JP2021113984A - Photosensitive resin composition and photosensitive resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin laminate which exhibits high resolution and good line width reproducibility even when the focus is deviated during exposure, and a support film for forming the photosensitive resin laminate. An object of the present invention is to provide a photosensitive resin composition, and to provide a method for forming a resist pattern and a method for forming a conductor pattern using the photosensitive resin laminate.
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film is provided, and at any 10 positions of the support film. When a square-shaped piece having a side of 5 mm is cut out, the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in each piece is 0 to 200 on average at the above 10 locations.
[Selection diagram] None

Description

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

In electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used for mounting parts, semiconductors and the like. Conventionally, as a resist for manufacturing a printed wiring board or the like, a photosensitive resin laminate formed by laminating a photosensitive resin layer on a support film and further laminating a protective film on the photosensitive resin layer as needed. So-called dry film photoresist (hereinafter, also referred to as DF) is used. As the photosensitive resin layer, an alkali-developing type that uses a weak alkaline aqueous solution as a developing solution is generally used at present. To manufacture a printed wiring board or the like using DF, for example, the following steps are performed. When the DF has a protective film, the protective film is first peeled off. After that, the DF is laminated on a permanent circuit manufacturing substrate such as a copper-clad laminate or a flexible substrate using a laminator or the like, and exposed through a wiring pattern mask film or the like. Next, if necessary, the support film is peeled off, the photosensitive resin layer of the uncured portion (for example, the unexposed portion in the negative type) is dissolved or dispersed and removed with a developing solution, and a cured resist pattern (hereinafter, simply referred to as simply) is applied on the substrate. (Sometimes called a resist pattern) is formed.

After forming the resist pattern, the process of forming the circuit is roughly divided into two methods. The first method is to remove the substrate surface (for example, the copper surface of a copper-clad laminate) that is not covered by the resist pattern by etching, and then remove the resist pattern portion with an alkaline aqueous solution stronger than the developer (etching method). Is. In the second method, the substrate surface is plated with copper, solder, nickel, tin, etc., and then the resist pattern portion is removed in the same manner as in the first method, and the exposed substrate surface (for example, This is a method (plating method) for etching (the copper surface of a copper-clad laminate). Copper chloride, ferric chloride, cuprammonium complex solution and the like are used for etching. In recent years, along with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have been progressing, and high resolution, good line width reproducibility, etc. are provided in the above-mentioned manufacturing process. High-performance DF is required. To realize such high resolution, Patent Document 1 describes a photosensitive resin composition whose resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. ..

JP-A-2010-249884

However, in the case of direct drawing of a drawing pattern, which has been widely used in recent years, or an exposure method in which an image of a photomask is projected through a lens, the position of the focal point has a great influence on the resolution and line width reproducibility. For example, if the position of the focal point at the time of exposure deviates from the surface of the substrate due to warpage and distortion of the substrate, setting defect of the exposure apparatus, etc., the resolution and the reproducibility of the resist line width are greatly deteriorated. As a result, a short-circuit problem may occur when the circuit is formed by the etching method, and problems such as chipping, disconnection, and poor plating may occur when the circuit is formed by the plating method. In addition, there is a problem that a desired circuit width cannot be obtained. From this point of view, the technique described in Patent Document 1 still has room for improvement.
Therefore, the present invention relates to a photosensitive resin laminate that exhibits high resolution and good line width reproducibility even when the focus is deviated during exposure, and a supporting film and photosensitive to form the photosensitive resin laminate. It is an object of the present invention to provide a sex resin composition, and to provide a method for forming a resist pattern and a method for forming a conductor pattern using the photosensitive resin laminate.

The present inventor has conducted extensive research and experiments in order to solve the above problems. As a result, it was found that the problem can be solved by the following technical means.
That is, the present invention is as follows.
[1]
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, wherein each of the support films has a side of 5 mm at any 10 positions. A photosensitive resin laminate in which the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in each of the square-shaped small pieces is 0 to 200 on average at the above 10 locations.
[2]
The photosensitive resin laminate according to [1], wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 200 on average at 10 locations.
[3]
The photosensitive resin laminate according to [1], wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 100 on average at 10 locations.
[4]
The photosensitive resin laminate according to [1], wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 50 on average at 10 locations.
[5]
The photosensitive resin laminate according to [1], wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 20 on average at 10 locations.
[6]
The photosensitive resin laminate according to [1], wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 10 on average at 10 locations.
[7]
The photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, and has the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
The photosensitive resin laminate according to any one of [1] to [6], which comprises.
[8]
The photosensitive resin laminate according to [7], wherein the monomer component of the alkali-soluble polymer (A) has an aromatic hydrocarbon group.
[9]
The photosensitive resin laminate according to [7] or [8], _{wherein the weight average value Tg total} of the glass transition temperature Tg of the alkali-soluble polymer (A) is 30 ° C. or higher and 135 ° C. or lower.
[10]
Based on the total solid content mass of the photosensitive resin composition, the following components:
(D) Phenol derivative: 0.001% by mass to 10% by mass;
The photosensitive resin laminate according to any one of [7] to [9], further comprising.
[11]
The photosensitive resin laminate according to any one of [1] to [10], wherein the amount of water contained in the photosensitive resin composition is 0.7% or less.
[12]
The photosensitive resin laminate according to [11], wherein the amount of water contained in the photosensitive resin composition is 0.6% or less.
[13]
The photosensitive resin laminate according to [11], wherein the amount of water contained in the photosensitive resin composition is 0.5% or less.
[14]
The photosensitive resin laminate according to any one of [1] to [13], wherein the laminate of the support film and the photosensitive resin composition layer has a transmittance of 80% or less at a wavelength of 630 nm.
[15]
The photosensitive resin laminate according to [14], wherein the laminate of the support film and the photosensitive resin composition layer has a transmittance of 70% or less at a wavelength of 630 nm.
[16]
The photosensitive resin laminate according to [14], wherein the laminate of the support film and the photosensitive resin composition layer has a transmittance of 60% or less at a wavelength of 630 nm.
[17]
The following steps:
A laminating step of laminating the photosensitive resin laminate according to any one of [1] to [16] on a substrate.
A method for forming a resist pattern, which comprises an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate and a developing step of developing and removing an unexposed portion of the photosensitive resin layer.
[18]
The method for forming a resist pattern according to [17], wherein the exposure step is performed by an exposure method in which a drawing pattern is directly drawn or an exposure method in which an image of a photomask is projected through a lens.

INDUSTRIAL APPLICABILITY The present invention provides a photosensitive resin laminate that exhibits high resolution and good line width reproducibility even when the focus is deviated during exposure, a support film for forming the photosensitive resin laminate, and a photosensitive resin composition. It is also possible to provide a method for forming a resist pattern and a method for forming a conductor pattern using the photosensitive resin laminate. As a result, even when the focal position at the time of exposure deviates from the surface of the substrate due to warpage and distortion of the substrate, setting error of the exposure device, etc., the short-circuit problem can be reduced when the circuit is formed by the etching method. It is possible to reduce problems such as chipping, disconnection, and poor plating when a circuit is formed by the plating method. It is also possible to obtain a desired circuit width.

Hereinafter, an exemplary embodiment for carrying out the present invention (hereinafter, abbreviated as “embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. Further, unless otherwise specified, various measured values in the present specification conform to 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. Is measured.

[Photosensitive resin laminate]
The photosensitive resin laminate of the present invention is a photosensitive resin laminate including a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, and is a support film. The number of fine particles of 1.5 μm or more and less than 4.5 μm contained in each of the small pieces when a square-shaped piece having a side of 5 mm is cut out at any of the 10 places is 0 to 200 on average at the 10 places. , A photosensitive resin laminate. The fine particles of 1.5 μm or more and less than 4.5 μm include primary particles having a diameter of 1.5 μm or more and less than 4.5 μm and primary particle aggregates having a diameter of 1.5 μm or more and less than 4.5 μm. included. If the primary particle is not a perfect sphere, the longest width of the primary particle is taken as the diameter of the primary particle. When the primary particle agglomerate is not a perfect sphere, the longest width of the primary particle agglomerate is taken as the diameter of the primary particle agglomerate. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support layer side of the photosensitive resin layer.

With the recent miniaturization and thinning of electronic devices, there is an increasing need for higher density wiring, application of flexible printed wiring boards, and further multi-layering. Then, as the number of layers increases, the waviness of the surface is amplified, and there is a concern that the resolution and the line width reproducibility may be deteriorated due to the defocusing during exposure. As a result, the problems of short-circuit defects, chips, disconnections, plating defects, and the inability to form a desired copper line become more and more important. Similar problems can occur due to poor adsorption when exposed on a large substrate, in-plane film thickness non-uniformity, and the like. Therefore, the present inventors have shifted the focal position between when the exposure is performed with the focal position aligned with the surface of the base material and the position shifted from the surface of the base material to the inside of the base material (such as the amount of waviness of the surface). The photosensitive resin laminate was designed by paying attention to the difference in line width and the difference in resolution from the time when the exposure was performed by adjusting the focal position to the reference value set as a very large deviation amount with respect to the amount. It was found that doing so is effective in solving the above problem.

When the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a square piece having a side of 5 mm of the support film is 0 to 200 on average at any 10 locations, the focal position at the time of exposure. It is possible to suppress the thickening of the line width and the deterioration of the resolution when the deviation occurs. If the size of the fine particles that affect these performances is 1.5 μm or more and less than 4.5 μm, there is no effect on these performances in normal exposure, but the substrate is used in the exposure method by direct drawing. If the exposed portion is out of focus due to the distortion of the substrate, insufficient adsorption of the substrate to the stage, or the influence of the unevenness of the substrate surface, the influence of light scattering by the fine particles becomes large. As a result, the line width becomes thicker and the resolution (particularly the omission) deteriorates. In the case of fine particles of 4.5 μm or more, the resolvability deteriorates even during normal exposure. In the case of fine particles smaller than 1.5 μm, no line width thickening or deterioration of resolution is observed even when the focus is deviated during exposure.

From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure, the average number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the support film is 10 points on average. 180 or less is preferable, 150 or less is preferable, 120 or less is preferable, 100 or less is preferable, 80 or less is more preferable, 50 or less is more preferable, 30 or less is further preferable, and 20 or less. More preferably, 15 or less, particularly preferably 10 or less, and most preferably 6 or less.

Further, the number of fine particles of 1.5 μm or more and less than 4.5 μm is preferably one or more in that the adhesion between the support film and the photosensitive resin layer is excellent. If the support film contains at least one fine particle of 1.5 μm or more and less than 4.5 μm on average at any 10 locations, the support film will slip better and it will be possible to reduce peeling of the support film. Become. If the support film is partially peeled off after laminating on the substrate, oxygen enters between the support film and the photosensitive resin composition layer, and even if exposed due to the oxygen, the photosensitive resin composition Poor curing may occur.
The number of fine particles of 1.5 μm or more and less than 4.5 μm in the support film may be 2 or more, 3 or more, 5 or more, or 8 or more. It may be 10 or more.

In the present application, the number of particles is measured at any 10 locations in the support film, and if there are 10 locations that satisfy the number of particles specified in the claim of the present application, the photosensitive resin laminate is the right of the present invention. It is assumed that it is within the range. That is, even if the specified number of particles is not satisfied when measured at a certain 10 points, if the specified number of particles is satisfied when measured at another 10 points, the photosensitive resin laminate is within the scope of the present invention. It shall be inside.

The fine particles of 1.5 μm or more and less than 4.5 μm contained in the support film are, for example, inorganic fine particles or organic fine particles, such as lubricants, aggregates of additives, foreign substances mixed in raw materials, foreign substances mixed in the manufacturing process, and the like. There is. Specific examples of the fine particles include inorganic particles such as calcium carbonate, calcium phosphate, silica (silicon dioxide), kaolin, talc, titanium dioxide, alumina (aluminum oxide), barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. , Crosslinked polymer particles, organic particles such as calcium oxalate, and the like. These may be used alone or in combination of two or more.
The fine particles are blended into the film according to a conventional method. In order to produce the support film of the present invention, for example, a method of filtering the resin with a filter having an eye size of 4.5 μm or less can be mentioned.

As the support film, a transparent support film that transmits light emitted from an exposure light source is preferable. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, and a polymethylmethacrylate copolymer film. Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films can also be stretched if necessary.
The support film preferably has a haze of 5% or less, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less, from the viewpoint of suppressing light scattering during exposure. preferable. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. The thinner the film, the more advantageous it is to improve the image forming property and the economic efficiency. However, in order to maintain the strength of the photosensitive resin laminate, a film having a thickness of 10 μm to 30 μm is preferably used.

Further, the support film may have a single-layer structure, or may have a multi-layer structure in which resin layers formed from a plurality of compositions are laminated. In the case of a multi-layer structure, there may be an antistatic layer. In the case of a multi-layer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one surface A, and fine particles are formed on the other surface B as in (1) surface A. , (2) contains a smaller amount of fine particles than the surface A, (3) contains fine particles finer than the surface A, and (4) 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, it is preferable that there is a resin layer containing fine particles on the surface A side from the viewpoint of film slipperiness and the like. The size of the fine particles at this time is preferably less than 1.5 μm from the viewpoint of the effect of the present invention.
An important property of the protective layer used in the photosensitive resin laminate is that the adhesive force with the photosensitive resin layer is sufficiently smaller than that of the holding layer and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as a protective layer. Further, a film having excellent peelability shown in JP-A-59-202457 can also be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

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

The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 μm. As for the thickness of the photosensitive resin layer, the thinner the thickness, the higher the resolution, and the thicker the thickness, the better the film strength.
Next, a method for producing the photosensitive resin laminate will be described.
A known method can be adopted as a method for producing a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, which is first applied onto the support layer using a bar coater or a roll coater, and then dried to obtain the solvent. By removing the above, a photosensitive resin layer made of a photosensitive resin composition can be laminated on the support layer. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

[Photosensitive resin composition]
In the present embodiment, the photosensitive resin composition preferably contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, and is (A) an alkali-soluble polymer: 10% by mass to 90% by mass; (B) a compound having an ethylenically unsaturated double bond. : 5% by mass to 70% by mass; and (C) photopolymerization initiator: preferably containing 0.01% by mass to 20% by mass. Hereinafter, each component will be described in order.

<(A) Alkali-soluble polymer>
In the present disclosure, the alkali-soluble polymer (A) includes a polymer that is easily dissolved in an alkaline substance. More specifically, the amount of the carboxyl group contained in the alkali-soluble polymer (A) is 100 to 600, preferably 250 to 450, in terms of acid equivalent. The acid equivalent refers to the mass (unit: gram) of a polymer having 1 equivalent of a carboxyl group in the molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary to impart developability and peelability to the alkaline aqueous solution to the photosensitive resin layer. It is preferable that the acid equivalent is 100 or more from the viewpoint of improving development resistance, resolution, and adhesion. And it is more preferable that the acid equivalent is 250 or more. On the other hand, it is preferable to set the acid equivalent to 600 or less from the viewpoint of improving developability and peelability. And it is more preferable that the acid equivalent is 450 or less. In the present disclosure, the acid equivalent is a value measured by a potentiometric titration method of titrating with a 0.1 mol / L NaOH aqueous solution using a potentiometric titrator.

The weight average molecular weight of the alkali-soluble polymer (A) is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolution and developability. The weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, setting the weight average molecular weight to 5,000 or more is a viewpoint of controlling the properties of the developed agglomerates and the properties of the unexposed film such as edge fuse properties and cut chip properties in the case of a photosensitive resin laminate. Is preferable. The weight average molecular weight is more preferably 10,000 or more, and even more preferably 20,000 or more. The edge fuse property refers to the degree of ease with which the photosensitive resin layer (that is, the layer made of the photosensitive resin composition) protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. .. The cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate or the like, it will be transferred to the mask in a later exposure process or the like, causing a defective product. The dispersity of the alkali-soluble polymer (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and preferably 1.0 to 4.0. It is more preferably 1.0 to 3.0, and even more preferably 1.0 to 3.0.

In the present embodiment, the photosensitive resin composition contains an aromatic hydrocarbon group as (A) an alkali-soluble polymer from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure. It is preferable that it contains a monomer component having. Examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer is preferably 20% by mass or more, preferably 40% by mass, based on the total mass of all the monomer components. The above is more preferable, 50% by mass or more is further preferable, 55% by mass or more is particularly preferable, and 60% by mass or more is most preferable. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 80% by mass or less. When a plurality of types of (A) alkali-soluble polymers were contained, the content ratio of the monomer component having an aromatic hydrocarbon group was determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl). Benzoic acid, styrene dimer, styrene trimer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
Examples of the comonomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate and the like; vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, vinylbenzyl alcohol and the like. Can be mentioned. Of these, benzyl (meth) acrylate is preferable.

The alkali-soluble polymer (A) containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or It is preferably obtained by polymerizing with at least one of the second monomers described later.
The alkali-soluble polymer (A), which does not contain a monomer component having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one of the first monomers described later, and is preferably the first simple polymer. It is more preferable to obtain it by copolymerizing at least one of the molecules and at least one of the second monomers described later.
The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid semiester and the like. Among these, (meth) acrylic acid is preferable.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(meth) acryloyl group" means an acryloyl group or methacrylic acid group, and "(meth) acrylate". "" Means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all the monomer components. It is preferable to set the copolymerization ratio to 10% by mass or more from the viewpoint of exhibiting good developability, controlling edge fuseability, etc., more preferably 15% by mass or more, still more preferably 20% by mass or more. .. It is preferable that the copolymerization ratio is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, 35% by mass. The following is more preferable, 30% by mass or less is further preferable, and 27% by mass or less is particularly preferable.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates; vinyl acetate Such as vinyl alcohol esters; as well as (meth) acrylonitrile and the like. Of these, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable.
It is preferable to contain a monomer having an aralkyl group and / or styrene as a monomer from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene and the like are preferable.

The alkali-soluble polymer (A) can be used alone or in combination of two or more. When two or more kinds are mixed and used, two kinds of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group are mixed and used, or a monomer component having an aromatic hydrocarbon group is used. It is preferable to mix and use an alkali-soluble polymer containing the above and an alkali-soluble polymer containing no monomer component having an aromatic hydrocarbon group. In the latter case, the proportion of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total amount of the (A) alkali-soluble polymer. It is more preferably mass% or more, preferably 80 mass% or more, and more preferably 90 mass% or more.

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

_{(A) The weight average value Tg total} of the glass transition temperature Tg of the alkali-soluble polymer is preferably 30 ° C. or higher and 135 ° C. or lower. The Tg _total is calculated by the method described in Examples described later. _{By using the (A) alkali-soluble polymer having a Tg total of} 135 ° C. or lower in the photosensitive resin composition, it is possible to suppress line width thickening and deterioration of resolution when the focal position is deviated during exposure. can. From this point of view, the Tg _{total of the} alkali-soluble polymer (A) is more preferably 120 ° C. or lower, further preferably 115 ° C. or lower, further preferably 110 ° C. or lower, and 105 ° C. or lower. It is more preferable that the temperature is 110 ° C. or lower. Further, it is preferable to use the alkali-soluble polymer (A) having _{a Tg total of} 30 ° C. or higher from the viewpoint of improving edge fuse resistance. _{From this viewpoint, the Tg total of the} alkali-soluble polymer (A) is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher.

The ratio of the alkali-soluble polymer (A) to the total solid content of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass. More preferably, it is 40% by mass to 60% by mass. It is preferable that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition is 10% by mass or more from the viewpoint of improving the edge fuse resistance.

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

Examples of the compound having two (meth) acryloyl groups in the molecule include a compound having (meth) acryloyl groups at both ends of the alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bonded at random or in a block. Examples thereof include compounds having (meth) acryloyl groups at both ends of the oxide chain.
Examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth). Polyethylene glycol (meth) acrylice such as meta) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain. In addition to ethylene glycol, polypropylene glycol di (meth) acrylic, polybutylene glycol di (meth) acrylic, and the like can be mentioned. As a polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide is added. Dimethacrylate of glycol, and dimethacrylate of glycol with an average of 15 mol of ethylene oxide added to both ends of polypropylene glycol with an average of 18 mol of propylene oxide, FA-023M, FA-024M, FA-027M (product name). , Made by Hitachi Kasei Kogyo), etc. These are preferable from the viewpoints of flexibility, resolution, adhesion and the like.

｛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。
例えば、ビスフェノ−ルＡの両端にそれぞれ平均５モルずつのエチレンオキサイドを付加したポリエチレングリコ−ルのジメタクリレ−ト、ビスフェノ−ルＡの両端にそれぞれ平均２モルずつのエチレンオキサイドを付加したポリエチレングリコ−ルのジメタクリレ−ト、ビスフェノ−ルＡの両端にそれぞれ平均１モルずつのエチレンオキサイドを付加したポリエチレングリコ−ルのジメタクリレ−トが、解像性、密着性の点で好ましい。
また、上記一般式（Ｉ）中の芳香環が、ヘテロ原子及び／又は置換基を有する化合物を用いてもよい。 As another example of a compound having two (meth) acryloyl groups in the molecule, a compound having (meth) acryloyl groups at both ends by modifying bisphenol A with an alkylene oxide has resolution and adhesion. It is preferable from the viewpoint of.
Specifically, the following general formula (I):

{In the formula, R1 and R2 independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n 1 and n 3 are independently 1 to 39, respectively. It is an integer, n1 + n3 is an integer of 2 to 40, n2 and n4 are independently integers of 0 to 29, and n2 + n4 is an integer of 0 to 30, − (A—O) − and − The sequence of repeating units of (BO)-may be random or block. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. }
The compound represented by can be used.
For example, a dimethacrylate of polyethylene glycol having an average of 5 mol of ethylene oxide added to both ends of bisphenol A, and a polyethylene glycol having an average of 2 mol of ethylene oxide added to both ends of bisphenol A. Polyethylene glycol dimethacrylates in which an average of 1 mol of ethylene oxide is added to both ends of the dimethacrylate and bisphenyl A are preferable in terms of resolution and adhesion.
Further, a compound in which the aromatic ring in the general formula (I) has a heteroatom and / or a substituent may be used.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group with 1 to 10 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 1 to 10 carbon atoms, aryl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocycle, or a group thereof. Examples thereof include an aryl group substituted with a substituent. These substituents may form a condensed ring, or the hydrogen atom in these substituents may be substituted with a 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.

As a compound having 3 or more (meth) acryloyl groups in the molecule, a compound having 3 mol or more of groups capable of adding an alkylene oxide group in the molecule as a central skeleton, to which ethyleneoxy group, propyleneoxy group, It is obtained by using an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group as a (meth) acrylate. In this case, examples of the compound capable of forming the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring. Examples of these compounds include tri (meth) acrylates, for example, glycerin tri (meth) acrylates ethoxylated, tri (meth) acrylates of isocyanuric acid ethoxylated, pentaerythritol tri (meth) acrylates, and trimethylolpropanthry (meth) acrylates (eg, trimethylolpropane tri (meth) acrylates). Trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane are preferable from the viewpoint of flexibility, adhesion, and suppression of bleed-out), etc .; Tetra (Meta) acrylates such as ditrimethylolpropanetetra (meth) acrylates, pentaerythritol tetra (meth) acrylates, dipentaerythritol tetra (meth) acrylates; penta (meth) acrylates such as dipentaerythritol penta (meth) acrylates. Etc .; Hexa (meth) acrylates, for example, dipentaerythritol hexa (meth) acrylate and the like can be mentioned. A compound having three or more (meth) acryloyl groups is preferable from the viewpoint of resolution, adhesion, and resist sso shape, and a compound having three or more methacrylic groups is more preferable.
As the tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. The pentaerythritol tetra (meth) acrylate may be a tetra (meth) acrylate or the like in which a total of 1 to 40 mol of alkylene oxide is added to the four ends of pentaerythritol.
As the hexa (meth) acrylate, a total of 1 to 40 mol of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 20 mol of ε is added to the six ends of dipentaerythritol. -Hexa (meth) acrylate with caprolactone added is preferred.

The (meth) acrylate compounds described above can be used independently or in combination, respectively. The photosensitive resin composition may also contain other compounds as the compound having the (B) ethylenically unsaturated bond. Other compounds include (meth) acrylate having a urethane bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid. Examples thereof include a compound obtained by subjecting the mixture, 1,6-hexanediol di (meth) acrylate and the like.
(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable that this ratio is 5% by mass or more from the viewpoint of sensitivity, resolution and adhesion. This ratio is more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the peeling delay of the edge fuse and the cured resist. It is more preferable that this ratio is 50% by mass or less.

<(C) Photopolymerization Initiator>
(C) The photopolymerization initiator is a compound that polymerizes a monomer by light. The photosensitive resin composition contains (C) a compound generally known in the art as a photopolymerization initiator.
The total content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% by mass to 10% by mass, and further preferably 0.1% by mass. It is in the range of% to 7% by mass, particularly preferably 0.1% by mass to 6% by mass. The total content of the photopolymerization initiator (C) 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 preferably 20% by mass or less from the viewpoint of obtaining.

(C) Examples of the photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoins or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, and oxime esters. , Acridines (eg, 9-phenylaclydin, bisacrydinylheptane, 9- (p-methylphenyl) acridin, 9- (m-methylphenyl) acridin are preferred in terms of sensitivity, resolution and adhesion). Further, hexaarylbiimidazole, pyrazoline compound, anthracene compound (for example, 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene are preferable in terms of sensitivity, resolution and adhesion), phenyl compound (for example, for example). 7-diethylamino-4-methylcoumarin is preferable in terms of sensitivity, resolution and adhesion), N-aryl amino acid or an ester compound thereof (for example, N-phenylglycine is preferable in terms of sensitivity, resolution and adhesion). ), And halogen compounds (eg, tribromomethylphenylsulfone) and the like. These can be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzo Irudiphenyl-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. Can be done. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Further, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3. It is in the range of mass%.

Examples of hexaarylbiimidazole are 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl). -4', 5'-diphenylbimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenyl biimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4' , 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- (3- Methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,5-difluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,6-difluorophenyl) -4 , 4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5,5'- Tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl)- Biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis -(2,4,5-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,5-tri Fluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-Tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrax- (3-methoxyphenyl) -biimidazole , And 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole and the like. , These can be used alone or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.
In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. %, More preferably 0.1% by mass to 6% by mass, still more preferably in the range of 1% by mass to 5% by mass.

From the viewpoint of 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) -pyrazolin and 1- (4- (benzoxazole-2-yl)). Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -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) -pyrazolin, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5) -Dimethoxyphenyl) -Pyrazoline, 1-Phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-Dimethoxyphenyl) -Pyrazoline, 1-Phenyl-3- (2,6-dimethoxystyryl)- 5- (2,6-dimethoxyphenyl) -pyrazolin, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazolin, 1-phenyl-3- (2, 3-Dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazolin, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazolin and the like are described above. It is preferable from the viewpoint, and can be mentioned. Of these, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is more preferred.

In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. , More preferably in the range of 0.1% by mass to 3% by mass.

<(D) Phenol derivative>
In the present embodiment, the photosensitive resin composition preferably further contains the (D) phenol derivative. Examples of the phenol derivative (D) include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis (4-methyl-6-). tert-Butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2 , 5-Di-tert-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-t-butyl-5-ethylphenyl) methane, triethylene glycol -Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate], pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t) -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-) Butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3) , 5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 4,4'-thiobis (6-tert-butyl) -M-cresol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, styrene Examples thereof include tert-butylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., tert-SP), tribenzylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), biphenol and the like. The inclusion of the (D) phenol derivative is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure, and hindered phenol or biphenol is preferable from the same viewpoint. From the same viewpoint, the phenol derivative (D) preferably has two or more phenol nuclei.

The ratio of the phenol derivative (D) to the total solid content mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more, and is 0.005% by mass or more, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure. Is more preferable, 0.01% by mass or more is further preferable, 0.05% by mass or more is more preferable, and 0.1% by mass or more is particularly preferable. On the other hand, this ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less in terms of less decrease in sensitivity and improvement in resolution. Is more preferable, 2% by mass or less is particularly preferable, and 1.5% by mass or less is most preferable.

<Additives>
The photosensitive resin composition may optionally contain additives such as dyes, plasticizers, antioxidants, stabilizers and the like. For example, the additives listed in JP2013-156369A may be used.
(Dyes and coloring substances)
In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluorane dyes, etc.) and coloring substances, if desired.
Examples of the coloring substance include fuxin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Examples include Basic Blue 20 and Diamond Green (for example, Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. It is preferable that the content is 0.001% by mass or more from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, setting the content to 1% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition.

The photosensitive resin composition is preferable in terms of visibility because the exposed portion develops color due to the inclusion of the dye, and when the inspection machine or the like reads the alignment marker for exposure, the exposed portion and the unexposed portion are used. The larger the contrast, the easier it is to recognize and the more advantageous it is. Preferred dyes from this viewpoint include leuco dyes and fluorane dyes.
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. In particular, from the viewpoint of improving the contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. It is preferable that this content is 0.1% by mass or more from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. This content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, it is preferable to make this content 10% by mass or less from the viewpoint of maintaining storage stability. This content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

Further, it is preferable to use the leuco dye in combination with the halogen compound described above in the (C) photopolymerization initiator in the photosensitive resin composition from the viewpoint of optimizing the adhesion and contrast. When the leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is 0.01 mass when the total solid content mass of the photosensitive resin composition is 100% by mass. It is preferably% to 3% by mass from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.

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

The total content of the radical polymerization inhibitor, benzotriazols, and carboxybenzotriazols is preferably 0.01% by mass to 100% by mass when the total solid content of the photosensitive resin composition is 100% by mass. It is 3% by mass, more preferably 0.05% by mass to 1% by mass. It is preferable that the content is 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, it is preferable to set the content to 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
The decolorization of the dye can be measured with a transmittance of a wavelength of 630 nm. A high transmittance at a wavelength of 630 nm indicates that the dye has been decolorized. The transmittance of the laminate of the support film and the photosensitive resin composition layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, and 72% or less. It is preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, and preferably 60% or less. It is preferably 58% or less, preferably 55% or less, preferably 52% or less, and preferably 50% or less. This transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer, and does not include the protective layer.

In the present embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of the epoxy compounds of bisphenol A include compounds in which bisphenol A is modified with polypropylene glycol and the ends are epoxidized.
In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (for example, diethyl frate, etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, and tri-acetyl citrate. Examples thereof include -n-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polyproprenene glycol alkyl ether and the like. In addition, Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (all manufactured by Asahi Denka Co., Ltd.), Nieuport BP-23P, Nieuport BP-3P, Nieuport BP-5P, New Pole BPE-20T, Nieuport BPE-60, Nieuport BPE-100, Nieuport BPE-180 (manufactured by Sanyo Kasei Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples thereof include compounds having a bisphenol skeleton such as 400, Nieuport DA-700 (manufactured by Nieuport Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nieuport Embroidery Co., Ltd.).

The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the total solid content mass of the photosensitive resin composition. Is. It is preferable that the content is 1% by mass or more from the viewpoint of suppressing the delay of the developing time and imparting flexibility to the cured film. On the other hand, it is preferable to reduce the content to 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow.

When the amount of water in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly promoted, and edge fuses are generated. From the viewpoint of suppressing edge fuse, the water content in the photosensitive resin composition should be 0.7% or less based on the photosensitive resin composition after applying the photosensitive resin composition preparation solution to the support film and drying it. Is preferable. The water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, and preferably 0.5% or less. It is preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, and 0. It is preferably 25% or less, and preferably 0.2% or less.

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

<Method of 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 laminating step of laminating a photosensitive resin laminate on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and a developing step of developing and removing an unexposed portion of the photosensitive resin layer. Can be included. Examples of the resist pattern include printed wiring boards, semiconductor elements, printed 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 PDP (plasma display panel) and electrodes for PDP (plasma display panel) can be mentioned. As an example, a method of manufacturing a printed wiring board will be described as follows.

The printed wiring board is manufactured through the following steps.
(1) Laminating Step First, in the laminating step, a photosensitive resin layer is formed on the substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-bonded to the substrate surface with a laminator and laminated. Examples of the substrate material include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.
In the present embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides if necessary. The heating temperature at the time of laminating is generally 40 ° C. to 160 ° C. Further, by performing heat pressure bonding at the time of laminating twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of heat crimping, a two-stage laminator provided with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly crimped several times through the rolls.

(2) Exposure step In this step, an exposure method in which a mask film having a desired wiring pattern is brought into close contact with the support layer and an active light source is used, an exposure method in which a drawing pattern which is a desired wiring pattern is directly drawn, or an exposure method is performed. The photosensitive resin layer is exposed by an exposure method in which an image of a photomask is projected through a lens. The advantage of the photosensitive resin composition according to the present embodiment is more remarkable in the exposure method by directly drawing the drawing pattern or the exposure method in which the image of the photomask is projected through the lens, and the exposure by direct drawing of the drawing pattern. Especially noticeable in the method.

(3) Development step In this step, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution to develop a resist pattern on the substrate. Form.
As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. _{The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na 2} CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and about 20 ° C. to about 40 ° C. is preferable.
A resist pattern can be obtained through each of the above steps (1) to (3). After these steps, in some cases, a heating step of about 100 ° C. to about 300 ° C. can be further performed. By carrying out this heating step, it is possible to further improve the chemical resistance. For heating, a heating furnace of hot air, infrared rays, or far infrared rays can be used. Further, this heating step may be performed after the exposure step.

(4) Etching step or plating step The surface of the substrate exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern.
(5) Peeling Step After that, the resist pattern is peeled from the substrate with an aqueous solution having a stronger alkalinity than the developing solution. The alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 ° C. is preferable. A small amount of water-soluble solvent can be added to the stripping solution.

The photosensitive resin laminate of the present embodiment has a conductor pattern such as a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, a transparent electrode for liquid crystal, a TFT wiring for liquid crystal, and an electrode for PDP. It is a photosensitive resin laminate suitable for the production of.
Unless otherwise specified, the above-mentioned various parameters are measured according to the measurement method in the examples described later or a method understood by those skilled in the art to be equivalent thereto.

Next, the present embodiment will be described more specifically with reference to Examples and Comparative Examples. However, the present embodiment is not limited to the following examples as long as it does not deviate from the gist thereof. The physical properties in the examples were measured by the following methods.
The measurement of the physical property value of the polymer, the calculation of the glass transition temperature of the polymer, and the method of preparing the evaluation sample of Examples and Comparative Examples will be described. Moreover, the evaluation method and the evaluation result about the obtained sample are shown.

(1) Measurement or calculation of physical property values <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex® manufactured by Showa Denko Corporation) (registered trademark). KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving layer solvent: tetrahydrofuran, polystyrene standard sample (using calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) Obtained as polystyrene conversion.
Further, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

<Acid equivalent>
As used herein, the acid equivalent means the mass (gram) of a polymer having 1 equivalent of a carboxyl group in the molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.

｛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｝
に従って求められる値である。
ここで、ガラス転移温度Ｔｇｉを求める際には、対応するアルカリ可溶性高分子を形成するコモノマーから成るホモポリマーのガラス転移温度として、Ｂｒａｎｄｒｕｐ，Ｊ． Ｉｍｍｅｒｇｕｔ， Ｅ． Ｈ．編集「Ｐｏｌｙｍｅｒ ｈａｎｄｂｏｏｋ， Ｔｈｉｒｄ ｅｄｉｔｉｏｎ， Ｊｏｈｎ ｗｉｌｅｙ ＆ ｓｏｎｓ， １９８９， ｐ．２０９ Ｃｈａｐｔｅｒ ＶＩ 『Ｇｌａｓｓ ｔｒａｎｓｉｔｉｏｎ ｔｅｍｐｅｒａｔｕｒｅｓ ｏｆ ｐｏｌｙｍｅｒｓ』」に示される値を使用するものとする。なお、実施例において計算に用いた各コモノマーから成るホモポリマーのガラス転移温度を表３に示す。 <Weight average value of glass transition temperature Tg Tg _total >
_{The weight average value Tg total} of the glass transition temperature Tg of the alkali-soluble polymer is the following formula:

{Wherein, _{W i} is the solid weight of each of the alkali-soluble polymer, Tg _i is the glass transition temperature determined by the Fox equation of each of the alkali-soluble _{polymer, W total,} each of the alkali-soluble It is the total solid weight of the polymer, and n is the number of types of alkali-soluble polymer contained in the photosensitive resin composition}.
It is a value obtained according to.
Here, when determining the glass transition temperature Tgi, the glass transition temperature of the homopolymer composed of the comonomer forming the corresponding alkali-soluble polymer is defined as the glass transition temperature of Brandrup, J. et al. Immunogut, E.I. H. Edit The values shown in "Polymer handbook, Third edition, John wiley & sons, 1989, p.209 Chapter VI" Glass transition temperatures of polymers ". Table 3 shows the glass transition temperature of the homopolymer composed of each comonomer used in the calculation in the examples.

(2) Method for preparing evaluation sample The evaluation sample was prepared as follows.
<Preparation of photosensitive resin laminate>
The components shown in Table 1 below (however, the numbers of each component indicate the blending amount (parts by mass) as a solid content) and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition preparation solution. rice field. The names of the components represented by abbreviations in Table 1 are shown in Table 2 below.
As a support film, a polyethylene terephthalate film having a thickness of 16 μm shown in Table 1 was prepared. The total number of fine particles of 1.5 μm or more and less than 4.5 μm contained in each polyethylene terephthalate film was determined by the following method.
That is, the number of fine particles of 1.5 μm or more and less than 4.5 μm existing in a square piece having a side of 5 mm of the polyethylene terephthalate film was measured in the entire thickness direction using an optical microscope. When the fine particles were not perfect spheres, the longest width of the fine particles was taken as the diameter of the fine particles. This measurement was performed at arbitrary 10 points in the plane of the polyethylene terephthalate film, and the average value was calculated.
This preparation was uniformly applied to the surface of the polyethylene terephthalate film using a bar coater, and dried in a dryer at 95 ° C. for 2.5 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 μm.
Next, a 19 μm-thick polyethylene film (manufactured by Tamapoli Co., Ltd., GF-818) was laminated as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated. I got a body.

<Board surface preparation>
In Examples 1 to 13 and Comparative Example 1, as an image quality evaluation substrate, a 0.4 mm thick copper-clad laminate in which 35 μm rolled copper foil was laminated was used as a soft etching agent (manufactured by Ryoe Chemical Co., Ltd., CPE-900). The substrate surface was washed with 10% by mass H ₂ SO _4.
<Laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was preheated to 60 ° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) on the copper-clad laminate. Laminated at a roll temperature of 105 ° C. The air pressure was 0.35 MPa and the laminating speed was 1.5 m / min.

<Exposure>
Direct drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-purple diode, main wavelength 405 ± 5 nm), a stofer 41-step step tablet or a mask pattern for predetermined direct imaging (DI) exposure. Was exposed under the condition of an illuminance of 85 mW / cm2. The exposure was performed with an exposure amount such that the maximum number of residual film stages when exposed and developed using the stofer 41-stage step tablet as a mask was 14.
<Development>
After peeling off the polyethylene terephthalate film (support layer), a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed over a predetermined time using an alkaline developing machine (manufactured by Fuji Kiko, a developing machine for dry film). The unexposed portion of the photosensitive resin layer was dissolved and removed in twice the minimum development time. At this time, the minimum development time required for the photosensitive resin layer in the unexposed portion to be completely dissolved was defined as the minimum development time.

<Evaluation of line width (normal)>
The evaluation substrate 2 hours after laminating was exposed using drawing data having a line pattern in which the widths of the exposed portion and the unexposed portion had a ratio of 1: 1. At this time, the position of the focal point at the time of exposure was aligned with the surface of the polyethylene terephthalate film. Next, after peeling off the polyethylene terephthalate film (support layer), development was performed in a development time twice the minimum development time. Then, the line width of the pattern of L / S = 70 μm / 70 μm was measured with an optical microscope. This measurement was performed on five lines, the line width of the widest portion of each line was measured, and the average value of the five line widths was taken as the line width (normal) value.

<Evaluation of line width A>
The position of the focal point at the time of exposure was shifted from the surface of the polyethylene terephthalate film to the inside of the evaluation substrate by 400 μm in the thickness direction of the evaluation substrate. Other than this, the same as the measurement of the line width (normal) described above was performed. Then, the value obtained by subtracting the above-mentioned line width (normal) from the line width at this time was used as the value of the line width thickening A.
<Evaluation of line width thick B>
The position of the focal point at the time of exposure was shifted from the surface of the polyethylene terephthalate film to the inside of the evaluation substrate by 800 μm in the thickness direction of the evaluation substrate. Other than this, the same as the measurement of the line width (normal) described above was performed. Then, the value obtained by subtracting the above-mentioned line width (normal) from the line width at this time was used as the value of the line width thickening B.

<Evaluation of resolution A>
The evaluation substrate 2 hours after laminating was exposed using drawing data having a pattern in which the unexposed portion became a circular hole. At this time, the position of the focal point at the time of exposure was aligned with the surface of the polyethylene terephthalate film. Next, after peeling off the polyethylene terephthalate film (support layer), development was performed in a development time twice the minimum development time. Then, the smallest circular hole diameter in which all the circular holes (32 pieces) in the unexposed portion are normally formed was set as the value of the resolution A. In the cured resist pattern, the minimum circular pore diameter normally formed was evaluated because there was no residual resist on the surface of the substrate in the unexposed portion and the surface of the substrate was exposed, and there were no protrusions of resist components from the cured resist. As the resolution value, 30 μm or less was obtained in 2 μm increments, 30 μm or more and 50 μm or less was obtained in 5 μm increments, and 50 μm or more was exposed using a drawing pattern obtained in 10 μm increments. The pattern in which the unexposed portion is a circular hole is evaluated much more severely than the normal resolution evaluation because the unexposed portion is difficult to develop because the unexposed portion is surrounded by the exposed portion.

<Evaluation of resolution B>
The position of the focal point at the time of exposure was shifted from the surface of the polyethylene terephthalate film to the inside of the evaluation substrate by 200 μm in the thickness direction of the evaluation substrate. Other than this, the measurement of the resolution A was the same as described above, and the resolution B was evaluated.
<Evaluation of resolution C>
The position of the focal point at the time of exposure was shifted from the surface of the polyethylene terephthalate film to the inside of the evaluation substrate by 400 μm in the thickness direction of the evaluation substrate. Other than this, the measurement of the resolution A was the same as described above, and the resolution C was evaluated.

The following contents can be read from the results in Tables 1 and 2.
In Examples 1 to 13, the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the support film is 0 to 200 on average at 10 locations. The difference, that is, the resolution B-resolution A and the resolution C-resolution A is suppressed to be smaller than that of Comparative Example 1 in which the number of fine particles is larger than 200, and the line width A and the line width B are also suppressed to be small. You can see that it is done.
Further, a 16 μm-thick polyethylene terephthalate film (16QS68 manufactured by Toray Industries, Inc.) having the same number of fine particles of 1.5 μm or more and less than 4.5 μm as in Example 3 was used, and the same photosensitive resin composition as in Example 3 was used. When the evaluation was performed using an object, the same result as in Example 3 was obtained.
In Example 1, partial peeling of the polyethylene terephthalate film was not observed after laminating on the substrate, but in Example 7, peeling of the polyethylene terephthalate film was partially observed after laminating on the substrate. It was observed. If the support film is peeled off from the photosensitive resin composition layer before exposure, oxygen enters between the support film and the photosensitive resin composition layer, and the photosensitive resin composition is cured even when exposed due to the oxygen. Defects may occur.

By comparing the examples and the comparative examples, if the support film or the photosensitive resin composition of the present embodiment is used, the line width is less thickened and the resolution is less deteriorated even when the focus is deviated during exposure. It turns out that it is possible. By using the polyethylene terephthalate film or the photosensitive resin composition, when a pattern is formed by an etching method or a plating method, the mask line width reproducibility is good even when there are irregularities or waviness on the substrate surface, and a short circuit occurs. It is possible to form a high-definition circuit without problems such as defects, chips, disconnection, and plating defects.

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

Since the photosensitive resin laminate of the present invention can suppress line width thickening and deterioration of resolution when the focal position is deviated during exposure, exposure is caused by warpage and distortion of the substrate, setting defects of the exposure apparatus, and the like. Even when the focal point position deviates from the substrate surface, short-circuit problems are prevented when the circuit is formed by the etching method, and problems such as chipping, disconnection, and poor plating are caused when the circuit is formed by the plating method. It is also possible to obtain a desired circuit width. Therefore, the photosensitive resin laminate includes a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip-on-film) substrate, a semiconductor package substrate, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, and a PDP (plasma display). It can be suitably used for manufacturing a conductor pattern such as an electrode for a panel).

Claims (18)

A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, wherein each of the support films has a side of 5 mm at any 10 positions. A photosensitive resin laminate in which the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in each of the square-shaped small pieces is 0 to 200 on average at the above 10 locations. The photosensitive resin laminate according to claim 1, wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 200 on average at 10 locations. The photosensitive resin laminate according to claim 1, wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 100 on average at 10 locations. The photosensitive resin laminate according to claim 1, wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in the small piece of the 5 mm square support film is 1 to 50 on average at 10 locations. The photosensitive resin laminate according to claim 1, wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 20 on average at 10 locations. The photosensitive resin laminate according to claim 1, wherein the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of the 5 mm square support film is 1 to 10 on average at 10 locations. The photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, and has the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
The photosensitive resin laminate according to any one of claims 1 to 6, which comprises. The photosensitive resin laminate according to claim 7, wherein the monomer component of the alkali-soluble polymer (A) has an aromatic hydrocarbon group. _{The photosensitive resin laminate according to claim 7 or 8, wherein the weight average value Tg total} of the glass transition temperature Tg of the alkali-soluble polymer (A) is 30 ° C. or higher and 135 ° C. or lower. Based on the total solid content mass of the photosensitive resin composition, the following components:
(D) Phenol derivative: 0.001% by mass to 10% by mass;
The photosensitive resin laminate according to any one of claims 7 to 9, further comprising. The photosensitive resin laminate according to any one of claims 1 to 10, wherein the amount of water contained in the photosensitive resin composition is 0.7% or less. The photosensitive resin laminate according to claim 11, wherein the amount of water contained in the photosensitive resin composition is 0.6% or less. The photosensitive resin laminate according to claim 11, wherein the amount of water contained in the photosensitive resin composition is 0.5% or less. The photosensitive resin laminate according to any one of claims 1 to 13, wherein the laminate of the support film and the photosensitive resin composition layer has a transmittance of 80% or less at a wavelength of 630 nm. The photosensitive resin laminate according to claim 14, wherein the laminate of the support film and the photosensitive resin composition layer has a transmittance of 70% or less at a wavelength of 630 nm. The photosensitive resin laminate according to claim 14, wherein the laminate of the support film and the photosensitive resin composition layer has a transmittance of 60% or less at a wavelength of 630 nm. The following steps:
A laminating step of laminating the photosensitive resin laminate according to any one of claims 1 to 16 on a substrate.
A method for forming a resist pattern, which comprises an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate and a developing step of developing and removing an unexposed portion of the photosensitive resin layer. The method for forming a resist pattern according to claim 17, wherein the exposure step is performed by an exposure method in which a drawing pattern is directly drawn or an exposure method in which an image of a photomask is projected through a lens.