JP2022082614A - Photosensitive resin composition and photosensitive resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in adhesion and resolution even on severe development conditions such as overdevelopment, overwashing and a developer at high temperature, and to provide a method for forming a resist pattern and a method for manufacturing a wiring board using the same.

SOLUTION: A photosensitive resin composition contains: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; and (D) an inhibitor, where (A) the alkali-soluble polymer contains 5 mass% or more of (A-1) an alkali-soluble polymer having an I/O value of 0.200-0.560 with respect to the solid content mass in the resin composition, (D) the inhibitor contains a phenol derivative, and when a substance other than (A) the alkali-soluble polymer and (B) the compound having the ethylenically unsaturated bond contained in the solid content is a component other than the (A) and the (B), a mass ratio of the component other than the (A) and the (B) with respect to the mass of (B) the compound having the ethylenically unsaturated bond is 0.190 or less.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a photosensitive resin composition, etc.

In electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used for mounting parts, semiconductors and the like. Conventionally, as a resist for manufacturing a printed wiring board or the like, a photosensitive resin laminate formed by laminating a photosensitive resin layer on a support film and further laminating a protective film on the photosensitive resin layer as needed. A so-called dry film photoresist (hereinafter, also referred to as DF) is used. As the photosensitive resin layer, an alkali-developing type that uses a weak alkaline aqueous solution as a developing solution is generally used at present. To manufacture a printed wiring board or the like using DF, for example, the following steps are performed. If the DF has a protective film, first peel off the protective film. After that, the DF is laminated on a permanent circuit manufacturing 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 photosensitive resin layer of the uncured portion (for example, the unexposed portion in the negative type) is dissolved or dispersed and removed with a developing solution, and a cured resist pattern (hereinafter, simply referred to as simply) is applied on the substrate. (Sometimes called a resist pattern) is formed.
After forming the resist pattern, the process of forming the circuit is roughly divided into two methods. The first method is to remove the substrate surface (for example, the copper surface of a copper-clad laminate) that is not covered by the resist pattern by etching, and then remove the resist pattern portion with an alkaline aqueous solution stronger than the developer (etching method). Is. In the second method, 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, for example) is removed. This is a method (plating method) for etching (the copper surface of a copper-clad laminate). A cupric chloride, ferric chloride, copper-ammonia complex solution or the like is used for etching. In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have been progressing, and high adhesion, high resolution, and good line width reproduction in the above-mentioned manufacturing process. A high-performance DF that gives sex and the like is required. To realize such high resolution, Patent Document 1 describes a photosensitive resin composition whose resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. ..

Japanese Unexamined Patent Publication No. 2010-249884

However, in recent years, with the miniaturization and weight reduction of electronic devices such as mobile phones and tablets, there is an increasing demand for miniaturization of wiring intervals in printed wiring boards. In order to meet such demands for miniaturization, the demands for high adhesion to DF, high resolution, good line width reproducibility, etc. are becoming more and more strict. Further, in order to realize high resolution, there are increasing cases where the development conditions are severe for the purpose of eliminating the resist residue on the substrate surface, and it is becoming very difficult to realize high adhesion of DF. The technique described in Patent Document 1 still has room for improvement from this point of view.
Therefore, the present invention relates to a photosensitive resin composition having excellent adhesion and resolution even under harsh development conditions such as overdevelopment, overwashing, and high temperature of the developer, and a method for forming a resist pattern and a wiring board using the same. The subject is to provide a manufacturing method.

The present inventor has conducted extensive research and experiments in order to solve the above problems. As a result, it was found that the problem can be solved by the following technical means.
That is, the present invention is as follows.
[1]
(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated bond;
(C) Photopolymerization initiator; and (D) Prohibition agent;
A photosensitive resin composition containing
The (A) alkali-soluble polymer has an I / O value of 0.200 to 0.560, and the (A-1) alkali-soluble polymer is 5 with respect to the total solid content mass in the photosensitive resin composition. The banning agent (D) contains a phenol derivative in an amount of% by mass or more, and contains.
Substances other than the (A) alkali-soluble polymer and the (B) compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
(B) A photosensitive resin composition, wherein the ratio of the mass of the components other than (A) and (B) to the mass of the compound 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 (A-1) alkali-soluble polymer to the mass of the compound having the (B) ethylenically unsaturated bond is 0.500 or more. ..
[3] The (A-1) alkali-soluble polymer has a constituent unit derived from (meth) acrylic acid based on the total mass of all the monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition according to [1] or [2], which comprises 21% by mass to 29% by mass.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the glass transition temperature Tg of the alkali-soluble polymer (A-1) is 128 ° C. or lower.
[5] The method according to any one of [1] to [4], wherein the ratio of the mass of the (A) alkali-soluble polymer to the mass of the compound having the (B) ethylenically unsaturated bond is 5.0 or less. Photosensitive resin composition.
[6]
(A) Alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator;
(D) Prohibition agent;
A photosensitive resin composition containing
The (A) alkali-soluble polymer has an I / O value of 0.200 to 0.560, and the (A-1) alkali-soluble polymer is 5 with respect to the total solid content mass in the photosensitive resin composition. Including mass% or more
The (A-1) alkali-soluble polymer contains 21% by mass of the structural unit derived from (meth) acrylic acid based on the total mass of all the monomer components constituting the (A-1) alkali-soluble polymer. Including ~ 29% by mass,
The (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128 ° C. or lower, and the (D) banning agent contains a phenol derivative.
Substances other than the (A) alkali-soluble polymer and the (B) compound having an ethylenically unsaturated bond 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 the 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 compound having the (B) ethylenically unsaturated bond is 0.500 or more, and the compound having the (B) ethylenically unsaturated bond. A photosensitive resin composition, wherein the ratio of the mass of the (A) alkali-soluble polymer to the mass of (A) 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 of [1] to [10], wherein the (C) photopolymerization initiator contains at least one selected from acridins, N-aryl amino 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 content mass in the photosensitive resin composition.
[14] The content of the alkali-soluble polymer (A) is 30% by mass or more with respect to the total solid content mass of the photosensitive resin composition, according to any one of [1] to [13]. Photosensitive resin composition.
[15] The photosensitive resin composition according to [14], wherein the content of the alkali-soluble polymer (A) is 40% by mass or more with respect to the total solid content mass in the photosensitive resin composition.
[16] The photosensitive resin composition according to any one of [1] to [15], wherein the banning agent (D) contains hindered phenol.
[17] The photosensitive resin composition according to any one of [1] to [16], wherein the banning agent (D) contains p-methoxyphenol.
[18] The photosensitive resin composition according to any one of [1] to [17], wherein the (D) banning agent contains 2,6-di-tert-butyl-p-cresol.
[19] The banning agent (D) comprises any of [1] to [18], which comprises triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate. The photosensitive resin composition according to the above.
[20] The photosensitive resin composition according to any one of [1] to [19], wherein the (D) banning agent contains 4,4'-butylidenebis (3-methyl-6-tert-butylphenol).
[21] The photosensitive resin composition according to any one of [1] to [20], wherein the banning agent (D) contains catechol.
[22] The photosensitive resin composition according to any one of [1] to [21], wherein the banning agent (D) contains tert-butylcatechol.
[23] The photosensitive resin composition according to any one of [1] to [22], wherein the (D) banning agent contains 2,5-di-tert-butylhydroquinone.
[24] The photosensitive resin composition according to any one of [1] to [23], wherein the banning agent (D) contains biphenol.
[25] The photosensitive resin composition according to any one of [1] to [24], wherein the banning agent (D) has two or more phenol nuclei.
[26] The (A-1) alkali-soluble polymer is a (meth) acrylic acid alkyl ester (alkyl) based on the total mass of all the monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition according to any one of [1] to [25], which contains 1% by mass to 20% by mass of a constituent unit derived from (having 4 or more carbon atoms).
[27] The photosensitive compound according to any one of [1] to [26], wherein the compound having the (B) ethylenically unsaturated bond contains a (meth) acrylate compound having 6 or more ethylenically unsaturated bonds. Resin composition.
[28] A photosensitive resin laminate in which a photosensitive resin layer composed of the photosensitive resin composition according to any one of [1] to [27] is laminated on a support layer.
[29]
The following steps:
Laminating step of laminating the photosensitive resin laminate according to [28] on a substrate;
An exposure step for exposing the photosensitive resin layer in the photosensitive resin laminate; and a developing step for developing and removing an unexposed portion of the photosensitive resin layer;
A method for forming a resist pattern, including.
[30]
The following steps:
Laminating step of laminating the photosensitive resin laminate according to [28] on a substrate;
An exposure step for 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;
Conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed; and peeling step of peeling off the resist pattern;
Manufacturing method of wiring board including.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive resin composition and a photosensitive resin laminate having good adhesion and resolution even under severe development conditions such as overdevelopment, overwashing, and a high temperature of a developer, and the photosensitive resin laminate. It is possible to provide a method for forming a resist pattern and a method for forming a conductor pattern using a sex resin laminate. As a result, even as the density of wiring increases, the mask line width reproducibility is good when forming a pattern by the etching method or the plating method, and problems such as short circuit defects, chipping, disconnection, and plating defects occur. It is possible to form a high-definition circuit.

Hereinafter, exemplary embodiments for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. Further, the various measured values in the present specification shall be in accordance with the method described in the [Example] section of the present disclosure or a method understood by those skilled in the art to be equivalent thereto, unless otherwise specified. Is measured.

[Photosensitive resin composition]
In this embodiment, the photosensitive composition comprises (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; and (D) a banning agent. In the resin composition, the alkali-soluble polymer (A) has an I / O value of 0.200 to 0.560 (A-1), and the alkali-soluble polymer has a solid content in the photosensitive resin composition. As a reference, a substance other than (A) an alkali-soluble polymer and (B) a compound having an ethylenically unsaturated bond contained in the solid content, which contains 5% by mass or more and (D) the banning agent contains a phenol derivative ( When the components other than A) and (B) are used, the ratio of the masses of the components other than (A) and (B) to the mass of the compound having (B) ethylenically unsaturated bonds ([(A) and ( The mass of components other than B)] / [also referred to as (B) the mass of the compound having an ethylenically unsaturated bond]) is 0.190 or less. The 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.
Hereinafter, each component will be described in order.

<(A) Alkali-soluble polymer>
In the present disclosure, as the (A) alkali-soluble polymer, the (A-1) alkali-soluble polymer having an I / O value of 0.200 to 0.560 is contained in an amount of 5% by mass or more of the total solid content.
The I / O value is a value that deals with the polarities of various organic compounds, which are also called (inorganic value) / (organic value), in an organic concept, and is one of the functional group contribution methods in which parameters are set for each functional group. It is one. The I / O values are described in detail in non-patent literature (organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); Area, Vol. 11, No. 10, 719-725 (1957); Fragrance Journal, No. 34, No. 97-111 (1979); Fragrance Journal, No. 50, No. 79-82 (1981). Year)); etc. are explained in detail in the literature.
The concept of the I / O value divides the properties of a compound into an organic group representing covalent bondability and an inorganic group representing ionic bondability, and all organic compounds are named as an organic axis and an inorganic axis. It is shown by positioning it at each point on the coordinates. The closer the I / O value is to 0, the more polar (hydrophobic, more organic) the organic compound is, and the larger the I / O value is, the more polar (hydrophilic, more 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, the adhesion and resolution are excellent even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developer. From the same viewpoint, the I / O value is preferably 0.550 or less, more preferably 0.520 or less, more preferably 0.510 or less, further preferably 0.500 or less, and even more preferably 0.490 or less. , 0.480 or less is particularly preferable, and 0.470 or less is most preferable. From the same viewpoint, 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, preferably 0.410 or more, and 0. 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 to make it hydrophobic, high adhesion and high resolution can be achieved even under harsh development conditions, while if the I / O value is too low, the minimum development time will be too long. As a result, the development conditions become more severe, and it is considered that the I / O value needs to be higher than a certain level.

From the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as over-development and over-washing with high temperature of the developing solution, (A-1) contains an alkali-soluble polymer in an amount of 5% by mass or more of the total solid content. It contains 8% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, still more preferably 25% by mass or more, and particularly preferably 30% by mass. % Or more, particularly preferably 35% by mass or more, and most preferably 40% by 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 Examples described later. By using the (A-1) alkali-soluble polymer having a Tg of 128 ° C. or lower in the photosensitive resin composition, it adheres even under extremely harsh development conditions such as overdevelopment and overwater washing and the temperature of the developer is high. Excellent in sex and resolution. From this viewpoint, the Tg of the (A-1) alkali-soluble polymer is preferably 125 ° C. or lower, more preferably 120 ° C. or lower, further preferably 115 ° C. or lower, and 110 ° C. or lower. More preferably, it is particularly preferably 105 ° C. or lower, and most preferably 100 ° C. or lower. Further, when the Tg of the (A-1) alkali-soluble polymer is 30 ° C. or higher, it is preferable from the viewpoint of improving the edge fuse resistance. From this viewpoint, the Tg of the (A-1) alkali-soluble polymer is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher.

A photosensitive resin composition having excellent adhesion and resolution in normal development is not necessarily a photosensitive resin composition having excellent adhesion and resolution even under harsh development conditions. In the present embodiment, from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with high water temperature, aromatic hydrocarbons are used as the (A-1) alkali-soluble polymer. It is preferable that the constituent unit of the monomer component having a hydrogen group is contained in an amount of 52% by mass or more. Examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group, and from the same viewpoint, as a monomer component having an aromatic hydrocarbon group. Is a monomer having a substituted or unsubstituted benzyl group (eg, benzyl (meth) acrylate), a styrene derivative (eg, styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid). , Styrene dimer, styrene trimmer, etc.), more preferably a styrene derivative, and particularly preferably styrene. (A-1) The content ratio of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer is preferably 52% by mass or more, preferably 55% by mass, based on the total mass of all the monomer components. % Or more, more preferably 57% by mass or more, particularly preferably 58% by mass or more, and most preferably 60% by mass or more. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 80% by mass or less. (A-1) The content ratio 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 the 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. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
The (A-1) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and the like. / Or it is preferably obtained by polymerizing with at least one of the second monomers described later.

The (A) alkali-soluble polymer containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and is preferably the first simple polymer. It is more preferable to obtain it by copolymerizing at least one of the merits and at least one of the second monomers described later.
The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like. Among these, (meth) acrylic acid is preferable, and methacrylic acid is more preferable, from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with water and a high temperature of the developer.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(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 the monomer components. It is preferable to set the copolymerization ratio to 10% by mass or more from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developing solution, and 15% by mass or more. Is more preferable, 18% by mass or more is further preferable, 21% by mass or more is more preferable, 23% by mass or more is particularly preferable, and 24% by mass or more is particularly preferable. It is preferable to set the copolymerization ratio to 50% by mass or less from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developing solution, and 35% by mass or less. Is more preferable, 30% by mass or less is further preferable, 29% by mass or less is more preferable, 27% by mass or less is particularly preferable, and 26% by mass or less is most preferable.
The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates; vinyl acetate And the like, esters of vinyl alcohols; as well as (meth) acrylonitrile and the like. Of these, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable.

As the second monomer, the (A-1) alkali-soluble polymer contains 1 to 20% by mass of a structural unit 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 harsh development conditions such as overdevelopment and overwashing with water and a high temperature of the developer. From this viewpoint, it is more preferably 3% by mass or more, further preferably 5% by mass or more, still more preferably 15% by mass or less, still more preferably 10% by mass or less. It is particularly preferably 8% by mass or less, and 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-mentioned I / O value and the copolymerization ratio of the first monomer are within the above-mentioned numerical range, and is appropriately appropriate depending on the purpose. It can be selected, for example, preferably 100 to 600, more preferably 250 to 450. The acid equivalent refers to the mass (unit: gram) of a polymer having 1 equivalent of a carboxyl group in the 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 harsh development conditions such as overdevelopment and overwashing with water and high temperature of the developer. .. From the same viewpoint, the acid equivalent is preferably 600 or less, and more preferably 450 or less. In the present disclosure, the acid equivalent is a value measured by a potentiometric titration method of titrating with a 0.1 mol / L NaOH aqueous solution using a potentiometric titrator.

(A-1) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. It is preferable to set the weight average molecular weight to 500,000 or less from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developer, and 100 from the same viewpoint. It is more preferably 000 or less, further preferably 60,000 or less, further preferably 50,000 or less, particularly preferably 40,000 or less, and 30,000 or less. Is the most preferable. From the same viewpoint, the weight average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, further 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. It is more preferably 1.0 to 3.0, and particularly preferably 1.0 to 3.0.
(A) The alkali-soluble polymer may be used alone or in combination of two or more.

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

<(B) Compound having ethylenically unsaturated double bond>
The compound having (B) an ethylenically unsaturated double bond preferably contains a compound having a (meth) acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) an alkali-soluble polymer. (B) The number of ethylenically unsaturated bonds in the compound may be one or more.
Examples of the compound (B) having one ethylenically unsaturated bond include a compound in which (meth) acrylic acid is added to one end of a polyalkylene oxide, or a (meth) acrylic compound at one end of a polyalkylene oxide. Examples thereof include compounds in which an acid is added and the other end is alkyl etherified or allyl etherified, and a phthalic acid-based compound is preferable from the viewpoint of peelability and flexibility of the cured film. Further, when the compound (B) having one ethylenically unsaturated bond is a methacrylate compound, it is preferable from the viewpoints of sensitivity, resolution and adhesion in addition to the above viewpoints.
Such compounds include, for example,
Phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group.
4-Normalrunonylphenoxyheptaethylene glycol dipropylene glycol, which is a (meth) acrylate of a compound obtained by adding polypropylene glycol having an average of 2 mol of propylene oxide and polyethylene glycol having an average of 7 mol of ethylene oxide added to nonylphenol. (Meta) acrylate,
4-Normal Nonylphenoxypentaethylene Glycol Monopropylene Glycol, which is a (meth) acrylate of a compound obtained by adding 1 mol of propylene oxide on average, polyethylene glycol with 5 mol of ethylene oxide on average, and nonylphenol added. 4-Normalrunonylphenoxyoctaethylene glycol (meth) acrylate (eg, manufactured by Toa Synthetic Co., Ltd., M-), which is an acrylate of a compound obtained by adding (meth) acrylate and polyethylene glycol to which an average of 8 mol of ethylene oxide is added to nonylphenol. 114) and the like.
Further, when a phthalic acid compound, for example, γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-о-phthalate is contained, in addition to the above viewpoints, particularly in terms of sensitivity, resolution and adhesion. preferable.

Examples of the compound having two ethylenically unsaturated bonds in the molecule include a compound having (meth) acryloyl groups at both ends of the alkylene oxide chain, or an alkylene in which the ethylene oxide chain and the propylene oxide chain are bonded at random or in a block. Examples thereof include compounds having (meth) acryloyl groups at both ends of the oxide chain.
Examples of such a compound include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (. Polyethylene glycol (meth) acrylice such as meta) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain. In addition to acrylic, etc.
Examples thereof include polypropylene glycoldi (meth) acrylice and polybutylene glycoldi (meth) acrylicate. 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. Dimethacrylate of glycol with an average of 18 mol of ethylene oxide added to both ends of polypropylene glycol with an average of 18 mol of ethylene oxide, FA-023M, and FA-024M, FA-027M of glycol with an average of 15 mol of ethylene oxide added to both ends, respectively. Name, manufactured by Hitachi Kasei Kogyo), etc. These are preferable from the viewpoints 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 has resolution and adhesion. It 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):

{In the formula, 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 , and n 1 and n 3 are independently 1 to 39, respectively. It is an integer, n1 + n3 is an integer of 2 to 40, n2 and n4 are independently integers of 0 to 29, and n2 + n4 is an integer of 0 to 30,-(AO)-and-. The sequence of repeating units of (BO)-may be random or block. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. }
The compound represented by is used.

For example, a dimethacrylate of polyethylene glycol having an average of 5 mol of ethylene oxide added to both ends of bisphenol A, and a polyethylene glycol having an average of 2 mol of ethylene oxide added to both ends of bisphenol A. A polyethylene glycol dimethacrylate having an average of 1 mol of ethylene oxide added to both ends of the dimethacrylate and bisphenol A is preferable in terms of resolution and adhesion.
Further, a compound in which the aromatic ring in the general formula (I) has a heteroatom and / or a substituent may be used.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms and a phenacil group. , Amino group, alkylamino group with 1 to 10 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 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 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, 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 heterocycle, or a group thereof. Examples thereof include an aryl group substituted with a substituent. These substituents may form a condensed ring, or the hydrogen atom in these substituents may be substituted with a heteroatom such as a halogen atom. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

As a compound having three or more ethylenically unsaturated bonds in the molecule, it has 3 mol or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, to which an ethyleneoxy group, a propyleneoxy group, and the like. It is obtained by using an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group as a (meth) acrylate. In this case, examples of the compound that can form a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring. Examples of these compounds include tri (meth) acrylates such as ethoxylated glycerin tri (meth) acrylates, ethoxylated isocyanuric acid tri (meth) acrylates, pentaerythritol tri (meth) acrylates, and trimethyl propanthry (meth) acrylates (eg, trimethylolpropantri (meth) acrylates). 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 viewpoints of flexibility, adhesion, and suppression of bleed-out). Tetra (meth) acrylates such as ditrimethylol propanetetra (meth) acrylates, pentaerythritol tetra (meth) acrylates, and dipentaerythritol tetra (meth) acrylates; penta (meth) acrylates such as dipentaerythritol penta (meth) acrylates. ) Acrylate and the like; Hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.
As the tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. The pentaerythritol tetra (meth) acrylate may be a tetra (meth) acrylate or the like in which a total of 1 to 40 mol of alkylene oxide is added to the four ends of pentaerythritol.
As the hexa (meth) acrylate, a total of 1 to 20 mol of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 20 mol of ε is added 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 independently or in combination, respectively. The photosensitive resin composition may also contain other compounds as the compound having the (B) ethylenically unsaturated bond. Other compounds include (meth) acrylate having a urethane bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid. Examples thereof include the compound obtained by subjecting the mixture, 1,6-hexanediol di (meth) acrylate and the like.

As the compound having (B) ethylenically unsaturated bond, 75% by mass or more of the (meth) acrylate compound having two or more ethylenically unsaturated bonds is contained in the compound having (B) ethylenically unsaturated bond. Is preferable. It is preferable to contain 75% by mass or more from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with water and a high temperature of the developer, and from the same viewpoint, it contains 78% by mass or more. It is more preferably 81% by mass or more, further preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 93% by mass or more.
As the compound having the (B) ethylenically unsaturated bond, it is preferable that the methacrylate compound is contained in the compound having the (B) ethylenically unsaturated bond in an amount of 75% by mass or more. It is preferable to contain 75% by mass or more from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with water and a high temperature of the developer, and from the same viewpoint, it contains 78% by mass or more. It is more preferably 81% by mass or more, further preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 93% by mass or more.

The compound having (B) ethylenically unsaturated bonds includes a (meth) acrylate compound having three or more ethylenically unsaturated bonds, which is extremely severe because it is overdeveloped and washed with water and the temperature of the developing solution is high. It is preferable from the viewpoint of excellent adhesion and resolution even under various development conditions. From the same viewpoint, as the (meth) acrylate compound having three or more ethylenically unsaturated bonds, a (meth) acrylate compound having three ethylenically unsaturated bonds is preferable, and it has four ethylenically unsaturated bonds (). A (meth) acrylate compound is more preferable, a (meth) acrylate compound having 5 ethylenically unsaturated bonds is further preferable, and a (meth) acrylate compound having 6 or more ethylenically unsaturated bonds is particularly preferable.
As the (meth) acrylate compound having three or more ethylenically unsaturated bonds, a methacrylate compound having three or more ethylenically unsaturated bonds is preferable, and a methacrylate compound having four ethylenically unsaturated bonds is preferable from the same viewpoint. The compound is more preferable, the methacrylate compound having 5 ethylenically unsaturated bonds is further preferable, and the methacrylate compound having 6 or more ethylenically unsaturated bonds is particularly preferable.
From the same viewpoint, the content of the (meth) acrylate compound having three or more ethylenically unsaturated bonds is preferably 5% by mass or more in the compound having (B) ethylenically unsaturated bonds, and is preferably 10% by mass. It is more preferably contained in an amount of% or more, further preferably contained in an amount of 15% by mass or more, further preferably contained in an amount of 20% by mass or more, particularly preferably contained in an amount of 30% by mass or more, and most preferably contained in an amount of 40% by mass or more.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content 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. It may be% or more, and may be 50% by mass or more. Further, it may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.
It is preferable that this ratio is 5% by mass or more from the viewpoint of sensitivity, resolution and adhesion. This ratio is more preferably 20% by mass or more, and further 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 cured resist. It is more preferable that this ratio is 50% by mass or less.

<(C) Photopolymerization Initiator>
(C) The photopolymerization initiator is a compound that polymerizes a monomer by light. The photosensitive resin composition contains (C) a compound generally known in the art as a photopolymerization initiator.
The total content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% by mass to 10% by mass, and further preferably 0.1% by mass. It is in the range of% to 7% by mass, particularly preferably 0.1% by mass to 6% by mass. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and light is sufficiently transmitted to the bottom surface of the resist to provide good high resolution. It is preferably 20% by mass or less from the viewpoint of obtaining.
(C) Examples of the photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoins or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, and oxime esters. , Acrydins (eg, 9-phenylaclydin, bisacridinylheptane, 9- (p-methylphenyl) acridin, and 9- (m-methylphenyl) acridin are preferred in terms of sensitivity, resolution and adhesion). Hexaaryl biimidazole, pyrazoline compounds, anthracene compounds (eg, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9,10-diphenylanthracene are sensitive, resolving, and adherent. (Preferably in terms of), coumarin compounds (eg 7-diethylamino-4-methylcoumarin are preferred in terms of sensitivity, resolution and adhesion), N-aryl amino acids or ester compounds thereof (eg N-phenylglycine are preferred in terms of sensitivity and solution). (Preferably in terms of image quality and adhesion), halogen compounds (for example, tribromomethylphenyl sulfone) and the like can be mentioned. These can be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzo Iludiphenyl-phosphine oxide and triphenylphosphine oxide may be used.

Examples of aromatic ketones include benzophenone, Michelers' ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. be able to. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is particularly preferable from the viewpoint of adhesion. Further, 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. It is in the range of mass%.
Examples of hexaarylbiimidazole are 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) ) -Diphenyl biimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4' , 5,5'-tetrax- (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'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5,5'- Tetrax- (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-tri) Fluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-Tetrakiss- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrax- (3-methoxyphenyl) -biimidazole , And 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole and the like. , These can be used alone or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.

In the present embodiment, the hexaarylbisimidazole compound can be added to the photosensitive resin composition, but the content thereof is preferably from the viewpoint of improving the peeling property and / or the sensitivity of the photosensitive resin layer. It is in the range of 0.05% by mass to 7% by mass, more preferably 0.1% by mass to 6% by mass, and further preferably 1% by mass to 5% by mass.

From the viewpoint of peeling characteristics or sensitivity of the photosensitive resin layer, resolution, and adhesion, the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer.
Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin and 1- (4- (benzoxazole-2-yl)). Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -Phenylzoline, 1-Phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -Pyrazolin, 1-Phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl) Phenyl) -Phenylzoline, 1-Phenyl-3- (4-methoxystyryl) -5- (4-Methenylphenyl) -Pyrazolin, 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) -pyrazolin, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazolin, 1-phenyl-3- (2) 3-Dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazolin, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazolin and the like are described above. From the viewpoint of Of 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 property and / or the sensitivity of the photosensitive resin layer. , More preferably in the range of 0.1% by mass to 3% by mass.

<(D) Phenolic derivative>
In the present embodiment, it is preferable that the photosensitive resin composition contains (D) a banning agent and (D) the banning agent contains a phenol derivative.
(D) Since the inhibitor contains a phenol derivative, the adhesion and resolution are very excellent even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developer.
Examples of the phenol derivative include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, and 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, styrated phenol (eg) Kawaguchi Chemical Industry Co., Ltd., tert-SP), tribenzylphenol (for example, Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), biphenol and the like are preferable. (D) Since the prohibited agent is a phenol derivative, it is preferable from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developing solution, and the same viewpoint. From 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 viewpoint, hindered phenol is preferable as the phenol derivative. Further, from the same viewpoint, it is preferable that the (D) banning agent has two or more phenol nuclei.

The ratio of the (D) inhibitor to the total solid content 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 excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment, overwashing and high temperature of the developing solution. It is more preferably 005% by mass or more, further preferably 0.01% by mass or more, further 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 more preferably 5% by mass or less in terms of less decrease in sensitivity and improvement in resolution. Is more preferable, 3% by mass or less is further preferable, 2% by mass or less is particularly preferable, and 1.5% by mass or less is most preferable.

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

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

<Additives>
The photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants and stabilizers, if desired. For example, the additives listed in JP2013-156369A may be used.
(Dyes and coloring substances)
In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluorane dyes, etc.) and coloring substances, if desired.
Examples of the coloring substance include fuchsin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.). Examples thereof include Basic Blue 20 and Diamond Green (for example, Eisen (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 mass of the photosensitive resin composition is 100% by mass. It is preferable that the content is 0.001% by mass or more from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, it is preferable to make the content 1% by mass or less 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 due to the inclusion of the dye, and when the inspection machine or the like reads the alignment marker for exposure, the exposed portion and the unexposed portion are used. The larger the contrast, the easier it is to recognize and the more advantageous it is. Preferred dyes from this viewpoint include leuco dyes and fluorane dyes.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. In particular, from the viewpoint of improving the contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.05% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. It is preferable that the content is 0.05% by mass or more 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, further preferably 0.15% by mass or more, and particularly preferably 0.2% by mass or more. On the other hand, it is preferable to reduce the content to 10% by mass or less from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with high temperature of the developing solution. From this viewpoint, the content is more preferably 2% by mass or less, further preferably 1% by mass or less, further preferably 0.6% by mass or less, and 0.5% by mass or less. It is even more preferable, it is particularly preferably 0.4% by mass or less, and most preferably 0.35% by mass or less.
Further, it is preferable to use the leuco dye in combination with the above-mentioned halogen compound in the (C) photopolymerization initiator in the photosensitive resin composition from the viewpoint of optimizing the 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 content mass of the photosensitive resin composition is 100% by 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. May be good.
Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. A nitrosophenylhydroxylamine 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, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.

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

In the present embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of the epoxy compounds of bisphenol A include compounds in which bisphenol A is modified with polypropylene glycol and the ends are epoxidized.
In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (for example, diethyl frate, etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, and triethyl acetyl citrate. Examples thereof include -n-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polyproprenene glycol alkyl ether and the like. In addition, Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (all manufactured by Asahi Denka Co., Ltd.), Nieuport BP-23P, Nieuport BP-3P, Nieuport BP-5P, New Pole BPE-20T, Nieuport BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Kasei Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples thereof include compounds having a bisphenol skeleton such as 400, Nieuport DA-700 (manufactured by Nieuport Co., Ltd.), BA-P4U glycol, and BA-P8 glycol (manufactured by Nieuport Embroidery 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 content mass of the photosensitive resin composition. It is more preferably 1% by mass to 30% by mass. It is preferable that the content is 1% by mass or more from the viewpoint of suppressing the delay of the developing time and imparting flexibility to the cured film. On the other hand, it is preferable to make the content 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow.

However, from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as overdevelopment and overwashing with water, the content of the plasticizer in the photosensitive resin composition is 10% by mass. % Or less is preferable, 5% by mass or less is more preferable, 2% by mass or less is further preferable, 1% by mass or less is particularly preferable, and 0% by mass is most preferable.

In the present embodiment, substances other than (A) an alkali-soluble polymer and (B) a compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition are other than (A) and (B). (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 (the mass of the component other than [(A) and (B)). ] / [(B) Mass of 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) Since the content of the component not incorporated into the crosslinked structure can be reduced with respect to the content of the compound having an ethylenically unsaturated bond, the temperature of the developing solution is extremely high due to overdevelopment and overwashing. It is preferable from the viewpoint of excellent adhesion and resolution even under harsh 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 preferable that it is 0.170 or less, and it may be 0.165 or less, or it may be 0.160 or less.
The lower limit is not limited, but this value may be 0.005 or more, 0.010 or more, 0.030 or more, or 0.050 or more. You may.

In the present embodiment, the ratio of the mass of the (A-1) alkali-soluble polymer to the mass of the (B) compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition ([(A). -1) Mass of alkali-soluble polymer] / [(B) 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 (A-1) alkali-soluble polymer having an I / O value of 0.200 to 0.560 is large, and the hydrophobicity of the photosensitive resin composition is enhanced. (B) Since the content of the compound having an ethylenically unsaturated bond is relatively small, it is possible to suppress the curing shrinkage when the photosensitive resin composition is cured, resulting in overdevelopment and overdevelopment. It is preferable from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as high water washing and high temperature of the developing solution. From the same viewpoint, it is more preferably 0.550 or more, more preferably 0.580 or more, further preferably 0.600 or more, further preferably 0.620 or more, and 0. It is particularly preferably .650 or more, particularly preferably 0.680 or more, and most preferably 0.700 or more. The upper limit is not particularly limited, but 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 of (A) the content of the alkali-soluble polymer to the content of (B) the compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition ([( A) Content of alkali-soluble polymer] / [(B) Content of compound having ethylenically unsaturated bond]) is preferably 5.00 or less. When it is 5.00 or less, it is preferable from the viewpoint of the flexibility of the cured film, from the same viewpoint, it is more preferably 4.00 or less, more preferably 3.00 or less, and preferably 2.00 or less. Further preferably, it is particularly preferably 1.800 or less, and most preferably 1.600 or less. The lower limit is not particularly limited, but this value may be 0.200 or more, 0.300 or more, or 0.500 or more.

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

<Photosensitive resin laminate>
In the present embodiment, it is possible to provide a photosensitive resin laminate having a support and a photosensitive resin layer made of the above-mentioned photosensitive resin composition laminated on the support. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer.
The support is not particularly limited, but a transparent one that transmits light emitted from an exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, and a polymethylmethacrylate copolymer film. Examples thereof include polystyrene films, polyvinylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films may be stretched if necessary.
The support film preferably has a haze of 5% or less, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less, from the viewpoint of suppressing light scattering during exposure. preferable. From the same viewpoint, 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. The thinner the film, the more advantageous it is to improve the image forming property and the economic efficiency. However, in order to maintain the strength of the photosensitive resin laminate, a film having a thickness of 10 μm to 30 μm is preferably used.

Further, the support film may have a single-layer structure or may have a multi-layer structure in which resin layers formed of a plurality of compositions are laminated. In the case of a multi-layer structure, there may be an antistatic layer. In the case of a multi-layer 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 fine particles are formed on the other surface B as in (1) surface A. , (2) contains a smaller amount of fine particles than the surface A, (3) contains fine particles finer than the surface A, and (4) contains no fine particles. In the case of the 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 that there is a resin layer containing fine particles on the surface A side from the viewpoint of slipperiness of the film and the like. The fine particles are, for example, inorganic fine particles or organic fine particles, and include lubricants, lubricants, aggregates of additives, foreign substances mixed in raw materials, foreign substances mixed in the manufacturing process, and the like. The size of the fine particles at this time is preferably less than 5 μm, more preferably less than 3 μm, still more preferably less than 2 μm, and particularly preferably less than 1.5 μm from the viewpoint of improving the resolution and the accuracy of the resist pattern. The support film is FB-40 (manufactured by Toray Industries, Inc.), QS65 (manufactured by Toray Industries, Inc.), 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 preferable, FB-40 and QS68 are more preferable, and QS68 is even more preferable.

Further, an important property of the protective layer used in the photosensitive resin laminate is that the protective layer has a smaller adhesion 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 peelability 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 fisheye may be present on the surface of the polyethylene film. When a polyethylene film having fish eyes is used as a protective layer, the fish eyes may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be entrained during laminating to form a void, which leads to a defect in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is preferable as the material of the protective layer. As a specific example, Alfan E-200A manufactured by Oji Paper Co., Ltd. can be mentioned.

In the present 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 smaller the thickness of the photosensitive resin layer, the better the resolution of the resist pattern, while the larger the thickness, the stronger the cured film, so that it can be selected according to the application.
As a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and, if desired, a protective layer, a known method may be used.
For example, the above-mentioned photosensitive resin composition formulation is prepared, then applied onto the support using a bar coater or a roll coater and dried, and the photosensitive resin composed of the photosensitive resin composition formulation is applied onto the support. Laminate the layers. Further, 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 for manufacturing a resist pattern using the photosensitive resin laminate of the present 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 an unexposed portion of the photosensitive resin layer. Can be included. Examples of the resist pattern include a printed wiring board, a semiconductor element, a printed plate, a liquid crystal display panel, a flexible substrate, a lead frame substrate, a COF (chip-on-film) substrate, a semiconductor package substrate, a transparent electrode for liquid crystal, and a TFT for liquid crystal. Patterns such as wiring for touch panels, wiring for touch panels, and electrodes for PDPs (plasma display panels) can be mentioned. As an example, a method of manufacturing a printed wiring board will be described as follows.

The printed wiring board is manufactured through the following steps.
(1) Laminating Step First, in the laminating 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-bonded to the substrate surface with a laminator and laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO) and the like.
In the present embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides if necessary. The heating temperature at the time of laminating is generally 40 ° C to 160 ° C. Further, by performing the heat crimping at the time of laminating twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of heat crimping, a two-stage laminator provided with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly crimped several times through the rolls. Further, it may be crimped using a vacuum laminator.
(2) Exposure step In this step, an exposure method in which a mask film having a desired wiring pattern is brought into close contact with a support layer and an active light source is used, an exposure method in which a drawing pattern which is a desired wiring pattern is directly drawn, or an exposure method is performed. The photosensitive resin layer is exposed by an exposure method in which an image of a photomask is projected through a lens.
(3) Development step In this step, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to develop 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 characteristics 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 about 20 ° C to about 40 ° C is preferable.

A resist pattern can be obtained through each of the above steps (1) to (3). After these steps, if necessary, a heating step of about 100 ° C. to about 300 ° C. can be further performed. By carrying out this heating step, it is possible to further improve the chemical resistance. For heating, a hot air, infrared ray, or far infrared ray type heating furnace can be used. Further, this heating step may be performed after the exposure step.

(4) Etching step or plating step The surface of the substrate exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to manufacture a conductor pattern.
(5) Peeling Step After that, the resist pattern is peeled off from the substrate with an aqueous solution having a stronger alkalinity than the developing solution. The alkaline aqueous solution for peeling 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 be added to the stripping solution.
The photosensitive resin laminate of the present embodiment includes a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, a transparent electrode for a liquid crystal display, a TFT wiring for a liquid crystal display, a wiring for a touch panel, and an electrode for a PDP. It is a photosensitive resin laminate suitable for manufacturing a conductor pattern such as.
Unless otherwise specified, the above-mentioned various parameters are measured according to the measurement method in the examples described later or a method understood by those skilled in the art to be equivalent thereto.

Next, the present embodiment will be described more specifically with reference to Examples and Comparative Examples. However, the present embodiment is not limited to the following examples as long as it does not deviate from the gist thereof. The physical properties in the examples were measured by the following methods.
The method of measuring the physical property value of the polymer, calculating the glass transition temperature of the polymer, and preparing the evaluation samples of Examples and Comparative Examples will be described. Moreover, the evaluation method and the evaluation result about the obtained sample 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 Nippon Kogaku Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex® manufactured by Showa Denko KK) (registered trademark). KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving layer solvent: tetrahydrofuran, polystyrene standard sample (using a calibration line by Showa Denko Corporation's Chromatography STANDARD SM-105) Obtained as polystyrene conversion.
Further, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
<Acid equivalent>
As used herein, the acid equivalent means the mass (gram) of a polymer having 1 equivalent of a carboxyl group in the molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.
<Glass transition temperature Tg>
The glass transition temperature Tg of the alkali-soluble polymer is a value obtained by the Fox formula. When determining the glass transition temperature Tg, the glass transition temperature of a homopolymer composed of a comonomer forming the corresponding alkali-soluble polymer is defined as the glass transition temperature of a non-patent document (Brandrup, J. Immergut, E. H., edited by "Polymer handbook, Third". The values shown in edition, John willy & sons, 1989, p.209 Chapter VI "Glass transition temperatures of polymers") shall be used. Table 1 shows the glass transition temperature of the homopolymer composed of each comonomer used in the calculation in the examples.
When the alkali-soluble polymer is composed of two or more kinds of polymers, the value obtained by the following formula is the glass transition temperature of the alkali-soluble polymer.

_{ In the formula, Wi is the solid weight of each alkali-soluble polymer, _Tgi is the glass transition temperature obtained by the Fox formula of each alkali-soluble polymer, and W _total is the alkali-soluble of each. It 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 preparing an evaluation sample The evaluation sample was prepared as follows.
<Manufacturing of photosensitive resin laminate>
The components shown in Table 1 below (however, the numbers of each component indicate the blending amount (parts by mass) as a solid content) and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition preparation solution. rice field. The names of the components represented by abbreviations in Table 1 are shown in Table 2 below. A 16 μm-thick polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) was used as a support film, and this formulation was uniformly applied to the surface of the film using a bar coater. It was dried for a minute to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 20 μm.
Next, a 19 μm-thick polyethylene film (manufactured by Tamapoli Co., Ltd., GF-818) was bonded as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated. A laminate was obtained.
<Board surface preparation>
As an image quality evaluation substrate, a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil is jetted with a grinding agent (manufactured by Uji Denka Kogyo Co., Ltd., # 400) at a spray pressure of 0.2 MPa. After scrubbing, the surface of the substrate was washed with a 10 mass% H ₂ SO ₄ aqueous solution.
<Laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was placed on a copper-clad laminate preheated to 50 ° C by using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). Laminated at a roll temperature of 105 ° C. The air pressure was 0.35 MPa and the laminating speed was 1.5 m / min.
<Exposure>
An evaluation substrate 1 hour after laminating was exposed to i-line monochromatic light by a projection exposure machine (UX2003 SM-MS04 manufactured by Ushio, Inc., using an i-line bandpass filter) through a glass mask. The exposure amount was from 100 mJ / cm ² to 350 mJ / cm ² in 10 mJ / cm ² increments with a plurality of exposure amounts.
<Development>
After peeling off the polyethylene terephthalate film (support layer), a 1% by mass Na ₂ CO ₃ aqueous solution at 32 ° C. is sprayed over a predetermined time using an alkaline developing machine (manufactured by Fuji Kiko, a developing machine for dry film) to develop. Was done. The time of the developing spray was set to 3 times the shortest developing time, and the time of the washing spray after developing was set to 8 times the shortest developing time. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved was defined as the shortest development time. The general development conditions are 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C., the development spray time is twice the shortest development time, and the washing spray time after development is twice the shortest development time. Since it is time, the development conditions of this embodiment are extremely harsh conditions.

<Image quality evaluation-1>
The resist line width of the pattern of the mask pattern L / S = 6 μm / 10 μm at the minimum exposure amount capable of normally forming the pattern of the mask pattern L / S = 4 μm / 12 μm was measured by an optical microscope. This measurement was performed on five lines, and the average value of the five line widths was obtained. Since the resist line width is narrower than the space width in this pattern, the evaluation is strict due to the adhesion of the cured resist.
<Image quality evaluation-2>
The resist line width of the pattern of the mask pattern L / S = 6 μm / 10 μm at the minimum exposure amount at which the pattern of the mask pattern L / S = 5 μm / 11 μm can be normally formed was measured by an optical microscope. This measurement was performed on five lines, and the average value of the five line widths was obtained. Since the resist line width is narrower than the space width in this pattern, the evaluation is strict due to the adhesion of the cured resist.
<Image quality evaluation-3>
The resist line width of the pattern of the mask pattern L / S = 6 μm / 10 μm at the minimum exposure amount capable of normally forming the pattern of the mask pattern L / S = 6 μm / 10 μm was measured by an optical microscope. This measurement was performed on five lines, and the average value of the five line widths was obtained. Since the resist line width is narrower than the space width in this pattern, the evaluation is strict due to the adhesion of the cured resist.
Of the image quality evaluations -1 to 3, the image quality evaluation -1 is the strictest evaluation for the adhesion of the cured resist.
<Image quality evaluation-4>
In the mask pattern (L: S = 1: 1) in which the widths of the exposed portion and the unexposed portion were 1: 1 the minimum mask line width in which the cured resist line was normally formed was obtained as the resolution value. This pattern requires both the adhesion of the cured resist and the resolution loss property of the space portion.
In the cured resist pattern, there is no residual resist on the surface of the substrate in the unexposed portion and the surface of the substrate is exposed, the cured resist does not meander, and there are no protrusions of resist components from the cured resist, and the resist is normally formed. The cured resist pattern was evaluated.

From the results of Tables 1 and 2, it was confirmed that in the examples within the scope of the constituent requirements of the present invention, the image quality evaluation results were superior to those in the comparative examples outside the scope of the present invention. ..
The development conditions of this embodiment are extremely harsh. For example, under the above-mentioned general development conditions, the compositions of Example 4 and Example 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 harsh development conditions of this example, neither the composition of Example 4 nor the composition of Example 5 can normally form a pattern of 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 normally formed in Example 4, but it can be seen that it was normally formed in Example 5. Further, in the mask pattern of L: S = 1: 1 in <Image quality evaluation-4>, the minimum resolution of each of the compositions of Examples 4 and 5 is 6 μm under the above-mentioned general development conditions. However, under the extremely harsh development conditions of this example, as can be seen from Table 1, Example 4 was 7 μm and Example 5 was 6.5 μm.
Similarly, under the above-mentioned general development conditions, the compositions of Example 6 and Comparative Example 3 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. We were able to. On the other hand, under the extremely harsh development conditions of this example, neither the composition of Example 6 nor the composition of Comparative Example 3 can normally form a pattern of 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 normally formed in Comparative Example 3, but it can be seen that it was normally formed in Example 6. Further, in the mask pattern of L: S = 1: 1 in <Image quality evaluation-4>, the minimum resolution of each of the compositions of Example 6 and Comparative Example 3 was 5 μm under the above-mentioned general development conditions. However, under the extremely harsh development conditions of this example, as can be seen from Table 1, Example 6 was 5.5 μm and Comparative Example 3 was 8 μm.
That is, even if the adhesion and resolution are good under the development conditions of general development time and washing time, the extremely severe development conditions that the temperature of the developer is high due to the overdevelopment and overwashing of the present invention. However, the present invention does not mean that the adhesion and the resolution are improved, but the present invention can improve the adhesion and the resolution even under the severe development conditions for the first time.

By using the photosensitive resin composition of the present invention, when a pattern is formed by an etching method or a plating method, the mask line width reproducibility is good, and there are no problems such as short circuit defect, chipping, wire breakage, and plating defect. Fine circuits can be formed.
Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

Since the photosensitive resin composition of the present invention has good adhesion and resolution even under harsh development conditions such as overdevelopment, overwashing, and high temperature of the developing solution, the density of wiring is increasing more and more. However, when a pattern is formed by an etching method or a plating method, it is possible to form a high-definition circuit having good mask line width reproducibility and having no problems such as short circuit defect, chipping, wire breakage, and plating defect. Therefore, the photosensitive resin composition includes a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip-on-film) substrate, a semiconductor package substrate, a transparent electrode for a liquid crystal display, a TFT wiring for a liquid crystal display, and a wiring for a touch panel. It can be suitably used for manufacturing conductor patterns such as electrodes for PDPs (plasma display panels).

Claims (30)

(A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated bond;
(C) Photopolymerization initiator; and (D) Prohibition agent;
A photosensitive resin composition containing
The photosensitive resin composition comprises a (A-1) alkali-soluble polymer having an I / O value of 0.200 to 0.560 among the (A) alkali-soluble polymers in the photosensitive resin composition. It was obtained by mixing 5% by mass or more with respect to the total solid content mass of the above.
The I / O value is a value calculated by proportionally dividing the I / O value of the comonomer of the alkali-soluble polymer by the mass ratio of the charged comonomer, and the (D) banning agent contains a phenol derivative. ,
Substances other than the (A) alkali-soluble polymer and the (B) compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
The ratio of the total mass of the components (C) and (D) other than the components (A) and (B) to the mass of the compound having the ethylenically unsaturated bond (B) is 0. A photosensitive resin composition characterized by being 190 or less. 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 compound having the (B) ethylenically unsaturated bond is 0.500 or more. The (A-1) alkali-soluble polymer contains 21% by mass of the constituent unit derived from (meth) acrylic acid based on the total mass of all the monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition according to claim 1 or 2, which comprises ~ 29% by mass. The photosensitive resin composition according to any one of claims 1 to 3, wherein the glass transition temperature Tg of the (A-1) alkali-soluble polymer is 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 compound having an ethylenically unsaturated bond (B) is 5.0 or less. Composition. (A) Alkali-soluble polymer;
(B) A compound having an ethylenically unsaturated bond;
(C) Photopolymerization initiator; and (D) Prohibition agent;
A photosensitive resin composition containing
The photosensitive resin composition comprises a (A-1) alkali-soluble polymer having an I / O value of 0.200 to 0.560 among the (A) alkali-soluble polymers in the photosensitive resin composition. It was obtained by mixing 5% by mass or more with respect to the total solid content mass of the above.
The I / O value is a value calculated by proportionally dividing the I / O value of the comonomer of the alkali-soluble polymer by the mass ratio of the charged comonomer.
The (A-1) alkali-soluble polymer contains 21% by mass of the structural unit derived from (meth) acrylic acid based on the total mass of all the monomer components constituting the (A-1) alkali-soluble polymer. Including ~ 29% by mass,
The (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128 ° C. or lower.
The (D) banning agent contains a phenol derivative and contains
Substances other than the (A) alkali-soluble polymer and the (B) compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition were used as components other than (A) and (B). sometimes,
The ratio of the total mass of the components (C) and (D) other than the components (A) and (B) to the mass of the compound having the 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 compound having the (B) ethylenically unsaturated bond is 0.500 or more, and the compound having the (B) ethylenically unsaturated bond. A photosensitive resin composition, wherein the ratio of the mass of the (A) alkali-soluble polymer to the mass of (A) is 5.0 or less. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (C) photopolymerization initiator contains hexaarylbiimidazole. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (C) photopolymerization initiator contains a pyrazoline compound. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (C) photopolymerization initiator contains an anthracene compound. The photosensitive resin composition according to any one of claims 1 to 9, wherein the (C) photopolymerization initiator contains aromatic ketones. The invention according to any one of claims 1 to 10, wherein the (C) photopolymerization initiator comprises at least one selected from acridins, N-aryl amino acids or ester compounds thereof, halogen compounds, and coumarin compounds. Photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 11, further comprising a leuco dye. The photosensitive resin composition according to claim 12, wherein the content of the leuco dye is 0.05% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. The photosensitive resin according to any one of claims 1 to 13, wherein the content of the alkali-soluble polymer (A) is 30% by mass or more with respect to the total solid content mass of the photosensitive resin composition. Composition. The photosensitive resin composition according to claim 14, wherein the content of the alkali-soluble polymer (A) is 40% by mass or more with respect to the total solid content mass of the photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 15, wherein the prohibited agent (D) contains hindered phenol. The photosensitive resin composition according to any one of claims 1 to 16, wherein the prohibited agent (D) contains p-methoxyphenol. The photosensitive resin composition according to any one of claims 1 to 17, wherein the prohibited agent (D) contains 2,6-di-tert-butyl-p-cresol. The photosensitive agent according to any one of claims 1 to 18, wherein the (D) inhibitor comprises triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate. Sex resin composition. The photosensitive resin composition according to any one of claims 1 to 19, wherein the prohibited agent (D) contains 4,4'-butylidenebis (3-methyl-6-tert-butylphenol). The photosensitive resin composition according to any one of claims 1 to 20, wherein the prohibited agent (D) contains catechol. The photosensitive resin composition according to any one of claims 1 to 21, wherein the banning agent (D) contains tert-butylcatechol. The photosensitive resin composition according to any one of claims 1 to 22, wherein the banning agent (D) contains 2,5-di-tert-butylhydroquinone. The photosensitive resin composition according to any one of claims 1 to 23, wherein the prohibited agent (D) contains biphenol. The photosensitive resin composition according to any one of claims 1 to 24, wherein the prohibited agent (D) has two or more phenol nuclei. The (A-1) alkali-soluble polymer has a (meth) acrylic acid alkyl ester (the number of carbon atoms of the alkyl is based on the total mass of all the monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition according to any one of claims 1 to 25, which comprises 1% by mass to 20% by mass of the constituent units derived from (4 or more). The photosensitive resin composition according to any one of claims 1 to 26, wherein the compound having the (B) ethylenically unsaturated bond contains a (meth) acrylate compound having 6 or more ethylenically unsaturated bonds. .. A photosensitive resin laminate obtained by laminating a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 27 on a support layer. The following steps:
Laminating step of laminating the photosensitive resin laminate according to claim 28 on a substrate;
An exposure step for exposing the photosensitive resin layer in the photosensitive resin laminate; and a developing step for developing and removing an unexposed portion of the photosensitive resin layer;
A method for forming a resist pattern, including. The following steps:
Laminating step of laminating the photosensitive resin laminate according to claim 28 on a substrate;
An exposure step for 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 conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling off the resist pattern;
Manufacturing method of wiring board including.