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

Abstract

The invention provides a photosensitive resin laminate, a method for forming a resist pattern, and a method for manufacturing a circuit board. The photosensitive resin laminate includes a support film and a photosensitive resin layer including a photosensitive resin composition including A an alkali-soluble polymer, B a compound having an ethylenically unsaturated bond, and C a polymerization initiator, component A including a copolymer including a monomer component as a structural unit, and component B including a copolymer including a monomer component as a structural unit. X > = 120 and 3y / 7 + 60 lt, where x DEG C is the value of the glass transition temperature Tg of the copolymer calculated by the Fox formula, and y mgKOH / g is the acid value of the copolymer; the component B contains 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 (meth) acrylate compound having more than four functional groups, and the component C contains 5.0-10 mass% of a biimidazole compound with respect to the total solid content mass of the composition.

Description

Technical Field

[0001] This invention relates to a photosensitive resin laminate, a method for forming resist patterns, and a method for manufacturing a circuit board. Background Technology

[0002] Printed circuit boards and semiconductor packaging substrates are typically manufactured using photolithography. Photolithography refers to 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. This coating is then patterned and developed to form a resist pattern. Next, a conductor pattern is formed through etching or plating. Finally, the desired wiring pattern is formed on the substrate by removing the resist pattern.

[0003] Typically, the formation of resist patterns in photolithography processes involves methods such as coating a solution of a photosensitive resin composition onto a substrate and allowing it to dry, or laminating a photosensitive resin layer (a photosensitive resin laminate containing a photosensitive resin layer and a support film) onto a substrate.

[0004] In the formation of wiring patterns in printed circuit boards and semiconductor packaging substrates, photosensitive resin laminates are often used. In the production and use of photosensitive resin laminates, the properties of the resist pattern, such as its peelability, developability, flexibility, resolution, adhesion, and release properties, as well as productivity, are important, determined by the type and combination of alkali-soluble polymers, compounds with olefinic unsaturated bonds, and photopolymerization initiators, as well as their content settings.

[0005] For example, Patent Document 1 discloses a photosensitive resin composition containing an adhesive polymer, a photopolymerizable compound having two or more reactive groups that react with free radicals and having a total of 2 to 40 oxoethylidene and / or oxopropylidene groups, a photopolymerizable compound, a photopolymerization initiator, and an anthracene sensitizer.

[0006] For example, Patent Document 2 discloses a pattern forming material having a support and at least a photosensitive layer on the support, the photosensitive layer comprising at least an adhesive, a polymerizable compound and a photopolymerization initiator, wherein the polymerizable compound comprises a polymerizable compound having a bisphenol backbone (a-1) and a polymerizable compound having four or more reactive groups in the molecule and having a molecular weight of 700 or more (a-2).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2021 / 192058

[0010] Patent Document 2: Japanese Patent Application Publication No. 2008-020629

[0011] Patent Document 3: Japanese Patent Application Publication No. 2022-027767

[0012] Patent Document 4: International Publication No. 2022 / 186389 Summary of the Invention

[0013] The problem the invention aims to solve

[0014] However, the photosensitive resin compositions described in the aforementioned patent documents 1 to 4 have room for improvement in terms of the peeling, developing and exfoliating properties of the resist pattern.

[0015] The purpose of this invention is to provide a photosensitive resin laminate with excellent resist pattern peeling, developability and release properties, a method for forming resist patterns and a method for manufacturing circuit boards.

[0016] Solution for solving the problem

[0017] The present invention is described below. [1]

[0019] A photosensitive resin laminate comprising a support film and a photosensitive resin layer containing a photosensitive resin composition.

[0020] The photosensitive resin composition comprises the following components:

[0021] (A) Alkali-soluble polymers,

[0022] (B) Compounds with olefinic unsaturated bonds, and

[0023] (C) Polymerization initiator,

[0024] Component (A) comprises a copolymer containing monomeric components as structural units.

[0025] When the glass transition temperature (Tg) of the copolymer calculated by the Fox formula is set as x (°C) and the acid value of the copolymer is set as y (mgKOH / g), x ≥ 120 and 3y / 7 + 60 <x,

[0026] Component (B) comprises the following components:

[0027] (b-1) A di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule, and

[0028] (b-2) Four or more functional (meth)acrylate compounds,

[0029] Relative to the total solid content of the photosensitive resin composition, component (C) comprises 5.0 to 10% by mass of a compound containing a bimidazole structure. [2]

[0031] According to the photosensitive resin laminate described in [1], wherein the acid value y of component (A) is 180 or less (y≤180). [3]

[0033] According to the photosensitive resin laminate described in [1], wherein the acid value y of component (A) is 160 or less (y≤160). [4]

[0035] The photosensitive resin laminate according to any one of [1] to [3], wherein the copolymer comprises a structural unit derived from (meth)acrylic acid as the monomer component, and the content of the structural unit derived from (meth)acrylic acid in component (A) is 10% by mass or more and less than 25% by mass. [5]

[0037] The photosensitive resin laminate according to any one of [1] to [4], wherein the copolymer comprises 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]

[0039] The photosensitive resin laminate according to any one of [1] to [5], wherein the copolymer comprises a structural unit derived from methyl methacrylate as the monomer component, and the content of the methyl methacrylate-derived structural unit in component (A) is 10% by mass or more and less than 40% by mass. [7]

[0041] The photosensitive resin laminate according to any one of [1] to [6], wherein the copolymer comprises structural units derived from dicyclopentyl methacrylate. [8]

[0043] The photosensitive resin laminate according to any one of [1] to [7], wherein the copolymer comprises structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from styrene.

[0044] The total content of the structural units derived from methacrylic acid, the structural units derived from methyl methacrylate, and the structural units derived from styrene is 90% or more by mass, and the content of the structural units derived from methacrylic acid is 18% or more and 25% or less by mass. [9]

[0046] The photosensitive resin laminate according to any one of [1] to [8], wherein the copolymer comprises structural units derived from methacrylic acid and structural units derived from dicyclopentyl methacrylate,

[0047] The content of the structural units derived from methacrylic acid is 15% or more and 30% or less by mass, and the copolymer contains 5% or more and 45% or less of the structural units derived from dicyclopentyl methacrylate.

[10]

[0049] The photosensitive resin laminate according to any one of [1] to [9] contains 10 to 35% by mass of the (b-1) component relative to the total solid content of the photosensitive resin composition.

[11]

[0051] 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]

[0053] 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 oxyethylene structures and four or more of the oxypropylene structures in one molecule.

[13]

[0055] The photosensitive resin laminate according to any one of [1] to

[12] contains 5 to 20% by mass of the (b-2) component relative to the total solid content of the photosensitive resin composition.

[14]

[0057] The photosensitive resin laminate according to any one of [1] to

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

[15]

[0059] The photosensitive resin laminate according to any one of [1] to

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

[16]

[0061] The photosensitive resin laminate according to any one of [1] to

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

[17]

[0063] The photosensitive resin laminate according to any one of [1] to

[16] , wherein the (B) component further comprises ethoxylated bisphenol A di(meth)acrylate having an average of 2 to 30 oxyethylene structures per molecule.

[18]

[0065] The photosensitive resin laminate according to any one of [1] to

[17] , wherein the above-mentioned component (C) further comprises an anthracene derivative.

[19]

[0067] According to the photosensitive resin laminate described in

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

[20]

[0069] A method for forming a resist pattern, which is a method for forming a resist pattern using any one of the photosensitive resin laminates [1] to

[19] , comprising the following steps:

[0070] In the lamination process, photosensitive resin layers are laminated onto the substrate;

[0071] The exposure process exposes the photosensitive resin layer; and

[0072] The developing process removes the unexposed portions of the photosensitive resin layer. [twenty one]

[0074] A method for manufacturing a circuit board, which is a method for manufacturing a circuit board using any one of the photosensitive resin laminates described in [1] to

[19] , comprising the following steps:

[0075] In the lamination process, photosensitive resin layers are laminated onto the substrate;

[0076] The exposure process exposes the photosensitive resin layer.

[0077] The developing process removes the unexposed portion of the photosensitive resin layer to form a resist pattern.

[0078] The conductor pattern forming process involves etching or plating a substrate on which the resist pattern is formed to form the conductor pattern; and

[0079] The stripping process removes the resist pattern from the substrate.

[0080] The effects of the invention

[0081] According to the present invention, a photosensitive resin laminate comprising a photosensitive resin layer containing a photosensitive resin composition, a method for forming a photosensitive pattern, and a method for manufacturing a circuit board are provided, which can provide excellent resist pattern peeling, developing, and exfoliating properties. Detailed Implementation

[0082] Hereinafter, an exemplary embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to this embodiment and can be implemented in various modifications within its scope. 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 value recorded within a certain numerical range can also be replaced with the value shown in the embodiment.

[0083] In addition, in this specification, the numerical range represented by "~" includes both upper and lower limits.

[0084] Regarding the term "process" in the following explanation, it goes without saying that an independent process is included in this term. Even if it cannot be clearly distinguished from other processes, it can be included in this term as long as the function of the "process" can be achieved.

[0085] In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means "acrylate" or "methacrylate".

[0086] <Photosensitive Resin Laminate>

[0087] In one embodiment, the photosensitive resin laminate includes a support film and a photosensitive resin layer comprising a photosensitive resin composition.

[0088] Furthermore, in particular, one embodiment of the photosensitive resin composition constituting the photosensitive resin laminate provides a photosensitive resin composition comprising:

[0089] (A) Alkali-soluble polymers,

[0090] (B) Compounds with olefinic unsaturated bonds, and

[0091] (C) Polymerization initiator.

[0092] In one embodiment, the photosensitive resin composition comprises a copolymer as (A) an alkali-soluble polymer, said copolymer containing monomer components as structural units.

[0093] In one mode, (A) the alkali-soluble polymer contains a copolymer in which the value of the glass transition temperature (Tg) calculated by the Fox formula is set as x (°C) and the acid value of the copolymer is set as y (mgKOH / g), and x ≥ 120 and 3y / 7 + 60 < x.

[0094] In one mode, the photosensitive resin composition of the present embodiment contains (b-1) a di(meth)acrylate compound containing at least 1 or more oxyethylene structures and at least 1 or more oxypropylene structures in one molecule and (b-2) a tetrafunctional or higher (meth)acrylate compound as (B) a compound having an ethylenically unsaturated bond.

[0095] In one mode, the photosensitive resin composition of the present embodiment contains 5.0 to 10% by mass of a compound containing an imidazole structure as (C) a polymerization initiator with respect to the total solid component mass of the photosensitive resin composition.

[0096] In the present specification, the above (A) to (C) may sometimes be abbreviated as “component (A)” to “component (C)”. The same applies to the respective components described later other than the components (A) to (C). Each component and raw materials of each component can be used alone in 1 kind, or 2 or more kinds can be used in combination. In the present specification, the “solid component” of the photosensitive resin composition means the components other than the solvent in the photosensitive resin composition.

[0097] The present inventors found that by combining the above-specified components (A), (B), and (C) as the components of the photosensitive resin composition of the present embodiment, the developability, the peeling property, and the stripping property of the resist pattern become good.

[0098] That is, according to the present embodiment, it is possible to provide a photosensitive resin laminate excellent in developability, peeling property, and stripping property of the resist pattern, a method for forming a resist pattern, and a method for manufacturing a circuit board.

[0099] <Support film>

[0100] The support film of the present embodiment is a layer or film for supporting the photosensitive resin layer, and is preferably a transparent base film that transmits actinic rays.

[0101] Examples of the transparent base film include films formed of synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), cellulose triacetate, and cycloolefin polymer.

[0102] Among them, it is preferable to use a high-quality film with few internal foreign matters.

[0103] Specifically, as a high-quality film, polyethylene terephthalate (PET) film, cellulose triacetate film, cyclic olefin polymer film, etc. are preferred, and polyethylene terephthalate (PET) film with moderate flexibility and strength is even more preferred.

[0104] Among PET films, it is more preferable to use PET films synthesized using Ti-based catalysts, PET films with small diameter and low lubricant content, PET films containing lubricant only on one side of the film, thin PET films, PET films that have undergone smoothing treatment on at least one side, and PET films that have undergone roughening treatment such as plasma treatment on at least one side.

[0105] Therefore, the light used for exposure can reach the photosensitive resin layer without being blocked by internal foreign matter, thereby improving the resolution of the photosensitive resin composition.

[0106] The thickness of the support film is preferably 5 μm or more and 25 μm or less, more preferably 6 μm or more and 20 μm or less. The thinner the support film, the fewer the number of internal foreign objects, and the better it can prevent the reduction of resolution. However, if the film thickness is too thin, elongation deformation in the winding direction caused by tension and / or damage caused by tiny scratches may occur during the coating / winding manufacturing process, or the film may be too weak and wrinkles may occur during lamination.

[0107] At least one side of the support film can be smoothed using a calendering apparatus or the like. This reduces the surface roughness of one side of the support film, particularly the side in contact with the photosensitive resin composition layer described later, thus improving the performance of this embodiment.

[0108] From the viewpoint of improving the parallelism of light irradiating the photosensitive resin layer and obtaining higher resolution after exposure and development of the photosensitive resin laminate, 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%.

[0109] <Photosensitive resin layer>

[0110] The photosensitive resin layer of this embodiment comprises a photosensitive resin composition. Alternatively, the photosensitive resin layer of this embodiment may, in one embodiment, be a resist layer.

[0111] In this embodiment, the thickness of the photosensitive resin layer is preferably 3 to 100 μm, more preferably 3 to 50 μm. The closer the thickness of the photosensitive resin layer is to 3 μm, the higher the resolution; the closer it is to 100 μm, the higher the film strength. Therefore, it can be appropriately selected according to the application.

[0112] In particular, the thickness of the photosensitive resin layer of the present embodiment is preferably 5 to 30 μm, more preferably 10 to 25 μm. By setting the thickness of the photosensitive resin layer of the present embodiment within the above range, it can be suitably used for applications such as semiconductor packaging substrates that require the formation of fine wirings.

[0113] On the other hand, the thickness of the photosensitive resin layer of the present embodiment can exceed 100 μm and be 500 μm or less. By setting the thickness of the photosensitive resin layer within the above range, it can also be suitably used for applications such as bump formation or copper pillar formation.

[0114] <Photosensitive Resin Composition>

[0115] The photosensitive resin composition of the present embodiment contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a polymerization initiator.

[0116] (A) Alkali-Soluble Polymer

[0117] In the present embodiment, the (A) alkali-soluble polymer (hereinafter referred to as the (A) component) contains a copolymer containing structural units derived from the following first monomer and second monomer as monomer components.

[0118] (A) component contains: a copolymer in which when the value of the glass transition temperature (Tg) calculated by the following Fox formula is set to x (°C) and the acid value is set to y (mgKOH / g), x ≥ 120 and 3y / 7 + 60 < x.

[0119] According to the photosensitive resin composition containing this (A) component, the peelability, developability, and stripping properties of the resist pattern are excellent. In addition, according to a preferred mode of the photosensitive resin composition, a photosensitive resin layer (resist layer) having excellent peelability, developability, and stripping properties of the resist pattern in at least one, at least two, or all of them can be formed. Furthermore, according to the photosensitive resin composition, a photosensitive resin laminate having a photosensitive resin layer, a method for forming a resist pattern, a method for manufacturing a circuit board, etc. can be provided.

[0120] 《Glass Transition Temperature (Tg)》

[0121] (A) The value of the glass transition temperature (Tg) of the copolymer contained in the component is calculated based on the Fox formula. The Tg of the copolymer can be controlled by the types and proportions of the monomers constituting the copolymer. In the copolymer, by containing each preferred component in a preferred proportion, a preferred Tg can be easily achieved.

[0122] For a copolymer composed of n kinds of monomers, the Fox formula for calculating the Tg (K: Kelvin) of the copolymer is represented by the following formula.

[0123] [Mathematical Formula 1]

[0124]

[0125] {where Tg i (K: Kelvin) is the glass transition temperature of the homopolymer composed of the monomers, c i The copolymerization ratio of each monomer.

[0126] In this application, the Tg values ​​of homopolymers composed of monomers that form alkali-soluble polymers are used as literature values ​​(Brandrup, J. Immergut, EH ed., Polymer handbook, Third edition, John Wiley & Sons, 1989, Chapter VI “GLASS transition temperatures of polymers”, p209). It should be noted that the glass transition temperature (Tg) of the homopolymer composed of each monomer is... i One example is described below.

[0127] [Table 1]

[0128]

[0129] Based on the above [Mathematical Formula 1] and [Table 1], the Tg of component (A) as illustrated below is derived as follows.

[0130] · Methacrylic acid / methyl methacrylate / styrene

[0131] (mass ratio = 21 / 39 / 40): Tg 123℃

[0132] (mass ratio = 29 / 19 / 52): Tg 131℃

[0133] (mass ratio = 25 / 50 / 25): Tg 128℃

[0134] • Methacrylate / styrene / dicyclopentyl methacrylate

[0135] (mass ratio = 30 / 50 / / 20): Tg 146℃

[0136] · Methacrylate / Benzyl methacrylate

[0137] (mass ratio = 20 / 80): Tg 78℃

[0138] • Methacrylic acid / methyl methacrylate / styrene / dicyclopentyl methacrylate

[0139] (mass ratio = 25 / 25 / 25 / 25): Tg 146℃

[0140] · Methacrylic acid / styrene / methacrylonitrile

[0141] (mass ratio = 25 / 45 / 30): Tg 132℃

[0142] · Methacrylic acid / styrene / methyl methacrylate / methacrylonitrile

[0143] (mass ratio = 28 / 15 / 10 / 47): Tg 140℃

[0144] (mass ratio = 27 / 16 / 15 / 42): Tg 138℃

[0145] • Methacrylic acid / dicyclopentenoxyethyl methacrylate / methyl methacrylate / styrene

[0146] (mass ratio = 25 / 26 / 5 / 44): Tg 131℃

[0147] When the glass transition temperature (Tg) of the copolymer in component (A) calculated based on the Fox formula is set as x (°C), from the viewpoint of improving peelability, x ≥ 120 is preferred. 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.

[0148] In this application, when component (A) contains multiple copolymers, the overall glass transition temperature (Tg) of component (A) is... total The weight-average Tg of each (A) component is used. total It is expressed in terms of form.

[0149] The average weight Tg total The value is obtained according to the following formula.

[0150] Tg total =Σ i (W i ×Tg i ) / W total

[0151] (where W) i Tg represents the solid component mass of each alkali-soluble polymer. i For each alkali-soluble polymer, the glass transition temperature (Tg) is calculated using the Fox formula. W total (This represents the total solid mass of each alkali-soluble polymer.)

[0152] From the perspective of improving peelability, this Tg total The preferred temperature is above 120°C.

[0153] Acid Value

[0154] (A) The component is a polymer soluble in an alkaline aqueous solution. Such a polymer is, for example, a vinyl polymer containing a carboxyl group.

[0155] In the present application, the acid equivalent is the weight (g / mol) of the alkali-soluble polymer per 1 mol of acidic groups, and satisfies the relationship "acid equivalent = 56100 / acid value".

[0156] When the acid value of the copolymer contained in the component (A) is set to y (mgKOH / g), from the viewpoint of contributing to the balance between the peelability of the resist pattern and the overall effect, it is preferably y ≤ 200, more preferably y ≤ 180, further preferably y ≤ 160, still further preferably y ≤ 150, and particularly preferably y ≤ 140. That is, from the viewpoint of contributing to the balance between the peelability of the resist pattern and the overall effect, the acid value of the copolymer contained in the component (A) is preferably 200 or less, more preferably 180 or less, further preferably 160 or less, still further preferably 150 or less, and particularly preferably 140 or less.

[0157] In addition, from the viewpoint of developability, it may be y ≥ 65, preferably y ≥ 80. That is, the acid value of the copolymer contained in the component (A) may be 65 or more, preferably 80 or more.

[0158] The acid value y (mgKOH / g) of the copolymer contained in the component (A) is defined by the amount (mg) of potassium hydroxide that can neutralize 1 g of the component (A).

[0159] That is, regarding the acid value y (mgKOH / g) of the copolymer contained in the component (A), about 1 g of the sample containing the component (A) can be accurately weighed, dissolved in 100 mL of acetone, and then neutral titrated with a 1 mol / L aqueous potassium hydroxide solution. Substitute the dropping amount of the aqueous potassium hydroxide solution into the following formula to calculate.

[0160] Acid value (mgKOH / g) = 56.1 × {dropping amount (mL) of 1 mol / L aqueous potassium hydroxide solution} / {mass (g) of the accurately weighed sample}

[0161] The neutral titration can be carried out, for example, using the Hiranuma Sangyo Co., Ltd. automatic titrator (COM-555).

[0162] In one mode, the component (A) contains a copolymer in which when the Tg value calculated by the Fox formula is set to x (°C) and the acid value is set to y (mgKOH / g), x ≥ 120 and 3y / 7 + 60 < x.

[0163] By making x and y of the copolymer satisfy the above-specified ranges, the photosensitive resin composition of the present embodiment has excellent stripping properties, developability, and peelability of the resist pattern.

[0164] Regarding the fact that the copolymer contained in the component (A) has the effects specified in the present application by satisfying the above-specified ranges, the present inventors presume as follows.

[0165] Hitherto, an alkali-soluble polymer containing methacrylic acid and styrene as monomer components has been used. In particular, the alkali-soluble polymer tends to have a high Tg by containing methacrylic acid, and the values of the acid value and Tg tend to change联动 with 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, the conventional alkali-soluble polymer tends to satisfy the inside of the Pareto line shown by the formula 1: 3y / 7 + 60 > x.

[0166] On the other hand, in the case of such a conventional alkali-soluble polymer, there is a problem that there is a trade-off relationship between the length of the stripping time of the resist pattern and the stripping properties and the length of the developing time of the resist pattern, and it is difficult to achieve a composition in which all of these properties are excellent.

[0167] Here, the present inventors have found that by using an alkali-soluble polymer that satisfies the outside of the Pareto line shown by the formula 2: 3y / 7 + 60 < x and combining it with a specific compound having an ethylenically unsaturated bond, the effects specified in the present application can be achieved.

[0168] When the value of the glass transition temperature (Tg) of the copolymer calculated by the Fox formula is x (°C) and the acid value of the copolymer is y (mgKOH / g), as means for making x ≥ 120 and 3y / 7 + 60 < x, for example, the following means (i) to (iii) can be cited.

[0169] (i) The copolymer contained in the component (A) contains a certain amount of methacrylic acid (Tg i = 501K) as a monomer component, and the methacrylic acid is a monomer having an acidic group and a high glass transition temperature Tg when made into a homopolymer. i large monomer.

[0170] Specifically, the lower limit of the content of methacrylic acid (in one mode, 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. In addition, 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 further preferably 25% by mass or less.

[0171] (ii)(A) ​​The copolymers included in the composition do not contain the glass transition temperature Tg when the homopolymer is made. i Small (in one way, Tg) i When compounds with a temperature ≤350K are used as monomer components, or when they are contained in a certain amount to form homopolymers, the glass transition temperature Tg is... i Small (in one way, Tg) i Compounds with a K value ≤350K are used as monomer components.

[0172] Specifically, the glass transition temperature Tg when forming homopolymers i The upper limit of the content of small monomers is preferably 10% by mass or less, more preferably 5% by mass or less. Additionally, the glass transition temperature Tg of the copolymer included in component (A) when forming a homopolymer is... i The lower limit for the content of small monomers can be 0 by mass.

[0173] (iii)(A) ​​The copolymer contained in the composition contains no acidic groups and has a glass transition temperature Tg when it is made into a homopolymer. i Large (in one way, Tg) i Compounds with a K value of ≥400K are used as monomer components.

[0174] Tg is the glass transition temperature when producing homopolymers. i Large monomers include dicyclopentyl methacrylate.

[0175] In the case where the copolymer contained in component (A) contains dicyclopentyl methacrylate, its content in the copolymer may be more than 5% by mass and less than 45% by mass.

[0176] More specifically, component (A) contains copolymers comprising structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from styrene.

[0177] The copolymer contains a 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) of 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 preferably 18% by mass or more and 25% by mass or less.

[0178] More specifically, the copolymer contained in component (A) preferably also contains structural units derived from methacrylic acid and structural units derived from dicyclopentyl methacrylate.

[0179] The copolymer contains 15% by mass or more and 30% by mass or less of methacrylic acid (in one embodiment, structural units derived from methacrylic acid), and the copolymer contains 5% by mass or more and 45% by mass or less of dicyclopentyl methacrylate (in one embodiment, structural units derived from dicyclopentyl methacrylate).

[0180] From the perspective of achieving a balance between the peeling, developing and exfoliating properties of the resist pattern, the content of the copolymer contained in component (A) can be 60% to 100% by mass, based on the total mass of component (A).

[0181] • First single unit (first structural unit)

[0182] The first monomer is a monomer having at least one olefinic unsaturated bond in its molecule and having an acidic group. In this invention, the acidic group is, for example, a carboxyl group.

[0183] Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half ester. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of improving the peelability of the resist pattern and the overall balance of the effect.

[0184] Based on the total mass of all monomer components, the copolymerization ratio of the first monomer is preferably in the range of 10 to 35% by mass.

[0185] From the viewpoint of excellent adhesion and resolution, the copolymerization ratio is preferably 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.

[0186] From the viewpoint of helping to improve the peeling of the anti-corrosion pattern and the overall balance of the effect, it is preferable that the copolymer percentage is 35% by mass or less, more preferably 30% by mass or less, even more preferably 27% by mass or less, even more preferably 25% by mass or less, particularly preferably 23% by mass or less, and most preferably 21% by mass or less.

[0187] When using two or more monomers as the first monomer, it is preferable that the total copolymerization ratio of each monomer falls within the above range.

[0188] From the viewpoint of contributing to improving the balance between the peeling property of the resist pattern and the overall effect, it is preferable that the copolymer contained in the component (A) contains a structural unit derived from (meth)acrylic acid as a monomer component, and the content of the structural unit derived from (meth)acrylic acid in the component (A) is 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 component (A) can be 10% by mass or more.

[0189] When the value of the glass transition temperature (Tg) of the copolymer calculated by the Fox formula is set as x (°C) and the acid value of the copolymer is set as y (mgKOH / g), from the viewpoint of making the copolymer contained in the component (A) 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.

[0190] The content of the structural unit derived from methacrylic acid in the component (A) 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 component (A) can be 10% by mass or more.

[0191] The copolymer contained in the component (A) preferably contains a structural unit derived from (meth)acrylic acid as a monomer component, and the content of the structural unit derived from (meth)acrylic acid in the component (A) is 10% by mass or more and less than 25% by mass.

[0192] · Second monomer (second structural unit)

[0193] The second monomer is a monomer having at least one ethylenically unsaturated bond in the molecule and no acidic group.

[0194] Examples of second monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glyceryl mono(meth)acrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenoxyethyl methacrylate, isobornyl methacrylate, nonylphenoxy polyethylene glycol (meth)acrylate, pentamethylpiperidinium (meth)acrylate, and so on. Tetramethylpiperidin acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, ethyl carbitol methacrylate, methoxyethyl acrylate, triethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methyl methacrylate (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methacrylate, cyclic trimethylolpropane acetal methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, and other methacrylates; styrene derivatives such as styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, N-phenylmaleimide, styrene dimers, and styrene trimers; vinyl acetate and other vinyl alcohol esters; and (meth)acrylonitrile, etc.

[0195] From the viewpoint of improving the peelability and adhesion of the resist pattern, it is preferable that the copolymer included in component (A) contains structural units derived from compounds having aromatic rings as monomer components, and 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 peelability and adhesion of the resist pattern, the content of structural units derived from compounds having aromatic rings in the copolymer included in component (A) is preferably 80% by mass or less.

[0196] (A) The content of structural units derived from compounds having aromatic rings in the copolymers included in the component 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.

[0197] The compound having an aromatic ring can be derived from the first monomer, or from the second monomer, or from both. However, from the perspective of easily achieving the desired component (A), the compound having an aromatic ring is preferably derived from the second monomer.

[0198] (A) The content of the structural unit derived from the compound having an aromatic ring in the component (A) can be calculated by taking the weighted average of the content of each monomer component in one component (A) with respect to the proportion of the aromatic ring contained in each monomer component. The proportion of the aromatic ring contained in each monomer component in one component (A) can be calculated by (the number of aromatic rings contained in one molecule of monomer / the molecular weight of the monomer).

[0199] Examples of the compound having an aromatic ring include styrene, benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0200] Among these, from the viewpoint of excellent adhesion to the substrate, it is preferable to include either or both of styrene and benzyl (meth)acrylate in the component (A). That is, the component (A) preferably contains a structural unit derived from styrene and / or benzyl (meth)acrylate.

[0201] When the alkali-soluble polymer in the component (A) contains a plurality of alkali-soluble polymers, an alkali-soluble polymer containing styrene and an alkali-soluble polymer containing benzyl (meth)acrylate may be contained respectively.

[0202] 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) can be 25% by mass or more, or can be 30% by mass or more, or can be 35% by mass or more.

[0203] In addition, the content of styrene in the component (A) can be 80% by mass or less, or can be 75% by mass or less, or can be 70% by mass or less, or can be 65% by mass or less, or can also be 60% by mass or less.

[0204] When the component (A) contains a structural unit derived from styrene, from the viewpoint of adhesion, the content of styrene in the component (A) can 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.

[0205] In addition, from the viewpoint of satisfying x≥120 and 3y / 7 + 60 < x for x and y in the copolymer contained in the component (A), the copolymer preferably contains any one of dicyclopentanyl methacrylate, styrene, methyl methacrylate, and 2-hydroxyethyl methacrylate as the second monomer.

[0206] 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.

[0207] From the viewpoint of the adhesion and detachment of the anti-corrosion pattern, the content of dicyclopentyl methacrylate (in one embodiment, structural units derived from dicyclopentyl methacrylate) in the copolymer included in component (A) may be 5% by mass or more. Alternatively, the content of dicyclopentyl methacrylate in the copolymer included in component (A) may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.

[0208] When the copolymer included in component (A) contains structural units derived from methyl methacrylate, from the viewpoint of the adhesion and peeling of the resist pattern, the content of the structural units derived from methyl methacrylate in component (A) may be 10% by mass or more, or 15% by mass or more, or 20% by mass or more. Alternatively, the content of the structural units derived from methyl methacrylate in the copolymer included in component (A) may be less than 40% by mass, less than 40% by mass, less than 35% by mass, or less than 30% by mass.

[0209] When the copolymer contained in component (A) includes structural units derived from methyl methacrylate as monomer components, from the viewpoint of the peeling and adhesion of the anti-corrosion pattern, the content of structural 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 less than 35% by mass, and even more preferably 20% by mass or more and less than 30% by mass.

[0210] From the viewpoint of achieving a balance between the peelability, developability, and release properties of the resist pattern, when the copolymer included 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 included in component (A) can be 1% or more by mass, 5% or more by mass, or 10% or more by mass. Alternatively, the content of 2-hydroxyethyl methacrylate in the copolymer included in component (A) can be 30% or less by mass, 20% or less by mass, or 15% or less by mass.

[0211] (A) The weight-average molecular weight Mw of the alkali-soluble polymer is preferably 10,000 to 60,000.

[0212] From the viewpoint of balancing the flexibility and resolution of the resist pattern, it is preferable to have a weight-average molecular weight (Mw) of 60,000 or less, and from the same viewpoint, it is more preferable to have a weight-average molecular weight (Mw) of 55,000 or less, and even more preferably to have a weight-average molecular weight (Mw) of 50,000 or less.

[0213] From the same point of view, it is preferable that the weight-average molecular weight Mw is 10,000 or more, more preferably 12,000 or more, and even more preferably 14,000 or more.

[0214] (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.

[0215] (A) Alkali-soluble polymers can be used alone or in combination of two or more.

[0216] When two or more (A) components are used in combination, the contents of the first monomer and the second monomer in the multiple (A) components are preferably selected in such a way that the weighted average of the weight-average molecular weight and polydispersity when the content ratio of each (A) component is set to fall within the following range.

[0217] It should be noted that, in this application, the weighted average value refers to the sum of the weight ratio of each alkali-soluble polymer relative to the total weight of the mixed (A) components when two or more (A) components are used in combination.

[0218] (A) The weighted average molecular weight of the component 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.

[0219] (A) The weighted average of the polydispersity of the 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.

[0220] (A) The synthesis of alkali-soluble polymers is preferably carried out by adding appropriate amounts of free radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile to a solution prepared by diluting the single or multiple monomers described above with solvents such as acetone, methyl ethyl ketone and isopropanol, and heating and stirring.

[0221] Sometimes, synthesis is carried out while a portion of a mixture containing monomers and solvents is added dropwise to a reaction solution such as a free radical polymerization initiator. After the polymerization reaction is complete, solvent can be added further to adjust the concentration to the desired level.

[0222] In addition to solution polymerization, other methods for synthesizing component (A) include living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization.

[0223] Furthermore, from the viewpoints of softness, resolution, and adhesion, based on the total mass of all solid components in the photosensitive resin composition, the total content of component (A) and component (B) 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.

[0224] From the viewpoints of sensitivity, resolution, and adhesion, based on the total mass of all solid components in the photosensitive resin composition, the total content of component (A) and component (B) in the photosensitive resin composition of this embodiment is preferably 98% by mass or less, more preferably 96% by mass or less.

[0225] Furthermore, from the viewpoints of developability, resolution, and adhesion, based on the total content of component (A) and component (B), the content of component (A) in the photosensitive resin composition is preferably 70% by mass or less, more preferably 65% ​​by mass or less, further preferably 63% by mass or less, and particularly preferably 60% by mass or less.

[0226] Furthermore, relative to the total content of component (A) and component (B), 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.

[0227] (B) Compounds containing olefinic unsaturated bonds

[0228] In this embodiment, (B) the compound having an olefinic unsaturated bond (hereinafter referred to as (B) component) includes (b-1) a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule and (b-2) a (meth)acrylate compound with more than four functions as a component.

[0229] As component (B) of the photosensitive resin composition of this embodiment, by combining (b-1) a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule and (b-2) a (meth)acrylate compound with more than four functions, the developability, the removal and peeling properties of the resist pattern become good.

[0230] (b-1) A di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule.

[0231] In this embodiment, (b-1) is a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule (hereinafter referred to as (b-1) compound or (b-1) component). There are no particular limitations as long as it is a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule.

[0232] In addition, (b-1) compound can be used alone or in combination with two or more compounds.

[0233] By including compound (b-1) in component (B), the photosensitive resin composition of this embodiment exhibits improved adhesion to the substrate and improved peelability of the resist pattern.

[0234] (b-1) The compound is a compound having a (meth)acryloyl group, more preferably a compound having a methacryloyl group.

[0235] (b-1) The compound is preferably a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule, and more preferably a di(meth)acrylate compound having a bisphenol A structure.

[0236] (b-1) The compound is preferably a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule, more preferably a di(meth)acrylate compound containing a compound having four or more oxyethylene structures and four or more oxypropylene structures in one molecule, and even more preferably a di(meth)acrylate compound containing a compound having four or more oxyethylene structures and four or more oxypropylene structures in one molecule.

[0237] Examples of (b-1) compounds include, for instance, di(meth)acrylates of polyalkylene glycols containing ethylene oxide and propylene oxide as epoxides, and epoxide-modified di(meth)acrylates of bisphenol A containing ethylene oxide and propylene oxide as epoxides.

[0238] Specifically, examples of the above-mentioned compound (b-1) include:

[0239] Dimethacrylate of a polyalkylene glycol with an average of 6 ethylene oxide molecules and an average of 2 propylene oxide molecules added to both ends of bisphenol A.

[0240] A dimethacrylate of a polyalkylene glycol, comprising an average of 12 propylene oxide molecules and an average of 3 ethylene oxide molecules, is formed by adding these two components to both ends of the polypropylene glycol.

[0241] The dimethacrylate of a polyalkylene glycol, which has an average of 15 ethylene oxide molecules and an average of 2 propylene oxide molecules added to both ends of bisphenol A, is formed.

[0242] In this specification, the average number of alkyl oxide structures, represented by ethylene oxide and / or propylene oxide, in compound (b-1) or compound (b-2) described later is expressed by number average.

[0243] From the viewpoint of excellent adhesion to the substrate, (B) the compound having an olefinic unsaturated bond preferably includes the di(meth)acrylate compound having a bisphenol A structure in component (b-1), and particularly preferably includes the compound represented by the following general formula (IV).

[0244]

[0245] (where R is in the formula) 10 R 11 Each can be independently a hydrogen atom or a methyl group.

[0246] R 12 O, R 13 O, R 14 O and R 15 Each of the O atoms is an oxoalkylene group.

[0247] p, q, r, and s are each independent integers from 0 to 40, p+q is from 1 to 40, and r+s is from 1 to 20.

[0248] R 12 O, R 13 O, R 14 O and R 15 O is preferably oxoethylidene and oxopropylidene, each independently.

[0249] As a compound having a bisphenol A structure, from the viewpoints of developability, removal of resist patterns, and adhesion, the average value of p+q+r+s can 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 can be 2 or more, preferably 4 or more.

[0250] p, q, r and s are each preferably 0 to 10, more preferably 1 to 8.

[0251] Component (b-1) can be synthesized, for example, by the following methods, but the synthesis method of component (b-1) in this embodiment is not limited to this.

[0252] 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, polyalkylene glycol-based di(meth)acrylates and bisphenol A-based di(meth)acrylates can be obtained.

[0253] (b-2)4 or higher functional (meth)acrylate compounds

[0254] In this embodiment, there are no particular limitations on (b-2)4 or more functional (meth)acrylate compounds (hereinafter referred to as (b-2) compounds or (b-2) components) as long as they are compounds with olefinic unsaturated bonds and have 4 or more functional groups containing (meth)acryloyl groups.

[0255] In this specification, "functional group number" refers to the number of olefinic unsaturated bonds in each molecule of a compound, for example, in the case of acrylate monomers, it is defined as the number of acryloyl groups in each molecule, and in the case of methacrylate monomers, it is defined as the number of methacryloyl groups in each molecule.

[0256] (b-2) The component preferably contains a (meth)acrylate compound with four or more functions, and more preferably a (meth)acrylate compound with five or more functions. From the viewpoint of improving the peelability and developability of the resist pattern, the component (b-2) preferably contains a (meth)acrylate compound with four to six functions.

[0257] Of which, component (b-2) is particularly preferably a polyglycerol-based (meth)acrylate represented by general formula (I).

[0258]

[0259] [In the formula, n is 2~20,]

[0260] Each i is a natural number from 1 to n.

[0261] Each of k, li, and m is independently between 0 and 30.

[0262] R1, R 2 i R and R3 each independently represent a hydrogen atom or a methyl group.

[0263] R4, R 5 i R6 and R6 are each independently selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a group represented by general formula (II) below, and a group represented by general formula (III) below.

[0264]

[0265] [In the formula, R7 and R8 are each independently an alkylene group having 1 to 10 carbon atoms.]

[0266]

[0267] [In the formula, R9 is an alkylene group having 1 to 10 carbon atoms.]

[0268] It has the properties of R4O, R 5 i Polyglycerol (meth)acrylates represented by repeating units O and R6O can be synthesized, for example, by the following methods, but the synthesis method of polyglycerol (meth)acrylates in this embodiment is not limited to this.

[0269] By reacting the hydroxyl groups of polyglycerol with epoxides, and then reacting the terminal hydroxyl groups with acrylic acid or methacrylic acid, R4 and R can be obtained. 5 i R6 is an alkylene polyglycerol-based (meth)acrylate.

[0270] By using compounds with leaving groups and epoxy groups, such as epichlorohydrin, instead of alkyl epoxides in the reaction, the above-mentioned R4 and R can be obtained. 5 i R6 is a polyglycerol-based (meth)acrylate represented by general formula (II).

[0271] By using lactone compounds instead of alkyl epoxides in the reaction, R4 and R can be obtained. 5 i R6 is a polyglycerol-based (meth)acrylate represented by general formula (III).

[0272] These reactions can be freely combined; alternatively, reactions can be carried out without the introduction of R4O and R. 5 i The repeating units represented by O and R6O cause acrylic acid or methacrylic acid to react with the hydroxyl groups of polyglycerol.

[0273] Specifically, as polyglycerol-based (meth)acrylates, SA-TE6 and SA-TE60 manufactured by Sakamoto Pharmaceutical Chemical Co., Ltd. can be used.

[0274] From the viewpoint of flexibility and fit, each of k, li and m in general formula (I) is preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 12, even more preferably 2 to 10, particularly preferably 2 to 8, and most preferably 2 to 6.

[0275] It should be noted that in this application, when the polyglycerol-based (meth)acrylate represented by general formula (I) is composed of a single type of molecule, each of k, li and m can be represented by an integer value.

[0276] In addition, when the polyglycerol-based (meth)acrylates represented by general formula (I) are composed of multiple molecules, each of k, li and m can be represented by a number mean.

[0277] From the viewpoint of softness 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.

[0278] In addition, when the polyglycerol-based (meth)acrylates represented by general formula (I) are composed of multiple molecules, n can be represented by the number mean.

[0279] In one embodiment, n in general formula (I) is preferably 2 to 15 in terms of numerical mean, more preferably 2 to 10, further preferably 2 to 8, even more preferably 2 to 6, and particularly preferably 2 to 4.

[0280] From the perspective of fit and distinguishability, R1 and R in general formula (I) 2 i R3 is preferably methyl.

[0281] From the perspective of fit and distinguishability, R4 and R in general formula (I) 5 i R6 is preferably an alkylene group.

[0282] More preferably, it is an alkylene group having 1 to 10 carbon atoms.

[0283] More preferably, it includes one or more alkylene groups selected from the group consisting of ethylene, propylene, and tetramethylene.

[0284] More preferably, it contains ethylene and / or propylene.

[0285] Particularly preferred are ethylene and / or propylene.

[0286] Ethylene is the preferred option.

[0287] As (meth)acrylate compounds with four or more functions, in addition to the polyglycerol-based (meth)acrylate compounds listed in general formula (I), examples include pentaerythritol (tetra) (meth)acrylate, bis(trimethylolpropane) (tetra / penta / hexa) (meth)acrylate, dipentaerythritol (tetra / penta / hexa) (meth)acrylate, etc.

[0288] In addition, (meth)acrylate compounds with four or more functionalities can also be epoxide-modified compounds.

[0289] Examples include polyglycerol epoxy-modified (tetra / penta / hexa)meth acrylate, epoxy-modified pentaerythritol (tetra)meth acrylate, epoxy-modified bis(trimethylolpropane) (tetra / penta / hexa)meth acrylate, and epoxy-modified dipentaerythritol (tetra / penta / hexa)meth acrylate.

[0290] From the viewpoint of excellent developability and resistance to pattern removal, compound (b-2) preferably contains polyglycerol epoxy-modified (tetra / penta / hexa)methacrylate or epoxy-modified pentaerythritol (tetra)methacrylate.

[0291] As for the aforementioned polyglycerol epoxy-modified (tetra / penta / hexa)methacrylates or epoxy-modified pentaerythritol (tetra)methacrylates, specifically, examples include:

[0292] A hexamethacrylate with an average of 21 ethylene oxide atoms is added to the terminal hydroxyl group of tetraglycerol.

[0293] The hydroxyl groups of triglycerides are added to the terminal of a pentamethacrylate containing an average of 12 ethylene oxide molecules.

[0294] The pentaerythritol is terminally compounded with an average of 15 ethylene oxide tetramethacrylates, and...

[0295] The pentaerythritol is terminally added with tetramethacrylates containing an average of nine ethylene oxide molecules.

[0296] (b-2) Components can be used alone or in combination with two or more compounds.

[0297] By including component (b-2) in component (B), the resist pattern of the photosensitive resin composition of this embodiment is improved in terms of its detachability, developability, and peelability.

[0298] (b-2) is preferably a compound containing a (meth)acryloyl group, more preferably a compound containing a methacryloyl group.

[0299] Commercially available products that are part of ingredient (b-2) include, for example, Sartomer (registered trademark) SR399 and SR494 (both manufactured by Arkema).

[0300] Based on the total mass of the solid components of the photosensitive resin composition, 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.

[0301] Based on the total mass of the solid components 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, more preferably 30% by mass or less.

[0302] Based on the total mass of the solid components 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, more preferably 20 to 30% by mass.

[0303] Based on the total mass of the solid components of the photosensitive resin composition, 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.

[0304] Based on the total mass of the solid components 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, more preferably 15% by mass or less.

[0305] Based on the total mass of the solid components 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, more preferably 10 to 15% by mass.

[0306] Based on the total mass of component (B), the total content of components (b-1) and (b-2) in component (B) can be 100% by mass or less. From the viewpoint of achieving a balance between the peeling, developing and exfoliating properties of the resist pattern, based on the total mass of component (B), the total content of components (b-1) and (b-2) is preferably 50% by mass or more, more preferably 60% by mass or more.

[0307] Based on the total mass of component (B), the total content of components (b-1) and (b-2) is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and less than 100% by mass.

[0308] To obtain a photosensitive resin composition with the desired superior properties, it is preferable to control the mass ratio of component (b-1) to component (b-2) {(b-1) / (b-2)}, sometimes simply referred to as "(b-1) / (b-2)}, within a specified range. Controlling the value of (b-1) / (b-2) improves the etch-resistant pattern's peelability, developability, and release properties of the photosensitive resin composition of this embodiment. (b-1) / (b-2) can be controlled by adjusting the feed ratio of component (b-1) to component (b-2) during the preparation of the photosensitive resin composition. (b-1) / (b-2) can be analyzed from the photosensitive resin layer using a specified method, and the resulting value is based on the aforementioned feed ratio during the preparation of the photosensitive resin composition.

[0309] From the viewpoint of improving the peelability, developability and exfoliation of the resist pattern, the ratio of the mass of solid components of component (b-1) to component (b-2) (i.e., the ratio of the mass of solid components of component (b-1) to the mass of solid components of component (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.

[0310] (B) Component may include a compound that is not equivalent to either (b-1) or (b-2) as component (b-3).

[0311] The content of component (b-3) relative to the total mass of component (B) can be 0% by mass or more than 0% by mass. From the viewpoint of achieving a balance between the peeling, developing and exfoliating properties of the resist pattern, the content of component (b-3) relative to the total mass of component (B) is preferably 50% by mass or less, more preferably 40% by mass or less.

[0312] As components (b-3), examples include (meth)acrylate compounds with 1 to 3 functions.

[0313] Examples of (meth)acrylate compounds with the aforementioned single functionality include, for instance, epoxy-modified phenol (meth)acrylate, epoxy-modified nonylphenol (meth)acrylate, epoxy-modified 2-ethylhexyl (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, phthalic acid mono(meth)acryloyloxyethyl ester, m-phenoxybenzyl (meth)acrylate, 1-naphthyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, and isometh)acrylate. Amyl acrylate, hexyl methacrylate, isodecanyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, isooctadecyl methacrylate, behenyl methacrylate, 2-decyl-1-tetradecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, and 3,3,4,4,5,5,6,6,7,7,8,8-dodecyl octyl methacrylate, etc.

[0314] Examples of the aforementioned difunctional (meth)acrylate compounds include alkyl di(meth)acrylates, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycol-modified (hydrogenated) bisphenol A di(meth)acrylate, etc.

[0315] Examples of the above-mentioned trifunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, isocyanurate tri(meth)acrylate, trimethylolpropane epoxy-modified tri(meth)acrylate, glycerol epoxy-modified tri(meth)acrylate, and epoxy-modified isocyanurate tri(meth)acrylate.

[0316] Among them, as component (b-3), ethoxylated (hydrogenated) bisphenol A di(meth) acrylate, propoxylated (hydrogenated) bisphenol A di(meth) acrylate or tetramethylene glycol modified (hydrogenated) bisphenol A di(meth) acrylate are preferred, ethoxylated (hydrogenated) bisphenol A di(meth) acrylate are more preferred, and ethoxylated bisphenol A di(meth) acrylate are particularly preferred.

[0317] The average number of ethylene oxide molecules in ethoxylated bisphenol A di(meth)acrylate is preferably 2 to 30 per molecule, more preferably 4 to 20.

[0318] (B) The component is further preferably ethoxylated bisphenol A di(meth)acrylate containing an average of 2 to 30 oxyethylene structures per molecule as component (b-3).

[0319] Based on the total solid content mass of the photosensitive resin composition, from the viewpoints of sensitivity, viscosity, and followability, the content of the compound (B) having an olefinic unsaturated bond in the photosensitive resin composition of this embodiment is preferably 30% by mass or more, preferably 35% by mass or more. Furthermore, based on the total solid content mass of the photosensitive resin composition, from the viewpoints of edge blending, viscosity, and resolution, the content of the compound (B) having an olefinic unsaturated bond in the photosensitive resin composition is preferably 50% by mass or less, preferably 45% by mass or less, preferably 43% by mass or less.

[0320] In one embodiment, from the viewpoints of resolution, adhesion, and peelability, based on the total solid components of the photosensitive resin composition, the content of (B) compounds having olefinic unsaturated bonds in the photosensitive resin composition of this embodiment is preferably 20% by mass or more and 60% by mass or less.

[0321] Furthermore, from the viewpoints of edge blending, adhesion, and resolution, the upper limit of the ratio of the content of the compound having olefinic unsaturated bonds (B) in the photosensitive resin composition of this embodiment to the content of the alkali-soluble resin (A) (i.e., the ratio of the content of the compound having olefinic unsaturated bonds (B) to the content of the alkali-soluble resin (A)) is preferably 1.4 or less, more preferably 1.3 or less, further 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.

[0322] The lower limit of the ratio of the content of the compound having olefinic unsaturated bonds to the content of the alkali-soluble resin (A) is preferably 0.50 or more, more preferably 0.60 or more, even more preferably 0.70 or more, and even more preferably 0.75 or more.

[0323] In the photosensitive resin composition of this embodiment, the number of olefinic unsaturated bonds per 100g of solid component is preferably 0.10 mol to 0.30 mol.

[0324] By setting it to 0.10 moles or more, it is possible to prevent the photosensitive resin composition from leaching out of the cured resist pattern during the water washing process after development, thus preventing contamination during the water washing process.

[0325] By setting it to below 0.30 mol, it is possible to prevent the cured resist pattern from being damaged and falling off during the water washing process after development, thus preventing contamination during the water washing process.

[0326] The amount of olefinic unsaturated bonds in each 100g solid component of the photosensitive resin composition of this embodiment is preferably 0.10 mol or more, more preferably 0.11 mol or more, even more preferably 0.12 mol or more, and even more preferably 0.13 mol or more.

[0327] Furthermore, the amount of olefinic unsaturated bonds in every 100g of solid component of the photosensitive resin composition of this embodiment is preferably 0.30 mol or less, more preferably 0.28 mol or less, even more preferably 0.25 mol or less, even more preferably 0.22 mol or less, particularly preferably 0.20 mol or less, particularly more preferably 0.18 mol or less, and extremely preferably 0.15 mol or less.

[0328] The amount of olefinic unsaturated bonds in each 100g solid component of the photosensitive resin composition of this embodiment is more preferably 0.10 mol to 0.25 mol, more preferably 0.10 mol to 0.20 mol, even more preferably 0.11 mol to 0.20 mol, and most preferably 0.11 mol to 0.15 mol.

[0329] (C) Polymerization initiator

[0330] In this embodiment, the photosensitive resin composition preferably includes a polymerization initiator (hereinafter referred to as component (C)). In this application, the polymerization initiator (C) refers to a compound that facilitates photopolymerization by absorbing active light. Specifically, it is a compound that absorbs active light to generate free radicals and initiates the polymerization of component (B), or a compound that absorbs active light and transfers the obtained energy to other components to promote photopolymerization.

[0331] The active light ray can be any light with a wavelength of 330nm to 450nm, such as i-line, h-line and g-line.

[0332] Examples of (C) polymerization initiators include compounds containing a bimidazole structure, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketals, thioxanone compounds, dialkylaminobenzoate compounds, oxime esters, acridine compounds, pyrazole derivatives, pyrazolinone derivatives, esters of N-aryl amino acids, and halogen compounds.

[0333] In one embodiment, component (C) preferably comprises a compound containing a bimidazole structure or an anthracene derivative.

[0334] Examples of compounds containing a biimidazole structure include hexaarylbiimidazole compounds. Examples of hexaarylbiimidazole compounds include phenanthrene dimers, specifically 2,4,5-triarylimidazole dimers.

[0335] Examples of phenanthrene dimers, specifically 2,4,5-triarylimidazole dimers, 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, the dimer of 2-(p-methoxyphenyl)-4,5-diphenylimidazole, 2,2',5-tri-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, and 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'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5' -Tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)- 4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc.

[0336] From the viewpoints of high sensitivity, resolution and tightness, component (C) preferably contains phenanthrene dimer, wherein 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer is preferred.

[0337] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0338] N-phenylglycine has a high sensitization effect and is therefore preferred.

[0339] 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-phenanthroquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0340] Examples of aromatic ketone compounds include benzophenone compounds. Examples of benzophenone compounds include benzophenone, michalcone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. From the viewpoint of sensitization effect and binding affinity, 4,4'-bis(diethylamino)benzophenone can also be listed as an aromatic ketone compound.

[0341] In this application, the term "anthracene derivative" includes both anthracene and compounds derived therefrom.

[0342] 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-anthraboronic acid.

[0343] From the viewpoint of sensitization effect and adhesion, 9,10-dibutoxyanthracene or 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0344] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenylone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, etc.

[0345] Commercially available acetophenone compounds include, for example, the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0346] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[0347] Commercially available acylphosphine oxide compounds include, for example, Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0348] Examples of benzoin compounds and benzoin ether compounds include, for example, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

[0349] Examples of dialkyl ketal compounds include, for example, benzoyl dimethyl ketal and benzoyl diethyl ketal.

[0350] Examples of thioxanthone compounds include, for example, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0351] Examples of dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4-(dimethylamino)benzoate.

[0352] 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.

[0353] Commercially available oxime ester compounds include, for example, CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0354] As acridine compounds, 1,7-bis(9,9'-acridyl)heptane or 9-phenylacridinium are preferred in terms of sensitivity, resolution and availability.

[0355] From the viewpoint of adhesion and the rectangularity of the anti-corrosion 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.

[0356] As a pyrazole derivative, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazole is preferred.

[0357] 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.

[0358] Examples of halogen compounds include pentyl bromide, isopentyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, pentyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, triazine chloride compounds, and diallyl iodonium compounds.

[0359] Among halogen compounds, tribromomethylphenyl sulfone is preferred.

[0360] Based on the total solid content of the photosensitive resin composition, 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.

[0361] By adjusting the content of (C) polymerization initiator to the above range, sufficient sensitivity can be easily obtained, thus allowing light to pass through sufficiently to the bottom of the photosensitive resin composition layer, thereby easily achieving improved resolution.

[0362] From the viewpoints of high sensitivity, resolution, and adhesion, the (C) polymerization initiator preferably contains a compound with a biimidazole structure, more preferably a hexaarylbiimidazole compound. In this case, based on the total solid content of the photosensitive resin composition, the content of the compound containing the 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.

[0363] As a (C) polymerization initiator, it is preferred to use an anthracene derivative with a compound containing a bimidazole structure (e.g., a hexaaryl bimidazole compound).

[0364] At this time, based on the total solid components of the photosensitive resin composition, the content of 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.

[0365] Furthermore, based on the total solid content of the photosensitive resin composition, the content of anthracene derivative included in the (C) polymerization initiator of the photosensitive resin composition of this embodiment is preferably 0.01% by mass or more. Based on the total solid content of the photosensitive resin composition, the content of anthracene derivative included in the (C) polymerization initiator of the photosensitive resin composition of this embodiment is preferably 0.5% by mass or less, more preferably 0.4% by mass or less.

[0366] Furthermore, based on the total solid content of the photosensitive resin composition, the content of the hexaaryl biimidazole compound contained in the polymerization initiator (C) of the photosensitive resin composition of this embodiment is preferably 0.1 to 10% by mass, or 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.

[0367] Based on the content of (B) compounds having olefinic unsaturated bonds, 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.

[0368] Furthermore, based on the content of (B) compounds having olefinic unsaturated bonds, 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.

[0369] ·additive

[0370] The photosensitive resin composition of this embodiment may contain additives such as dyes, binding agents, plasticizers, and polymerization inhibitors.

[0371] ·dye

[0372] In this embodiment, the photosensitive resin composition may contain a dye. Alternatively, in another embodiment, the photosensitive resin composition may contain a color-developing dye that develops color upon light irradiation.

[0373] In the dry film resist provided as one type of photosensitive resin laminate in this embodiment, a dye is preferably added. By adding a dye, the resist pattern formed on the developed substrate can be seen with good contrast, which also helps to improve the resolution.

[0374] As a dye, salt-based dyes such as salt-based dyes are preferred.

[0375] As colorimetric dyes, combinations of leuco dyes and halogen compounds are known.

[0376] Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [dye name: leuco crystal violet] and tris(4-dimethylamino-2-methylphenyl)methane [dye name: leuco malachite green].

[0377] Examples of halogenated compounds include pentyl bromide, isopentyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, pentyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane.

[0378] • Sealing agent

[0379] In this embodiment, the photosensitive resin composition may contain a binding agent.

[0380] In the dry film resist provided as one type of photosensitive resin laminate in this embodiment, an adhesion promoter is preferably added. By adding an adhesion promoter, it is helpful to improve the adhesion of the resist pattern formed on the substrate after development to copper.

[0381] As a sealing aid, triazoles, benzotriazoles, etc. are preferred, and carboxybenzotriazoles are more preferred.

[0382] As a sealing aid, an example is a 1:1 (mass ratio) mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole.

[0383] Plasticizers

[0384] In this embodiment, the photosensitive resin composition may contain additives such as plasticizers, as needed.

[0385] As plasticizers and other additives, examples include phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetylglucoside, tri-n-propyl acetylglucoside, tri-n-butyl acetylglucoside, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ethers, and polypropylene glycol alkyl ethers.

[0386] Polymerization inhibitors

[0387] In this embodiment, the photosensitive resin composition may contain a polymerization inhibitor.

[0388] Examples of polymerization inhibitors include free radical polymerization inhibitors, phenolic polymerization inhibitors, hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine, catechol and their derivatives.

[0389] Examples of free radical polymerization inhibitors include nitroso compounds such as p-nitrosophenol, nitrosobenzene, N-nitrosodiphenylamine, isononyl nitrite, N-nitrosocyclohexylhydroxyamine, N-nitrosophenylhydroxyamine, N,N'-dinitrosophenylenediamine, and their salts (e.g., aluminum salts), as well as hindered amine compounds such as 2,2,6,6-tetramethylpiperidin-1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxy, and 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine.

[0390] 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-pentylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). Methylbis(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], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2 2-Thio-diethylidene bis[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-hydroxyphenylpropionamide), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-di-tert-butyl-4-hydroxyphenylpropionamide) Tert-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol (e.g., manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzylphenol (e.g., manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenols having 1 to 3 benzyl groups), and biphenol, etc.

[0391] In this application, the term "hydroquinone, quinone, nitrobenzene, phenothiazine, phenothiazine and catechol and their derivatives" includes both hydroquinone, quinone, nitrobenzene, phenothiazine, phenothiazine and catechol, and compounds derived therefrom.

[0392] Examples of hydroquinone derivatives include methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butylhydroquinone.

[0393] Examples of quinone derivatives include tert-butylbenzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, and 2,5-di-tert-butyl-1,4-benzoquinone.

[0394] Examples of nitrobenzene derivatives include 4-nitrotoluene.

[0395] 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.

[0396] Examples of phenoxazine derivatives include 1-methyl-phenoxazine, 2-methyl-phenoxazine, 3-methyl-phenoxazine, 4-methyl-phenoxazine, 10-methyl-phenoxazine, 2-hydroxy-phenoxazine, 3-hydroxy-phenoxazine, 4-hydroxy-phenoxazine, 10-bromo-phenoxazine, 3,7-dimethyl-phenoxazine, 2,8-dimethyl-phenoxazine, 1-amino-phenoxazine, 2-amino-phenoxazine, 3-amino-phenoxazine, 2-ethyl-phenoxazine, 3-ethyl-phenoxazine, 2-formonitrile-phenoxazine, 3-formonitrile-phenoxazine, 2-methoxy-phenoxazine, 3-methoxy-phenoxazine, and 12H-benzophenoxazine.

[0397] 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.

[0398] By including phenothiazine or phenothiazine derivatives and a phenolic polymerization inhibitor, the NH group in the phenothiazine site and the OH group of the phenolic polymerization inhibitor form hydrogen bonds, which can prevent the phenolic polymerization inhibitor from volatilizing or diffusing from the photosensitive resin composition layer.

[0399] That is, it provides photosensitive resin compositions and methods for forming resist patterns that are not affected by manufacturing and storage conditions determined by film thickness and have excellent sensitivity and resolution.

[0400] Based on the above viewpoint, the photosensitive resin composition of this embodiment preferably contains phenothiazine or phenothiazine derivatives as a polymerization inhibitor.

[0401] At this time, based on the total solid content of the photosensitive resin composition of this embodiment, 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.

[0402] Furthermore, based on the total solid content of the photosensitive resin composition of this embodiment, 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.

[0403] From a distinguishing point of view, the photosensitive resin composition of this embodiment preferably contains catechol or a catechol derivative as a polymerization inhibitor, wherein, particularly preferably, it contains 3-tert-butylcatechol or 4-tert-butylcatechol.

[0404] At this time, based on the total solid content of the photosensitive resin composition of this embodiment, 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.

[0405] Furthermore, based on the total solid content of the photosensitive resin composition of this embodiment, 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.

[0406] Based on the total solid content of the photosensitive resin composition of this embodiment, the content of the polymerization inhibitor in the photosensitive resin composition of this embodiment is preferably 0.0001% to 10% by mass.

[0407] From the viewpoint of excellent adhesion and resolution, the content of the polymerization inhibitor 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.

[0408] On the other hand, considering the aspects of minimizing sensitivity reduction and improving resolution, the content of the polymerization inhibitor in this embodiment is preferably 10% by mass or less, more preferably 8% by mass or less, further 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.

[0409] <Photosensitive resin laminate>

[0410] The photosensitive resin laminate of this embodiment includes a support film and a photosensitive resin layer (in one embodiment, a photosensitive resin composition layer) containing a photosensitive resin composition, and the support film and the photosensitive resin layer are the same as described above.

[0411] As a photosensitive resin laminate in this embodiment, for example, it is formed by laminating at least one photosensitive resin layer on a support film, or two or more photosensitive resin layers can be laminating on the support film.

[0412] From the viewpoint that the effects of this embodiment can be easily and significantly realized, the photosensitive resin laminate of this embodiment is preferably a dry film resist or a transfer film, and more preferably a dry film resist.

[0413] In addition to the supporting film and the photosensitive resin layer, the photosensitive resin laminate of this embodiment may also include a protective film.

[0414] In this embodiment, when the photosensitive resin laminate includes a support film, a photosensitive resin layer, and a protective film, the protective film is adhered to the side of the photosensitive resin layer that is not laminated with the support film, and functions as a cover layer.

[0415] Compared to the adhesion between the photosensitive resin composition layer and the support film in this embodiment, the adhesion between the photosensitive resin composition layer and the protective film is sufficiently small, so the protective film can be easily peeled off from the photosensitive resin composition layer.

[0416] For example, polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc. can be preferred as protective films.

[0417] Among these, polypropylene film and polyester film are preferred, and polyethylene terephthalate film is even more preferred as polyester film.

[0418] Alternatively, a release layer can be applied to the surface of the protective film.

[0419] The thickness of the protective film is preferably 10 to 100 μm, more preferably 10 to 50 μm. Examples of protective films include ALPHAN (registered trademark) EM-501, ALPHAN E-200, ALPHAN E-201F, ALPHAN FG-201, and ALPHAN MA-411 (all manufactured by Oji F-Tex Co., Ltd.).

[0420] TORAYFAN (registered trademark) KW37, TORAYFAN2578, TORAYFAN2548, TORAYFAN2500, TORAYFAN YM17S; Cerapeel (registered trademark) PJ271, Cerapeel PJ111, Cerapeel HP2, Cerapeel PJ101, Cerapeel WZ, Cerapeel MDA, Cerapeel MFA, Cerapeel TK07, Cerapeel BKE, Cerapeel BX8A, Cerapeel SY (all manufactured by Toray Industries, Inc.);

[0421] GF-18, GF-818, GF-858 (all manufactured by Tamapoly Co., Ltd.), etc.

[0422] The photosensitive resin laminate of this embodiment may also have an intermediate layer between the support film and the photosensitive resin layer, or between the support film and the protective film.

[0423] [Photosensitive resin laminate roll]

[0424] The photosensitive resin laminate described above can be rolled into a roll by winding a strip of photosensitive resin laminate onto a core for use.

[0425] [Methods for forming anti-corrosion patterns]

[0426] The method for forming the resist pattern of the photosensitive resin laminate using this embodiment includes, for example, the following steps:

[0427] In the lamination process, a photosensitive resin layer (in one embodiment, a photosensitive resin composition layer) constituting the photosensitive resin laminate of this embodiment is laminated onto a substrate.

[0428] The exposure process exposes the photosensitive resin layer of the photosensitive resin laminate to light; and

[0429] The developing process removes the unexposed portions of the photosensitive resin layer.

[0430] It is preferable to perform the procedures in the order described above.

[0431] <Lamination Process>

[0432] In the lamination process, specifically, after the protective film is peeled off from the photosensitive resin laminate of this embodiment, the photosensitive resin layer is heated and pressed onto the substrate surface using a laminator, and the lamination is performed once or multiple times.

[0433] Materials used as substrates include, for example, copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc., with copper-clad laminates being preferred.

[0434] Depending on the needs, the substrate can also be cleaned and its surface adjusted using an aqueous solution of H2SO4 with a concentration of about 10% by mass.

[0435] The heating temperature during lamination is typically between 40℃ and 160℃. Heat lamination can be performed using a laminator equipped with rollers, or by repeatedly passing the substrate and the photosensitive resin composition layer through the rollers. Heat lamination can also be performed under reduced pressure as needed.

[0436] <Exposure Process>

[0437] In the exposure process, exposure machines such as contact aligners, mirror projectors, and steppers are used to expose the photosensitive resin layer through a patterned photomask or mask, or directly using an ultraviolet light source to expose the photosensitive resin layer.

[0438] The exposure process can be performed either after the support film is peeled off or through the support film, as needed.

[0439] When exposure is performed using a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can be measured using a photometer. Direct imaging exposure can also be performed during the exposure process. In direct imaging exposure, exposure is performed on the substrate using a direct drawing apparatus without using a photomask.

[0440] As a light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350nm~410nm is used.

[0441] When the pattern is drawn under computer control, the exposure is determined by the illuminance of the exposure light source and the speed at which the substrate moves.

[0442] The exposure method used in the exposure process is preferably selected from at least one of the following methods: projection exposure, proximity exposure, contact exposure, direct imaging exposure, and direct electron beam mapping. More preferably, it is performed by projection exposure or direct imaging exposure.

[0443] <Heating Process>

[0444] A heating process can also be set between the exposure process and the development process.

[0445] The heating temperature is preferably 30℃~200℃, more preferably 30℃~150℃, and even more preferably 35℃~120℃. Implementing this heating process improves resolution and sealing. Heating can be performed using hot air, infrared, or far-infrared heating furnaces, constant temperature baths, hot plates, hot air dryers, infrared dryers, hot rollers, etc.

[0446] The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0447] The elapsed time from the exposure step to the heating step, or more precisely, from the point when exposure stops to the point when heating starts, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The elapsed time from the point when heating starts to the point when heating stops is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0448] <Developing Process>

[0449] In the developing process, a developing device is used to remove the unexposed portions of the exposed photosensitive resin layer using a developing solution to form a resist pattern.

[0450] After exposure, if a support film is present on the photosensitive resin layer, the support film is removed. Then, a developer solution composed of an alkaline aqueous solution is used to develop and remove the unexposed areas, resulting in a resist pattern.

[0451] As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as spin spraying, paddle spraying, and immersion methods accompanied by ultrasonic treatment.

[0452] Regarding 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, and a Na₂CO₃ aqueous solution with a concentration of 0.2% to 2% by mass is typically used. Surfactants, defoamers, and small amounts of organic solvents for promoting development can be added to the alkaline aqueous solution. The temperature of the developer in the developing process is preferably kept constant within the range of 20°C to 40°C.

[0453] The developing process preferably includes a water washing step for removing the developer contained in the resist pattern after developing. The washing water can be pure water, industrial water, etc., and can also be selected according to the characteristics of the photosensitive resin layer. To improve resolution and the shape of the resist pattern, a polyvalent metal salt such as MgSO4 at a concentration of 0.001% to 1% by mass can be added. The temperature of the washing water in the water washing step is preferably kept constant within the range of 20°C to 40°C.

[0454] The above process yields an anti-corrosion pattern, but it can also be further heat-treated at 60°C to 300°C for 1 to 120 minutes as needed. This heat treatment improves the chemical resistance of the anti-corrosion pattern. The heat treatment can be performed using a furnace employing hot air, infrared radiation, or far-infrared radiation.

[0455] To obtain a conductor pattern, a conductor pattern forming process can be performed after the developing or heating process, where the substrate with the resist pattern is etched or plated.

[0456] <Conductor Pattern Forming Process>

[0457] The conductor patterning process is a process of forming conductor patterns on the surface of a substrate (e.g., a copper surface) that has been developed with resist patterns using known etching or plating methods.

[0458] One method for forming conductor patterns using plating is described below.

[0459] 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 immersion, the substrate is washed with water and then immersed in a 1-50% by mass sulfuric acid aqueous solution at room temperature for 1-60 minutes.

[0460] Prepare aqueous solutions containing 1-15% by mass copper sulfate, 0.1-30% by mass sulfuric acid, and 1-1000 ppm hydrochloric acid.

[0461] Next, copper sulfate plating solutions were prepared by adding gloss agents (in one method, Cupracid HL and Cupracid GS manufactured by Atotech) at concentrations of 0.01~40 ml / l and 1~200 ml / l, respectively.

[0462] Using the prepared copper sulfate plating solution, a conductor pattern is formed by applying a current of 0.01 to 10 A for 1 to 300 minutes using a Haring tank uniform plating apparatus (manufactured by Yamamoto Gold Plating Tester Co., Ltd.).

[0463] The thickness of the copper plating film also depends on the thickness of the resist pattern, and is preferably 1 μm or more (resist pattern thickness (μm) - 2 μm) or less. In this application, the thickness of the resist pattern refers to the thickness of the cured photosensitive resin layer.

[0464] As a method of forming conductor patterns using etching, flash etching is an example.

[0465] In rapid etching, the copper seed layer can be removed using a prescribed etching solution. Examples of etching solutions include, but are not limited to, a mixture of sulfuric acid and hydrogen peroxide (manufactured by Ebara Densha Co., Ltd.).

[0466] [Methods for manufacturing conductor patterns]

[0467] The conductor pattern is manufactured, for example, by using a metal plate or metal film insulating plate as a substrate, forming a resist pattern by the resist pattern forming method described above, and then proceeding to a conductor pattern forming process.

[0468] <Stripping Process>

[0469] Furthermore, after manufacturing the conductor pattern using the aforementioned method, a stripping process can be performed to peel the resist pattern off the substrate using an aqueous solution with a stronger alkalinity than the developer. By performing the stripping process, a circuit board (in one embodiment, a printed circuit board) with the desired wiring pattern can be obtained.

[0470] There are no particular restrictions on the alkaline aqueous solution (hereinafter also referred to as "stripping solution") used for stripping. Usually, an aqueous solution of NaOH or KOH with a concentration of 2% to 20% by mass or an organic amine-based stripping solution is used.

[0471] A small amount of water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohols. The temperature of the stripping solution in the stripping process is preferably in the range of 40°C to 70°C, and the immersion time in the stripping solution is preferably 1 to 60 minutes.

[0472] [Circuit Board Manufacturing Method]

[0473] In one embodiment, a method for manufacturing a circuit board using the photosensitive resin laminate of this embodiment includes the following steps:

[0474] In the lamination process, photosensitive resin layers are laminated onto the substrate;

[0475] The exposure process exposes the photosensitive resin layer to light;

[0476] The developing process removes the unexposed portions of the photosensitive resin layer to form a resist pattern.

[0477] The conductor patterning process involves etching or plating a substrate with a resist pattern to form the conductor pattern; and

[0478] The stripping process removes the resist pattern from the substrate.

[0479] The circuit board manufacturing method of this embodiment includes the same processes as described above, namely, the lamination process, the exposure process, the development process, the conductor pattern formation process, and the stripping process.

[0480] The photosensitive resin laminate in this embodiment can be used in the manufacture of printed circuit boards, lead frames for IC chip mounting, precision metal foil processing such as metal mask manufacturing, the manufacture of packages such as ball grid arrays (BGA) and chip-scale packages (CSP), the manufacture of strip substrates such as chip-on-film (COF) and tape-on-board (TAB), the manufacture of semiconductor bumps, and the manufacture of spacers for flat panel displays such as ITO electrodes, addressing electrodes, and electromagnetic wave shielding.

[0481] It should be noted that, unless otherwise specified, the values ​​of the above parameters shall be determined according to the measurement methods in the embodiments described later.

[0482] [Method for manufacturing photosensitive resin laminates]

[0483] The photosensitive resin laminate of this embodiment can be manufactured by the method shown below.

[0484] That is, in one embodiment, the method for manufacturing the photosensitive resin laminate of this embodiment is a method for manufacturing a photosensitive resin laminate having a support film and a photosensitive resin layer comprising a photosensitive resin composition, and includes the following steps:

[0485] The preparation process involves preparing a photosensitive resin composition solution comprising a compound having an olefinic unsaturated bond as component (A), an alkali-soluble resin as component (B), and a solvent.

[0486] In the coating process, a photosensitive resin composition solution is coated onto a support film;

[0487] In the photosensitive resin layer formation process, a support film coated with a photosensitive resin composition solution is heated to form a photosensitive resin layer.

[0488] In one embodiment, component (A) comprises a polyglycerol-based (meth)acrylate (A1) and a compound (A2) that does not have a carboxyl group but has an olefinic unsaturated bond.

[0489] The method for manufacturing photosensitive resin laminates according to this embodiment enables the production of photosensitive resin laminates with excellent sensitivity and resolution, which are unaffected by manufacturing and storage conditions determined by the film thickness of the photosensitive resin layer.

[0490] <Preparation Process>

[0491] This process involves adding a solvent to (A) the compound having olefinic unsaturated bonds and (B) the alkali-soluble resin to prepare a photosensitive resin composition solution (preparation solution).

[0492] Preferred solvents include ketones such as methyl ethyl ketone (MEK) and alcohols such as methanol, ethanol and isopropanol.

[0493] One solvent can be used, or two or more solvents can be mixed.

[0494] The solvent content relative to the photosensitive resin composition solution is preferably 30-60% by mass, more preferably 33-55% by mass, and even more preferably 35-57% by mass.

[0495] Preferably, a solvent is added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution reaches 500~4000 mPa·sec at 25°C.

[0496] Viscosity was measured using a Brookfield viscometer (DVNext, manufactured by Ingfield) at 25°C.

[0497] <Coating Process>

[0498] This process involves coating a photosensitive resin composition solution onto a support film.

[0499] The coating of the photosensitive resin composition solution onto the support film can be performed using conventional methods, such as coating with a roller coater, spin coater, bar coater, doctor blade coater, curtain coater, and screen printer, or spray coating with a sprayer.

[0500] <Photosensitive resin layer formation process>

[0501] This process involves heating a support film coated with a photosensitive resin composition solution to distill off the solvent in the photosensitive resin composition solution, thereby forming a photosensitive resin layer made of the photosensitive resin composition.

[0502] 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. By heating to 70°C or higher, the evaporation of the solvent contained in the photosensitive resin composition solution is accelerated, thereby improving the production efficiency of the photosensitive resin laminate.

[0503] The heating temperature of the support film coated with the photosensitive resin composition solution is preferably below 140°C, more preferably below 130°C, and even more preferably below 120°C. By maintaining the temperature below 140°C, thermal polymerization of the photosensitive resin composition can be prevented.

[0504] The heating time for the support film coated with the photosensitive resin composition solution is preferably 1 to 10 minutes.

[0505] If necessary, a protective process can be performed after the photosensitive resin layer formation process, where a protective film or other protective layer is laminated onto the photosensitive resin layer. The protective layer is attached to the side of the photosensitive resin layer where the supporting film is not laminated, functioning as a cover layer.

[0506] The protective film used in the protection process is the same as described above.

[0507] Example

[0508] Next, examples and comparative examples will be given to describe this embodiment in more detail. However, this embodiment is not limited to the following examples as long as it does not depart from its spirit. The physical properties in the examples were measured by the following methods.

[0509] [Preparation of Evaluation Samples]

[0510] The evaluation samples were prepared as follows.

[0511] <(A) Synthesis of Components>

[0512] The monomers (polymer components) such as methacrylic acid, methyl methacrylate, and styrene shown in Table 2 were mixed with 3.0 parts by mass of azobisisobutyronitrile (AIOnitrile) to prepare solution (a). 200 g of methyl ethyl ketone (MEK) and 100 g of ethanol were added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen inlet tube. The mixture was stirred while blowing nitrogen into the flask, and the temperature was raised to 80°C. 300 g of solution (a) was added dropwise over 4 hours at a constant dropping rate to the mixture in the flask, followed by stirring at 80°C for 2 hours.

[0513] Next, 0.5 parts by mass of azobisisobutyronitrile (AIB) were dissolved in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone (MEK) and 20 parts by mass of ethanol (EQU) to prepare solution (b). 50 g of solution (b) was added dropwise over 10 minutes at a constant dropping rate to the solution in the flask, and then the solution in the flask was stirred at 80°C for 3 hours. Subsequently, the solution in the flask was heated to 90°C over 30 minutes, held at 90°C for 2 hours, then stirring was stopped, and the solution was cooled to room temperature (25°C). Thus, solutions of alkali-soluble polymers A-1 to A-10 were obtained. 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.

[0514] (A) The weight-average molecular weight of the alkali-soluble polymer was determined by gel permeation chromatography (GPC) and then derived using a standard curve of standard polystyrene. The GPC conditions are shown below.

[0515] (GPC conditions)

[0516] Pump: PU-980 manufactured by Japan Seiko Co., Ltd.

[0517] Chromatographic columns: 2 in total

[0518] Shodex KF-80Y / KF-806M

[0519] Eluent: Tetrahydrofuran

[0520] Measurement temperature: 40℃

[0521] Flow rate: 2.05 mL / min

[0522] Detector: RI-1530 manufactured by Japan Spectrophotometer Co., Ltd.

[0523] Standard monodisperse polystyrene: Manufactured by Tosoh Corporation, product name TSKgel standard polystyrene

[0524] (A) The glass transition temperature (Tg) of alkali-soluble polymers is obtained by applying the following Fox formula to the Tg values ​​listed in Table 1 above. i and c i And calculated.

[0525]

[0526] {where Tg i (K: Kelvin) is the glass transition temperature of the homopolymer composed of the monomers, c i The copolymerization ratio of each monomer.

[0527] The Tg values ​​of the copolymers included in component (A) are shown in Table 2.

[0528] (A) The acid value of the copolymer contained in the alkali-soluble polymer is based on the definition of the amount (mg) of potassium hydroxide that can neutralize 1g of component (A) and is calculated assuming that all the methacrylic acid contained in each component (A) reacts with the potassium hydroxide.

[0529] The acid values ​​of the copolymers contained in component (A) are shown in Table 2.

[0530] The photosensitive resin laminate is prepared as follows.

[0531] <Preparation of Photosensitive Resin Laminates>

[0532] The photosensitive resin compositions (Examples 1-16 and Comparative Examples 1-9) were prepared by mixing the components (A) to (D) shown in Table 3 below (where the numbers for each component indicate the content (parts by mass) based on the solid content).

[0533] The photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-9, along with ethanol measured in such a way that the solid component concentration of these photosensitive resin compositions is 60% by mass, were thoroughly stirred and mixed to obtain a formulation containing the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-9.

[0534] For Examples 1-16 and Comparative Examples 1-9, a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, QS71) was used as a support film. The prepared liquid was uniformly coated on its surface using a bar coater (trade name: Type A automatic coating machine, manufactured by Toyo Seiki Co., Ltd.). The film was then heated / dried in a dryer at 95°C for 2 minutes and 30 seconds to form a photosensitive resin layer with a film thickness of 25 μm.

[0535] Next, a 19 μm thick polyethylene film (manufactured by Tamapoly, GF-858) was laminated as a protective layer on the surface of the unlaminated polyethylene terephthalate film of the photosensitive resin layer to obtain a photosensitive resin laminate containing the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-9 (Examples 1-16 and Comparative Examples 1-9).

[0536] As a support film, a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, QS71) was used. A preparation solution containing the photosensitive resin composition of Example 1 was uniformly coated on its surface using a bar coater (trade name: Type A automatic film application machine, manufactured by Toyo Seiki Co., Ltd.). The film was then heated / dried in a dryer at 95°C for 1 minute to form a photosensitive resin layer with a film thickness of 10 μm.

[0537] Next, a 19 μm thick polyethylene film (manufactured by Tamapoly, GF-858) was laminated as a protective layer on the surface of the unlaminated polyethylene terephthalate film of the photosensitive resin layer to obtain a photosensitive resin laminate containing the photosensitive resin composition of Example 1 (Example 1').

[0538] Fabrication of substrates for performance evaluation

[0539] The substrate used for performance evaluation is fabricated as follows.

[0540] <Substrate Surface Adjustment>

[0541] Prepare a 0.4 mm thick copper-clad laminate with rolled copper foil of 18 μm thickness. Clean the surface of the substrate with a 10% by mass H2SO4 aqueous solution.

[0542] Lamination

[0543] While peeling off the polyethylene film from the aforementioned photosensitive resin laminate, the aforementioned photosensitive resin laminate was laminated onto a copper-clad laminate preheated to 50°C using a hot roller laminator (manufactured by Asahi Kasei Corporation, AL-700) at a roller temperature of 105°C, to obtain a substrate for performance evaluation. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0544] <Exposure Process>

[0545] Two hours after lamination, the performance evaluation substrate was exposed at a wavelength of 365 nm using a projection exposure machine (manufactured by Ushio Electric Co., Ltd., UX-44101SM) through a glass mask. Similarly, the performance evaluation substrate was exposed at a wavelength of 402 nm using a direct imaging (DI) exposure machine (manufactured by ORC Corporation, FDi-3) with a specified direct imaging (DI) exposure pattern.

[0546] <Heating Process>

[0547] After exposure for 1 minute, the substrate used for performance evaluation was heated for 30 seconds using a constant-temperature thermostat (manufactured by Yamatoscientific, DKM600) with a forced-airflow setting of 60°C.

[0548] <Developing Process>

[0549] After the polyethylene terephthalate film (support film) is peeled off, it is developed using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer) by spraying a 1% by mass Na2CO3 aqueous solution at 30°C for a specified time.

[0550] The developing spray time is twice the shortest developing time, and the post-developing wash spray time is twice the shortest developing time.

[0551] <Plating Process>

[0552] For substrates that have undergone the same surface conditioning and lamination as described above, a pattern is drawn using a linewidth (L) / space width (S) (hereinafter referred to as "L / S") of x / x (x = 1~20 (varying in 1μm intervals)) (unit: μm). Exposure is performed with an energy level of 17 segments (residual number of segments) on a Hitachi 41-segment staged exposure meter, followed by the same heating and development processes as described above, thereby forming a resist pattern. The developed substrate is then immersed in an acidic degreasing FRX bath (10% by mass sulfuric acid aqueous solution, manufactured by Atotech Japan) at 40°C for 4 minutes. After rinsing with water, it is immersed in a 10% by mass sulfuric acid aqueous solution at room temperature for 2 minutes.

[0553] Prepare a 121 g / L copper sulfate aqueous solution, dilute it with 19% (w / w) sulfuric acid to a volume ratio of 3.6, and then add concentrated hydrochloric acid at a concentration of 200 ppm. Next, as a glossing agent, add Cupracid HL and Cupracid GS at concentrations of 0.4 ml / L and 20 ml / L respectively to prepare the copper sulfate plating solution.

[0554] For the plating resistance evaluation substrate (6cm × 12.5cm) after pre-plating treatment, the prepared copper sulfate plating solution was used, and plating was performed for 65 minutes with an applied current of 0.4A using a Haring bath uniform plating apparatus (manufactured by Yamamoto Gold Plating Tester Co., Ltd.). The thickness of the copper plating film at this time was 20μm.

[0555] <Stripping Process>

[0556] A stripping solution with a total concentration of 20% by mass was prepared by mixing products under the trade name "CLEAN ETCH (registered trademark) R-100S" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and "CLEAN ETCH (registered trademark) R-101" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) at a volume ratio of 2 / 1 and then diluting with pure water. A substrate used for performance evaluation after plating treatment was immersed in the stripping solution heated to 50°C for 4 minutes without stirring to remove the resist pattern.

[0557] <Evaluation>

[0558] <Reproducibility>

[0559] The substrate for performance evaluation is exposed and developed according to the above method, and the shortest development time is the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve. Specifically, in this embodiment, the development time is changed at 0.5-second intervals for evaluation, and the shortest development time is the shortest time among those development times in which the unexposed portion of the photosensitive resin layer can be visually confirmed to be completely dissolved.

[0560] The shorter the minimum development time, the higher the developability. The minimum development time is evaluated according to the following criteria.

[0561] If the rating is ◎ or 〇, it can be used as a photosensitive resin laminate for use in resist patterning.

[0562] ◎: Minimum developing time of 20 seconds or less is "Excellent".

[0563] ○: A minimum development time of 20 seconds but less than 22 seconds is considered "good".

[0564] ×: Minimum developing time of 22 seconds or more is "not allowed".

[0565] <Resistant pattern peeling>

[0566] For the substrate used for performance evaluation, a pattern is drawn using a line width (L) / space width (S) (hereinafter referred to as "L / S") of 3x / x (x=1~20 (varying in 1μm intervals)) (unit: μm). After exposure with an energy of 15 segments (the highest number of residual film segments when developing using a Stoutffer 41-segment staged exposure table as a mask), the above-mentioned heating and development processes are performed to form a resist pattern.

[0567] The resist pattern was observed at 100x magnification using an optical microscope. The flaking property of the resist pattern was evaluated by the minimum linewidth required to remove the unexposed portion (space) without residue. A smaller value indicates higher flaking property.

[0568] If the rating is ◎ or 〇, it can be used as a photosensitive resin laminate for use in resist patterning.

[0569] ◎: Minimum linewidth less than 4.0μm "Excellent"

[0570] ○: Minimum linewidth between 4.0μm and 5.0μm is considered "Good".

[0571] ×: Minimum linewidth exceeding 5.0μm is "not allowed".

[0572] <Stripping Evaluation>

[0573] After performing the above-described plating process on the substrate used for performance evaluation, the above-described peeling process is performed. The time until the cured resist lines between the plating patterns are completely peeled off is taken as the peelability value after plating. The smaller this value, the higher the peelability, and the evaluation is carried out according to the following criteria.

[0574] If the rating is ◎ or 〇, it is suitable for use as a printed circuit board for plating after resist patterning is formed.

[0575] ◎: Less than 60 seconds "Excellent"

[0576] ○: 60 seconds or more but less than 75 seconds is considered "Good".

[0577] ×: 75 seconds or more is "not allowed".

[0578] The evaluation results of the substrate used for performance evaluation of the embodiments are shown in Table 3. Furthermore, details of the components shown in Table 3 are shown in Table 2. Regarding component (A) in Table 2, the content ratio of each monomer component in components A-1 to A-10 is the mass ratio of each monomer component.

[0579] [Table 2]

[0580]

[0581] [Table 3-1]

[0582]

[0583] [Table 3-2]

[0584]

[0585] As shown in Table 3, in the embodiments that meet the requirements of this embodiment, the developability, the peeling and detachment of the resist pattern are all good.

[0586] On the other hand, when component (A) contains monomeric components that do not meet the specified requirements, the developability, the removal and peeling properties of the resist pattern are all poor.

[0587] In addition, when (B) is not composed of (b-1) a di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule and (b-2) a (meth)acrylate compound with more than four functions, the developability, the removal and peeling properties of the resist pattern are all poor.

[0588] The embodiments of the present invention have been described above, but the present invention is not limited thereto and can be appropriately modified within the scope of the spirit of the invention.

[0589] Industrial availability

[0590] By using the photosensitive resin laminate of the present invention, the developing properties, the removal and peeling properties of the resist pattern are excellent, unaffected by the coating / drying conditions and / or storage conditions of the photosensitive resin laminate. That is, it can be widely used as a photosensitive resin laminate for forming resist patterns, and is particularly suitable for resist pattern forming applications 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 photosensitive resin composition comprises the following components: (A) Alkali-soluble polymers, (B) Compounds with olefinic unsaturated bonds, and (C) Polymerization initiator, Component (A) comprises a copolymer containing monomeric components as structural units. When the value of the glass transition temperature (Tg) of the copolymer calculated by the Fox formula is set as x and the acid value of the copolymer is set as y, x ≥ 120 and 3y / 7 + 60 < x, where, The unit of x is ℃, and the unit of y is mgKOH / g. Component (B) comprises the following components: (b-1) A di(meth)acrylate compound containing at least one oxyethylene structure and at least one oxypropylene structure in one molecule, and (b-2) Four or more functional (meth)acrylate compounds, Relative to the total solid content of the photosensitive resin composition, component (C) comprises 5.0 to 10% by mass of a compound containing a bimidazole structure.

2. The photosensitive resin laminate according to claim 1, wherein, The acid value y of component (A) is below 180, i.e., y≤180.

3. The photosensitive resin laminate according to claim 1, wherein, The acid value y of component (A) is below 160, i.e., y≤160.

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

5. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The copolymer comprises structural units derived from compounds having aromatic rings as monomeric components, wherein the content of the structural units derived from compounds having aromatic rings 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 structural units derived from methyl methacrylate as the monomer component, and the content of the methyl methacrylate-derived structural units in component (A) is more than 10% by mass and less than 40% by mass.

7. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The copolymer contains structural units derived from dicyclopentyl methacrylate.

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

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

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

11. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The (b-1) component contains 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 oxyethylene structures and four or more of the oxypropylene structures in one molecule.

13. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The (b-2) component contains 5 to 20% by mass relative to the total solid content of the photosensitive resin composition.

14. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The (b-2) component contains (meth)acrylate compounds with more than 5 functionalities.

15. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The ratio of the solid components of component (b-1) to component (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 combined content of component (b-1) and component (b-2) is 50% by mass and less than 100% by mass relative to the total mass of component (B).

17. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The (B) component also contains ethoxylated bisphenol A di(meth)acrylate having an average of 2 to 30 oxyethylene structures per molecule.

18. The photosensitive resin laminate according to any one of claims 1 to 3, wherein, The (C) component also includes anthracene derivatives.

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, comprising the steps of forming a resist pattern using a photosensitive resin laminate according to any one of claims 1 to 3: In the lamination process, photosensitive resin layers are laminated onto the substrate; The exposure process involves exposing the photosensitive resin layer to light. as well as The developing process removes the unexposed portions of the photosensitive resin layer.

21. A method for manufacturing a circuit board, comprising the following steps: (The method describes the manufacturing of a circuit board using the photosensitive resin laminate according to any one of claims 1 to 3.) In the lamination process, photosensitive resin layers are laminated onto the substrate; The exposure process involves exposing the photosensitive resin layer to light. The developing process removes the unexposed portion of the photosensitive resin layer to form a resist pattern. The conductor pattern forming process involves etching or plating the substrate on which the resist pattern is formed to form the conductor pattern; as well as The stripping process removes the resist pattern from the substrate.

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