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

Abstract

To provide a photosensitive resin laminate with excellent resist pattern release properties, developability, and peelability, a resist pattern formation method, and a manufacturing method for a wiring board. [Solution] The photosensitive resin composition comprises: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; wherein component (A) includes a copolymer containing monomer components as constituent units, and when the glass transition temperature of the copolymer calculated by Fox's formula is x (°C) and the acid value of the copolymer is y (mgKOH / g), x ≥ 120 and 3y / 7 + 60

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin laminate, a method for forming a resist pattern, and a method for manufacturing a wiring board. [Background technology]

[0002] Printed circuit boards and semiconductor package substrates are generally manufactured using photolithography processes. Photolithography is a method of forming a desired wiring pattern on a substrate through the following steps: First, a layer containing a photosensitive resin composition is formed on the substrate, and a resist pattern is formed by pattern exposure and development of the coating film. Next, a conductor pattern is formed by etching or plating. After that, the desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.

[0003] Generally, in photolithography processes, resist patterns are formed by methods such as coating a solution of a photosensitive resin composition onto a substrate and drying it, or by laminating a photosensitive resin layer of a dry film resist (a photosensitive resin laminate including a photosensitive resin layer and a support film) onto a substrate.

[0004] In the formation of wiring patterns on printed circuit boards and semiconductor package substrates, photosensitive resin laminates are often used. In the production and use of photosensitive resin laminates, the properties and productivity of the resist pattern, such as its permeability, developability, flexibility, resolution, adhesion, and peelability, are important, as are the type, combination, and content of alkali-soluble polymers, compounds having ethylenically unsaturated bonds, and photopolymerization initiators.

[0005] For example, Patent Document 1 discloses a photosensitive resin composition containing a binder polymer, a photopolymerizable compound containing a polyfunctional monomer having two or more reactive groups that react with radicals and a total of 2 to 40 oxyethylene groups and / or oxypropylene groups, a photopolymerization initiator, and an anthracene-based sensitizer. For example, in Patent Document 2, there is disclosed a pattern forming material comprising a support and at least a photosensitive layer on the support, the photosensitive layer containing at least a binder, a polymerizable compound, and a photopolymerization initiator, the polymerizable compound containing a polymerizable compound (a-1) having a bisphenol skeleton and a polymerizable compound (a-2) having four or more reactive groups in the molecule and a molecular weight of 700 or more.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the photosensitive resin compositions and the like described in Patent Documents 1 to 4 above had room for improvement in terms of the peeling property, developability, and stripping property of the resist pattern.

[0008] An object of the present invention is to provide a photosensitive resin laminate excellent in the peeling property, developability, and stripping property of a resist pattern, a method for forming a resist pattern, and a method for manufacturing a wiring board.

Means for Solving the Problems

[0009] The present invention is as follows.

[0010] [1] A photosensitive resin laminate comprising a support film and a photosensitive resin layer containing a photosensitive resin composition, The aforementioned photosensitive resin composition comprises the following components: (A) Alkali-soluble polymers; (B) Compounds having ethylenically unsaturated bonds; and (C) Polymerization initiator; Includes, The aforementioned component (A) includes a copolymer containing monomer components as constituent units, When x (°C) is the glass transition temperature (Tg) of the copolymer calculated using Fox's formula, and y (mgKOH / g) is the acid value of the copolymer, then x ≥ 120 and 3y / 7 + 60 <xであり、 The aforementioned component (B) consists of the following components: (b-1) Di(meth)acrylate compounds containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule; and (b-2) Tetrafunctional (meth)acrylate compounds; Includes, The (C) component is a photosensitive resin laminate containing a compound with a biimidazole structure in an amount of 5.0 to 10% by mass relative to the total solid content mass of the photosensitive resin composition. [2] The photosensitive resin laminate according to [1], wherein the component (A) has an acid value y of 180 or less (y ≤ 180). [3] The photosensitive resin laminate according to [1], wherein the component (A) has an acid value y of 160 or less (y ≤ 160). [4] The photosensitive resin laminate according to any one of [1] to [3], wherein the copolymer contains a constituent unit derived from (meth)acrylic acid as the monomer component, and the content of the constituent unit derived from (meth)acrylic acid in component (A) is 10% by mass or more and less than 25% by mass. [5] The photosensitive resin laminate according to any one of [1] to [4], wherein the copolymer contains a structural unit derived from a compound having an aromatic ring as the monomer component, and the content of the structural unit derived from the compound having an aromatic ring in component (A) is 30% by mass or more and 80% by mass or less. [6] The photosensitive resin laminate according to any one of [1] to [5], wherein the copolymer contains a constituent unit derived from methyl methacrylate as the monomer component, and the content of the constituent unit derived from methyl methacrylate in component (A) is 10% by mass or more and less than 40% by mass. [7] The copolymer comprises a structural unit derived from dicyclopentanyl methacrylate, and is a photosensitive resin laminate according to any one of [1] to [6]. [8] The copolymer is It contains constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, and constituent units derived from styrene, A photosensitive resin laminate according to any one of [1] to [7], wherein the total proportion of the content of the constituent units derived from methacrylic acid, the constituent units derived from methyl methacrylate, and the constituent units derived from styrene is 90% by mass or more, and the content of the constituent units derived from methacrylic acid is 18% by mass or more and 25% by mass or less. [9] The copolymer is It contains constituent units derived from methacrylic acid and constituent units derived from dicyclopentanyl methacrylate, A photosensitive resin laminate according to any one of [1] to [8], wherein the content of constituent units derived from methacrylic acid is 15% by mass or more and 30% by mass or less, and the content of constituent units derived from dicyclopentanyl methacrylate is 5% by mass or more and 45% by mass or less.

[10] A photosensitive resin laminate according to any one of [1] to [9], wherein the (b-1) component is contained in an amount of 10 to 35% by mass relative to the total solid content mass of the photosensitive resin composition.

[11] The photosensitive resin laminate according to any one of [1] to

[10] , wherein the (b-1) component comprises a compound having a bisphenol A structure.

[12] The photosensitive resin laminate according to any one of [1] to

[11] , wherein the (b-1) component is a compound having four or more of the ethylene oxide structure and the propylene oxide structure in one molecule.

[13] A photosensitive resin laminate according to any one of [1] to

[12] , wherein the (b-2) component is contained in an amount of 5 to 20% by mass relative to the total solid content mass of the photosensitive resin composition.

[14] The photosensitive resin laminate according to any one of [1] to

[13] , wherein the (b-2) component comprises a (meth)acrylate compound with five or more functionalities.

[15] The photosensitive resin laminate according to any one of [1] to

[14] , wherein the ratio of the solid content mass of component (b-1) to component (b-2), (b-1):(b-2), is in the range of 4:6 to 8:2.

[16] The photosensitive resin laminate according to any one of [1] to

[15] , wherein the total content of component (b-1) and component (b-2) is 50% by mass or more and 100% by mass or less based on the total mass of component (B).

[17] The aforementioned component (B) is further, A photosensitive resin laminate according to any one of [1] to

[16] , comprising ethoxylated bisphenol A di(meth)acrylate having an average of 2 to 30 ethylene oxide structures per molecule.

[18] The photosensitive resin laminate according to any one of [1] to

[17] , further comprising an anthracene derivative for component (C).

[19] The photosensitive resin laminate according to

[18] , wherein the content of the anthracene derivative is 0.01% by mass or more and 0.5% by mass or less.

[20] A method for forming a resist pattern using a photosensitive resin laminate described in any of [1] to

[19] , comprising the following steps: Lamination process for depositing a photosensitive resin layer onto a substrate; An exposure step of exposing the photosensitive resin layer; and A developing step for developing and removing the unexposed portion of the photosensitive resin layer; A method for forming a resist pattern, including [a specific component]. [twenty one] A method for manufacturing a wiring board using a photosensitive resin laminate as described in any of [1] to

[19] , comprising the following steps: Lamination process for depositing a photosensitive resin layer onto a substrate; An exposure step of exposing the photosensitive resin layer; A developing step to develop and remove the unexposed portion of the photosensitive resin layer to form a resist pattern; A conductor pattern forming step involves etching or plating the substrate on which the resist pattern is formed to form a conductor pattern; and A peeling step for peeling the resist pattern from the substrate; A method for manufacturing a wiring board, including the method described above. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a photosensitive resin laminate comprising a photosensitive resin layer containing a photosensitive resin composition that has excellent resist pattern release properties, developability, and peelability, a method for forming a resist pattern, and a method for manufacturing a wiring board. [Modes for carrying out the invention]

[0012] The following describes in detail an exemplary embodiment of the present invention (hereinafter abbreviated as "this embodiment"). The present invention is not limited to this embodiment and can be implemented in various modifications within the scope of its gist. In this specification, the upper and lower limits of each numerical range can be arbitrarily combined. Furthermore, in this embodiment, the upper or lower limit of a numerical range can be replaced with the value shown in the example. In this specification, numerical ranges indicated using "~" include both upper and lower limits. In the following explanation, the term "process" refers not only to independent processes but also to processes that cannot be clearly distinguished from others, as long as their function is achieved.

[0013] In the present specification, “(meth)acrylic acid” means acrylic acid or methacrylic acid, “(meth)acryloyl group” means acryloyl group or methacryloyl group, and “(meth)acrylate” means “acrylate” or “methacrylate”.

[0014] <Photosensitive resin laminate> In one aspect, the photosensitive resin laminate of the present embodiment includes a support film and a photosensitive resin layer containing a photosensitive resin composition. And the photosensitive resin composition constituting the photosensitive resin laminate provided by one aspect of the present embodiment, in particular, (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a polymerization initiator. In one aspect, the photosensitive resin composition of the present embodiment includes, as the (A) alkali-soluble polymer, a copolymer containing monomer components as constituent units. In one aspect, when the value of the glass transition temperature (Tg) calculated by Fox's formula is x (°C) and the acid value of the copolymer is y (mgKOH / g) for the (A) alkali-soluble polymer, the copolymer satisfies x ≥ 120 and 3y / 7 + 60 < x. In one aspect, the photosensitive resin composition of the present embodiment includes, as the (B) compound having an ethylenically unsaturated bond, (b-1) a di(meth)acrylate compound containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule, and (b-2) a tetrafunctional or higher (meth)acrylate compound. In one aspect, the photosensitive resin composition of the present embodiment includes, as the (C) polymerization initiator, a compound containing a biimidazole structure in an amount of 5.0 to 10% by mass based on the total solid mass of the photosensitive resin composition.

[0015] In this specification, components (A) to (C) above may be simply referred to as "component (A)" to "component (C)". The same applies to components other than components (A) to (C) described later. Each component and its raw materials may be used alone or in combination of two or more. In this specification, "solids" of a photosensitive resin composition means components of the photosensitive resin composition other than the solvent.

[0016] The present inventors have found that by combining the above-mentioned predetermined components (A), (B), and (C) as components of the photosensitive resin composition of this embodiment, the developability, resist pattern release properties, and peelability are improved. In other words, according to this embodiment, it is possible to provide a photosensitive resin laminate with excellent developability, resist pattern release properties, and peelability, a method for forming a resist pattern, and a method for manufacturing a wiring board.

[0017] <Support film> The support film according to this embodiment is a layer or film for supporting the photosensitive resin layer, and is preferably a transparent substrate film that transmits active light.

[0018] Examples of transparent base films include films made from synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), cellulose triacetate, and cycloolefin polymers. Among these, it is preferable to use a high-quality film with fewer internal foreign matter. Specifically, as high-quality films, polyethylene terephthalate (PET) film, cellulose triacetate film, cycloolefin polymer film, etc. are preferred, with polyethylene terephthalate (PET) film, which has appropriate flexibility and strength, being more preferably used. Among PET films, it is more preferable to use PET films synthesized using a Ti-based catalyst, PET films with a small diameter and low lubricant content, PET films containing lubricant on only one side, thin-film PET films, PET films with a smoothing treatment on at least one side, or PET films with a roughening treatment such as plasma treatment on at least one side. This allows the light to be exposed to the photosensitive resin layer without being blocked by internal foreign matter, thereby improving the resolution of the photosensitive resin composition.

[0019] The thickness of the support film is preferably 5 μm to 25 μm, and more preferably 6 μm to 20 μm. A thinner support film reduces the number of internal foreign matter, thus preventing a decrease in resolution. However, if the film is too thin, it can lead to stretching deformation in the winding direction due to tension during the coating and winding manufacturing process, tearing due to minute scratches, or insufficient film strength resulting in wrinkles during lamination.

[0020] At least one side of the support film may be subjected to a smoothing treatment using a calender or the like. This reduces the surface roughness of one side of the support film, particularly the side that comes into contact with the photosensitive resin composition layer described later, thereby improving the effects of this embodiment.

[0021] The haze of the support film 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 light rays irradiated onto the photosensitive resin layer and obtaining higher resolution after exposure and development of the photosensitive resin laminate.

[0022] <Photosensitive resin layer> The photosensitive resin layer according to this embodiment comprises a photosensitive resin composition. In one embodiment, the photosensitive resin layer according to this embodiment is a resist layer. The thickness of the photosensitive resin layer according to this embodiment is preferably 3 to 100 μm, more preferably 3 to 50 μm. As the thickness of the photosensitive resin layer approaches 3 μm, the resolution improves, and as it approaches 100 μm, the film strength improves. Therefore, it can be appropriately selected according to the application. In particular, the thickness of the photosensitive resin layer according to this embodiment is preferably 5 to 30 μm, more preferably 10 to 25 μm. When the thickness of the photosensitive resin layer according to this embodiment is within the above range, it can be suitably used for applications such as semiconductor package substrates where the formation of fine wiring is required. On the other hand, the thickness of the photosensitive resin layer according to this embodiment may be more than 100 μm and 500 μm or less. When the thickness of the photosensitive resin layer is within the above range, it can also be suitably used for bump formation and copper pillar formation.

[0023] <Photosensitive Resin Composition> The photosensitive resin composition of this embodiment contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a polymerization initiator.

[0024] (A) Alkali-soluble polymer In this embodiment, the (A) alkali-soluble polymer (hereinafter referred to as component (A)) includes a copolymer containing structural units derived from the first monomer and the second monomer described below as monomer components. When the value of the glass transition temperature (Tg) calculated by Fox's formula described below is x (°C) and the acid value is y (mgKOH / g) for component (A), component (A) includes a copolymer where x ≥ 120 and 3y / 7 + 60 < x. According to the photosensitive resin composition containing such component (A), it is excellent in the release property, developability, and peelability of the resist pattern. Further, according to a preferred embodiment of such a photosensitive resin composition, it is possible to form a photosensitive resin layer (resist layer) excellent in at least one, at least two, or all of the release property, developability, and peelability of the resist pattern. Furthermore, according to such a photosensitive resin composition, it is possible to provide a photosensitive resin laminate having a photosensitive resin layer, a method for forming a resist pattern, a method for manufacturing a wiring board, and the like.

[0025] ≪Glass transition temperature (Tg)≫ The glass transition temperature (Tg) of the copolymer containing component (A) is calculated based on Fox's formula. The Tg of the copolymer can be controlled by the types and proportions of monomers that make up the copolymer. A desirable Tg can be easily achieved by including desirable components in desirable proportions in the copolymer.

[0026] For a copolymer composed of n monomers, Fox's formula for calculating the Tg (K: Kelvin) of the copolymer is as follows:

number

[0027] In this disclosure, the Tg values ​​of homopolymers composed of monomers forming alkali-soluble polymers are taken from literature (Brandrup, J. Immergut, EH eds., Polymer Handbook, Third edition, John Wiley & Sons, 1989, Chapter VI “GLASS transition temperatures of polymers”, p209). The glass transition temperatures (Tg) of homopolymers composed of each monomer are also used. i An example of this is as follows:

[0028] [Table 1]

[0029] Based on the above [Equation 1] and [Table 1], for example, the Tg of component (A) exemplified below can be derived as follows. • Methacrylic acid / methyl methacrylate / styrene (mass ratio=21 / 39 / 40):Tg 123℃ (Mass ratio = 29 / 19 / 52): Tg 131°C (Mass ratio = 25 / 50 / 25): Tg 128°C · Methacrylic acid / Styrene / Dicyclopentanyl methacrylate (Mass ratio = 30 / 50 / / 20): Tg 146°C · Methacrylic acid / Benzyl methacrylate (Mass ratio = 20 / 80): Tg 78°C · Methacrylic acid / Methyl methacrylate / Styrene / Dicyclopentanyl methacrylate (Mass ratio = 25 / 25 / 25 / 25): Tg 146°C · Methacrylic acid / Styrene / Methacrylonitrile (Mass ratio = 25 / 45 / 30): Tg 132°C · Methacrylic acid / Styrene / Methyl methacrylate / Methacrylonitrile (Mass ratio = 28 / 15 / 10 / 47): Tg 140°C (Mass ratio = 27 / 16 / 15 / 42): Tg 138°C · Methacrylic acid / Dicyclopentenyloxyethyl methacrylate / Methyl methacrylate / Styrene (Mass ratio = 25 / 26 / 5 / 44): Tg 131°C

[0030] When the value of the glass transition temperature (Tg) of the copolymer in component (A) is x (°C) calculated based on the Fox equation, from the viewpoint of improving peelability, it is preferable that x ≥ 120. That is, from the viewpoint of improving peelability, the glass transition temperature (Tg) of the copolymer in component (A) is preferably 120°C or higher.

[0031] In the present disclosure, when component (A) contains a plurality of types of copolymers, the glass transition temperature (Tg total ) of the entire component (A) is represented as the weight average value Tg total of the Tg of each component (A). Such a weight average value Tg total is expressed by the following formula: Tg total = Σ i (W i × Tgi ) / W total (In the formula, W i This is the solid content mass of each alkali-soluble polymer, and Tg i This is the glass transition temperature (Tg) of each alkali-soluble polymer, determined by the Fox equation, and W total This represents the total solid content mass of each alkali-soluble polymer. This is the value obtained according to [the formula / method]. This Tg total From the viewpoint of improving peelability, the value is preferably 120°C or higher.

[0032] Acid Value Component (A) is a polymer soluble in an alkaline aqueous solution, and such polymer is, for example, a vinyl polymer containing a carboxyl group. In this disclosure, acid equivalent refers to the weight (g / mol) of alkali-soluble polymer per mole of acidic groups, and satisfies the relationship "acid equivalent = 56100 / acid value".

[0033] When the acid value of the copolymer contained in component (A) is denoted as y (mgKOH / g), from the viewpoint of contributing to improved resist pattern permeability and overall balance of effects, it is preferable that y ≤ 200, more preferably y ≤ 180, even more preferably y ≤ 160, even more preferably y ≤ 150, and particularly preferable y ≤ 140. In other words, from the viewpoint of contributing to improved resist pattern permeability and overall balance of effects, the acid value of the copolymer contained in component (A) is preferably 200 or less, more preferably 180 or less, even more preferably 160 or less, even more preferably 150 or less, and particularly preferable 140 or less. Furthermore, from the viewpoint of developability, y may be ≥ 65, and preferably y ≥ 80. That is, the acid value of the copolymer contained in component (A) may be 65 or higher, and preferably 80 or higher.

[0034] The acid value y (mgKOH / g) of the copolymer contained in component (A) is defined as the amount (mg) of potassium hydroxide that can neutralize 1 g of component (A). That is, the acid value y (mgKOH / g) of the copolymer contained in component (A) is determined by accurately weighing approximately 1 g of a sample containing component (A), dissolving this in 100 mL of acetone, and then performing neutral titration with a 1 mol / L aqueous potassium hydroxide solution and, by applying the drop volume of the aqueous potassium hydroxide solution to the following formula: Acid value (mgKOH / g) = 56.1 × {drop volume (mL) of 1 mol / L aqueous potassium hydroxide solution} / {mass (g) of the accurately weighed sample}, it can be calculated. Neutral titration can be performed, for example, using a Hiranuma Sangyo Co., Ltd. automatic titrator (COM-555).

[0035] In one aspect, component (A) contains a copolymer when the value of Tg calculated by Fox's formula is x (°C) and the acid value is y (mgKOH / g), where x ≥ 120 and 3y / 7 + 60 < x. When x and y of the copolymer satisfy the above-mentioned predetermined ranges, the photosensitive resin composition of the present embodiment is excellent in the release property, developability, and peelability of the resist pattern. Regarding the fact that when the copolymer contained in component (A) satisfies the above-mentioned predetermined ranges, it has the effects specified in the present application, the inventor of the present invention speculates as follows. Conventionally, an alkali-soluble polymer containing methacrylic acid and styrene as monomer components has been used. In particular, by containing methacrylic acid, the alkali-soluble polymer tends to have a high Tg, and the acid value and the value of Tg tend to be interlocked depending on the increase or decrease of the methacrylic acid content. When the acid value of the alkali-soluble polymer is y and the Tg of the alkali-soluble polymer is x, conventional alkali-soluble polymers tend to satisfy the inside of the Pareto line represented by the formula 1: 3y / 7 + 60 > x. On the other hand, in the case of such a conventional alkali-soluble polymer, there is a trade-off relationship between the length of the resist pattern peeling time, the resist pattern release property, and the length of the development time, and there has been a problem that it is difficult to realize a composition excellent in all of these performances. Therefore, the present inventor has found that the predetermined effects of the present application can be achieved by using an alkali-soluble polymer that satisfies the outside of the Pareto line represented by Formula 2: 3y / 7 + 60 < x and combining it with a compound having a specific ethylenic unsaturated bond.

[0036] When the value of the glass transition temperature (Tg) of the copolymer calculated by Fox's formula is x (°C) and the acid value of the copolymer is y (mgKOH / g), examples of the means for setting x ≥ 120 and 3y / 7 + 60 < x include the following means (i) to (iii). (i) The copolymer contained in the component (A) contains, as a monomer component, a monomer having an acidic group and a high glass transition temperature Tg i when it is a homopolymer. Specifically, it contains a certain amount of methacrylic acid (Tg i = 501K). Specifically, the lower limit of the content of methacrylic acid (in one aspect, the structural unit derived from methacrylic acid) in the copolymer contained in the component (A) is preferably 15% by mass or more, more preferably 18% by mass or more. The upper limit of the content of methacrylic acid in the copolymer contained in the component (A) is preferably 30% by mass or less, more preferably 28% by mass or less, and even more preferably 25% by mass or less. (ii) The copolymer contained in the component (A) does not contain, or contains a certain amount or less of, a compound having a low glass transition temperature Tg i (in one aspect, Tg i ≤ 350K) when it is a homopolymer. Specifically, the upper limit of the content of the monomer having a low glass transition temperature Tg when it is a homopolymer is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the content of the monomer having a low glass transition temperature Tg in the copolymer contained in the component (A) when it is a homopolymer may be 0% by mass. i Specifically, the upper limit of the content of the monomer having a low glass transition temperature Tg when it is a homopolymer is preferably 10% by mass or less, more preferably 5% by mass or less. Also, the lower limit of the content of the monomer having a low glass transition temperature Tg in the copolymer contained in the component (A) when it is a homopolymer may be 0% by mass. i Specifically, the upper limit of the content of the monomer having a low glass transition temperature Tg when it is a homopolymer is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the content of the monomer having a low glass transition temperature Tg in the copolymer contained in the component (A) when it is a homopolymer may be 0% by mass. (iii) The copolymer contained in the component (A) contains, as a monomer component, a monomer having no acidic group and a glass transition temperature Tg iLarge (in one aspect, Tg i Contains compounds with a temperature of ≥400K. Glass transition temperature Tg when used as a homopolymer i Dicyclopentanyl methacrylate is an example of a monomer with a large molecular weight. If the copolymer contained in component (A) contains dicyclopentanyl methacrylate, its content may be 5% by mass or more and 45% by mass or less in the copolymer.

[0037] More specifically, the copolymer contained in component (A) includes constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, and constituent units derived from styrene. Preferably, the total content of methacrylic acid (in one embodiment, a structural unit derived from methacrylic acid), methyl methacrylate (in one embodiment, a structural unit derived from methyl methacrylate), and styrene (in one embodiment, a structural unit derived from styrene) in the copolymer is 90% by mass or more, and the content of methacrylic acid (in one embodiment, a structural unit derived from methacrylic acid) in the copolymer is 18% by mass or more and 25% by mass or less. More specifically, the copolymer contained in component (A) includes constituent units derived from methacrylic acid and constituent units derived from dicyclopentanyl methacrylate, It is also preferable that the copolymer contains 15% by mass or more and 30% by mass or less of methacrylic acid (or, in one embodiment, a structural unit derived from methacrylic acid), and that it also contains 5% by mass or more and 45% by mass or less of dicyclopentanyl methacrylate (or, in one embodiment, a structural unit derived from dicyclopentanyl methacrylate).

[0038] From the viewpoint of balancing the transparency, developability, and peelability of the resist pattern, the copolymer content in component (A) may be 60% to 100% by mass, based on the total mass of component (A).

[0039] • The first monomer (the first constituent unit) The first monomer is a monomer having at least one ethylenically unsaturated bond in its molecule and having an acidic group. In this disclosure, the acidic group is, for example, a carboxyl group. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of improving the transparency of the resist pattern and balancing the overall effect.

[0040] The copolymerization ratio of the first monomer is preferably in the range of 10 to 35% by mass, based on the total mass of all monomer components. From the viewpoint of excellent adhesion and resolution, it is preferable that the copolymerization ratio be 10% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, and even more preferably 20% by mass or more. From the viewpoint of improving the permeability of the resist pattern and contributing to the overall balance of the effect, it is preferable to set the copolymerization ratio to 35% by mass or less, more preferably to 30% by mass or less, even more preferably to 27% by mass or less, even more preferably to 25% by mass or less, particularly preferably to 23% by mass or less, and most preferably to 21% by mass or less. When two or more monomers are polymerized and used as the first monomer, it is preferable that the sum of the copolymerization ratios of each monomer falls within the above range.

[0041] From the viewpoint of improving the transparency of the resist pattern and contributing to the overall balance of the effect, the copolymer contained in component (A) contains constituent units derived from (meth)acrylic acid as monomer components, and the content of constituent units derived from (meth)acrylic acid in component (A) is preferably less than 25% by mass, more preferably 23% by mass or less, and even more preferably 21% by mass or less. The content of constituent units derived from (meth)acrylic acid in component (A) may be 10% by mass or more.

[0042] When the value of the glass transition temperature (Tg) calculated by Fox's equation of the copolymer is x (°C) and the acid value of the copolymer is y (mgKOH / g), from the viewpoint of making the copolymer contained in the (A) component satisfy x ≥ 120 and 3y / 7 + 60 < x, it is preferable that the copolymer contains a structural unit derived from methacrylic acid as the first monomer. The content of the structural unit derived from methacrylic acid in the (A) component is preferably less than 25% by mass, more preferably 23% by mass or less, and still more preferably 21% by mass or less. The content of the structural unit derived from (meth)acrylic acid in the (A) component may be 10% by mass or more.

[0043] The copolymer contained in the (A) component contains a structural unit derived from (meth)acrylic acid as a monomer component, and it is preferable that the content of the structural unit derived from (meth)acrylic acid in the (A) component is 10% by mass or more and less than 25% by mass.

[0044] ·Second monomer (second structural unit) The second monomer is a monomer having at least one ethylenically unsaturated bond in the molecule and no acidic group. Examples of second monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tert-butyl (meth)acrylate. Examples include (meth)acrylates such as tramethylpiperidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate; styrene derivatives such as styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, N-phenylmaleimide, styrene dimer, and styrene trimer; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile.

[0045] From the viewpoint of improving the permeability and adhesion of the resist pattern, it is preferable that the copolymer contained in component (A) contains structural units derived from compounds having aromatic rings as monomer components, and that the content of structural units derived from compounds having aromatic rings in component (A) is 30% by mass or more. Furthermore, from the viewpoint of improving the permeability and adhesion of the resist pattern, it is preferable that the content of structural units derived from compounds having aromatic rings in the copolymer contained in component (A) is 80% by mass or less. (A) The content of constituent units derived from aromatic ring compounds in the copolymer is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass or more and 60% by mass or less, and even more preferably 40% by mass or more and 55% by mass or less. The compound having an aromatic ring may originate from the first monomer, or from the second monomer, or from both the first and second monomers. However, it is preferable that the compound having an aromatic ring originates from the second monomer, as this makes it easier to realize the desired component (A). The content of constituent units derived from compounds having aromatic rings in component (A) can be calculated by taking the weighted average of the proportion of aromatic rings contained in each monomer component in component (A) and the content of each monomer component in component (A). The proportion of aromatic rings contained in each monomer component in component (A) can be calculated by (number of aromatic rings contained in one monomer molecule / molecular weight of the monomer).

[0046] Examples of compounds having an aromatic ring include styrene, benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0047] Among these, from the viewpoint of excellent adhesion to the substrate, it is preferable that component (A) contains either styrene or benzyl (meth)acrylate, or both. In other words, it is preferable that component (A) contains constituent units derived from styrene and / or benzyl (meth)acrylate. (A) When the alkali-soluble polymer contains a plurality of alkali-soluble polymers, it may contain an alkali-soluble polymer containing styrene and an alkali-soluble polymer containing benzyl (meth) acrylate, respectively.

[0048] (A) When the copolymer contained in the component (A) contains a structural unit derived from styrene, from the viewpoint of adhesion, the content of styrene (in one embodiment, the structural unit derived from styrene) in the component (A) may be 25% by mass or more, or 30% by mass or more, or 35% by mass or more. Also, the content of styrene in the component (A) may be 80% by mass or less, or 75% by mass or less, or 70% by mass or less, or 65% by mass or less, or 60% by mass or less.

[0049] (A) When the component (A) contains a structural unit derived from styrene, from the viewpoint of adhesion, the content of styrene in the component (A) may be 25% by mass or more and 80% by mass or less, or 30% by mass or more and 80% by mass or less, or 35% by mass or more and 80% by mass or less.

[0050] Also, from the viewpoint of ensuring that for x and y in the copolymer contained in the component (A), x ≧ 120 and 3y / 7 + 60 < x are satisfied, the copolymer preferably contains any one of dicyclopentanyl methacrylate, styrene, methyl methacrylate, and 2-hydroxyethyl methacrylate as the second monomer.

[0051] From the viewpoints of the peeling property and adhesion of the resist pattern, the copolymer contained in the component (A) preferably contains a structural unit derived from dicyclopentanyl methacrylate. From the viewpoint of the resist pattern's permeability and adhesion, the content of dicyclopentanyl methacrylate (in one embodiment, a constituent unit derived from dicyclopentanyl methacrylate) in the copolymer contained in component (A) may be 5% by mass or more. Alternatively, the content of dicyclopentanyl methacrylate in the copolymer contained in component (A) may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.

[0052] If the copolymer contained in component (A) contains structural units derived from methyl methacrylate, the content of structural units derived from methyl methacrylate in component (A) may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, from the viewpoint of resist pattern permeability and adhesion. Alternatively, the content of structural units derived from methyl methacrylate in the copolymer contained in component (A) may be less than 40% by mass, 40% by mass or less, 35% by mass or less, or 30% by mass or less. When the copolymer contained in component (A) contains constituent units derived from methyl methacrylate as monomer components, from the viewpoint of resist pattern permeability and adhesion, the content of constituent units derived from methyl methacrylate in the copolymer contained in component (A) is preferably 10% by mass or more and less than 40% by mass, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less.

[0053] From the viewpoint of balancing the permeability, developability, and peelability of the resist pattern, if the copolymer contained in component (A) contains structural units derived from 2-hydroxyethyl methacrylate, the content of 2-hydroxyethyl methacrylate (in one embodiment, structural units derived from 2-hydroxyethyl methacrylate) in the copolymer contained in component (A) may be 1% by mass or more, 5% by mass or more, or 10% by mass or more. Alternatively, the content of 2-hydroxyethyl methacrylate in the copolymer contained in component (A) may be 30% by mass or less, 20% by mass or less, or 15% by mass or less.

[0054] (A) The weight-average molecular weight Mw of the alkali-soluble polymer is preferably 10,000 to 60,000. Setting the weight-average molecular weight Mw to 60,000 or less is preferable from the viewpoint of achieving both flexibility and resolution of the resist pattern, more preferably to 55,000 or less, and even more preferably to 50,000 or less. From a similar viewpoint, it is preferable to have a weight-average molecular weight Mw of 10,000 or more, more preferably 12,000 or more, and even more preferably 14,000 or more.

[0055] (A) The polydispersity (Mw / Mn: weight-average molecular weight / number-average molecular weight) of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0056] (A) Alkali-soluble polymers may be used individually or in combination of two or more types. When using a mixture of two or more (A) components, it is preferable that the content of the first and second monomers in the multiple (A) components be selected such that the weight-average molecular weight and polydispersity weight-average value, with the content ratio of one type of (A) component as the weight, fall within the following ranges. In this disclosure, the weighted average value is calculated by multiplying the weight ratio of each alkali-soluble polymer to the total weight of the mixed (A) components by the weight-average molecular weight or polydispersity of each alkali-soluble polymer, and then summing these values. (A) The weight-average molecular weight of component (A) is preferably 10,000 or more, or 15,000 or more, or 20,000 or more, and preferably 60,000 or less, or 55,000 or less, or 50,000 or less. (A) The weighted mean of the polydispersity of component is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0057] (A) The synthesis of alkali-soluble polymers is preferably carried out by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, and isopropanol, adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to the solution, and then heating and stirring. In some cases, the synthesis is carried out by adding a portion of the mixture containing the monomer and solvent dropwise to a reaction solution such as a radical polymerization initiator. After the polymerization reaction is complete, the solvent may be further added to adjust the concentration to the desired level. (A) In addition to solution polymerization, living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used as means for synthesizing component (A).

[0058] Furthermore, from the viewpoint of flexibility, resolution, and adhesion, the total content of component (A) and component (B) contained in the photosensitive resin composition of this embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more, based on the total solid content mass of the photosensitive resin composition. From the viewpoint of sensitivity, resolution, and adhesion, the total content of component (A) and component (B) contained in the photosensitive resin composition of this embodiment is preferably 98% by mass or less, and more preferably 96% by mass or less, based on the total solid content mass of the photosensitive resin composition.

[0059] Furthermore, from the viewpoint of developability, resolution, and adhesion, the content of component (A) in the photosensitive resin composition is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 63% by mass or less, and particularly preferably 60% by mass or less, based on the total content of component (A) and component (B). Furthermore, the content of component (A) in the photosensitive resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, relative to the total content of component (A) and component (B).

[0060] (B) Compounds having ethylenically unsaturated bonds In this embodiment, (B) a compound having an ethylenically unsaturated bond (hereinafter referred to as component (B)) includes, as components, (b-1) a di(meth)acrylate compound containing at least one ethylene oxide structure and one propylene oxide structure in one molecule, and (b-2) a (meth)acrylate compound with four or more functions. The photosensitive resin composition of this embodiment includes, as component (B), a combination of (b-1) a di(meth)acrylate compound containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule, and (b-2) a tetrafunctional or higher (meth)acrylate compound, which improves developability, resist pattern release, and peelability.

[0061] (b-1) Di(meth)acrylate compounds containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule. In this embodiment, (b-1) a di(meth)acrylate compound containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule (hereinafter referred to as (b-1) compound or (b-1) component) is not particularly limited as long as it is a di(meth)acrylate compound containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule. Furthermore, compound (b-1) may be used alone or in combination of two or more compounds. The inclusion of compound (b-1) in component (B) improves the adhesion of the photosensitive resin composition of this embodiment to the substrate and the peelability of the resist pattern.

[0062] (b-1) The compound is a compound having a (meth)acryloyl group, and more preferably a compound having a methacryloyl group.

[0063] (b-1) The compound is preferably a di(meth)acrylate compound containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule, and more preferably a di(meth)acrylate compound having a bisphenol A structure. (b-1) The compound is preferably a di(meth)acrylate compound containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule, more preferably a di(meth)acrylate compound containing a compound having four or more ethylene oxide structures and at least four propylene oxide structures in one molecule, and even more preferably a di(meth)acrylate compound that is a compound having four or more ethylene oxide structures and at least four propylene oxide structures in one molecule. (b-1) Examples of compounds include polyalkylene glycol di(meth)acrylates containing ethylene oxide and propylene oxide as alkylene oxides, and alkylene oxide-modified di(meth)acrylates of bisphenol A containing ethylene oxide and propylene oxide as alkylene oxides. Specifically, the above (b-1) compound is, for example: Dimethacrylate of polyalkylene glycol, in which an average of 6 ethylene oxide groups and an average of 2 propylene oxide groups are attached to each end of bisphenol A. Dimethacrylate of polyalkylene glycol, in which an average of 12 propylene oxide groups and an average of 3 ethylene oxide groups are added to each end of polypropylene glycol, and Examples include dimethacrylates of polyalkylene glycols, in which an average of 15 ethylene oxide groups and an average of 2 propylene oxide groups are attached to each end of bisphenol A. Herein, in this specification, the average number of alkylene oxide structures, represented by ethylene oxide and / or propylene oxide, in compound (b-1) or compound (b-2) described below is expressed by the number mean.

[0064] From the viewpoint of excellent adhesion to the substrate, (B) the compound having an ethylenically unsaturated bond preferably includes a di(meth)acrylate compound having a bisphenol A structure among the components of (b-1), and The following general formula (IV): [ka] (In the formula, R 10、 R 11 Each of these is independently either a hydrogen atom or a methyl group. R 12 O, R 13 O, R 14 O and R 15 Each of the O groups is independently an oxyalkylene group. p, q, r, and s are each independent integers between 0 and 40, p+q is between 1 and 40, and r+s is between 1 and 20. It is particularly preferable that the compound represented by [formula] be included.

[0065] R 12 O, R 13 O, R 14 O and R 15 Preferably, O is independently an oxyethylene group and an oxypropylene group. As for compounds having a bisphenol A structure, from the viewpoint of developability, resist pattern transparency, and adhesion, the average value of p+q+r+s may be 40 or less, preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, and particularly preferably 10 or less. The average value of p+q+r+s may be 2 or more, preferably 4 or more. p, q, r, and s are each preferably independently between 0 and 10, and more preferably between 1 and 8.

[0066] Component (b-1) can be synthesized, for example, by the following method, but the synthesis method of component (b-1) according to this embodiment is not limited thereto. Polyalkylene glycol-based di(meth)acrylates and bisphenol A-based di(meth)acrylates can be obtained by reacting the hydroxyl groups at both ends of polyalkylene glycol and bisphenol A with ethylene oxide and propylene oxide, respectively, and then reacting the terminal hydroxyl groups with acrylic acid or methacrylic acid.

[0067] • (b-2) (meth)acrylate compounds with four or more functions In this embodiment, the (b-2) tetrafunctional or greater (meth)acrylate compound (hereinafter referred to as (b-2) compound or (b-2) component) is not particularly limited as long as it is a compound having four or more functional (meth)acryloyl groups in a compound having an ethylenically unsaturated bond. In this specification, "number of functional groups" refers to the number of ethylenically unsaturated bonds per molecule of a compound. For example, in the case of acrylate monomers, it is defined as the number of acryloyl groups per molecule, and in the case of methacrylate monomers, it is defined as the number of methacryloyl groups per molecule.

[0068] Component (b-2) preferably contains a tetrafunctional or higher (meth)acrylate compound, and more preferably contains a pentafunctional or higher (meth)acrylate compound. From the viewpoint of improving the transparency of the resist pattern and developability, component (b-2) preferably contains a tetrafunctional to hexafunctional (meth)acrylate compound. Among these, component (b-2) is general formula (I): [ka] [In the formula, n is between 2 and 20, Each i is a natural number between 1 and n. Each of k, li, and m is independently between 0 and 30. R1, R 2 i R3, and R3 each independently represent a hydrogen atom or a methyl group. R4, R 5 i , and R6 are each independently an alkylene group having 1 to 10 carbon atoms, as shown in the general formula (II): [ka] [In the formula, R7 and R8 are each independently alkylene groups having 1 to 10 carbon atoms.] A base represented by, The following general formula (III): [ka] [In the formula, R9 is an alkylene group having 1 to 10 carbon atoms.] It is one selected from the group consisting of groups represented by . It is particularly preferable to include a polyglycerin-based (meth)acrylate represented by ].

[0069] R4O, R 5 i Polyglycerin-based (meth)acrylates having repeating units represented by O and R6O can be synthesized, for example, by the following method, but the synthesis method of polyglycerin-based (meth)acrylates according to this embodiment is not limited thereto. By reacting the hydroxyl groups of polyglycerin with alkylene oxide, and then reacting the terminal hydroxyl groups with acrylic acid or methacrylic acid, R4, R 5 i And a polyglycerin-based (meth)acrylate in which R6 is an alkylene group can be obtained. By using a compound having a leaving group and an epoxy group, such as epichlorohydrin, instead of alkylene oxide in the reaction, the above R4, R 5 i And R6 can be represented by general formula (II) to obtain a polyglycerin-based (meth)acrylate. By using a lactone compound instead of alkylene oxide in the reaction, R4, R 5 i And R6 can be represented by general formula (III) to obtain a polyglycerin-based (meth)acrylate. These reactions can be freely combined, and also R4O, R 5 i Alternatively, acrylic acid or methacrylic acid may be reacted with the hydroxyl groups of polyglycerin without introducing repeating units represented by O and R6O. Specifically, as polyglycerin-based (meth)acrylates, products such as SA-TE6 and SA-TE60 manufactured by Sakamoto Pharmaceutical Chemical Industry Co., Ltd. can be used.

[0070] From the viewpoint of flexibility and adhesion, each k, each li, and m in general formula (I) are preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 12, even more preferably 2 to 10, particularly preferably 2 to 8, and most preferably 2 to 6. In this disclosure, if the polyglycerin-based (meth)acrylate represented by general formula (I) consists of a single type of molecule, then k, li, and m can be expressed as integer values. Furthermore, when a polyglycerin-based (meth)acrylate represented by general formula (I) consists of multiple types of molecules, each of k, li, and m can be expressed as a numerical average value.

[0071] From the viewpoint of flexibility and peelability, n in general formula (I) is preferably an integer from 2 to 15, more preferably from 2 to 10, even more preferably from 2 to 8, even more preferably from 2 to 6, and particularly preferably from 2 to 4. Furthermore, if the polyglycerin-based (meth)acrylate represented by general formula (I) consists of multiple types of molecules, n can be expressed as a numerical average value. In one embodiment, n in general formula (I) is a numerical mean, preferably 2 to 15, more preferably 2 to 10, even more preferably 2 to 8, even more preferably 2 to 6, and particularly preferably 2 to 4.

[0072] From the viewpoint of adhesion and resolution, R1 and R of general formula (I) 2 i , and R3 are preferably methyl groups.

[0073] From the viewpoint of adhesion and resolution, R4 and R of general formula (I) 5 i , and R6 are, It is preferable that the group is an alkylene group. It is more preferably an alkylene group having 1 to 10 carbon atoms. It is more preferably an alkylene group containing one or more selected from the group consisting of an ethylene group, a propylene group, and a tetramethylene group. It is even more preferable to contain an ethylene group and / or a propylene group. It is particularly preferable that the group be an ethylene group and / or a propylene group. It is extremely preferable that the group be an ethylene group.

[0074] Examples of (meth)acrylate compounds with four or more functions include, in addition to the polyglycerin-based (meth)acrylate compounds listed in general formula (I), pentaerythritol (tetra)(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0075] Furthermore, the (meth)acrylate compound with four or more functions may also be an alkylene oxide modified compound. Examples include polyglycerin alkylene oxide modified (tetra / penta / hexa)(meth)acrylate, alkylene oxide modified pentaerythritol (tetra)(meth)acrylate, alkylene oxide modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and alkylene oxide modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate. From the viewpoint of excellent developability and resist pattern release, it is preferable that compound (b-2) contains polyglycerol alkylene oxide modified (tetra / penta / hexa)(meth)acrylate or alkylene oxide modified pentaerythritol (tetra)(meth)acrylate. The above polyglycerin alkylene oxide-modified (tetra / penta / hexa)(meth)acrylate or alkylene oxide-modified pentaerythritol (tetra)(meth)acrylate specifically include, for example, Hexamethacrylate, in which an average of 21 ethylene oxide groups are added to the terminal end of the hydroxyl group of tetraglycerol. Pentamethacrylate, in which an average of 12 ethylene oxide groups are attached to the terminal end of the hydroxyl group of triglycerin. Tetramethacrylate obtained by adding an average of 15 ethylene oxide groups to the terminal hydroxyl groups of pentaerythritol, and Examples include tetramethacrylate, which has an average of nine ethylene oxide groups attached to the terminal ends of the hydroxyl groups of pentaerythritol.

[0076] (b-2) The component may be a single compound or two or more compounds may be used in combination. The inclusion of component (b-2) in component (B) improves the transparency, developability, and peelability of the resist pattern of the photosensitive resin composition of this embodiment. Component (b-2) is preferably a compound containing a (meth)acryloyl group, and more preferably a compound containing a methacryloyl group.

[0077] (b-2) Examples of commercially available products of component (b-2) include Sartomer® SR399 and SR494 (both manufactured by Arkema Co., Ltd.).

[0078] The content of component (b-1) in the photosensitive resin composition of this embodiment is preferably 10% by mass or more, and more preferably 20% by mass or more, based on the total solid content mass of the photosensitive resin composition. The content of component (b-1) in the photosensitive resin composition of this embodiment is preferably 35% by mass or less, and more preferably 30% by mass or less, based on the total solid content mass of the photosensitive resin composition. The content of component (b-1) in the photosensitive resin composition of this embodiment is preferably 10 to 35% by mass, and more preferably 20 to 30% by mass, based on the total solid content mass of the photosensitive resin composition.

[0079] The content of component (b-2) in the photosensitive resin composition of this embodiment is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total solid content mass of the photosensitive resin composition. The content of component (b-2) in the photosensitive resin composition of this embodiment is preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total solid content mass of the photosensitive resin composition. The content of component (b-2) in the photosensitive resin composition of this embodiment is preferably 5 to 20% by mass, and more preferably 10 to 15% by mass, based on the total solid content mass of the photosensitive resin composition.

[0080] The total content of components (b-1) and (b-2) in component (B) may be 100% by mass or less, or less than 100% by mass, based on the total mass of component (B). From the viewpoint of balancing the transparency, developability and peelability of the resist pattern, the total content of components (b-1) and (b-2) is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total mass of component (B). The total content of component (b-1) and component (b-2) is preferably 50% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and less than 100% by mass, based on the total mass of component (B).

[0081] To obtain a photosensitive resin composition with excellent desired properties, it is preferable to control the mass ratio of component (b-1) and component (b-2) {(b-1) component / (b-2) component; sometimes abbreviated as "(b-1) / (b-2)"} within a predetermined range. Controlling the value of (b-1) / (b-2) improves the resist pattern release, developability, and peelability of the photosensitive resin composition of this embodiment. (b-1) / (b-2) can be controlled by adjusting the charging ratio of component (b-1) and component (b-2) when preparing the photosensitive resin composition. (b-1) / (b-2) can be analyzed from the photosensitive resin layer by a predetermined method, and the value obtained therefrom is based on the charging ratio at the time of preparing the photosensitive resin composition.

[0082] From the viewpoint of improving the transparency, developability, and peelability of the resist pattern, the ratio of the solid content masses of component (b-1) and component (b-2), i.e., the ratio of the solid content mass of component (b-1) to the solid content mass of component (b-2), (b-1):(b-2), is preferably in the range of 4:6 to 8:2, and more preferably in the range of 7:3 to 8:2.

[0083] Component (B) may include, as component (b-3), a compound that is not one of components (b-1) or (b-2). The content of component (b-3) may be 0% by mass or greater than 0% by mass relative to the total mass of component (B). From the viewpoint of balancing the transparency, developability and peelability of the resist pattern, the content of component (b-3) is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total mass of component (B).

[0084] (b-3) Examples of components include 1-3 functional (meth)acrylate compounds. Examples of the monofunctional (meth)acrylate compounds mentioned above include alkylene oxide-modified phenol (meth)acrylate, alkylene oxide-modified nonylphenol (meth)acrylate, alkylene oxide-modified 2-ethylhexyl (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 1-naphthalenemethyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, isoamide Examples include hexyl(meth)acrylate, isodecyl(meth)acrylate, n-lauryl(meth)acrylate, tetradecyl(meth)acrylate, n-stearyl(meth)acrylate, isostearyl(meth)acrylate, behenyl(meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, isobolonyl(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, 1H,1H,5H-octafluoropentyl(meth)acrylate, and 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl(meth)acrylate. Examples of the above-mentioned bifunctional (meth)acrylate compounds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycoxified (hydrogenated) bisphenol A di(meth)acrylate. Examples of the above trifunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, alkylene oxide-modified tri(meth)acrylate of glycerin, and alkylene oxide-modified isocyanuric acid tri(meth)acrylate.

[0085] Among these, the (b-3) component is preferably ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, or tetramethylene glycoxified (hydrogenated) bisphenol A di(meth)acrylate, more preferably ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, and particularly preferably ethoxylated bisphenol A di(meth)acrylate. The average number of ethylene oxide molecules in ethoxylated bisphenol A di(meth)acrylate is preferably 2 to 30 per molecule, and more preferably 4 to 20. Component (B) preferably further contains, as component (b-3), ethoxylated bisphenol A di(meth)acrylate having an average of 2 to 30 ethylene oxide structures per molecule.

[0086] The content of (B) the compound having an ethylenically unsaturated bond in the photosensitive resin composition of this embodiment is preferably 30% by mass or more, and preferably 35% by mass or more, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of sensitivity, tackiness, and conformability. Furthermore, the content of (B) the compound having an ethylenically unsaturated bond in the photosensitive resin composition is preferably 50% by mass or less, preferably 45% by mass or less, and preferably 43% by mass or less, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of edge fusion properties, tackiness, and resolution. In one embodiment, the content of (B) compounds having ethylenically unsaturated bonds in the photosensitive resin composition of this embodiment is preferably 20% by mass or more and 60% by mass or less, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of resolution, adhesion and peelability.

[0087] Furthermore, from the viewpoint of edge fusion properties, tackiness, and resolution, the upper limit of the ratio of the content of (B) a compound having an ethylenically unsaturated bond to the content of (A) an alkali-soluble resin contained in the photosensitive resin composition of this embodiment (i.e., the ratio of the content of (B) a compound having an ethylenically unsaturated bond / the content of (A) an alkali-soluble resin) is preferably 1.4 or less, more preferably 1.3 or less, even more preferably 1.2 or less, even more preferably 1.1 or less, particularly preferably 1.0 or less, and most preferably 0.9 or less. The lower limit of the ratio of the content of (B) compounds having ethylenically unsaturated bonds to the content of (A) alkali-soluble resin is preferably 0.50 or higher, more preferably 0.60 or higher, even more preferably 0.70 or higher, and even more preferably 0.75 or higher.

[0088] In this embodiment, the photosensitive resin composition preferably has a value of 0.10 moles to 0.30 moles of ethylenically unsaturated bonds per 100 g of solid content. By setting the amount to 0.10 moles or more, the photosensitive resin composition components can be leached from the cured resist pattern during the water washing process after development, thus preventing contamination during the water washing process. By keeping the amount below 0.30 moles, the hardened resist pattern will chip and fall off during the water washing process after development, preventing contamination during the washing process.

[0089] The amount of ethylenically unsaturated bonds per 100g of solids in the photosensitive resin composition of this embodiment is preferably 0.10 moles or more, more preferably 0.11 moles or more, even more preferably 0.12 moles or more, and even more preferably 0.13 moles or more. Furthermore, the amount of ethylenically unsaturated bonds per 100g of solids in the photosensitive resin composition of this embodiment is preferably 0.30 moles or less, more preferably 0.28 moles or less, even more preferably 0.25 moles or less, even more preferably 0.22 moles or less, particularly preferably 0.20 moles or less, particularly more preferably 0.18 moles or less, and extremely preferably 0.15 moles or less. The amount of ethylenically unsaturated bonds per 100g of solids in the photosensitive resin composition of this embodiment is more preferably 0.10 to 0.25 moles, even more preferably 0.10 to 0.20 moles, even more preferably 0.11 to 0.20 moles, and most preferably 0.11 to 0.15 moles.

[0090] (C) Polymerization initiator In this embodiment, the photosensitive resin composition preferably contains (C) polymerization initiator (hereinafter referred to as component (C)). In this disclosure, (C) polymerization initiator is a compound that contributes to the photopolymerization reaction by absorbing active light, and specifically is a compound that absorbs active light to generate radicals and initiate the polymerization of component (B), or a compound that absorbs active light and transfers the obtained energy to other components to promote the photopolymerization reaction. The active light ray may be any light having a wavelength of 330 nm to 450 nm, and may be, for example, i-rays, h-rays, and g-rays. (C) Examples of polymerization initiators include compounds containing a biimidazole structure, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazole derivatives, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds. In one embodiment, component (C) preferably includes a compound containing a biimidazole structure or an anthracene derivative.

[0091] Examples of compounds containing a biimidazole structure include hexaarylbiimidazole compounds. Examples of hexaarylbiimidazole compounds include rophine dimers, i.e., dimers of 2,4,5-triarylimidazole.

[0092] The rophine dimers, i.e., dimers of 2,4,5-triarylimidazole, include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), the dimer of 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole, and the dimer of 2-(p-methoxyphenyl)-4,5-diphenylimidazole. 2,2',5-Tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-Tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole , 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-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-(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,Examples include 5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0093] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that the (C) component contains a rofin dimer, and among these, the 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0094] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0095] 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-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0096] Examples of aromatic ketone compounds include benzophenone compounds. Examples of benzophenone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. 4,4'-bis(diethylamino)benzophenone is also an example of an aromatic ketone compound, from the viewpoint of sensitizing effect and adhesion.

[0097] In this disclosure, the term “anthracene derivative” includes both anthracene and compounds derived therefrom. Examples of 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, and 10-phenyl-9-anthraceneboronic acid. From the viewpoint of sensitizing effect and adhesion, 9,10-dibutoxyanthracene or 9,10-diphenylanthracene is preferred, and 9,10-diphenylanthracene is particularly preferred.

[0098] 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, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0099] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0100] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of dialkylketal compounds include benzyldimethyl ketal and benzyldiethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0101] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime 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 Ciba Specialty Chemicals).

[0102] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0103] From the viewpoint of adhesion and the rectangularity of the resist pattern, 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, or 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred as pyrazoline derivatives.

[0104] As a pyrazole derivative, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazole is preferred.

[0105] Examples of ester compounds of N-aryl amino acids 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, heptyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0106] Examples of halogen compounds 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 diallylodonium compounds. Among halogen compounds, tribromomethylphenylsulfone is preferred.

[0107] The content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.01 to 20% by mass, or preferably 5.0 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 5.5 to 10% by mass, based on the total solid content mass of the photosensitive resin composition. (C) By adjusting the content of the polymerization initiator to within the above range, sufficient sensitivity can be easily obtained, making it easier to transmit light sufficiently to the bottom of the photosensitive resin composition layer, and consequently, easier to achieve improved resolution.

[0108] From the viewpoint of high sensitivity, resolution, and adhesion, the (C) polymerization initiator preferably contains a compound containing a biimidazole structure, and more preferably contains a hexaarylbiimidazole compound. In this case, the content of the compound containing a biimidazole structure in the photosensitive resin composition is preferably 2.5 to 15% by mass, more preferably 5.0 to 10% by mass, and even more preferably 5.5 to 9.0% by mass, based on the total solid content mass of the photosensitive resin composition.

[0109] (C) As a polymerization initiator, it is preferable to use an anthracene derivative in combination with a compound containing a biimidazole structure (for example, a hexaarylbiimidazole compound). In this case, the content of the anthracene derivative contained in the (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.01% to 0.5% by mass, based on the total solid content mass of the photosensitive resin composition. Furthermore, the content of the anthracene derivative contained in the (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.01% by mass or more, based on the total solid content mass of the photosensitive resin composition. The content of the anthracene derivative contained in the (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.5% by mass or less, and more preferably 0.4% by mass or less, based on the total solid content mass of the photosensitive resin composition. Furthermore, in this case, the content of the hexaarylbiimidazole compound contained in the (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.1 to 10% by mass, or more preferably 5.0 to 10% by mass, more preferably 0.5 to 8% by mass, or more preferably 5.5 to 9.0% by mass, based on the total solid content mass of the photosensitive resin composition.

[0110] The content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, based on the content of (B) compound having an ethylenically unsaturated bond. Furthermore, the content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and particularly preferably 5% by mass or more, based on the content of (B) compound having an ethylenically unsaturated bond.

[0111] • Additives The photosensitive resin composition according to this embodiment may contain additives such as dyes, adhesion aids, plasticizers, and polymerization inhibitors.

[0112] ·dye In this embodiment, the dye may be included in the photosensitive resin composition. In another embodiment, the photosensitive resin composition may also contain a color-developing dye that develops color upon light irradiation. In the dry film resist provided by the photosensitive resin laminate of this embodiment, it is preferable to add a dye. By adding a dye, the resist pattern formed on the substrate after development becomes visible with good contrast, and also helps to improve resolution.

[0113] Diamond green is a preferred dye. As for color-developing dyes, for example, combinations of leuco dyes and halogen compounds are known. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [pigment name: leucocrystal violet] and tris(4-dimethylamino-2-methylphenyl)methane [pigment name: leucomalachite green]. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal 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, and hexachloroethane.

[0114] • Adhesion enhancer In this embodiment, the adhesion aid may be included in the photosensitive resin composition. In one embodiment of the photosensitive resin laminate provided by this embodiment, it is preferable to add an adhesion aid to the dry film resist. Adding an adhesion aid helps to improve the adhesion of the resist pattern formed on the substrate after development to the copper.

[0115] Preferred adhesion aids include triazoles and benzotriazoles, with carboxybenzotriazole being more preferred. Examples of adhesion aids include a 1:1 (mass ratio) mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole.

[0116] • Plasticizer In this embodiment, additives such as plasticizers may be included in the photosensitive resin composition as needed. Examples of additives such as plasticizers include phthalate esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

[0117] • Polymerization inhibitors In this embodiment, the photosensitive resin composition may contain a polymerization inhibitor. Examples of polymerization inhibitors include free radical polymerization inhibitors, phenolic polymerization inhibitors, hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine, catechol, and their derivatives.

[0118] Examples of free radical polymerization inhibitors include nitroso compounds such as p-nitrosophenol, nitrosobenzene, N-nitrosodiphenylamine, isononyl nitrite, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, N,N'-dinitrosophenylenediamine, and their salts (e.g., aluminum salts); and hindered amine compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine.

[0119] Examples of phenolic polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,2'-methylenebis(4-methyl-6- tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5 [-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-te Examples include rt-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrene-phenols (e.g., Antege SP, manufactured by Kawaguchi Chemical Industries, Ltd.), tripenzylphenols (e.g., TBP, manufactured by Kawaguchi Chemical Industries, Ltd., phenols having 1 to 3 benzyl groups), and biphenols.

[0120] In this disclosure, the terms “hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine and catechol and their derivatives” include both hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine and catechol, and compounds derived therefrom. Examples of hydroquinone derivatives include methyl hydroquinone, 2-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, and 2,6-di-tert-butyl hydroquinone. Examples of quinone derivatives include tert-butylbenzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, and 2,5-di-tert-butyl-1,4-benzoquinone.

[0121] Examples of nitrobenzene derivatives include 4-nitrotoluene. Examples of phenothiazine derivatives include 2,8-dioctylphenothiazine, 2-methoxyphenothiazine, 3-methoxyphenothiazine, 2-methylphenothiazine, 2-ethylphenothiazine, 2-trifluoromethylphenothiazine, 3,7-dibutylphenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 2-cyano-8-methoxyphenothiazine, 2-cyanophenothiazine, 2-bromophenothiazine, 2-chlorophenothiazine, bis-(α-dimethylbenzyl)phenothiazine, and bis-(α-methylbenzyl)phenothiazine. Examples of phenoxazine derivatives include 1-methylphenoxazine, 2-methylphenoxazine, 3-methylphenoxazine, 4-methylphenoxazine, 10-methylphenoxazine, 2-hydroxyphenoxazine, 3-hydroxyphenoxazine, 4-hydroxyphenoxazine, 10-bromophenoxazine, 3,7-dimethylphenoxazine, 2,8-dimethylphenoxazine, 1-aminophenoxazine, 2-aminophenoxazine, 3-aminophenoxazine, 2-ethylphenoxazine, 3-ethylphenoxazine, 2-carbonitrile-phenoxazine, 3-carbonitrile-phenoxazine, 2-methoxyphenoxazine, 3-methoxyphenoxazine, and 12H-benzophenoxazine.

[0122] Examples of catechol derivatives include 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol.

[0123] By including phenothiazine or a phenothiazine derivative and a phenolic polymerization inhibitor, the NH group in the phenothiazine moiety and the OH group of the phenolic polymerization inhibitor form hydrogen bonds, preventing the phenolic polymerization inhibitor from volatilizing or diffusing from the photosensitive resin composition layer. In other words, it is possible to provide a photosensitive resin composition with excellent sensitivity and resolution that is not affected by manufacturing conditions or storage conditions determined by the film thickness, and a method for forming a resist pattern.

[0124] From the above viewpoint, the photosensitive resin composition of this embodiment preferably contains phenothiazine or a phenothiazine derivative as a polymerization inhibitor. In this case, the content of phenothiazine or phenothiazine derivative in the photosensitive resin composition of this embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, based on the total solid content mass of the photosensitive resin composition of this embodiment. Furthermore, the content of phenothiazine or phenothiazine derivative in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more, based on the total solid content mass of the photosensitive resin composition of this embodiment.

[0125] From the viewpoint of resolution, the photosensitive resin composition of this embodiment preferably contains catechol or a catechol derivative as a polymerization inhibitor, and is particularly preferably 3-tert-butylcatechol or 4-tert-butylcatechol. In this case, the content of catechol or catechol derivative in the photosensitive resin composition of this embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, based on the total solid content mass of the photosensitive resin composition of this embodiment. Furthermore, the content of catechol or catechol derivative in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more, based on the total solid content mass of the photosensitive resin composition of this embodiment.

[0126] The content of the polymerization inhibitor in the photosensitive resin composition of this embodiment is preferably 0.0001% to 10% by mass, based on the total solid content mass of the photosensitive resin composition of this embodiment. The polymerization inhibitor content in this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, even more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more, from the viewpoint of having excellent adhesion and resolution. On the other hand, the polymerization inhibitor content in this embodiment is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less, in terms of minimizing sensitivity reduction and improving resolution.

[0127] <Photosensitive resin laminate> The photosensitive resin laminate of this embodiment comprises a support film and a photosensitive resin layer containing a photosensitive resin composition (in one embodiment, a photosensitive resin composition layer), the support film and the photosensitive resin layer being the same as described above. The photosensitive resin laminate of this embodiment may, for example, consist of at least one photosensitive resin layer laminated on a support film, and may also consist of two or more photosensitive resin layers laminated on the support film. The photosensitive resin laminate of this embodiment is preferably a dry film resist or a transfer film, and more preferably a dry film resist, from the viewpoint of making the effects of this embodiment more pronounced.

[0128] The photosensitive resin laminate of this embodiment may also include a protective film in addition to the support film and the photosensitive resin layer. In this embodiment, if the photosensitive resin laminate includes a support film, a photosensitive resin layer, and a protective film, the protective film is attached to the side of the photosensitive resin layer where the support film is not laminated, and functions as a cover.

[0129] In this embodiment, the adhesion force between the photosensitive resin composition layer and the protective film is significantly less than the adhesion force between the photosensitive resin composition layer and the support film; therefore, the protective film can be easily peeled off the photosensitive resin composition layer. For example, polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc., can be preferably used as protective films. Among these, polypropylene film and polyester film are more preferred, and among polyester films, polyethylene terephthalate film is even more preferred. Furthermore, a release layer may be provided on the surface of the protective film.

[0130] The thickness of the protective film is preferably 10 to 100 μm, and more preferably 10 to 50 μm. Examples of protective films include Alphan® EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd.). Toray Industries® (registered trademark) KW37, 2578, 2548, 2500, YM17S, Therapeuil® (registered trademark) PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, SY (all manufactured by Toray Industries, Inc.) Examples include GF-18, GF-818, and GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0131] The photosensitive resin laminate of this embodiment may further include an intermediate layer between the support film and the photosensitive resin layer, or between the support film and the protective film.

[0132] [Photosensitive resin laminate roll] The photosensitive resin laminate described above may be used as a roll-shaped photosensitive resin laminate roll by winding a long photosensitive resin laminate onto a core.

[0133] [Method for forming a resist pattern] A method for forming a resist pattern using a photosensitive resin laminate according to this embodiment includes, for example, the following steps: A lamination process for laminating a photosensitive resin layer (in one embodiment, a photosensitive resin composition layer) constituting the photosensitive resin laminate of this embodiment onto a substrate; An exposure step for exposing the photosensitive resin layer of a photosensitive resin laminate; and A developing process that removes unexposed portions of the photosensitive resin layer; It includes. Preferably, the steps are carried out in the order described above.

[0134] <Lamination process> In the lamination process, specifically, after peeling off the protective film from the photosensitive resin laminate of this embodiment, the photosensitive resin layer is heated and pressed onto the substrate surface using a laminator, and laminated once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO), with copper-clad laminates being preferred. If desired, the substrate may be cleaned and smoothed using, for example, an aqueous H2SO4 solution with a concentration of about 10% by mass. The heating temperature during lamination is generally between 40°C and 160°C. Heat bonding can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rolls. Heat bonding can be performed under reduced pressure if desired.

[0135] <Exposure process> In the exposure process, an exposure machine such as a contact aligner, mirror projection machine, or stepper is used to expose the photosensitive resin layer with an ultraviolet light source, either through a patterned photomask or reticle, or directly. The exposure process may be performed either after peeling off the support film or through the support film, as desired. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter. Direct imaging exposure may also be performed in the exposure process. In direct imaging exposure, exposure is performed directly onto the substrate using a writing device without using a photomask. As the light source, a semiconductor laser with a wavelength of 350 nm to 410 nm or an ultra-high pressure mercury lamp is used. When the drawing pattern is controlled by a computer, the amount of exposure is determined by the illuminance of the exposure light source and the speed at which the substrate moves.

[0136] The exposure method used in the exposure process is preferably at least one method selected from projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and is more preferably performed by projection exposure or direct imaging exposure.

[0137] <Heating process> A heating step may be included between the exposure step and the development step. The heating temperature is preferably 30°C to 200°C, more preferably 30°C to 150°C, and even more preferably 35°C to 120°C. This heating process improves resolution and adhesion. For heating, heating furnaces, constant temperature baths, hot plates, hot air dryers, infrared dryers, hot rolls, etc., can be used, employing methods such as hot air, infrared, or far infrared heating. The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0138] The elapsed time from the exposure process to the heating process, or more precisely, the elapsed time from the point when exposure is stopped to the point when heating is started, is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds. The elapsed time from the start of heating to the point when heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.

[0139] <Developing process> In the development process, the unexposed portions of the photosensitive resin layer after exposure are removed using a developing device with a developing solution to form a resist pattern. After exposure, if a support film is present on the photosensitive resin layer, remove the support film. Then, using a developer consisting of an alkaline aqueous solution, develop and remove the unexposed areas to obtain a resist pattern. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected and used from among conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment.

[0140] As the alkaline aqueous solution used as the developer, aqueous solutions of Na2CO3, K2CO3, and tetramethylammonium hydroxide are preferred. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, but an aqueous solution of Na2CO3 with a concentration of 0.2% to 2% by mass is generally used. Surface surfactants, defoamers, and small amounts of organic solvents to promote development may be added to the alkaline aqueous solution. The temperature of the developer solution during the development process is preferably kept constant within the range of 20°C to 40°C.

[0141] The development process preferably includes a water washing step to remove the developer solution contained in the resist pattern after development. The washing water can be pure water, industrial water, or other types of water, and is selected according to the characteristics of the photosensitive resin layer. However, polyvalent metal salts such as MgSO4 may be added at a concentration of 0.001% to 1% by mass to improve resolution and the shape of the resist pattern. The temperature of the washing water in the water washing step is preferably kept constant within the range of 20°C to 40°C.

[0142] The resist pattern can be obtained through the above process, but if desired, a further heat treatment can be performed at 60°C to 300°C for 1 to 120 minutes. This heat treatment can improve the chemical resistance of the resist pattern. For the heat treatment, a heating furnace using hot air, infrared rays, or far-infrared rays can be used.

[0143] To obtain a conductor pattern, a conductor pattern formation step may be performed after the development step or heating step, in which the substrate on which the resist pattern has been formed is etched or plated.

[0144] <Conductor pattern formation process> The conductor pattern formation process is a process of forming a conductor pattern on a substrate surface (for example, a copper surface) on which a resist pattern has been formed by development, using a known etching method or plating method.

[0145] Examples of methods for forming conductor patterns by plating include the following: After the development process, the substrate is immersed in an acidic degreasing bath such as a 1-50% by mass sulfuric acid aqueous solution at 20-60°C for 1-60 minutes. After rinsing the immersed substrate with water, it is immersed in a 1-50% by mass sulfuric acid aqueous solution at room temperature for 1-60 minutes.

[0146] Prepare aqueous solutions containing 1-15% by mass of copper sulfate, 0.1-30% by mass of sulfuric acid, and 1-1000 ppm of hydrochloric acid. Next, a brightener (in one embodiment, Caparacid HL and Caparacid GS manufactured by Attec Co., Ltd.) is added at concentrations of 0.01 to 40 ml / l and 1 to 200 ml / l, respectively, to prepare a copper sulfate plating solution. Using the prepared copper sulfate plating solution, a conductor pattern is formed by plating with a Harling cell uniform plating apparatus (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.) at an applied current of 0.01 to 10 A for 1 to 300 minutes. The thickness of the copper plating film depends on the thickness of the resist pattern, but is preferably 1 μm or more (resist pattern thickness (μm) - 2 μm). In this disclosure, the thickness of the resist pattern refers to the thickness of the photosensitive resin layer after curing.

[0147] One example of a method for forming conductive patterns by etching is flash etching. Flash etching allows for the removal of the copper seed layer using a predetermined etching solution. Examples of etching solutions include, but are not limited to, a mixed etching solution of sulfuric acid and hydrogen peroxide (manufactured by Ebara Electric Industries, Ltd.).

[0148] [Method for manufacturing conductor patterns] The method for manufacturing the conductor pattern is, for example, to use a metal plate or a metal film insulating plate as a substrate, to form a resist pattern using the resist pattern formation method described above, and then to go through a conductor pattern formation step.

[0149] <Peeling process> Furthermore, after manufacturing the conductor pattern using the method described above, a peeling step may be performed to peel the resist pattern from the substrate using an aqueous solution that is more alkaline than the developer. By performing the peeling step, a wiring board (in one embodiment, a printed wiring board) having a desired wiring pattern can be obtained.

[0150] While there are no particular restrictions on the alkaline aqueous solution used for stripping (hereinafter also referred to as "stripping solution"), aqueous solutions of NaOH or KOH with a concentration of 2% to 20% by mass, or organic amine-based stripping solutions, are generally used. A small amount of water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohol. The temperature of the stripping solution during the stripping process is preferably in the range of 40°C to 70°C, and the immersion time of the stripping solution is preferably 1 to 60 minutes.

[0151] [Manufacturing method for wiring boards] A method for manufacturing a wiring board using a photosensitive resin laminate according to this embodiment involves the following steps in one embodiment: Lamination process for depositing a photosensitive resin layer onto a substrate; Exposure process for exposing a photosensitive resin layer; A developing process in which unexposed portions of a photosensitive resin layer are developed and removed to form a resist pattern; A conductor pattern formation step involves etching or plating a substrate on which a resist pattern has been formed to form a conductor pattern; and A peeling process to remove the resist pattern from the substrate; Includes. The steps included in the manufacturing method of the wiring board according to this embodiment—the lamination step, exposure step, development step, conductor pattern formation step, and peeling step—are the same as described above.

[0152] 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 machining 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 (COF) and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields. Unless otherwise specified, the values of the parameters described above are measured in accordance with the measurement methods in the examples described later.

[0153] [Manufacturing Method of Photosensitive Resin Laminate] The photosensitive resin laminate according to this embodiment can be manufactured by the following method. That is, in one aspect, the manufacturing method of the photosensitive resin laminate of this embodiment is a manufacturing method of a photosensitive resin laminate including a support film and a photosensitive resin layer containing a photosensitive resin composition, and includes the following steps: A preparation step of preparing a photosensitive resin composition solution containing a compound having an ethylenically unsaturated bond as component (A), an alkali-soluble resin as component (B), and a solvent; A coating step of coating the photosensitive resin composition solution on the support film; A photosensitive resin layer forming step of heating the support film coated with the photosensitive resin composition solution to form a photosensitive resin layer. It includes. In one aspect, component (A) includes a polyglycerol-based (meth) acrylate (A1) and a compound (A2) having no carboxyl group and having an ethylenically unsaturated bond.

[0154] By the manufacturing method of the photosensitive resin laminate according to this embodiment, a photosensitive resin laminate excellent in sensitivity and resolution can be manufactured without being affected by manufacturing conditions and storage conditions determined by the film thickness of the photosensitive resin layer.

[0155] <Preparation Step> This process involves adding a solvent to the above-mentioned (A) compound having an ethylenically unsaturated bond and (B) alkali-soluble resin to prepare a photosensitive resin composition solution (compound).

[0156] Suitable solvents include ketones, such as methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. You may use one type of solvent, or you may use a mixture of two or more solvents. The solvent content is preferably 30 to 60% by mass, more preferably 33 to 55% by mass, and even more preferably 35 to 57% by mass, relative to the photosensitive resin composition solution. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution is 500 to 4000 mPa·sec at 25°C. Viscosity was measured at 25°C using a Brookfield viscometer (Eikohsha, model DVNext).

[0157] <Coating Process> This process involves coating a photosensitive resin composition solution onto a support film. For coating the support film with the photosensitive resin composition solution, conventional methods such as application using a roll coater, spin coater, bar coater, blade coater, curtain coater, and screen printing machine, or spray application using a spray coater can be used.

[0158] <Photosensitive resin layer formation process> This process involves heating a support film coated with a photosensitive resin composition solution to form a photosensitive resin layer made of the photosensitive resin composition by heating and distilling off the solvent in the photosensitive resin composition solution. Furthermore, the heating temperature of the support film coated with the photosensitive resin composition solution is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. Heating to 70°C or higher accelerates the evaporation of the solvent contained in the photosensitive resin composition solution, thereby improving the production efficiency of the photosensitive resin laminate. The heating temperature of the support film coated with the photosensitive resin composition solution is preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower. Maintaining a temperature of 140°C or lower prevents the thermal polymerization of the photosensitive resin composition from progressing. The heating time for the support film coated with the photosensitive resin composition solution is preferably 1 to 10 minutes.

[0159] If necessary, the process may include a protective step after the photosensitive resin layer formation step in which a protective layer, such as a protective film, is laminated onto the photosensitive resin layer. The protective layer is applied to the side of the photosensitive resin layer where the support film is not laminated and functions as a cover. The protective film used in the protection process is the same as described above. [Examples]

[0160] Next, this embodiment will be described in more detail with reference to examples and comparative examples. However, this embodiment is not limited to the following examples unless it deviates from its essence. The physical properties in the examples were measured by the following methods.

[0161] [Preparation of evaluation samples] The evaluation samples were prepared as follows: <(A) Synthesis> Monomers (copolymer components) such as methacrylic acid, methyl methacrylate, and styrene, as shown in Table 2, were mixed with 3.0 parts by mass of azobisisobutyronitrile in the amounts (unit: parts by mass) shown in Table 2 to prepare solution (a). 200 g of methyl ethyl ketone and 100 g of ethanol were added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. The mixture was then stirred while blowing nitrogen gas into the flask and the temperature was raised to 80°C. 300 g of solution (a) was added to the mixture in the flask dropwise at a constant dropping rate over 4 hours, and then the mixture was stirred at 80°C for 2 hours.

[0162] Next, solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol. 50 g of solution (b) was added to the solution in the flask dropwise over 10 minutes at a constant dropping rate, and the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the solution in the flask was heated to 90°C over 30 minutes, maintained at 90°C for 2 hours, then the stirring was stopped and the solution was cooled to room temperature (25°C). This yielded solutions of alkali-soluble polymers A-1 to A-10. The calculated glass transition temperature (Tg), weight-average molecular weight (Mw), and acid value of alkali-soluble polymers A-1 to A-10 are shown in Table 2.

[0163] (A) The weight-average molecular weight of alkali-soluble polymers was determined by gel permeation chromatography (GPC) and then converted using a calibration curve for standard polystyrene. The GPC conditions were as follows:

[0164] (GPC conditions) Pump: PU-980, manufactured by JASCO Corporation. Columns: A total of 2 columns as follows Shodex KF-80Y / KF-806M Eluent: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: RI-1530, manufactured by JASCO Corporation Standard monodisperse polystyrene: manufactured by Tosoh Corporation, product name TSKgel Standard Polystyrene

[0165] (A) The glass transition temperature (Tg) of the alkali-soluble polymer is calculated using Fox's equation: [Equation number] {In the formula, Tg i (K: Kelvin) is the glass transition temperature of the homopolymer composed of each monomer, and c i is the copolymerization ratio of each monomer} by applying the Tg i and c i listed in Table 1 above. The values were calculated by applying the values of Tg and c listed in Table 1 above. Table 2 shows the Tg of the copolymer contained in component (A).

[0166] (A) The acid value of the copolymer contained in the alkali-soluble polymer is a value calculated on the assumption that all the methacrylic acid contained in each (A) component reacts with potassium hydroxide, based on the definition of the amount (mg) of potassium hydroxide that can neutralize 1 g of component (A). Table 2 shows the acid value of the copolymer contained in component (A).

[0167] The photosensitive resin laminate was prepared as follows. <Preparation of Photosensitive Resin Laminate> Components (A) to (D) shown in Table 3 below (however, the numbers of each component indicate the content (parts by mass) as a solid content) were mixed to prepare photosensitive resin compositions (Examples 1 to 16 and Comparative Examples 1 to 9). The photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 9, and ethanol weighed so that the solid content concentration of these photosensitive resin compositions became 60% by mass were sufficiently stirred and mixed to obtain a preparation liquid containing the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 9. For Examples 1-16 and Comparative Examples 1-9, a 16 μm thick polyethylene terephthalate film (QS71, manufactured by Toray Industries, Inc.) was used as a support film. The prepared solutions were uniformly applied to its surface using a bar coater (product name: Type A Automatic Applicator, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and then heated and dried in a 95°C dryer for 2 minutes and 30 seconds to form a photosensitive resin layer with a thickness of 25 μm. Next, a 19 μm thick polyethylene film (GF-858, manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer onto the surface of the photosensitive resin layer that did not have a polyethylene terephthalate film laminated on it, thereby obtaining photosensitive resin laminates (Examples 1-16 and Comparative Examples 1-9) containing the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-9. A 16 μm thick polyethylene terephthalate film (QS71, manufactured by Toray Industries, Inc.) was used as a support film. A mixture containing the photosensitive resin composition of Example 1 was uniformly applied to its surface using a bar coater (product name: Type A Automatic Applicator, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the mixture was heated and dried in a 95°C dryer for 1 minute to form a photosensitive resin layer with a thickness of 10 μm. Next, a 19 μm thick polyethylene film (GF-858, manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer onto the surface of the photosensitive resin layer that did not have a polyethylene terephthalate film laminated on it, to obtain a photosensitive resin laminate containing the photosensitive resin composition of Example 1 (Example 1').

[0168] [Fabrication of performance evaluation substrates] The performance evaluation board was fabricated as follows.

[0169] <Substrate surface preparation> A 0.4 mm thick copper-clad laminate was prepared by laminating 18 μm thick rolled copper foils. The surface of this substrate was cleaned with a 10 mass% H2SO4 aqueous solution.

[0170] <Laminate> While peeling off the polyethylene film from the photosensitive resin laminate prepared above, the substrate surface was prepared using the above method, and then the photosensitive resin laminate was laminated onto a copper-clad laminate preheated to 50°C using a hot roll laminator (Asahi Kasei Corporation, AL-700) at a roll temperature of 105°C to obtain a substrate for performance evaluation. The air pressure was set to 0.35 MPa and the lamination speed to 1.5 m / min.

[0171] <Exposure process> Two hours after lamination, the performance evaluation substrate was exposed at a wavelength of 365 nm through a glass mask using a projection exposure machine (UX-44101SM, manufactured by Ushio Inc.). Similarly, the performance evaluation substrate was exposed at a wavelength of 402 nm using a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined direct imaging (DI) exposure pattern.

[0172] <Heating process> The performance evaluation substrate, one minute after exposure, was heated for 30 seconds in a forced-air constant-temperature incubator (Yamato Scientific Co., Ltd., DKM600) set to 60°C.

[0173] <Developing process> After peeling off the polyethylene terephthalate film (support film), development was performed by spraying a 1% by mass Na2CO3 aqueous solution at 30°C for a predetermined time using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., for dry film). The time for applying the developing spray was set to twice the minimum development time, and the time for applying the rinsing spray after development was also set to twice the minimum development time.

[0174] <Plating Process> On a substrate that had undergone the same surface preparation and lamination as described above, a resist pattern was formed by exposure using a drawing pattern with a line width (L) / space width (S) (hereinafter referred to as "L / S") of x / x (x = 1 to 20 (varying at 1 μm intervals)) (unit: μm) at an energy level that resulted in 17 remaining steps on a Hitachi 41-step step tablet. After exposure, the same heating and development processes as described above were performed to form a resist pattern. The developed substrate was immersed in an acidic degreasing FRX bath (10% by mass sulfuric acid aqueous solution, manufactured by Attec Japan Co., Ltd.) at 40°C for 4 minutes. After rinsing with water, it was immersed in a 10% by mass sulfuric acid aqueous solution at room temperature for 2 minutes.

[0175] A 121 g / l copper sulfate aqueous solution was prepared and diluted with 19% sulfuric acid until its volume was 3.6 times its original volume. Then, concentrated hydrochloric acid was added to a concentration of 200 ppm. Next, caparacid HL and caparacid GS were added as brighteners at concentrations of 0.4 ml / l and 20 ml / l, respectively, to prepare a copper sulfate plating solution. A pre-treated substrate (6 cm x 12.5 cm) for evaluating plating resistance was plated using a Harling cell uniform plating apparatus (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.) with a current of 0.4 A for 65 minutes using the prepared copper sulfate plating solution. The thickness of the copper plating film at this time was 20 μm.

[0176] <Peeling process> Product names "Clean Etch (registered trademark) R-100S" (manufactured by Mitsubishi Gas Chemical Company, Inc.) and "Clean Etch (registered trademark) R-101" (manufactured by Mitsubishi Gas Chemical Company, Inc.) were mixed in a volume ratio of 1 / 2, and then diluted with pure water to prepare a stripping solution with a total concentration of 20% by mass of R-100S and R-101. A performance evaluation substrate that had undergone plating treatment was immersed in the stripping solution, heated to 50°C, for 4 minutes without stirring to remove the resist pattern.

[0177] [evaluation] <Developability> The fabricated performance evaluation substrate was subjected to exposure and development processes according to the method described above, and the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was defined as the shortest development time. Specifically, in this embodiment, the development time was changed every 0.5 seconds for evaluation, and the shortest development time among those in which the unexposed portion of the photosensitive resin layer could be confirmed to have completely dissolved by visual inspection was defined as the shortest development time. A shorter minimum development time indicates higher developability, and the minimum development time was evaluated according to the following criteria. If the evaluation is ◎ or ○, it can be suitably used as a photosensitive resin laminate for forming resist patterns. ◎: Minimum development time of 20 seconds or less. "Excellent" ○: Minimum development time between 20 and 22 seconds. "Good" ×: Minimum development time of 22 seconds or more. "Not allowed."

[0178] <Perfection in the resist pattern> A resist pattern was formed on the fabricated performance evaluation substrate by exposing it to an energy level that resulted in a maximum of 15 layers of residual film when developed using a 41-step step tablet as a mask, with a drawing pattern where the line width (L) / space width (S) (hereinafter referred to as "L / S") was 3x / x (x = 1 to 20 (varying at 1 μm intervals)) (unit: μm), followed by the heating and development process described above. The resist pattern was observed under an optical microscope at 100x magnification, and the permeability of the resist pattern was evaluated by the minimum line width at which the empty areas (unexposed areas) were completely removed without residue. A smaller value indicates higher permeability of the resist pattern. If the evaluation is ◎ or ○, it can be suitably used as a photosensitive resin laminate for forming resist patterns. ◎: Minimum line width is less than 4.0 μm. "Excellent" ○: Minimum line width is 4.0 μm or more and 5.0 μm or less. "Good" ×: Minimum line width exceeds 5.0 μm. "Not allowed."

[0179] <Evaluation of peelability> The fabricated performance evaluation substrate was subjected to the plating process described above, followed by the stripping process described above. The time it took for the hardened resist lines between the plating patterns to be completely removed was defined as the post-plating peelability value. A smaller value indicates higher peelability, and it was evaluated according to the following criteria. If the evaluation is ◎ or ○, it can be suitably used as a printed circuit board after plating is performed following the formation of the resist pattern. ◎: Less than 60 seconds "Excellent" ○: 60 seconds or more but less than 75 seconds "Good" ×: 75 seconds or more “Not possible”

[0180] Table 3 shows the evaluation results for the performance evaluation substrates of the examples. Table 2 shows the details of the components shown in Table 3. For component (A) in Table 2, the content ratio of each monomer component in components A-1 to A-10 represents the mass ratio of each monomer component.

[0181] [Table 2]

[0182] [Table 3-1]

[0183] [Table 3-2]

[0184] As is clear from Table 3, the embodiments that met the requirements of this embodiment showed good developability, resist pattern release, and peelability. On the other hand, when component (A) contained monomer components that did not meet the specified requirements, the developability, resist pattern release, and peelability were all poor. Furthermore, when component (B) did not contain (b-1) a di(meth)acrylate compound containing at least one ethylene oxide structure and one propylene oxide structure in a single molecule, and (b-2) a tetrafunctional or higher (meth)acrylate compound, the developability, resist pattern release, and peelability were all unsatisfactory.

[0185] While embodiments of the present invention have been described above, the present invention is not limited thereto and can be modified as appropriate without departing from the spirit of the invention. [Industrial applicability]

[0186] By using the photosensitive resin laminate according to the present invention, the photosensitive resin laminate is unaffected by coating, drying, and storage conditions, and exhibits excellent developability, resist pattern release properties, and peelability. In other words, it can be widely used as a photosensitive resin laminate for resist pattern formation, and is particularly suitable for use in forming resist patterns on printed circuit boards where plating is required after resist pattern formation.

Claims

1. A photosensitive resin laminate comprising a support film and a photosensitive resin layer containing a photosensitive resin composition, The aforementioned photosensitive resin composition comprises the following components: (A) Alkali-soluble polymers; (B) Compounds having ethylenically unsaturated bonds; and (C) Polymerization initiator; Includes, The aforementioned component (A) includes a copolymer containing monomer components as constituent units, When the glass transition temperature (Tg) of the copolymer calculated by Fox's formula is x (°C) and the acid value of the copolymer is y (mg KOH / g), then x ≥ 120 and 3y / 7 + 60 < x. The aforementioned component (B) consists of the following components: (b-1) Di(meth)acrylate compounds containing at least one ethylene oxide structure and at least one propylene oxide structure in one molecule; and (b-2) Tetrafunctional (meth)acrylate compounds; Includes, The (C) component is a photosensitive resin laminate containing a compound having a biimidazole structure in an amount of 5.0 to 10% by mass relative to the total solid content mass of the photosensitive resin composition.

2. The photosensitive resin laminate according to claim 1, wherein the component (A) has an acid value y of 180 or less (y ≤ 180).

3. The photosensitive resin laminate according to claim 1, wherein the component (A) has an acid value y of 160 or less (y ≤ 160).

4. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the copolymer contains a constituent unit derived from (meth)acrylic acid as the monomer component, and the content of the constituent unit derived from (meth)acrylic acid in component (A) is 10% by mass or more and less than 25% by mass.

5. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the copolymer contains a constituent unit derived from a compound having an aromatic ring as the monomer component, and the content of the constituent unit derived from the compound having an aromatic ring in component (A) is 30% by mass or more and 80% by mass or less.

6. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the copolymer contains a constituent unit derived from methyl methacrylate as the monomer component, and the content of the constituent unit derived from methyl methacrylate in component (A) is 10% by mass or more and less than 40% by mass.

7. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the copolymer comprises a structural unit derived from dicyclopentanyl methacrylate.

8. The copolymer is It contains constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, and constituent units derived from styrene, A photosensitive resin laminate according to any one of claims 1 to 3, wherein the total proportion of the content of the constituent units derived from methacrylic acid, the constituent units derived from methyl methacrylate, and the constituent units derived from styrene is 90% by mass or more, and the content of the constituent units derived from methacrylic acid is 18% by mass or more and 25% by mass or less.

9. The copolymer is It contains constituent units derived from methacrylic acid and constituent units derived from dicyclopentanyl methacrylate, A photosensitive resin laminate according to any one of claims 1 to 3, wherein the content of the constituent units derived from methacrylic acid is 15% by mass or more and 30% by mass or less, and the laminate contains 5% by mass or more and 45% by mass or less of the constituent units derived from dicyclopentanyl methacrylate.

10. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (b-1) component is contained in an amount of 10 to 35% by mass relative to the total solid content mass of the photosensitive resin composition.

11. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (b-1) component comprises a compound having a bisphenol A structure.

12. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (b-1) component is a compound having four or more of the ethylene oxide structure and the propylene oxide structure in one molecule.

13. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (b-2) component is contained in an amount of 5 to 20% by mass with respect to the total solid content mass of the photosensitive resin composition.

14. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (b-2) component comprises a (meth)acrylate compound with five or more functionalities.

15. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the ratio of the solid content mass of component (b-1) to component (b-2), (b-1):(b-2), is in the range of 4:6 to 8:

2.

16. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the total content of component (b-1) and component (b-2) is 50% by mass or more and 100% by mass or less with respect to the total mass of component (B).

17. The aforementioned component (B) is further, A photosensitive resin laminate according to any one of claims 1 to 3, comprising ethoxylated bisphenol A di(meth)acrylate having an average of 2 to 30 ethylene oxide structures per molecule.

18. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (C) component further comprises an anthracene derivative.

19. The photosensitive resin laminate according to claim 18, wherein the content of the anthracene derivative is 0.01% by mass or more and 0.5% by mass or less.

20. A method for forming a resist pattern using a photosensitive resin laminate according to any one of claims 1 to 3, comprising the following steps: Lamination process for stacking a photosensitive resin layer onto a substrate; An exposure step of exposing the photosensitive resin layer; and A developing step for developing and removing the unexposed portion of the photosensitive resin layer; A method for forming a resist pattern, including [a specific component].

21. A method for manufacturing a wiring board using a photosensitive resin laminate according to any one of claims 1 to 3, comprising the following steps: Lamination process for stacking a photosensitive resin layer onto a substrate; An exposure step of exposing the photosensitive resin layer; A developing step to develop and remove the unexposed portion of the photosensitive resin layer to form a resist pattern; A conductor pattern forming step involves etching or plating the substrate on which the resist pattern is formed to form a conductor pattern; and A peeling step for peeling the resist pattern from the substrate; A method for manufacturing a wiring board, including the method described above.

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