Photosensitive resin laminate, method for forming resist pattern, and method for manufacturing wiring board having conductor pattern

Abstract

The present disclosure provides a photosensitive resin laminate which has a provisional support and a photosensitive resin layer that contains a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator. The alkali-soluble polymer (A) includes (A-1) a copolymer which has the following constituent unit: (a1) a constituent unit that is derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group.

Description

Photosensitive resin laminate, method for forming resist pattern, and method for manufacturing wiring board having conductive pattern

[0001] The present invention relates to a photosensitive resin laminate, a method for forming a resist pattern, and a method for producing a wiring board having a conductor pattern.

[0002] In wiring boards and the like included in electronic devices, wiring patterns (hereinafter also referred to as "conductor patterns") are generally produced using a photolithography process. The photolithography process includes, for example, the following steps: forming a resist pattern by laminating a photosensitive resin layer of a photosensitive resin laminate on a substrate and then exposing and developing the layer; etching or plating the substrate on which the resist pattern has been formed to form a conductor pattern; and removing the resist pattern on the substrate.

[0003] Patent Document 1 proposes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an anthracene-based sensitizer, the binder polymer having hydroxyalkyl(meth)acrylate units and styrene or styrene derivative units, and the content of the styrene or styrene derivative units is 40 mass% or more. Patent Document 1 reports that the use of such a photosensitive resin composition makes it possible to form a resist pattern with excellent adhesion and resolution.

[0004] International Publication No. 2021 / 193232

[0005] In the photolithography process, not only are excellent adhesion and resolution of the resist pattern required, but also excellent developability of the photosensitive resin layer and strength of the resist pattern are required. However, Patent Document 1 leaves room for improvement in terms of achieving a balance between these requirements and satisfying all of them.

[0006] Therefore, an object of the present invention is to provide a photosensitive resin laminate that balances the developability of the photosensitive resin layer and the strength of the resist pattern in addition to the adhesion and resolution of the resist pattern, and satisfies all of these requirements; and to provide a method for forming a resist pattern and a method for producing a wiring board having a conductor pattern, using such a photosensitive resin laminate.

[0007] One aspect of the present invention is as follows. [1] A photosensitive resin laminate having a temporary support and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator; and the (A) alkali-soluble polymer contains an (A-1) copolymer having the following structural units: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group, and (a3) ​​a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate. [2] The photosensitive resin laminate according to item 1, wherein the (a1) structural unit derived from the compound is glycerin mono(meth)acrylate. [3] The photosensitive resin laminate according to item 1 or 2, wherein the content of the (a1) structural unit in the component (A) is 0.5 to 30% by mass. [4] The photosensitive resin laminate according to any one of items 1 to 3, wherein the content of the (a1) structural unit in the component (A) is 1.0 to 10% by mass. [5] The photosensitive resin laminate according to any one of items 1 to 4, wherein the content of the (a1) structural unit in the component (A) is 1.0 to 5.0% by mass. [6] The photosensitive resin laminate according to any one of items 1 to 5, wherein the (A-1) copolymer further contains the following structural unit: (a2) a structural unit derived from a compound having a carboxyl group and an ethylenically unsaturated bond. [7] The photosensitive resin laminate according to any one of items 1 to 6, wherein the content of the (a3) ​​structural unit in the component (A) is 10% by mass or more. [8] The photosensitive resin laminate according to any one of items 1 to 7, wherein the content of the (a3) ​​structural unit in the component (A) is 20 to 70 mass%. [9] The photosensitive resin laminate according to any one of items 1 to 8, wherein the weight-average molecular weight of the component (A) is 10,000 to 60,000.

[10] The photosensitive resin laminate according to any one of items 1 to 9, wherein the component (B) includes a compound having two ethylenically unsaturated bonds in one molecule.

[11] The photosensitive resin laminate according to any one of items 1 to 10, wherein the component (C) includes a hexaarylbiimidazole compound.

[12] The photosensitive resin laminate according to any one of items 1 to 11, wherein the total content of the component (A), the component (B), and the component (C) is 90 mass% or more based on the total solid content of the photosensitive resin composition.

[13] The photosensitive resin laminate according to any one of items 1 to 13, further comprising a protective film.

[14] A photosensitive resin laminate for forming a conductor pattern, comprising the photosensitive resin laminate according to any one of items 1 to 13.

[15] A photosensitive resin laminate roll formed by winding the photosensitive resin laminate according to any one of items 1 to 14.

[16] A method for forming a resist pattern, comprising: a step of laminating a photosensitive resin layer in the photosensitive resin laminate according to any one of items 1 to 14 on a substrate, a step of exposing the photosensitive resin layer, and a step of developing the photosensitive resin layer after exposure to form a resist pattern.

[17] A method for producing a wiring board having a conductor pattern, comprising: a step of laminating a photosensitive resin layer in the photosensitive resin laminate according to any one of items 1 to 14 on a substrate, a step of exposing the photosensitive resin layer, and a step of developing the photosensitive resin layer after exposure to form a resist pattern, and a step of etching or plating the substrate on which the resist pattern has been formed to form a conductor pattern on the substrate.

[0008] Note that aspects related to one aspect of the present invention are as follows. [1] A photosensitive resin laminate having a temporary support and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator; and the (A) alkali-soluble polymer contains an (A-1) copolymer having the following structural unit: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group. [2] The photosensitive resin laminate according to Item 1, wherein the (a1) structural unit derived from the compound is glycerin mono(meth)acrylate. [3] The photosensitive resin laminate according to Item 1 or 2, wherein the content of the (a1) structural unit in the component (A) is 0.5 to 30 mass %. [4] The photosensitive resin laminate according to any one of items 1 to 3, wherein the content of the (a1) structural unit in the component (A) is 1.0 to 10 mass%. [5] The photosensitive resin laminate according to any one of items 1 to 4, wherein the content of the (a1) structural unit in the component (A) is 1.0 to 5.0 mass%. [6] The photosensitive resin laminate according to any one of items 1 to 5, wherein the (A-1) copolymer further comprises the following structural unit: (a2) a structural unit derived from a compound having a carboxyl group and an ethylenically unsaturated bond. [7] The photosensitive resin laminate according to any one of items 1 to 6, wherein the (A-1) copolymer further comprises the following structural unit: (a3) ​​a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate. [8] The photosensitive resin laminate according to item 7, wherein the content of the (a3) ​​structural unit in the component (A) is 20 to 70 mass%. [9] The photosensitive resin laminate according to any one of items 1 to 8, wherein the weight-average molecular weight of the component (A) is 10,000 to 60,000.

[10] The photosensitive resin laminate according to any one of items 1 to 9, wherein the component (B) includes a compound having two ethylenically unsaturated bonds in one molecule.

[11] The photosensitive resin laminate according to any one of items 1 to 10, wherein the component (C) includes a hexaarylbiimidazole compound.

[12] The photosensitive resin laminate according to any one of items 1 to 11, wherein the total content of the component (A), the component (B), and the component (C) is 90% by mass or more based on the total solid content of the photosensitive resin composition.

[13] The photosensitive resin laminate according to any one of items 1 to 12, further comprising a protective film.

[14] A photosensitive resin laminate for forming a conductor pattern, comprising the photosensitive resin laminate according to any one of items 1 to 13.

[15] A photosensitive resin laminate roll formed by winding the photosensitive resin laminate according to any one of items 1 to 14.

[16] A method for forming a resist pattern, comprising: a step of laminating a photosensitive resin layer in the photosensitive resin laminate according to any one of items 1 to 14 on a substrate; a step of exposing the photosensitive resin layer; and a step of developing the photosensitive resin layer after exposure to form a resist pattern.

[17] A method for producing a wiring board having a conductor pattern, comprising: a step of laminating a photosensitive resin layer on a substrate, the photosensitive resin layer being the photosensitive resin laminate according to any one of items 1 to 14; a step of exposing the photosensitive resin layer; and a step of developing the exposed photosensitive resin layer to form a resist pattern; and a step of etching or plating the substrate on which the resist pattern has been formed to form a conductor pattern on the substrate.

[0009] According to the present invention, it is possible to provide a photosensitive resin laminate that balances the developability of the photosensitive resin layer and the strength of the resist pattern in addition to the adhesion and resolution of the resist pattern, and satisfies all of these requirements. Furthermore, according to the present invention, it is possible to provide a method for forming a resist pattern and a method for producing a wiring board having a conductor pattern using such a photosensitive resin laminate.

[0010] 1 is a plan view showing the configuration of a mask pattern related to this embodiment. 2 is a plan view showing the configuration of a mask pattern related to this embodiment. 3 is a plan view showing the configuration of a mask pattern related to this embodiment. 4 is a plan view showing the configuration of a mask pattern related to this embodiment.

[0011] The present invention is not limited to the present embodiment, but can be practiced in various modifications within the scope of the present invention.

[0012] In the present specification, when a plurality of structures represented by the same symbol exist in the same formula, the structures may be independently selected and may be the same or different from each other, unless otherwise specified. When a plurality of structures represented by the same symbol exist in different formulas, the structures may be independently selected and may be the same or different from each other, unless otherwise specified. In the present specification, various measurements are carried out based on the methods described in the Examples unless otherwise specified. In the present specification, the upper or lower limit of a numerical range described in a stepwise manner may be replaced by the upper or lower limit of a corresponding numerical range described in another stepwise manner, and may further be replaced by the corresponding value described in the Examples.

[0013] In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic", "(meth)acrylate" means "acrylate" and / or "methacrylate", and "(meth)acryloyl" means "acryloyl" and / or "methacryloyl". A "compound containing a (meth)acryloyl group" is referred to as, for example, a "(meth)acrylate compound". In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the function of the process is achieved. In the drawings, the scale, shape, and length may be exaggerated for clarity. In this specification, the "solid content" of a photosensitive resin composition means components of the photosensitive resin composition other than the solvent.

[0014] In one embodiment, unless otherwise specified, "developability" means the developability of a photosensitive resin layer (resist); "sensitivity" means the exposure sensitivity of a photosensitive resin layer (resist); "adhesion" means the adhesion performance between a resist pattern and a substrate; "resolution" means the resolution performance of a resist pattern; and "thin line strength" means the strength of a resist pattern.

[0015] [Photosensitive Resin Laminate] One aspect of this embodiment is a photosensitive resin laminate. This photosensitive resin laminate includes a support film and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator; and the (A) alkali-soluble polymer contains an (A-1) copolymer having the following structural unit: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group.

[0016] Another aspect of this embodiment is also a photosensitive resin laminate. This photosensitive resin laminate includes a support film and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator; and the (A) alkali-soluble polymer contains an (A-1) copolymer having the following structural units: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group, and (a3) ​​a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate. That is, in one embodiment, the (A-1) copolymer has (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group, and in a further embodiment, in addition to the above (a1), it has (a3) ​​a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate.

[0017] In recent years, with the trend toward miniaturization of electronic devices and increasing density of wiring in electronic devices, there has been a demand for photosensitive resin laminates capable of forming fine resist patterns with various excellent properties. Examples of fine resist patterns with various excellent properties include resist patterns having a line width of 7 μm or less and excellent adhesion, resolution, and fine line strength. In addition, from the viewpoint of efficient production and use of photosensitive resin laminates, excellent developability of the photosensitive resin layer is also expected.

[0018] One way to satisfy the various properties expected of a photosensitive resin layer and a resist pattern is to control the structural units and physical properties of the component (A). In this regard, it is conceivable to use a copolymer containing a highly hydrophobic monomer as the component (A) in order to improve resolution and adhesion. On the other hand, in this case, the high hydrophobicity of the copolymer tends to reduce its solubility in the developer, which in turn tends to reduce developability. To address this issue, it is conceivable to use a compound having a hydroxy group as a copolymerization component to impart hydrophilicity to the copolymer.

[0019] The present inventors have focused on using a monomer having two or more alcoholic hydroxyl groups as a copolymer component to form a (meth)acrylic resin copolymer. In such a copolymer, two or more alcoholic hydroxyl groups derived from the monomer remain, making it possible to achieve a copolymer with excellent localized hydrophilicity even when a highly hydrophobic monomer is used in combination. According to this embodiment, by controlling the structural units and physical properties of component (A), it is possible to provide a photosensitive resin laminate that achieves a balance between the adhesion and resolution of the resist pattern, as well as the developability of the photosensitive resin layer and the strength of the resist pattern, and satisfies all of these requirements.

[0020] [Temporary Support] The temporary support is peeled off from the photosensitive resin layer before the exposure step in which the photosensitive resin layer is exposed or before the development step in which the photosensitive resin layer is developed. The temporary support is a layer or film for supporting the photosensitive resin layer, and is preferably a transparent substrate that can transmit exposure light (actinic rays). This type of substrate is sometimes called a "support film" or "support", but is referred to as a "temporary support" in this specification.

[0021] Examples of substrates that can be used as temporary supports, particularly transparent substrates, include synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate (PET) is preferred as a temporary support because it has appropriate flexibility and strength.

[0022] From the viewpoint of easily ensuring adhesion, the absorbance of the temporary support at a wavelength of 365 nm is preferably 0.3 or less, more preferably 0.2 or less, even more preferably 0.1 or less, and most preferably 0.08 (e.g., 0.080) or less. The absorbance may be 0 or more.

[0023] As the temporary support, it is preferable to use a film with few internal foreign matters, for example, a high-quality film.Specifically, as high-quality films, PET films synthesized using Ti-based catalysts, PET films with small lubricant diameters and low content, PET films containing lubricant only on one side of the film, thin PET films, PET films with smoothing treatment on at least one side, and PET films with roughening treatment such as plasma treatment on at least one side can be mentioned.By using a high-quality film as the temporary support, the exposure light is less likely to be blocked by internal foreign matters in the temporary support, and in this case, it is easier to irradiate the exposure light onto the photosensitive resin layer, and as a result, the resolution of the photosensitive resin laminate is easily improved.

[0024] The thickness of the temporary support is preferably 5 to 25 μm, more preferably 6 to 20 μm. The thinner the temporary support, the fewer internal foreign matter tends to be present, making it easier to prevent a decrease in resolution. On the other hand, if the thickness is less than 5 μm, stretching deformation in the winding direction due to tension during the coating and winding manufacturing process is likely to occur, and tearing due to minute scratches is likely to occur. As a result, the strength of the temporary support is likely to be insufficient, and therefore, wrinkles are likely to occur in the photosensitive resin laminate when it is laminated on a substrate.

[0025] At least one surface of the temporary support may be subjected to a smoothing treatment using a calender or the like. This reduces the surface roughness of one surface of the support film, particularly the surface that comes into contact with the photosensitive resin layer, and in this case, the effects of the present invention are easily achieved.

[0026] The haze of the temporary support is preferably 0.01 to 1.5%, more preferably 0.01 to 1.2%, and even more preferably 0.01 to 0.95%, from the viewpoint of improving the parallelism of the exposure light irradiated onto the photosensitive resin layer and from the viewpoint of obtaining high resolution.

[0027] [Photosensitive Resin Layer] The photosensitive resin layer contains a photosensitive resin composition. The photosensitive resin composition contains "(A) an alkali-soluble polymer," "(B) a compound having an ethylenically unsaturated bond," and "(C) a photopolymerization initiator." The photosensitive resin composition may optionally contain "(D) a dye" and / or "(E) other components." In this specification, the above (A) to (E) may be simply referred to as "component (A)" to "component (E)." Each of the components (A) to (E) or the raw materials for each component may be used alone, or two or more may be used in combination.

[0028] From the viewpoint of easily achieving the effects of this embodiment and being suitable for forming a conductive pattern, the total content of the component (A), the component (B), and the component (C) is preferably 90 mass % or more, and more preferably 95 mass % or more, based on the total solid content of the photosensitive resin composition.

[0029] The thickness of the photosensitive resin layer is preferably 3 to 100 μm, which is specifically preferred. The smaller the thickness, the easier it is to improve the resolution, and the greater the thickness, the easier it is to improve the strength of the photosensitive resin layer. The thickness of the photosensitive resin layer may be, for example, 7 μm or more, 15 μm or more, 25 μm or more, or 40 μm or more, and may be 60 μm or less, or 50 μm or less.

[0030] The thickness of the photosensitive resin layer may be selected depending on the configuration and use of the photosensitive resin laminate, the configuration and use of the resist pattern obtained using the photosensitive resin laminate, and the configuration and use of the conductor pattern or electronic device produced using the photosensitive resin laminate, etc. When plating is performed on a substrate on which a resist pattern has been formed, the thickness of the photosensitive resin layer is preferably 10 to 30 μm, more preferably 15 to 25 μm.

[0031] <Component (A): Alkali-Soluble Polymer> The component (A) is a polymer that is soluble in an alkaline aqueous solution, such as a polymer having a carboxyl group.

[0032] The component (A) includes an (A-1) copolymer having the following structural unit: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group. The component (A) may include multiple copolymers, for example, multiple (A-1) copolymers, or may include copolymers other than the (A-1) copolymer (hereinafter referred to as "other copolymers"). When the component (A) includes multiple copolymers, the content of the repeating unit of the component (A) represents a weighted average of the proportions of the repeating units of each copolymer, with the ratio of the content of each copolymer being used as the weight. Furthermore, when the component (A) includes multiple copolymers, the molecular weight and polydispersity of the entire component (A) are preferably selected so that the weighted average value, when the content ratio of each copolymer is used as the weight, falls within the range described below.

[0033] The weight-average molecular weight (Mw) of the component (A) is preferably 5,000 to 500,000, more preferably 10,000 to 200,000, even more preferably 20,000 to 100,000, and particularly preferably 23,000 to 60,000. When the weight-average molecular weight (Mw) of the component (A) is 5,000 or more, it becomes easier to maintain a uniform thickness of the photosensitive resin laminate and to ensure resistance to a developing solution. When the weight-average molecular weight (Mw) of the component (A) is 500,000 or less, it becomes easier to maintain the developability of the photosensitive resin laminate.

[0034] The dispersity (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) of component (A) to the number average molecular weight (Mn) of component (A), is preferably 1.0 to 6.0.

[0035] The content of the (a1) structural unit in the component (A) is preferably 0.5% by mass or more from the viewpoint of excellent adhesion and fine line strength, and is preferably 30% by mass or less from the viewpoint of excellent developability. From the same viewpoints, the content is more preferably 1.0 to 10% by mass, and even more preferably 1.0 to 5% by mass.

[0036] The content of the (a1) structural unit is also preferably selected so that the number of hydroxyl groups contained per gram of component (A) falls within a predetermined range. From the viewpoint of excellent adhesion, the number of hydroxyl groups is preferably 0.050 mmol or more, and from the viewpoint of excellent developability, the number of hydroxyl groups is preferably 3.50 mmol or less. From the same viewpoint, the number of hydroxyl groups is more preferably 0.11 to 1.25 mmol, and even more preferably 0.20 to 0.65 mmol.

[0037] The number of hydroxyl groups is expressed by the following formula: Number of hydroxyl groups = (X x Y) / (Z x 100) {wherein X represents the number of hydroxyl groups contained in the (a1) structural unit, Y represents the amount (% by mass) of the (a1) structural unit contained in the component (A), and Z represents the molecular weight of the (a1) compound.} When a compound having multiple hydroxyl groups is contained as the (a1) structural unit or a structural unit other than the (a1) structural unit, the compounds having each of the hydroxyl groups are designated Compound 1 to Compound n, and the number of hydroxyl groups is calculated as follows: where X ｉ represents the number of hydroxyl groups contained in compound i (i = 1 to n), and Y ｉ indicates the content (mass%) of compound i (i = 1 to n) contained in component (A), and Z ｉ indicates the molecular weight of compound i (i = 1 to n).

[0038] From the viewpoint of favorably exhibiting the alkali solubility of the component (A) and the developability of the photosensitive resin composition, the acid value of the component (A) is preferably 50 to 600 mgKOH / g. The acid value of the component (A) may be 60 mgKOH / g or more, or 80 mgKOH / g or more, and may be 500 mgKOH / g or less, or 400 mgKOH / g or less. From the same viewpoint, the photosensitive resin composition preferably has an acid value of 20 to 300 mgKOH / g. From the same viewpoint, the acid value of the photosensitive resin composition may be 30 mgKOH / g or more, or 40 mgKOH / g or more, and may be 200 mgKOH / g or less, or 150 mgKOH / g or less.

[0039] The acid value can be calculated by accurately weighing out about 1 g of a sample, dissolving it in 100 mL of acetone, and then neutralizing titrating it with a 1 mol / L aqueous potassium hydroxide solution, and using the amount of potassium hydroxide solution dropped to calculate the acid value using the following formula: Acid value (mg KOH / g) = 56.1 × {amount of 1 mol / L aqueous potassium hydroxide solution dropped (mL)} / {mass of precisely weighed sample (g)}. The neutralizing titration can be performed using, for example, a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

[0040] The component (A) may further include an (a3) ​​structural unit, which will be described later. The content of the (a3) ​​structural unit in the component (A) is preferably 10% by mass or more from the viewpoint of excellent adhesion, and is preferably 85% by mass or less from the viewpoint of excellent developability. From the same viewpoints, the content is more preferably 20 to 80% by mass, and even more preferably 30 to 75% by mass.

[0041] The (a3) ​​structural unit is preferably a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate, and among these, a structural unit derived from styrene is preferred from the viewpoint of excellent adhesion. The content of the structural unit derived from styrene in the (A) component is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. From the viewpoint of excellent developability, the content of the structural unit derived from styrene may be 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0042] The content of component (A) may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total solids content of the photosensitive resin composition. The content may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less. A content of 90% by mass or less is preferred from the viewpoint of ease of control of development time, and a content of 10% by mass or more is preferred from the viewpoint of excellent edge fusion resistance.

[0043] <<(A-1) Copolymer>> The (A-1) copolymer has the following structural unit: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group (in this specification, a "compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group" may be simply referred to as the "(a1) compound"). In this specification, an "alcoholic hydroxyl group" refers to a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group, and a "structural unit derived from the (a1) compound" refers to a structural unit formed when the (a1) compound is used in copolymerization. Note that a "structural unit derived from the (a1) compound" is a structural unit containing two or more alcoholic hydroxyl groups that was possessed by the (a1) compound. In this specification, a "structural unit derived from the (a1) compound" may be simply referred to as the "(a1) structural unit". The number of alcoholic hydroxyl groups in the (a1) compound or the (a1) structural unit may be 5 or less, 4 or less, or 3 or less.

[0044] The weight-average molecular weight (Mw) of the copolymer (A-1) is preferably 5,000 to 500,000, more preferably 10,000 to 200,000, even more preferably 20,000 to 100,000, and particularly preferably 23,000 to 60,000. When the weight-average molecular weight (Mw) of the copolymer (A-1) is 5,000 or more, it is easy to maintain a uniform thickness of the photosensitive resin laminate and to ensure resistance to a developing solution. When the weight-average molecular weight (Mw) of the copolymer (A-1) is 500,000 or less, it is easy to maintain the developability of the photosensitive resin laminate.

[0045] The dispersity (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) of the copolymer (A-1) to the number average molecular weight (Mn) of the copolymer (A-1), is preferably 1.0 to 6.0.

[0046] The content of the (A-1) copolymer is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, even more preferably 5 to 60% by mass, and particularly preferably 10 to 55% by mass, based on the total solids content of the photosensitive resin composition. When the content is 5% or more, excellent adhesion and fine line strength are likely to be achieved. When the content is 80% or less, resistance to the developer is likely to be ensured. From the same viewpoint, the content of the (A-1) copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the (A) component. The photosensitive resin composition may contain one type of (A-1) copolymer, or two or more different types. When two or more different types of (A-1) copolymers are used, the above content is the total content of the two or more types of (A-1) copolymers corresponding to the (A-1) copolymer.

[0047] (a1) Compound Examples of the (a1) compound include glycerin mono(meth)acrylate, 2-hydroxy-1-(hydroxymethyl)ethyl(meth)acrylate, 3,4-dihydroxybutyl(meth)acrylate, 2,4-dihydroxybutyl(meth)acrylate, 4,5-dihydroxypentyl(meth)acrylate, 2,3,4-trihydroxybutyl(meth)acrylate, and 2-hydroxy-3-(2-hydroxyethoxy)(meth)acrylate. Of these, glycerin mono(meth)acrylate is preferred as the (a1) compound.

[0048] Commercially available glycerin mono(meth)acrylate products include Blemmer (registered trademark) GLM, GLM-EX, and GLM-R (all trade names, manufactured by NOF Corporation).

[0049] The proportion of the (a1) structural unit in the (A-1) copolymer is preferably 0.5% by mass or more from the viewpoint of excellent adhesion and fine line strength, and preferably 30% by mass or less from the viewpoint of excellent adhesion and resolution. From the same viewpoint, the proportion of the (a1) structural unit is more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass. The (A-1) copolymer may have a plurality of (a1) structural units that are different from one another. In this case, it is preferable that the total proportion of all structural units corresponding to the (a1) structural unit be within the above range.

[0050] (a2) Compound It is preferable that the (A-1) copolymer further comprises the following structural unit: (a2) a structural unit derived from a compound having a carboxyl group and an ethylenically unsaturated bond (in this specification, "a compound having a carboxyl group and an ethylenically unsaturated bond" may be simply referred to as "(a2) compound"). In this specification, "a structural unit derived from (a2) compound" may be simply referred to as "(a2) structural unit".

[0051] Examples of the (a2) compound include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and 4-vinylbenzoic acid. Among these, the (a2) compound is preferably (meth)acrylic acid, and more preferably methacrylic acid, from the viewpoint of excellent adhesion and resolution.

[0052] From the viewpoint of excellent developability and resolution, the proportion of the (a2) structural unit in the copolymer (A-1) is preferably from 10 to 40% by mass, more preferably from 15 to 35% by mass, and even more preferably from 18 to 30% by mass.

[0053] (a3) Compound It is preferable that the (A-1) copolymer further comprises the following structural unit: (a3) ​​a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate (in this specification, "styrene, a styrene derivative, or benzyl (meth)acrylate" may be simply referred to as "(a3) compound"). In this specification, the "structural unit derived from the (a3) ​​compound" may be simply referred to as "(a3) structural unit". In the (a3) ​​compound, the styrene derivative may be a styrene derivative that does not have a carboxyl group, and examples include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, and 4-(chloromethyl)styrene. Of these, styrene is preferred as the (a3) ​​compound from the viewpoints of excellent adhesion and resolution.

[0054] The proportion of the (a3) ​​structural unit in the copolymer (A-1) is preferably 10% by mass or more from the viewpoint of excellent developability and resolution, and is preferably 85% by mass or less from the viewpoint of excellent developability. From the same viewpoint, the proportion of the (a3) ​​structural unit is more preferably 20 to 80% by mass, and even more preferably 30 to 75% by mass.

[0055] Of the above, the (a3) ​​structural unit is preferably a structural unit derived from styrene, from the viewpoint of excellent adhesion. The content of the structural unit derived from styrene in the component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. From the viewpoint of excellent developability, the content of the structural unit derived from styrene may be 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0056] Other Monomers The copolymer (A-1) may have structural units (hereinafter referred to as "other structural units") derived from monomers (hereinafter referred to as "other monomers") other than the above compounds (a1) to (a3).

[0057] The other monomer is a compound other than the above-mentioned compounds (a1) to (a3), and is, for example, a compound having at least one ethylenically unsaturated bond in the molecule. Specific examples of the other monomer include (meth)acrylic acid esters, vinyl alcohol, vinyl acetate, esters (e.g., (meth)acrylonitrile, etc.), N-phenylmaleimide, and maleic anhydride.

[0058] The (meth)acrylic acid ester is a concept that encompasses chain alkyl esters, cyclic alkyl esters, and compounds in which the hydrogen atoms in these ester compounds have been substituted with hydroxyl groups or the like. Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. The other monomer may be, for example, a compound having one alcoholic hydroxyl group and a (meth)acryloyl group.

[0059] Other Copolymers The component (A) may optionally contain other copolymers. The other copolymers preferably have structural units derived from a monomer comprising at least one type of first monomer described below, and more preferably have structural units derived from a monomer component comprising at least one type of first monomer and at least one type of second monomer described below.

[0060] First Monomer The first monomer is a compound having a carboxyl group and an ethylenically unsaturated group in the molecule. This first monomer corresponds to the compound (a2) above.

[0061] From the viewpoint of excellent developability and resolution, the content of the structural unit derived from the first monomer is preferably from 10 to 40% by mass, more preferably from 15 to 35% by mass, and even more preferably from 18 to 30% by mass, based on the component (A).

[0062] The content of the structural unit derived from the first monomer is preferably selected so that the acid value of the component (A) or the acid value of the photosensitive resin composition falls within the above range.

[0063] Second Monomer The second monomer is a compound that is non-acidic and has at least one radically polymerizable ethylenically unsaturated bond in the molecule. That is, the second monomer may be the above-mentioned (a3) ​​compound, or may be a compound other than the (a1) compounds to (a3) ​​compounds. These are compounds that have at least one radically polymerizable ethylenically unsaturated bond in the molecule.

[0064] Synthesis of Component (A) Component (A) can be synthesized by mixing an appropriate amount of benzoyl peroxide and azoisobutyronitrile, etc., with a solution prepared by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, followed by heating and stirring. Component (A) may also be synthesized by adding a portion of the mixture dropwise to a reaction solution. After the reaction is complete, additional solvent may be added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as a synthesis method. Synthesis may also be performed by living radical polymerization.

[0065] <Component (B): Photopolymerizable Compound> The component (B) is a photopolymerizable compound, and is, for example, a compound having at least one or two or more ethylenically unsaturated bonds in one molecule.

[0066] From the viewpoint of obtaining a photosensitive resin layer having appropriate flexibility, the photosensitive resin composition preferably contains a compound having two ethylenically unsaturated bonds in one molecule as the compound having an ethylenically unsaturated bond. Furthermore, from the viewpoint of excellent crosslinking efficiency in the exposure step, the photosensitive resin composition may contain a compound having three, four, five, or six ethylenically unsaturated bonds in one molecule, together with or separately from the compound having two ethylenically unsaturated bonds in one molecule.

[0067] From the viewpoint of excellent resolution, the content of the compound having two ethylenically unsaturated bonds in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total amount of component (B). This content may be 100% by mass or less, based on the total amount of component (B).

[0068] When component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule, from the viewpoint of improving crosslinking efficiency in the exposure step and thereby improving adhesion, the content of this compound is preferably 30% by mass or less or 20% by mass or less, based on the total amount of component (B). The content may be 1% by mass or more or 5% by mass or more, based on the total amount of component (B).

[0069] The component (B) preferably contains a (meth)acrylate compound. With regard to the component (B), "a (meth)acrylate compound having n (meth)acryloyl groups in one molecule" may be referred to as "n-functional." For example, with regard to the component (B), having one, two, three, four, five, or six ethylenically unsaturated bonds in one molecule may be referred to as "monofunctional (or monofunctional)," "bifunctional," "trifunctional," "tetrafunctional," "pentafunctional," or "hexafunctional," respectively.

[0070] Examples of the difunctional (meth)acrylate compound include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, and tricyclodecanol di(meth)acrylate.

[0071] Examples of the bifunctional (meth)acrylate compound include polyalkylene glycol di(meth)acrylate and di(meth)acrylate having a bisphenol A structure. Here, the term "bisphenol A structure" is a concept that includes a hydrogenated bisphenol A structure.

[0072] Examples of polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and compounds represented by the following general formula (I): (In the formula, R １ are each independently a hydrogen atom or a methyl group, and X １ O and Y １ O are each independently an oxyethylene group or an oxypropylene group, (X １ O) m1, (X １ O) m2, and (Y １ O) n1 are each independently a (poly)oxyethylene chain or a (poly)oxypropylene chain, m1, m2, and n1 are each independently an integer of 0 to 40, m1+m2 is 1 to 40, and n1 is 1 to 20.

[0073] The polyalkylene glycol di(meth)acrylate represented by the above formula (I) includes R １ = methyl group, m1 + m2 = 6 (average value), n1 = 12 (average value), X １ O is an oxyethylene group, and Y １ Examples include a vinyl compound in which O is an oxypropylene group (manufactured by Resonac, product name "FA-024M").

[0074] The di(meth)acrylate having a bisphenol A structure includes a di(meth)acrylate represented by the following general formula (II): (In the formula, R ２ are each independently a hydrogen atom or a methyl group, and X ２ O and Y ２O are each independently an oxyethylene group or an oxypropylene group, m3, m4, n2, and n3 are each independently an integer of 0 to 40, m3 + m4 is 1 to 40, and n2 + n3 is 0 to 20. A di(meth)acrylate having a hydrogenated bisphenol A structure is a compound in which hydrogen is added to the aromatic ring of the compound represented by formula (II).

[0075] The compound represented by the above formula (II) is BPE-200 (R ２ = methyl group, X ２ O = oxyethylene group, m3 + m4 = 4, and n2 = n3 = 0), BPE-500 (R ２ = methyl group, X ２ O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), BPE-900 (R ２ = methyl group, X ２ O = oxyethylene group, m3 + m4 = 17, and n2 = n3 = 0) (all of these are product names manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-321M (R ２ = methyl group, X ２ O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), and FA-P321M (R ２ = methyl group, X ２ O = oxypropylene group, m3 + m4 = 10, and n2 = n3 = 0 (all of these are product names manufactured by Resonac Co., Ltd.).

[0076] From the viewpoint of excellent adhesion and resolution, the component (B) preferably contains a compound represented by the general formula (II). The content of the compound is preferably 1% by mass or more, more preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the total amount of the component (B). The content may be 100% by mass or less, based on the total amount of the component (B).

[0077] In the compound represented by formula (II), the average value of n2+n3+m3+m4 is preferably 20 or less, and more preferably 10 or less, from the viewpoint of excellent resolution and adhesion. Here, component (B) more preferably contains a compound in which the average value of n2+n3+m3+m4 is more than 5 and 10 or less, and a compound in which the average value of n2+n3+m3+m4 is 5 or less. The average value of n2+n3+m3+m4 may be 2 or more. The number of structural units of oxyethylene groups or oxypropylene groups represents an integer value in a single molecule, and represents a rational number that is the average value in an aggregate of multiple molecules.

[0078] Commercially available bifunctional (meth)acrylate compounds include NK Ester (registered trademark) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, NOD-N, and DOD-N, NPG, 701, 2G, 3G, 4G, 9G, 14G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BP E-1300N, NK Oligo (registered trademark) UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA (manufactured by Shin-Nakamura Chemical Co., Ltd.), LightAction Related (registered trademark) 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, 1.9ND-A, DCP-A, BP-4EAL, BP-4PA, HPP-A, Light Ester G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.), Fancryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129 AS, FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Resonac), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel Allnex Co., Ltd.), SR212, SR213, SR230, SR238F, SR259, SR268,SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema), KAYARAD (registered trademark) Examples of such polyglycerides include NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0079] Examples of the tri- or higher functional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin penta(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0080] Examples of tri- or higher functional (meth)acrylate compounds include compounds obtained by forming a (meth)acrylate from (meth)acrylic acid and an alcohol having, as a central skeleton, three or more groups to which alkylene oxide groups can be added within the molecule, and having an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group added to the central skeleton. Examples of such compounds include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified diglycerin tetra(meth)acrylate, alkylene oxide-modified triglycerin penta(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified isocyanuric acid tri(meth)acrylate. Preferred alkylene oxide groups include ethylene oxide, propylene oxide, and butylene oxide.

[0081] The tri- or higher functional (meth)acrylate compound may contain alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate and / or alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate from the viewpoint of excellent developability.

[0082] Commercially available tri- or higher functional (meth)acrylate compounds include NK Ester (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, and A-9550. A-DPH-12E, TPOA-50, NK Oligo (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) TMP-A, cPE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (manufactured by Resonac Co., Ltd.), TMPTA, EBECRYL 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel-Allnex Co., Ltd.), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema), KAYARAD (registered trademark) GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, and DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.).

[0083] The content of component (B) is preferably 30% by mass or more, more preferably 35% by mass or more, based on the total solid content of the photosensitive resin composition, from the viewpoint of excellent sensitivity, tackiness, and followability. Furthermore, from the viewpoint of excellent edge fusion resistance, tackiness, and resolution, the content is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 42% by mass or less. "Edge fusion resistance" refers to the tendency of resist to protrude from the edge of a photosensitive resin laminate roll during storage, and the smaller the amount of protrusion, the better. Furthermore, "tackiness" refers to the adhesiveness of the photosensitive resin composition.

[0084] From the viewpoint of excellent edge fusion resistance, tackiness, and resolution, the ratio of the content of component (B) to the content of component (A) (value of the content of component (B) / the content of component (A)) based on the total solid content of the photosensitive resin composition is preferably 1.2 or less, more preferably 1.1 or less, even more preferably 1.0 or less, and particularly preferably 0.9 or less. Furthermore, this ratio is preferably 0.5 or more, more preferably 0.55 or more, and particularly preferably 0.6 or more.

[0085] The number of ethylenically unsaturated double bonds per 100 g of solids in the photosensitive resin composition is preferably 0.1 to 0.3 mol. When this number is 0.1 mol or more, when a water washing step is performed after development, elution of the photosensitive resin component from the cured resist pattern during the water washing step, and thus contamination of the water washing step, is easily prevented. Furthermore, when this number is 0.3 mol or less, when a water washing step is performed after development, chipping and detachment of the cured resist pattern during the water washing step are less likely to occur, and therefore contamination of the water washing step is easily prevented. From the same viewpoint, the number is more preferably 0.1 to 0.25 mol, even more preferably 0.1 to 0.2 mol, and particularly preferably 0.11 to 0.2 mol or 0.11 to 0.15 mol.

[0086] The number of ethylenically unsaturated double bonds per 100 g of solid content of the photosensitive resin composition is preferably 0.1 mol or more, more preferably 0.11 mol or more, even more preferably 0.12 mol or more, particularly preferably 0.13 mol or more, and is preferably 0.3 mol or less, more preferably 0.28 mol or less, even more preferably 0.25 mol or less, particularly preferably 0.22 mol or less, 0.20 mol or less, 0.18 mol or less, or 0.15 mol or less.

[0087] <Component (C): Photopolymerization Initiator> The component (C) is a compound that generates radicals when exposed to exposure light (actinic rays) and promotes the radical polymerization of the component (B).

[0088] Examples of the component (C) include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene or anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.

[0089] The content of component (C) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to transmit light sufficiently to the bottom of the photosensitive resin layer even with a small amount of exposure, and ultimately making it easier to achieve high resolution.

[0090] From the viewpoint of excellent sensitivity, resolution, and adhesion, it is preferable that component (C) contains a hexaarylbiimidazole compound. In this case, from the same viewpoint, the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%.

[0091] As component (C), it is preferable to use a hexaarylbiimidazole compound in combination with a photopolymerization initiator other than the hexaarylbiimidazole compound (for example, an aromatic ketone compound). In this case, the content of the photopolymerization initiator other than the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.5 mass% or less, more preferably 0.01 to 0.4 mass%. In this case, the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%.

[0092] The hexaarylbiimidazole compound includes a dimer of a compound having a lophine structure (lophine dimer), that is, a dimer of 2,4,5-triarylimidazole.Examples of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2 , 2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)- Biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis Examples thereof include tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.Of these, the hexaarylbiimidazole compound is preferably a dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole, from the viewpoint of excellent sensitivity, resolution, and adhesion.

[0093] Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine, etc. Among these, N-phenylglycine is preferred as the N-aryl-α-amino acid compound because of its excellent sensitizing effect.

[0094] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0095] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.

[0096] Examples of anthracene or anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 10-phenyl-9-anthraceneboronic acid, etc. Among these, as anthracene or anthracene derivatives, from the viewpoint of excellent sensitization effect and adhesion, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0097] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, etc. Commercially available acetophenone compounds include the Irgacure (registered trademark) series (manufactured by BASF: Irgacure-907, Irgacure-369, Irgacure-379, etc.).

[0098] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. Commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by BASF).

[0099] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. Examples of dialkyl ketal compounds include benzil dimethyl ketal and benzil diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0100] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF).

[0101] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred from the viewpoint of excellent sensitivity, resolution, availability, etc. As the pyrazoline derivative, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, etc. are preferred from the viewpoint of excellent adhesion and ease of forming a highly rectangular resist pattern.

[0102] Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0103] Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds. Of these, tribromomethylphenylsulfone is preferred as the halogen compound.

[0104] <Component (D): Dye> Component (D) is a dye such as a leuco dye or a base dye. Note that the "dye" here is soluble in water or an organic solvent and differs from a "pigment" which is poorly soluble in or insoluble in water or an organic solvent. This type of pigment is often contained as a colorant in, for example, a photosensitive resin composition for a color filter.

[0105] By including a leuco dye as component (D), the photosensitive resin laminate tends to have excellent color development in unexposed areas and excellent peeling properties of the resist pattern. Examples of leuco dyes include leuco crystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide. Of these, leuco crystal violet is preferred as the leuco dye.

[0106] The content of the leuco dye is preferably 0.01 to 2 mass %, more preferably 0.1 to 1.5 mass %, based on the total solid content of the photosensitive resin composition. By adjusting the content of the leuco dye within this range, good color development and excellent sensitivity can be easily achieved.

[0107] Examples of base dyes include Diamond Green [CAS Number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2]. Among these, Diamond Green is preferred as the base dye from the viewpoints of excellent coloring properties, hue stability, and exposure contrast.

[0108] The content of the base dye is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total solid content of the photosensitive resin composition. The content of the base dye is preferably equal to or greater than the above lower limit from the viewpoint of obtaining good colorability, and is preferably equal to or less than the above upper limit from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0109] Component (E): Other Components The photosensitive resin composition may contain, as desired, antioxidants, stabilizers, sensitizers, plasticizers, etc. Other components are components other than the above (A) to (D).

[0110] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by ADEKA under the trade name of TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., manufactured by ADEKA under the trade name of 2112), tris(mononylphenyl)phosphite (e.g., manufactured by ADEKA under the trade name of 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA under the trade name of 329K). These can be used alone or in combination of two or more.

[0111] The content of the antioxidant in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass. From the viewpoints of achieving good hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, the content of the antioxidant is preferably equal to or greater than the above-mentioned lower limit. On the other hand, from the viewpoints of achieving good hue stability while suppressing the color development of the resist pattern and improving adhesion, the content of the antioxidant is preferably equal to or less than the above-mentioned upper limit.

[0112] The stabilizer can be used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used alone or in combination of two or more.

[0113] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (e.g., aluminum salt with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosamine. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], phenothiazine, tert-butylcatechol, and / or aluminum salt with 3 moles of nitrosophenylhydroxylamine added are preferred. These may be used alone or in combination of two or more.

[0114] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These compounds can be used alone or in combination of two or more.

[0115] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %. From the viewpoint of imparting good storage stability to the photosensitive resin composition, the total content is preferably equal to or greater than the above-mentioned lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the total content is preferably equal to or less than the above-mentioned upper limit.

[0116] [Protective Film] The photosensitive resin laminate of this embodiment may further include a protective film. The temporary support, the photosensitive resin layer, and the protective film may be laminated in this order. The protective film can be laminated on the photosensitive resin layer side of the laminate having the temporary support and the photosensitive resin layer, and functions as a cover to protect the photosensitive resin layer.

[0117] When the adhesion between the photosensitive resin layer and the protective film is sufficiently weaker than the adhesion between the photosensitive resin layer and the temporary support, the protective film is easily peeled off from the photosensitive resin layer. Examples of the protective film include polyethylene film, polypropylene film, oriented polypropylene film, and polyester film. A release layer may be provided on the surface of the protective film.

[0118] The thickness of the protective film is preferably 10 to 100 μm, more preferably 10 to 50 μm. Examples of the protective film include Alphan (registered trademark) EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Torayfan (registered trademark) KW37, 2578, 2548, 2500, and YM17S, Therapeel (registered trademark) PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, and SY (all manufactured by Toray Industries, Inc.), and GF-18, GF-818, and GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0119] [Photosensitive resin laminate roll] Another aspect of the present embodiment is a photosensitive resin laminate roll formed by winding the photosensitive resin laminate described above. The photosensitive resin laminate constituting the roll may be long and may have a winding core at the center of the roll.

[0120] [Method for forming a resist pattern] Another aspect of this embodiment is a method for forming a resist pattern (production method) using the photosensitive resin laminate. The production method includes the following steps: a step of laminating a photosensitive resin layer in the photosensitive resin laminate on a substrate (lamination step); a step of exposing the photosensitive resin layer (exposure step); and a step of developing the photosensitive resin layer after exposure (development step). A resist pattern is produced through these steps.

[0121] (Lamination Step) In the lamination step, the photosensitive resin layer of the photosensitive resin laminate is laminated on a substrate. Specifically, in the lamination step, if the photosensitive resin laminate includes a protective film, the protective film is peeled off from the photosensitive resin laminate to expose the photosensitive resin laminate, and the photosensitive resin layer is then heat-pressed onto the surface of the substrate using a laminator, laminating once or multiple times. Examples of materials for the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is generally 40 to 160°C. Heat-pressure bonding can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rolls several times. Heat-pressure bonding may be performed in a reduced pressure environment, if desired.

[0122] (Exposure Step) In the exposure step, the photosensitive resin layer is exposed. Specifically, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. The exposure can be performed after peeling off the temporary support, if desired. In the exposure step, when exposure is performed through a photomask, the exposure amount may be determined by the illuminance of the light source and the exposure time, and may also be measured using an actinometer.

[0123] In the exposure step, direct imaging exposure may be performed. In direct imaging exposure, the photosensitive resin layer is exposed by a direct imaging device without using a photomask. A semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used as the light source. When the imaging pattern is controlled by a computer, the exposure dose may be determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0124] In the exposure step, the method of irradiating the exposure light is preferably at least one method selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and more preferably projection exposure or direct imaging exposure.

[0125] The exposure step may include a step of heating the substrate and the exposed photosensitive resin layer after the exposure and before the development step (heating step). In this heating step, the heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By carrying out the heating step, excellent resolution and adhesion tend to be obtained. Heating may be carried out using an infrared or far-infrared heating furnace, hot air, a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like.

[0126] The time elapsed from the exposure step to the heating step, more precisely, the time from the completion of exposure (i.e., the stop of exposure) to the start of heating, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The time from the start of heating to the stop of heating is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0127] (Development step) In the development step, the photosensitive resin layer after exposure is developed. Specifically, in the development step, the unexposed or exposed portions of the photosensitive resin layer after exposure are removed with a developer using a developing device. Subsequently, the unexposed or exposed portions are removed using a developer containing or consisting of an alkaline aqueous solution, thereby obtaining a resist pattern. Note that, if there is a temporary support on the photosensitive resin layer after exposure, this is peeled off from the photosensitive resin layer before the above development is carried out.

[0128] The alkaline aqueous solution in the developer is Na ２ CO ３ , K. ２ CO ３ The alkaline aqueous solution is selected depending on the properties of the photosensitive resin layer. For example, an aqueous solution of Na with a concentration of 0.2 to 2% by mass is preferable. ２ CO ３An aqueous solution is used. The developer may contain a surfactant and / or an antifoaming agent, and may also contain a small amount of an organic solvent to promote development. In the development step, the temperature of the developer is preferably kept constant within the range of 20 to 40°C.

[0129] The developing step preferably includes, after development, a step of washing the substrate and the resist pattern with water (water washing step). The water washing step makes it easy to remove the developer remaining on the substrate and the resist pattern. Examples of water used for washing in the water washing step include pure water and industrial water. From the viewpoint of achieving excellent resolution and facilitating the formation of a resist pattern with high rectangularity, a polyvalent metal salt may be mixed into the water for washing at a concentration of 0.001 to 1% by mass in accordance with the properties of the photosensitive resin layer. Examples of polyvalent metal salts include MgSO ４ In the washing step, the temperature of the washing water is preferably kept constant within the range of 20 to 40°C.

[0130] The development step may include a step of heating the substrate and the formed resist pattern after the development, or after the development and the water washing. In this heating step, the heating temperature is preferably 60 to 300°C. By carrying out this heating step, the chemical resistance of the resist pattern is easily improved. Heating may be carried out using an infrared or far-infrared heating furnace, hot air, or the like.

[0131] [Method for producing a conductive pattern] Another aspect of this embodiment is a method for producing a conductive pattern using the photosensitive resin laminate described above. This method includes the following steps: a step of laminating a photosensitive resin layer of the photosensitive resin laminate described above on a substrate, a step of exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a resist pattern, and a step of etching or plating the substrate on which the resist pattern has been formed (a conductive pattern formation step).

[0132] In the conductive pattern forming step, the substrate on which the resist pattern has been formed is subjected to etching or plating treatment. Specifically, in the conductive pattern forming step, a conductive pattern is formed on the surface (e.g., copper surface) of the substrate (e.g., a metal plate, a metal-coated insulating plate, etc., as described above) exposed by development using a known etching method or plating method.

[0133] The conductive pattern forming step may include a step of, after forming the conductive pattern, peeling off the resist pattern remaining on the substrate from the substrate (peeling step). By removing the resist pattern from the substrate in the peeling step, a wiring board (e.g., a printed wiring board) having a desired conductive pattern is obtained.

[0134] In the stripping step, an aqueous solution having a stronger alkalinity than the developer is used. Examples of the alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution") include an aqueous solution of NaOH or KOH with a concentration of 2 to 5% by mass, and also an aqueous solution of an organic amine. The stripping solution may contain a small amount of a water-soluble solvent. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably within the range of 40 to 70°C.

[0135] In this embodiment, the photosensitive resin laminate can be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGAs) and chip size packages (CSPs); the manufacture of tape substrates such as chip-on-film (COFs) and tape automated bonding (TABs); the manufacture of semiconductor bumps; and the manufacture of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.

[0136] The conductive pattern forming step provides a method for manufacturing a wiring board, which is another aspect of the present embodiment. Such a wiring board has a conductive pattern formed by the conductive pattern forming step.

[0137] Unless otherwise specified, the values ​​of the parameters described above in this specification are measured in accordance with the measurement methods in the examples described below.

[0138] The present embodiment will be described below with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples. Regarding the examples and comparative examples, various productions, measurements, evaluations, etc. were carried out by the following methods.

[0139] Example 1 Synthesis of Component (A) As shown in the table below, predetermined monomers (copolymerization components) were mixed with azobisisobutyronitrile in predetermined amounts (parts by mass) to prepare solution (a)-1. 140 g of methyl ethyl ketone and 40 g of ethanol were placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and the mixture was stirred while blowing nitrogen gas into the flask and heated to 80°C. Next, solution (a)-1 was added dropwise to the flask at a constant rate over 4 hours, followed by stirring at 80°C for 2 hours.

[0140] Next, 0.5 parts by mass of azobisisobutyronitrile was dissolved in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol to prepare solution (b). 50.5 g of solution (b) was added dropwise to the flask at a constant rate over 10 minutes, followed by stirring at 80°C for 3 hours. The mixture in the flask was then heated to 90°C over 30 minutes, and then kept at 90°C for 2 hours with stirring. After this, stirring was stopped and the mixture was cooled to room temperature (25°C). This yielded solutions of alkali-soluble polymers A1 to A9. The weight-average molecular weights (Mw) of the alkali-soluble polymers A1 to A9 are shown in the table below.

[0141] The weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated by conversion using a calibration curve of standard polystyrene. The GPC conditions were as follows: (GPC conditions) Pump: PU-4580 manufactured by JASCO Degasser: DG-2080-53 Column oven: CO-1560 Columns: Total of four columns: KF-807, KF-806M x 2, KF-802.5 manufactured by Shodex Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 1.00 mL / min Detector: RI-1560 manufactured by JASCO

[0142] <Preparation of Photosensitive Resin Layer and Photosensitive Resin Laminate> The components shown in the table below were mixed in the amounts shown in the table below (the number for each component is the amount of solid content (unit: parts by mass)). Methyl ethyl ketone measured to give a solid content concentration of 60% was then added and thoroughly stirred to obtain a prepared solution of a photosensitive resin composition. The amounts (parts by mass) shown in the table below are the mass of non-volatile content (solid content).

[0143] A 16 μm-thick polyethylene terephthalate film (QS71, manufactured by Toray Industries, Inc.) was prepared as a support film. The above-mentioned preparation was uniformly applied to the surface of the support film using a bar coater, and then dried for 2 minutes and 30 seconds in a dryer at 95° C. This resulted in a photosensitive resin laminate having a 25 μm-thick photosensitive resin layer on the support film.

[0144] Next, a 19 μm thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) was attached as a protective film to the surface of the photosensitive resin layer opposite to the support film. Here, the laminate of the support film, the photosensitive resin layer, and the protective film was treated as a photosensitive resin laminate.

[0145] <Preparation of Photosensitive Resin Roll> The obtained photosensitive resin laminate was rolled by a conventional method to prepare a photosensitive resin roll.

[0146] <Surface preparation of substrate> The surface of a copper-clad laminate having a total thickness of 0.4 mm and a rolled copper foil having a thickness of 18 μm on the surface was prepared by subjecting the surface to 10 mass % H ２SO ４ The substrate was washed with an aqueous solution and then with pure water.

[0147] <Lamination Step> The washed copper-clad laminate was preheated to 50°C. While peeling off the protective film from the photosensitive resin laminate, the preheated copper-clad laminate was laminated at a roll temperature of 105°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) so that the photosensitive resin layer was in contact with the surface of the preheated copper-clad laminate. This resulted in a substrate for evaluation. The air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0148] <Exposure Step> Two hours after lamination, the evaluation substrate was exposed to light at a wavelength of 365 nm using a predetermined mask pattern for projection exposure with a projection exposure machine (UX-2003SM-AGG01, manufactured by Ushio Inc.).

[0149] <Heating Step> One minute after exposure, the evaluation substrate was heated for 30 seconds using a constant temperature incubator (manufactured by Yamato Scientific Co., Ltd., DKM600) set at 60°C.

[0150] <Developing Step> The support film was peeled off from the photosensitive resin layer. Thereafter, the photosensitive resin layer was developed with 1% by mass NaCl solution at 30°C under a spray pressure of 0.15 Pa using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer). ２ CO ３ Development was carried out using an aqueous solution for a predetermined time (development spray step). Thereafter, pure water was sprayed onto the photosensitive resin layer for a predetermined time to perform water rinsing (water rinsing spray step). This resulted in the formation of a resist pattern on the evaluation substrate. The development spray and water rinsing spray times were each set to twice the shortest development time described below.

[0151] [Examples 2 to 24] and [Comparative Examples 1 to 6] Component (A), a photosensitive resin layer, a photosensitive resin laminate, and a photosensitive resin roll were prepared, and resist patterns were formed in the same manner as in Example 1, except that the contents shown in the table below were changed as shown in the table below.

[0152] [Evaluation] <Developability (shortest development time: sec)> The above-mentioned development process was carried out on the evaluation substrate after the lamination process, and the shortest time required for the photosensitive resin layer to completely dissolve was measured visually, and this time was taken as the shortest development time. Using the measured shortest development time, the developability was evaluated based on the following criteria. In this example, the shorter the shortest development time, the better the developability. A shortest development time of 20 seconds or less was considered to be acceptable, and a shortest development time of 18 seconds or less was considered to be particularly good.

[0153] Sensitivity (optimum exposure: mJ / cm ２ A mask pattern with a line width (L) / space width (S) (hereinafter abbreviated as "L / S") ratio of 8 / 8 (unit: μm) was prepared. Then, a pattern was formed on an evaluation substrate by carrying out the above-mentioned exposure step, heating step, and development step using this mask pattern. Then, the exposure dose (10 mJ / cm) at which the line width of the formed pattern was closest to 8 μm was determined. ２ Spacing) (unit: mJ / cm ２ ) was derived. The smaller this exposure dose (optimum exposure dose), the higher the sensitivity was considered to be. The line width of the pattern was measured based on an observation image obtained at a magnification of 100 times using an optical microscope.

[0154] FIG. 1 is a plan view showing an example of the configuration of a mask pattern for this evaluation. In the figure, in a region 100 of the photomask, regions that transmit the exposure light are indicated by the reference numeral 10 (transmissive region 10), and regions that do not transmit the exposure light are indicated by the reference numeral 1 (light-shielding region 1). In the figure, the light-shielding region 1 is indicated by diagonal lines. The transparent region 10 has a predetermined width and extends in the x direction. A plurality of such transparent regions 10 are arranged in the width direction (y direction) at predetermined intervals. In this example, since the unexposed portions of the photosensitive resin layer are removed through the development process described above, it is theoretically expected that, based on the mask pattern shown in the figure, a resist pattern having an L / S corresponding to the width of the transparent region 10 (L: line) and the width of the light-shielding region 1 (S: space) will be formed.

[0155] <Adhesion> Evaluation was performed using a photomask having a mask pattern with an L / S ratio of x / 3x (x = 1 to 20 (varying in 0.5 μm intervals)) (unit: μm). That is, the evaluation substrate obtained through the above surface preparation and lamination processes was exposed to light at an optimal exposure dose through the photomask. Thereafter, the substrate was subjected to the above heating process and development process to form a resist pattern with a line length of 7 mm.

[0156] 2 is a plan view showing an example of the configuration of a mask pattern for this evaluation. In the figure, a region 100A of the photomask shows a transmissive region 10 and a light-shielding region 1. In the region 100A shown in the figure, the value of L / S is different from that of the region 100 shown in FIG.

[0157] The formed resist pattern was observed under an optical microscope at 100x magnification. In the observed image, lines (exposed portions) formed without meandering or chipping were detected, and their minimum line width (L1) was used to evaluate adhesion based on the following criteria. In this example, the smaller the minimum line width (L1), the better the adhesion. A minimum line width (L1) of 6.0 μm or less was considered acceptable, and a minimum line width (L1) of 5.0 μm or less was considered particularly good.

[0158] <Resolution> Evaluation was performed using a photomask having a mask pattern with an L / S ratio of x / x (x = 1 to 20 (varying in 0.5 μm intervals)) (unit: μm). That is, the evaluation substrate obtained through the above surface preparation and lamination processes was exposed to light at an optimal exposure dose through the photomask. Thereafter, the substrate was subjected to the above heating process and development process to form a resist pattern with lines (exposed portions) 7 mm long.

[0159] FIG. 3 is a plan view showing an example of the configuration of a mask pattern for this evaluation. In the figure, a transmissive region 10 and a light-shielding region 1 are shown in region 100B of the photomask. The light-shielding region 1 has a predetermined width and extends in the x direction, and a plurality of such light-shielding regions 1 are arranged in the width direction (y direction) at predetermined intervals. Based on the mask pattern of FIG. 3, it is theoretically expected that a resist pattern having an L / S corresponding to the width of the transmissive region 10 (L: line) and the width of the light-shielding region 1 (S: space) will be formed, similar to the case based on the mask pattern of FIG. 1.

[0160] The formed resist pattern was observed under an optical microscope at 100x magnification. In the observed image, lines (exposed portions) without meandering or chipping and with spaces (unexposed portions) formed without resist residue were detected, and the resolution was evaluated using the minimum line width (L2) based on the following criteria. In this example, the smaller the minimum line width (L2), the better the resolution. A minimum line width (L2) of 7.0 μm or less was considered acceptable, and a minimum line width (L2) of 6.0 μm or less was considered particularly good.

[0161] <Fine Line Strength> Evaluation was performed using a photomask having a mask pattern with L / S of x / 200x {x = 1 to 20 (varied in 0.5 μm intervals)} (unit: μm). That is, the evaluation substrate obtained through the above surface preparation and lamination processes was exposed to light at an optimal exposure dose through the photomask. Thereafter, the substrate was subjected to the above heating process and development process to form a resist pattern with lines (exposed portions) 7 mm long.

[0162] 4 is a plan view showing an example of the configuration of a mask pattern for this evaluation. In the figure, a region 100C of the photomask shows a transmissive region 10 and a light-shielding region 1. In the region 100C shown in the figure, the value of L / S is different from that of the region 100 shown in FIG.

[0163] The formed resist pattern was observed under an optical microscope at 100x magnification. In the observed image, lines (exposed portions) formed without meandering or chipping were detected, and their minimum line width (L3) was used to evaluate the fine line strength based on the following criteria. In this example, the smaller the minimum line width (L3), the better the fine line strength. A minimum line width (L3) of 7.0 μm or less was considered acceptable, and a minimum line width (L3) of 6.0 μm or less was considered particularly good.

[0164] The results of the above are shown in the table below. It was confirmed that in all examples, wiring boards having conductor patterns could be produced by conventional methods.

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] As can be seen from the table, it was confirmed that the examples provided a photosensitive resin laminate that achieved a balance between the developability of the photosensitive resin layer and the strength of the resist pattern in addition to the adhesion and resolution of the resist pattern, and that satisfied all of these requirements.

[0171] By using the photosensitive resin laminate of the present invention, it is possible to provide a photosensitive resin laminate that satisfies all of the following requirements: adhesion and resolution of the resist pattern, as well as developability of the photosensitive resin layer and strength of the resist pattern. Such a photosensitive resin laminate can be widely used as a photosensitive resin laminate for forming resist patterns on printed wiring boards, etc.

[0172] 1: Light-shielding area 10: Transmitting area 100, 100A to 100C: Areas in the photomask L: Line S: Space

Claims

1. A photosensitive resin laminate having a temporary support and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator; and the (A) alkali-soluble polymer contains an (A-1) copolymer having the following structural units: (a1) a structural unit derived from a compound having two or more alcoholic hydroxyl groups and a (meth)acryloyl group, and (a3) ​​a structural unit derived from styrene, a styrene derivative, or benzyl (meth)acrylate.

2. The photosensitive resin laminate according to claim 1, wherein, for the (a1) structural unit derived from the compound, the compound is glycerin mono(meth)acrylate.

3. The photosensitive resin laminate according to claim 1 or 2, wherein the content of the (a1) structural unit in the component (A) is 0.5 to 30 mass %.

4. The photosensitive resin laminate according to claim 1 or 2, wherein the content of the (a1) structural unit in the component (A) is 1.0 to 10 mass %.

5. The photosensitive resin laminate according to claim 1 or 2, wherein the content of the (a1) structural unit in the component (A) is 1.0 to 5.0 mass %.

6. The photosensitive resin laminate according to claim 1 or 2, wherein the (A-1) copolymer further comprises the following structural unit: (a2) a structural unit derived from a compound having a carboxyl group and an ethylenically unsaturated bond.

7. The photosensitive resin laminate according to claim 1 or 2, wherein the content of the (a3) ​​structural unit in the component (A) is 10 mass% or more.

8. The photosensitive resin laminate according to claim 1 or 2, wherein the content of the (a3) ​​structural unit in the component (A) is 20 to 70 mass %.

9. The photosensitive resin laminate according to claim 1 or 2, wherein the weight average molecular weight of the component (A) is 10,000 to 60,000.

10. The photosensitive resin laminate according to claim 1 or 2, wherein the component (B) contains a compound having two ethylenically unsaturated bonds in one molecule.

11. The photosensitive resin laminate according to claim 1 or 2, wherein the component (C) contains a hexaarylbiimidazole compound.

12. A photosensitive resin laminate described in claim 1 or 2, wherein the total content of the (A) component, the (B) component, and the (C) component is 90 mass% or more based on the total solid content of the photosensitive resin composition.

13. The photosensitive resin laminate according to claim 1 or 2, further comprising a protective film.

14. A photosensitive resin laminate for forming a conductor pattern, comprising the photosensitive resin laminate according to claim 1 or 2.

15. A photosensitive resin laminate roll, formed by winding the photosensitive resin laminate according to claim 1 or 2.

16. A method for forming a resist pattern comprising the steps of: laminating a photosensitive resin layer in the photosensitive resin laminate according to claim 1 or 2 on a substrate; exposing the photosensitive resin layer; and developing the exposed photosensitive resin layer to form a resist pattern.

17. A method for manufacturing a wiring board having a conductor pattern, comprising the steps of: laminating a photosensitive resin layer on a substrate in the photosensitive resin laminate according to claim 1 or 2; exposing the photosensitive resin layer; and developing the photosensitive resin layer after exposure to light to form a resist pattern. The method comprises the steps of etching or plating the substrate on which the resist pattern has been formed to form a conductor pattern on the substrate.

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