with an abrasive (#400, manufactured by Ujiden Chemical Industry Co., Ltd.) at a spray pressure of 0.2 MPa. After scrub polishing, the substrate surface was washed with a 10 mass % H ₂ SO ₄ aqueous solution.
<Lamination>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, a copper clad laminate preheated to 50 ° C. is coated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.). Lamination was performed at a roll temperature of 105°C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.
<Exposure>
One hour after lamination, the substrate for evaluation was exposed to i-line monochromatic light through a glass mask using a projection exposure machine (UX2003 SM-MS04 manufactured by Ushio Inc., using an i-line bandpass filter). Exposure was performed at a plurality of exposure doses from 100 mJ/cm ² to 350 mJ/cm ² in increments of 10 mJ/cm ² .
<Development>
After peeling off the polyethylene terephthalate film (support layer), using an alkali developing machine (Fuji Kiko, dry film developing machine), develop by spraying a 1% by mass Na ₂ CO ₃ aqueous solution at 32° C. over a predetermined period of time. did The development spray time was three times the shortest development time, and the washing spray time after development was eight times the shortest development time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest developing time. General development conditions are as follows: 1% by weight Na ₂ CO ₃ aqueous solution at 30° C., developer spray time twice the shortest development time, washing spray time after development twice the shortest development time. Since it takes time, the developing conditions in this example are extremely severe.

<Image property evaluation-1>
A resist line width of a pattern of mask pattern L/S=6 μm/10 μm was measured with an optical microscope at the minimum exposure amount for normally forming a pattern of mask pattern L/S=4 μm/12 μm. This measurement was performed for 5 lines, and the average value of the 5 line widths was obtained. Since the resist line width of this pattern is narrower than the space width, the evaluation is severe due to the adhesion of the hardened resist.
<Image property evaluation-2>
A resist line width of a pattern of mask pattern L/S=6 μm/10 μm was measured with an optical microscope at the minimum exposure amount for normally forming a pattern of mask pattern L/S=5 μm/11 μm. This measurement was performed for 5 lines, and the average value of the 5 line widths was obtained. Since the resist line width of this pattern is narrower than the space width, the evaluation is severe due to the adhesion of the hardened resist.
<Image property evaluation-3>
A resist line width of a pattern of mask pattern L/S=6 μm/10 μm was measured with an optical microscope at the minimum exposure amount for forming a pattern of mask pattern L/S=6 μm/10 μm normally. This measurement was performed for 5 lines, and the average value of the 5 line widths was obtained. Since the resist line width of this pattern is narrower than the space width, the evaluation is severe due to the adhesion of the hardened resist.
Incidentally, among the image quality evaluations -1 to -3, the image quality evaluation -1 is the most severe evaluation for the adhesion of the cured resist.
<Image property evaluation-4>
In a mask pattern (L:S=1:1) in which the width of the exposed area and the unexposed area is 1:1, the minimum mask line width at which the cured resist line is normally formed was obtained as the value of resolution. This pattern requires both the adhesiveness of the hardened resist and the lack of resolution in the space portion.
In the cured resist pattern, there is no residual resist on the substrate surface of the unexposed portion, the substrate surface is exposed, the cured resist does not meander, and there is no protrusion of the resist component from the cured resist, and it is formed normally. The cured resist pattern was evaluated.

From the results in Tables 1 and 2, it was confirmed that the results of evaluation of image quality were superior in the examples within the scope of the constituent elements of the present invention than in the comparative examples outside the scope of the present invention. .
The development conditions in this example are extremely severe conditions. For example, under the general development conditions described above, the compositions of Examples 4 and 5 both form a pattern of mask pattern L/S=3 μm/13 μm and a pattern of mask pattern L/S=4 μm/12 μm. I was able to On the other hand, under the extremely severe development conditions of this example, the compositions of Examples 4 and 5 could not normally form a mask pattern L/S=3 μm/13 μm, and the mask pattern As can be seen from Table 1, the pattern of L/S=4 μm/12 μm was not formed normally in Example 4, but was formed normally in Example 5. Further, in the mask pattern of L:S=1:1 in <Image property evaluation-4>, the minimum resolution of both the compositions of Examples 4 and 5 was 6 μm under the general development conditions described above. However, as can be seen from Table 1, under the extremely severe development conditions of this example, Example 4 was 7 μm, and Example 5 was 6.5 μm.
Similarly, under the general development conditions described above, the compositions of Example 6 and Comparative Example 3 both form a mask pattern L/S=3 μm/13 μm and a mask pattern L/S=4 μm/12 μm. We were able to. On the other hand, under the extremely severe development conditions of this example, the compositions of Example 6 and Comparative Example 3 could not normally form a pattern of mask pattern L/S=3 μm/13 μm. As can be seen from Table 1, the pattern of L/S=4 μm/12 μm was not formed normally in Comparative Example 3, but was formed normally in Example 6. In addition, in the mask pattern of L:S=1:1 of <Image Quality Evaluation-4>, the minimum resolution was 5 μm for both the compositions of Example 6 and Comparative Example 3 under the general development conditions described above. However, as can be seen from Table 1, under the extremely severe developing conditions of this example, Example 6 had a thickness of 5.5 μm, and Comparative Example 3 had a thickness of 8 μm.
In other words, even if adhesion and resolution are good under general development conditions such as development time and water washing time, the extremely severe development conditions of the present invention, in which the temperature of the developer is high due to overdevelopment and overwashing, are used. However, the present invention makes it possible for the first time to improve the adhesion and resolution even under these severe development conditions.

By using the photosensitive resin composition of the present invention, when a pattern is formed by an etching method or a plating method, the reproducibility of the mask line width is good, and the problem of short failure, chipping, disconnection, plating failure, etc. is eliminated. A fine circuit can be formed.
Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the gist of the invention.

The photosensitive resin composition of the present invention exhibits good adhesion and resolution even under severe development conditions such as overdevelopment, overwashing, and high-temperature developer. Also, when a pattern is formed by an etching method or a plating method, it is possible to form a high-definition circuit with good mask line width reproducibility and free from problems such as short circuits, chipping, disconnection, and plating defects. Therefore, the photosensitive resin composition can be used for printed wiring boards, flexible substrates, lead frame substrates, COF (chip-on-film) substrates, semiconductor package substrates, transparent electrodes for liquid crystals, wiring for liquid crystal TFTs, wiring for touch panels, And it can be suitably used for manufacturing conductor patterns such as electrodes for PDP (Plasma Display Panel).

Claims (27)

(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond;
(C) a photoinitiator;
(D) an inhibitor;
at least one selected from the group consisting of dyes and coloring substances; and benzotriazoles;
A photosensitive resin composition comprising
The (A) alkali-soluble polymer is
(A-1) an alkali-soluble polymer having an I/O value of 0.200 to 0.504 when the predetermined alkali-soluble polymer alone is used;
In the case of a mixture of two or more alkali-soluble polymers obtained by different syntheses, the alkali-soluble polymer (A-1) having an I/O value of 0.200 to 0.504 in the photosensitive resin composition (A-1) the mixture containing the alkali-soluble polymer, and the (D) inhibitor containing a phenol derivative,
Substances other than the (A) alkali-soluble polymer and the (B) ethylenically unsaturated bond-containing compound contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
A photosensitive resin composition, wherein the ratio of the mass of components other than (A) and (B) to the mass of the compound having an ethylenically unsaturated bond (B) is 0.190 or less. . 2. The photosensitive resin composition according to claim 1, wherein the ratio of the mass of the (A-1) alkali-soluble polymer to the mass of the (B) compound having an ethylenically unsaturated bond is 0.500 or more. The (A-1) alkali-soluble polymer contains 21% by mass of structural units derived from (meth)acrylic acid, based on the total weight of all monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition according to claim 1 or 2, comprising ~29% by mass. 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble polymer (A-1) has a glass transition temperature Tg of 128°C or lower. The photosensitive resin according to any one of claims 1 to 4, wherein the ratio of the mass of the (A) alkali-soluble polymer to the mass of the (B) compound having an ethylenically unsaturated bond is 5.0 or less. Composition. (A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond;
(C) a photoinitiator;
(D) an inhibitor;
at least one selected from the group consisting of dyes and coloring substances; and benzotriazoles;
A photosensitive resin composition comprising
The (A) alkali-soluble polymer is
(A-1) an alkali-soluble polymer having an I/O value of 0.200 to 0.504 when the predetermined alkali-soluble polymer alone is used;
In the case of a mixture of two or more alkali-soluble polymers obtained by different syntheses, the alkali-soluble polymer (A-1) having an I/O value of 0.200 to 0.504 in the photosensitive resin composition The mixture containing the (A-1) alkali-soluble polymer, wherein the mixing ratio of the total solid content is 5% by mass or more,
The (A-1) alkali-soluble polymer contains 21% by mass of structural units derived from (meth)acrylic acid, based on the total weight of all monomer components constituting the (A-1) alkali-soluble polymer. Contains ~29% by mass,
The (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128° C. or less,
The (D) inhibitor contains a phenol derivative,
Substances other than the (A) alkali-soluble polymer and the (B) ethylenically unsaturated bond-containing compound contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
The ratio of the mass of the components other than (A) and (B) to the mass of the compound having an ethylenically unsaturated bond (B) is 0.190 or less,
The ratio of the mass of the (A-1) alkali-soluble polymer to the mass of the (B) compound having an ethylenically unsaturated bond is 0.500 or more, and the (B) compound having an ethylenically unsaturated bond The ratio of the mass of the alkali-soluble polymer (A) to the mass of the photosensitive resin composition is 5.0 or less. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (C) photopolymerization initiator comprises hexaarylbiimidazole. The (C) photopolymerization initiator comprises a pyrazoline compound, the photosensitive resin composition according to any one of claims 1 to 7. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (C) photopolymerization initiator comprises an anthracene compound. The photosensitive resin composition according to any one of claims 1 to 9, wherein the (C) photopolymerization initiator comprises aromatic ketones. The photopolymerization initiator (C) comprises at least one selected from acridines, N-arylamino acids or ester compounds thereof, halogen compounds, and coumarin compounds, according to any one of claims 1 to 10. A photosensitive resin composition. The photosensitive resin according to any one of claims 1 to 11, wherein the content of the (A) alkali-soluble polymer is 30% by mass or more relative to the total solid mass of the photosensitive resin composition. Composition. The photosensitive resin composition according to any one of claims 1 to 12, wherein the (D) inhibitor comprises a hindered phenol. The photosensitive resin composition according to any one of claims 1 to 13, wherein the (D) inhibitor comprises p-methoxyphenol. The photosensitive resin composition according to any one of claims 1 to 14, wherein the (D) inhibitor comprises 2,6-di-tert-butyl-p-cresol. The photosensitizer of any one of claims 1 to 15, wherein said (D) inhibitor comprises triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate. elastic resin composition. The photosensitive resin composition according to any one of claims 1 to 16, wherein the (D) inhibitor comprises 4,4'-butylidenebis(3-methyl-6-tert-butylphenol). The photosensitive resin composition according to any one of claims 1 to 17, wherein the inhibitor (D) comprises catechol. The photosensitive resin composition according to any one of claims 1 to 18, wherein the inhibitor (D) comprises tert-butylcatechol. The photosensitive resin composition according to any one of claims 1 to 19, wherein the (D) inhibitor comprises 2,5-di-tert-butylhydroquinone. The photosensitive resin composition according to any one of claims 1 to 20, wherein the (D) inhibitor comprises biphenol. The photosensitive resin composition according to any one of claims 1 to 21, wherein the inhibitor (D) has two or more phenolic nuclei. The (A-1) alkali-soluble polymer is a (meth)acrylic acid alkyl ester (where the number of carbon atoms in the alkyl is 4 or more) containing 1% by mass to 20% by mass of structural units derived from the photosensitive resin composition according to any one of claims 1 to 22. The (B) compound having an ethylenically unsaturated bond comprises a (meth)acrylate compound having 6 or more ethylenically unsaturated bonds, the photosensitive resin composition according to any one of claims 1 to 23. . A photosensitive resin laminate comprising a support layer and a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 24 laminated on the support layer. The following steps:
A lamination step of laminating the photosensitive resin laminate according to claim 25 on a substrate;
an exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate; and a developing step of developing and removing an unexposed portion of the photosensitive resin layer;
A method of forming a resist pattern, comprising: The following steps:
A lamination step of laminating the photosensitive resin laminate according to claim 25 on a substrate;
an exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate;
a developing step of developing the photosensitive resin layer after exposure to obtain a substrate on which a resist pattern is formed;
A conductive pattern forming step of etching or plating the substrate on which the resist pattern is formed; and a stripping step of stripping the resist pattern;
A wiring board manufacturing method comprising: