Photosensitive resin composition and photosensitive resin laminate

Abstract

Provided is a photosensitive resin laminate in which a photosensitive resin layer is layered on a support film, the photosensitive resin layer containing a photosensitive resin composition containing (A) an alkali-soluble polymer 10 to 90 mass%, (B) a compound having an ethylenic unsaturated double bond 5 to 70 mass%, and (C) a photopolymerization initiator 0.01 to 20 mass%, the aforementioned (A) alkali-soluble polymer containing a copolymer containing a (meth)acrylic acid ester having an alkyl group having 3 to 12 carbon atoms as a copolymerization component, as the aforementioned (B) compound having an ethylenic unsaturated double bond, an acrylic acid ester monomer is contained at 51 to 100 mass% relative to the total amount of the aforementioned (B) compound having an ethylenic unsaturated double bond, a relationship indicated by 0 < A / T ≤ 0.007 is satisfied, where the film thickness of the photosensitive resin layer containing the aforementioned photosensitive resin composition is T (μm), and the absorbance at a wavelength of 365 nm is A, and the film thickness of the photosensitive resin layer containing the aforementioned photosensitive resin composition is 40 μm or more and 600 μm or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive resin composition and a photosensitive resin laminate using the same, and a method for forming a resist pattern or a semiconductor bump, and the like. BACKGROUND

[0002] Conventionally, in the manufacture of a printed circuit board, precision processing of metals, and the like, manufacturing is performed by a photolithography method. A photosensitive resin composition used in the photolithography method is classified into a negative type composition in which an unexposed portion is removed by dissolution and a positive type composition in which an exposed portion is removed by dissolution.

[0003] When the photosensitive resin composition is applied to a substrate in the photolithography method, any of the following methods is used:

[0004] (1) a method in which a photoresist solution is applied to a substrate and dried; and

[0005] (2) a method in which a photosensitive resin layer is laminated to a substrate using a photosensitive resin laminate obtained by sequentially laminating a support and a layer containing a photosensitive resin composition (hereinafter also referred to as a "photosensitive resin layer"), and a protective layer as necessary. In the manufacture of a printed circuit board, the latter method is often used.

[0006] A method for forming a pattern using the photosensitive resin laminate described above is briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Next, using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate, a copper sputtering film, or the like, in the order of the substrate, the photosensitive resin layer, and the support. Next, the photosensitive resin layer is exposed through a photomask having a desired wiring pattern. Next, the support is peeled off from the laminated body after exposure, and the non-pattern portion is dissolved or dispersed and removed using a developer, whereby a resist pattern is formed on the substrate.

[0007] Further, by subjecting a substrate provided with the resist pattern to plating treatment such as copper plating, soldering, or the like, a bump for a semiconductor or the like can be formed.

[0008] Various photosensitive resin compositions have been studied for the purpose of forming a resist pattern or a semiconductor bump. For example, in Patent Documents 1 to 5, a photosensitive resin composition containing a specific alkali-soluble polymer, a monomer, and a photopolymerization initiator is described.

[0009] PRIOR ART DOCUMENTS

[0010] PATENT DOCUMENTS

[0011] Patent Document 1: International Publication No. 2018 / 164217

[0012] Patent Document 2: Japanese Patent Application Publication No. 5-341532

[0013] Patent Literature 3: Japanese Patent Application Laid-Open No. 5-241340

[0014] Patent Literature 4: Japanese Patent Application Laid-Open No. 3-200804

[0015] Patent Literature 5: International Publication No. 2015 / 178462 SUMMARY

[0016] The problem to be solved by the invention

[0017] In recent years, with the miniaturization and high density of wiring, the precision of the finished line width of the conductor line (e.g., copper line) after etching is strictly required. In addition, the following phenomena have been reported: a phenomenon in which the cured resist pattern dissolves depending on the type of stripping solution (hereinafter also referred to as "stripping sheet dissolution"); a phenomenon in which, after plating treatment, the plating layer penetrates to the bottom of a post of a substrate from which the cured resist pattern has been stripped (hereinafter also referred to as "plating layer penetration"); and the like.

[0018] However, the photosensitive resin compositions described in Patent Literatures 1 to 5 do not take into account the stripping sheet dissolution and the plating layer penetration, or there is room for improvement in the stripping sheet dissolution and the plating layer penetration.

[0019] Therefore, an object of the present application is to provide a photosensitive resin composition capable of improving properties related to stripping sheet dissolution and plating layer penetration, and a photosensitive resin laminate using the same, and a resist pattern or semiconductor bump forming method.

[0020] The solution to the problem

[0021] The present inventors have conducted intensive studies and repeated experiments and have found that the above problems can be solved by the following technical means, thereby completing the present application. The present application exemplifies the following embodiments.

[0022] (1) A photosensitive resin laminate in which a photosensitive resin layer containing a photosensitive resin composition is layered on a support film, the photosensitive resin composition containing:

[0023] (A) an alkali-soluble polymer: 10 to 90 mass%,

[0024] (B) a compound having an ethylenic unsaturated double bond: 5 to 70 mass%, and

[0025] (C) a photopolymerization initiator: 0.01 to 20 mass%,

[0026] The aforementioned (A) alkali-soluble polymer contains a copolymer containing a (meth)acrylic acid ester having an alkyl group having 3 to 12 carbon atoms as a copolymerization component,

[0027] As the aforementioned (B) compound having an ethylenically unsaturated double bond, an acrylic ester monomer is contained at 51 mass% to 100 mass% relative to the total amount of the aforementioned (B) compound having an ethylenically unsaturated double bond,

[0028] When the film thickness of the photosensitive resin layer containing the aforementioned photosensitive resin composition is denoted as T [pm], and the absorbance at a wavelength of 365 nm is denoted as A, the following relation shown by formula (I) is satisfied:

[0029] 0 < A / T < 0.007 Formula (I)

[0030] Further, the film thickness of the photosensitive resin layer containing the aforementioned photosensitive resin composition is 40 pm or more and 600 pm or less.

[0031] (2) The photosensitive resin layer stack according to item (1), wherein the aforementioned (A) alkali-soluble polymer contains a copolymer containing 2-ethylhexyl acrylate as a copolymerization component.

[0032] (3) The photosensitive resin layer stack according to item (1) or (2), wherein the aforementioned (A) alkali-soluble polymer contains a copolymer containing benzyl (meth)acrylate as a copolymerization component.

[0033] (4) The photosensitive resin layer stack according to any one of items (1) to (3), wherein the aforementioned (A) alkali-soluble polymer further contains a (meth)acrylate other than the aforementioned (meth)acrylate having an alkyl group having 3 to 12 carbon atoms and / or a vinyl compound as a copolymerization component, and

[0034] The aforementioned (A) alkali-soluble polymer contains 6.0 mass% to 30 mass% of the aforementioned (meth)acrylate having an alkyl group having 3 to 12 carbon atoms as a copolymerization component.

[0035] (5) The photosensitive resin layer stack according to any one of items (1) to (4), wherein, as the aforementioned (B) compound having an ethylenically unsaturated double bond, a compound having an acrylate group of tri-functionality or more is contained.

[0036] (6) The photosensitive resin layer stack according to item (5), wherein, as the aforementioned compound having an acrylate group of tri-functionality or more, a compound having an acrylate group on any of a trimethylolpropane, a pentaerythritol, or a dipentaerythritol skeleton is contained.

[0037] (7) The photosensitive resin laminate according to any one of items (5) or (6), wherein, as the aforementioned compound having an acrylate group of three or more functionalities, a compound having an acrylate group on any one of a trimethylolpropane, a pentaerythritol, or a dipentaerythritol skeleton is contained in an amount of 1% by mass or more with respect to the total amount of the aforementioned (B) compound having an ethylenically unsaturated double bond.

[0038] (8) The photosensitive resin laminate according to any one of items (5) to (7), wherein, as the aforementioned compound having an acrylate group of three or more functionalities, a compound having an acrylate group on any one of a trimethylolpropane, a pentaerythritol, or a dipentaerythritol skeleton is contained in an amount of 10% by mass or more with respect to the total amount of the aforementioned (B) compound having an ethylenically unsaturated double bond.

[0039] (9) The photosensitive resin laminate according to any one of items (5) to (8), wherein, as the aforementioned compound having an acrylate group of three or more functionalities, a compound having an acrylate group on any one of a trimethylolpropane, a pentaerythritol, or a dipentaerythritol skeleton is contained in an amount of 80% by mass or more with respect to the total amount of the aforementioned (B) compound having an ethylenically unsaturated double bond.

[0040] (10) The photosensitive resin laminate according to any one of items (1) to (9), wherein, when a compound having an aromatic ring is contained as the aforementioned (B) compound having an ethylenically unsaturated double bond, the compound having an aromatic ring is represented by the following formula (VII).

[0041]

[0042] {wherein Y each independently represents an alkylene group having 2 to 10 carbon atoms, R1and R2each independently represent a methyl group or a hydrogen atom, and n1and n2each independently represent an integer of 1 to 100.}

[0043] (11) The photosensitive resin laminate according to any one of items (1) to (10), wherein, as the aforementioned (C) photopolymerization initiator, an imidazole compound is contained.

[0044] (12) The photosensitive resin laminate according to any one of items (1) to (11), wherein, as the aforementioned (C) photopolymerization initiator, a 2,4,5-triarylimidazole dimer is contained.

[0045] (13) The photosensitive resin laminate according to any one of items (1) to (12), wherein, when the film thickness of a photosensitive resin layer containing the aforementioned photosensitive resin composition is denoted as T [μm], and the absorbance at a wavelength of 365 nm is denoted as A, the following relationship indicated by the following formula (II) is satisfied.

[0046] 0 < A / T < 0.005 Formula (II)

[0047] (14) The photosensitive resin laminate according to any one of items (1) to (13), wherein the film thickness of the photosensitive resin layer containing the aforementioned photosensitive resin composition is more than 50 μm and 400 μm or less.

[0048] (15) The photosensitive resin laminate according to any one of items (1) to (14), which is a dry film resist.

[0049] (16) A method for forming a resist pattern, comprising the following steps:

[0050] a step of laminating the photosensitive resin laminate according to any one of items (1) to (15) on a substrate;

[0051] a step of exposing the laminated photosensitive resin laminate; and

[0052] a step of developing the exposed photosensitive resin laminate.

[0053] (17) A method for forming a semiconductor bump, comprising the following steps:

[0054] a step of laminating the photosensitive resin laminate according to any one of items (1) to (15) on a sputtered copper thin film;

[0055] a step of exposing the laminated photosensitive resin laminate;

[0056] a step of developing the exposed photosensitive resin laminate; and

[0057] a step of copper plating or soldering the developed sputtered copper thin film.

[0058] Effects of the invention

[0059] According to the present application, the properties of a resist pattern related to the dissolution of a release sheet and the underlying plating can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0060] Figure 1 is an SEM photograph showing an example in which the resist bottom (a) and the underlying plating (b) are small.

[0061] Figure 2 is an SEM photograph showing an example in which the resist bottom (a) and the underlying plating (b) are large. DETAILED DESCRIPTION

[0062] Hereinafter, a mode for carrying out the present application (hereinafter, simply referred to as "embodiment") will be described in detail. The present application is not limited to the following embodiment, and can be carried out in various modifications within the scope of the gist thereof.

[0063] <Photosensitive resin composition>

[0064] One embodiment provides a photosensitive resin composition comprising:

[0065] (A) an alkali-soluble polymer: 10 to 90 mass%,

[0066] (B) a compound having an ethylenically unsaturated double bond: 5 to 70 mass%, and

[0067] (C) a photopolymerization initiator: 0.01 to 20 mass%,

[0068] The (A) alkali-soluble polymer contains a copolymer containing a (meth)acrylic acid ester having an alkyl group having 3 to 12 carbon atoms as a copolymerization component,

[0069] As the (B) compound having an ethylenically unsaturated double bond, an acrylate monomer is contained at 51 to 100 mass% relative to the total amount of the (B) compound having an ethylenically unsaturated double bond.

[0070] It is understood that the photosensitive resin composition of the present application can achieve improvement in properties of the resist pattern related to the peeling sheet dissolution and plating under-embedding by using each component of (A) to (C) in a specific ratio and by means such as exemplified below (not limited thereto). In addition, the photosensitive resin composition described in the present embodiment can contain, on the basis of the components of (A) to (C), a polymer other than the (A) component, a monomer other than the (B) component, an initiator other than the (C) component, a dye, an adhesion aid, a plasticizer, and the like, as desired. Hereinafter, each component contained in the photosensitive resin composition of the present embodiment will be described in order.

[0071] <(A) alkali-soluble polymer>

[0072] The alkali-soluble polymer (A) in this embodiment refers to a polymer that is soluble in an alkaline aqueous solution, and may be, for example, a vinyl polymer containing a carboxyl group. In this embodiment, the alkali-soluble polymer (A) comprises a copolymer comprising a (meth)acrylate (A1) having an alkyl group having 3 to 12 carbon atoms as a copolymer component, preferably a copolymer comprising 6.0 to 30% by mass of the (meth)acrylate (A1) relative to the mass of the alkali-soluble polymer (A), and more preferably a copolymer comprising the (meth)acrylate (A1) and, in addition to the (meth)acrylate (A1), a (meth)acrylate (A2) and / or a vinyl compound (A3) as copolymer components. The alkali-soluble polymer (A) may be, for example, a copolymer containing, in addition to the (meth)acrylate (A1) having an alkyl group having 3 to 12 carbon atoms, a monomer selected from (meth)acrylic acid, a (meth)acrylate having an alkyl group having 2 or less and / or 13 or more carbon atoms, a (meth)acrylate having an aromatic group, (meth)acrylonitrile, (meth)acrylamide, and the like as a copolymerization component.

[0073] (A) The alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent refers to the mass in grams of the alkali-soluble polymer having one equivalent of a carboxyl group. From the viewpoint of improving development tolerance, resolution and adhesion, it is preferred that the acid equivalent be set to 100 or more. On the other hand, from the viewpoint of improving developability and peelability, it is preferred that the acid equivalent be set to 600 or less. The acid equivalent can be determined using a titrator (e.g., Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) by potentiometric titration using a 0.1 mol / L sodium hydroxide aqueous solution. The acid equivalent of the (A) alkali-soluble polymer is more preferably 250 to 450, and even more preferably 300 to 440.

[0074] (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more and 500,000 or less. From the viewpoint of the properties of the developed aggregate and the properties of the unexposed film such as edge fusion, cut chip properties, and the like in the photosensitive resin laminate, it is preferable to set the weight average molecular weight to be 5,000 or more, and on the other hand, from the viewpoint of improving the solubility in the developer, it is preferable to set the weight average molecular weight to be 500,000 or less. The edge fusion refers to the property of suppressing the 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. The cut chip property refers to the property of suppressing the phenomenon in which the chipping scatters when the unexposed film is cut with a cutting machine. If the cut chip property is poor, the following adverse situations occur: the chipping that scatters adheres to, for example, the upper surface of the photosensitive resin laminate, and the like, the chip is transferred to the mask in the subsequent exposure process to become a cause of defects, and the like. The weight average molecular weight of the alkali-soluble polymer is more preferably 5,000 or more and 300,000 or less, further preferably 10,000 or more and 200,000 or less, and still further preferably 25,000 or more and 120,000 or less.

[0075] From the viewpoint of improving the properties related to the peeling sheet dissolution and the plating layer subsidence, the number of carbon atoms of the alkyl group of the copolymer component of the (A) alkali-soluble polymer, that is, the (meth) acrylate ester, is preferably 4 or more and 12 or less, and more preferably 5 or more and 12 or less.

[0076] As the alkyl group having 3 to 12 carbon atoms of the copolymer component of the (A) alkali-soluble polymer, that is, the (meth) acrylate ester, a linear or branched C 3～12 The alkyl group can have, for example, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylhexyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, and the like. Among them, from the viewpoint of the development time and the presence or absence, shape, and length of the lower edge of the resist pattern, the alkyl group having 4 to 10 carbon atoms is preferable, the alkyl group having 5 to 10 carbon atoms is more preferable, and the alkyl group having 6 to 8 carbon atoms is further preferable, and the 2-ethylhexyl group is still further preferable. When the number of carbon atoms of the alkyl group of the copolymer component of the (A) alkali-soluble polymer, that is, the (meth) acrylate ester, is in the above range, the free volume of the photosensitive resin layer becomes large, and therefore, the developer is easily penetrated and easily swells, and thus, there is a tendency that the development time becomes short. By using the (meth) acrylate compound having a 2-ethylhexyl group, for example, 2-ethylhexyl (meth) acrylate, and the like, in a part of the monomers used at the time of synthesis, it is possible to introduce the 2-ethylhexyl group into the (A) alkali-soluble polymer, and to obtain a copolymer containing 2-ethylhexyl (meth) acrylate as a copolymer component.

[0077] The (A) alkali-soluble polymer preferably has an aromatic hydrocarbon group.

[0078] By having the (A) alkali-soluble high molecule have an aromatic hydrocarbon group, there is a tendency for resolution and adhesion to improve, and properties related to peeling of the resist sheet and submergence of the plating layer to be improved. By using an aromatic vinyl compound, a (meth)acrylate compound having a benzyl group, such as benzyl (meth)acrylate, or the like, in a portion of the monomers used at the time of synthesis, an aromatic hydrocarbon group can be introduced into the (A) alkali-soluble high molecule, and a copolymer containing benzyl (meth)acrylate as a copolymerization component is obtained.

[0079] Further, the (A) alkali-soluble high molecule can also be obtained by copolymerizing each of one or two or more of the following two monomers.

[0080] The first monomer is a carboxylic acid or an anhydride having one polymerizable unsaturated group in the molecule. Examples that can be given include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. (Meth)acrylic acid is particularly preferable. Here, (meth)acrylic acid refers to either acrylic acid or methacrylic acid.

[0081] The copolymerization ratio of the first monomer in the (A) alkali-soluble high molecule can be easily calculated according to the desired acid equivalent value in the alkali-soluble high molecule. The copolymerization ratio of the first monomer in the (A) alkali-soluble high molecule is preferably 10 to 50 mass% based on the total mass of the total monomer components. From the viewpoint of exhibiting good developability, the viewpoint of controlling edge coalescence, and the like, it is preferable to set the copolymerization ratio to 10 mass% or more. From the viewpoint of improving resolution, the viewpoint of suppressing the occurrence of the lower edge of the resist layer, and the like, it is preferable to set the copolymerization ratio to 50 mass% or less. From these viewpoints, the copolymerization ratio of the first monomer is more preferably 20 to 40 mass%, and further preferably 20 to 30 mass%.

[0082] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. As the second monomer, the (meth)acrylate compounds having an alkyl group having 3 to 12 carbon atoms described in the above explanation, such as n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like, or the (meth)acrylate compounds having an aromatic hydrocarbon group described in the above explanation, such as benzyl (meth)acrylate, and the like, can be used.

[0083] Further, as the second monomer, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, esters of vinyl alcohol; vinyl acetate; (meth)acrylonitrile; aromatic vinyl compounds; and the like can be used.

[0084] As the aromatic vinyl compound, for example, styrene and styrene derivatives can be mentioned. As the styrene derivatives, for example, oxy styrene, hydroxy styrene, acetoxy styrene, alkyl styrene, halogenated alkyl styrene and the like can be mentioned.

[0085] In the present embodiment, when the total solid content of the photosensitive resin composition is set to 100 mass%, the compounding amount of the (A) alkali-soluble high molecule in the photosensitive resin composition is in the range of 10 to 90 mass%, preferably in the range of 40 to 80 mass%, and more preferably in the range of 50 to 70 mass%. Setting the compounding amount to 10 mass% or more is advantageous from the viewpoint of alkali development, and on the other hand, setting the compounding amount to 90 mass% or less is advantageous from the viewpoint of controlling the development time.

[0086] <(B) compound having an ethylenically unsaturated double bond>

[0087] In the present embodiment, as the (B) compound having an ethylenically unsaturated double bond in the photosensitive resin composition, an acrylate monomer is contained in an amount of 51 mass% to 100 mass% with respect to the total amount of the (B) compound having an ethylenically unsaturated double bond.

[0088] If 51 to 100 mass% of the (B) compound having an ethylenically unsaturated double bond is an acrylate monomer, there is a tendency to further improve the properties of the resist pattern related to the dissolution of the release sheet compared to the case where 51 to 100 mass% thereof is a methacrylate monomer. From the viewpoint of improving the plating resistance on the basis of improving the release sheet solubility, the content of the acrylate monomer with respect to the total amount of the (B) compound is preferably 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, or 90 mass% or more, and more preferably 91 mass% or more.

[0089] In the photosensitive resin composition described in the present embodiment, as the (B) compound having an ethylenically unsaturated double bond, a compound having an acrylate group of three or more functionalities (i.e., having three or more acryloyl groups in one molecule) is preferably contained. When the photosensitive resin composition contains a compound having an acrylate group of three or more functionalities as the (B) compound, there is a tendency to improve the properties of the resist pattern related to the dissolution of the release sheet and the underplating. More preferably, a compound having an acrylate group of three or more functionalities is used in combination with the (A) alkali-soluble high molecule containing the (meth)acrylate (A1) described above and containing the (meth)acrylate (A2) and / or the vinyl compound (A3) as the copolymerization component.

[0090] If at least 1% by mass of the compound (B) having an ethylenically unsaturated double bond is composed of a compound having a trifunctional or higher acrylate group (having three or more acryloyl groups per molecule), the resist pattern's properties related to release sheet dissolution and plating layer penetration tend to be further improved compared to a case where more than 0% by mass and less than 1% by mass of the compound (B) is composed of a compound having three or more acryloyl groups per molecule, or a case where no compound having three or more acryloyl groups per molecule is present. From this perspective, the content of the compound having a trifunctional or higher acrylate group is preferably 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, or 10% by mass or more, and more preferably 20% by mass or more, 40% by mass or more, 60% by mass or more, or 80% by mass or more, and may be 100% by mass or less.

[0091] The above-described compound having a trifunctional or higher-functional acrylate group is preferably a compound having an acrylate group on a skeleton of trimethylolpropane, pentaerythritol, or dipentaerythritol, from the viewpoint of release sheet solubility and plating resistance.

[0092] When the photosensitive resin composition contains a compound having an acrylate group on a trimethylolpropane skeleton, the compound having a trifunctional or higher functional acrylate group preferably contains a compound represented by the following general formula (III).

[0093]

[0094] {wherein, n1, n2 and n3 are each independently an integer of 1 to 25, wherein n1+n2+n3 is an integer of 3 to 75,

[0095] R1, R2 and R3 are each independently a hydrogen atom.

[0096] In the general formula (V), the value of n1+n2+n3 is preferably 3 or more and 50 or less. From the viewpoint of suppressing the generation of the bottom edge of the resist layer, imparting flexibility to the cured film, and improving film strength, it is preferred that n1+n2+n3 be 3 or more. On the other hand, from the viewpoint of obtaining high resolution and adhesion, and good peeling properties, it is preferred that n1+n2+n3 be 50 or less. A more preferred range of n1+n2+n3 is 6 or more and 40 or less, and an even more preferred range is 9 or more and 30 or less.

[0097] Specific examples of the compound represented by the general formula (III) include:

[0098] a triacrylate obtained by adding an average of 3 moles of ethylene oxide to the terminal of the hydroxyl group of trimethylolpropane,

[0099] a triacrylate obtained by adding an average of 9 moles of ethylene oxide to the terminal of the hydroxyl group of trimethylolpropane,

[0100] a triacrylate obtained by adding an average of 15 moles of ethylene oxide to the terminal of the hydroxyl group of trimethylolpropane,

[0101] a triacrylate obtained by adding an average of 30 moles of ethylene oxide to the terminal of the hydroxyl group of trimethylolpropane, and the like.

[0102] When the photosensitive resin composition contains a compound having an acrylate group on a pentaerythritol skeleton, as a compound having a tri-functional or more acrylate group, it is preferable to contain a compound represented by the following general formula (IV).

[0103]

[0104] {in the formula, n1, n2, n3, and n4 each independently represent an integer of 1 to 25, n1 + n2 + n3 + n4 is an integer of 4 to 100,

[0105] R1, R2, R3, and R4 each independently represent a hydrogen atom,

[0106] R5, R6, R7, and R8 each independently represent an alkylene group, and when a plurality of R5, R6, R7, and R8 each exist, the plurality of R5, R6, R7, and R8 are optionally the same as or different from each other.}.

[0107] In the general formula (IV), n1 + n2 + n3 + n4 is preferably 9 or more and 60 or less. From the viewpoint of suppressing the generation of the lower edge of the resist layer, the viewpoint of improving the film strength, and the viewpoint of imparting softness to the cured film, it is preferable to set n1 + n2 + n3 + n4 to be 9 or more, and on the other hand, from the viewpoint of improving the resolution and the adhesion, the viewpoint of obtaining good peeling properties, and the viewpoint of controlling the edge coalescence, it is preferable to set n1 + n2 + n3 + n4 to be 60 or less. Further, a more preferable range of n1 + n2 + n3 + n4 is 16 or more and 60 or less.

[0108] As R5, R6, R7, and R8 in the general formula (IV), 1,2-ethylene group, 1,2-propylene group, butylene group, and the like can be respectively mentioned, and from the viewpoint of imparting softness to the cured film, the viewpoint of improving the film strength, the viewpoint of suppressing the development coalescence, and the viewpoint of improving the reactivity of the olefinic unsaturated double bond, 1,2-ethylene group is preferable. Therefore, as the compound represented by the general formula (IV), a compound represented by the following general formula (V) is preferable.

[0109]

[0110] {in the formula, n1, n2, n3, and n4 are each independently an integer of 1 to 25, wherein n1 + n2 + n3 + n4 is an integer of 4 to 100;

[0111] R1, R2, R3, and R4 are each independently a hydrogen atom.

[0112] The preferable range of n1 + n2 + n3 + n4 is the same as the aforementioned.

[0113] As specific examples of the compound represented by the aforementioned general formula (IV), there can be mentioned, for example:

[0114] tetraacrylate obtained by adding an average of 4 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol,

[0115] tetraacrylate obtained by adding an average of 9 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol,

[0116] tetraacrylate obtained by adding an average of 12 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol,

[0117] tetraacrylate obtained by adding an average of 15 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol,

[0118] tetraacrylate obtained by adding an average of 20 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol,

[0119] tetraacrylate obtained by adding an average of 28 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol,

[0120] tetraacrylate obtained by adding an average of 35 moles of ethylene oxide to the hydroxyl terminal of pentaerythritol, and the like.

[0121] When the photosensitive resin composition contains a compound having an acrylate group on a dipentaerythritol skeleton, as a compound having a tri- or higher-functional acrylate group, it is preferable to contain a hexaacrylate compound represented by the following general formula (VI).

[0122]

[0123] {in the formula, R each independently represents a hydrogen atom, and n is an integer of 0 to 30.}

[0124] In general formula (VI), n is an integer of 0 to 30, and thus the presence or absence of an ethylene oxide moiety is not limited.

[0125] As preferable specific examples of the hexaacrylate compound represented by General Formula (VI), mention can be made of dipentaerythritol hexaacrylate, a hexaacrylate obtained by adding a total of 1 to 36 moles of ethylene oxide to the 6 terminals of dipentaerythritol, and a hexaacrylate obtained by adding a total of 1 to 10 moles of ε-caprolactone to the 6 terminals of dipentaerythritol.

[0126] The compound according to the present embodiment contains preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, 40% by mass or more, or 60% by mass or more, particularly preferably 80% by mass or more, of the compound having an acrylate group on any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeleton described above, relative to the total amount of the compound (B). If the content of the compound having an acrylate group on any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeleton is 1% by mass or more, relative to the total amount of the compound (B), there is a tendency to further improve the properties of the resist pattern related to the peeling sheet dissolution and plating underplating. The upper limit of the content of the compound having an acrylate group on any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeleton may be, for example, 100% by mass or less, or less than 100% by mass, relative to the total amount of the compound (B).

[0127] From the viewpoint of further improving the properties of the resist pattern related to the peeling sheet dissolution and plating underplating, the compound (B) having an ethylenic unsaturated double bond preferably has an aromatic ring. From the viewpoint of plating resistance, the compound having an aromatic ring and an ethylenic unsaturated double bond as the component (B) is preferably a compound having a (meth)acryloyl group at both terminals of a bisphenol A modified with an alkylene oxide, and from the viewpoint of further improving the properties related to the peeling sheet dissolution and plating underplating, it is more preferable to be represented by the following Formula (VII).

[0128]

[0129] {in which Y each independently represents an alkylene group having 2 to 10 carbon atoms, R1and R2each independently represent a methyl group or a hydrogen atom, and n1and n2each independently represent an integer of 1 to 100.}

[0130] In Formula (VII), Y each independently is preferably an alkylene group having 2 to 4 carbon atoms, and the (Y-O) moiety can also be a random, alternating, or block arrangement of alkylene oxide repeating units having different carbon atom numbers. R1and R2each independently represent a methyl group or a hydrogen atom, and from the viewpoint of further improving the properties related to the peeling sheet dissolution and plating underplating, it is preferable that one or both of R1and R2be a methyl group. It is preferable that n1and n2each independently represent an integer of 1 to 100, and 2 ≤ n1+ n2≤ 200.

[0131] The compound represented by formula (VII) can include a di(meth)acrylate compound of ethylene glycol obtained by adding an alkylene oxide to both ends of bisphenol A. This di(meth)acrylate compound is preferably a diacrylate or dimethacrylate compound, and preferably a dimethacrylate compound. As a specific example of the dimethacrylate compound, for example, the following can be given:

[0132] a dimethacrylate of ethylene glycol obtained by adding an average of 1 mole of ethylene oxide to each of both ends of bisphenol A,

[0133] a dimethacrylate of ethylene glycol obtained by adding an average of 2 moles of ethylene oxide to each of both ends of bisphenol A,

[0134] a dimethacrylate of ethylene glycol obtained by adding an average of 5 moles of ethylene oxide to each of both ends of bisphenol A,

[0135] a dimethacrylate of alkylene glycol obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to each of both ends of bisphenol A,

[0136] a dimethacrylate of alkylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A, and the like.

[0137] In one embodiment, as the (B) compound having an ethylenic unsaturated double bond in the photosensitive resin composition, the compound described above can be used, or other (B) compounds can be included in addition to them. As the other (B) compounds, an ethylenic unsaturated compound capable of photopolymerization can be used. As such an ethylenic unsaturated compound capable of photopolymerization, for example, a compound having one ethylenic double bond, a compound having two ethylenic unsaturated double bonds, and a compound having three or more ethylenic unsaturated double bonds can be exemplified.

[0138] As the compound having one ethylenic double bond described above, for example, the following can be given:

[0139] a compound obtained by adding a (meth)acrylic acid to a single terminal of a polyalkylene oxide;

[0140] a compound obtained by adding a (meth)acrylic acid to a single terminal of a polyalkylene oxide, and the other terminal is subjected to alkyl etherification or allyl etherification, and the like.

[0141] As the compound having two ethylenic unsaturated double bonds in the molecule, for example, the following can be given:

[0142] a compound having a (meth)acryloyl group at both terminals of an alkylene oxide chain;

[0143] a compound having a (meth)acryloyl group at both terminals of an alkylene oxide chain having oxirane units and propylene oxide units bonded at random, alternately, or in blocks, etc.

[0144] As the above alkylene oxide modification, there can be mentioned, for example, oxirane modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification, etc. More preferred is a compound having a (meth)acryloyl group at both terminals of bisphenol A modified with oxirane. Of these, from the viewpoint of plating resistance, preferred is a diacrylate compound of ethylene glycol obtained by adding oxirane to both terminals of bisphenol A as described above.

[0145] A compound having 3 or more ethylenic unsaturated double bonds in the molecule can be obtained by, for example, using a compound having 3 or more groups capable of adding an alkylene oxide group to the molecule as a central skeleton, and adding an alkyleneoxy group such as an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, etc. to the compound, and making a (meth)acrylate of the alcohol thus obtained. In this case, as the compound having 3 or more ethylenic unsaturated double bonds in the molecule as the other (B) compound, as a compound capable of being a central skeleton, there can be mentioned, for example, glycerol, a compound having an isocyanurate ring, etc. Of these, as a trifunctional glycerol (meth)acrylate optionally modified with an alkylene oxide, preferred is a compound represented by the following formula (VIII).

[0146]

[0147] {in the formula, Y each independently represents an alkylene group having 2 to 10 carbon atoms, R each independently represents a methyl group or a hydrogen atom, and n each independently represents an integer of 0 to 200.}

[0148] In formula (VIII), n each independently is an integer of 0 to 200, preferably at least one n is an integer of 1 to 200, and more preferably 3 n's are integers of 1 to 200. Further, -(Y-O) n The alkylene oxide moiety can be a single alkylene oxide repeating unit, or can contain a plurality of alkylene oxide units differing in the number of carbon atoms in a random, block, alternating, etc. arrangement.

[0149] The other (B) compound can be used alone, or two or more can be used in combination.

[0150] The compounding amount of the (B) compound having an ethylenically unsaturated double bond in the photosensitive resin composition is 5 to 70% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. The compounding amount is set to 5% by mass or more based on the viewpoint of improving sensitivity, resolution, and adhesiveness, and on the other hand, the compounding amount is set to 70% by mass or less based on the viewpoint of suppressing edge fusion and the viewpoint of suppressing peeling delay of the cured resist layer. The compounding amount is preferably 10 to 50% by mass, more preferably 20 to 45% by mass.

[0151] <(C) Photopolymerization Initiator>

[0152] In the present embodiment, an imidazole compound is preferably contained as the (C) photopolymerization initiator in the photosensitive resin composition. The imidazole compound contained in the photosensitive resin composition has a tendency to provide plating resistance or suppress the generation of a lower edge of the resist layer for the resist pattern.

[0153] As the imidazole compound, for example, the following can be given:

[0154] Imidazoles having an aliphatic group, such as methyl imidazole, 2-ethyl-4-methyl imidazole, 1-isobutyl-2-methyl imidazole, 2-ethyl-4-methyl imidazole, ethyl imidazole, isopropyl imidazole, 2,4-dimethyl imidazole, undecyl imidazole, heptadecyl imidazole, and the like; and

[0155] Imidazoles having an aromatic group, such as 1-benzyl-2-methyl imidazole, phenyl imidazole (2-phenyl imidazole or the like), 2-phenyl-4-methyl imidazole, 2-phenyl-4,5-dihydroxymethyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, triaryl imidazole, or a dimer thereof, or the like.

[0156] Among them, from the viewpoint of plating resistance and suppression of the generation of a lower edge of the resist layer, imidazoles having an aromatic group are preferable, and triaryl imidazole (e.g., lophine or the like) or a dimer thereof is more preferable, and a triaryl imidazole dimer is further preferable.

[0157] As the triaryl imidazole dimer, for example, 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer, and the like 2,4,5-triaryl imidazole dimers can be given.

[0158] (C) The content of the imidazole compound in the photopolymerization initiator (C) is preferably 99% by mass or more and 100% by mass or less relative to the total amount of the photopolymerization initiator (C). From the viewpoints of good sensitivity, high resolution, and inhibition of aggregation in a developing solution, the content is preferably adjusted to 99 to 100% by mass relative to the total amount of the photopolymerization initiator (C). From these viewpoints, the imidazole compound can constitute 100% by mass of the photopolymerization initiator (C).

[0159] In the present embodiment, the photosensitive resin composition can contain, on the basis of the imidazole compound, various substances that can be used as a photopolymerization initiator for a photosensitive resin, as desired. As the photopolymerization initiator other than the imidazole compound, for example, an aromatic ketone, an acridine-based compound, and / or an N-aryl-a-amino acid compound can be used.

[0160] From the viewpoint of improving sensitivity, an aromatic ketone is preferred. As the aromatic ketone, for example, benzophenone, N,N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, and the like are preferred. Among them, 4,4'-bis(diethylamino)benzophenone is preferred.

[0161] From the viewpoint of exhibiting high sensitivity, and also from the viewpoint of giving consideration to both high sensitivity and suppression of the occurrence of under-etching of the resist layer, an acridine-based compound is preferred. As the acridine-based compound, 1,7-bis(9,9'-acridinyl)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-t-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-acetylphenyl)acridine, 9-(4-dimethylaminophenyl)acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-t-butylphenyl)acridine, 9-(3-acetylphenyl)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, and 9-(4-pyridyl)acridine, for example, can be listed. Among these, from the viewpoints of sensitivity, resolution, availability, and the like, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred.

[0162] From the viewpoint of improving sensitivity, an N-aryl-α-amino acid compound is preferred. As the N-aryl-α-amino acid compound, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like can be listed.

[0163] Further, as other examples of the photopolymerization initiator other than the imidazole compound, for example, the following can be listed:

[0164] 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and the like quinones;

[0165] benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and the like benzoin ether compounds;

[0166] benzil derivatives such as benzil methyl ketal;

[0167] coumarin-based compounds;

[0168] 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-octyl-phenyl)-dihydropyrazole, and the like.

[0169] (C) The photopolymerization initiator can be used alone or in combination with two or more kinds.

[0170] The compounding amount of the (C) photopolymerization initiator in the photosensitive resin composition is 0.01 to 20 mass% when the total solid content of the photosensitive resin composition is 100 mass%. The compounding amount is set to 0.01 mass% or more based on the viewpoint of obtaining an exposed pattern having a sufficient residual film rate after development, and on the other hand, the compounding amount is set to 20 mass% or less based on the viewpoint of making the light sufficiently permeate to the bottom surface of the resist layer to obtain high resolution, and the viewpoint of suppressing development aggregation in the developing solution. The preferable range of the compounding amount is 0.3 to 10 mass%, and the more preferable range is 1 to 5 mass%.

[0171] <Leuco dye, fluoran dye, coloring substance>

[0172] The photosensitive resin composition according to the present application can contain one or more kinds selected from a leuco dye, a fluoran dye, and a coloring substance. By containing these components in the photosensitive resin composition, the exposed part is colored. Therefore, it is preferable from the viewpoint of visual recognition. Furthermore, when an alignment mark used for exposure is read by an inspection machine or the like, it is also advantageous from the viewpoint that the contrast between the exposed part and the unexposed part becomes large and is easily recognized.

[0173] As the leuco dye, tri(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], and the like can be exemplified. In particular, from the viewpoint that the contrast becomes good, as the leuco dye, it is preferable to use leuco crystal violet.

[0174] Fluoran dyes include, for example, 2-(dibenzylamino)fluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-isopentylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, Alkane, 2-anilino-3-methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3-methyl-6-piperidinylaminofluoran, 2-(o-chloroanilino)-6-diethylaminofluoran, 2-(3,4-dichloroanilino)-6-diethylaminofluoran, etc.

[0175] The content of the leuco dye or fluoran dye in the photosensitive resin composition is preferably 0.1 to 10% by mass, based on the total solids content of the photosensitive resin composition as 100% by mass. To improve the contrast between the exposed and unexposed portions, this content is preferably 0.1% by mass or greater. It is more preferably 0.2% by mass or greater, and even more preferably 0.3% by mass or greater. On the other hand, to maintain the storage stability of the photosensitive resin composition and to suppress the formation of aggregates during development, it is preferably 10% by mass or less. It is more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0176] Examples of the coloring substance include fuchsin, phthalocyanine green, auramine base, para-fuchsin, crystal violet, methyl orange, Nile Blue 2B, malachite green (manufactured by Hodogaya Chemical Co., Ltd., AIZEN (registered trademark) MALACHITE GREEN), basic blue 7 (for example, AIZEN (registered trademark) Victoria Pure Blue BOH conc., etc.), basic blue 20, and diamond green (manufactured by Hodogaya Chemical Co., Ltd., AIZEN (registered trademark) DIAMOND GREEN GH).

[0177] The content of the coloring matter in the photosensitive resin composition is preferably 0.001% to 1% by mass, based on the total solid content of the photosensitive resin composition as 100% by mass. From the perspective of improving handling properties, this content is preferably 0.001% by mass or more, while from the perspective of maintaining storage stability, this content is preferably 1% by mass or less.

[0178] <Halogen compounds>

[0179] From the viewpoint of adhesion and contrast, it is a preferred embodiment to use a leuco dye and the following halogen compound in combination in the photosensitive resin composition of the present embodiment.

[0180] As the halogen compound, for example, pentyl bromide, isopentyl bromide, isobutylene bromide, bromoethylene, diphenylmethyl bromide, benzyl bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, pentyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compound, and the like can be exemplified. Trisbromomethyl phenyl sulfone is particularly preferable. From the viewpoints of remarkable effects when used in combination with the acridine compound, improvement of resolution, improvement of adhesion, improvement of sensitivity, improvement of contrast, improvement of resistance of the resist layer to puncture, suppression of generation of the lower edge of the resist layer, and improvement of etching resistance, a halogen compound such as trisbromomethyl phenyl sulfone is preferable.

[0181] From the above viewpoints, the content of the halogen compound in the photosensitive resin composition is preferably 0.01% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. The content is more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. In addition, from the viewpoints of maintaining the storage stability of the color tone in the photosensitive layer and suppressing the generation of aggregates at the time of development, the content is preferably 3% by mass or less. The content is more preferably 2% by mass or less, and further preferably 1.5% by mass or less.

[0182] <Radical polymerization inhibitor, benzotriazole-based compound, carboxybenzotriazole-based compound>

[0183] In the present embodiment, in order to improve the heat stability and the storage stability of the photosensitive resin composition, the photosensitive resin composition can further contain at least one or more compounds selected from the group consisting of a radical polymerization inhibitor, a benzotriazole-based compound, and a carboxybenzotriazole-based compound.

[0184] As the radical polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, diphenylolpropane, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(6-t-butyl-m-cresol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, styrenated phenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name "ANTAGE SP"), trisbenzylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name "TBP", a phenol compound having 1 to 3 benzyl groups), diphenylnitrosamine, and the like can be exemplified.

[0185] As the benzotriazoles, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)amino methylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)amino methylene-1,2,3-methylbenzotriazole, bis(N-2-hydroxyethyl)amino methylene-1,2,3-benzotriazole, and the like can be exemplified.

[0186] As the carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)amino methylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)amino methylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)amino ethylene carboxybenzotriazole, or a mixture thereof, and the like can be exemplified. Among them, a 1:1 mixture of 4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole is preferred.

[0187] The total content of the radical polymerization inhibitor, the benzotriazoles, and the carboxybenzotriazoles, when the total solid content of the photosensitive resin composition is taken as 100 mass%, is preferably 0.01 to 3 mass%, and more preferably 0.05 to 1 mass%. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01 mass% or more, and on the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, the content is preferably 3 mass% or less.

[0188] <Plasticizer>

[0189] The photosensitive resin composition of the present embodiment can contain a plasticizer as needed. As the plasticizer, for example, glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, and the like;

[0190] Phthalic acid esters such as diethyl phthalate, and the like;

[0191] O-Toluene sulfonamide, p-Toluene sulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, and the like;

[0192] Propylene glycol obtained by adding an epoxide of propylene to both ends of bisphenol A, ethylene glycol obtained by adding an epoxide of ethylene to both ends of bisphenol A, and the like;

[0193] Aluminum salts and the like to which 1 to 3 moles of nitroso phenyl hydroxylamine are added.

[0194] They can be used singly, or in combination of two or more.

[0195] In particular, from the viewpoints of the peeling sheet solubility or plating resistance, as the plasticizer, an aluminum salt having 3 moles of nitrosophenylhydroxylamine added thereto is preferred.

[0196] When the total solid content of the photosensitive resin composition is taken as 100 mass%, the content of the plasticizer in the photosensitive resin composition is preferably 1 to 50 mass%, and more preferably 1 to 30 mass%. From the viewpoints of inhibiting the delay of the development time and imparting softness to the cured film, the content is preferably 1 mass% or more, and on the other hand, from the viewpoints of inhibiting the undercuring and the edge fusion, the content is preferably 50 mass% or less.

[0197] <solvent>

[0198] The photosensitive resin composition can be dissolved in a solvent and used in the form of a solution. As the solvent used, for example, the following can be cited:

[0199] Ketones represented by methyl ethyl ketone (MEK);

[0200] Alcohols represented by methanol, ethanol, and isopropanol, and the like.

[0201] The solvent is preferably added to the photosensitive resin composition in such a manner that the solution viscosity of the photosensitive resin composition coated on a support film reaches 500 to 4,000 mPa-s at 25°C.

[0202] <Properties of the photosensitive resin composition>

[0203] The photosensitive resin composition of the present embodiment satisfies the relationship shown in the following formula (I):

[0204] 0 < A / T < 0.007 Formula (I)

[0205] {In the formula, the film thickness of the photosensitive resin layer containing the photosensitive resin composition is T (μm), and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.}

[0206] The photosensitive resin composition satisfying the relationship shown in the formula (I) is easy to improve the properties of the resist pattern related to the peeling sheet solubility or plating layer subsidence, compared with the photosensitive resin composition of A / T > 0.007. From the viewpoint of further improving the properties of the resist pattern related to the peeling sheet solubility or plating layer subsidence, the photosensitive resin composition preferably satisfies the relationship shown in the following formula (II):

[0207] 0 < A / T < 0.005 Formula (II)

[0208] {wherein T (μm) is the thickness of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.}

[0209] From the same viewpoint, the A / T value of the photosensitive resin composition is more preferably more than 0 and less than 0.005, and further preferably more than 0 and 0.004 or less.

[0210] <Photosensitive resin layer laminate>

[0211] The photosensitive resin layer laminate according to the present embodiment is preferably a dry film resist. Typically, the photosensitive resin layer laminate has a support film and a layer of the photosensitive resin composition described above laminated on the support film. The photosensitive resin layer laminate can have a protective layer on the surface on the side opposite to the support film as necessary.

[0212] The photosensitive resin layer laminate according to the present embodiment satisfies the relationship shown in the following formula (I):

[0213] 0 < A / T < 0.007 Formula (I)

[0214] {wherein T (μm) is the thickness of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.}

[0215] The photosensitive resin layer laminate satisfying the relationship shown in formula (I) has a tendency that the properties related to the peeling of the resist pattern or the plating underlayer sinking are improved compared to the photosensitive resin layer laminate in which A / T > 0.007.

[0216] From the viewpoint of further improving the properties related to the peeling of the resist pattern or the plating underlayer sinking, the photosensitive resin layer laminate preferably satisfies the relationship shown in the following formula (II):

[0217] 0 < A / T < 0.005 Formula (II)

[0218] {wherein T (μm) is the thickness of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.}

[0219] From the same viewpoint, the A / T value of the photosensitive resin layer laminate is more preferably more than 0 and less than 0.005, and further preferably more than 0 and 0.004 or less.

[0220] As the support film, a transparent support film which can transmit light emitted from an exposure light source is desirable. As such a support film, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, and the like can be exemplified. These films can also be used as a film which is stretched as needed.

[0221] The haze of the support film is preferably 5 or less.

[0222] The thickness of the support film is preferably 10 to 30 μm when the film is thin, which is advantageous in terms of image formation and economy, but is preferably 10 to 30 μm in view of the function of maintaining strength.

[0223] The layer of the photosensitive resin composition described above can contain the photosensitive resin composition or can be composed of the photosensitive resin composition. From the viewpoint of the thickness suitable for plating applications, the film thickness of the layer of the photosensitive resin composition in the photosensitive resin laminate is preferably 40 μm or more and 600 μm or less, more preferably 50 to 400 μm, further preferably more than 50 μm and 400 μm or less, more further preferably 100 to 400 μm, particularly preferably 200 to 400 μm.

[0224] An important characteristic of the protective layer used in the photosensitive resin laminate is to have an appropriate adhesion. In other words, it is preferable that the adhesion of the protective layer to the photosensitive resin layer be sufficiently smaller than the adhesion of the support film to the photosensitive resin layer, and the protective layer can be easily peeled from the photosensitive resin laminate. As the protective layer, for example, a polyethylene film, a polypropylene film, a film having excellent peelability shown in Japanese Patent Application Laid-Open No. 59-202457, and the like can be used. The film thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

[0225] <Method for producing a photosensitive resin laminate>

[0226] The photosensitive resin laminate can be produced by sequentially laminating the photosensitive resin layer and the protective layer as needed on the support film. As the method therefor, known methods can be employed. For example, a coating solution in which the photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent for dissolving the same to form a uniform solution is prepared. Then, the coating solution can be applied to the support film using a bar coater or a roll coater, followed by drying to laminate the photosensitive resin layer composed of the photosensitive resin composition on the aforementioned support film. Subsequently, as needed, the photosensitive resin laminate can be produced by laminating the protective layer on the photosensitive resin layer.

[0227] <Resist pattern forming method>

[0228] Another embodiment of the present application provides a resist pattern forming method including the following steps:

[0229] a step of laminating the aforementioned photosensitive resin laminate on a substrate (laminating step) ;

[0230] a step of exposing the laminated photosensitive resin laminate (exposing step) ; and

[0231] a step of developing the exposed photosensitive resin laminate (developing step).

[0232] <Semiconductor bump forming method>

[0233] Still another embodiment of the present application provides a semiconductor bump forming method including the following steps:

[0234] a step of plating copper or soldering tin on the substrate on which the resist pattern is formed by the aforementioned resist pattern forming method (plating step).

[0235] According to the desire, the semiconductor bump forming method can further include a step of etching the substrate on which the resist pattern is formed.

[0236] According to the desire, the semiconductor bump forming method can perform a descum and a pre-plating treatment step before the plating step.

[0237] According to the desire, the semiconductor bump forming method can further include a peeling step of peeling the resist pattern from the substrate after the above series of steps.

[0238] Hereinafter, an example of a method of forming a resist pattern and a semiconductor bump using a photosensitive resin laminate and a sputtered copper thin film as a substrate will be described.

[0239] (1) Laminating step

[0240] The laminating step is a step of laminating the photosensitive resin laminate on a substrate such as a sputtered copper thin film by peeling off the protective layer of the photosensitive resin laminate using, for example, a heated roll laminator. The sputtered copper thin film to be used in the laminating step is preferably a copper sputtered silicon wafer on which a copper layer is formed on a silicon wafer using a sputtering device.

[0241] (2) Exposing step

[0242] The exposing step can be, for example, a step of:

[0243] a step of performing exposure through a mask thin film having a desired wiring pattern in a state where the photosensitive resin layer of the photosensitive resin laminate laminated on the aforementioned substrate is closely adhered to the mask thin film;

[0244] a process of exposing the desired wiring pattern by a direct imaging exposure method; or

[0245] a process of exposing the image of the photomask by an exposure method of projecting through a lens.

[0246] (3) Developing process

[0247] After the exposing process, on the basis of peeling off the support film on the photosensitive resin layer, a process of forming a resist pattern on the substrate by developing and removing the unexposed portion (in the case of negative type) or the exposed portion (in the case of positive type) using a developing solution of an aqueous alkali solution.

[0248] As the aqueous alkali solution, an aqueous solution of Na2CO3or K2CO3may be used. The aqueous alkali solution can be appropriately selected depending on the characteristics of the photosensitive resin layer, and an aqueous solution of Na2CO3having a concentration of about 0.2 to 2 mass% and a temperature of about 20 to 40°C is preferably used.

[0249] The resist pattern can be obtained by going through the above-described processes. Depending on the case, a heating process at about 100°C to 300°C for 1 minute to 5 hours can be further performed after these processes. By performing the heating process, the adhesion and chemical resistance of the obtained cured resist pattern can be further improved. The heating at this time can be performed using, for example, a heating furnace of a hot air, infrared, or far infrared type.

[0250] Note that, regarding the obtained resist pattern, an example in which the lower edge of the resist layer is small is shown in (a) of FIG. 1, Figure 1 and an example in which the lower edge of the resist layer is large is shown in (a) of FIG. 2. Figure 2

[0251] (Deslagging and pre-plating treatment)

[0252] According to the desire, the substrate on which the resist pattern is formed is subjected to plasma treatment and / or water immersion treatment, and thus deslagging and pre-plating treatment can be performed.

[0253] (4) Plating process

[0254] By performing copper plating or soldering on the surface of the substrate (for example, the copper surface of a sputtered copper thin film) exposed by developing, a conductor pattern can be manufactured. The plating solution is preferably a copper sulfate plating solution.

[0255] Note that an example in which the plating layer is small in submergence is shown in (b) of FIG. 3, Figure 1 and an example in which the plating layer is large in submergence is shown in (b) of FIG. 4. Figure 2

[0256] (Etching process)

[0257] ​​If desired, an etching solution can be sprayed from above onto the resist pattern formed through the above steps to etch the copper surface not covered by the resist pattern, thereby forming a circuit pattern. Examples of etching methods include acid etching and alkaline etching, which are performed using a method suitable for the photosensitive resin laminate used.

[0258] (Peeling process)

[0259] The laminate is then treated with an aqueous solution having a stronger alkalinity than the developer to remove the resist pattern from the substrate. The stripping solution is preferably at least one selected from the group consisting of an aqueous solution of NaOH or KOH at a concentration of approximately 2-5% by mass and a temperature of approximately 40-70°C, SPR920 (product name), and R-101 (product name). A small amount of a water-soluble solvent may be added to the stripping solution.

[0260] The photosensitive resin composition, photosensitive resin laminate, resist pattern, and semiconductor bump described above can be used, for example, to form a semiconductor package.

[0261] Example

[0262] Hereinafter, examples of embodiments of the present invention will be described in detail using Examples and Comparative Examples.

[0263] First, the method for preparing the evaluation samples of Examples and Comparative Examples will be described. Next, the evaluation method and evaluation results of the obtained samples will be shown.

[0264] (Examples 1 to 13 and Comparative Examples 1 to 4)

[0265] First, the method for preparing the evaluation samples of Examples and Comparative Examples will be described. Next, the evaluation method and the evaluation results of the obtained samples will be shown.

[0266] 1. Preparation of evaluation samples

[0267] The samples for evaluation in Examples and Comparative Examples were prepared as follows.

[0268] <Production of Photosensitive Resin Laminate>

[0269] A photosensitive resin composition having the composition shown in Table 1 below (where the numbers for each component represent the amount (parts by mass) of each component as a solid component) and a solvent were thoroughly stirred and mixed to prepare a photosensitive resin composition solution. This solution was then evenly coated onto the surface of a 16 μm thick polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) serving as a support using a bar coater. The solution was then dried in a dryer at 95°C for 12 minutes to form a photosensitive resin layer. The thickness (T) of the photosensitive resin layer was 240 μm.

[0270] Next, a 19-μm-thick polyethylene film (TAMA POLY Co., Ltd., GF-18) was attached to the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, as a protective layer, to obtain a photosensitive resin laminate. Further, the absorbance (A) at a wavelength of 365 nm of the photosensitive resin laminate was measured using an ultraviolet-visible light (UV-Vis) measuring device (Hitachi High-Technologies Corporation, U-3010 spectrophotometer) in the following manner.

[0271] The polyethylene film of the photosensitive resin laminate was peeled off, and the absorbance at 365 nm was measured, and the obtained value was taken as the absorbance (A). Further, air was used as a blank sample.

[0272] The compounding amounts and evaluation results in the photosensitive resin composition formulation liquid are shown in Table 1 below, respectively, and the names of the material components in the photosensitive resin composition formulation liquid shown in Table 1 are shown in Table 2 below.

[0273] 2. Production of semiconductor bump

[0274] <Substrate>

[0275] In the production of the copper stud, a copper sputtering silicon wafer on which a copper layer of 2000 angstroms thick was formed on a 6-inch silicon wafer using a sputtering device manufactured by ANELVA Co., Ltd. was used.

[0276] <Laminating>

[0277] While the polyethylene film of the photosensitive resin laminate was peeled off, it was laminated on a silicon wafer preheated to 70°C using a heating roll laminator (Daisei Laminating Machine Co., Ltd., VA-400III) at a roll temperature of 70°C. The air pressure was set to 0.20 MPa, and the lamination speed was set to 0.18 m / min.

[0278] <Exposure>

[0279] Exposure was performed at 300 mJ / cm 2 using an Ultratech Prisma ghi Stepper (Ultratech Co., Ltd.) using a glass chromium mask. The illuminance measured on the substrate surface was 2400 mW / cm 2 .

[0280] <Developing>

[0281] At 30°C, a 1% by mass aqueous Na2CO3 solution was sprayed to the exposed laminate at a flow rate of 200 mL / min. using a rotary developing machine (Takasago Industries Co., Ltd., Rotary Developing Machine AD-1200), and developing was performed.

[0282] <Deslagging and pre-plating treatment>

[0283] The deslagging and pre-plating treatment was performed by subjecting the evaluation substrate to plasma treatment using a low-pressure plasma device (EXAM, manufactured by Shinkuu Seiki Co., Ltd.) under conditions of 50 Pa, 133 W, 02 40 mL / min., CF4 1 mL / min., and immersing in pure water for 5 minutes.

[0284] <Plating of copper sulfate>

[0285] The copper plating was performed as follows, and the peeling was performed as described later, to produce a copper stud.

[0286] A copper sulfate plating solution was prepared by adding SC-50R1 (manufactured by the same company) 20 mL and SC-50R2 (manufactured by the same company) 12 mL to SC-50MU MA (manufactured by MICROFAB (registered trademark)) 968 mL. The copper plating was performed using the prepared copper sulfate plating solution with respect to the plating resistance evaluation substrate (6 cm x 12.5 cm) after the pre-plating treatment, and using a Haring cell uniform plating device (manufactured by Yamamoto Gold Plating Tester Co., Ltd.), the current value was adjusted in such a manner that copper was deposited at a height of 1 μm per minute, and the plating was performed. At this time, the thickness of the copper plating film was 100 μm.

[0287] <Peeling>

[0288] The peeling was performed by heating at 65°C for 100 minutes using a peeling solution of 3% NaOH, SPR920 (manufactured by KANTO-PPC Co., Ltd.), and R-101 (manufactured by Mitsubishi Gas Chemical Co., Inc.) with respect to the evaluation substrate on which the plating treatment was performed.

[0289] 3. Minimum developing time evaluation

[0290] The minimum time required for complete dissolution of the photosensitive resin layer with respect to the unexposed portion was measured as "minimum developing time", and the classification was performed as follows:

[0291] S: The value of the minimum developing time was 210 seconds or less;

[0292] A: The value of the minimum developing time was more than 210 seconds and 220 seconds or less;

[0293] B: The value of the minimum developing time was more than 220 seconds and 230 seconds or less;

[0294] C: The value of the minimum developing time was more than 230 seconds.

[0295] 4. Evaluation of lower edge of resist layer

[0296] The substrate on which a 150 μm circular hole pattern was formed and subjected to dross removal was cut, and the lower edge length of the resist layer bottom was observed by SEM. Grading was performed as follows.

[0297] S: lower edge length of 1 μm or less;

[0298] A: more than 1 μm and 1.5 μm or less;

[0299] B: more than 1.5 μm and 2.0 μm or less;

[0300] C: more than 2.0 μm.

[0301] 5. Plating resistance evaluation

[0302] The copper stud bottom of the substrate on which the cured resist layer was peeled after copper plating was observed by SEM, and grading was performed as follows.

[0303] S: no copper plating layer subsidence;

[0304] A: copper plating layer subsidence of 1 μm or less;

[0305] B: copper plating layer subsidence of more than 1 μm and 3 μm or less;

[0306] C: copper plating layer subsidence of more than 3 μm.

[0307] 6. Peel sheet solubility evaluation

[0308] <Exposure>

[0309] The photosensitive resin laminate was exposed from the support film side to produce a cured resist layer. An Ultratech Prisma ghl Stepper (manufactured by Ultratech, Inc.) was used for exposure. The exposure dose was 300 mJ / cm 2 .

[0310] <Development>

[0311] The support film was peeled from the exposed photosensitive resin laminate, and development was performed by spraying a 30°C, 1 mass% Na2CO3 aqueous solution for a time twice that of the "minimum development time". Thereafter, the protective layer was peeled to obtain a cured resist layer.

[0312] <Peel sheet solubility evaluation 1>

[0313] About 50 mg of the obtained cured resist layer was immersed in 20 mL of a 3% NaOH peeling solution at 65°C for 75 minutes. Thereafter, the remaining cured film was filtered and vacuum-dried, and the residual film rate was calculated by dividing the mass of the obtained filtrate by the mass of the initially immersed cured resist layer, and the "peel sheet solubility" was evaluated. Grading was performed as follows.

[0314] S: The residual film rate is 0%;

[0315] A: The residual film rate is greater than 0% and less than 10%;

[0316] B: The residual film rate is greater than 10% and less than 25%;

[0317] C: The residual film ratio exceeds 25%.

[0318] <Peel Sheet Solubility Evaluation 2>

[0319] In the above-mentioned evaluation 1, SPR920 was used as the stripping liquid, and the evaluation was performed in the same manner.

[0320] S: The residual film rate is 0%;

[0321] A: The residual film rate is greater than 0% and less than 10%;

[0322] B: The residual film rate is greater than 10% and less than 25%;

[0323] C: The residual film ratio exceeds 25%.

[0324] <Peel Sheet Solubility Evaluation 3>

[0325] In the above-mentioned evaluation 1, R-101 was used as the stripping liquid, and the evaluation was performed in the same manner.

[0326] S: The residual film rate is 0%;

[0327] A: The residual film rate is greater than 0% and less than 10%;

[0328] B: The residual film rate is greater than 10% and less than 25%;

[0329] C: The residual film ratio exceeds 25%.

[0330] 7. Evaluation of resist wrinkles during storage

[0331] The photosensitive resin laminate was wound in a plastic bottle having a diameter of 8.5 cm and allowed to stand for a certain period of time under the conditions of 23° C. and 50% RH. The degree of wrinkling on the resist layer surface was evaluated and classified as follows.

[0332] S: No wrinkles after more than 12 hours;

[0333] A: Wrinkles occur within more than 6 hours and less than 12 hours;

[0334] B: Wrinkles occur within more than 3 hours and less than 6 hours;

[0335] C: Wrinkles occurred within 3 hours.

[0336] [table 1]

[0337]

[0338] [table 2]

[0339]

Claims

1. A photosensitive resin laminate comprising a photosensitive resin layer comprising a photosensitive resin composition laminated on a support film, wherein the photosensitive resin composition comprises: (A) Alkali-soluble polymer: 10% to 90% by mass, (B) Compounds having an ethylenically unsaturated double bond: 5% to 70% by mass, and (C) Photopolymerization initiator: 0.01% to 20% by mass, The (A) alkali-soluble polymer includes a copolymer containing a (meth)acrylate having an alkyl group having 3 to 12 carbon atoms as a copolymer component. The compound (B) having an ethylenically unsaturated double bond contains an acrylate monomer in an amount of 51% to 100% by mass relative to the total amount of the compound (B) having an ethylenically unsaturated double bond. The (C) photopolymerization initiator contains an imidazole compound in an amount of 99% by mass or more and 100% by mass or less based on the total amount of the (C) photopolymerization initiator. When the thickness of the photosensitive resin layer containing the photosensitive resin composition is represented by T [μm] and the absorbance at a wavelength of 365 nm is represented by A, the relationship represented by the following formula (I) is satisfied: Furthermore, the thickness of the photosensitive resin layer comprising the photosensitive resin composition is 40 μm or more and 600 μm or less. The (A) alkali-soluble polymer contains a carboxyl group and has an acid equivalent of 100 to 600.

2. The photosensitive resin laminate according to claim 1, wherein The weight average molecular weight of the (A) alkali-soluble polymer is 5,000 or more and 500,000 or less.

3. The photosensitive resin laminate according to claim 1, wherein The (A) alkali-soluble polymer has an aromatic hydrocarbon group.

4. The photosensitive resin laminate according to claim 1, wherein The (A) alkali-soluble polymer includes a copolymer containing 2-ethylhexyl acrylate as a copolymerization component.

5. The photosensitive resin laminate according to claim 1, wherein The (A) alkali-soluble polymer includes a copolymer containing benzyl (meth)acrylate as a copolymerization component. 6 . The photosensitive resin laminate according to claim 1 , wherein The alkali-soluble polymer (A) further contains a (meth)acrylate other than the (meth)acrylate having an alkyl group having 3 to 12 carbon atoms and / or a vinyl compound as a copolymerization component, and 7. The photosensitive resin laminate according to any one of claims 1 to 5, wherein The (A) alkali-soluble polymer contains 6.0% by mass to 30% by mass of the (meth)acrylate having an alkyl group having 3 to 12 carbon atoms as a copolymerization component. The compound (B) having an ethylenically unsaturated double bond includes a compound having a trifunctional or higher-functional acrylate group.

8. The photosensitive resin laminate according to any one of claims 1 to 5, wherein The compound having trifunctional or higher-functional acrylate groups includes a compound having an acrylate group on a skeleton of trimethylolpropane, pentaerythritol, or dipentaerythritol.

9. The photosensitive resin laminate according to claim 8, wherein The compound having trifunctional or higher-functional acrylate groups contains 1% by mass or more of a compound having acrylate groups on a skeleton of trimethylolpropane, pentaerythritol, or dipentaerythritol relative to the total amount of the compound (B) having an ethylenically unsaturated double bond.

10. The photosensitive resin laminate according to claim 8, wherein The compound having trifunctional or higher-functional acrylate groups contains 10% by mass or more of a compound having acrylate groups on a skeleton of trimethylolpropane, pentaerythritol, or dipentaerythritol relative to the total amount of the compound (B) having an ethylenically unsaturated double bond.

11. The photosensitive resin laminate according to claim 8, wherein ​ 12. The photosensitive resin laminate according to claim 8, wherein The compound having trifunctional or higher-functional acrylate groups contains 80% by mass or more of a compound having acrylate groups on a skeleton of trimethylolpropane, pentaerythritol, or dipentaerythritol relative to the total amount of the compound (B) having an ethylenically unsaturated double bond. 13 . The photosensitive resin laminate according to claim 1 , wherein When a compound having an aromatic ring is included as the compound (B) having an ethylenically unsaturated double bond, the compound having an aromatic ring is represented by the following formula (VII): In formula (VII), Y each independently represents an alkylene group having 2 to 10 carbon atoms, R1 and R2 each independently represent a methyl group or a hydrogen atom, and n1 and n2 each independently represent an integer of 1 to 100.

14. The photosensitive resin laminate according to any one of claims 1 to 5, wherein The (C) photopolymerization initiator contains a 2,4,5-triarylimidazole dimer.

15. The photosensitive resin laminate according to any one of claims 1 to 5, wherein When the thickness of the photosensitive resin layer containing the photosensitive resin composition is represented by T [μm] and the absorbance at a wavelength of 365 nm is represented by A, the relationship represented by the following formula (II) is satisfied: When the film thickness of the photosensitive resin layer containing the photosensitive resin composition is represented by T [μm] and the absorbance at a wavelength of 365 nm is represented by A, the relationship represented by the following formula (III) is satisfied:

16. The photosensitive resin laminate according to any one of claims 1 to 5, wherein The thickness of the photosensitive resin layer containing the photosensitive resin composition is more than 50 μm and 400 μm or less. The thickness of the photosensitive resin layer comprising the photosensitive resin composition is 100 to 400 μm.

17. The photosensitive resin laminate according to any one of claims 1 to 5, wherein The thickness of the photosensitive resin layer comprising the photosensitive resin composition is 200 to 400 μm.

18. The photosensitive resin laminate according to any one of claims 1 to 5, wherein 20 . The photosensitive resin laminate according to claim 1 , which is a dry film resist.

19. The photosensitive resin laminate according to any one of claims 1 to 5, wherein 21. A method for forming a resist pattern, comprising the following steps: a step of laminating the photosensitive resin laminate according to any one of claims 1 to 20 on a substrate; a step of exposing the laminated photosensitive resin stack; and A step of developing the exposed photosensitive resin laminate.

22. A method for forming a semiconductor bump, comprising the following steps: a step of laminating the photosensitive resin laminate according to any one of claims 1 to 20 on a sputtered copper thin film; a step of exposing the laminated photosensitive resin stack; a step of developing the exposed photosensitive resin laminate; and The developed sputtered copper thin film is subjected to a copper plating or soldering step. ​ ​

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