JP2018136531A - 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

Description

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

For electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used to mount components, semiconductors, and the like. As a resist for production of printed wiring boards and the like, conventionally, a photosensitive resin laminate comprising a photosensitive resin layer laminated on a support film, and further a protective film laminated on the photosensitive resin layer as necessary, A so-called dry film photoresist (hereinafter sometimes referred to as DF) is used. Currently, the photosensitive resin layer is generally of an alkali development type using a weak alkaline aqueous solution as a developer. In order to manufacture a printed wiring board or the like using DF, for example, the following steps are performed. When DF has a protective film, the protective film is first peeled off. Thereafter, DF is laminated on a permanent circuit fabrication substrate such as a copper clad laminate or a flexible substrate using a laminator or the like, and exposure is performed through a wiring pattern mask film or the like. Next, if necessary, the support film is peeled off, and a photosensitive resin layer of an uncured portion (for example, an unexposed portion in a negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (hereinafter simply referred to as a resist pattern) (Sometimes called a resist pattern).
After forming the resist pattern, the process of forming a circuit is roughly divided into two methods. The first method is a method in which a substrate surface not covered with a resist pattern (for example, a copper surface of a copper clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than a developer (etching method). It is. In the second method, the substrate surface is plated with copper, solder, nickel, tin, etc., and then the resist pattern portion is removed in the same manner as in the first method. This is a method (plating method) for etching a copper surface of a copper-clad laminate. For etching, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used. In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have progressed, and high adhesion, high resolution, and good line width reproduction in the above manufacturing process. There is a need for a high-performance DF that imparts properties and the like. As a technique for realizing 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. .

JP 2010-249844 A

However, in recent years, with the reduction in size and weight of electronic devices such as mobile phones and tablets, there has been an increasing demand for miniaturization of wiring intervals in printed wiring boards. In order to meet such demands for miniaturization, demands such as high adhesion to DF, high resolution, and good line width reproducibility are becoming increasingly severe. Furthermore, in order to achieve high resolution, there are increasing cases of severe development conditions for the purpose of eliminating resist residues on the surface of the substrate, and it has become very difficult to achieve high adhesion of DF. The technique described in Patent Document 1 still has room for improvement from this viewpoint.
Accordingly, the present invention provides a photosensitive resin composition that is excellent in adhesion and resolution even under severe development conditions such as over-development, over-washing, and high-temperature developer, and a method for forming a resist pattern and a wiring board using the same. It is an object to provide a manufacturing method.

The inventor conducted intensive studies and experiments in order to solve the above problems. As a result, the inventors have found that the following technical means can solve the problem.
That is, the present invention is as follows.
[1]
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond;
(C) a photopolymerization initiator; and (D) an inhibitor;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an I / O value of 0.200 to 0.560. (A-1) The alkali-soluble polymer is 5 with respect to the total solid mass in the photosensitive resin composition. And (D) the inhibitor contains a phenol derivative,
Substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition are components other than (A) and (B). sometimes,
The ratio of the mass of components other than said (A) and (B) with respect to the mass of the compound which has the said (B) ethylenically unsaturated bond is 0.190 or less, The photosensitive resin composition characterized by the above-mentioned.
[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 (B) having an ethylenically unsaturated bond is 0.500 or more. .
[3] The (A-1) alkali-soluble polymer is a structural unit derived from (meth) acrylic acid based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition as described in [1] or [2] containing 21 mass%-29 mass%.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the glass transition temperature Tg of the (A-1) alkali-soluble polymer is 128 ° C. or lower.
[5] The ratio of the mass of the (A) alkali-soluble polymer to the mass of the compound (B) having an ethylenically unsaturated bond is 5.0 or less, according to any one of [1] to [4]. Photosensitive resin composition.
[6]
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator;
(D) Inhibitor;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an I / O value of 0.200 to 0.560. (A-1) The alkali-soluble polymer is 5 with respect to the total solid mass in the photosensitive resin composition. Including mass% or more,
The (A-1) alkali-soluble polymer has 21% by mass of a structural unit derived from (meth) acrylic acid, based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. Containing ~ 29 mass%,
The (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128 ° C. or lower, and the (D) inhibitor contains a phenol derivative,
Substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition are components other than (A) and (B). sometimes,
The ratio of the mass of components other than (A) and (B) to the mass of the compound (B) having an ethylenically unsaturated bond is 0.190 or less,
The ratio of the mass of the (A-1) alkali-soluble polymer to the mass of the compound (B) having an ethylenically unsaturated bond is 0.500 or more, and (B) the compound having an ethylenically unsaturated bond The ratio of the mass of the (A) alkali-soluble polymer to the mass of the photosensitive resin composition is 5.0 or less.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the (C) photopolymerization initiator includes hexaarylbiimidazole.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (C) photopolymerization initiator includes a pyrazoline compound.
[9] The photosensitive resin composition according to any one of [1] to [8], wherein the (C) photopolymerization initiator includes an anthracene compound.
[10] The photosensitive resin composition according to any one of [1] to [9], wherein the (C) photopolymerization initiator includes an aromatic ketone.
[11] Any of [1] to [10], wherein (C) the photopolymerization initiator includes at least one selected from acridines, N-arylamino acids or ester compounds thereof, halogen compounds, and coumarin compounds. The photosensitive resin composition as described in 2.
[12] The photosensitive resin composition according to any one of [1] to [11], further comprising a leuco dye.
[13] The photosensitive resin composition according to [12], wherein the content of the leuco dye is 0.05% by mass to 10% by mass with respect to the total solid mass in the photosensitive resin composition.
[14] The content of the (A) alkali-soluble polymer is 30% by mass or more based on the total solid 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 (A) alkali-soluble polymer is 40% by mass or more with respect to the total solid mass in the photosensitive resin composition.
[16] The photosensitive resin composition according to any one of [1] to [15], wherein the (D) inhibitor includes a hindered phenol.
[17] The photosensitive resin composition according to any one of [1] to [16], wherein the (D) inhibitor includes p-methoxyphenol.
[18] The photosensitive resin composition according to any one of [1] to [17], wherein the (D) inhibitor includes 2,6-di-tert-butyl-p-cresol.
[19] In any one of [1] to [18], the (D) inhibitor includes triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate. The photosensitive resin composition as described.
[20] The photosensitive resin composition according to any one of [1] to [19], wherein the (D) inhibitor comprises 4,4′-butylidenebis (3-methyl-6-tert-butylphenol).
[21] The photosensitive resin composition according to any one of [1] to [20], wherein the (D) inhibitor includes catechol.
[22] The photosensitive resin composition according to any one of [1] to [21], wherein the (D) inhibitor includes tert-butylcatechol.
[23] The photosensitive resin composition according to any one of [1] to [22], wherein the (D) inhibitor includes 2,5-di-tert-butylhydroquinone.
[24] The photosensitive resin composition according to any one of [1] to [23], wherein the (D) inhibitor includes biphenol.
[25] The photosensitive resin composition according to any one of [1] to [24], wherein the (D) inhibitor has two or more phenol nuclei.
[26] The (A-1) alkali-soluble polymer is based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition in any one of [1]-[25] containing 1 mass%-20 mass% of structural units derived from C4 or more.
[27] The photosensitive compound according to any one of [1] to [26], wherein the compound (B) having an ethylenically unsaturated bond includes 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:
A laminating step of laminating the photosensitive resin laminate according to [28] on a substrate;
An exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate; and a development step of developing and removing an unexposed portion of the photosensitive resin layer;
A method for forming a resist pattern, comprising:
[30]
The following steps:
A laminating step of laminating the photosensitive resin laminate according to [28] on a substrate;
An exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate;
A development 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 the substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern;
A method of manufacturing a wiring board including:

  According to the present invention, there are provided a photosensitive resin composition and a photosensitive resin laminate that have good adhesion and resolution even under severe development conditions such as over-development, over-washing, and high-temperature developer. A method for forming a resist pattern and a method for forming a conductor pattern using a conductive resin laminate can be provided. As a result, even when the wiring density is increasing, the mask line width reproducibility is good when the pattern is formed by the etching method or plating method, and problems such as short-circuit failure, chipping, disconnection, plating failure, etc. High definition circuit can be formed.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. In addition, unless otherwise specified, various measured values in the present specification are based on 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. Measured.

[Photosensitive resin composition]
In the present embodiment, the photosensitive composition includes (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; and (D) a photosensitive agent containing an inhibitor. The resin composition, wherein the alkali-soluble polymer (A) has an I / O value of 0.200 to 0.560. (A-1) The alkali-soluble polymer has a solid content in the photosensitive resin composition. A substance other than (A) an alkali-soluble polymer and (B) a compound having an ethylenically unsaturated bond (B) containing a phenol derivative and containing (P) a phenol derivative and containing (B) an ethylenically unsaturated bond. When the component other than (A) and (B) is used, the ratio of the mass of the component other than (A) and (B) to the mass of the compound (B) having an ethylenically unsaturated bond ([(A) and ( B) Mass other than components] / [(B) ethylenically unsaturated bond Mass] with referred to compounds having) is 0.190 or less. Components other than (A) and (B) refer to substances obtained by removing (A) an alkali-soluble polymer and (B) a compound having an ethylenically unsaturated bond from the solid content.
Hereinafter, each component will be described in order.

<(A) Alkali-soluble polymer>
In the present disclosure, the (A) alkali-soluble polymer contains (A-1) an alkali-soluble polymer having an I / O value of 0.200 to 0.560 in an amount of 5% by mass or more based on the total solid content.
The I / O value is a value obtained by organically treating the polarity of various organic compounds, also called (inorganic value) / (organic value), and is a functional group contribution method in which parameters are set for each functional group. One. As the I / O value, in detail, non-patent literature (Organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, No. 1-16 (1954)); Region, Vol. 11, No. 10, 719-725 (1957); Fragrance Journal, No. 34, 97-111 (1979); Fragrance Journal, No. 50, 79-82 (1981) Year)); and the like.
The concept of the I / O value is a straight line in which the properties of a compound are divided into an organic group representing a covalent bond and an inorganic group representing an ionic bond, and all organic compounds are named as an organic axis and an inorganic axis. Each point on the coordinates is shown. The closer the I / O value is to 0, the more non-polar (hydrophobic and organic) organic compounds are, and the larger the I / O value is, the more polar (hydrophilic and inorganic) organic compounds are. Show.

  (A-1) The I / O value of the alkali-soluble polymer is 0.200 to 0.560. When the I / O value is 0.200 to 0.560, adhesion and resolution are excellent even under extremely severe development conditions such as overdevelopment and overwashing and the temperature of the developer is high. 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 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 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 making the I / O value low and making it hydrophobic, high adhesion and high resolution can be realized even under severe development conditions. On the other hand, if the I / O value is too low, the minimum development time is too long. As a result, since the development conditions become more severe, 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 severe development conditions such as over-development and over-washing and high developer temperature, (A-1) containing 5% by mass or more of the alkali-soluble polymer based on the total solid content Preferably 8% by weight or more, more preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 30% by weight. % 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 the examples described later. By using an alkali-soluble polymer (A-1) having a Tg of 128 ° C. or lower in the photosensitive resin composition, the adhesive composition can be adhered even under extremely severe development conditions such as over-development and over-washing and high developer temperature. Excellent in resolution 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 less, and most preferably 100 ° C. or less. In addition, (A-1) Tg of the alkali-soluble polymer is preferably 30 ° C. or higher from the viewpoint of improving edge fuse resistance. In this respect, 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 excellent in adhesion and resolution in normal development is not necessarily a photosensitive resin composition excellent in adhesion and resolution even under severe development conditions. In this embodiment, from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and the temperature of the developer is high, (A-1) aromatic carbonization as an alkali-soluble polymer. It is preferable that 52 mass% or more of the structural unit of the monomer component having a hydrogen group is contained. Examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. From the same viewpoint, as a monomer component having an aromatic hydrocarbon group Is a monomer having a substituted or unsubstituted benzyl group (for example, benzyl (meth) acrylate), a styrene derivative (for example, styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid) Styrene dimer, styrene trimer, etc.), styrene derivatives are more preferable, and styrene is particularly preferable. (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 based on the total mass of all monomer components, and 55% by mass. % Or more, more preferably 57% by weight or more, particularly preferably 58% by weight or more, and most preferably 60% by weight or more. Although it does not specifically limit as an upper limit, Preferably it is 95 mass% or less, More preferably, it is 80 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 monomer components. It is more preferably 57% by mass or more, particularly preferably 58% by mass or more, and most preferably 60% by mass or more. Although it does not specifically limit as an upper limit, Preferably it is 95 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.
The (A-1) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group includes at least one of a monomer having an aromatic hydrocarbon group and a first monomer described later, and It is preferably obtained by polymerizing at least one of the second monomers described below.

The (A) alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below. More preferably, it is obtained by copolymerizing at least one monomer and at least one second monomer described below.
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 anhydride, maleic acid half ester, and the like. Among these, (meth) acrylic acid is preferred, and methacrylic acid is more preferred from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment and overwashing and a high developer temperature.
In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acryloyl group” means acryloyl group or methacryloyl group, and “(meth) acrylate” "Means" acrylate "or" methacrylate ".

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. Setting the copolymerization ratio to 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and the temperature of the developer is high, and is 15% by mass or more. Is more preferably 18% by mass or more, more preferably 21% by mass or more, particularly preferably 23% by mass or more, and particularly preferably 24% by mass or more. Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and high developer temperature, and 35% by mass or less. Is more preferably 30% by mass or less, more preferably 29% by mass or less, particularly preferably 27% by mass or less, and most preferably 26% by mass or less.
The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylates such as 2-ethylhexyl (meth) acrylate; vinyl acetate And vinyl alcohol esters; and (meth) acrylonitrile. Among these, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable.

  As the second monomer, (A-1) the alkali-soluble polymer contains 1 to 20% by mass of a structural unit derived from (meth) acrylic acid alkyl ester (alkyl having 4 or more carbon atoms). It is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and the developer temperature is high. From this viewpoint, it is more preferably 3% by mass or more, further preferably 5% by mass or more, more preferably 15% by mass or less, still more preferably 10% by mass or less, The content 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 I / O value and the copolymerization ratio of the first monomer are within the numerical ranges, and are appropriately determined depending on the purpose. Although it can select, For example, Preferably it is 100-600, More preferably, it is 250-450. The acid equivalent means 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 severe development conditions such as overdevelopment and overwashing and the developer temperature is high. . 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 using a potentiometric titrator and titrating with a 0.1 mol / L NaOH aqueous solution.

(A-1) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and a high developer temperature. More preferably, it is more preferably 60,000 or less, more preferably 50,000 or less, particularly preferably 40,000 or less, and 30,000 or less. Is most preferred. From the same 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 further more preferable and it is especially preferable that it is 1.0-3.0.
(A) The alkali-soluble polymer can be used alone or in combination of two or more.

(A) The synthesis of the alkali-soluble polymer is carried out by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc., and adding benzoyl peroxide, azoisobutyronitrile, etc. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As 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 mass of the photosensitive resin composition may be 10% by mass or more, 20% by mass or more, and 25% by mass or more. May be 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, and 50% by mass or more. May be 55 mass% or more, and may be 60 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.
Setting the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition to 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, it is preferable from the viewpoint of improving edge fuse resistance that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition be 10% by mass or more.

<(B) Compound having an ethylenically unsaturated double bond>
(B) The compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth) acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) an alkali-soluble polymer. (B) The number of ethylenically unsaturated bonds in the compound may be one or more.
As the compound (B) having one ethylenically unsaturated bond, for example, a compound obtained by adding (meth) acrylic acid to one end of polyalkylene oxide, or (meth) acrylic at one end of polyalkylene oxide A compound in which an acid is added and the other end is alkyl etherified or allyl etherified, a phthalic acid compound, and the like can be mentioned, which is preferable from the viewpoint of peelability and cured film flexibility. In addition to the above viewpoint, the compound (B) having one ethylenically unsaturated bond is preferably a methacrylate compound from the viewpoints of sensitivity, resolution, and adhesion.
As such a compound, 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-Normal nonylphenoxyheptaethylene glycol dipropylene glycol, which is a (meth) acrylate of a compound in which polypropylene glycol added with an average of 2 mol of propylene oxide and polyethylene glycol added with an average of 7 mol of ethylene oxide is added to nonylphenol. (Meth) acrylate,
4-Normal nonylphenoxypentaethylene glycol monopropylene glycol, which is a (meth) acrylate of a compound in which polypropylene glycol added with an average of 1 mol of propylene oxide and polyethylene glycol added with an average of 5 mol of ethylene oxide is added to nonylphenol. 4- (normal) nonylphenoxyoctaethylene glycol (meth) acrylate (for example, M-, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol added with ethylene oxide with an average of 8 moles of ethylene oxide to nonylphenol. 114).
In addition, in addition to the above viewpoints, in addition to the above viewpoint, including phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-ethyl phthalate preferable.

Examples of the compound having two ethylenically unsaturated bonds in the molecule include a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. 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, octaethylene glycol di ( Poly (ethylene glycol) (meth) acrylates such as (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of 12 mol ethylene oxide chain Other than
Examples thereof include polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate. As polyalkylene oxide di (meth) acrylate compounds containing ethylene oxide groups and propylene oxide groups in the compound, for example, an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide is added. Glycol dimethacrylate, glycol dimethacrylate with an average of 15 moles of ethylene oxide added to each end of polypropylene glycol with an average of 18 moles of propylene oxide added, FA-023M, FA-024M, FA-027M (Products) Name, manufactured by Hitachi Chemical Co., Ltd.). 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 improved resolution and adhesion. From the viewpoint, it is preferable.

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

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

For example, polyethylene glycol dimethacrylate having an average of 5 moles of ethylene oxide added to both ends of bisphenol A, and polyethylene glycol having an average of 2 moles of ethylene oxide added to both ends of bisphenol A. A dimethacrylate of polyethylene glycol having an average of 1 mole of ethylene oxide added to both ends of the dimethacrylate and bisphenol A is preferable in terms of resolution and adhesion.
Moreover, you may use the compound in which the aromatic ring in the said general formula (I) has a hetero atom and / or a substituent.

  Examples of the hetero atom include a halogen atom, and the substituent includes 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 phenacyl group. , Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C2-C10 alkylcarbonyl group, C2-C10 alkenyl group, C2-C10 - alkylcarbamoyl group or a group containing a heterocyclic ring, or an aryl group substituted by these substituents. These substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom 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.

The compound having 3 or more ethylenically unsaturated bonds in the molecule has 3 moles or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and includes an ethyleneoxy group, a propyleneoxy group, It can be obtained by using (meth) acrylate as an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group. In this case, examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and an isocyanurate ring. These compounds include tri (meth) acrylates such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (eg Trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane are preferable from the viewpoints of flexibility, adhesion, and bleed-out suppression). Tetra (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate Rate, and the like; penta (meth) acrylate, for example, dipentaerythritol penta (meth) acrylate; hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate.
As the tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. Pentaerythritol tetra (meth) acrylate may be tetra (meth) acrylate in which 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol.
Hexa (meth) acrylate is hexa (meth) acrylate in which 1 to 40 moles of ethylene oxide is added to 6 terminals of dipentaerythritol, and 1 to 20 moles of ε in total at 6 terminals of dipentaerythritol. -Hexa (meth) acrylate with added caprolactone is preferred.

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

(B) As a compound which has an ethylenically unsaturated bond, 75 mass% or more of (meth) acrylate compounds which have 2 or more of ethylenically unsaturated bonds are included in the compound which has an ethylenically unsaturated bond (B). Is preferred. Containing 75% by mass or more is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment and overwashing and the temperature of the developer is high, and from the same viewpoint, 78% by mass or more is included. More preferably, it is more preferably 81% by mass or more, more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 93% by mass or more.
The compound (B) having an ethylenically unsaturated bond preferably contains a methacrylate compound in an amount of 75% by mass or more in the compound (B) having an ethylenically unsaturated bond. Containing 75% by mass or more is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment and overwashing and the temperature of the developer is high, and from the same viewpoint, 78% by mass or more is included. More preferably, it is more preferably 81% by mass or more, more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 93% by mass or more.

The (B) compound having an ethylenically unsaturated bond includes a (meth) acrylate compound having three or more ethylenically unsaturated bonds, and is extremely severe such that the temperature of the developer is high due to over-development and washing with water. From the viewpoint of excellent adhesion and resolution even under various development conditions. From the same viewpoint, the (meth) acrylate compound having 3 or more ethylenically unsaturated bonds is preferably a (meth) acrylate compound having 3 ethylenically unsaturated bonds, and having 4 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 3 or more ethylenically unsaturated bonds, from the same viewpoint, a methacrylate compound having 3 or more ethylenically unsaturated bonds is preferable, and a methacrylate having 4 ethylenically unsaturated bonds. More preferred are compounds, more preferred are methacrylate compounds having 5 ethylenically unsaturated bonds, and particularly preferred are methacrylate compounds having 6 or more ethylenically unsaturated bonds.
As content of the (meth) acrylate compound which has 3 or more of ethylenically unsaturated bonds, it is preferable to contain 5 mass% or more in the compound which has (B) ethylenically unsaturated bond from the same viewpoint, and 10 masses. %, More preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably 30% by mass or more, and most preferably 40% by mass or more.

(B) The ratio with respect to the total solid mass of the photosensitive resin composition of the compound having an ethylenically unsaturated double bond may be 5% by mass or more, 10% by mass or more, and 20% by mass. % Or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% % Or more, or 50 mass% or more. Moreover, 70 mass% or less may be sufficient, 60 mass% or less may be sufficient, and 50 mass% or less may be sufficient.
Setting this ratio to 5% by mass or more is preferable from the viewpoints 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 delay of peeling of the edge fuse and the cured resist. More preferably, this ratio is 50% by mass or less.

<(C) Photopolymerization initiator>
(C) A 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 photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, and still more preferably 0.1% by mass. % To 7% by mass, particularly preferably in the range of 0.1% 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 sufficiently transmits light to the bottom surface of the resist to provide good high resolution. It is preferable that it is 20 mass% or less from a viewpoint of obtaining.
(C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters , Acridines (for example, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, and 9- (m-methylphenyl) acridine are preferable in terms of sensitivity, resolution, and adhesion) In addition, hexaarylbiimidazole, pyrazoline compounds, anthracene compounds (for example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9,10-diphenylanthracene have sensitivity, resolution, and adhesion properties). Point)), coumarinization Products (for example, 7-diethylamino-4-methylcoumarin is preferable in terms of sensitivity, resolution, and adhesion), N-aryl amino acids or ester compounds thereof (for example, N-phenylglycine is suitable for sensitivity, resolution, and adhesion). Preferred), and halogen compounds (for example, tribromomethylphenyl sulfone). 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-morpholinopropan-1-one, 2,4,6-trimethylbenzo Ir-diphenyl-phosphine oxide and triphenylphosphine oxide may be used.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, and 4-methoxy-4′-dimethylaminobenzophenone. be able to. These can be used alone or in combination of two or more. Among these, 4,4′-bis (diethylamino) benzophenone is particularly preferable from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3%. It is in the range of mass%.
Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5,5′-teto Kiss- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,6- Difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3 -Methoxyphenyl) -biimidazole, 2,2'-bis- 2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,5-trifluorophenyl) ) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3 -Methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole And 2,2'-bis- (2,3,4,5,6-pentaph Orophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole and the like, and these may 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, a hexaarylbisimidazole compound can be added to the photosensitive resin composition, but the content is preferably from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. It is 0.05 mass%-7 mass%, More preferably, it is 0.1 mass%-6 mass%, More preferably, it exists in the range of 1 mass%-5 mass%.

From the viewpoints of the peeling characteristics or sensitivity, resolution, and adhesion of the photosensitive resin layer, 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) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl) Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- 3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1 -Phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxy Phenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, and 1-phenyl-3- (2,4-dimethoxystyryl) -5 -(2,4-Dimethoxyphenyl) -pyrazoline and the like are preferably mentioned from the above viewpoint. Among these, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is more preferable.
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 sensitivity of the photosensitive resin layer. More preferably, it is in the range of 0.1% by mass to 3% by mass.

<(D) Phenol derivative>
In the present embodiment, the photosensitive resin composition preferably contains (D) an inhibitor, and (D) the inhibitor contains a phenol derivative.
(D) When the inhibitor contains a phenol derivative, adhesion and resolution are very excellent even under extremely severe development conditions such as overdevelopment and overwashing and the temperature of the developer is high.
As phenol derivatives, p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di -Tert-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-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) benze , Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, styrenated phenol (for example, ANTAGE SP manufactured by Kawaguchi Chemical Industry Co., Ltd.) Tribenzylphenol (for example, TBP, phenol having 1 to 3 benzyl groups), biphenol, and the like are preferable. (D) Since the inhibitor is a phenol derivative, it is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as overdevelopment and overwashing and the temperature of the developer is high, and the same viewpoint To p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4 ′ -Butylidenebis (3-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2,5-di-tert-butylhydroquinone and biphenol are more preferred. From the same viewpoint, hindered phenol is preferable as the phenol derivative. From the same viewpoint, it is preferable that the (D) inhibitor has two or more phenol nuclei.

  (D) It is preferable that the ratio with respect to the total solid content mass of the photosensitive resin composition of an inhibitor is 0.001 mass%-10 mass%. This ratio is preferably 0.001% by mass or more from the viewpoint of extremely excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and a high developer temperature. It is more preferably 005% by mass or more, further preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, this ratio is preferably 10% by mass or less, more preferably 8% by mass or less, and more preferably 5% by mass or less from the viewpoint of little sensitivity reduction and improved resolution. Is more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less.

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

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

<Additives>
The photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as desired. For example, you may use the additive currently enumerated by Unexamined-Japanese-Patent No. 2013-156369.
(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, fluoran dyes, etc.) and coloring substances, if desired.
Examples of the coloring substance include fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20 and Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) may be mentioned. 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 mass of the photosensitive resin composition is 100% by mass. The content of 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, 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 by containing a dye, and when the inspection machine reads the alignment marker for exposure, the exposed portion and the unexposed portion The higher the contrast, the easier to recognize and the more advantageous. Preferred dyes from this viewpoint include leuco dyes and fluoran dyes.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like. In particular, from the viewpoint of good contrast, it is preferable to use leuco crystal violet as the leuco dye. It is preferable that content of the leuco dye in the photosensitive resin composition is 0.05 mass%-10 mass% with respect to the total solid content mass of the photosensitive resin composition. Setting the content to 0.05% by mass or more is preferable from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. The 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 that the content is 10% by mass or less from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and high developer temperature. In this respect, 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 still more preferable to set it to 0.4 mass% or less, and it is most preferable to set it to 0.35 mass% or less.
In addition, it is preferable to use a combination of the leuco dye and the halogen compound described above in (C) the photopolymerization initiator in the photosensitive resin composition from the viewpoint of optimizing adhesion and contrast. When a 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 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. Also good.
Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxyamine aluminum salt is preferred.
Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, 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, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.

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

In the present embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the ends.
In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (eg, diethyl flate), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl citrate tri -N-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. Also, Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Pole BP-23P, New Pole BP-3P, New Pole BP-5P, New Pole Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples thereof include compounds having a bisphenol skeleton such as 400, Uniol DA-700 (manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, and BA-P8 glycol (manufactured by Nippon Emulsifier 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. More preferably, it is 1 to 30% by mass. Setting the content to 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film. On the other hand, setting the content to 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.

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

In the present embodiment, substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond, contained in the solid content in the photosensitive resin composition, other than (A) and (B) (B) Ratio of mass of components other than (A) and (B) to mass of compound having ethylenically unsaturated bond ([mass of components other than (A) and (B) ] / [(B) Mass of compound having ethylenically unsaturated bond] value is preferably 0.190 or less, and if this value is 0.190 or less, a crosslinked structure is formed. (B) Since the content of components that are not incorporated into the crosslinked structure can be reduced relative to the content of the compound having an ethylenically unsaturated bond, the temperature of the developer is extremely high due to overdevelopment and overwashing. Adhesion and even under harsh development conditions From the viewpoint of excellent resolution, it is more preferably 0.185 or less, further preferably 0.180 or less, particularly preferably 0.175 or less, and 0.170 from the same viewpoint. Most preferably, it may be 0.165 or less, or 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. May be.

  In the present embodiment, (A-1) the ratio of the mass of the alkali-soluble polymer to the mass of the compound (B) having an ethylenically unsaturated bond contained in the solid content in the photosensitive resin composition ([(A -1) The mass of the alkali-soluble polymer] / [(B) the mass of the compound having an ethylenically unsaturated bond]) is preferably 0.500 or more. When it is 0.500 or more, the I / O value is 0.200 to 0.560, indicating that the content of the alkali-soluble polymer (A-1) is large, and increasing the hydrophobicity of the photosensitive resin composition. (B) The content of the compound having an ethylenically unsaturated bond is relatively small, so that the curing shrinkage when the photosensitive resin composition is cured can be suppressed. It is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as washing with water and the temperature of the developer being high. 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, 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, may be 2.5 or less, may be 2.0 or less, or may be 1.5 or less. .

  In the present embodiment, the ratio of the content of (A) the alkali-soluble polymer to the content of (B) the compound having an ethylenically unsaturated bond contained in the solid content in the photosensitive resin composition ([( The value of (A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated bond] is preferably 5.00 or less. 5.00 or less is preferable from the viewpoint of flexibility of the cured film, and from the same viewpoint, 4.00 or less is more preferable, 3.00 or less is more preferable, and 2.00 or less is preferable. More 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 dissolved in a solvent and used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition preparation. 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. In the production of the photosensitive resin laminate, the solvent is photosensitive in such an amount that the viscosity at 25 ° C. of the photosensitive resin composition preparation applied on the support layer is 500 mPa · s to 4,000 mPa · s. It is preferable to add to the resin composition.

<Photosensitive resin laminate>
In this embodiment, the photosensitive resin laminated body which has a support body and the photosensitive resin layer which consists of the said photosensitive resin composition laminated | stacked on the support body can be provided. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer.
Although it does not specifically limit as a support body, The transparent thing which permeate | transmits the light radiated | 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, a polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary.
The support film is preferably one having a haze of 5% or less, more preferably 2% or less, still more preferably 1.5% or less, 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 is, the more advantageous it is to improve the image forming property and the economical 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.

  The support film may have a single layer structure or a multilayer structure in which resin layers formed of a plurality of compositions are laminated. In the case of a multilayer structure, there may be an antistatic layer. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one side A, and fine particles are formed on the other side B in the same manner as (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) does not contain 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, if there is a resin layer containing fine particles on the surface A side, it is preferable from the viewpoint of the slipperiness of the film. The fine particles are, for example, inorganic fine particles or organic fine particles, and include lubricants, lubricants, aggregates of additives, foreign matters mixed in raw materials, foreign matters 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 resolution and resist pattern accuracy. From the viewpoint of improving resolution and resist pattern accuracy as a polyethylene terephthalate film, the support film is FB-40 (manufactured by Toray Industries, Inc.), QS65 (manufactured by Toray Industries, Inc.), QS66 (manufactured by Toray Industries, Inc.). QS67 (manufactured by Toray Industries, Inc.) and QS68 (manufactured by Toray Industries, Inc.) are preferred, FB-40 and QS68 are more preferred, and QS68 is even more preferred.

In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. are preferable, for example. For example, a film having excellent peelability described in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.
There may be a gel called fish eye 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 lamination to form voids, leading to a defect in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is preferred as the material of the protective layer. Specific examples include Alfane E-200A manufactured by Oji Paper Co., Ltd.

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. As the thickness of the photosensitive resin layer is smaller, the resolution of the resist pattern is improved. On the other hand, the larger the thickness is, the more the strength of the cured film is improved.
A known method may be used as a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and, if desired, a protective layer.
For example, the photosensitive resin composition preparation liquid is prepared, and then coated on the support using a bar coater or a roll coater and dried, and the photosensitive resin comprising the photosensitive resin composition preparation liquid on the support. Laminate the layers. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

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

A printed wiring board is manufactured through the following steps.
(1) Laminating process First, in the laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. 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 surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature during lamination is generally 40 ° C to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained can be improved by performing the thermocompression bonding at the time of lamination twice or more. At the time of thermocompression bonding, a two-stage laminator provided with two rolls may be used, or the lamination of the substrate and the photosensitive resin layer may be repeated several times and passed through the roll. Moreover, you may crimp | bond using a vacuum laminator.
(2) Exposure step In this step, an exposure method using an active light source by closely attaching a mask film having a desired wiring pattern on a support layer, an exposure method by direct drawing of a drawing pattern which is a desired wiring pattern, or 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 area is developed and removed using a developer of an alkaline aqueous solution, whereby the resist pattern is formed 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 in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ 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 the above steps (1) to (3). After these steps, a heating step of about 100 ° C. to about 300 ° C. can be further performed in some cases. By carrying out this heating step, chemical resistance can be further improved. For heating, a hot-air, infrared, or far-infrared heating furnace can be used. Moreover, you may implement this heating process after an exposure process.

(4) Etching process or plating process The substrate surface exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern.
(5) Stripping process Thereafter, the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than the developer. 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 a water-soluble solvent can also 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 liquid crystal transparent electrode, a liquid crystal TFT wiring, a touch panel wiring, and a PDP electrode. It is the photosensitive resin laminated body suitable for manufacture of conductor patterns, such as.
Note that the various parameters described above are measured according to a method understood by a person skilled in the art to be equivalent to the measurement method in Examples described later or the same unless otherwise specified.

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 unless departing from the gist thereof. The physical properties in the examples were measured by the following methods.
The measurement of the physical property value of the polymer, the calculation of the glass transition temperature of the polymer, and the method for producing samples for evaluation of Examples and Comparative Examples will be described. Moreover, the evaluation method about the obtained sample and its evaluation result 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 properties <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK). KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) It calculated | required as polystyrene conversion.
Furthermore, 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>
In this specification, an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule | numerator. Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and acid equivalent was measured by potentiometric titration using 0.1 mol / L sodium hydroxide aqueous solution.
<Glass transition temperature Tg>
The glass transition temperature Tg of the alkali-soluble polymer is a value determined by the Fox equation. When the glass transition temperature Tg is determined, the glass transition temperature of a homopolymer composed of a comonomer forming a corresponding alkali-soluble polymer is used as a non-patent document (Brandrup, J. Immergut, EH, “Polymer handbook, Third”). edition, John Wiley & Sons, 1989, p. 209 Chapter VI “Glass transition temperatures of polymers” ”). In addition, 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.

{Wherein W _i is the solid weight of each alkali-soluble polymer, T g _i is the glass transition temperature determined by the Fox formula of each alkali-soluble polymer, and W _total is each alkali-soluble polymer. 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) Preparation method of evaluation sample The evaluation sample was prepared as follows.
<Preparation of photosensitive resin laminate>
The photosensitive resin composition preparation liquid is obtained by sufficiently stirring and mixing the components shown in Table 1 to be described later (however, the numbers of the respective components indicate the blending amount (part by mass) as the solid content) and the solvent. It was. The names of the components represented by abbreviations in Table 1 are shown in Table 2 below. A 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) was used as a support film, and this mixture was uniformly applied to the surface using a bar coater. It dried for minutes and formed the 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 Tamapoly Co., Ltd., GF-818) is bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated. A laminate was obtained.
<Board surface preparation>
As a substrate for evaluating image quality, a 0.4 mm thick copper clad laminate on which 35 μm rolled copper foil is laminated is jetted using a grinding agent (# 400, manufactured by Ujiden Chemical Co., Ltd.) at a spray pressure of 0.2 MPa. After scrub polishing, the substrate surface was washed with a 10 mass% H ₂ SO ₄ aqueous solution.
<Laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper clad laminate preheated to 50 ° C. using a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). Lamination was performed at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
<Exposure>
The substrate for evaluation 1 hour after lamination was exposed to i-line monochromatic light through a glass mask with a projection exposure machine (UX2003 SM-MS04 manufactured by USHIO INC., Using i-line bandpass filter). The exposure amount was exposed by a plurality of exposure at 10 mJ / cm ² increments from 100 mJ / cm ² to 350 mJ / cm ^2.
<Development>
After peeling off the polyethylene terephthalate film (support layer), using an alkaline developer (Fuji Kiko Co., Ltd., dry film developer), a 1 mass% Na ₂ CO ₃ aqueous solution at 32 ° C. is sprayed over a predetermined time for development. Went. The development spray time was 3 times the shortest development time, and the water spray time after development was 8 times the shortest development time. At this time, the shortest time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the shortest development time. The general development conditions are 1% 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. Because of the time, the development conditions in this embodiment are extremely severe conditions.

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

From the results of Tables 1 and 2, it was confirmed that in the examples falling within the constituent requirements of the present invention, the image quality evaluation results were superior to those in the comparative examples that were outside the scope of the present invention. .
The development conditions in this embodiment are extremely severe conditions. For example, under the general development conditions described above, the compositions of Example 4 and Example 5 form a mask pattern L / S = 3 μm / 13 μm pattern and a mask pattern L / S = 4 μm / 12 μm pattern. I was able to. On the other hand, under the extremely severe development conditions of this example, neither of the compositions of Example 4 and Example 5 can form a mask pattern L / S = 3 μm / 13 μm normally, and the mask pattern As can be seen from Table 1, the pattern of L / S = 4 μm / 12 μm was not formed normally in Example 4, but was found to be formed normally in Example 5. Further, in the mask pattern of <image quality evaluation-4> of L: S = 1: 1, the composition of Example 4 and Example 5 had a minimum resolution of 6 μm under the general development conditions described above. However, as can be seen from Table 1 under the extremely severe development conditions of this example, Example 4 was 7 μm and Example 5 was 6.5 μm.
Similarly, under the general development conditions described above, the compositions of Example 6 and Comparative Example 3 both form a mask pattern L / S = 3 μm / 13 μm pattern and a mask pattern L / S = 4 μm / 12 μm pattern. We were able to. On the other hand, under the extremely severe development conditions of this example, neither of the compositions of Example 6 and Comparative Example 3 can normally form a mask pattern L / S = 3 μm / 13 μm. As can be seen from Table 1, the pattern of L / S = 4 μm / 12 μm cannot be formed normally in Comparative Example 3, but can be formed normally in Example 6. Further, in the mask pattern of <image quality evaluation-4> of L: S = 1: 1, the composition of Example 6 and Comparative Example 3 had a minimum resolution of 5 μm under the general development conditions described above. However, as can be seen from Table 1 under extremely severe development conditions of this example, Example 6 was 5.5 μm and Comparative Example 3 was 8 μm.
In other words, even if the adhesion and resolution are good in the development conditions of general development time and water washing time, the extremely severe development conditions that the temperature of the developer is high in the over-development and over-water washing of the present invention. However, the adhesiveness and the resolution are not necessarily improved, but the present invention can improve the adhesiveness 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 is no problem such as short circuit failure, chipping, disconnection, plating failure, etc. A fine circuit can be formed.
Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

  The photosensitive resin composition of the present invention has good adhesion and resolution even under severe development conditions such as over-development, over-washing, and high-temperature developer. 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 free from problems such as short circuit defects, chipping, disconnection, and plating defects. 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 liquid crystal transparent electrode, a liquid crystal TFT wiring, a touch panel wiring, And can be suitably used for manufacturing conductor patterns such as electrodes for plasma display panels (PDP).

Claims (30)

(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond;
(C) a photopolymerization initiator; and (D) an inhibitor;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an I / O value of 0.200 to 0.560. (A-1) The alkali-soluble polymer is 5 with respect to the total solid mass in the photosensitive resin composition. And (D) the inhibitor contains a phenol derivative,
Substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition are components other than (A) and (B). sometimes,
The ratio of the mass of components other than said (A) and (B) with respect to the mass of the compound which has the said (B) ethylenically unsaturated bond is 0.190 or less, The photosensitive resin composition characterized by the above-mentioned.   The photosensitive resin composition of Claim 1 whose ratio of the mass of the said (A-1) alkali-soluble polymer with respect to the mass of the compound which has the said (B) ethylenically unsaturated bond is 0.500 or more.   The (A-1) alkali-soluble polymer has 21% by mass of a structural unit derived from (meth) acrylic acid, based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition of Claim 1 or 2 containing -29 mass%.   The photosensitive resin composition as described in any one of Claims 1-3 whose glass transition temperature Tg of the said (A-1) alkali-soluble polymer is 128 degrees C or less.   The photosensitive resin according to any one of claims 1 to 4, wherein a ratio of the mass of the (A) alkali-soluble polymer to the mass of the compound (B) having an ethylenically unsaturated bond is 5.0 or less. Composition. (A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator;
(D) Inhibitor;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an I / O value of 0.200 to 0.560. (A-1) The alkali-soluble polymer is 5 based on the total solid mass in the photosensitive resin composition. Including mass% or more,
The (A-1) alkali-soluble polymer is 21% by mass of a structural unit derived from (meth) acrylic acid, based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. Containing ~ 29 mass%,
The (A-1) alkali-soluble polymer has a glass transition temperature Tg of 128 ° C. or lower,
The (D) inhibitor includes a phenol derivative,
Substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content of the photosensitive resin composition are components other than (A) and (B). sometimes,
The ratio of the mass of components other than (A) and (B) to the mass of the compound (B) having an ethylenically unsaturated bond is 0.190 or less,
The ratio of the mass of the (A-1) alkali-soluble polymer to the mass of the compound (B) having an ethylenically unsaturated bond is 0.500 or more, and (B) the compound having an ethylenically unsaturated bond The ratio of the mass of the (A) alkali-soluble polymer to the mass of the photosensitive resin composition is 5.0 or less.   The photosensitive resin composition as described in any one of Claims 1-6 in which the said (C) photoinitiator contains hexaaryl biimidazole.   The photosensitive resin composition as described in any one of Claims 1-7 in which the said (C) photoinitiator contains a pyrazoline compound.   The photosensitive resin composition as described in any one of Claims 1-8 in which the said (C) photoinitiator contains an anthracene compound.   The photosensitive resin composition as described in any one of Claims 1-9 in which the said (C) photoinitiator contains aromatic ketones.   The (C) photopolymerization initiator includes at least one selected from acridines, N-arylamino acids or ester compounds thereof, halogen compounds, and coumarin compounds, according to any one of claims 1 to 10. Photosensitive resin composition.   The photosensitive resin composition as described in any one of Claims 1-11 which further contains 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 mass of the photosensitive resin composition.   The photosensitive resin as described in any one of Claims 1-13 whose content of the said (A) alkali-soluble polymer is 30 mass% or more with respect to the total solid content mass of the said photosensitive resin composition. Composition.   The photosensitive resin composition according to claim 14, wherein the content of the (A) alkali-soluble polymer is 40% by mass or more based on the total solid mass of the photosensitive resin composition.   The photosensitive resin composition as described in any one of Claims 1-15 in which the said (D) inhibitor contains hindered phenol.   The photosensitive resin composition as described in any one of Claims 1-16 in which the said (D) inhibitor contains p-methoxyphenol.   The photosensitive resin composition according to any one of claims 1 to 17, wherein the (D) inhibitor comprises 2,6-di-tert-butyl-p-cresol.   The photosensitivity 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. Resin composition.   The photosensitive resin composition according to claim 1, wherein the (D) inhibitor comprises 4,4′-butylidenebis (3-methyl-6-tert-butylphenol).   The photosensitive resin composition as described in any one of Claims 1-20 in which the said (D) inhibitor contains catechol.   The photosensitive resin composition according to any one of claims 1 to 21, wherein the (D) inhibitor comprises tert-butylcatechol.   The photosensitive resin composition according to any one of claims 1 to 22, wherein the (D) inhibitor comprises 2,5-di-tert-butylhydroquinone.   The photosensitive resin composition as described in any one of Claims 1-23 in which the said (D) inhibitor contains a biphenol.   The photosensitive resin composition according to any one of claims 1 to 24, wherein the (D) inhibitor has two or more phenol nuclei.   The (A-1) alkali-soluble polymer is based on the total mass of all monomer components constituting the (A-1) alkali-soluble polymer. The photosensitive resin composition as described in any one of Claims 1-25 which contains 1 mass%-20 mass% of structural units derived from 4 or more.   27. The photosensitive resin composition according to claim 1, wherein the compound (B) having an ethylenically unsaturated bond includes a (meth) acrylate compound having 6 or more ethylenically unsaturated bonds. .   The photosensitive resin laminated body by which the photosensitive resin layer comprised from the photosensitive resin composition as described in any one of Claims 1-27 is laminated | stacked on a support layer. The following steps:
A laminating step of laminating the photosensitive resin laminate according to claim 28 on a substrate;
An exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate; and a development step of developing and removing an unexposed portion of the photosensitive resin layer;
A method for forming a resist pattern, comprising: The following steps:
A laminating step of laminating the photosensitive resin laminate according to claim 28 on a substrate;
An exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate;
A development 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 the substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern;
A method of manufacturing a wiring board including: