TW201944171A - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition containing an alkali-soluble polymer, a compound having an ethylenic double bond, and a photo polymerization initiator, wherein the photosensitive resin composition is characterized in that: a photosensitive resin layer comprising the photosensitive resin composition is laminated to a thickness of 25 [mu]m onto a copper-clad laminated plate laminated with 18-[mu]m-thick copper foil; a cured resist pattern is formed through light irradiation in a pattern where the line/space ratio is 50 [mu]m/30 [mu]m and a development treatment; and a copper etching process is performed for 55 seconds at 50 DEG C, whereupon the bottom width of the copper line pattern obtained by removing the cured resist pattern is 38 [mu]m or greater.

Description

Photosensitive resin composition

<Technical Field Related to the First Embodiment of the Present Invention>
A first embodiment of the present invention relates to a photosensitive resin composition.
<Technical Field Related to the Second Embodiment of the Present Invention>
A second embodiment of the present invention relates to a photosensitive resin composition and the like.
<Technical Field Related to the Third Embodiment of the Present Invention>
A third embodiment of the present invention relates to a photosensitive resin composition and the like.
<Technical field related to the fourth embodiment of the present invention>
A fourth embodiment of the present invention relates to a photosensitive resin composition.

<Related Background Art of the First Embodiment of the Present Invention>
The printed wiring board is generally manufactured by a photolithography method. The so-called photolithography method is a method of forming a layer containing a photosensitive resin composition on a substrate, pattern-exposing and developing the coating film to form a resist pattern, and then forming a conductor by etching or plating. After patterning, the resist pattern on the substrate is removed, thereby forming a desired wiring pattern on the substrate.
In this photolithography method, when a photosensitive resin composition layer is formed on a substrate, a method of removing a solvent after applying a composition solution is known, and laminating a support and a photosensitive resin composition layer on a substrate, and A method of peeling the above-mentioned support after the photosensitive element or the dry film photoresist is completed.
In the manufacture of printed wiring boards, photosensitive elements are often used. There are many known examples of a method for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable therefor.
For example, Patent Document 1 discloses a method capable of easily forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used in the method;
Patent Document 2 discloses a photosensitive resin composition containing an addition polymerizable monomer having a specific ethylenic double bond.
In addition, in recent years, many substrates have been multilayered to increase the density of printed wiring boards. Through-holes are provided in the multi-layer substrate to conduct conduction between the substrates stacked on top and bottom. When a wiring pattern is formed by a photolithography method on a substrate having a through hole used in a multilayer substrate, it is required to have a resist film (cover hole film) formed on the through hole not to be developed or washed with water. The property of being damaged by the spray pressure (caphole film resistance or caphole property).
In response to this, Patent Document 3 discloses a photosensitive resin composition containing a binder polymer having a small dispersion (Mw / Mn), a photopolymerizable compound, and an acridine compound, and it is described that a lid can be formed by using the composition. A resist film with excellent porosity.
<Related Background Art of the Second Embodiment of the Present Invention>
The printed wiring board is generally manufactured by a photolithography method. The so-called photolithography method is a method in which a coating film containing a layer containing a photosensitive resin composition is formed on a substrate, and the coating film is subjected to pattern exposure and development to form a resist pattern, followed by etching or plating treatment. After forming the conductor pattern, the resist pattern on the substrate is removed, thereby forming a desired wiring pattern on the substrate.
In the photolithography method, when a photosensitive resin layer is formed on a substrate, a method of removing a solvent after applying a composition solution is known, and a photosensitive element formed by laminating a support and a photosensitive resin layer on a substrate is laminated. Or the method of peeling off the above support after dry film photoresist.
In the manufacture of printed wiring boards, photosensitive elements are often used. There are many known examples of a method for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable therefor.
For example, Patent Document 1 discloses a method capable of easily forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used in the method, and Patent Document 4 discloses an addition containing a specific vinylic double bond. A photosensitive resin composition of a polymerizable monomer.
<Related Background Art of the Third Embodiment of the Present Invention>
Previously, printed wiring boards were generally manufactured by photolithography. In the photolithography method, first, the photosensitive resin composition layer laminated on the substrate is subjected to pattern exposure. The exposed portion of the photosensitive resin composition undergoes polymerization hardening (in the case of a negative type) or becomes soluble in a developing solution (in the case of a positive type). Next, a resist pattern is formed on the substrate by removing the unexposed portion (in the case of a negative type) or the exposed portion (in the case of a positive type) with a developing solution. Furthermore, after etching or plating is performed to form a conductor pattern, the resist pattern is removed from the substrate. A conductor pattern is formed on the substrate by going through these steps.
In the photolithography method, a method in which a solution of a photosensitive resin composition is applied to a substrate and dried is generally used, or a dry film photoresist is laminated on the substrate (a photosensitive resin layer formed by laminating a layer of the photosensitive resin composition Any of the methods of the photosensitive resin composition layer of the photosensitive resin laminated body). The latter is often used in the manufacture of printed wiring boards.
In recent years, with the miniaturization of wiring intervals in printed wiring boards, various characteristics have been required for dry film photoresists. With the miniaturization of the wiring interval, the thickness of the dry film photoresist also tends to be thinner, but it is still required to have a strong cover hole property to protect the through holes on the substrate.
When developing a resist pattern, moisture remaining between the patterns causes the resist component to elute out between the patterns and cause a short circuit of residual water. In order to alleviate this residual water short circuit defect, it is necessary to improve the hydrophobicity of the hardened resist.
In order to improve the characteristics of a resist, various photosensitive resin compositions have been proposed (Patent Documents 5 and 6).
<Related Background Art of the Fourth Embodiment of the Present Invention>
The printed wiring board is generally manufactured by a photolithography method. The so-called photolithography method is a method of forming a layer containing a photosensitive resin composition on a substrate, pattern-exposing and developing the coating film to form a resist pattern, and then forming a conductor by etching or plating. After patterning, the resist pattern on the substrate is removed, thereby forming a desired wiring pattern on the substrate.
In the photolithography method, when a photosensitive resin layer is formed on a substrate, a method of removing a solvent after applying a composition solution is known, and a photosensitive element formed by laminating a support and a photosensitive resin layer on a substrate is laminated. Or the method of peeling off the above support after dry film photoresist.
In the manufacture of printed wiring boards, photosensitive elements are often used. A method for forming a wiring pattern using a photosensitive element and a photosensitive resin composition suitable for the wiring pattern are known in the industry (Patent Documents 1 and 2). Patent Document 1 describes a general method for forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used therefor. Patent Document 2 describes a photosensitive resin composition containing an addition polymerizable monomer having a specific ethylenically unsaturated bond.
In addition, in recent years, with the miniaturization of wiring intervals in printed wiring boards, dry film photoresists are required to have characteristics such as resolvability. For example, in order to improve the characteristics of a resist pattern, various photosensitive resin compositions have been proposed (Patent Documents 5 and 6).
[Prior technical literature]
[Patent Literature]
[Patent Document 1] Japanese Patent Laid-Open No. 2011-233769
[Patent Document 2] International Publication No. 2009/022724
[Patent Document 3] Japanese Patent Laid-Open No. 2013-109321
[Patent Document 4] Japanese Patent Laid-Open No. 2015-60120
[Patent Document 5] International Publication No. 2015/098870
[Patent Document 6] Japanese Patent Laid-Open No. 2014-048340

[Problems to be solved by the invention]
<Problems to be Solved by the First Embodiment of the Present Invention>
In recent years, the manufacture of wiring boards is generally performed by a pipeline process in which the substrates are sequentially processed while the substrates are transported in a certain direction. Here, when a conductor pattern such as a line / gap pattern is formed on the substrate, a case where the conductor line is parallel to the substrate transport direction (line in the MD direction), a case where it is perpendicular (line in the TD direction), And tilting. If the conductor pattern of the line / gap pattern is formed by pipeline processing using the resist material of the prior art, there is a difference between the line of the wiring width in the MD direction and the line of the TD direction, resulting in the so-called vertical and horizontal difference in wiring width. In most cases, the lines in the MD direction are more susceptible to erosion by the etchant than the lines in the TD direction. Therefore, there is a tendency that the etching amount increases and the wiring width becomes narrower. In order to form a fine conductor pattern by pipeline processing, it is preferable to reduce the wiring width difference between the wiring in the MD direction and the wiring in the TD direction.
However, in the prior art represented by the aforementioned Patent Documents 1 to 3, no research has been conducted from this point of view, and a resist material for reducing the vertical and horizontal differences in wiring width has not been known.
The first embodiment of the present invention has been made in view of the foregoing circumstances. Therefore, it is an object of the first embodiment of the present invention to provide a resist material that suppresses the vertical and horizontal differences in wiring width when forming a fine conductive pattern by pipeline processing.
<Problems to be Solved by the Second Embodiment of the Present Invention>
In order to form a resist pattern using a photosensitive resin composition, a development step is required. In this developing step, the composition of the exposed area is dissolved and removed during the positive composition, and the composition of the unexposed area is dissolved and removed during the negative composition, thereby forming a resist pattern. In this developing step, the composition of the useless area is not all "dissolved" in the developing solution, and at least a part of it is kept insoluble and dispersed in the developing solution, thereby being removed from the substrate. Therefore, each time the development step is repeated, the amount of useless substances in the developing solution will increase accordingly, and eventually insoluble components with poor dispersibility will form aggregates. Such agglomerates may adhere and remain on a substrate to be developed thereafter, causing short-circuit defects and the like.
Therefore, from the viewpoint of improving the product yield in the developing step and further reducing the manufacturing cost of the printed wiring board, it is strongly desired that the photosensitive resin composition used has a good developer dispersibility.
In addition, in recent years, demands for miniaturization and refinement of printed wiring boards have been increasing. Therefore, the photosensitive resin composition for forming this printed wiring board is also required to be capable of forming a fine pattern. Here, the minimum size of the pattern formed on the substrate depends on the exposure wavelength. Therefore, it is not theoretically difficult to form a fine pattern by exposing a photosensitive polymerization initiator corresponding to the exposure wavelength used. . On the other hand, a fine pattern formed by exposure, for example, having a size of several tens of μm or less, may peel off from the substrate in subsequent steps such as a developing step, which restricts the miniaturization of the printed wiring board.
Therefore, in order to form a fine printed wiring board, it is necessary to use a photosensitive resin composition having high adhesion to a fine pattern.
However, the photosensitive resin compositions described in Patent Documents 1 and 4 fail to meet today's stringent requirements in terms of development dispersibility and adhesion of fine patterns, and there is still room for improvement in this field.
The second embodiment of the present invention has been made in view of such a situation.
Therefore, an object of the second embodiment of the present invention is to provide a novel photosensitive material that has properties generally required for photosensitive materials such as resolution at a high level, and is excellent in development dispersibility and fine pattern adhesion.
<Problems to be Solved by the Third Embodiment of the Present Invention>
In Patent Document 5, from the viewpoints of developability of a photosensitive resin composition and resolution, adhesion, and flexibility of a resist pattern, in the photosensitive resin composition, a binder polymer and bisphenol are used. The combination of type di (meth) acrylate monomers is studied. The above-mentioned adhesive polymer has a structural unit of (meth) acrylic acid, a structural unit of styrene or α-methylstyrene, and has a carbon number of 1-12. The structural unit of the hydroxyalkyl (meth) acrylic hydroxyalkyl ester. The number of the structural units of the ethoxy group in the bisphenol type di (meth) acrylate monomer is 1-20, and the propoxy group is The number of structural units is 0-7.
In Patent Document 6, from the viewpoint of the gap width and the pore-covering property of the positive resist pattern, it is proposed to set the content of the structural unit of styrene or a styrene derivative in the alkali-soluble polymer to 30% by mass or more. It is also proposed to set the weight average molecular weight of the addition polymerizable monomer to 1,100 or more.
Patent Documents 5 and 6 both focus on a photosensitive resin composition containing a polymer having a structural unit of styrene in a specific ratio and a specific monomer, but the photosensitive resin compositions described in Patent Documents 5 and 6 have both There is still room for improvement in terms of the coverage of the resist pattern and the poor suppression of the residual water short circuit.
Therefore, a problem to be solved by the third embodiment of the present invention is to provide a photosensitive resin composition capable of having both the hole-covering property of the resist pattern and the suppression property of the residual water short-circuit defect.
<Problems to be Solved by the Fourth Embodiment of the Present Invention>
In recent years, the manufacture of wiring boards is usually performed by a pipeline process in which the substrates are sequentially processed while the substrates are transported in a certain direction. At this time, the developing solution processing or the etching solution processing performed on the substrate is performed by a spray method. In the case of forming a resist pattern by a photolithography method, it is important that there is no deviation in the line width of the resist after development. However, if a resist pattern is formed by jet development, there may be a case where the developing solution is unevenly distributed in the substrate surface when the development time is short, and the above-mentioned problem may occur. Therefore, the development time is required to be extended.
Here, the development time refers to the time during which the substrate stays in the development tank and undergoes development processing, and is set to, for example, twice the minimum development time. The so-called minimum development time refers to the minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed, and varies depending on the concentration or temperature of the developing solution, the spray direction or spray amount, pressure, and oscillation frequency.
Here, it is considered that the dissolution reaction of the resist due to the development proceeds substantially based on the diffusion rate of the developing solution. Therefore, from the viewpoint of promoting development, it is necessary to actively supply the developer to the substrate by spraying or the like. This supply lasts for a short period of time. Therefore, when the development time is short, it is considered that the supply of the developer solution cannot be spread over the entire substrate surface, and the variation in resist line width is significantly increased. On the other hand, it is considered that when the development time is long, the supply of the developer on the substrate is uniform, so the variation in line width is also reduced. Therefore, from the viewpoint of suppressing line width deviation, it is considered effective to use a photosensitive resin composition in which the minimum development time itself is relatively slow.
In Patent Document 5, from the viewpoints of developability of a photosensitive resin composition and resolution, adhesion, and flexibility of a resist pattern, in the photosensitive resin composition, a binder polymer and bisphenol are used. The combination of type di (meth) acrylate monomers is studied. The above-mentioned adhesive polymer has a structural unit of (meth) acrylic acid, a structural unit of styrene or α-methylstyrene, and has a carbon number of 1-12. The structural unit of the hydroxyalkyl (meth) acrylic hydroxyalkyl ester. The number of the structural units of the ethoxy group in the bisphenol type di (meth) acrylate monomer is 1-20, and the propoxy group is The number of structural units is 0-7.
In Patent Document 6, from the viewpoint of the gap width and the pore-covering property of the positive resist pattern, it is proposed to set the content of the structural unit of styrene or a styrene derivative in the alkali-soluble polymer to 30% by mass or more. It is also proposed to set the weight average molecular weight of the addition polymerizable monomer to 1,100 or more.
Patent Documents 5 and 6 both focus on a photosensitive resin composition containing a polymer having a structural unit of styrene in a specific ratio and a specific monomer, but the photosensitive resin compositions described in Patent Documents 5 and 6 have both There is still room for improvement in terms of the good resolution of the resist pattern and the extension of the minimum development time.
Therefore, a problem to be solved by the fourth embodiment of the present invention is to provide a photosensitive resin composition that has both good resolution of a resist pattern and extended minimum development time.
[Technical means to solve the problem]
＜ Means for solving the first problem ＞
The present inventors have found that the above-mentioned objects can be achieved by the following technical means, thereby completing the first embodiment of the present invention. A first embodiment of the present invention is described below.
[1] A photosensitive resin composition, characterized in that it contains each of the following components (A) to (C),
(A) Ingredient: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and
(C) Ingredient: a photopolymerization initiator, and a photosensitive resin layer containing the above-mentioned photosensitive resin composition having a thickness of 25 μm is laminated on a copper-clad laminate having a copper foil with a thickness of 18 μm, passing through the line / gap = A 50 μm / 30 μm pattern of light was irradiated and developed to form a hardened resist pattern. After performing copper etch treatment at 50 ° C for 55 seconds, the hardened resist pattern was removed, and the bottom width of the copper wire pattern obtained was obtained. It is 38 μm or more.
[2] The photosensitive resin composition according to [1], wherein the component (A) is a copolymer having a content ratio of a (meth) acrylic unit of 10% by mass or more and 24% by mass or less.
[3] The photosensitive resin composition according to [1] or [2], wherein the component (A) is a copolymer having a styrene unit content ratio of 32% by mass or more and 60% by mass or less.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (C) contains an acridine compound.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (B) contains a pentaerythritol compound.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) contains a trimethylolpropane compound.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) contains a bisphenol A compound.
[8] A photosensitive resin composition containing the following components (A) to (C),
(A) Ingredient: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and
(C) component: a photopolymerization initiator, and the content ratio of the (A) component containing a (meth) acrylic unit is 10% by mass or more and 24% by mass or less, and the content ratio of the styrene unit is 32% by mass or more Copolymer,
The component (C) includes an acridine compound.
[9] The photosensitive resin composition according to [8], wherein the content ratio of the (A) component containing a (meth) acrylic unit is 10% by mass or more and 24% by mass or less, and the content ratio of the styrene unit is 32 Copolymer of more than 60% by mass.
[10] The photosensitive resin composition according to [8] or [9], wherein the component (B) contains a pentaerythritol compound.
[11] The photosensitive resin composition according to any one of [8] to [10], wherein the component (B) contains a trimethylolpropane compound.
[12] The photosensitive resin composition according to any one of [8] to [11], wherein the component (B) contains a bisphenol A compound.
[13] A photosensitive element comprising a photosensitive resin layer comprising a photosensitive resin composition according to any one of [1] to [12] laminated on a support.
[14] A method for forming a resist pattern, comprising:
The laminating step is to laminate a photosensitive resin layer of a photosensitive element as described in [13] on a conductor substrate;
The exposure step is to expose the above-mentioned laminated photosensitive resin composition layer; and the development step is to use a developing solution to remove the unexposed portions after the exposure.
[15] The method for forming a resist pattern according to [14], wherein the laminating step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent.
[16] A method for manufacturing a wiring board, comprising:
The laminating step is to laminate a photosensitive resin composition layer of a photosensitive element as described in [13] on a conductor substrate;
An exposure step, which exposes the photosensitive resin composition layer of the above-mentioned laminated layer;
A developing step, which uses a developing solution to remove the unexposed portions after the exposure;
The conductor pattern forming step is for etching or plating a conductor substrate on which a resist pattern is formed by the development; and the peeling step is for peeling the resist pattern.
[17] The method for manufacturing a wiring board according to [16], wherein the laminating step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent.
＜ Means for solving the second problem ＞
The present inventors have found that the above-mentioned objects can be achieved by the following technical means, thereby completing the second embodiment of the present invention. A second embodiment of the present invention is as follows.
[1] A photosensitive resin composition, characterized in that it contains each of the following components (A) to (C),
(A) component: alkali-soluble polymer with an acid equivalent of 100 to 600,
(B) component: a compound having an ethylenic double bond, and
(C) component: a photopolymerization initiator, and the component (A) contains a copolymer containing 50% by mass or more of a styrene unit,
The component (B) contains the following general formula (I):
[Chemical 1]

{In the formula, each of R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2, and n3 are each independently an integer of 0 to 30, wherein n1 + n2 + n3 ≧ 6 is satisfied} Content of the compound represented by this general formula (I) is 5 mass% or more with respect to the solid content of the said photosensitive resin composition, and the said (C) component contains an acridine compound.
[2] The photosensitive resin composition according to [1], wherein n1, n2, and n3 in the general formula (I) satisfy 20 ≧ n1 + n2 + n3> 9.
[3] The photosensitive resin composition according to [1] or [2], wherein R in the general formula (I) is a hydrogen atom.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (B) further contains a pentaerythritol-modified monomer.
[5] A photosensitive element comprising a photosensitive resin layer comprising a photosensitive resin composition according to any one of [1] to [4] laminated on a support.
[6] A method for forming a resist pattern, comprising:
The laminating step is to laminate a photosensitive resin layer of a photosensitive element as described in [5] on a conductor substrate;
The exposure step is to expose the photosensitive resin layer of the above-mentioned stacked layer; and the development step is to remove the unexposed portion after the exposure using a developing solution.
[7] A method for manufacturing a wiring board, comprising:
The laminating step is to laminate a photosensitive resin layer of a photosensitive element as described in [5] on a conductor substrate;
An exposure step, which exposes the photosensitive resin layer of the above-mentioned laminated layer;
A developing step, which uses a developing solution to remove the unexposed portions after the exposure;
The conductor pattern forming step is for etching or plating a conductor substrate on which a resist pattern is formed by the development; and the peeling step is for peeling the resist pattern.
＜ Means for solving the third problem ＞
The inventors have found that the above-mentioned problems can be solved by the following technical means. A third embodiment of the present invention is described below.
[1] A photosensitive resin composition comprising
(A) Alkali-soluble polymers,
(B) a compound containing an ethylenically unsaturated bond, and
(C) A photopolymerization initiator, and the (A) alkali-soluble polymer includes (A) 10 to 24% by mass based on the total mass of the monomers constituting the (A) alkali-soluble polymer. Base) a structural unit of acrylic acid and a structural unit of 35 to 90% by mass of styrene, and the weight average molecular weight of the compound (B) containing an ethylenically unsaturated bond is 1,200 or more.
[2] The photosensitive resin composition according to [1], wherein the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is 1,300 or more.
[3] The photosensitive resin composition according to [1] or [2], wherein 40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is the following general formula (II):
[Chemical 2]

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n _3, and n ₄ satisfy n ₁ + n ₂ + N ₃ + n ₄ = an integer with a relationship of 2 to 50. The arrangement of repeating units of-(AO)-and-(BO)-can be random or block. In the case of block,-(AO) -And- (BO) -Either can be biphenyl side}
The represented alkylene oxide modified bisphenol A type di (meth) acrylate compound.
[4] The photosensitive resin composition according to [3], wherein n ₁ , n ₂ , n _3, and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30-50 .
[5] The photosensitive resin composition according to [3], wherein n ₁ , n ₂ , n _3, and n ₄ in the general formula (II) satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 .
[6] The photosensitive resin composition according to [1] or [2], wherein the (B) ethylenic unsaturated bond-containing compound contains the following general formula (III):
[Chemical 3]

{In the formula, R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ are each independently 0 to 40 Integer, m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, a plurality of X may be the same or different from each other}
The indicated tri (meth) acrylate compound.
[7] The photosensitive resin composition according to [1] or [2], wherein the compound (B) containing an ethylenically unsaturated bond includes the following general formula (IV):
[Chemical 4]

{In the formula, R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t are each independently an integer of 0 to 40 And s ＋ t ≧ 1}
The bis (meth) acrylate urethane compound represented.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (A) alkali-soluble polymer further includes a structural unit of butyl (meth) acrylate.
[9] The photosensitive resin composition according to any one of [1] to [8], which is for direct image exposure.
[10] A method for forming a resist pattern, including:
A laminating step of a photosensitive resin layer comprising a photosensitive resin composition according to any one of [1] to [9] in a supporting volume layer;
The exposure step is to expose the photosensitive resin layer; and the developing step is to develop the exposed photosensitive resin layer.
[11] A method for manufacturing a wiring board, including:
A laminating step in which a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [9] is laminated on a substrate;
An exposure step of exposing the photosensitive resin layer;
A developing step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
The conductor pattern forming step includes etching or plating the substrate on which the resist pattern is formed; and the peeling step includes peeling the resist pattern.
＜ Means for solving the fourth problem ＞
The present inventors have found that the above-mentioned object can be achieved by the following technical means, thereby completing the fourth embodiment of the present invention. A fourth embodiment of the present invention is described below.
[1] A photosensitive resin composition comprising
(A) Alkali-soluble polymers,
(B) a compound containing an ethylenically unsaturated bond, and
(C) Photopolymerization initiator, and the first copolymerization in which (A) the alkali-soluble polymer contains an acid monomer unit with a content ratio of less than 25% by mass and an aromatic monomer unit with a content ratio of 30% by mass or more And the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is 900 or less.
[2] The photosensitive resin composition according to [1], wherein the (C) photopolymerization initiator includes an acridine compound.
[3] The photosensitive resin composition according to [1] or [2], wherein the (A) alkali-soluble polymer comprises a second copolymer having an aromatic monomer unit in a content ratio of 45% to 90% by mass .
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the (B) ethylenically unsaturated bond-containing compound contains the following general formula (III):
[Chemical 5]

{In the formula, R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ are each independently 0 to 40 Integer, m ₂ + m ₃ + m ₄ is 0 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, a plurality of X may be the same or different from each other}
The indicated tri (meth) acrylate compound.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the (B) ethylenically unsaturated bond-containing compound contains the following general formula (II):
[Chemical 6]

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n _3, and n ₄ satisfy n ₁ + n ₂ + N ₃ + n ₄ = an integer with a relationship of 2 to 50. The arrangement of repeating units of-(AO)-and-(BO)-can be random or block. In the case of block,-(AO) -And- (BO) -Either can be biphenyl side}
The represented alkylene oxide modified bisphenol A type di (meth) acrylate compound.
[6] The photosensitive resin composition according to any one of [1] to [5], further comprising a hindered phenol of the following general formula (V):
[Chemical 7]

{Wherein R ⁵¹ represents a substituted linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group connected via a divalent linking group, and a branched alkyl group connected via a divalent linking group Cyclohexyl linked via a divalent linking group or aryl linked via a divalent linking group, and each of R ⁵² , R ⁵³ and R ⁵⁴ independently represents hydrogen, or a linear or branched alkyl group which may be substituted , Aryl, cyclohexyl, linear alkyl linked via a divalent linking group, branched alkyl linked via a divalent linking group, cyclohexyl linked via a divalent linking group, or aryl linked via a divalent linking group }.
[7] The photosensitive resin composition according to any one of [1] to [6], which is for direct image exposure.
[8] A photosensitive element comprising a photosensitive resin layer comprising a photosensitive resin composition according to any one of [1] to [7] laminated on a support.
[9] A method for forming a resist pattern, including:
A lamination step of laminating the above-mentioned photosensitive resin layer of a photosensitive element as described in [8] on a conductor substrate;
The exposure step involves exposing the above-mentioned photosensitive resin layer, and the developing step comprises developing the exposed photosensitive resin layer.
[10] A method for manufacturing a wiring board, including:
A lamination step of laminating the above-mentioned photosensitive resin layer of a photosensitive element as described in [8] on a conductor substrate;
An exposure step, which exposes the above-mentioned photosensitive resin layer;
A developing step of developing the exposed photosensitive resin layer to form a resist pattern on the conductive substrate;
The conductive pattern forming step includes etching or plating the conductive substrate on which the resist pattern is formed; and the peeling step includes peeling the resist pattern.
[Effect of the invention]
<Effects of the First Embodiment>
According to a first embodiment of the present invention, there is provided a resist material that suppresses a vertical and horizontal difference in wiring width when a fine conductive pattern is formed by pipeline processing.
<Effect of the Second Embodiment>
According to a second embodiment of the present invention, there is provided a novel photosensitive material that has properties generally required for photosensitive materials such as sensitivity and resolution, and has excellent development dispersibility and fine pattern adhesion.
<Effect of the Third Embodiment>
According to a third embodiment of the present invention, there is provided a photosensitive resin composition capable of having both a hole-covering property of a resist pattern and a suppression effect of a residual water short-circuit defect.
<Effects of the Fourth Embodiment>
According to a fourth embodiment of the present invention, there is provided a photosensitive resin composition capable of ensuring good resolution of a resist pattern and extending a minimum development time, and a method for forming a resist pattern or a wiring board using the same.

<First Embodiment>
The form for implementing the first embodiment of the present invention will be specifically described below (hereinafter referred to as "the first embodiment").
<Photosensitive resin composition>
In this first embodiment, the photosensitive resin composition contains the following components (A) to (C),
(A) Ingredient: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and
(C) component: A photoinitiator.
[(A) component: alkali-soluble polymer]
The component (A) is not particularly limited as long as it is soluble in the developer described below. Copolymers of (meth) acrylic acid and other monomers are preferred. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight (described below) of the copolymer to the number average molecular weight is preferably 1 or more and 6 or less.
Examples of (meth) acrylic acid include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, fumaric acid, citraconic anhydride, and the like. Among these, (meth) acrylic acid is preferred.
The copolymerization ratio of the (meth) acrylic acid unit in the component (A) is preferably 10% to 24% by mass, and more preferably 15% to 23% by mass relative to the total mass of all the monomer units. . The content ratio of the (meth) acrylic unit in this range is preferable from the viewpoints of suppression of the etching rate when the conductor pattern is formed (the bottom width of the above-mentioned conductor line pattern is kept constant or more), and suppression of the vertical and horizontal difference of the wiring width. .
Examples of other monomers include unsaturated aromatic compounds (also sometimes referred to as "aromatic monomers"), alkyl (meth) acrylates, aralkyl (meth) acrylates, and conjugated dimers. Olefin compounds, polar monomers, crosslinkable monomers, and the like.
Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, and vinylnaphthalene. Among them, styrene is preferred.
The concept of alkyl (meth) acrylate includes both chain alkyl esters and cyclic alkyl esters. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Hexyl ester, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Lauryl acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate and the like;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butadiene. Diene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3- Butyl-1,3-octadiene and the like.
Examples of the polar monomer include:
Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
Amine group-containing monomers such as 2-aminoethyl methacrylate;
(Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and other monomers containing amidine groups;
Cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate, divinylbenzene, and the like.
The component (A) is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.
The copolymerization ratio of the styrene unit in the component (A) is preferably 32% by mass or more and more preferably 35% by mass or more with respect to the total mass of all the monomer units. The copolymerization ratio of the styrene unit in the component (A) is preferably 60% by mass or less, more preferably 55% by mass or less, based on the total mass of all the monomer units. It is preferable to set the copolymerization ratio of styrene having high hydrophobicity and being difficult to be dissolved in a developing solution and a developing water washing water within the above range, from the viewpoint of suppressing the vertical and horizontal differences in wiring width.
The weight average molecular weight of the component (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 15,000 to 100,000. Adjusting the weight-average molecular weight of the component (A) within this range is preferable from the viewpoint of making the development time at the time of forming the resist pattern suitable for the working state of the pipeline processing used.
In the first embodiment, the content of the component (A) in the photosensitive resin composition is based on the total amount of solid components of the photosensitive resin composition (hereinafter, unless otherwise specified, each contained component is based on this) 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 60% by mass. This content is preferably 10% by mass or more from the viewpoint of maintaining alkaline developability, and is more preferably from the viewpoint of fully exhibiting the performance of the resist pattern formed by exposure as a resist pattern. 90% by mass or less.
For a copolymer having a (meth) acrylic unit content ratio of 10% to 24% by mass and a styrene unit content ratio of 32% to 60% by mass, the total solid content of the photosensitive resin composition is The reference meter is preferably 8% or more, more preferably 10% by mass or more, and particularly preferably 13.5 / 99.19 × 100% by mass or more. In addition, regarding a copolymer having a (meth) acrylic unit content ratio of 10% to 24% by mass and a styrene unit content ratio of 32% to 60% by mass, the total solid content of the photosensitive resin composition The amount is based on a standard, and may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 27 / 99.19 × 100% by mass, or 20% by mass or less.
[(B) component: compound having an ethylenic double bond]
(B) A component should just have one or more ethylenic double bonds. It is preferable to use a compound having two or more ethylenic double bonds.
As the (B) compound having two ethylenic double bonds, for example, a bisphenol A compound can be preferably used, and the two ends of the bisphenol A are preferably added with an average of 2 mol to 15 mol of alkylene oxide. The poly (alkylene glycol) di (meth) acrylate and the like.
In addition, as the (B) compound having three ethylenic double bonds, for example, a trimethylolpropane compound can be preferably used, and in particular, trimethylolpropane is added to an average of 3 to 25 mol of epoxy. Poly (alkylenetriol) tris (meth) acrylates and the like.
Furthermore, as the (B) compound having four ethylenic double bonds, for example, a pentaerythritol compound, especially a polyhydric alcohol obtained by adding an average of 4 mol to 35 mol of alkylene oxide to pentaerythritol can be preferably used. (Meth) acrylates and the like.
Examples of such commercially available products include: "BPE-500", "A-TMPT-3EO", "A-9300-1CL", etc. (the above are all manufactured by Shin Nakamura Chemical Co., Ltd.);
"ARONIX M-327", etc. (manufactured by Toa Kosei).
The content of the component (B) in the photosensitive resin composition of the first embodiment is preferably 1% to 70% by mass, more preferably 5% to 60% by mass, and even more preferably 10% to 50%. quality%. This content is preferably 1% by mass or more from the viewpoints of suppressing poor curing and retardation of development time. On the other hand, from the viewpoint of suppressing cold flow and suppressing peeling delay of the cured resist, it is preferably 70% by mass or less.
As the component (B), a high molecular weight compound having a molecular weight of 1,000 or more is preferably used. The molecular weight of the high molecular weight compound is more preferably 1,300 or more and 3,000 or less. Containing such a high molecular weight compound is preferred from the viewpoints of suppression of the etching rate when forming the conductor pattern and suppression of the vertical and horizontal differences in the wiring width.
The ratio of such a high molecular weight compound to the component (B) is preferably 20% by mass or more, and more preferably 20 to 50% by mass.
Here, the DD value is defined as an index of the double bond concentration of the component (B). The DD value is the number of double bonds of a monomer having an average molecular weight per unit weight, and is a value unique to each monomer.
When a monomer having a small DD value is used in the photosensitive resin composition, the film after photocuring tends to be soft.
When the component (B) contains a plurality of ethylenically unsaturated bond-containing compounds, a weighted average of the DD value and the blending ratio of each ethylenically unsaturated bond-containing compound is considered as the DD value of the composition.
From the viewpoint of suppressing the vertical and horizontal difference of the wiring width or improving the capping property, the range of the DD value of the preferred composition is 0.10 to 0.13. More preferably, it is 0.10 to 0.125.
[(C) component: Photopolymerization initiator]
The component (C) is a component which generates a radical capable of starting the polymerization of the component (B) by irradiation with light.
Examples of such a component (C) include aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzoin compounds, hexaarylbisimidazole compounds, and acridine compounds.
Among these, an acridine compound is preferably used from the viewpoint of high resolvability and good pore-covering property.
The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass, even more preferably 0.3% by mass, and more preferably It was 0.4% by mass.
The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, more preferably 1.7% by mass or less, and even more preferably 1.6% by mass. the following. If it is the said range, it is preferable to be able to provide the resist material which suppresses the width-to-width difference of a wiring width.
Examples of the acridine compound include acridine, 9-phenylacridine, 1,6-bis (9-acridyl) hexane, 1,7-bis (9-acridyl) heptane, 1 , 8-bis (9-acridyl) octane, 1,9-bis (9-acridyl) nonane, 1,10-bis (9-acridyl) decane, 1,11-bis ( 9-acridyl) undecane, 1,12-bis (9-acridyl) dodecane, and the like.
As the component (C), an acridine compound and a hexaarylbisimidazole compound are preferably used.
Examples of the hexaarylbisimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,2 ', 5-tri- (o-chlorophenyl)- 4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylimidazole dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-di (Methoxyphenyl) -diphenylimidazole dimer, 2,4,5-tri- (o-chlorophenyl) -diphenylimidazole dimer, 2- (o-chlorophenyl) -bis-4 , 5- (3,4-dimethoxyphenyl) -imidazole dimer, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetra- (3 -Methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetra- (3-methoxy Phenyl) -imidazole dimer, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl)- Imidazole dimer, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,6-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'- Bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- ( 2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3 , 6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetra- (3- (Methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxy Phenyl) -imidazole dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxybenzene ) -Imidazole dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl ) -Imidazole dimer, 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxybenzene ) -Imidazole dimer and the like.
The content of the (C) component in the photosensitive resin composition of the first embodiment is preferably in a range of 0.1% to 2% by mass, more preferably in a range of 0.2% to 1.8% by mass, and further preferably 0.3% by mass. The range is from -1.7% by mass, particularly preferably from 0.4% by mass to 1.6% by mass. Setting the content of the (C) component to such a range is preferable from the viewpoint of obtaining good light sensitivity and peeling characteristics.
From the viewpoint of improving sensitivity and resolution, the component (C) may further contain a sensitizer. Examples of such sensitizers include N-arylamino acids, organic halogen compounds, and other sensitizers.
Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like;
Examples of the organic halogen compound include bromopentane, bromoisopentane, brominated isobutylene, 1,2-dibromoethane, benzhydryl bromide, benzyl bromide, dibromomethane, and tribromomethylphenyl. Samarium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, isobutyl iodide, 1,1,1-trichloro-2,2-bis (P-chlorophenyl) ethane, trichloride Compounds etc.
Examples of the other sensitizer include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, and 2 1,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone , 3-chloro-2-methylanthraquinone and other quinone compounds;
Aromatic ketones such as benzophenone, Michelin [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone Compound
Benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin and other benzoin ether compounds;
Benzophenone dimethyl ketal, Benzophenone diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione Oxime ester compounds such as 2- (O-ethoxycarbonyl) oxime and the like.
From the viewpoints of the photosensitivity of the composition and the peelability of the resist cured film, the content of the sensitizer in the first embodiment is preferably from 0.01% by mass to 5% by mass, and more preferably from 0.05% by mass to 3 mass%, more preferably 0.1 mass% to 2 mass%.
In addition, in the photosensitive resin composition of the first embodiment, it is preferable to use an acridine compound and an N-aryl group in terms of suppression of the etching rate when forming the conductor pattern, and suppression of the vertical and horizontal differences in the wiring width. The amino acid is used in combination as the component (C) within a range equal to the above-mentioned usage ratio.
[Other ingredients]
The photosensitive resin composition of the first embodiment may contain components other than the components (A) to (C) described above. Examples of such other components include leuco dyes, base dyes, plasticizers, antioxidants, stabilizers, radical polymerization inhibitors, solvents, and the like.
[Hide dye]
The leuco dye may be blended in the photosensitive resin composition of the first embodiment in order to impart a moderate color rendering property and an excellent peeling property to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tri [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl)- 6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4 -Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 1,3-dimethyl -6-diethylaminofluoran, 2-chloro-3-methyl-6-dimethylaminofluoran, 3-dibutylamino-6-methyl-7-anilinefluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 2- (2-chloroaniline) -6-dibutylaminofluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluorane, 1,2-benzo-6-diethylaminofluorine Alkanes, 1,2-benzo-6-dibutylaminofluoranes, 1,2-benzo-6-ethylisoamylaminofluoranes, 2-methyl-6- (N-p-toluene -N-ethylamino) fluoran, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethylamino) fluoran, 2- ( 3'-trifluoromethylaniline) -6-diethylaminofluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylamine Fluorane, 3-methoxy-4-dodecyloxystyrylquinoline, etc. Among these, leuco crystal violet is preferred.
The content of the leuco dye in the photosensitive resin composition of the first embodiment is preferably 0.6% by mass to 1.6% by mass, and more preferably 0.7% by mass to 1.2% by mass. By setting the use ratio of the leuco dye within this range, good color rendering properties and good peelability can be achieved.
[Basic dye]
Examples of the basic dye include basic green 1 [CAS number (the same applies hereinafter): 633-03-4] (for example, Aizen Diamond Green GH (trade name), manufactured by Hodogaya Chemical Industry), and malachite [2437-29-8] (for example, Aizen Malachite Green (trade name), manufactured by Hodogaya Chemical Industry), bright green [633-03-4], magenta [632-99-5], methyl violet [603- 47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], alkali Sex blue 7 [2390-60-5] (for example, Aizen Victoria Pure Blue BOH (trade name), manufactured by Hodogaya Chemical Industry), rhodamine B [81-88-9], rhodamine 6G [989-38- 8], Basic Yellow 2 [2465-27-2], Diamond Green, etc. Among these, one or more selected from the group consisting of basic green 1, malachite greenate, basic blue 7, and diamond green are preferred. From the viewpoint of hue stability and exposure contrast, alkali is particularly preferred. Sex green 1.
The content of the basic dye in the photosensitive resin composition of the first embodiment is preferably 0.001% to 3% by mass, more preferably 0.01% to 2% by mass, and still more preferably 0.01% to 1.2% by mass. Range of mass%. By setting the use ratio within this range, both good color rendering and high sensitivity can be achieved.
[Solvent]
The photosensitive resin composition according to the first embodiment may be a mixture of the components (A) to (C) and any other components used arbitrarily, or a photosensitive resin composition prepared by adding an appropriate solvent to these components may be blended. Use as a liquid.
Examples of the solvent used here include:
Ketone compounds such as methyl ethyl ketone (MEK);
Alcohols such as ethanol, ethanol and isopropanol.
The use ratio of the solvent is preferably a ratio such that the viscosity of the photosensitive resin composition preparation solution at 25 ° C. becomes 500 to 4,000 mPa · sec.
<Photosensitive element>
In this first embodiment, the photosensitive element is a laminated body (photosensitive resin laminated body) in which a photosensitive resin layer containing the above-mentioned photosensitive resin composition is laminated on a support. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer on the side opposite to the support.
[Support body]
The support is preferably a transparent substrate that can transmit light emitted from the exposure light source. 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, and a vinylidene chloride copolymer film. , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. As these films, an extender may be used as necessary.
The haze of the support is preferably 5 or less.
The thickness of the support is thin, which is conducive to image formation and economy, but the strength must be maintained. Considering these two parties, a support of 10 μm to 30 μm can be preferably used.
[Photosensitive resin composition layer]
When the photosensitive resin composition for forming a photosensitive resin composition layer contains a solvent, it is preferable to remove the solvent from the photosensitive resin composition layer, but the solvent may remain.
The thickness of the photosensitive resin composition layer is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.
[The protective layer]
An important characteristic of the protective layer is that the adhesive force between the protective layer and the photosensitive resin composition layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin composition layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferably used, and a film having excellent peelability disclosed in, for example, Japanese Patent Laid-Open No. 59-202457 can also be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.
[Manufacturing method of photosensitive element]
The photosensitive element can be manufactured by sequentially laminating a support, a photosensitive resin layer, and a protective layer as necessary. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be adopted.
For example, the photosensitive resin composition is prepared in the form of the above-mentioned photosensitive resin composition blending solution. First, the photosensitive resin composition is coated on a support using a bar coater or a roll coater, and dried to form a support. A photosensitive resin composition layer containing a photosensitive resin composition. Then, a protective layer is laminated on the formed photosensitive resin composition layer as necessary, whereby a photosensitive element can be manufactured.
<Formation method of resist pattern>
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The method for forming the resist pattern preferably includes the following order:
A laminating step in which a photosensitive resin layer of a photosensitive element is laminated on a conductor substrate;
An exposure step of exposing the above-mentioned laminated photosensitive resin composition layer; and
The developing step is to remove the unexposed portions after the exposure by using a developing solution.
The laminating step is preferably a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent. The humectant preferably contains one or more copper chelating agents selected from pure water, deionized water, and electrolytic water (for example, selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). One or more of them).
In the method for forming a resist pattern of the first embodiment, first, in a laminating step, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin composition layer is heated and pressure-bonded to the substrate surface using a laminator to be laminated.
As the substrate, a metal plate or an insulating substrate having a metal film is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). These substrates may also have through holes for dealing with multilayer substrates.
Here, the photosensitive resin composition layer may be laminated only on one side of the substrate surface, and the photosensitive resin composition layer may be laminated on both sides of the substrate as necessary. The heating temperature at this time is preferably 40 ° C to 160 ° C. From the viewpoint of further improving the adhesiveness between the obtained resist pattern and the substrate, it is preferable to perform the thermocompression bonding twice or more. When performing crimping more than two times, a two-stage laminator equipped with a double roll can be used, or the laminate of the substrate and the photosensitive resin composition layer can be repeatedly crimped through the roll several times.
Then, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. The exposure may be performed through the support without peeling the support, or may be performed after the support is peeled as necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after the following development steps. The patterned exposure may be either a method of exposing through a mask, or a method of exposure without a mask. When exposure is performed through a mask, the exposure amount is determined according to the illuminance of the light source and the exposure time. The exposure amount can be measured using a light meter.
In the maskless exposure, a drawing device is directly used for exposure on a substrate without using a mask. As a light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, and the like are used. In maskless exposure, the pattern drawn is controlled by a computer, and the exposure amount depends on the illuminance of the exposure light source and the moving speed of the substrate.
Then, in a developing step, the unexposed part of the photosensitive resin composition layer is removed with a developing solution. In the case where a support is present on the photosensitive resin composition layer, it is preferable to remove it after exposure and then provide it to the development step.
In the developing step, a developing solution containing an alkaline aqueous solution is used to develop and remove the unexposed portion to obtain a resist image. As the alkaline aqueous solution, for example, Na is preferably used. ₂ CO ₃ K ₂ CO ₃ And other aqueous solutions. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, and it is preferable to use Na at a concentration of 0.2% to 2% by mass. ₂ CO ₃ Aqueous solution. A surfactant, a defoaming agent, and a small amount of an organic solvent for promoting development can also be mixed into the alkaline aqueous solution.
The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 ° C to 40 ° C.
A resist pattern is obtained through the above steps. Depending on the circumstances, a heating step of 100 ° C to 300 ° C may be performed. It is preferable to implement this heating step from the viewpoint of further improving chemical resistance. Heating can be performed using a suitable heating furnace such as hot air, infrared, or far infrared.
＜ How to form a wiring board ＞
The method for forming a wiring board according to the first embodiment preferably includes the following sequence:
A laminating step in which a photosensitive resin composition layer of a photosensitive element is laminated on a conductor substrate;
An exposure step, which exposes the photosensitive resin composition layer of the above-mentioned laminated layer;
A developing step, which uses a developing solution to remove the unexposed portions after the exposure;
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above development; and
The peeling step is to peel the resist pattern.
The laminating step is preferably a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent. The humectant preferably contains one or more copper chelating agents selected from pure water, deionized water, and electrolytic water (for example, selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). One or more of them).
In the conductive pattern forming step, a conductive pattern may be formed on a substrate surface (for example, a copper surface) exposed through the development step by using a known etching method or plating method on the substrate on which the resist pattern is formed.
In the above-mentioned peeling step, the resist pattern is peeled off by contacting the substrate on which the conductor pattern is formed with an appropriate peeling solution. Through this step, the required wiring board is obtained.
The peeling liquid used in the peeling step is preferably an alkaline aqueous solution. As this alkaline aqueous solution, it is preferable to use, for example, a 2 to 5 mass% NaOH aqueous solution or a KOH aqueous solution. A small amount of a water-soluble solvent such as an alcohol may be added to the peeling solution. The temperature of the peeling liquid in the peeling step is preferably set to 40 ° C to 70 ° C.
Generally, when a conductor pattern is formed by etching, the etching time to achieve a desired wiring width can be adjusted, for example, by adjusting the transfer speed of the etching line, regardless of the etching speed. However, when the etching speed is too fast, the conveying speed becomes too fast, and there are cases in which the etching time cannot be set in actual operation.
Furthermore, in recent years, the manufacture of wiring boards is usually performed by a pipeline process in which the substrates are sequentially transported while the substrates are transported in a certain direction, and the conductor lines may be parallel to the substrate transport direction (lines in the MD direction). Vertical case (line in TD direction) and inclined case. In particular, when the etching rate is fast, the vertical and horizontal differences in the width of the wiring tend to become more pronounced.
The inventors of the present inventors have worked hard to find out that when the photosensitive resin composition forming the hardened resist pattern has specific physical properties, it can be provided to suppress the vertical and horizontal differences in wiring width when forming a fine conductive pattern by pipeline processing. Resist material.
That is, the photosensitive resin composition of the first embodiment has the following characteristics: a photosensitive resin layer containing the above-mentioned photosensitive resin composition is laminated on a copper-clad laminate having a copper foil with a thickness of 18 μm and a thickness of 25 μm; The hardened resist pattern was formed by patterned light irradiation with a line / gap = 50 μm / 30 μm and development treatment. After performing a copper etch treatment at 50 ° C for 55 seconds, the hardened resist pattern was removed to obtain copper. The bottom width of the line pattern is 38 μm or more (preferably 38 μm to 50 μm, more preferably 40 μm to 45 μm).
However, the resist pattern may swell / shrink in each step of the development, water washing step, and etching step, especially the swelling / shrinkage is larger in the water washing step. It is considered that the swelling / shrinkage of the resist pattern reduces the adhesion between the wiring and the resist pattern. The resist pattern formed from the photosensitive resin composition of the first embodiment has less swelling / shrinkage in any of the development, washing steps, and etching steps, and is not likely to be etched at the interface between the resist pattern and the wiring. Suppresses vertical and horizontal differences in wiring width.
In the first embodiment, the specific photosensitive resin composition is strictly distinguished from the characteristic when the specific analysis method (specific etching conditions) is adopted (the bottom width of the conductor line width is equal to or more than a certain value), and the invention effect is exhibited. means.
The adjustment of the bottom width of the conductor line width can be adjusted by appropriately setting the composition of the photosensitive resin composition.
In addition, the conductor pattern (wiring) formed by the method for forming a wiring board according to the first embodiment described above can achieve a very small vertical and horizontal difference in the width of the conductor pattern. The vertical and horizontal difference in wiring width is the difference between the wiring width (TD) of the conductor line in the TD direction and the wiring width (MD) of the conductor line in the MD direction, which is the amount represented by TD-MD.
The absolute value of the vertical and horizontal difference of the wiring width in the conductor pattern formed by the method for forming a conductor pattern according to the first embodiment is preferably 0 μm to 5 μm, and more preferably 0 μm to 3 μm.
The method for forming a photosensitive resin composition, a photosensitive element, and a wiring board in the first embodiment can be used to manufacture, for example, a printed wiring board, a lead frame, a substrate having a concave-convex pattern, and a semiconductor package.
It should be noted that the measurement methods of the above-mentioned various parameters are measured according to the measurement methods in the following examples unless otherwise specified.
<Second Embodiment>
The form for implementing the second embodiment of the present invention will be specifically described below (hereinafter referred to as "this second embodiment").
<Photosensitive resin composition>
In this second embodiment, the photosensitive resin composition contains the following components (A) to (C),
(A) component: alkali-soluble polymer with an acid equivalent of 100 to 600,
(B) component: a compound having an ethylenic double bond, and
(C) component: A photoinitiator.
[(A) component: alkali-soluble polymer]
The component (A) contains a copolymer having an acid equivalent of 100 to 600 (preferably 200 to 500, more preferably 250 to 450) and containing 50% by mass or more of a styrene unit. Herein, the styrene unit in the present specification means substituted or unsubstituted styrene. The substituent is not particularly limited, and examples thereof include an alkyl group, a halogen group, and a hydroxyl group.
(A) The copolymer of a component type styrene derivative and other monomers, such as an acid monomer, is preferable.
Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, fumaric acid, and citraconic anhydride. Among these, (meth) acrylic acid is preferred.
Examples of other monomers include unsaturated aromatic compounds (also sometimes referred to as "aromatic monomers"), alkyl (meth) acrylates, aralkyl (meth) acrylates, and conjugated dimers. Olefin compounds, polar monomers, crosslinkable monomers, and the like.
Examples of the unsaturated aromatic compound include vinylnaphthalene.
The concept of alkyl (meth) acrylate includes both chain alkyl esters and cyclic alkyl esters. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Hexyl ester, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Lauryl acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate and the like;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butadiene. Diene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3- Butyl-1,3-octadiene and the like.
Examples of the polar monomer include:
Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
Amine group-containing monomers such as 2-aminoethyl methacrylate;
(Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and other monomers containing amidine groups;
Cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate, divinylbenzene, and the like.
The component (A) is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.
(A) The component 1 contains the copolymer 1 containing a styrene unit of 50 mass% or more. The amount of the styrene unit in the copolymer 1 is preferably 50% by mass to 80% by mass, and more preferably 51% by mass to 70% by mass.
The component (A) in the second embodiment may be composed of only the copolymer 1 or a mixture of the copolymer 1 and another polymer. The content of the copolymer 1 in the component (A) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass.
The other polymer is preferably a copolymer of the acid monomer and other monomers described above and does not belong to the copolymer 1 (copolymer 2).
The weight average molecular weight of the component (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 15,000. ~ 100,000. Adjusting the weight-average molecular weight of the component (A) within this range is preferable from the viewpoint of making the development time at the time of forming the resist pattern suitable for the working state of the pipeline processing used. The dispersion degree of the copolymer represented by the ratio of the weight average molecular weight to the number average molecular weight of the component (A) is preferably 1 or more and 6 or less.
In this second embodiment, the content of the component (A) in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition as a basis (unless otherwise specified, each contained component is based on this) 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 60% by mass. This content is preferably 10% by mass or more from the viewpoint of maintaining alkaline developability, and is more preferably from the viewpoint of fully exhibiting the performance of the resist pattern formed by exposure as a resist pattern. 90% by mass or less.
[(B) component: compound having an ethylenic double bond]
The component (B) is not particularly limited as long as it has one or more ethylenic double bonds. However, the component (B) in the second embodiment includes the following general formula (I) as a compound (B1) which must be contained:
[Chemical 8]

{In the formula, each of R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2, and n3 are each independently an integer of 0 to 30, wherein the condition represented by n1 + n2 + n3 ≧ 6 is satisfied}.
In the formula (I), R is preferably each independently a hydrogen atom or a methyl group, and more preferably a hydrogen atom. n1, n2, and n3 are each preferably an integer of 1 to 30, and more preferably an integer of 3 to 21.
In formula (I), from the viewpoint of improving the development dispersibility, the value of n1 + n2 + n3 is preferably more than 9 and 20 or less, and more preferably 15 or more and 20 or less.
In the formula (I), from the viewpoint of improving the development dispersibility, it is preferred that at least one R is a hydrogen atom, and it is more preferred that all R be a hydrogen atom.
Further, in the formula (I), from the viewpoint of having both development dispersibility and adhesion, it is particularly preferred that all R are hydrogen atoms and the value of n1 + n2 + n3 is 15 or more and 20 or less.
The compound represented by formula (I) can be synthesized by a known method, for example, an adduct obtained by adding trimethylolpropane to more than 6 equivalents of ethylene oxide, and further, to 3 mol of (meth) acrylic acid Obtained by addition or transesterification.
Preferred specific examples of the compound represented by the formula (I) include ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (the total number of EO addition moles is 6 to 20). Wait.
The component (B) in the second embodiment may be composed of only the compound (B1), or may be a mixture of the compound (B1) and other (B) components.
When the component (B) of the second embodiment is a mixture, the content of the compound (B1) in the mixture is based on the total mass of the mixture, preferably 10% by mass or more, more preferably 10% by mass to 50% The mass% is more preferably 15 mass% to 35 mass%.
The content of the compound (B1) in the photosensitive resin composition of the second embodiment is based on the total solid content of the photosensitive resin composition, and is preferably 5% by mass or more, and more preferably 5.5% by mass or more. 30 mass%, more preferably 6 mass% to 20 mass%.
Here, by including an alkali-soluble polymer having a specific acid equivalent and a specific amount of styrene units, the above-mentioned (B1) component and acridine, a photosensitive resin excellent in both development dispersibility and fine pattern adhesion is realized. The mechanism of the composition is not clear. It is speculated that the interaction between the styrene unit and the acridine component (based on the π-electron stack) and the interaction between the acid monomer and the above-mentioned (B1) component (based on hydrogen bonding) are well developed, and the overall Compatibility is improved, thereby contributing to the above characteristics.
In the second embodiment, from the viewpoint of development dispersibility, the component (B) preferably contains the compound (B1) and a pentaerythritol-modified monomer (hereinafter referred to as "compound (B2)"). As the compound (B2), an alkylene oxide added to pentaerythritol is preferably 4 mol to 35 mol on average, more preferably 8 mol to 28 mol, and still more preferably 12 mol to 20 mol. Tetrakis (meth) acrylate of polyhydric alcohols.
The content of the compound (B2) in the component (B) is based on the total mass of the component (B), and is preferably 10% by mass to 40% by mass, and more preferably 15% by mass to 30% by mass.
The content of the compound (B2) in the photosensitive resin composition of the second embodiment is preferably 1% by mass or more, more preferably 1% by mass to 20% by mass, and still more preferably 5% by mass to 15% by mass.
The component (B) may include a compound having an ethylenic double bond other than the compounds (B1) and (B2).
(B) Ingredients may also include the following ingredients:
Bisphenol A compounds, for example, poly (alkyl) glycol di (meth) acrylates obtained by adding an average of 2 mol to 15 mol of alkylene oxide to both ends of bisphenol A;
Compounds with three ethylenic double bonds (except for B1), such as poly (alkylene triol) (trimethylol) added to trimethylolpropane to an average of 3 mol to 25 mol of alkylene oxide ) Acrylate, etc.
The content of the component (B) in the photosensitive resin composition of the second embodiment is preferably 1% to 70% by mass, more preferably 5% to 60% by mass, and even more preferably 10% to 50%. quality%. This content is preferably 1% by mass or more from the viewpoint of suppressing poor curing and delaying the development time, and is preferably 70% by mass or less from the viewpoint of suppressing generation of agglomerates in the developing solution.
[(C) component: Photopolymerization initiator]
The component (C) is a component which generates a radical capable of starting the polymerization of the component (B) by irradiation with light.
In the second embodiment, as the (B) photopolymerization initiator, an acridine compound can be used. Further, an acridine compound may be used in combination with another photopolymerization initiator. The acridine-based compound is preferably used for improving the sensitivity and resolution of the photosensitive resin composition of the second embodiment.
Examples of the acridine compound include 1,7-bis (9,9'-acridyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9- Chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-third-butylphenyl) acridine, 9- (4-methoxybenzene Group) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetamidophenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9 -(4-chlorophenyl) acridine, 9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine , 9- (3-ethylaminophenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- ( 3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl ) Acridine and so on.
Examples of other photopolymerization initiators include:
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,2 ', 5-tri- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) ) -4 ', 5'-diphenylimidazole dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazole dimer Compounds, 2,4,5-tri- (o-chlorophenyl) -diphenylimidazole dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxybenzene ) -Imidazole dimer, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2 '-Bis- (2,4-difluorophenyl) -4,4', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- ( 2,5-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,6-di (Fluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3,4-trifluorophenyl ) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4 , 4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4' , 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,4,5-trifluoro (Phenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl)- 4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4 , 4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3,4,5,6-pentafluorophenyl)- Hexarylbisimidazole compounds such as 4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer;
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2- ( O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl ) 2,4,5-triarylimidazole dimers such as 4,5-diphenylimidazole dimer (except those corresponding to the above-mentioned hexaarylbisimidazole compounds);
Benzophenone, N, N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michlerone), N, N'-tetraethyl-4,4'-di Aminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -Aromatic ketones such as butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-acetone-1;
2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2 , Quinone compounds such as 3-dimethylanthraquinone;
Benzoyl ether compounds such as benzoin methyl ether, benzoin ether, benzoin phenyl ether;
Benzopyrene derivatives such as benzoylpyrene;
N-phenylglycinic acid derivatives, coumarin-based compounds, 4,4'-bis (diethylamino) benzophenone, and the like.
The content of the acridine compound in the photosensitive resin composition of the second embodiment is preferably 0.001% to 2% by mass, more preferably 0.01% to 1.5% by mass, and still more preferably 0.1% to 1% by mass. Within the range of%.
The content of the (C) component (including the entire content of the (C) component of the acridine compound) in the photosensitive resin composition of the second embodiment is preferably 0.1% by mass to 2% by mass, and more preferably 0.2% by mass ∼1.8% by mass, more preferably 0.3% to 1.7% by mass, and particularly preferably 0.4% to 1.6% by mass.
From the viewpoint of improving sensitivity and resolution, the component (C) may further contain a sensitizer. Examples of such sensitizers include N-arylamino acids, organic halogen compounds, and other sensitizers.
Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like;
Examples of the organic halogen compound include bromopentane, bromoisopentane, brominated isobutylene, 1,2-dibromoethane, benzhydryl bromide, benzyl bromide, dibromomethane, and tribromomethylphenyl. Samarium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, isobutyl iodide, 1,1,1-trichloro-2,2-bis (P-chlorophenyl) ethane, trichloride Compounds etc.
Examples of the other sensitizers include:
2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1- Chloanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone Isoquinone compounds
Aromatic ketones such as benzophenone, Michelin [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone Compound
Benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin and other benzoin ether compounds;
Benzophenone dimethyl ketal, Benzophenone diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione Oxime ester compounds such as 2- (O-ethoxycarbonyl) oxime and the like.
From the viewpoints of the photosensitivity of the composition and the peelability of the resist cured film, the content of the sensitizer in the photosensitive resin composition of the second embodiment is preferably 0.01% by mass to 5% by mass, more It is preferably from 0.05% by mass to 3% by mass, and more preferably from 0.1% by mass to 2% by mass.
[Other ingredients]
The photosensitive resin composition of this second embodiment may contain components other than the components (A) to (C) described above. Examples of the other components include a coloring substance, a halogen compound, a stabilizer, and a solvent.
Examples of coloring substances include leuco dyes and other coloring substances;
Examples of the stabilizer include a radical polymerization inhibitor, a benzotriazole compound, a carboxybenzotriazole compound, and the like.
<Hydrochrome>
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [crypto crystal violet], bis (4-dimethylaminophenyl) phenylmethane [crypto malachite green] Wait. From the viewpoint of good contrast, it is particularly preferable to use leuco crystal violet.
The content of the leuco dye in the photosensitive resin composition is preferably from 0.1% by mass to 10% by mass. From the viewpoint of obtaining the contrast between the exposed portion and the unexposed portion, it is preferable to adjust the content of the leuco dye to 0.1% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, it is preferable to adjust the content of the leuco dye. The content is adjusted to 10% by mass or less.
＜ Other coloring substances ＞
Examples of other coloring substances include magenta, phthalocyanine green, golden amine base, para-magenta, crystal violet, methyl orange, Nero Blue 2B, Victoria Blue, and Malachite Green (manufactured by Hodogaya Chemical Co., Ltd., Aizen (Registered trademark) MALACHITE GREEN), basic blue 20, diamond green (manufactured by Hodogaya Chemical Co., Ltd., Aizen (registered trademark) DIAMOND GREEN GH), and the like.
The content of the other coloring matter in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass. From the viewpoint of improving workability, the content is preferably adjusted to 0.001% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, the content is preferably adjusted to 1% by mass or less.
<Halogen compound>
From a viewpoint of adhesiveness and contrast, it is preferable to use a leuco dye and the following halogen compound in combination in a photosensitive resin composition.
Examples of the halogen compound include bromopentane, bromoisopentane, brominated isobutylene, 1,2-dibromoethane, diphenylmethyl bromide, benzyl bromide, dibromomethane and tribromomethylphenyl Samarium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, isobutyl iodide, 1,1,1-trichloro-2,2-bis (P-chlorophenyl) ethane, trichloride Compounds etc. Especially preferred is tribromomethylphenylphosphonium. From the viewpoint of maintaining the storage stability of the hue in the photosensitive layer, the content of the halogen compound in the photosensitive resin composition is preferably from 0.01% by mass to 3% by mass.
<Free-radical polymerization inhibitor, benzotriazole compound, and carboxybenzotriazole compound>
Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, and 2,6-di-tert-butyl P-cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butyl) Phenol), aluminum nitrosophenylhydroxylamine, diphenylnitrosamine, and the like.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) amino Methyl-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) ) Aminomethylene-1,2,3-benzotriazole and the like.
Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di 2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N -Di-2-ethylhexyl) aminoethylethylcarboxybenzotriazole and the like.
The total content of the radical polymerization inhibitor, the benzotriazole compound, and the carboxybenzotriazole compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably adjusted to 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, it is more preferred to adjust the content. The content is adjusted to 3% by mass or less.
＜ Plasticizers ＞
The photosensitive resin composition may contain a plasticizer as needed. Examples of the plasticizer include phthalates such as diethyl phthalate, o-tosylamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, and ethyl citrate Triethyl ester, tri-n-propyl citrate, tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like.
The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, and more preferably 1% by mass to 30% by mass. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, the content is preferably adjusted to 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient curing and edge melting, The content is adjusted to 50% by mass or less.
<Solvent>
The photosensitive resin composition may contain a solvent. Examples of the solvent include ketones typified by methyl ethyl ketone (MEK); alcohols typified by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition such that the viscosity of the solution for the photosensitive resin composition applied on the support film at 500C becomes 500 mPa · s to 4,000 mPa · s.
<Photosensitive element>
In this second embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer containing the above-mentioned photosensitive resin composition is laminated on a support. The photosensitive element may have a protective layer on the surface of the photosensitive resin layer on the side opposite to the support if necessary.
[Support body]
The support is preferably a transparent substrate that can transmit light emitted from the exposure light source. Examples of the 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 copolymerization film, and a polymer film. Methyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. As these films, an extender may be used as necessary.
The haze of the support is preferably 5 or less.
The thinner support is advantageous in terms of image formation and economy, but the strength must be maintained. Considering these two parties, a support of 10 μm to 30 μm can be preferably used.
[Photosensitive resin layer]
When the photosensitive resin composition for forming a photosensitive resin layer contains a solvent, it is preferable to remove the solvent from the photosensitive resin layer, but it may remain in the photosensitive resin layer.
The thickness of the photosensitive resin layer is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the photosensitive resin layer can be appropriately selected from the range of 5 μm to 100 μm depending on the application.
[The protective layer]
An important characteristic of the protective layer is that the adhesive force between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferably used, and a film having excellent peelability disclosed in, for example, Japanese Patent Laid-Open No. Sho 59-202457 can also be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.
[Manufacturing method of photosensitive element]
The photosensitive element can be manufactured by sequentially laminating a support, a photosensitive resin layer, and a protective layer as necessary. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be adopted.
For example, a solvent is added to the photosensitive resin composition and mixed to prepare a blending solution. The mixture is then coated on a support using a bar coater or a roll coater and dried to form a photosensitive resin composition on the support. A photosensitive resin layer. Then, a protective layer is laminated on the formed photosensitive resin layer as necessary, whereby a photosensitive element can be manufactured.
<Formation method of resist pattern>
The photosensitive element as described above can be used to form a resist pattern on a substrate.
The method for forming the resist pattern preferably includes the following order:
A laminating step in which a photosensitive resin layer of a photosensitive element is laminated on a conductor substrate;
An exposure step of exposing the photosensitive resin layer of the above-mentioned laminated layer; and
The developing step is to remove the unexposed portions after the exposure by using a developing solution.
The laminating step is preferably a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent. The humectant preferably contains one or more copper chelating agents selected from pure water, deionized water, and electrolytic water (for example, selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). One or more of them).
In the method for forming a resist pattern according to the second embodiment, first, in a laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressure-bonded to the substrate surface using a laminator to be laminated.
As the substrate, a metal plate or an insulating substrate having a metal film can be used. Examples of the material of the metal include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). These substrates may also have through holes for dealing with multilayer substrates.
The photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides of the substrate as necessary. The heating temperature during lamination is preferably 40 ° C to 160 ° C. From the viewpoint of further improving the adhesiveness between the obtained resist pattern and the substrate, it is preferable to perform the thermocompression bonding twice or more. When performing crimping more than two times, a two-stage laminating machine equipped with a double roll can be used, or the laminate of the substrate and the photosensitive resin layer can be repeatedly crimped through the roll several times.
Then, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. The exposure may be performed through the support without peeling the support, and may be performed after the support is peeled if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after the following development steps. The pattern-shaped exposure can be performed by either a method of exposing through a mask and a method of maskless exposure. In the case of exposure through a mask, the amount of exposure depends on the illuminance of the light source and the exposure time. The exposure amount can be measured using a light meter.
In the maskless exposure, a drawing device is directly used for exposure on a substrate without using a mask. As a light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, and the like are used. In maskless exposure, the pattern drawn is controlled by a computer, and the exposure amount depends on the illuminance of the exposure light source and the moving speed of the substrate.
Then, in the developing step, the unexposed portion of the photosensitive resin layer is removed using a developing solution. When a support is provided on the photosensitive resin layer, it is preferable to remove it after exposure and supply it to a developing step.
In the developing step, a developing solution containing an alkaline aqueous solution is used to develop and remove the unexposed portion to obtain a resist image. As the alkaline aqueous solution, for example, Na is preferably used. ₂ CO ₃ K ₂ CO ₃ And other aqueous solutions. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, and it is preferable to use Na at a concentration of 0.2% to 2% by mass. ₂ CO ₃ Aqueous solution. Surfactants, defoamers, and small amounts of organic solvents used to promote development can also be mixed into the alkaline aqueous solution.
The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 ° C to 40 ° C.
A resist pattern is obtained through the above steps. Depending on the situation, a heating step of 100 ° C to 300 ° C may be further performed. It is preferable to implement this heating step from the viewpoint of further improving chemical resistance. Heating can be performed using a suitable heating furnace such as hot air, infrared, or far infrared.
＜ How to form a wiring board ＞
The method for forming a wiring board according to the second embodiment preferably includes the following order:
A laminating step in which a photosensitive resin layer of a photosensitive element is laminated on a conductor substrate;
An exposure step, which exposes the photosensitive resin layer of the above-mentioned laminated layer;
A developing step, which uses a developing solution to remove the unexposed portions after the exposure;
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above development; and
The peeling step is to peel the resist pattern.
The laminating step is preferably a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent. The humectant preferably contains one or more copper chelating agents selected from pure water, deionized water, and electrolytic water (for example, selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). One or more of them).
In the conductor pattern forming step, a conductor pattern may be formed on a substrate surface (for example, a copper surface) exposed through the development step using a known etching method or plating method on the substrate on which the resist pattern is formed.
In the peeling step, the resist pattern is peeled off by contacting the substrate on which the conductor pattern is formed with a suitable peeling solution. Through this step, the required wiring board can be obtained.
The peeling liquid used in the peeling step is preferably an alkaline aqueous solution. As this alkaline aqueous solution, it is preferable to use, for example, a 2 to 5 mass% NaOH aqueous solution or a KOH aqueous solution. A small amount of a water-soluble solvent such as an alcohol may be added to the peeling solution. The temperature of the peeling liquid in the peeling step is preferably 40 ° C to 70 ° C.
The method for forming a photosensitive resin composition, a photosensitive element, and a wiring board in the second embodiment can be used to manufacture, for example, a printed wiring board, a lead frame, a substrate having an uneven pattern, and a semiconductor package.
In addition, about the measurement method of the various parameters mentioned above, unless otherwise stated, it measured based on the measurement method in the following example.
<Third Embodiment>
Hereinafter, a form for implementing the third embodiment of the present invention will be specifically described (hereinafter referred to as "this third embodiment").
<Photosensitive resin composition>
In this third embodiment, the photosensitive resin composition includes (A) an alkali-soluble polymer, (B) a compound containing an ethylenically unsaturated bond, and (C) a photopolymerization initiator. The photosensitive resin composition may further contain other components, such as an (D) additive, as needed.
In addition, in the present specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid, the "(meth) acrylfluorenyl group" means acrylfluorenyl group or methacrylfluorenyl group, and the "(formaldehyde "Base" acrylate "means" acrylate "or" methacrylate ".
(A) Alkali soluble polymer
(A) Alkali-soluble polymers are polymers that are soluble in alkaline substances. In the third embodiment, from the standpoint of having both the hole-covering property of the resist pattern and the suppression ability of the residual water short circuit, the (A) alkali-soluble polymer is preferably included to constitute (A) the alkali-soluble polymer. The total mass of the monomers is a structural unit of (meth) acrylic acid and a structural unit of 35% to 90% by mass of styrene based on 10% to 24% by mass.
Regarding the content of the structural unit of (meth) acrylic acid in the (A) alkali-soluble polymer, based on the total mass of the monomers constituting the (A) alkali-soluble polymer, from the viewpoint of suppressing the short circuit of residual water. It is preferably 24% by mass or less, and from the viewpoint of ensuring alkaline developability and alkaline peelability, it is preferably 10% by mass or more. The upper limit of the content is more preferably 23% by mass or 22.5% by mass, and the lower limit is more preferably 11% by mass, 15% by mass, 18% by mass, or 20% by mass. The residual water short circuit defect is closely related to the hydrophobicity of the hardened resist. By increasing the hydrophobicity of the resist, that is, the water contact angle, the residual water short circuit defect can be suppressed.
The acid equivalent of the (A) alkali-soluble polymer (in the case where the component (A) contains a plurality of copolymers), it is related to the content of the structural unit of (meth) acrylic acid in the (A) alkali-soluble polymer The entire acid equivalent) is preferably 100 or more from the viewpoints of the development resistance of the photosensitive resin layer, and the development resistance, resolution, and adhesion of the resist pattern. From the standpoint of releasability, it is preferably 900 or less. (A) The acid equivalent of the alkali-soluble polymer is more preferably 250 to 600, and still more preferably 350 to 500. The so-called acid equivalent refers to the mass of a linear polymer having one equivalent of a carboxyl group therein.
Regarding the content of the structural unit of styrene in the (A) alkali-soluble polymer, based on the total mass of the monomers constituting the (A) alkali-soluble polymer, 90 mass is preferred from the viewpoint of developability. % Or less is preferably 35% by mass or more from the viewpoint of resolvability and suppression of residual water short circuit failure. The upper limit of the content is more preferably 85% by mass, 80% by mass, 70% by mass, or 60% by mass from the viewpoints of developability and prevention of peeling time delay, and the lower limit is in terms of resolvability and residual short-circuit failure. From the viewpoint of suppression, 36% by mass, 38% by mass, 40% by mass, or 42% by mass is more preferable.
From the viewpoint of improving the pore-covering property of the resist pattern, the (A) alkali-soluble polymer is preferably a structural unit further including butyl (meth) acrylate. The structural unit of butyl (meth) acrylate may include at least one selected from the group consisting of n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tertiary butyl (meth) acrylate. 1 repeat unit.
Regarding the content of the structural unit of butyl (meth) acrylate in the (A) alkali-soluble polymer, from the standpoint of having both pore-capping properties and suppression of poor residual water short circuit, the (A) alkali-soluble polymer is constituted. The total mass of the monomer is based on a range of preferably from 0.1% by mass to 5% by mass, and more preferably from 0.3% by mass to 1% by mass.
(A) Alkali-soluble polymer, as long as it contains the structural unit of (meth) acrylic acid in an amount of 10% to 24% by mass based on the total mass of monomers constituting the (A) alkali-soluble polymer, and 35% to 90% The structural unit of styrene by mass may be a single copolymer or a mixture of a plurality of copolymers and / or a mixture of a plurality of homopolymers.
(A) The alkali-soluble polymer may contain poly (meth) acrylic acid, polybutyl (meth) acrylate, polystyrene, or (meth) acrylic acid and / or styrene and one of the following first monomers: A copolymer and the like obtained by copolymerizing a copolymerization component of one or more of the following second monomers and / or one or more of the following second monomers.
The first monomer is a monomer (excluding (meth) acrylic acid) containing a carboxyl group in the molecule. Examples of the first monomer include fumaric acid, cinnamic acid, butenoic acid, itaconic acid, maleic anhydride, and maleic acid half esters.
The second monomer is a non-acidic monomer (excluding styrene) having 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, and n- (meth) acrylate Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic ring Hexyl esters, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate and other vinyl alcohols; (meth) acrylonitrile; polymerizable styrene derivatives and the like.
Among these, from the viewpoint of improving the hole coverage of the resist pattern, n-butyl (meth) acrylate, isobutyl (meth) acrylate, or third butyl (meth) acrylate is preferred, From the viewpoint of pore-capping properties, n-butyl (meth) acrylate is more preferred, and from the viewpoint of improving resolvability and suppression of residual short-circuit failure, a styrene derivative capable of polymerizing is preferred. .
Examples of the polymerizable styrene derivative include methylstyrene, vinyltoluene, tertiary butoxystyrene, ethoxylated styrene, 4-vinylbenzoic acid, styrene dimer, Styrene trimer and so on.
The alkali-soluble polymer is preferably a solution obtained by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, n-propanol, or isopropanol, and adding an appropriate amount of free radicals. A polymerization initiator, such as benzophenazine peroxide and azoisobutyronitrile, is synthesized by heating and stirring. There is also a case where synthesis is performed while a part of the mixture is dropped in the reaction solution. After completion of the reaction, a solvent may be added to adjust the concentration to a desired concentration. As the synthesis means, in addition to solution polymerization, block polymerization, suspension polymerization, or emulsion polymerization can also be used.
The weight average molecular weight of the (A) alkali-soluble polymer (when the component (A) contains a plurality of types of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. The weight average molecular weight of the (A) alkali-soluble polymer is preferably 5,000 or more from the viewpoint of uniformly maintaining the thickness of the dry film photoresist and obtaining resistance to the developing solution. From a viewpoint, it is preferable that it is 500,000 or less. (A) The weight-average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, and still more preferably 20,000 to 100,000. (A) The degree of dispersion of the alkali-soluble polymer is preferably 1.0 to 6.0.
In the third embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition as a basis (unless otherwise specified, each All the ingredients are based on this), preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 60% by mass. (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer. The resist pattern formed by exposure is fully utilized as a resist material. From the viewpoint of performance, it is preferably 90% by mass or less.
(B) Compounds containing ethylenic unsaturated bonds
(B) The ethylenically unsaturated bond-containing compound is a compound having a polymerizability by containing an ethylenically unsaturated group in its structure. From the viewpoint of addition polymerizability, the ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.
In the third embodiment, when (A) an alkali-soluble polymer and (B) an ethylenically unsaturated bond-containing compound are used in combination, (B) contains ethylene from the viewpoint of ensuring the pore-covering property of the resist pattern. The weight-average molecular weight of the compound having an unsaturated bond is preferably 1,200 or more. In the present specification, the weight average molecular weight of the (B) ethylenic unsaturated bond-containing compound means that when (B) the ethylenic unsaturated bond-containing compound is a single kind, it means from a single kind of ethylenic unsaturated bond-containing compound The weight average molecular weight derived from the structural formula of the compound, when (B) the compound containing an ethylenically unsaturated bond contains a plurality of types, it means the weighted average of the weight average molecular weight of each compound containing an ethylenic unsaturated bond and the compounding ratio.
(B) The weight-average molecular weight of the compound containing an ethylenically unsaturated bond is more preferably 1,300 or more, more preferably 1,400 or more, from the viewpoint of further improving the pore-covering property of the resist pattern. From the viewpoint of resolvability and releasability, it is more preferably 5,000 or less, still more preferably 4,000 or less, and even more preferably 3,000 or less.
(B) The ethylenically unsaturated bond-containing compound may include a compound selected from the following (b ₁ ) ～ (b ₅ ):
(b ₁ ) The following general formula (I):
[Chemical 9]

{Where R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group, and m ₁ To satisfy the number of 2 to 40}
The ethylene glycol di (meth) acrylate compound represented;
(b ₂ ) The following general formula (II):
[Chemical 10]

{Where R ₃ And R ₄ Each independently represents a hydrogen atom or a methyl group, and A is C ₂ H ₄ , B is C ₃ H ₆ , N ₁ , N ₂ , N ₃ And n ₄ To satisfy n ₁ + N ₂ + N ₃ + N ₄ = An integer with a relationship of 2 to 50. The arrangement of repeating units of-(AO)-and-(BO)-can be random or block. In the case of blocks,-(AO)-and-( BO) -Either can be biphenyl side}
The alkylene oxide modified bisphenol A type di (meth) acrylate compound;
(b ₃ ) The following general formula (III):
[Chemical 11]

{Where R ₅ ~ R ₇ Each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , M ₃ And m ₄ Each independently an integer from 0 to 40, m ₂ + M ₃ + M ₄ 1 to 40 and less than m ₂ + M ₃ + M ₄ When it is 2 or more, a plurality of X may be the same or different from each other}
The indicated tri (meth) acrylate compound;
(b ₄ ) The following general formula (IV):
[Chemical 12]

{Where R ₈ And R ₉ Each independently represents a hydrogen atom or a methyl group, Y is an alkylene group having 2 to 6 carbon atoms, Z is a divalent organic group, and s and t are each independently an integer of 0 to 40, and s + t ≧ 1}
The bis (meth) acrylate urethane compound represented; and
(b ₅ (B) ₁ ) ～ (b ₄ Addition polymerizable monomer
At least one of the groups formed.
From the viewpoint of adjusting the peeling time of the resist pattern and the size of the peeling sheet, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₁ ) An ethylene glycol di (meth) acrylate compound represented by the general formula (I).
In the general formula (I), m ₁ From the viewpoint of the peeling time and the size of the peeling sheet, it is preferably 2 or more, and from the viewpoint of resolution, plating resistance and etching resistance, it is preferably 40 or less. m ₁ It is more preferably 4 to 20, and even more preferably 6 to 12.
As a specific example of the ethylene glycol di (meth) acrylate compound represented by the general formula (I), m is preferred ₁ = 4 of tetraethylene glycol di (meth) acrylate, m ₁ = 9 nonaethylene glycol di (meth) acrylate, or m ₁ = 14 polyethylene glycol di (meth) acrylate.
From the viewpoint of resolvability and capping property, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₂ ) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). B in the general formula (II) may be -CH ₂ CH ₂ CH ₂ -Or-CH (CH ₃ ) CH ₂ -.
The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and / or a substituent.
Examples of the hetero atom include a halogen atom and the like. 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 benzyl. Fluorenylmethyl, amine, alkyl amine having 1 to 10 carbons, dialkyl amine having 2 to 20 carbons, nitro, cyano, carbonyl, mercapto, alkyl thiol having 1 to 10 carbons, Aryl, hydroxy, hydroxyalkyl with 1 to 20 carbons, carboxyl, carboxyalkyl with 1 to 10 carbons, fluorenyl with 1 to 10 carbons and 1 to 20 carbons Alkoxy, alkoxycarbonyl having 1 to 20 carbons, alkylcarbonyl having 2 to 10 carbons, alkenyl having 2 to 10 carbons, N-alkylamine formamyl having 2 to 10 carbons or including A heterocyclic group, or an aryl group substituted with such a substituent. 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 (II) has a plurality of substituents, the plurality of substituents may be the same or different.
R in general formula (II) ₃ And R ₄ Each may be independently a hydrogen atom or a methyl group, and from the viewpoint of ensuring the contrast of the photosensitive resin layer containing the photosensitive resin composition immediately after exposure, R is preferred ₃ With R ₄ One or both of them is a hydrogen atom, more preferably R ₃ With R ₄ All are hydrogen atoms.
From the perspective of capping, (b ₂ ) The alkylene oxide added to the alkylene oxide-modified bisphenol A di (meth) acrylate compound represented by the general formula (II) is preferably an alkylene oxide having a relatively long chain length. More specifically, in the general formula (II), n ₁ , N ₂ , N ₃ And n ₄ Preferably n ₁ + N ₂ + N ₃ + N ₄ = 4 to 50, more preferably n ₁ + N ₂ + N ₃ + N ₄ = 10 to 50, and it is more preferable to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 20 to 50 relationship, especially preferred to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 30-50 relationship.
From the viewpoint of pore-capping, 40% by mass or more of (B) an ethylenically unsaturated bond-containing compound is preferred (b ₂ ) The alkylene oxide modified bisphenol A type di (meth) acrylate compound represented by the general formula (II), more preferably n in the general formula (II) ₁ , N ₂ , N ₃ And n ₄ Satisfy n ₁ + N ₂ + N ₃ + N ₄ = 30 to 50 alkylene oxide modified bisphenol A di (meth) acrylate compound. More preferably, it is 50% by mass, more preferably 55% by mass or more, and most preferably 60% by mass in (B) an ethylenically unsaturated bond-containing compound. ₂ ) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II).
As (b ₂ ) Preferable specific examples of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) include the following: Adding an average of 1 unit of ring to each end of bisphenol A Diethylene glycol di (meth) acrylate derived from ethylene oxide, and polyethylene glycol di (methyl) obtained by adding an average of 2 units of ethylene oxide to each end of bisphenol A Acrylate, polyethylene glycol di (meth) acrylate obtained by adding an average of 5 units of ethylene oxide to both ends of bisphenol A, and adding an average of 7 units to both ends of bisphenol A Diethylene glycol di (meth) acrylate made of ethylene oxide, which is obtained by adding an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide to each end of bisphenol A. Di (meth) acrylate of polyalkylene glycol, and di (meth) acrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide to each end of bisphenol A 2. Di (meth) acrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide to both ends of bisphenol A.
In the general formula (II), from the viewpoint of resolution and poor suppression of residual water short circuit, n ₁ , N ₂ , N ₃ And n ₄ Also preferably to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 2 to 10, and it is particularly preferable to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 2 to 4 relationship.
From the standpoint of having both capping properties and poor suppression of residual water short circuit, (B) an ethylenically unsaturated bond-containing compound is particularly preferred to contain n in the general formula (II). ₁ + N ₂ + N ₃ + N ₄ = 30 to 50 compounds, R in general formula (II) ₃ With R ₄ A compound in which one or both of them is a hydrogen atom, and n in the general formula (II) ₁ + N ₂ + N ₃ + N ₄ = 2 to 10 compounds.
From the viewpoint of resolvability and capping property, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₃ ) A tri (meth) acrylate compound represented by the general formula (III). X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -Wait.
From the perspective of capping, (b ₃ The tri (meth) acrylate compound represented by the general formula (III) preferably has an alkylene oxide portion having a relatively long chain length. More specifically, in the general formula (III), m ₂ + M ₃ + M ₄ It is preferably 10 to 40, and more preferably 20 to 40.
As (b ₃ ) Preferred specific examples of the tri (meth) acrylate compound represented by the general formula (III) include: ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (EO average Addition mole number: 10 to 40), propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate (average addition mole number of PO: 10 to 40), and the like.
From the viewpoint of pore-capping properties, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₄ ) A bis (meth) acrylate urethane compound represented by the general formula (IV).
In the general formula (IV), Z represents a divalent organic group, and may be, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, or 2 to 3 carbon atoms having a substituent Valence alicyclic groups and the like.
In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and may be -CH, for example. ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -Wait.
From the viewpoint of further improving the hole-capping property,-(YO) in the general formula (IV) is also preferable. _s -Part and-(YO) _t -Parts are independently replaced by-(C ₂ H ₅ O)-(C ₃ H ₆ O) ₉ -.
As (b ₄ ) Preferred specific examples of the di (meth) acrylic acid urethane compound represented by the general formula (IV) include a (meth) acrylic monomer having a hydroxyl group at the β position and isophorone di Addition reactants of diisocyanate compounds such as isocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethyl) Diol isocyanate) hexamethylene isocyanurate, EO modified di (meth) acrylate urethane and EO / PO modified di (meth) acrylate urethane. In addition, EO means ethylene oxide, and the compound modified by EO has a block structure of ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide. Examples of the EO-modified di (meth) acrylate urethane include a trade name "UA-11" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and the like. Examples of the EO / PO modified di (meth) acrylic acid urethane include the trade name "UA-13" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and the like. These can be used individually by 1 type or in combination of 2 or more types.
(B) Compounds containing ethylenic unsaturated bonds may also be included as (b ₅ (B) ₁ ) ～ (b ₄ ) Additive polymerizable monomers other than components.
As (b ₅ ) Ingredients, including the following:
(b ₃ ) Other tris (meth) acrylates, such as trimethylolpropane tris (meth) acrylate, ethoxylated glycerol tris (meth) acrylate, ethoxylated isotricyanate tris ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, etc .;
Tetra (meth) acrylates, such as di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxy Tetra (meth) acrylate, etc .;
Penta (meth) acrylate, such as dipentaerythritol penta (meth) acrylate, etc .;
Hexa (meth) acrylates, such as dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylates made by adding 1 to 24 moles of ethylene oxide to the 6 ends of dipentaerythritol, Six (meth) acrylic acid esters formed by adding 1 to 10 mol of ε-caprolactone to the 6 ends of dipentaerythritol;
An acrylate compound having one (meth) acrylfluorenyl group;
A compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyol;
A compound obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl-containing compound; and
Phthalic acid-based compounds such as γ-chloro-2-hydroxypropyl phthalate-β '-(meth) acryloxyethyl and β-hydroxyalkyl phthalate-β'-( (Meth) acryloxyalkyl esters and the like.
In the third embodiment, the total content of all (B) ethylenically unsaturated bond-containing compounds in the photosensitive resin composition is preferably 1 from the viewpoints of capping properties and adhesion of the resist pattern. Mass% to 70% by mass, more preferably 2% to 60% by mass, and still more preferably 4% to 50% by mass.
(C) Photopolymerization initiator
(C) A photopolymerization initiator is a compound which polymerizes a monomer by light. The photosensitive resin composition contains a compound generally known in the art as a photopolymerization initiator.
The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably from 0.01 to 20% by mass, more preferably from 0.05 to 10% by mass, and still more preferably from 0.1 to 7% by mass. Inside. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and from the viewpoint of sufficiently transmitting light until reaching the bottom surface of the resist to obtain good high resolution. In other words, it is preferably 20% by mass or less.
Examples of the (C) photopolymerization initiator include quinones, aromatic ketones, acetophenones, fluorenylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, and 9-oxysulfur. Compounds, dialkylaminobenzoates, oxime esters, acridines, and the like, and further include: hexaarylbiimidazole, pyrazoline compounds, N-arylamino acids or ester compounds thereof (for example, N -Phenylglycine), organic halogen compounds, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, acridines are particularly suitable for direct imaging exposure.
Examples of acridines include acridine, 9-phenylacridine, 1,6-bis (9-acridyl) hexane, 1,7-bis (9-acridyl) heptane, 1 , 8-bis (9-acridyl) octane, 1,9-bis (9-acridyl) nonane, 1,10-bis (9-acridyl) decane, 1,11-bis ( Acridine derivatives such as 9-acridyl) undecane and 1,12-bis (9-acridyl) dodecane. From the viewpoint of the suitability for direct imaging exposure, the content of acridines in the photosensitive resin composition is preferably from 0.1% by mass to 5% by mass, more preferably from 0.3% by mass to 3% by mass, and even more preferably Within the range of 0.5% by mass to 2% by mass.
Examples of the aromatic ketones include benzophenone, Michelin [4,4'-bis (dimethylamino) benzophenone], and 4,4'-bis (diethylamine). Group) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone. These can be used individually by 1 type or in combination of 2 or more types. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from a viewpoint of adhesiveness. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably in a range of 0.01% by mass to 0.5% by mass, and more preferably in a range of 0.02% by mass to 0.3% by mass.
Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ', 5-tri- (o-chlorophenyl) -4- ( 3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) ) -Diphenylbiimidazole, 2,4,5-tri- (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-di (Methoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,5- Difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,6-difluorophenyl) -4 , 4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5 , 5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetra -(3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methyl (Oxyphenyl) -biimidazole, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxy (Phenyl) -biimidazole, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -bi Imidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2 , 2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, and 2,2 '-Bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, etc. These can be used alone or in combination of two or more. From the viewpoints of high sensitivity, resolution, and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferred.
In the third embodiment, from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably from 0.05% by mass to 7% by mass. It is more preferably within a range of 0.1% to 6% by mass, and even more preferably within a range of 1% to 4% by mass.
Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. Among them, N-phenylglycine is particularly preferred. From the viewpoint of improving the peeling characteristics and / or sensitivity, the content of N-arylamino acid in the photosensitive resin composition is preferably 0.05% by mass to the total amount of the solid content of the photosensitive resin composition. 5 mass%, more preferably 0.1 to 2 mass%.
Examples of the organic halogen compound include bromopentane, bromoisopentane, brominated isobutylene, 1,2-dibromoethane, benzhydryl bromide, benzyl bromide, dibromomethane, and tribromomethylphenyl. Samarium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, isobutyl iodide, 1,1,1-trichloro-2,2-bis (P-chlorophenyl) ethane and trichloride Among the compounds, tribromomethylphenylphosphonium is particularly preferably used. From the viewpoint of improving the peeling characteristics and / or sensitivity, the content of the organic halogen compound in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass relative to the total amount of solid components of the photosensitive resin composition. More preferably, it is 0.1 to 3 mass%.
Examples of other photosensitizers include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, and 2 1,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone And quinones such as 3-chloro-2-methylanthraquinone, benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin and ethyl benzoin, benzoin dimethyl ketal, benzoin diethyl Ketal and 1-phenyl-1,2-propanedione-2-O-benzoin oxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime And other oxime esters. From the viewpoint of improving the peeling characteristics and / or sensitivity, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass relative to the total amount of the solid content of the photosensitive resin composition. , More preferably from 0.1% by mass to 3% by mass.
In the third embodiment, the photosensitive resin composition preferably contains a pyrazoline compound as a photosensitizer. As the pyrazoline compound, 1-phenyl-3- (4-third butyl-styryl) -5- (4-third butyl-phenyl) -pyrazoline, 1- ( 4- (benzo Azole-2-yl) phenyl) -3- (4-third-butyl-styryl) -5- (4-third-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-third butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-third octyl -Phenyl) -pyrazoline.
(D) Additives
The photosensitive resin composition may further contain additives such as a color changer, a dye, a plasticizer, an antioxidant, and a stabilizer, if necessary. For example, the additives listed in Japanese Patent Laid-Open No. 2013-156369 and International Publication No. 2009/093706 can be used.
Examples of the color changing agent include leuco dyes and fluoran dyes. It is preferable to use a discoloration agent from the point which the exposed part develops color and shows visibility. In addition, when the registration mark used for exposure is read by an inspection machine or the like, the contrast between the exposed portion and the unexposed portion is large, which facilitates position recognition and is advantageous.
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [crypto crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green], and the like . Especially from the viewpoint of good 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 from 0.1% by mass to 10% by mass. The content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed portion and the unexposed portion, and is preferably 10% by mass or less from the viewpoint of maintaining storage stability.
Examples of the basic dye include basic green 1 [CAS number (the same applies hereinafter): 633-03-4] (for example, Aizen Diamond Green GH (trade name), manufactured by Hodogaya Chemical Industry Co., Ltd.), and malachite green salt [ 2437-29-8] (such as Aizen Malachite Green (trade name), manufactured by Hodogaya Chemical Industry), bright green [633-03-4], magenta [632-99-5], methyl violet [603-47 -4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], basic Blue 7 [2390-60-5] (for example, Aizen Victoria Pure Blue BOH (trade name), manufactured by Hodogaya Chemical Industry), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8 ], Basic Yellow 2 [2465-27-2], etc. Among them, basic green 1, malachite greenate, and basic blue 7 are preferred. From the viewpoint of improving hue stability and exposure contrast, basic green 1 is particularly preferred.
In the third embodiment, the content of the base dye in the photosensitive resin composition is preferably 0.001% to 3% by mass, more preferably 0.01% to 2% by mass, and still more preferably 0.01% to 1% by mass. Within the range of%. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good coloring properties, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
In the third embodiment, in order to suppress the delay in peeling off the resist pattern caused by the alkali-soluble polymer having a content of the structural unit of (meth) acrylic acid of 10% to 24% by mass and shorten the peeling time, it is preferred The photosensitive resin composition contains, as a plasticizer, tosulamide, such as o-tosylsulfonamide and p-tosylsulfonamide. The content of tosyl sulfonamide in the photosensitive resin composition is preferably within a range from 0.1% by mass to 5% by mass, and more preferably from 1% by mass to 4% by mass.
Examples of other plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, Diols and esters such as polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; phthalates such as diethyl phthalate; tributyl citrate, triethyl citrate Ester, triethyl acetate, tri-n-propyl citrate, and tri-n-butyl acetate; propylene glycol obtained by adding propylene oxide to both sides of bisphenol A, and bisphenol A Ethylene oxide is added to both sides of ethylene oxide.
From the viewpoint of thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition preferably contains a stabilizer selected from a radical polymerization inhibitor such as p-methoxyphenol and hydroquinone as a stabilizer. , Pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tertiary-butyl-p-cresol, 2,2'-methylenebis (4-methyl -6-Third-butylphenol), 2,2'-methylenebis (4-ethyl-6-third-butylphenol), diphenylnitrosamine, triethylene glycol-bis (3 -3-Third-butyl-5-methyl-4-hydroxyphenylpropionate), and nitrosophenylhydroxylamine aluminum salts, etc .; benzotriazoles, such as 1,2,3-benzo Triazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2 -Ethylhexyl) aminomethylene-1,2,3-tolyltriazole, 1- (2-di-n-octylaminomethyl) -benzotriazole, and bis (N-2- Hydroxyethyl) aminomethylene-1,2,3-benzotriazole, etc .; carboxybenzotriazoles, such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1 , 2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole, 1- (2-di-n-butylaminomethyl) -5-carboxy 1: 1 mixture of benzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amine Methylmethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzobenzotriazole, and N- (N, N-di-2-ethyl Hexyl) amino ethyl carboxy benzotriazole, etc .; and alkylene oxide compounds having glycidyl groups, such as neopentyl glycol diglycidyl ether (such as Kyoeisha Chemical Co., Ltd., Epolight 1500NP), Jiuyi Glycol diglycidyl ether (eg, Kyoeisha Chemical Co., Ltd., Epolight 400E), bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (eg, Kyoeisha Chemical Co., Ltd., Epolight 3002), hydrogenated bisphenol A diglycidyl ether (such as Kyoeisha Chemical Co., Ltd., Epolight 4000), 1,6-hexanediol diglycidyl ether (such as Kyoeisha Chemical Co., Ltd., Epolight 1600 ) And so on.
In the third embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, and still more preferably 0.05% by mass. % To 0.7% by mass. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. %the following.
The additives described above can be used alone or in combination of two or more.
<Photosensitive resin composition preparation liquid>
In this third embodiment, a photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition. Preferred solvents include ketones, such as acetone, methyl ethyl ketone (MEK), and the like; and alcohols, such as methanol, ethanol, and isopropanol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid at 25 ° C. becomes 500 mPa · sec to 4000 mPa · sec.
<Photosensitive resin laminate>
In the third embodiment, a photosensitive resin laminate including a support and a photosensitive resin layer including the above-mentioned photosensitive resin composition laminated on the support can be provided. The photosensitive resin laminated body may have a protective layer on the opposite side of the photosensitive resin layer from the support side as necessary.
Although it does not specifically limit as a support body, The transparent support body which can transmit the light radiated 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, and a vinylidene chloride copolymer film. , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film and cellulose derivative film. These films can also be extended if necessary. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. Regarding the thickness of the film, although the thinner the film, the more favorable it is for image formation and economy, but since the strength must be maintained, it is preferably 10 μm to 30 μm.
In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive force between the protective resin layer and the photosensitive resin layer is smaller than the adhesive force between the support and 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 Japanese Patent Laid-Open No. 59-202457 can be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.
In the third embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer, the higher the resolution of the resist pattern. On the other hand, the larger the thickness, the higher the strength of the cured film. Therefore, it can be selected according to the application.
As a method for producing a photosensitive resin laminated body by sequentially laminating a support, a photosensitive resin layer, and a protective layer as necessary, a known method can be used.
For example, the above-mentioned photosensitive resin composition preparation liquid is prepared, and then applied to a support using a bar coater or a roll coater and dried, and the support containing the photosensitive resin composition preparation liquid is laminated on the support. Photosensitive resin layer. Furthermore, a photosensitive resin layer can be produced by laminating a protective layer on a photosensitive resin layer as needed.
<Method for forming resist pattern>
The method for forming the resist pattern preferably includes, in order, a lamination step of laminating a photosensitive resin layer containing the above-mentioned photosensitive resin composition on a support, and an exposure step of exposing the photosensitive resin layer; And a developing step of developing the exposed photosensitive resin layer. An example of a specific method for forming a resist pattern in the third embodiment will be described below.
First, in a laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminated body has a protective layer, the protective resin layer is peeled off, and then the photosensitive resin layer is heated and pressure-bonded to the substrate surface using a laminator to be laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).
In this third embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, and the photosensitive resin layer may be laminated on both sides as necessary. The heating temperature during lamination is generally 40 ° C to 160 ° C. By performing heat and pressure bonding twice or more during lamination, the adhesion between the obtained resist pattern and the substrate can be improved. For thermal compression bonding, a two-stage laminator equipped with double rollers can be used, or the laminate of the substrate and the photosensitive resin layer can be repeatedly pressed through the rollers for pressure bonding.
Then, in the exposure step, the photosensitive resin composition layer is exposed to active light using an exposure machine. Exposure can be performed after peeling a support body as needed. In the case of exposure through a photomask, the exposure amount depends on the illuminance of the light source and the exposure time, and can be measured using a light meter. In the exposure step, direct imaging exposure may also be performed. In the direct imaging exposure, a drawing device is directly used for exposure on the substrate without using a photomask. As a light source, a semiconductor laser or an ultra-high-pressure mercury lamp with a wavelength of 350 nm to 410 nm is used. When the pattern drawn by a computer is controlled, the exposure amount depends on the illuminance of the exposure light source and the moving speed of the substrate.
Then, in the developing step, a developing device is used to remove unexposed portions or exposed portions in the exposed photosensitive resin layer using a developing solution. When there is a support on the photosensitive resin layer, it is removed after exposure. Then, the unexposed part or the exposed part was developed and removed using a developing solution containing an alkaline aqueous solution to obtain a resist image.
The alkaline aqueous solution is preferably Na ₂ CO ₃ K ₂ CO ₃ And other aqueous solutions. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer. Generally, a concentration of 0.2% to 2% by mass of Na is used. ₂ CO ₃ Aqueous solution. The alkaline aqueous solution may also be mixed with a surfactant, a defoaming agent, and a small amount of an organic solvent for promoting development. The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 ° C to 40 ° C.
A resist pattern is obtained by the above steps, and a heating step of 100 ° C to 300 ° C may be further performed if necessary. By performing this heating step, the chemical resistance of the resist pattern can be improved. The heating step may be a heating furnace using hot air, infrared or far infrared.
The photosensitive resin composition of the third embodiment can be preferably used for forming a circuit of a printed circuit board. As a circuit forming method for a printed circuit board, a subtractive process and a semi-additive process (SAP) are generally used.
The subtractive process is a method of forming a circuit by removing only non-circuit parts from a conductor disposed on the entire substrate surface by etching.
SAP is a method of forming a resist on a non-circuit portion of a conductor seed layer disposed on the entire substrate surface, and then forming only a circuit portion by plating.
＜ Manufacturing method of conductor pattern ＞
The manufacturing method of the conductor pattern preferably includes, in order, a lamination step of laminating a photosensitive resin layer containing the above-mentioned photosensitive resin composition on a substrate such as a metal plate, a metal film insulation plate, and the like; and an exposure step, which The resin layer is exposed; the developing step is to obtain a substrate on which a resist pattern is formed by removing unexposed or exposed portions of the exposed photosensitive resin layer with a developing solution; and the conductor pattern forming step is to The substrate on which the resist pattern is formed is etched or plated.
In the third embodiment, the method for manufacturing a conductor pattern is performed by using a metal plate or a metal film insulation plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then performing a conductor pattern forming step. In the conductive pattern forming step, a known etching method or a plating method is used to form a conductive pattern on the surface of the substrate (for example, a copper surface) exposed through development.
Furthermore, the third embodiment is preferably used for the following applications, for example.
＜ Manufacturing method of wiring board ＞
After the conductor pattern is produced by the method for producing a conductor pattern, a stripping step of peeling the resist pattern from the substrate using an aqueous solution having a stronger alkalinity than a developing solution is performed, thereby obtaining a wiring board having a desired wiring pattern (such as printed wiring board).
The alkaline aqueous solution for peeling (hereinafter also referred to as "peeling solution") is not particularly limited. Generally, an aqueous solution of NaOH or KOH having a concentration of 2 to 5 mass% or an organic amine-based peeling solution is used. It is also possible to add a small amount of a water-soluble solvent to the peeling solution. Examples of the water-soluble solvent include alcohols. The temperature of the peeling liquid in the peeling step is preferably within a range of 40 ° C to 70 ° C.
＜ Manufacture of lead frames ＞
A lead frame can be manufactured by using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate and forming a resist pattern by a resist pattern forming method through the following steps. First, a step of forming a conductive pattern by etching the exposed substrate is performed. Thereafter, a stripping step of stripping the resist pattern by the same method as the method of manufacturing a wiring board is performed, and a desired lead frame can be obtained.
＜ Manufacturing of substrate with uneven pattern ＞
A resist pattern formed by a resist pattern forming method can be used as a protective cover member when a substrate is processed by a sandblasting method. In this case, examples of the substrate include glass, silicon wafers, amorphous silicon, polycrystalline silicon, ceramics, sapphire, and metal materials. A resist pattern is formed on these substrates by the same method as the resist pattern forming method. Thereafter, a sandblasting treatment step of spraying a sandblasting material on the formed resist pattern and cutting to a target depth, and a stripping step of removing a resist pattern portion remaining on the substrate from the substrate using an alkaline stripping solution, etc. A substrate having a fine uneven pattern on a substrate is manufactured.
In the blasting step, a well-known blasting material can be used, for example, generally including SiC, SiO ₂ , Al ₂ O ₃ CaCO ₃ , ZrO, glass, stainless steel and other particles with a particle diameter of 2 μm to 100 μm.
＜ Manufacturing of semiconductor package ＞
A semiconductor package can be manufactured by using a resist pattern forming method to form a resist pattern on a wafer using a wafer having a large-scale integrated circuit (LSI) formed as a substrate, and then performing the following steps. First, a step of forming a conductive pattern by performing columnar plating of copper, solder, or the like on the opening exposed through development is performed. Thereafter, a stripping step of stripping the resist pattern by the same method as the method of manufacturing a wiring board is performed, and then a step of removing a thinner metal layer other than the columnar plating by etching is performed, thereby obtaining Required semiconductor package.
In this third embodiment, the photosensitive resin composition can be used in the manufacture of printed wiring boards; manufacture of lead frames for IC chip mounting; precision processing of metal foils such as metal cover manufacturing; ball grid array (BGA) and crystal-size package (CSP) ) And other package manufacturing; film-on-chip (COF), tape-and-tape (TAB) and other tape substrates; semiconductor bumps; and ITO electrodes, address electrodes, electromagnetic wave shields and other flat panel displays Manufacturing next door.
The values of the above parameters are measured according to the measurement methods in the following examples unless otherwise specified.
<Fourth Embodiment>
The form for implementing the fourth embodiment of the present invention will be specifically described below (hereinafter referred to as "the fourth embodiment").
<Photosensitive resin composition>
In this fourth embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. The photosensitive resin composition may further contain other components, such as a (D) stabilizer, as needed.
In addition, in the present specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid, the "(meth) acrylfluorenyl group" means acrylfluorenyl group or methacrylfluorenyl group, and the "(formaldehyde "Base" acrylate "means" acrylate "or" methacrylate ".
[(A) Alkali soluble polymer]
From the standpoint of resolvability and extension of the minimum development time, the content ratio of the (A) alkali-soluble polymer containing an acid monomer unit is less than 25% by mass and the content ratio of the aromatic monomer unit is 30% by mass or more. The first copolymer. The first copolymer may include other monomer units other than the acid monomer unit and the aromatic monomer unit, if necessary. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight (described below) of the copolymer to the number average molecular weight is preferably 1 or more and 6 or less.
Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, fumaric acid, citraconic anhydride, and the like. Among these, (meth) acrylic acid is preferred.
The copolymerization ratio of the acid monomer unit in the component (A) is preferably less than 25% by mass, more preferably 10% by mass to 24% by mass, and more preferably relative to the total mass of all the monomer units. It is 15 to 23 mass%. The content ratio of the acid monomer unit in this range is preferable from the viewpoints of improvement in resolution and extension of minimum development time.
Aromatic monomers are also called unsaturated aromatic compounds. Examples of the aromatic monomer include styrene, α-methylstyrene, vinylnaphthalene, and the like; and aralkyl (meth) acrylate. Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate and the like.
The copolymerization ratio of the aromatic monomer unit (preferably a styrene unit) in the component (A) is preferably 30% by mass or more, more preferably 32% by mass relative to the total mass of all the monomer units. -60 mass%, more preferably 35 mass% to 55 mass%. Setting the copolymerization ratio of the aromatic monomer having high hydrophobicity and being difficult to be fused with a developing solution and a developing water washing water to the above range is preferable from the viewpoints of improvement in resolution and extension of minimum development time.
Examples of other monomers include alkyl (meth) acrylate, conjugated diene compounds, polar monomers, and crosslinkable monomers.
The concept of alkyl (meth) acrylate includes both chain alkyl esters and cyclic alkyl esters. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Hexyl ester, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Lauryl acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butadiene. Diene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3- Butyl-1,3-octadiene and the like.
Examples of the polar monomer include:
Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
Amine group-containing monomers such as 2-aminoethyl methacrylate;
(Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and other monomers containing amidine groups;
Cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate, divinylbenzene, and the like.
The first copolymer is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.
In the fourth embodiment, from the viewpoints of resolvability, developability, and cohesiveness, it is also preferable that the second copolymer includes the aromatic monomer unit having a content ratio of 45% to 90% by mass. Thing. In the second copolymer, when the content ratio of the aromatic monomer unit is 45% by mass, there is a tendency to ensure the hydrophobicity of the resist pattern including the second copolymer. From the viewpoint of improving cohesiveness, the weight ratio of the second copolymer to the total weight of the entire copolymer is preferably 25% by mass or more.
The second copolymer may also include the acid monomer unit and other monomer units described above. As the aromatic monomer for polymerizing the second copolymer, styrene is preferred from the viewpoint of hydrophobicity. The upper limit of the content ratio of the aromatic monomer unit in the second copolymer is more preferably 80% by mass or 70% by mass from the viewpoint of developability.
The second copolymer may include the acid monomer unit and other monomer units described above. From the viewpoints of resolvability, developability, and agglutinability, the content ratio of the acid monomer units described above is preferably 25 mass. % To 50% by mass, and more preferably 25% to 40% by mass. As the acid monomer for polymerizing the second copolymer, (meth) acrylic acid is preferred from the viewpoint of developability.
The weight average molecular weight of the component (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 15,000 to 100,000. Adjusting the weight-average molecular weight of the component (A) within this range is preferable from the viewpoint of making the development time at the time of forming the resist pattern suitable for the working state of the pipeline processing used.
In the fourth embodiment, the content of the component (A) in the photosensitive resin composition is based on the total amount of solid components of the photosensitive resin composition (hereinafter, unless otherwise specified, each contained component is based on this 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 60% by mass. This content is preferably 10% by mass or more from the viewpoint of maintaining alkaline developability, and is more preferably from the viewpoint of fully exhibiting the performance of the resist pattern formed by exposure as a resist pattern. 90% by mass or less.
The first copolymer having a content ratio of an acid monomer unit of less than 25% by mass and a content ratio of an aromatic monomer unit of 30% by mass or more is preferably 5% by mass based on the total solid content of the photosensitive resin composition. % To 50% by mass. It is more preferably 10% by mass or more and 40% by mass or less.
[(B) Compound containing ethylenic unsaturated bond]
(B) The ethylenically unsaturated bond-containing compound is a compound having a polymerizability by containing an ethylenically unsaturated group in its structure. From the viewpoint of addition polymerizability, the ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.
In the fourth embodiment, when (A) an alkali-soluble polymer and (B) an ethylenically unsaturated bond-containing compound are used in combination, the viewpoint of ensuring good resolution of the resist pattern and extending the minimum development time Specifically, the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is preferably 900 or less. In this specification, the average molecular weight of (B) an ethylenically unsaturated bond-containing compound means that when (B) the ethylenic unsaturated bond-containing compound is a single species, it means a single type of ethylenically unsaturated bond-containing compound The weight average molecular weight derived from the structural formula, when (B) the compound containing an ethylenic unsaturated bond contains a plurality of types, means the weighted average of the weight average molecular weight and the compounding ratio of each compound containing an ethylenic unsaturated bond.
(B) The weight-average molecular weight of the compound containing an ethylenically unsaturated bond is more preferably 850 or less from the viewpoint of improvement in resolution and extension of the minimum development time, and further preferably 800 or less, and suppresses the sensitivity From the viewpoint of the edge melting property of the resin laminate, it is preferably 50 or more, and more preferably 100 or more. Here, the term “edge meltability” refers to a phenomenon in which the photosensitive resin composition layer is exposed from the end surface of the roll when the photosensitive resin laminate is wound into a roll shape.
(B) The ethylenically unsaturated bond-containing compound may include a compound selected from the following (b ₁ ) ～ (b ₆ ):
(b ₁ ) The following general formula (I):
[Chemical 13]

{Where R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group, and m ₁ To satisfy the number of 2 to 40}
The ethylene glycol di (meth) acrylate compound represented;
(b ₂ ) The following general formula (II):
[Chemical 14]

{Where R ₃ And R ₄ Each independently represents a hydrogen atom or a methyl group, and A is C ₂ H ₄ , B is C ₃ H ₆ , N ₁ , N ₂ , N ₃ And n ₄ To satisfy n ₁ + N ₂ + N ₃ + N ₄ = An integer with a relationship of 2 to 50. The arrangement of repeating units of-(AO)-and-(BO)-can be random or block. In the case of blocks,-(AO)-and-( BO) -Either can be biphenyl side}
The alkylene oxide modified bisphenol A type di (meth) acrylate compound;
(b ₃ ) The following general formula (III):
[Chemical 15]

{Where R ₅ ~ R ₇ Each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , M ₃ And m ₄ Each independently an integer from 0 to 40, m ₂ + M ₃ + M ₄ 0 to 40 and less than m ₂ + M ₃ + M ₄ When it is 2 or more, a plurality of X may be the same or different from each other}
The indicated tri (meth) acrylate compound;
(b ₄ ) The following general formula (IV):
[Chemical 16]

{Where R ₈ And R ₉ Each independently represents a hydrogen atom or a methyl group, Y is an alkylene group having 2 to 6 carbon atoms, Z is a divalent organic group, and s and t are each independently an integer of 0 to 40, and s + t ≧ 1}
The bis (meth) acrylate urethane compound represented;
(b ₅ ) The following general formula (XI):
[Chemical 17]

{Where R ₅ ~ R ₈ Each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , M ₃ , M ₄ And m ₅ Each independently an integer from 0 to 40, m ₂ + M ₃ + M ₄ + M ₅ 0 to 50 and less than m ₂ + M ₃ + M ₄ + M ₅ When it is 2 or more, a plurality of X may be the same or different from each other}
The tetra (meth) acrylate compound represented; and
(b ₆ (B) ₁ ) ～ (b ₅ Addition polymerizable monomer
At least one of the groups formed.
From the viewpoint of adjusting the peeling time of the resist pattern and the size of the peeling sheet, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₁ ) An ethylene glycol di (meth) acrylate compound represented by the general formula (I).
In the general formula (I), m ₁ From the viewpoint of the peeling time and the size of the peeling sheet, it is preferably 2 or more, and from the viewpoint of resolution, plating resistance and etching resistance, it is preferably 40 or less. m ₁ It is more preferably 4 to 20, and even more preferably 6 to 12.
As a specific example of the ethylene glycol di (meth) acrylate compound represented by the general formula (I), m is preferred ₁ = 4 of tetraethylene glycol di (meth) acrylate, m ₁ = 9 nonaethylene glycol di (meth) acrylate, or m ₁ = 14 polyethylene glycol di (meth) acrylate.
From the viewpoint of suppressing generation of aggregates in the photosensitive resin layer containing the photosensitive resin composition during development, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₂ ) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). B in the general formula (II) may be -CH ₂ CH ₂ CH ₂ -Or-CH (CH ₃ ) CH ₂ -.
The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and / or a substituent.
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 benzamidine Methyl, amine, 1 to 10 carbon alkyl amine, 2 to 20 carbon dialkyl amine, nitro, cyano, carbonyl, mercapto, 1 to 10 carbon thiol, aromatic Group, hydroxy group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms, fluorenyl group having 1 to 10 carbon atoms in the alkyl group, and alkane having 1 to 20 carbon atoms in the alkyl group Oxygen, alkoxycarbonyl with 1 to 20 carbons, alkylcarbonyl with 2 to 10 carbons, alkenyl with 2 to 10 carbons, N-alkylamine formamyl with 2 to 10 carbons or containing hetero A cyclic group, or an aryl group substituted with such a substituent. 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 (II) has a plurality of substituents, the plurality of substituents may be the same or different.
R in general formula (II) ₃ And R ₄ Each may be independently a hydrogen atom or a methyl group, and from the viewpoint of ensuring the contrast of the photosensitive resin layer containing the photosensitive resin composition immediately after exposure, R is preferred ₃ With R ₄ One or both of them is a hydrogen atom, more preferably R ₃ With R ₄ Both are hydrogen atoms.
From the viewpoint of improvement in resolution and extension of the minimum development time, (b ₂ ) The alkylene oxide modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) is preferably an alkylene oxide having a relatively short chain length. More specifically, in the general formula (II), n ₁ , N ₂ , N ₃ And n ₄ Preferably n ₁ + N ₂ + N ₃ + N ₄ = 0 to 30, more preferably n ₁ + N ₂ + N ₃ + N ₄ = 0 to 25, and more preferably satisfies n ₁ + N ₂ + N ₃ + N ₄ = 0 to 20, especially to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 0 to 10 relationship.
From the viewpoint of improvement in resolution and extension of the minimum development time, 40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is preferably (b ₂ ) The alkylene oxide modified bisphenol A type di (meth) acrylate compound represented by the general formula (II), more preferably n in the general formula (II) ₁ , N ₂ , N ₃ And n ₄ Satisfy n ₁ + N ₂ + N ₃ + N ₄ An alkylene oxide modified bisphenol A type di (meth) acrylate compound having a relationship of = 0 to 20. More preferably, it is 50% by mass, more preferably 55% by mass or more, and most preferably 60% by mass in (B) an ethylenically unsaturated bond-containing compound. ₂ ) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II).
As (b ₂ ) Preferable specific examples of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) include the following: Adding an average of 1 unit of ring to each end of bisphenol A Diethylene glycol di (meth) acrylate derived from ethylene oxide, and polyethylene glycol di (methyl) obtained by adding an average of 2 units of ethylene oxide to each end of bisphenol A Acrylate, polyethylene glycol di (meth) acrylate obtained by adding an average of 5 units of ethylene oxide to both ends of bisphenol A, and adding an average of 7 units to both ends of bisphenol A Diethylene glycol di (meth) acrylate made of ethylene oxide, which is obtained by adding an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide to each end of bisphenol A. Di (meth) acrylate of polyalkylene glycol, and di (meth) acrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide to each end of bisphenol A 2. Di (meth) acrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide to both ends of bisphenol A.
In general formula (II), from the viewpoint of improvement in resolution, n ₁ , N ₂ , N ₃ And n ₄ Also preferably to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 2 to 20, and it is particularly preferable to satisfy n ₁ + N ₂ + N ₃ + N ₄ = 2 to 10 relationship.
From the viewpoints of improvement in resolution and extension of the minimum development time, (B) an ethylenically unsaturated bond-containing compound is particularly preferred to contain n in the general formula (II). ₁ + N ₂ + N ₃ + N ₄ = 2 to 20 compounds, R in general formula (II) ₃ With R ₄ A compound in which one or both of them is a methyl group, and n in the general formula (II) ₁ + N ₂ + N ₃ + N ₄ = 2-16 compounds.
From the viewpoint of suppressing generation of aggregates in the photosensitive resin layer containing the photosensitive resin composition during development, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₃ ) A tri (meth) acrylate compound represented by the general formula (III). X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -Wait.
From the perspective of resolution, (b ₃ The tri (meth) acrylate compound represented by the general formula (III) preferably has an alkylene oxide portion having a relatively short chain length. More specifically, in the general formula (III), m ₂ + M ₃ + M ₄ It is preferably 8 to 40, and more preferably 9 to 25.
As (b ₃ ) Preferred specific examples of the tri (meth) acrylate compound represented by the general formula (III) include: ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (EO average Addition mole number: 1 to 40), propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate (average addition mole number of PO: 1 to 40), and the like.
From the viewpoint of resolvability, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₄ ) A bis (meth) acrylate urethane compound represented by the general formula (IV).
In the general formula (IV), Z represents a divalent organic group, and may be, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, or 2 to 3 carbon atoms having a substituent Valence alicyclic groups and the like.
In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and may be -CH, for example. ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -Wait.
From the viewpoint of further improving the resolution, it is also preferred to be-(YO) in the general formula (IV). _s -Part and-(YO) _t -Parts are independently replaced by-(C ₂ H ₅ O)-(C ₃ H ₆ O) ₉ -.
As (b ₄ ) Preferred specific examples of the di (meth) acrylic acid urethane compound represented by the general formula (IV) include a (meth) acrylic monomer having a hydroxyl group at the β position and isophorone di Addition reactants of diisocyanate compounds such as isocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethyl) Diol isocyanate) hexamethylene isocyanurate, EO modified di (meth) acrylate urethane and EO / PO modified di (meth) acrylate urethane. In addition, EO means ethylene oxide, and the compound modified by EO has a block structure of ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide. Examples of the EO-modified di (meth) acrylate urethane include a trade name "UA-11" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and the like. Examples of the EO / PO modified di (meth) acrylic acid urethane include the trade name "UA-13" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and the like. These can be used individually by 1 type or in combination of 2 or more types.
From the viewpoint of suppressing generation of aggregates in the photosensitive resin layer containing the photosensitive resin composition during development, (B) the ethylenically unsaturated bond-containing compound preferably contains (b ₅ ) A tetra (meth) acrylate compound represented by the general formula (XI).
X in the general formula (XI) is an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -Wait.
As (b ₅ ) Preferred specific examples of the tetra (meth) acrylate compound represented by the general formula (XI) include pentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxytetra (meth) acrylate, and the like. .
(B) Compounds containing ethylenic unsaturated bonds may also be included as (b ₆ (B) ₁ ) ～ (b ₅ ) Additive polymerizable monomers other than components.
As (b ₆ ) Ingredients include the following
(b ₃ ) Other tris (meth) acrylates, such as trimethylolpropane tris (meth) acrylate, ethoxylated glycerol tris (meth) acrylate, ethoxylated isotricyanate tris ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, etc .;
(b ₅ ) Tetra (meth) acrylates other than the ingredients, such as di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc .;
Penta (meth) acrylate, such as dipentaerythritol penta (meth) acrylate, etc .;
Hexa (meth) acrylates, such as dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylates made by adding 1 to 24 moles of ethylene oxide to the 6 ends of dipentaerythritol, Six (meth) acrylic acid esters formed by adding 1 to 10 mol of ε-caprolactone to the 6 ends of dipentaerythritol;
An acrylate compound having one (meth) acrylfluorenyl group;
A compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyol;
A compound obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl-containing compound; and
Phthalic acid-based compounds such as γ-chloro-2-hydroxypropyl-β '-(meth) acryloxyethyl-phthalate and β-hydroxyalkyl-β'-(methyl ) Acrylic alkoxyalkyl-phthalate and the like.
In the fourth embodiment, the total content of all the (B) ethylenically unsaturated bond-containing compounds in the photosensitive resin composition is preferably from the viewpoint of the edge melting properties and adhesiveness of the photosensitive resin laminate. The range is 1 to 70% by mass, more preferably 2 to 60% by mass, and still more preferably 4 to 50% by mass.
[(C) Photopolymerization initiator]
The component (C) is a component which generates a radical capable of starting the polymerization of the component (B) by irradiation with light.
As such a component (C), an aromatic ketone compound, a quinone compound, a benzoin ether compound, a benzoin compound, a benzoin compound, a hexaarylbisimidazole compound, an acridine compound, etc. can be used, for example. Among these, it is preferable to use one or more types selected from the group consisting of a hexaaryl bisimidazole compound and an acridine compound from the viewpoint of high resolvability and good pore-covering property. From the viewpoint of the sensitivity of the photosensitive resin composition, the (C) component preferably contains an acridine compound.
Examples of the hexaarylbisimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,2 ', 5-tri- (o-chlorophenyl)- 4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylimidazole dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-di (Methoxyphenyl) -diphenylimidazole dimer, 2,4,5-tri- (o-chlorophenyl) -diphenylimidazole dimer, 2- (o-chlorophenyl) -bis-4 , 5- (3,4-dimethoxyphenyl) -imidazole dimer, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetra- (3 -Methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetra- (3-methoxy Phenyl) -imidazole dimer, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl)- Imidazole dimer, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,6-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'- Bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- ( 2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,3 , 6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetra- (3- (Methoxyphenyl) -imidazole dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxy Phenyl) -imidazole dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxybenzene ) -Imidazole dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl ) -Imidazole dimer, 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxybenzene ) -Imidazole dimer and the like.
Examples of the acridine compound include acridine, 9-phenylacridine, 1,6-bis (9-acridyl) hexane, and 1,7-bis (9-acridyl) heptane. Alkane, 1,8-bis (9-acridyl) octane, 1,9-bis (9-acridyl) nonane, 1,10-bis (9-acridyl) decane, 1,11 -Bis (9-acridyl) undecane, 1,12-bis (9-acridyl) dodecane, and the like.
The content of the (C) component in the photosensitive resin composition of the fourth embodiment is preferably 0.1% to 2% by mass, more preferably 0.2% to 1.8% by mass, and further preferably 0.3% by mass. The range is from -1.7% by mass, particularly preferably from 0.4% by mass to 1.6% by mass. Setting the content of the (C) component to such a range is preferable from the viewpoint of obtaining good light sensitivity and peeling characteristics.
From the viewpoint of improving sensitivity and resolution, the component (C) may further contain a sensitizer. Examples of such sensitizers include N-arylamino acids, organic halogen compounds, and other sensitizers.
Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like;
Examples of the organic halogen compound include bromopentane, bromoisopentane, brominated isobutylene, 1,2-dibromoethane, benzhydryl bromide, benzyl bromide, dibromomethane, and tribromomethylphenyl. Samarium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, isobutyl iodide, 1,1,1-trichloro-2,2-bis (P-chlorophenyl) ethane, trichloride Compounds etc.
Examples of the other sensitizers include:
2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1- Chloanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone Isoquinone compounds
Aromatic ketones such as benzophenone, Michelin [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone Compound
Benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin and other benzoin ether compounds;
Benzophenone dimethyl ketal, Benzophenone diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione Oxime ester compounds such as 2- (O-ethoxycarbonyl) oxime and the like.
From the viewpoints of the photosensitivity of the composition and the peelability of the resist cured film, the content of the sensitizer in the fourth embodiment is preferably from 0.01% by mass to 5% by mass, and more preferably from 0.05% by mass to 3 mass%, more preferably 0.1 mass% to 2 mass%.
In addition, in the photosensitive resin composition of the fourth embodiment, it is preferable to use an acridine compound and an N-aryl group from the viewpoints of suppression of the etching rate when forming the conductor pattern and suppression of the vertical and horizontal differences in the wiring width. The amino acid is used in combination as the component (C) within a range equal to the above-mentioned usage ratio.
[(D) Stabilizer]
The photosensitive resin composition may contain a stabilizer as needed. In the fourth embodiment, it is preferable to use a hindered phenol as a stabilizer from the viewpoint of improving resolution. In general, the so-called hindered phenol refers to phenol having a large steric hindrance. The photosensitive resin composition contains the following general formula (V):
[Chemical 18]

{Where R ⁵¹ Represents a linear alkyl group, branched alkyl group, aryl group, cyclohexyl group which may be substituted, a linear alkyl group connected via a divalent linking group, a branched alkyl group connected via a divalent linking group, and a divalent linking group A linked cyclohexyl group or an aryl group linked via a divalent linking group, and R ⁵² , R ⁵³ And R ⁵⁴ Each independently represents hydrogen, or a substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group connected via a divalent linking group, and branched alkyl group connected via a divalent linking group A compound represented by a cyclohexyl group linked via a divalent linking group or an aryl group linked via a divalent linking group} is a hindered phenol.
The compound represented by the general formula (V) is excellent from the viewpoint of improving the resolution of the photosensitive resin composition and from the viewpoint of suppressing a decrease in the sensitivity of the photosensitive resin composition. Furthermore, the compound represented by the general formula (V) is characterized in that it does not have two or more phenolic hydroxyl groups on one aromatic ring, and only one ortho position of two ortho positions of the phenolic hydroxyl group has a substituent. Controls steric hindrance around phenolic hydroxyl groups. It is considered that the above excellent performance is exhibited by having such a structure.
The compound represented by general formula (V) is preferably R in formula (V) from the viewpoint of improving the resolvability of the photosensitive resin composition and from the viewpoint of suppressing a decrease in the sensitivity of the photosensitive resin composition. ⁵¹ , R ⁵² , R ⁵³ And R ⁵⁴ At least one of them has an aromatic ring. From the same viewpoint, the hydroxyl concentration of the hindered phenol is preferably from 0.10 mol / 100 g to 0.75 mol / 100 g. From the same viewpoint, in the general formula (V), R ⁵¹ , R ⁵² , R ⁵³ And R ⁵⁴ At least one of them is preferably a linear or branched alkyl group, or an aryl group connected through a divalent linking group. Examples of the preferable alkyl group include methyl, ethyl, n-propyl, and isopropyl. Propyl, n-butyl, second butyl, isobutyl, third butyl, etc., and examples of preferred divalent linking groups include thioether groups, substituted or unsubstituted alkylene groups Etc., and the aryl group may be substituted with a hydroxyl group or an alkyl group.
From the same viewpoint, as the compound represented by the general formula (V), for example, the following general formula (VI) is preferred:
[Chemical 19]

{Where R ⁵⁵ Formula (VII):
[Chemical 20]

[Where, R ⁵⁹ And R ⁶⁰ Each independently represents hydrogen, or a substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group], and R ⁵⁶ , R ⁵⁷ And R ⁵⁸ Each independently represents hydrogen, or a compound represented by the general formula (VII)} and the following general formula (VIII):
[Chemical 21]

{Where R ⁶¹ And R ⁶⁴ Each independently represents a linear or branched alkyl group, and R ⁶² , R ⁶³ , R ⁶⁵ And R ⁶⁶ Each independently represents hydrogen, or a linear or branched alkyl group, X ¹ Represents a compound represented by a divalent linking group} and the following general formula (IX):
[Chemical 22]

{Where R ⁶⁷ , R ⁷⁰ And R ⁷³ Each independently represents a linear or branched alkyl group, and R ⁶⁸ , R ⁶⁹ , R ⁷¹ , R ⁷² , R ⁷⁴ And R ⁷⁵ Each independently represents hydrogen, or a linear or branched alkyl group, Y ¹ Represents a compound represented by a trivalent linking group} and the following general formula (X):
[Chemical 23]

{Where R ⁷⁶ , R ⁷⁹ , R ⁸² And R ⁸⁵ Each independently represents a linear or branched alkyl group, and R ⁷⁷ , R ⁷⁸ , R ⁸⁰ , R ⁸¹ , R ⁸³ , R ⁸⁴ , R ⁸⁶ And R ⁸⁷ Each independently represents hydrogen, or a linear or branched alkyl group, Z ¹ Represents a compound represented by a tetravalent linking group}. And, as X in the general formula (VIII), ¹ Examples include thioether groups, substituted or unsubstituted alkylene groups, and the like.
The compound represented by the general formula (V) preferably has a molecular weight of about 130 to about 1,000 from the viewpoint of improving the resolution of the photosensitive resin composition and from the viewpoint of suppressing a decrease in the sensitivity of the photosensitive resin composition. More preferably, it has a molecular weight of about 200 to about 800, more preferably has a molecular weight of about 300 to about 500, and most preferably has a molecular weight of about 300 to about 400. Further, it preferably has a specific gravity of about 1.02 to about 1.12 or a melting point of about 155 ° C or higher (for example, about 208 ° C or higher), or is poorly soluble in water and easily soluble in organic solvents such as methanol, acetone, and toluene, or When used, it is solid (e.g. powder, crystal, etc.) or liquid.
Examples of the compound represented by the general formula (V) include 4,4'-thiobis (6-third-butyl-m-cresol) and 4,4'-butylenebis (3-methyl-6) -Third butyl phenol), styrenated phenol (Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzyl phenol (Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups) Wait. Among these, 4,4 'is preferable from the viewpoint of improving the resolvability by increasing the content of the compound represented by the general formula (I) and suppressing the decrease in the sensitivity of the photosensitive resin composition. -Thiobis (6-third-butyl-m-cresol), 4,4'-butylenebis (3-methyl-6-third-butylphenol).
The ratio of the compound represented by the general formula (V) to the total mass of the photosensitive resin composition is 0.001% by mass to 10% by mass. In terms of improving the resolution, the ratio is 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. , The best is 0.7 mass% or more. On the other hand, in terms of a small decrease in sensitivity and an improvement in resolution, the ratio is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2 Mass% or less, particularly preferably 1.5 mass% or less.
In the fourth embodiment, the hindered phenol may further contain a compound other than the compound represented by the general formula (V). Examples of the compound other than the compound represented by the general formula (V) include 2,6-di-third-butyl-4-methylphenol, 2,5-di-third-pentylhydroquinone, and 2, 5-Di-Third-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5- Ethylphenyl) methane, triethylene glycol-bis [3- (3-third-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [ 3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], pentaerythritol group · tetra [3- (3,5-di-third-butyl-4-hydroxyphenyl) Propionate], 2,2-thio-diethylidenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-third-butyl-4-hydroxy-phenylpropyl) Hydrazine), 3,5-di-third-butyl-4-hydroxybenzylphosphonic acid-diethyl ester, 1,3,5-trimethyl-2,4,6-tri (3,5- Di-third-butyl-4-hydroxybenzyl) benzene, tri- (3,5-di-third-butyl-4-hydroxybenzyl) -isocyanurate, and the like.
In the fourth embodiment, the total content of all the hindered phenols in the photosensitive resin composition is preferably 0.001% to 10% by mass relative to the total mass of the photosensitive resin composition.
In this fourth embodiment, the photosensitive resin composition may contain a stabilizer other than a hindered phenol. As the stabilizer other than the hindered phenol, it is preferable to include a stabilizer selected from radical polymerization inhibitors such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tertiary butyl catechol, and subchloride Copper, 2,6-di-third-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-third-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-tert-butylphenol), diphenylnitrosoamine, triethylene glycol-bis (3-3-tert-butyl-5-methyl-4-hydroxyphenylpropionic acid Esters), and nitrosophenylhydroxylamine aluminum salts, etc .; benzotriazoles, such as 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis ( N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltri Azole, 1- (2-di-n-octylaminomethyl) -benzotriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole Etc; carboxybenzotriazoles, such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 6-carboxy-1,2,3- Benzotriazole, 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzo Triazole 1: 1 Mix N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzo Triazoles, and N- (N, N-di-2-ethylhexyl) amino phenylethylcarboxybenzotriazole, etc .; and alkylene oxide compounds with glycidyl groups, such as neopentyl glycol diglycidyl ether (Such as Kyoeisha Chemical Co., Ltd., Epolight 1500NP), nonaethylene glycol diglycidyl ether (such as Kyoeisha Chemical Co., Ltd., Epolight 400E), bisphenol A-propylene oxide 2 mol addition Diglycidyl ether (such as Kyoeisha Chemical Co., Ltd., Epolight 3002), hydrogenated bisphenol A diglycidyl ether (such as Kyoeisha Chemical Co., Ltd., Epolight 4000), 1,6-hexanediol Diglycidyl ether (e.g., Kyoeisha Chemical Co., Ltd., Epolight 1600) and at least one member of the group.
In the fourth embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, and still more preferably 0.05% by mass. % To 0.7% by mass. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. %the following.
[Other ingredients]
The photosensitive resin composition of the fourth embodiment may contain components other than the components (A) to (D) described above. Examples of such other components include leuco dyes, base dyes, plasticizers, antioxidants, radical polymerization inhibitors, solvents, and the like.
[Hide dye]
In order to impart suitable color rendering properties and excellent peeling properties to the resist cured film, the leuco dye may be blended in the photosensitive resin composition of the fourth embodiment.
Specific examples of the leuco dye include leuco crystal violet (tri [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl)- 6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4 -Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 1,3-dimethyl -6-diethylaminofluoran, 2-chloro-3-methyl-6-dimethylaminofluoran, 3-dibutylamino-6-methyl-7-anilinefluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 2- (2-chloroaniline) -6-dibutylaminofluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluorane, 1,2-benzo-6-diethylaminofluorine Alkanes, 1,2-benzo-6-dibutylaminofluoranes, 1,2-benzo-6-ethylisoamylaminofluoranes, 2-methyl-6- (N-p-toluene -N-ethylamino) fluoran, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethylamino) fluoran, 2- ( 3'-trifluoromethylaniline) -6-diethylaminofluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylamine Fluorane, 3-methoxy-4-dodecyloxystyrylquinoline, etc. Among these, leuco crystal violet is preferred.
The content of the leuco dye in the photosensitive resin composition of the fourth embodiment is preferably 0.6% by mass to 1.6% by mass, and more preferably 0.7% by mass to 1.2% by mass. By setting the use ratio of the leuco dye within this range, good color rendering properties and good peelability can be achieved.
[Basic dye]
Examples of the basic dye include basic green 1 [CAS number (the same applies hereinafter): 633-03-4] (for example, Aizen Diamond Green GH (trade name), manufactured by Hodogaya Chemical Industry), and malachite [2437-29-8] (for example, Aizen Malachite Green (trade name), manufactured by Hodogaya Chemical Industry), bright green [633-03-4], magenta [632-99-5], methyl violet [603- 47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], alkali Sex blue 7 [2390-60-5] (for example, Aizen Victoria Pure Blue BOH (trade name), manufactured by Hodogaya Chemical Industry), rhodamine B [81-88-9], rhodamine 6G [989-38- 8], Basic Yellow 2 [2465-27-2], Diamond Green, etc. Among these, one or more selected from the group consisting of basic green 1, malachite greenate, basic blue 7, and diamond green are preferred. From the viewpoint of hue stability and exposure contrast, alkali is particularly preferred. Sex green 1.
The content of the base dye in the photosensitive resin composition of the fourth embodiment is preferably 0.001% to 3% by mass, more preferably 0.01% to 2% by mass, and still more preferably 0.01% to 1.2% by mass. Range of mass%. By setting the use ratio within this range, both good color rendering and high sensitivity can be achieved.
[Solvent]
The photosensitive resin composition of the fourth embodiment may be a mixture of the above-mentioned components (A) to (C) and any other components used arbitrarily, or a photosensitive resin composition prepared by adding a suitable solvent to these components Use as a liquid.
Examples of the solvent used herein include ketone compounds such as methyl ethyl ketone (MEK); alcohols such as ethanol, ethanol, and isopropanol.
The use ratio of the solvent is preferably a ratio such that the viscosity of the photosensitive resin composition preparation solution at 25 ° C. becomes 500 to 4,000 mPa · sec.
<Photosensitive element>
In this fourth embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer containing the above-mentioned photosensitive resin composition is laminated on a support. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer on the side opposite to the support.
[Support body]
The support is preferably a transparent substrate that can transmit light emitted from the exposure light source. 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, and a vinylidene chloride copolymer film. , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. As these films, an extender may be used as necessary.
The haze of the support is preferably 5 or less.
The thickness of the support is thin, which is conducive to image formation and economy, but the strength must be maintained. Considering these two parties, a support of 10 μm to 30 μm can be preferably used.
[Photosensitive resin layer]
When the photosensitive resin composition for forming a photosensitive resin layer contains a solvent, the solvent may remain in the photosensitive resin layer, but it is preferably removed.
The thickness of the photosensitive resin layer is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.
[The protective layer]
An important characteristic of the protective layer is that the adhesive force between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferably used, and a film having excellent peelability disclosed in, for example, Japanese Patent Laid-Open No. Sho 59-202457 can also be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.
[Manufacturing method of photosensitive element]
The photosensitive element can be manufactured by sequentially laminating a support, a photosensitive resin layer, and a protective layer as necessary. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be adopted.
For example, the photosensitive resin composition is prepared in the form of the above-mentioned photosensitive resin composition blending solution. First, the photosensitive resin composition is coated on a support using a bar coater or a roll coater, dried, and formed on the support. A photosensitive resin layer containing a photosensitive resin composition. Then, a protective layer is laminated on the formed photosensitive resin layer as necessary, whereby a photosensitive element can be manufactured.
<Formation method of resist pattern>
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The method for forming the resist pattern preferably includes the following steps in the order described below:
A laminating step in which a photosensitive resin layer of a photosensitive element is laminated on a conductor substrate;
An exposure step of exposing the laminated photosensitive resin layer; and
The developing step involves developing the exposed photosensitive resin layer.
In the method for forming a resist pattern according to the fourth embodiment, first, in a lamination step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressure-bonded to the substrate surface using a laminator to be laminated.
As the substrate, a metal plate or an insulating substrate having a metal film is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). These substrates may also have through holes for dealing with multilayer substrates.
Here, the photosensitive resin layer may be laminated only on one side of the substrate surface, and if necessary, the photosensitive resin layer may be laminated on both sides of the substrate. The heating temperature at this time is preferably 40 ° C to 160 ° C. From the viewpoint of further improving the adhesiveness between the obtained resist pattern and the substrate, it is preferable to perform the thermocompression bonding twice or more. When performing crimping more than two times, a two-stage laminating machine equipped with a double roll can be used, or the laminate of the substrate and the photosensitive resin layer can be repeatedly crimped through the roll several times.
In the laminating step, the photosensitive resin layer of the photosensitive element may be laminated on the conductor substrate via a wetting agent. This is a better lamination method from the viewpoint of followability and yield improvement. The humectant preferably contains one or more copper chelating agents selected from pure water, deionized water, and electrolytic water (for example, selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). One or more of them).
Then, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. The exposure may be performed through the support without peeling the support, and may be performed after the support is peeled if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after the following development steps. The pattern-shaped exposure can be performed by either of a mask exposure and a maskless exposure. In the case of exposure through a mask, the amount of exposure depends on the illuminance of the light source and the exposure time. The exposure amount can be measured using a light meter.
In the maskless exposure, a drawing device is directly used for exposure on a substrate without using a mask. As a light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, and the like are used. In maskless exposure, the pattern drawn is controlled by a computer, and the exposure amount depends on the illuminance of the exposure light source and the moving speed of the substrate.
Then, in the developing step, the exposed photosensitive resin layer is developed. For example, the unexposed part of the photosensitive resin layer is removed with a developing solution. When a support is provided on the photosensitive resin layer, it is preferable to remove it after exposure and supply it to a developing step.
In the developing step, a developing solution containing an alkaline aqueous solution is used to develop and remove the unexposed portion to obtain a resist image. As the alkaline aqueous solution, for example, Na is preferably used. ₂ CO ₃ K ₂ CO ₃ And other aqueous solutions. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, and it is preferable to use Na at a concentration of 0.2% to 2% by mass. ₂ CO ₃ Aqueous solution. A surfactant, a defoaming agent, and a small amount of an organic solvent for promoting development can also be mixed into the alkaline aqueous solution.
The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 ° C to 40 ° C.
A resist pattern is obtained through the above steps. Depending on the circumstances, a heating step of 100 ° C to 300 ° C may be performed. It is preferable to implement this heating step from the viewpoint of further improving chemical resistance. Heating can be performed using a suitable heating furnace such as hot air, infrared, or far infrared.
＜ How to form a wiring board ＞
The method for forming a wiring board according to the fourth embodiment preferably includes the following steps in the order described below:
A laminating step in which a photosensitive resin layer of a photosensitive element is laminated on a conductor substrate;
An exposure step, which exposes the laminated photosensitive resin layer;
A developing step, which develops the exposed photosensitive resin layer;
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by development; and
The stripping step is to strip the resist pattern.
In the conductive pattern forming step, a conductive pattern may be formed on a substrate surface (for example, a copper surface) exposed through the development step by using a known etching method or plating method on the substrate on which the resist pattern is formed.
In the above-mentioned peeling step, the resist pattern is peeled off by contacting the substrate on which the conductor pattern is formed with an appropriate peeling solution. Through this step, the required wiring board is obtained.
The peeling liquid used in the peeling step is preferably an alkaline aqueous solution. As this alkaline aqueous solution, it is preferable to use, for example, a 2 to 5 mass% NaOH aqueous solution or a KOH aqueous solution. A small amount of a water-soluble solvent such as an alcohol may be added to the peeling solution. The temperature of the peeling liquid in the peeling step is preferably set to 40 ° C to 70 ° C.
The photosensitive resin composition, the photosensitive element, the method for forming a resist pattern, and the method for manufacturing a wiring board according to the fourth embodiment can be excellently used for manufacturing, for example, a printed wiring board, a lead frame, a substrate having an uneven pattern, Semiconductor packages, etc.
In addition, the measurement methods of the various parameters mentioned above are measured according to the measurement methods in the following examples unless otherwise specified.
[Example]
<Related Examples and Comparative Examples of the First Embodiment>
Hereinafter, the photosensitive resin composition of the first embodiment will be specifically described by way of examples.
(1) Measurement of physical properties of raw materials
＜ Measurement of weight average molecular weight ＞
The weight average molecular weight of the polymer is a gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Corporation) ( KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, mobile layer solvent: tetrahydrofuran, calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) ) Was obtained as a polystyrene conversion value.
<Acid equivalent>
In the present specification, the term "acid equivalent" means the mass (g) of a polymer having 1 equivalent of a carboxyl group in a molecule. An Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Industry Co., Ltd. was used to measure the acid equivalent by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.
(2) Production method and analysis of evaluation samples
＜ Production of photosensitive element ＞
The components shown in Table 1 and the following components:
0.04 parts by mass of diamond green as a coloring substance;
0.6 parts by mass of leuco crystal violet as a leuco dye;
0.7 parts by mass of tribromomethylphenylphosphonium as a halogen compound;
2 parts by mass of p-toluenesulfonamide as a plasticizer;
0.05 parts by mass of carboxybenzotriazole as benzotriazoles;
0.15 parts by mass of 1- (2-di-n-octylaminomethyl) -benzotriazole as benzotriazoles;
0.05 parts by mass of hydrogenated bisphenol A diglycidyl ether (Kyoeisha Chemical, Epolight 4000) as an antioxidant; and
0.004 parts by mass of tris (nitrosophenylhydroxylamine) aluminum as a radical polymerization inhibitor
These were mixed, and methyl ethyl ketone (MEK) was added to prepare a photosensitive resin composition having a solid content concentration of 53% by mass. The number in each component column in Table 1 is the amount (parts by mass) of each component for preparing the composition.
The obtained photosensitivity was uniformly coated on a 16 μm-thick polyethylene terephthalate film (R310 manufactured by Mitsubishi Resins Co., Ltd., a haze value of 2.1%) using a bar coater. After the resin composition, it was heated and dried in a dryer whose temperature was adjusted to 95 ° C. for 2.5 minutes to form a photosensitive resin composition layer having a thickness of 25 μm on a support.
Next, a 19 μm-thick polyethylene film (GF-18 manufactured by Tamapoly Co., Ltd.) was attached as a protective layer on the surface of the photosensitive resin composition layer on the side opposite to the support, thereby obtaining photosensitivity. element.
＜ Substrate for evaluation ＞
As a substrate for evaluating the hole coverability, a substrate formed by forming a copper clad laminated substrate having a thickness of 35 μm and a copper foil of 1.6 mm in thickness and forming 1,008 through holes having a diameter of 6 mm was used;
As the evaluation substrate other than the hole-cavity property, a copper-clad laminated substrate having a thickness of 0.4 mm and a copper foil having a thickness of 18 μm was used.
The substrate for evaluation of the hole-cavity property was subjected to surface treatment using a sandblasting brush mill, and the entire surface was used for evaluation.
The substrates for evaluation other than the hole-cavity properties were sequentially subjected to a surface treatment using a soft etchant (manufactured by Lingjiang Chemical Co., Ltd., CPE-900), and using 10% by mass of H ₂ SO ₄ The surface of the aqueous solution was cleaned and the entire surface was used for evaluation.
＜ Lamination ＞
While peeling the polyethylene film of the photosensitive element obtained in each example or comparative example, a heated roller laminator (manufactured by Asahi Kasei Co., Ltd., AL-70) was used at a roller temperature of 105 ° C, an air pressure of 0.35 MPa, and a layer. Laminated on the entire substrate at a pressing speed of 1.5 m / min.
＜ Exposure ＞
The exposure was performed by a direct drawing exposure method using a direct drawing exposure apparatus (manufactured by Nippon Orbotech Co., Ltd., Paragon Ultra 200, dominant wavelength 355 nm).
The exposure pattern is described in each evaluation item below.
＜ Development ＞
After the support was peeled off from the photosensitive resin composition layer after the exposure, an alkaline developing machine (manufactured by Fuji Machine Works, developing machine for dry film) was used, and sprayed with 1 mass% Na at 30 ° C for 2 times the minimum development time. ₂ CO ₃ The unexposed part of the photosensitive resin composition layer is dissolved and removed with an aqueous solution. After the development, the substrate was cleaned with pure water for 1.5 times the development time, and then subjected to warm air drying after dewatering treatment with an air knife, thereby obtaining a substrate having a cured film for evaluation.
The above-mentioned minimum development time means the minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.
＜ Evaluation of sensitivity ＞
The sensitivity was evaluated by using a laminated substrate 15 minutes after the aforementioned <Lamination>.
After directly drawing an exposure line / gap = 40 μm / 40 μm and a mask pattern of 10 lines on the laminated substrate, development was performed by the method described in the above <Development>. The resist top width of the obtained resist pattern was measured with an optical microscope, and the sensitivity was evaluated according to the following criteria.
The width of the top of the resist is 39.0 μm, and the exposure is 28 mJ or less: Sensitivity “○ (Good)”
The width of the top of the resist is 39.0 μm, and the exposure exceeds 28 mJ: Sensitivity “× (defective)”
Here, the measurement portion of the resist line is set to a position of about 5 mm from the one end of the fifth line in the lengthwise direction from the end of the fifth line, and the average value of three measurements is used as the measurement value. The line width of the pattern at the end portion and the center portion is different due to the influence of the diffusion of the developer and the washing water, and the resist line on the end side tends to be thinner.
The exposure amounts in the following evaluation items were as described in the above <Evaluation of Sensitivity>, and the exposure amount was set so that the resist top width of the mask pattern with line / gap = 40 μm / 40 μm was 39.0 μm.
＜ Evaluation of resolution ＞
The evaluation of the resolvability was based on the use of a laminated substrate 15 minutes after the above-mentioned <lamination>.
After directly drawing and exposing a pattern of lines / gap of various sizes = 1/1 on the laminated substrate, development was performed by the method described in the above <Development>.
With respect to the obtained pattern, the smallest pattern width formed was observed with an optical microscope, and the resolvability was evaluated according to the following criteria.
When the minimum pattern width is 20 μm or less: Resolution "○ (Good)"
When the minimum pattern width exceeds 20 μm and is less than 24 μm: Resolution "△ (Possible)"
When the minimum pattern width exceeds 24 μm: Resolution "× (defective)"
＜ Adhesiveness ＞
The adhesiveness was evaluated by using a laminated substrate 15 minutes after the aforementioned <Lamination>.
After directly drawing and exposing patterns of independent lines of various sizes on the laminated substrate, development is performed by the method described in the above <Development>.
The obtained pattern was observed with an optical microscope, and adhesiveness was evaluated according to the following criteria.
When the minimum pattern width that is normally formed is 18 μm or less: Adhesiveness "○ (Good)"
In the case where the minimum pattern width normally formed exceeds 18 μm and is less than 22 μm: Adhesiveness "△ (Possible)"
Normally formed minimum pattern width exceeding 22 μm: Adhesiveness "× (bad)"
Here, the case where the line pattern is abnormally formed refers to a case where the line pattern collapses, a case where the line pattern is bent, or a case where the line pattern does not exist.
＜ Cover hole property ＞
The evaluation of the hole covering property was performed by observing the above-mentioned laminated substrate obtained using a substrate having through holes.
The number of pores in which the photosensitive resin composition layer (cap hole film) formed on the through hole was broken was measured, and the ratio to all the holes (cap hole film breakage rate) was calculated, and evaluated based on the following criteria.
Case where the damage rate of the cap hole film is less than 0.1%: Capability "◎ (very good)"
When the damage rate of the cap hole film is 0.1% or more and less than 2%: the cap hole property is "○ (good)"
When the damage rate of the cap hole film is 2% or more: Cap hole property "× (bad)"
＜ Etching speed (width of wiring bottom) ＞
The evaluation of the etching rate (width of the bottom of the wiring) was based on the use of the laminated substrate 15 minutes after the aforementioned <Lamination>.
Directly draw the pattern of the exposure line / gap = 50 μm / 30 μm and 10 lines on the laminated substrate. 15 minutes after the exposure, the support was peeled from the photosensitive resin composition layer, and an alkaline developing machine (manufactured by Fuji Machinery Engineering, dry film developing machine) was used, and sprayed at a temperature of 30 ° C for 1 time that was twice the minimum development time. Mass% Na ₂ CO ₃ The unexposed part of the photosensitive resin composition layer is dissolved and removed with an aqueous solution. After development, it was washed with pure water for 1.5 times the development time.
Then, it is not necessary to dry the washed substrate with a line / gap pattern, and introduce it into a copper chloride etching device (manufactured by Tokyo Chemical Industry, NLE) in a state where the line / gap direction of the substrate is orthogonal to the conveying direction (MD). -2000), etching was performed at a linear velocity of 2.0 m / min for 55 seconds under the conditions of a hydrochloric acid concentration of 3.2 mol / L, a copper chloride concentration of 2.0 mol / L, an etching spray pressure of 0.2 MPa, and an etching solution temperature of 50 ° C.
After the above-mentioned etching, a 3.0% by mass NaOH aqueous solution was used as a stripping solution, and the bottom width of the wiring pattern in the MD direction of the copper wire obtained by peeling and removing the cured film on the substrate at a temperature of 50 ° C. was measured using an optical microscope.
Here, the measurement portion of the wiring pattern line is set to a position of about 5 mm from the end of the fifth line in the length direction from one end of the ten existing lines, and the average value of three measurements is used as the measurement value. . At the end and the center of the pattern, the influence on the resist caused by the diffusion of the developing solution and the washing water is different. Therefore, the line width of the final wiring is different, and the width of the wiring on the end side tends to be narrow.
＜ Vertical width and width difference ＞
The evaluation of the vertical and horizontal differences in wiring width was performed using the laminated substrate 15 minutes after the above-mentioned <lamination>.
Directly draw an exposure line / gap = 50 μm / 30 μm and a pattern with 10 lines on the laminated substrate, and arrange the exposure pattern in a tile shape along the MD direction and the TD direction.
15 minutes after the exposure, the support was peeled from the photosensitive resin composition layer, and an alkaline developing machine (manufactured by Fuji Machinery Engineering, dry film developing machine) was used, and sprayed at a temperature of 30 ° C for 1 time that was twice the minimum development time. Mass% Na ₂ CO ₃ The unexposed part of the photosensitive resin composition layer is dissolved and removed with an aqueous solution. After development, it was washed with pure water for 1.5 times the development time.
Then, there is no need to dry the water-washed substrate having a line / gap pattern, and introduce it into a copper chloride vacuum etching device (manufactured by Fuji Mechanical Engineering) in a state where the line / gap direction of the substrate is orthogonal to the conveying direction (MD). Mouth width 750 mm, slot length 2.6 m), there are 14 lines of etching solution pipes in the MD direction (pipe spacing is about 18 cm), and each pipe has 14 nozzles in the TD direction (slit nozzle, spray direction and TD The directions are parallel, the nozzle interval is about 14 cm, and the distance from the substrate is about 5 cm), without vibration, hydrochloric acid concentration 2.85 mol / L, copper chloride concentration 2.0 mol / L, etching spray pressure 0.3 MPa, vacuum pressure 0.15 MPa and etching The etching was performed at a liquid temperature of 48 ° C for 71 seconds at a linear velocity of 2.2 m / min.
After the above-mentioned etching, a 3.0% by mass NaOH aqueous solution was used as a stripping solution, and the cured film on the substrate was peeled off at a temperature of 50 ° C. The obtained two sets of copper wire patterns in the MD direction and the TD direction were measured by an optical microscope width.
Here, the measurement portion of the wiring pattern line is set to a position of about 5 mm from the end of the fifth line in the length direction from one end of the ten existing lines, and the average of the three measured values is used as the measurement. value. At the end and the center of the pattern, the effect on the resist caused by the diffusion of the developing solution and the washing water is different. Therefore, the final wiring has different line widths, and the wiring width on the end side tends to be narrow.
And, according to the following formula:
Vertical and horizontal difference in wiring width (μm) = TD-MD
The vertical and horizontal differences in wiring width were calculated and evaluated based on the following criteria.
When the width and width difference of the wiring width is 1 μm or less: The width and width difference of the bottom of the wiring is "◎ (very good)"
When the width and width difference of the wiring width exceeds 1 μm and is less than 2 μm: The width and width difference of the bottom of the wiring is "○ (good)"
When the vertical and horizontal difference of the wiring width is more than 2 μm and less than 4 μm: The vertical and horizontal difference of the width of the wiring bottom is "△ (OK)"
When the vertical and horizontal difference of the wiring width exceeds 4 μm: The vertical and horizontal difference of the width at the bottom of the wiring is "× (defective)"
Examples 1 to 23 and Comparative Examples 1 to 8
The compositions of the photosensitive resin compositions used in the examples and comparative examples are shown in Table 1.
The detailed description of each component name shown in Table 1 is shown in Table 2. The blending amounts of each component in Table 1 are all parts by mass in terms of solid content.
The evaluation results using each composition are shown in Table 1.

[Table 1]

[Table 2]


[Table 2]


<Related Examples and Comparative Examples of the Second Embodiment>
Hereinafter, the photosensitive resin composition of the second embodiment will be specifically described by way of examples.
(1) Measurement of physical properties of raw materials
<Acid equivalent>
The so-called acid equivalent refers to the mass of an alkali-soluble polymer having one equivalent of a carboxyl group therein. The measurement of the acid equivalent is performed by a potentiometric titration method using an automatic titration device (for example, the Hiranuma Automatic Titration Device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) and a 0.1 mol / L sodium hydroxide aqueous solution.
＜ Measurement of weight average molecular weight ＞
The weight average molecular weight of the polymer is a gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Corporation) ( KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, mobile layer solvent: tetrahydrofuran, calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) ) Was obtained as a polystyrene conversion value.
(2) Preparation method of evaluation samples
＜ Production of photosensitive element ＞
Each component shown in Table 3 was mixed, and methyl ethyl ketone (MEK) was added to prepare a photosensitive resin composition having a solid content concentration of 55% by mass.
Using a bar coater, uniformly coat the obtained photosensitive resin composition on a 16 μm-thick polyethylene terephthalate film (manufactured by Teijin Dupont Films Co., Ltd., GR-16) as a support. After the object was dried, it was heated and dried in a dryer at a temperature of 95 ° C. for 4 minutes to form a photosensitive resin layer having a thickness of 33 μm on the support.
Then, a 19 μm-thick polyethylene film (GF-18 manufactured by Tamapoly Co., Ltd.) as a protective layer was attached to the surface of the photosensitive resin layer on the side opposite to the support, thereby obtaining a photosensitive element.
＜ Substrate for evaluation ＞
As a substrate for evaluation, the entire surface of a copper-clad laminated board having a thickness of 1.6 mm having a rolled copper foil of 35 μm laminated was polished by a wet polishing roller. The polishing was performed twice using Scotch-Brite (registered trademark) HD # 600 manufactured by 3M Co., Ltd.
＜ Lamination ＞
While peeling the polyethylene film of the photosensitive element obtained in each example or comparative example, a heated roller laminator (manufactured by Asahi Kasei Co., Ltd., AL-70) was used at a roller temperature of 105 ° C, an air pressure of 0.35 MPa, and a layer. Laminate on a substrate preheated to 60 ° C on the entire surface at a pressing speed of 1.5 m / min.
＜ Exposure ＞
Direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, dominant wavelength 405 ± 5 nm), using Stouffer 41-stage exposure ruler or specific DI exposure mask Hood pattern at 80 mW / cm ² Under the conditions, exposure is achieved with an equivalent amount of 14 steps in the Stouffer 41-stage step scale.
＜ Development ＞
After the support was peeled off from the photosensitive resin layer after the exposure, an alkaline developing machine (manufactured by Fuji Machinery Engineering, dry film developing machine) was used, and sprayed with 1 mass% Na at 30 ° C for 2 times the minimum development time. ₂ CO ₃ An aqueous solution is used to dissolve and remove the unexposed portion of the photosensitive resin layer. After the development, the substrate was cleaned with pure water for 1.5 times the development time, and then subjected to warm air drying after dewatering treatment with an air knife, thereby obtaining a substrate having a cured film for evaluation.
The minimum development time is the minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed.
＜ Etching ＞
Using a copper chloride etching device (copper chloride etching device, manufactured by Tokyo Chemical Industry Co., Ltd.), a copper chloride etching solution (chlorine at 50 ° C.) The copper concentration is 250 g / L, and the HCl concentration is 3 mol / L), and the copper foil on the copper-clad laminate is not dissolved and removed.
＜ Peeling ＞
The hardened resist was peeled off by spraying a 3 mass% sodium hydroxide aqueous solution heated to 50 ° C. on the evaluation substrate after the etching.
(3) Evaluation method
(i) Development agglutination test
Photopolymerizable resin laminate with a thickness of 50 μm and an area of 0.6 m ² The photosensitive layer (resist layer) is dissolved in 200 ml of 1% by mass Na ₂ CO ₃ The aqueous solution was sprayed using a circulating spray device at a spray pressure of 0.1 MPa for 3 hours. Thereafter, the developing solution was left to stand for one day, and the presence or absence of agglomerates was observed. If a large amount of agglomerates are generated, powder or oil is observed at the bottom and sides of the spray device. In addition, the aggregate may be suspended in the developing solution. As long as the composition has a good agglutination property of the developer, such agglomerates are not generated at all, or even if they are generated, they are extremely minute and can be easily removed by washing with water. The generation state of the aggregate was classified into the following grades by visual observation.
((Significantly good): Aggregates were not generated at all.
○ (Good): There is no agglomerate on the bottom or side of the spray device, and a very small amount of suspended agglomerate that can be visually confirmed is observed in the developing solution, but can be removed by simple water washing.
△ (possible): Suspended agglomerates are present in the bottom or side of the spray device and in the developing solution. Even with water washing, all aggregates cannot be removed.
× (bad): Aggregates were seen in the entire spray device, and suspended aggregates were present in the developing solution. Even with water washing, the aggregates could not be completely removed, and most of them remained.
(ii) Sensitivity test
Using the photosensitive elements obtained in each of the examples and comparative examples, lamination and exposure were performed according to the method described above, and based on each exposure amount and the number of levels remaining after development, it was investigated that the 14th level of the Stouffer 41-level stepped exposure ruler was equivalent. Exposure (mj / cm ² , 14 / 41ST exposure amount), and evaluated according to the following criteria.
Sensitivity “〇” (Good): 14 / 41ST exposure is 25 mj / cm ² The following situations
Sensitivity "×" (bad): 14 / 41ST exposure exceeds 25 mj / cm ² Situation
(iii) Resolution test
The photosensitive elements obtained in each of the examples and comparative examples were used for lamination according to the method described above, and the sample 15 minutes after lamination was used, and the line / gap was set to 1/1, and direct drawing exposure was performed according to the method described above. Then, development is performed according to the method described above.
Furthermore, the minimum mask line width in which the hardened resist line was normally formed was investigated, and evaluated in accordance with the following criteria.
Resolution "0" (Good): When the minimum line width is less than 25 μm
Resolution "△" (possible): when the minimum line width is 25 μm or more and less than 30 μm
Resolution "×" (Bad): When the minimum line width is 30 μm or more
(iv) Adhesion test
The photosensitive elements obtained in each of the Examples and Comparative Examples were used for lamination according to the above-mentioned method, and the samples that had passed 15 minutes after lamination were used for direct drawing exposure according to the above-mentioned method. Then, development is performed according to the method described above.
Furthermore, the line / gap was set to line / gap = X / 200, and the minimum mask line width normally formed at this time was investigated as X, and evaluation was performed according to the following criteria.
Adhesiveness “〇” (Good): When the minimum line width is less than 25 μm
Adhesiveness "△" (possible): when the minimum line width is 25 μm or more and less than 30 μm
Adhesiveness "×" (bad): When the minimum line width is 30 μm or more
Examples 1 to 6 and Comparative Examples 1 to 5
Table 3 shows the composition of the photosensitive resin composition used in the examples and comparative examples, and Table 4 shows the detailed descriptions of the respective component names in Table 3. The blending amounts of each component in Table 4 are all parts by mass in terms of solid content.
The evaluation results using each composition are shown in Table 4.
[table 3]



[Table 4]


<Related Examples and Comparative Examples of the Third Embodiment>
Hereinafter, the photosensitive resin composition according to the third embodiment will be specifically described by way of examples.
The measurement of physical property values of polymers and monomers, and the methods of preparing samples for evaluation in Examples and Comparative Examples will be described, and then the evaluation methods and evaluation results for the obtained samples will be disclosed.
(1) Measurement or calculation of physical property values
<Determination of weight average molecular weight or number average molecular weight of a polymer>
The weight average molecular weight or number average molecular weight of the polymer is a gel permeation chromatography (GPC) (pump: Gulliver, PU-1580 type, column: Shodex (manufactured by Showa Denko) Co., Ltd.) (Registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, mobile layer solvent: tetrahydrofuran, using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) The calibration curve) is obtained as a polystyrene conversion.
Furthermore, the dispersion degree of the polymer is 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 the present specification, the term "acid equivalent" means the mass (g) of a polymer having 1 equivalent of a carboxyl group in a molecule. An Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Industry Co., Ltd. was used to measure an acid equivalent by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.
(2) Preparation method of evaluation samples
The evaluation samples in Examples 1 to 12 and Comparative Examples 1 to 5 were prepared as follows.
＜ Production of photosensitive resin laminated body ＞
The components shown in the following Table 5 or 6 (where the number of each component represents the compounding amount (parts by mass) as a solid component) and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. The names of the components indicated by abbreviations in Tables 5 and 6 are shown in Table 7 below. A 16 μm-thick polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., R310-16B) was used as a supporting film, and the preparation solution was uniformly coated on the surface using a rod coater at 95 ° C. It dried in the dryer for 3 minutes, and formed the photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 μm.
Next, a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was laminated on the surface of the non-layered polyethylene terephthalate film side of the photosensitive resin composition layer as a protective layer. A photosensitive resin laminate was obtained.
＜ The whole surface of the substrate ＞
Grinding materials (manufactured by Japan Carlit Co., Ltd., Sakurundum R (registered trademark # 220)) were used to sandblast the copper-clad laminates with a thickness of 0.4 mm and rolled copper foil with a thickness of 0.4 mm with a spray pressure of 0.2 MPa. This produced a substrate for evaluation.
＜ Lamination ＞
While peeling the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was laminated to the entire surface at a roll temperature of 105 ° C using a heated roll laminator (manufactured by Asahi Kasei Corporation, AL-700). A copper-clad laminate was heated to 60 ° C to obtain a test piece. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.
＜ Exposure ＞
Using a direct drawing type exposure apparatus (manufactured by Via Mechanics, DE-1DH, dominant wavelength 405 nm) at 15 mJ / cm ² Exposure.
＜ Development ＞
After the polyethylene terephthalate film was peeled from the photosensitive resin laminate, a developing device manufactured by Fuji Machine Engineering Co., Ltd. was used, and a full cone nozzle was used to spray 30 ° C for 30 minutes at a developing injection pressure of 0.15 MPa. 1 mass% Na ₂ CO ₃ The aqueous solution is developed, and the unexposed portion of the photosensitive resin layer is dissolved and removed. At this time, the minimum development time, that is, the minimum time required for the photosensitive resin layer in the unexposed portion to completely dissolve, is measured, and development is performed twice as long as the minimum development time to prepare a resist pattern. At this time, the water washing step is performed at the same time as the developing step using a flat nozzle at a water washing spray pressure of 0.15 MPa.
(3) Evaluation method of samples
＜ Cover hole property ＞
A sandblasting brush mill was used to surface-treat a double-sided copper-clad laminate with a width of 2.0 mm x a length of 15 mm and a thickness of 0.6 mm with through holes. Lamination was performed on both sides by the method described in the above <Lamination>, and both sides were fully exposed using a direct drawing exposure apparatus (manufactured by Via Mechanics Co., Ltd., DE-1DH, dominant wavelength 405 nm). Develop by the method described in the above <Development>, measure the number of cap holes that are broken at this time, calculate the breakage rate with respect to all cap holes, and classify according to the following criteria.
◎ (best): The film breakage rate after development was 2% or less.
((Very good): The film breakage rate after development exceeds 2% and is 4% or less.
(Good): The film breakage rate after development exceeds 4% and is 10% or less.
× (defective): The film breakage rate after development exceeds 10%.
<Contact angle (residual water short-circuit suppression)>
In the evaluation of the contact angle (residual short-circuit resistance), after lamination was performed by the method described in the above <Lamination>, full exposure was performed by the method described in the above <Exposure>, and then by Development is performed by the method described in the above <Development>.
After the development, the sample was subjected to the measurement of the contact angle within 30 minutes.
The measurement of the contact angle is based on the static drop method of JIS R3257, using an optical microscope-type contact angle meter "LSE-B100" manufactured by NIC Corporation, and dripping 0.5 μL onto the cured film under the environment of a temperature of 23 ° C and a humidity of 50RH%. After measuring pure water, the contact angle was measured, and the value after 120 seconds was used for classification according to the following criteria. When the value of the contact angle is large, it means that the hydrophobicity of the hardened resist is high, and it is possible to suppress the residual short circuit defect.
(Excellent): The contact angle is 35 ° or more.
(Good): The contact angle is 30 ° or more and less than 35 °.
△ (Xu capacity): The contact angle is 25 ° or more and less than 30 °.
× (bad): The contact angle did not reach 25 °.
(4) Evaluation results
The evaluation results of Examples 1 to 12 are shown in Table 5 below, and the evaluation results of Comparative Examples 1 to 5 are shown in Table 6 below.

[table 5]


[TABLE 6]



[TABLE 7]


<Related Examples and Comparative Examples of the Fourth Embodiment>
Hereinafter, the photosensitive resin composition of the fourth embodiment will be specifically described by way of examples.
(1) Measurement of physical properties of raw materials
＜ Measurement of weight average molecular weight ＞
The weight average molecular weight of the polymer is a gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Corporation) ( KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, mobile layer solvent: tetrahydrofuran, calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) ) Was obtained as a polystyrene conversion value.
<Acid equivalent>
In the present specification, the term "acid equivalent" means the mass (g) of a polymer having 1 equivalent of a carboxyl group in a molecule. An Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Industry Co., Ltd. was used to measure the acid equivalent by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.
(2) Production method and analysis of evaluation samples
＜ Production of photosensitive element ＞
Each component shown in Table 8 was mixed, and methyl ethyl ketone (MEK) was further added, and the photosensitive resin composition of 56 mass% of solid content concentration was prepared. The number in each component column in Table 8 is the quantity (mass part) of each component for preparing a composition.
Obtained uniformly using a rod coater on a 16 μm-thick polyethylene terephthalate film (GR-16 manufactured by Teijin Dupont Films Co., Ltd., haze value 2.7%). After the photosensitive resin composition was heated and dried in a dryer whose temperature was adjusted to 95 ° C. for 3 minutes and 20 seconds, a photosensitive resin layer having a thickness of 33 μm was formed on the support.
Then, a 19 μm-thick polyethylene film (GF-18 manufactured by Tamapoly Co., Ltd.) as a protective layer was attached to the surface of the photosensitive resin layer on the side opposite to the support, thereby obtaining a photosensitive element.
＜ Substrate for evaluation ＞
As a substrate for evaluation, the entire surface of a copper-clad laminated board having a thickness of 1.6 mm having a rolled copper foil of 35 μm laminated was polished by a wet polishing roller. The polishing was performed twice using Scotch-Brite (registered trademark) HD # 600 manufactured by 3M Co., Ltd.
＜ Lamination ＞
While peeling the polyethylene film of the photosensitive element obtained in each example or comparative example, a heated roller laminator (manufactured by Asahi Kasei Co., Ltd., AL-70) was used at a roller temperature of 105 ° C, an air pressure of 0.35 MPa, and a layer. Laminated on the entire substrate at a pressing speed of 1.5 m / min.
＜ Exposure ＞
Direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1AH, light source: GaN blue-violet diode, dominant wavelength 405 ± 5 nm), using a specific mask pattern for DI exposure, at an illumination intensity of 15 mW / cm ² Exposure under these conditions.
The exposure pattern and exposure amount are described in each evaluation item below.
＜ Development ＞
After the support was peeled off from the photosensitive resin layer after exposure, an alkaline developing machine (manufactured by Fuji Machine Works, developing machine for dry film) was used, and sprayed with 0.8% by mass of Na at 29 ° C for 2 times the minimum development time ₂ CO ₃ An aqueous solution is used to dissolve and remove the unexposed portion of the photosensitive resin layer. After the development, pure water washing was performed for the same time as the development time. After the water washing, the substrate was naturally dried without being subjected to a warm air drying treatment, thereby obtaining a substrate having a cured film for evaluation.
The above-mentioned minimum development time refers to the minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed, and varies depending on the concentration or temperature of the developing solution, the spray direction or spray amount, pressure, and oscillation frequency.
Here, the minimum development time is classified as follows:
○: The minimum development time exceeds 30 seconds.
×: The minimum development time is 30 seconds or less.
＜ Evaluation of sensitivity ＞
The sensitivity was evaluated by using a laminated substrate 15 minutes after the aforementioned <Lamination>.
After directly drawing an exposure line / gap = 40 μm / 40 μm and a mask pattern of 10 lines on the laminated substrate, development was performed by the method described in the above <Development>. The resist top width of the obtained resist pattern was measured with an optical microscope, and the sensitivity was evaluated based on the exposure amount at which the resist top width became 39 μm.
Here, the measurement position of the resist line is set to a position of about 5 mm from the end of the fifth line in the length direction from one end of the ten existing lines, and the average value of three measurements is used as the measurement value. . The line width of the pattern at the end portion and the center portion differs due to the influence of the diffusion of the developer and the washing water, and there is a tendency that the resist line on the end side becomes thinner. Therefore, it is important to specify the measurement position.
The exposure amount in the following evaluation items is as described in the above <Evaluation of Sensitivity>, and it is set to an exposure amount of 39 μm with respect to the mask pattern of line / gap = 40 μm / 40 μm. Here, based on the exposure, the sensitivity is classified as follows:
○: Line width is 39 μm and exposure is 28 mJ / cm ² the following.
×: Line width becomes 39 μm, and the exposure exceeds 28 mJ / cm ² .
＜ Evaluation of resolution ＞
The evaluation of the resolvability was based on the use of a laminated substrate 15 minutes after the above-mentioned <lamination>.
After directly drawing and exposing a pattern of lines / gap of various sizes = 1/1 on the laminated substrate, development was performed by the method described in the above <Development>.
The obtained pattern was observed for the smallest pattern width with an optical microscope, and the resolution was evaluated according to the following criteria.
○: The smallest pattern width formed is 28 μm or less.
×: The smallest pattern width formed exceeds 28 μm.
＜ Evaluation of tightness ＞
The adhesiveness was evaluated by using a laminated substrate 15 minutes after the aforementioned <Lamination>.
After directly drawing and exposing patterns of independent lines of various sizes on the laminated substrate, development is performed by the method described in the above <Development>.
The obtained pattern was observed with an optical microscope, and adhesiveness was evaluated according to the following criteria.
Here, the case where the line pattern is abnormally formed refers to a case where the line pattern collapses, a case where the line pattern is bent, or a case where the line pattern does not exist.
○: The smallest pattern width formed is 28 μm or less.
×: The smallest pattern width formed exceeds 28 μm.
＜ Evaluation of agglutination ＞
Photopolymerizable resin laminate with a thickness of 50 μm and an area of 0.6 m ² The photosensitive layer (resist layer) is dissolved in 200 ml of 1% by mass Na ₂ CO ₃ The aqueous solution was sprayed using a circulating spray device at a spray pressure of 0.1 MPa for 3 hours. Thereafter, the developing solution was left to stand for one day, and the presence or absence of agglomerates was observed. If a large amount of agglomerates are generated, powder or oil is observed on the bottom and sides of the spray device. If it is a composition with good agglutination property of a developing solution, the agglomerate mentioned above does not generate | occur | produce at all. According to the generation state of agglutination, the agglutination is classified as follows:
(Circle): There is no aggregation at all.
△: Aggregates were visible on the bottom or side of the spray device.
×: Aggregates were seen in the entire spray device.
＜ Evaluation of peelability ＞
Using the substrate 15 minutes after the treatment described in the above <Lamination>, the laminated substrate was directly drawn and exposed to a rectangular pattern of 4 cm x 6 cm, and then developed by the method described in the above <Development>.
The hardened resist on the obtained substrate was immersed in NaOH at 50 ° C and 3% by mass, and the time until the resist was completely peeled from the substrate was measured and recorded as the peel time.
Here, the releasability is classified as follows:
○: The time until complete peeling is 40 seconds or less.
×: The time until complete peeling exceeds 40 seconds.
Examples 1 to 7 and Comparative Examples 1 to 4
Table 8 shows the composition of the photosensitive resin compositions used in the examples and comparative examples, and Table 9 shows the detailed descriptions of the respective component names described in Table 8. The blending amounts of each component in Table 8 are all parts by mass in terms of solid content.
The evaluation results using each composition are shown in Table 8 together.

[TABLE 8]



[TABLE 9]

Claims (11)

A photosensitive resin composition containing (A) Alkali-soluble polymers, (B) a compound containing an ethylenically unsaturated bond, and (C) a photopolymerization initiator, and The (A) alkali-soluble polymer includes a structural unit of (meth) acrylic acid in an amount of 10% to 24% by mass based on the total mass of the monomers constituting the (A) alkali-soluble polymer, and 35% by mass to 90% by mass of structural units of styrene, and The weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is 1,200 or more. The photosensitive resin composition according to claim 1, wherein the (B) ethylenically unsaturated bond-containing compound has a weight average molecular weight of 1,300 or more. The photosensitive resin composition according to claim 1 or 2, wherein 40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is an alkylene oxide-modified bisphenol represented by the following general formula (II) Type A di (meth) acrylate compound: [Chem 2] {In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ , n ₂ , n _3, and n ₄ satisfy n ₁ + n ₂ + N ₃ + n ₄ = an integer with a relationship of 2 to 50. The arrangement of repeating units of-(AO)-and-(BO)-can be random or block. In the case of block,-(AO) Either-and-(BO)-may be biphenyl side}. The photosensitive resin composition according to claim 3, wherein n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30-50. The photosensitive resin composition according to claim 3, wherein n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2-10. The photosensitive resin composition according to claim 1 or 2, wherein the (B) ethylenically unsaturated bond-containing compound includes a tri (meth) acrylate compound represented by the following general formula (III): [化 3] {Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ are each independently 0 to 40 Integer, m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, a plurality of X may be the same or different from each other}. The photosensitive resin composition according to claim 1 or 2, wherein the (B) ethylenic unsaturated bond-containing compound includes a bis (meth) acrylate urethane compound represented by the following general formula (IV): [Chemical 4] {In the formula, R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t are each independently an integer of 0 to 40 And s + t ≧ 1}. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (A) alkali-soluble polymer further includes a structural unit of butyl (meth) acrylate. The photosensitive resin composition according to any one of claims 1 to 8, which is used for direct image exposure. A method for forming a resist pattern includes: A laminating step in which the supporting volume layer comprises a photosensitive resin layer of the photosensitive resin composition according to any one of claims 1 to 9; An exposure step of exposing the photosensitive resin layer; and The developing step involves developing the exposed photosensitive resin layer. A method for manufacturing a wiring board includes: A laminating step of laminating a photosensitive resin layer comprising a photosensitive resin composition according to any one of claims 1 to 9 on a substrate; An exposure step of exposing the photosensitive resin layer; A developing step of developing the exposed photosensitive resin layer 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 The stripping step is to strip the resist pattern.