Photosensitive resin layered product

Abstract

Provided is a photosensitive resin layered product comprising a support film and a photosensitive resin layer containing a photosensitive resin composition. The thickness T of the photosensitive resin layer is 200 µm or more. The photosensitive resin composition contains, relative to the total mass of solids in the photosensitive resin composition, 30 mass% to 70 mass% of an alkali-soluble polymer (A), 20 mass% to 50 mass% of a compound (B) having an ethylenically unsaturated bond, 0.01 mass% to 20 mass% of a photopolymerization initiator (C), and an organic solvent (D). The ratio S of the content of the organic solvent (D) contained in the photosensitive resin composition is 0.01 mass% to 3 mass%. Among the organic solvent (D) contained in the photosensitive resin composition, the proportion of organic solvents having boiling points of 100°C or lower is 50 mass% or more.

Description

Photosensitive resin laminate

[0001] The present disclosure relates to a photosensitive resin laminate.

[0002] Conventionally, the production of printed wiring boards, precision machining of metals, etc. have been manufactured by photolithography methods. The photosensitive resin laminates used in photolithography methods are classified into negative types that dissolve and remove unexposed parts and positive types that dissolve and remove exposed parts.

[0003] A general method of forming a pattern using a photosensitive resin laminate will be briefly described. First, the protective layer is peeled off from the photosensitive resin laminate. Using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate or a copper sputtered thin film in the order of the substrate, the photosensitive resin layer, and the support. The photosensitive resin layer is exposed through a photomask having a desired wiring pattern. The support is peeled off from the exposed laminate, and a resist pattern is formed on the substrate by dissolving or dispersing and removing the unexposed part or the exposed part with a developer. Metal pattern formation, wiring, metal pillar or semiconductor bump formation, semiconductor mounting, etc. can be performed by subjecting the substrate provided with the resist pattern to plating treatments such as copper plating and solder plating and then peeling off the resist pattern.

[0004] Various photosensitive resin laminates have been studied for forming a resist pattern or a metal pattern using the same. For example, Patent Documents 1 to 3 describe a photosensitive resin laminate having a photosensitive resin layer containing a specific alkali-soluble polymer, a photopolymerizable monomer, and a photopolymerization initiator. Further, Patent Document 2 also studies the relationship between the film thickness and absorbance of the photosensitive resin layer.

[0005] International Publication No. 2011 / 037182 International Publication No. 2021 / 095784 International Publication No. 2022 / 085366

[0006] In recent years, wiring miniaturization and high density have been demanded, and accordingly, the plating method has been expanding as a method for forming metal wiring. The shape of the wiring formed by the plating method depends on the shape and thickness of the resist pattern. In the plating method, generally, a photosensitive resin laminate having a thick film photosensitive resin layer is used.

[0007] Generally, the photosensitive resin layer is dried to remove the solvent from the photosensitive resin layer. However, when the photosensitive resin layer becomes thick, it becomes difficult for the solvent to volatilize from the photosensitive resin layer. Therefore, even when normal drying is performed, the amount of the solvent remaining in the photosensitive resin layer (the amount of residual solvent in the photosensitive resin layer) increases. When the amount of the solvent remaining in the photosensitive resin layer increases, the photosensitive resin layer becomes too soft, so that the curing of the photosensitive resin layer does not proceed sufficiently, and there is room for improvement in resolution. In addition, when the amount of the solvent remaining in the photosensitive resin layer increases, the photosensitive resin layer becomes too soft, so that bleeding (edge fuse) at the end when the photosensitive resin laminate is formed into a roll deteriorates, and there is room for improvement in storage stability in the roll state.

[0008] On the other hand, when drying is performed strongly (strong drying), the monomer contained in the photosensitive resin composition gels, so that there is room for improvement in developability. In addition, when drying is performed strongly, the dye reacts with heat to develop color, so that the absorbance of the photosensitive resin layer increases, and there is room for improvement in sensitivity.

[0009] Therefore, an object of the present disclosure is to provide a photosensitive resin laminate capable of enhancing drying, reducing the amount of the solvent remaining in the photosensitive resin layer, and improving performance (resolution and storage stability).

[0010] Examples of embodiments of the present disclosure are listed below: (1) A photosensitive resin laminate comprising a support film and a photosensitive resin layer containing a photosensitive resin composition, wherein the thickness T of the photosensitive resin layer is 80 μm or more, and the photosensitive resin composition comprises, with respect to the total solid content mass of the photosensitive resin composition: (A) 30% to 70% by mass of an alkali-soluble polymer; (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond; (C) 0.01% to 20% by mass of a photopolymerization initiator; and (D) an organic solvent; wherein the proportion S of the content of the organic solvent (D) contained in the photosensitive resin layer is 0.01% to 3% by mass. (2) The photosensitive resin laminate according to (1), wherein the proportion S of the content of the organic solvent contained in the photosensitive resin layer is 0.01% to 2% by mass. (3) The photosensitive resin laminate according to (1), wherein the proportion S of the organic solvent content contained in the photosensitive resin layer is 0.01% by mass to 1% by mass. (4) The photosensitive resin laminate according to any one of (1) to (3), wherein the value of the formula: (Proportion S of the organic solvent content contained in the photosensitive resin layer / Thickness T of the photosensitive resin layer) × 100 is 1 or less. (5) The photosensitive resin laminate according to any one of (1) to (4), wherein the thickness T of the photosensitive resin layer is 200 μm or more. (6) The photosensitive resin laminate according to any one of (1) to (4), wherein the thickness T of the photosensitive resin layer is 270 μm or more. (7) The photosensitive resin laminate according to any one of (4) to (6), wherein the value of the formula: (S / T) × 100 is 0.75 or less. (8) A photosensitive resin laminate according to any one of (4) to (6), wherein the value of the formula: (S / T) × 100 is 0.5 or less. (9) A photosensitive resin laminate according to any one of (1) to (8), wherein the photosensitive resin composition contains (E) a thermal polymerization inhibitor. (10) A photosensitive resin laminate according to (9), wherein the content of (E) the thermal polymerization inhibitor is 0.01% by mass to 5% by mass with respect to the total solid content mass of the photosensitive resin composition. (11) A photosensitive resin laminate according to (9) or (10), wherein the (E) thermal polymerization inhibitor contains an amine compound. (12) A photosensitive resin laminate according to any one of (9) to (11), wherein the (E) thermal polymerization inhibitor contains an aromatic amine compound.(13) The photosensitive resin laminate according to any one of (1) to (12), wherein the absorbance of the photosensitive resin layer at a wavelength of 630 nm is 3 or less. (14) The photosensitive resin laminate according to any one of (1) to (12), wherein the absorbance of the photosensitive resin layer at a wavelength of 630 nm is 2 or less. (15) The photosensitive resin laminate according to any one of (1) to (14), wherein the proportion of organic solvents with a boiling point of 100°C or less among the (D) organic solvents contained in the photosensitive resin layer is 50% by mass or more. (16) The photosensitive resin laminate according to any one of (1) to (14), wherein the proportion of organic solvents with a boiling point of 80°C or less among the (D) organic solvents contained in the photosensitive resin layer is 50% or more. (17) The photosensitive resin laminate according to any one of (1) to (16), wherein the (D) organic solvent contained in the photosensitive resin layer contains toluene, and the toluene content is 0.5% by mass or less. (18) The photosensitive resin laminate according to any one of (1) to (17), wherein the (D) organic solvent contained in the photosensitive resin layer contains ethanol, and the ethanol content is 0.5% by mass or less. (19) The photosensitive resin laminate according to any one of (1) to (18), wherein the (D) organic solvent contained in the photosensitive resin layer contains acetone and / or methyl ethyl ketone, and the total content of acetone and / or methyl ethyl ketone is 3.0% by mass or less.

[0011] Other embodiments of the present disclosure are listed in the following section: [1] A photosensitive resin laminate comprising a support film and a photosensitive resin layer containing a photosensitive resin composition, wherein the thickness T of the photosensitive resin layer is 200 μm or more, and the photosensitive resin composition comprises, with respect to the total solid content mass of the photosensitive resin composition: (A) 30% to 70% by mass of an alkali-soluble polymer; (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond; (C) 0.01% to 20% by mass of a photopolymerization initiator; and (D) an organic solvent; wherein the proportion S of the content of the (D) organic solvent contained in the photosensitive resin layer is 0.01% to 3% by mass, and the proportion of the (D) organic solvent contained in the photosensitive resin layer that has a boiling point of 100°C or less is 50% by mass or more. [2] The photosensitive resin laminate according to [1], wherein the proportion S of the organic solvent content in the photosensitive resin layer is 0.01% by mass to 2% by mass. [3] The photosensitive resin laminate according to [1], wherein the proportion S of the organic solvent content in the photosensitive resin layer is 0.01% by mass to 1% by mass. [4] The photosensitive resin laminate according to any one of [1] to [3], wherein the value of the formula: (Proportion S of the organic solvent content in the photosensitive resin layer / Thickness T of the photosensitive resin layer) × 100 is 1 or less. [5] The photosensitive resin laminate according to any one of [1] to [4], wherein the thickness T of the photosensitive resin layer is 270 μm or more. [6] The photosensitive resin laminate according to [4] or [5], wherein the value of the formula: (S / T) × 100 is 0.75 or less. [7] The photosensitive resin laminate according to [4] or [5], wherein the value of the formula: (S / T) × 100 is 0.5 or less. [8] The photosensitive resin laminate according to any one of [1] to [7], wherein the photosensitive resin layer further comprises a leuco dye. [9] The photosensitive resin laminate according to any one of [1] to [8], wherein the absorbance of the photosensitive resin layer at a wavelength of 630 nm is 3 or less.

[10] The photosensitive resin laminate according to any one of [1] to [8], wherein the absorbance of the photosensitive resin layer at a wavelength of 630 nm is 2 or less.

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

[10] , wherein the photosensitive resin composition contains (E) a thermal polymerization inhibitor.

[12] The photosensitive resin laminate according to

[11] , wherein the content of the (E) thermal polymerization inhibitor is 0.01% by mass to 5% by mass with respect to the total solid content mass of the photosensitive resin composition.

[13] The photosensitive resin laminate according to

[11] or

[12] , comprising an amine compound as the (E) thermal polymerization inhibitor.

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

[11] to

[13] , comprising an aromatic amine compound as the (E) thermal polymerization inhibitor.

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

[11] to

[14] , comprising a secondary amine compound as the (E) thermal polymerization inhibitor.

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

[15] , wherein the proportion of organic solvents with a boiling point of 80°C or lower among the (D) organic solvents contained in the photosensitive resin layer is 50% by mass or more.

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

[16] , wherein the (D) organic solvent contained in the photosensitive resin layer contains toluene, and the toluene content is 0.5% by mass or less.

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

[17] , wherein the (D) organic solvent contained in the photosensitive resin layer contains ethanol, and the ethanol content is 0.5% by mass or less.

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

[18] , wherein the (D) organic solvent contained in the photosensitive resin layer contains acetone and / or methyl ethyl ketone, and the total content of acetone and / or methyl ethyl ketone is 3.0% by mass or less.

[0012] The present disclosure provides a photosensitive resin laminate that can improve performance (sensitivity, resolution, and storage stability) while enhancing drying and reducing the amount of solvent remaining in the photosensitive resin layer.

[0013] Photosensitive resin laminate The photosensitive resin laminate of this disclosure includes a support film and a photosensitive resin layer laminated on the support film. The photosensitive resin laminate is preferably a dry film resist. The photosensitive resin layer may optionally have a protective layer on the surface opposite to the support film.

[0014] The photosensitive resin layer comprises a photosensitive resin composition, the photosensitive resin composition comprising, with respect to the total solid content mass of the photosensitive resin composition, (A) 30% to 70% by mass of an alkali-soluble polymer, (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond, (C) 0.01% to 20% by mass of a photopolymerization initiator, and (D) an organic solvent. Alternatively, the photosensitive resin layer may also comprise, based on the total solid content mass of the photosensitive resin layer, (A) 30% to 70% by mass of an alkali-soluble polymer, (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond, (C) 0.01% to 20% by mass of a photopolymerization initiator, and (D) an organic solvent. The photosensitive resin layer may optionally include, in addition to components (A) to (D), (E) a thermal polymerization inhibitor and (F) other additive components such as dyes and plasticizers.

[0015] In this disclosure, a photosensitive resin laminate capable of improving the peelability of the resist pattern is identified by optimizing the thickness of the photosensitive resin layer, the structure and content of each component, for example, the structure and content of component (B) and / or component (A).

[0016] One example of this disclosure provides a photosensitive resin laminate in which the composition of component (B) is specified. Specifically, the component (B) may include at least two types of monomers, namely a difunctional monomer and a polyfunctional monomer with three or more functions, or it may include a component (B) that not only contains a difunctional monomer but also specifies the mass ratio (methacrylate monomer / acrylate monomer) of a compound having a methacryloyl group to a compound having an acryloyl group. These embodiments offer excellent developability, resolution, and solubility of the resist pattern with a stripping solution. As a difunctional monomer, for example, (b-1) a compound having a cyclic group, an ethylene oxide chain, and two acryloyl groups in one molecule (hereinafter, (b-1) compound). As a polyfunctional monomer, for example, (b-2) a compound having three or more acryloyl groups (hereinafter, (b-2) compound).

[0017] Another example of this disclosure provides a photosensitive resin laminate comprising a difunctional monomer as component (B), and in which the content or composition of components other than component (B) is specified. Specifically, the difunctional monomer may include, for example, (b-1) a compound having a cyclic group, an ethylene oxide chain, and two acryloyl groups in one molecule, and the composition of component (A) and / or the combination of component (A) and component (B) is specified, which can contribute to improving the peelability of the resist pattern.

[0018] The common configurations and preferred embodiments described in this disclosure are explained below.

[0019] <(A) Alkali-soluble polymer> The photosensitive resin composition and photosensitive resin layer according to this disclosure contain an alkali-soluble polymer. The amount of alkali-soluble polymer is 30% to 70% by mass, preferably 40% to 70% by mass, and more preferably 50% to 70% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer. In this specification, an alkali-soluble polymer is a polymer that can be dissolved in an alkaline aqueous solution.

[0020] The alkali-soluble polymer preferably contains a copolymer in which a monomer having an aromatic ring is used as a copolymer component. The alkali-soluble polymer containing a monomer having an aromatic ring as a copolymer component is hydrophobic and has a swelling-suppressing effect, and therefore exhibits excellent resolution of the resist pattern. From the viewpoint of swelling-suppressing effect and resolution, the mass ratio of the monomer having an aromatic ring included as a copolymer component in the alkali-soluble polymer is preferably in the range of 50 to 90% by mass, more preferably 70 to 90% by mass, and even more preferably 75 to 85% by mass.

[0021] Examples of monomers having an aromatic ring include (meth)acrylates having an aromatic group, and aromatic vinyl compounds such as styrene and styrene derivatives. In this specification, (meth)acrylate means acrylate or methacrylate, (meth)acrylic means acrylic or methacrylic, and (meth)acryloyl means acryloyl or methacryloyl. Examples of styrene derivatives include oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene. Among these, (meth)acrylates having an aromatic group are preferred from the viewpoint of the developability of the resist pattern.

[0022] The aromatic group of the (meth)acrylate having an aromatic group is preferably an aromatic group having 6 to 20 carbon atoms, such as a phenyl group, benzyl group, biphenyl group, and naphthyl group. The hydrogen atoms of the aromatic group may be unsubstituted or substituted, and if substituted, examples of substituents include hydrocarbon groups having 1 to 5 carbon atoms, hydroxyl groups, and halogen groups.

[0023] The alkali-soluble polymer preferably contains a copolymer with benzyl (meth)acrylate as the copolymer component, as it has an aromatic group (meth)acrylate. Generally, aromatic rings are hydrophobic and therefore have poor developability, whereas benzyl (meth)acrylate is highly flexible and has excellent developability, making it preferable.

[0024] The ratio of benzyl (meth)acrylate included as a copolymer component in the alkali-soluble polymer is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of monomers constituting the alkali-soluble polymer. A higher ratio of benzyl (meth)acrylate included as a copolymer component in the alkali-soluble polymer results in better peelability of the resist pattern. The content of benzyl (meth)acrylate included as a copolymer component in the alkali-soluble polymer is preferably less than 100% by mass, more preferably 95% by mass or less, and even more preferably 90% by mass or less, based on the total amount of monomers constituting the alkali-soluble polymer.

[0025] The alkali-soluble polymer has an acid equivalent of 350 or more, preferably 370 or more, more preferably 380 or more, even more preferably 390 or more, even more preferably 400 or more, and particularly preferably 410 or more. Here, in this disclosure, acid equivalent refers to the weight of the alkali-soluble polymer per 1 mol of acidic groups, and the unit is g / mol. The acid equivalent can be calculated from the acid value (mgKOH / g) obtained from the weight of potassium hydroxide that reacts with 1 g of alkali-soluble polymer. That is, the acid equivalent can be measured by potentiometric titration using an aqueous potassium hydroxide solution (JIS K2501 (2003)), etc. An acid equivalent of 350 or more of the alkali-soluble polymer offers advantages such as shortening the minimum development time, improving resolution, reducing stripping solution fatigue, and preventing resist wrinkles during storage. There is no upper limit to the acid equivalent of the alkali-soluble polymer, but it is preferably 600 or less, for example. By keeping the acid equivalent to 600 or less, the developability and peelability can be improved.

[0026] The lower the ratio of acid groups in the alkali-soluble polymer, the more effectively swelling can be suppressed, and the better the resolution tends to be. Therefore, the ratio of acid groups is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the solid content mass of the alkali-soluble polymer. The lower limit of the ratio of acid groups in the alkali-soluble polymer is not particularly limited, but for example, it may be 0% by mass, may exceed 0% by mass, or may be 1% by mass or more.

[0027] The weight-average molecular weight of the alkali-soluble polymer tends to be better in terms of developability and dissolution of peeling fragments as the weight-average molecular weight decreases, so it is preferably 60,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less, and particularly preferably 30,000 or less. The lower limit of the weight-average molecular weight of the alkali-soluble polymer is preferably 5,000 or more, more preferably 6,000 or more, from the viewpoint of reducing developed aggregates and improving the properties of the unexposed film in the photosensitive resin laminate, such as edge fusing and cut-tip properties. Edge fusing refers to the property of suppressing the phenomenon of the photosensitive resin layer protruding from the end face of the roll when the photosensitive resin laminate is wound into a roll shape. Cut-tip properties refer to the property of suppressing the phenomenon of chips flying off when the unexposed film is cut with a cutter. If the cut-tip properties are poor, the scattered chips may adhere to, for example, the upper surface of the photosensitive resin laminate, and these chips may be transferred to the mask in the subsequent exposure process, potentially causing defects.

[0028] The alkali-soluble polymer may contain copolymer components other than monomers having aromatic rings. Examples of such copolymer components include carboxylic acids, carboxylates, and acid anhydrides having at least one polymerizable unsaturated group in the molecule, such as (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid semi-ester (meth)acrylic acid, alkyl (meth)acrylate; (meth)acrylonitrile, and (meth)acrylamide. Among these, it is preferable that the copolymer component contains a constituent unit derived from (meth)acrylic acid. The total amount of methacrylic acid and acrylic acid in the alkali-soluble polymer is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the solid content mass of the alkali-soluble polymer.

[0029] Alkali-soluble polymers are preferable if they contain constituent units derived from methacrylic acid, as this allows for a balance between excellent developability and resolution. When methacrylic acid is contained in the alkali-soluble polymer, the ratio is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the solid content mass of the alkali-soluble polymer. The lower limit of the mass ratio of constituent units derived from methacrylic acid in the alkali-soluble polymer is not limited, but may be, for example, 0% by mass or greater than 0% by mass.

[0030] Alkali-soluble polymers are preferable if they contain constituent units derived from acrylic acid, as this results in excellent flexibility of the cured film and cured resist pattern, and consequently, excellent developability. From the viewpoint of flexibility and developability, the mass ratio of constituent units derived from acrylic acid in the alkali-soluble polymer is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the solid content mass of the alkali-soluble polymer. The lower limit of the mass ratio of constituent units derived from acrylic acid in the alkali-soluble polymer is not limited, but may be, for example, 0% by mass, greater than 0% by mass, or 1% by mass or more.

[0031] It is preferable for the alkali-soluble polymer to contain alkyl group-containing monomers (e.g., alkyl (meth)acrylates) because this results in excellent flexibility of the cured film and cured resist pattern, and consequently, excellent developability. From the viewpoint of flexibility and developability, the mass ratio of constituent units derived from alkyl group-containing monomers in the alkali-soluble polymer is preferably in the range of 1 to 20% by mass, more preferably 1 to 10% by mass, based on the solid content mass of the alkali-soluble polymer.

[0032] Since the alkyl chains of alkyl group-containing monomers in alkali-soluble polymers tend to be more flexible and developable the longer they are, alkali-soluble polymers preferably contain alkyl group-containing monomers having 1 to 10 carbon atoms, more preferably contain alkyl group-containing monomers having 4 to 10 carbon atoms, and even more preferably contain alkyl group-containing monomers having 6 to 10 carbon atoms.

[0033] The alkyl group in the alkyl (meth)acrylate may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate may be, for example, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may be 12 or less, 11 or less, 10 or less, 9 or less, or 8 or less. More specifically, examples of alkyl groups in alkyl (meth)acrylate include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Among these, the 2-ethylhexyl group is more preferred from the viewpoint of shortening the development time and reducing the trailing of the resist pattern. By using, for example, 2-ethylhexyl (meth)acrylate as part of the monomer used in the synthesis of alkali-soluble polymers, an alkali-soluble polymer containing 2-ethylhexyl acrylate as a copolymer component can be obtained.

[0034] Preferred copolymerization components in alkali-soluble polymers include, for example, (meth)acrylic acid and benzyl (meth)acrylate; (meth)acrylic acid, benzyl (meth)acrylate and aromatic vinyl compounds; and (meth)acrylic acid, benzyl (meth)acrylate and alkyl (meth)acrylate. More specifically, examples include methacrylic acid and benzyl methacrylate; acrylic acid, benzyl methacrylate and styrene; and acrylic acid, benzyl methacrylate and 2-ethylhexyl acrylate.

[0035] <(B) Compounds having ethylenically unsaturated bonds> The photosensitive resin composition and photosensitive resin layer according to this disclosure contain compounds having ethylenically unsaturated bonds. The amount of compound having ethylenically unsaturated bonds is 20% to 50% by mass, preferably 20% to 40% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer. The ethylenically unsaturated bonds can be polymerized by irradiation with light in the presence of a photopolymerization initiator, thereby curing the photosensitive resin layer.

[0036] Compounds having ethylenically unsaturated bonds may have a double bond equivalent of 150 or more, preferably 160 or more, more preferably 170 or more, even more preferably 180 or more, even more preferably 190 or more, and particularly preferably 200 or more. When the double bond equivalent of a compound having ethylenically unsaturated bonds is 150 or more, the resistance to plating penetration and peeling tend to improve. The upper limit of the double bond equivalent of a compound having ethylenically unsaturated bonds is not limited, but may be, for example, 500 or less, 400 or less, or 300 or less. In this specification, "double bond equivalent" means the molecular weight per ethylenically unsaturated bond.

[0037] From the viewpoint of improving resolution, the concentration of ethylenically unsaturated bonds in the photosensitive resin layer is preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more, and even more preferably 2.0 mmol / g or more. When the concentration of ethylenically unsaturated bonds in the photosensitive resin layer is 1.0 mmol / g or more, a strong crosslinked film is formed as a resist pattern, which has a swelling suppression effect and tends to have excellent resolution. The ethylenically unsaturated bonds in the photosensitive resin layer are preferably derived from at least ethylenically unsaturated methacryloyl groups or acryloyl groups. The upper limit of the concentration of ethylenically unsaturated bonds in the photosensitive resin layer is not limited, but may be, for example, 5.0 mmol / g or less, 3.0 mmol / g or less, or 2.0 mmol / g or less. In this specification, "concentration of ethylenically unsaturated bonds in the photosensitive resin layer" means the total number of moles of ethylenically unsaturated bonding groups per gram of the photosensitive resin layer.

[0038] As a compound having an ethylenically unsaturated bond, for example, a compound having a (meth)acryloyl group can be used. In this disclosure, we do not wish to be bound by theory, but the dissolution mechanism of a photosensitive resin laminate or resist pattern in a stripping solution such as an aqueous solution of tetraalkylammonium hydroxide is thought to be that the compound having an ethylenically unsaturated bond contained in the photosensitive resin layer is hydrolyzed, and the crosslinked portion of the photosensitive resin layer decomposes and dissolves in the stripping solution. Based on the above dissolution mechanism, a compound having an acryloyl group (acrylate monomer) is preferred over a compound having a methacryloyl group (methacrylate monomer) because it has better hydrolysis properties and the acrylate monomer is easier to dissolve and peel off in the stripping process.

[0039] Similar to the dissolution mechanism described above, from the viewpoint of solubility of the resist pattern in the stripping solution, the mass ratio of the compound having a methacryloyl group (methacrylate monomer) to the compound having an acryloyl group (acrylate monomer) in the compound having an ethylenically unsaturated bond: the mass ratio of methacrylate monomer to acrylate monomer (methacrylate monomer / acrylate monomer) is preferably 0 or more and less than 0.5, and more preferably 0 or more and less than 0.1. Since acrylate monomers are more hydrolyzable than methacrylate monomers and tend to decompose more easily in the stripping solution, it is preferable that the compound having an ethylenically unsaturated bond contains a larger amount of acrylate monomer than methacrylate monomer. Furthermore, it is preferable that the compound having an ethylenically unsaturated bond does not contain methacrylate monomer, or that it contains it in a mass ratio of less than half that of acrylate monomer.

[0040] Similar to the dissolution mechanism described above, the ratio of methacrylate monomer in the compound having an ethylenically unsaturated bond is preferably less than 50% by mass, more preferably less than 30% by mass, even more preferably less than 20% by mass, even more preferably less than 10% by mass, still even more preferably less than 5% by mass, particularly preferably less than 3% by mass, and most preferably 0% by mass, based on the mass of the compound having an ethylenically unsaturated bond, from the viewpoint of solubility in the stripping solution and hydrolysis.

[0041] Compounds having an ethylenically unsaturated bond can, if desired, be modified with alkylene oxides, specifically, they can have one or more alkylene oxide chains in their molecule. Examples of alkylene oxides include methylene oxide (MO), ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO).

[0042] Compounds having ethylenically unsaturated bonds tend to have better solubility in stripping solutions containing large amounts of water or hydrophilic solvents when they have relatively hydrophilic side chains. Therefore, compounds having ethylenically unsaturated bonds modified with EO are preferred over PO-modified and BO-modified compounds having ethylenically unsaturated bonds, which are relatively hydrophobic. Furthermore, the mass ratio of PO and / or BO-modified monomers to EO-modified monomers in compounds having ethylenically unsaturated bonds: the mass ratio of PO and / or BO-modified monomers to EO-modified monomers {(PO-modified monomer and / or BO-modified monomer) / EO-modified monomer} is preferably 0 or more and less than 0.1 from the viewpoint of solubility in stripping solutions. Monomers without alkylene oxide chains are calculated as EO-modified monomers. From a similar viewpoint, the ratio of PO-modified monomers and / or BO-modified monomers in a compound having an ethylenically unsaturated bond is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 0% by mass, based on the total solid content mass of the compound having an ethylenically unsaturated bond.

[0043] Regarding the length of the EO chain in compounds having ethylenically unsaturated bonds, shorter chains tend to result in better resolution, while longer chains tend to result in better developability. The number of moles of units having EO chains in compounds having ethylenically unsaturated bonds is preferably in the range of 1 to 30, more preferably 4 to 20, and even more preferably 4 to 10 per mole of compound, from the viewpoint of balancing resolution and developability. Note that if the number of moles of units having EO chains exceeds 1, the compound having ethylenically unsaturated bonds includes repeating units having EO chains.

[0044] The number of functional groups in a compound having ethylenically unsaturated bonds tends to be better in terms of resolution when there are more, and better in terms of exfoliation when there are fewer, so it can be determined according to the balance between resolution and exfoliation. The number of functional groups in a compound having ethylenically unsaturated bonds may be, for example, monofunctional (hereinafter also called monofunctional), two or more functional, three or more functional, four or more functional, five or more functional, six or more functional, three to ten functional, three to six functional, or four to six functional, or multiple types of compounds with different numbers of functional groups may be combined. In this specification, "number of functional groups" refers to the number of ethylenically unsaturated bonds per molecule of the compound, and for example, in the case of acrylate monomers, it is defined as the number of acryloyl groups per molecule, and in the case of methacrylate monomers, it is defined as the number of methacryloyl groups per molecule.

[0045] Compounds having a monofunctional ethylenically double bond are preferred because they have excellent solubility in the stripping solution. Examples of compounds having a monofunctional ethylenically double bond include compounds in which (meth)acrylic acid is added to one end of (poly)alkylene glycol, and compounds in which (meth)acrylic acid is added to one end of (poly)alkylene glycol and a group without an ethylenically double bond, such as an alkyl group or an alkylphenyl group, is added to the other end. The alkylene in (poly)alkylene glycol is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, or a butylene group. From the viewpoint of solubility in the stripping solution, the content ratio of monofunctional monomers in the compound having an ethylenically double bond is preferably in the range of 1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 15% by mass, based on the total solid content mass of the compound having an ethylenically unsaturated bond.

[0046] Examples of compounds with two or more functionalities include compounds having a backbone such as (poly)alkylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, or dipentaerythritol, in which at least two or all of the hydrogen atoms of the hydroxyl groups are substituted with functional groups having ethylenically unsaturated bonds, preferably functional groups having (meth)acryloyl groups, and more preferably functional groups having acryloyl groups.

[0047] A compound having a (poly)alkylene glycol backbone and a bifunctional ethylenically unsaturated bond is given by the following general formula (I): {In the formula, Y independently represents an alkylene group, and R １ and R ２ Examples of compounds represented by} include those in which each of the following independently represents a methyl group or a hydrogen atom, and each of the following independently represents an integer from 1 to 50.

[0048] In the above general formula (I), Y is independently an alkylene group preferably having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, and a butylene group. The (Y-O) portion may contain repeating units of different alkylene oxides or consist of repeating units of the same alkylene oxide. When the (Y-O) portion contains different alkylene oxides, its arrangement may be random, alternating, or block arrangement. n represents an integer from 1 to 50, preferably 3 to 20, more preferably 6 to 10.

[0049] More specifically, examples of compounds represented by the above general formula (I) include: hexaethylene glycol diacrylate, heptaethylene glycol diacrylate, octaethylene glycol diacrylate, nonaethylene glycol diacrylate, decaethylene glycol diacrylate, hexapropylene glycol diacrylate, heptapropylene glycol diacrylate, octapropylene glycol diacrylate, nonapropylene glycol diacrylate, and decapropylene glycol diacrylate.

[0050] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (I) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0051] In one example of this disclosure, the difunctional monomer is preferably a compound having a cyclic group, an ethylene oxide (EO) chain, and two acryloyl groups in one molecule (b-1). When a photosensitive resin composition or photosensitive resin layer contains the (b-1) compound, it tends to have excellent developability, resolution, and solubility in stripping solutions. Furthermore, the presence of a cyclic group in the (b-1) compound tends to improve resistance to plating penetration. In the (b-1) compound, there may be one or more cyclic groups, the EO chain may be located on one or both sides of the cyclic group, and the two acryloyl groups may be in any position.

[0052] (b-1) The EO chain of the compound is preferably located on both sides of the cyclic group, as the higher the proportion of the EO chain, the better the solubility in stripping solutions containing a large amount of water or hydrophilic solvent. (b-1) The number of moles of the EO chain of the compound is preferably in the range of 1 to 30, more preferably 4 to 20, and even more preferably 4 to 10, from the viewpoint of balancing resolution and developability.

[0053] (b-1) An example of a compound is a compound having hydrogenated bisphenol A as its skeleton, in which both sides of the hydrogenated bisphenol A skeleton are modified with EO, and which has acryloyl groups at both ends. Hydrogenated bisphenol A is a compound in which hydrogen is added to the aromatic ring of bisphenol A.

[0054] (b-1) Compounds in which the cyclic group is an aromatic ring are preferred. That is, (b-1) compounds that have an aromatic ring, an ethylene oxide (EO) chain, and two acryloyl groups in one molecule are preferred. The presence of an aromatic ring as the cyclic group tends to improve resistance to plating penetration. Examples of such compounds include those with a bisphenol A skeleton, in which both sides of the bisphenol A skeleton are EO-modified and have acryloyl groups at both ends. The bisphenol A skeleton in (b-1) compounds not only improves the strength of the crosslinked film but also improves resolution.

[0055] A compound having a bisphenol A skeleton, in which both sides of the bisphenol A skeleton are modified with ethylene oxide (EO), and having acryloyl groups at both ends, is preferably a diacrylate of ethylene oxide (EO)-modified bisphenol A. The following general formula (II) is used for diacrylates of ethylene oxide-modified bisphenol A: Examples of compounds represented by {Formula (II) {wherein EO each independently represents ethylene oxide, A each independently represents an acryloyl group, and m and n each independently represent an integer from 1 to 100} include those compounds. In Formula (II), from the viewpoint of improving the peelability of the resist pattern, m and n preferably satisfy the relationship 5 ≤ m + n ≤ 20, more preferably 7 ≤ m + n ≤ 15, even more preferably 8 ≤ m + n ≤ 12, and particularly preferably m + n ≈ 10.

[0056] More specifically, as compounds represented by the above general formula (II), for example: Diacrylate of polyethylene glycol obtained by adding an average of 1 mole of ethylene oxide to each end of bisphenol A; Diacrylate of polyethylene glycol obtained by adding an average of 2 moles of ethylene oxide to each end of bisphenol A; Diacrylate of polyethylene glycol obtained by adding an average of 3 moles of ethylene oxide to each end of bisphenol A (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "ABE-300"); Diacrylate of polyethylene glycol obtained by adding an average of 4 moles of ethylene oxide to each end of bisphenol A (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "A-BPE-4"); Diacrylate of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A; Diacrylate of polyethylene glycol obtained by adding an average of 6 to 9 moles of ethylene oxide to each end of bisphenol A. Examples include polyethylene glycol diacrylate with an average of 10 moles of ethylene oxide added to each end of bisphenol A (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "A-BPE-10"), polyethylene glycol diacrylate with an average of 11 to 19 moles of ethylene oxide added to each end of bisphenol A, polyethylene glycol diacrylate with an average of 20 moles of ethylene oxide added to each end of bisphenol A (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "A-BPE-20"), polyethylene glycol diacrylate with an average of 21 to 29 moles of ethylene oxide added to each end of bisphenol A, polyethylene glycol diacrylate with an average of 30 moles of ethylene oxide added to each end of bisphenol A, and polyethylene glycol diacrylate with an average of 31 moles or more of ethylene oxide added to each end of bisphenol A.

[0057] The double bond equivalent of the compound represented by the above general formula (II) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0058] In one example of this disclosure, the photosensitive resin composition or photosensitive resin layer preferably contains a polyfunctional monomer with three or more functions as a compound having an ethylenically unsaturated bond.

[0059] In another example of this disclosure, at least two monomers are preferred as the compound having an ethylenically unsaturated bond, and a combination of a difunctional monomer and a trifunctional or polyfunctional monomer is more preferred.

[0060] As a polyfunctional monomer with three or more functions, a compound having three or more (b-2) acryloyl groups is preferred. When a photosensitive resin composition or photosensitive resin layer contains a (b-2) compound, it tends to have excellent developability, resolution, and solubility in stripping solutions. As a (b-2) compound, for example, among the polyfunctional monomers with three or more functions described later, those having an acryloyl group as a group having an ethylenically unsaturated bond may be used.

[0061] A compound with a trimethylolpropane backbone and a trifunctional ethylenically unsaturated bond is given by the following general formula (III): Examples of compounds represented by the formula {wherein n1, n2, and n3 are each independently integers from 0 to 25, except that n1 + n2 + n3 is an integer from 0 to 75, and R1, R2, and R3 are each independently a methyl group or a hydrogen atom}.

[0062] In the above general formula (III), n1, n2, and n3 are each an integer from 0 to 25, preferably 0 to 10 or 1 to 10, more preferably 0 to 3 or 1 to 3. n1 + n2 + n3 is an integer from 0 to 75, preferably 0 to 30 or 3 to 30, more preferably 0 to 15 or 3 to 15, and even more preferably 0 to 9 or 3 to 9. From the viewpoint of suppressing the formation of resist edges, improving film strength, and imparting flexibility to the cured film, it is preferable that n1 + n2 + n3 is 0 or greater, more preferably 3 or greater, and particularly preferable 9 or greater. When n1 + n2 + n3 is 75 or less, it is preferable from the viewpoint of high resolution and adhesion, good peel characteristics, and control of edge fusing.

[0063] Specific examples of compounds represented by the above general formula (III) include, for example: triacrylates obtained by adding a total of an average of 3 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane; triacrylates obtained by adding a total of an average of 9 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane; triacrylates obtained by adding a total of an average of 15 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane; and triacrylates obtained by adding a total of an average of 30 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane.

[0064] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (III) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0065] A compound with a glycerol backbone and a trifunctional ethylenically unsaturated bond is given by the following general formula (IV): Examples of compounds represented by the formula {wherein Y independently represents an alkylene group, R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 200} include:

[0066] In general formula (IV), Y is each independently preferably an alkylene group having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and examples thereof include a 1,2-ethylene group, a 1,2-propylene group, and a butylene group. From the viewpoints of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and enhancing the reactivity of ethylenically unsaturated bonds, at least one or all of Y are preferably 1,2-ethylene groups. The (Y—O) moiety may contain repeating units of different alkylene oxides or may consist of repeating units of the same alkylene oxide. When the (Y—O) moiety contains different alkylene oxides, the arrangement may be a random, alternating, or block arrangement. n is each independently an integer of 0 to 200, and it is preferable that at least one n is an integer of 1 to 200, and more preferably three ns are integers of 1 to 200. In general formula (IV), n may be 0, that is, the alkylene oxide moiety may not be present. When the total of n is 1 or more, it is preferable from the viewpoints of suppressing the occurrence of resist skirts, improving film strength, and imparting flexibility to the cured film. When the total of n is 200 or less, it is preferable from the viewpoints of high resolution and adhesion, good peeling characteristics, and controlling edge fusing properties.

[0067] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (IV) is preferably 150 or more, more preferably 160 or more, still more preferably 170 or more, and even more preferably 180 or more, and optionally 500 or less, 400 or less, or 300 or less, from the viewpoints of plating resistance, stripping liquid treatability, and stripping liquid fatigue resistance.

[0068] As a compound having a pentaerythritol skeleton and a tetrafunctional ethylenically unsaturated bond, the following general formula (V): {In the formula, n １ , n ２ , n ３ and n ４ each independently represent an integer of 0 to 25, and n １ +n ２ +n ３ +n ４ is an integer of 0 to 100, and R１ , R ２ , R ３ and R ４ Each of these independently represents a methyl group or a hydrogen atom, R ５ , R ６ , R ７ , and R ８ Each of these independently represents an alkylene group, R ５ , R ６ , R ７ and R ８ If there are multiple instances of each, then the multiple R ５ , R ６ , R ７ and R ８ Compounds represented by} may be identical or different from each other.

[0069] In general formula (V), R ５ , R ６ , R ７ and R ８ Each of these is independently preferably an alkylene group having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, for example, a 1,2-ethylene group, a 1,2-propylene group, a butylene group, etc. From the viewpoint of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and enhancing the reactivity of ethylenically unsaturated bonds, R ５ , R ６ , R ７ and R ８ Preferably, at least one or all of them are 1,2-ethylene groups. １ +n ２ +n ３ +n ４ n is 0 to 100, preferably 0 to 80 or 4 to 80, more preferably 0 to 40 or 4 to 40, even more preferably 0 to 20 or 4 to 20, and particularly preferably 0 to 16 or 4 to 16. From the viewpoint of suppressing the formation of resist hem, improving film strength, and imparting flexibility to the cured film, １ +n ２ +n ３ +n ４ It is preferable that n is 0 or greater, and more preferably 4 or greater. １ +n ２ +n ３ +n４ A value of 100 or less is preferable from the viewpoint of high resolution and adhesion, good peeling characteristics, and control of edge fusing properties.

[0070] Specific examples of compounds represented by the above general formula (V) include, for example: tetraacrylate obtained by adding a total of an average of 4 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 9 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 12 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 15 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 20 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 28 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; and tetraacrylate obtained by adding a total of an average of 35 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "ATM-35E").

[0071] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (V) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0072] Among compounds with a pentaerythritol backbone and four functional ethylenically unsaturated bonds, the (b-2) compound is the following general formula (V1): Compounds represented by the formula {wherein EO each independently represents ethylene oxide, A each independently represents an acryloyl group, and k, l, m, and n each independently represent an integer from 0 to 100} are preferred. Compounds represented by the general formula (V1) can improve crosslinking density and, consequently, contribute to good resolution. In the general formula (V1), k, l, m, and n preferably satisfy the relationship 4 ≤ k + l + m + n ≤ 100, more preferably 10 ≤ k + l + m + n ≤ 50, even more preferably 12 ≤ k + l + m + n ≤ 25, and particularly preferably k + l + m + n ≈ 15 from the viewpoint of improving the peelability of the resist pattern.

[0073] A compound with a dipentaerythritol backbone and six functional ethylenically unsaturated bonds is given by the following general formula (VI): Examples of compounds represented by the formula {wherein R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 30} include:

[0074] In general formula (VI), n is an integer from 0 to 30, preferably 1 to 20, more preferably 2 to 10, and even more preferably 3 to 5. The sum of n is from 0 to 180, preferably 6 to 120, more preferably 12 to 60, and even more preferably 18 to 30. In general formula (VI), n may be 0, that is, the alkylene oxide portion may not be present. A sum of n of 1 or more is preferable from the viewpoint of suppressing the generation of resist trimming, improving film strength, and imparting flexibility to the cured film. A sum of n of 180 or less is preferable from the viewpoint of high resolution and adhesion, good peelability, and control of edge fusing.

[0075] Specific examples of hexaacrylate compounds represented by general formula (VI) include, for example: dipentaerythritol hexaacrylate, hexaacrylate in which a total of 1 to 36 moles of ethylene oxide are added to the six ends of dipentaerythritol, hexaacrylate in which a total of 6 to 30 moles of ethylene oxide are added to the six ends of dipentaerythritol, hexaacrylate in which a total of 12 to 30 moles of ethylene oxide are added to the six ends of dipentaerythritol, hexaacrylate in which a total of 18 to 30 moles of ethylene oxide are added to the six ends of dipentaerythritol, and hexaacrylate in which a total of 1 to 10 moles of ε-caprolactone are added to the six ends of dipentaerythritol.

[0076] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (VI) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, stripping solution treatment, and stripping solution fatigue.

[0077] The mass ratio (A / B) of the alkali-soluble polymer to the compound having an ethylenically unsaturated bond tends to improve the curability of the bottom of the resist film, resulting in superior stripping fluid fatigue resistance and resolution, while a lower mass ratio tends to improve developability. From the viewpoint of balancing resolution and developability, the mass ratio (A / B) is preferably in the range of 1.2 to 3.0, more preferably 1.5 to 2.5, even more preferably 1.7 to 2.5, even more preferably 1.8 to 2.3, and particularly preferably 1.8 to 2.2.

[0078] <(C) Photopolymerization initiator> A photopolymerization initiator is a compound that, when irradiated with light in the presence of a compound having an ethylenically unsaturated bond, can initiate the polymerization of the compound having the ethylenically unsaturated bond.

[0079] The amount of photopolymerization initiator in the photosensitive resin composition and the photosensitive resin layer is 0.01% to 20% by mass, preferably 0.3% to 10% by mass, and more preferably 1% to 5% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. If the amount of photopolymerization initiator is 0.01% by mass or more, an exposure pattern with a sufficient residual film rate can be obtained after development. If the amount of photopolymerization initiator is 20% by mass or less, light can be sufficiently transmitted to the bottom surface of the resist, high resolution can be obtained, and development aggregation in the developer can be suppressed.

[0080] Examples of photopolymerization initiators include triarylimidazole dimers, aromatic ketones, acridine compounds, and N-aryl-α-amino acid compounds. A single photopolymerization initiator may be used, or two or more may be used in combination.

[0081] Examples of triarylimidazole dimers include 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0082] Aromatic ketones are preferred from the viewpoint of improving sensitivity. Examples of aromatic ketones include benzophenone, N,N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-monofornophenyl)butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0083] Acridine compounds are preferred from the viewpoint of improving sensitivity and achieving both high sensitivity and suppression of stabilization. Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, and 9-(4-acetylphenyl) Examples include 1,7-(9,9'-acridinyl)acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetylphenyl)acridine, 9-(3-dimethylaminophenyl)acridine, 9-(3-diethylaminophenyl)acridine, 9-(3-chlorophenyl)acridine, 9-(3-bromophenyl)acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, and 9-(4-pyridyl)acridine. Among these, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0084] N-aryl-α-amino acid compounds are preferred from the viewpoint of improving sensitivity. Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0085] Further examples of photopolymerization initiators include, for example, quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzyl derivatives such as benzyl methyl ketal; and coumarin compounds such as coumarin 1 and coumarin 102. Examples include pyrazoline derivatives such as 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline; anthracene derivatives such as 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid; and others.

[0086] Among these, it is preferable to include a triarylimidazole dimer as a photopolymerization initiator. When a triarylimidazole dimer is included as a photopolymerization initiator, the content of the triarylimidazole dimer in the photosensitive resin composition is preferably 0.3% to 10% by mass, and more preferably 1% to 5% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer.

[0087] When the content of triarylimidazole dimer in the photosensitive resin composition is within the above range, the content of other photopolymerization initiators is preferably 0% by mass or more and 0.20% by mass or less, more preferably 0% by mass or more and 0.10% by mass or less, even more preferably 0% by mass or more and 0.01% by mass or less, and most preferably 0% by mass or more and 0.005% by mass or less.

[0088] <(D) Organic Solvent> The organic solvent is a compound capable of dissolving or dispersing the photosensitive resin composition. The photosensitive resin layer can be formed by applying a solution of the above components (A) to (C) in an organic solvent onto a support film, and then drying it. The photosensitive resin composition according to this disclosure may optionally contain an organic solvent in addition to the above components. The resulting photosensitive resin layer may also contain residual organic solvent.

[0089] The content of the organic solvent is preferably 30% to 60% by mass, more preferably 33% to 50% by mass, and even more preferably 35% to 45% by mass, relative to the coating liquid of the photosensitive resin composition.

[0090] The percentage S of organic solvent content in the photosensitive resin layer is preferably 0.01% to 3% by mass, more preferably 0.01% to 2% by mass, and even more preferably 0.01% to 1% by mass. The upper limit of the percentage S of organic solvent content in the photosensitive resin layer is preferably as small as possible, but may be 3.0% by mass or less, or 2.0% by mass or less, or 1.0% by mass or less, or 0.5% by mass or less. The lower limit of the percentage S of organic solvent content in the photosensitive resin layer may be 0.01% by mass or more. If the upper limit of the percentage S of organic solvent content in the photosensitive resin layer is too high compared to the predetermined range, the photosensitive resin layer becomes flexible and difficult to harden, which tends to result in poor resolution. When the proportion S of organic solvent content in the photosensitive resin layer of this embodiment is within a predetermined range, the hardening of the photosensitive resin layer proceeds sufficiently, resulting in excellent resolution and suppression of edge bleeding (edge ​​fusing) when the photosensitive resin laminate is rolled, thus providing excellent storage stability in roll form. Furthermore, if the photosensitive resin layer contains two or more organic solvents, the effects of this embodiment can be obtained as long as the total content S of the two or more organic solvents is controlled within a predetermined range.

[0091] The proportion S of organic solvent content in the photosensitive resin layer is controlled to a predetermined range by drying as described below. The proportion S of organic solvent content in the photosensitive resin layer is preferably low, and since the photosensitive resin layer of this disclosure is a thick film, strong drying is preferred, and particularly strong drying conditions are more preferred. In this disclosure, strong drying refers to drying under conditions such that the proportion S of organic solvent content in a photosensitive resin layer with a thickness of 80 μm or more is 0.5% by mass or less, or drying under conditions such that the proportion S of organic solvent content in a photosensitive resin layer with a thickness of 200 μm or more is 1.0% by mass or less. The proportion S of organic solvent content in the photosensitive resin layer is measured by the method described in the examples.

[0092] Examples of organic solvents include ketones such as methyl ethyl ketone (boiling point 80°C) and acetone (boiling point 56°C), alcohols such as methanol (boiling point 65°C), ethanol (boiling point 78°C), and isopropanol (boiling point 82°C), and toluene (boiling point 111°C), methyl cellosolve (boiling point 125°C), propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether (boiling point 120°C), and tetrahydrofuran (boiling point 66°C). These organic solvents may be used individually or mixed in combination of two or more. Among these organic solvents, at least one selected from toluene, ethanol, methyl ethyl ketone (MEK), and acetone is preferred, and toluene, ethanol, or methyl ethyl ketone is more preferred. In one embodiment, toluene and methyl ethyl ketone may be used in combination as organic solvents, for example, by mixing toluene and methyl ethyl ketone in a ratio of 3:7 (mass ratio). In one embodiment, ethanol and methyl ethyl ketone may be used as the organic solvent in combination, for example, by mixing ethanol and methyl ethyl ketone in a ratio of 3:7 (by mass). In another embodiment, acetone and methyl ethyl ketone may be used as the organic solvent in combination.

[0093] From the viewpoint of resolution, it is preferable that the proportion of organic solvents with a boiling point of 100°C or lower in the photosensitive resin layer is 50% by mass or more, and it is more preferable that the proportion of organic solvents with a boiling point of 80°C or lower is 50% by mass or more. When the organic solvents contained in the photosensitive resin layer are within the above range, the organic solvents volatilize due to the heat generated when laminating the photosensitive resin film, making it possible to laminate a photosensitive resin layer with a low organic solvent content on the substrate and obtain good resolution. Examples of organic solvents with a boiling point of 100°C or lower include isopropanol, tetrahydrofuran, ethanol, and methyl ethyl ketone (MEK). Examples of organic solvents with a boiling point of 80°C or lower include tetrahydrofuran, ethanol, and methyl ethyl ketone (MEK).

[0094] In one embodiment, the organic solvent contained in the photosensitive resin layer contains toluene, with a toluene content of 0.5% by mass or less. In another embodiment, the organic solvent contained in the photosensitive resin layer contains ethanol, with an ethanol content of 0.5% by mass or less. In yet another embodiment, the organic solvent contained in the photosensitive resin layer contains acetone and / or methyl ethyl ketone, with a total content of acetone and / or methyl ethyl ketone of 3.0% by mass or less.

[0095] <(E) Thermal polymerization inhibitors> The photosensitive resin composition and the photosensitive resin layer may each further contain thermal polymerization inhibitors. Thermal polymerization inhibitors can improve the thermal stability and storage stability of the photosensitive resin layer. Radical polymerization inhibitors are preferred as thermal polymerization inhibitors.

[0096] When drying is performed strongly (strong drying or intensified drying), the monomers contained in the photosensitive resin composition gel, which tends to result in poor developability. Furthermore, when the photosensitive resin composition contains the dyes described later, strong drying tends to result in poor sensitivity because the dyes, which normally do not develop color, decompose due to heat and develop color, increasing the absorbance. The photosensitive resin composition of this embodiment, by containing a thermal polymerization inhibitor, maintains excellent performance (developability, sensitivity, and resolution) even when drying is intensified and the amount of solvent in the photosensitive resin layer is reduced.

[0097] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, phenothiazine, biphenol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 4,4'-thiobis(6-tert-butyl-m Examples include 1,4'-cresol, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrene-phenols (e.g., manufactured by Kawaguchi Chemical Industries, Ltd., trade name "Antage SP"), tripenzylphenols (e.g., manufactured by Kawaguchi Chemical Industries, Ltd., trade name "TBP", phenol compounds having 1 to 3 benzyl groups), and amine compounds.

[0098] Among these radical polymerization inhibitors, amine compounds are preferred. Among amine compounds, secondary amine compounds or aromatic amine compounds are more preferred. The photosensitive resin composition of this embodiment, by including an amine compound (particularly at least one selected from secondary amine compounds and aromatic amine compounds) as a thermal polymerization inhibitor, enhances drying and reduces the amount of organic solvent in the photosensitive resin layer, thereby providing excellent performance (sensitivity and resolution).

[0099] Examples of amine compounds include dioctylamine and pentamethylpiperidyl methacrylate (FA-711MM). Examples of aromatic amine compounds include aniline derivatives, phenylenediamine derivatives, and aromatic nitrosamines. Examples include aluminum salts with 3 moles of nitrosophenylhydroxylamine added, N-nitrosodiphenylamine, and 4-(2-octylamino)diphenylamine (e.g., Ozonone 35, manufactured by Seiko Chemical Co., Ltd.). These may be used individually or in combination of two or more. Examples of secondary amine compounds include 4-(2-octylamino)diphenylamine, diethylamine, diphenylamine, and dioctylamine. Among these, aluminum salts with 3 moles of nitrosophenylhydroxylamine added, N-nitrosodiphenylamine, or 4-(2-octylamino)diphenylamine are preferred from the viewpoint of achieving both enhanced drying and excellent performance (sensitivity and resolution). Among these, 4-(2-octylamino)diphenylamine, which is a secondary amine compound and an aromatic amine compound, is particularly preferred.

[0100] The total content of the thermal polymerization inhibitor is preferably 0.01% to 5% by mass, more preferably 0.01% to 1% by mass, even more preferably 0.01% to 0.1% by mass, particularly preferably 0.01% to 0.05% by mass, and most preferably 0.01% to 0.025% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer. When the thermal polymerization inhibitor content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is enhanced, and when it is 5% by mass or less, sensitivity is maintained and dye decolorization tends to be suppressed.

[0101] (F) Other additives The photosensitive resin composition may optionally contain dyes, halogen compounds, plasticizers, benzotriazoles, and benzotriazoles and carboxybenzotriazoles.

[0102] <Dyes> The photosensitive resin composition and the photosensitive resin layer may each further contain dyes. The dye may contain at least one selected from leuco dyes, fluorane dyes, and other coloring substances. In particular, it is preferable that the photosensitive resin composition and the photosensitive resin layer contain leuco dyes as dyes. The inclusion of these components in the photosensitive resin layer causes the exposed area to develop color, improving visibility. Furthermore, when an inspection machine or the like reads the alignment marker for exposure, the contrast between the exposed and unexposed areas increases, making it easier to recognize.

[0103] Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leucocrystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green]. From the viewpoint of good contrast, leucocrystal violet is preferred as the leuco dye.

[0104] Examples of fluorane dyes include 2-(dibenzylamino)fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chlor-6-diethylaminofluorane, and 2-ani Examples include lino-3-methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, and 2-(3,4-dichloroanilino)-6-diethylaminofluorane.

[0105] The amount of leuco dye or fluoran dye in the photosensitive resin composition and the photosensitive resin layer is preferably 0.1% to 10% by mass, more preferably 0.2% to 5% by mass, and even more preferably 0.3% to 1% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. When the amount of the dye is 0.1% by mass or more, the contrast between the exposed and unexposed areas tends to improve. When the amount of the dye is 10% by mass or less, the storage stability of the photosensitive resin layer improves and the occurrence of aggregates during development tends to be suppressed.

[0106] Examples of coloring substances include fuchsin, phthalocyanine green, auramine base, paramazienta, crystal violet, methyl orange, Nile Blue 2B, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen® MALACHITE GREEN), Basic Blue 7 (e.g., Eisen® Victoria Pure Blue BOH conc.), Basic Blue 20, and Diamond Green (manufactured by Hodogaya Chemical Co., Ltd., Eisen® DIAMOND GREEN GH).

[0107] The amount of coloring substance in the photosensitive resin composition and the photosensitive resin layer is preferably 0.001% by mass to 1% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. When the amount of coloring substance is 0.001% by mass or more, the contrast improves, and when it is 1% by mass or less, the storage stability tends to improve.

[0108] <Halogen Compounds> The photosensitive resin composition and the photosensitive resin layer may each further contain halogen compounds, and it is preferable that they further contain halogen compounds in combination with leuco dyes. When a combination of leuco dyes and halogen compounds is included, adhesion and contrast tend to improve.

[0109] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and chlorinated triazine compounds. Among these, tribromomethylphenylsulfone is preferred as the halogen compound. Halogen compounds such as tribromomethylphenylsulfone are particularly effective when used in combination with acridine compounds as photopolymerization initiators, and are preferred from the viewpoint of improving resolution, adhesion, sensitivity, contrast, tent film puncture resistance, suppression of resist trimming, and etching resistance.

[0110] From the viewpoint of the above, the content of halogen compounds in the photosensitive resin composition and the photosensitive resin layer is preferably 0.01% by mass or more, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. More preferably, this content is 0.1% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. Furthermore, a content of 3% by mass or less is preferable from the viewpoint of maintaining the storage stability of hue in the photosensitive resin layer and suppressing the generation of aggregates during development. More preferably, this content is 2% by mass or less, and even more preferably 1.5% by mass or less.

[0111] <Plasticizers> The photosensitive resin composition or photosensitive resin layer may contain plasticizers as needed. Examples of plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; phthalate esters such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, etc.; propylene glycol obtained by adding propylene oxide to both ends of bisphenol A, ethylene glycol obtained by adding ethylene oxide to both ends of bisphenol A, etc. These can be used individually or in combination of two or more.

[0112] The amount of plasticizer in the photosensitive resin composition and the photosensitive resin layer is preferably 1% to 50% by mass, and more preferably 1% to 30% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. When the amount of plasticizer is 1% by mass or more, the delay in development time is suppressed and flexibility is imparted to the cured film, while when it is 50% by mass or less, insufficient curing and edge fusing tend to be suppressed.

[0113] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0114] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, and mixtures thereof. Among these, a mixture of 4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole is preferred, with a preferred mixing ratio of approximately 1:1 by mass.

[0115] <Thickness of the photosensitive resin layer> The thickness of the photosensitive resin layer (hereinafter referred to as the thickness T of the photosensitive resin layer) is 80 μm or more, preferably more than 80 μm, more preferably 100 μm or more, even more preferably 200 μm or more, even more preferably 270 μm or more, particularly preferably 300 μm or more, and most preferably 400 μm or more. In this disclosure, the thickness T of the photosensitive resin layer is the thickness of the photosensitive resin layer formed by coating the photosensitive resin composition onto the support film and then drying it. Normally, when the thickness of the photosensitive resin layer is 270 μm or more or exceeds 270 μm, the solvent does not volatilize easily during lamination, so the resolution tends to be poor. By keeping the amount of solvent in the photosensitive resin layer within the range specified in this application, it becomes easier to obtain good resolution even with a thickness of 270 μm or more.

[0116] In plating processes, photosensitive resin laminates having a thick photosensitive resin layer (in one embodiment, 80 μm or more or 200 μm or more) are sometimes used. Furthermore, a thicker photosensitive resin layer suppresses the generation of lamination air, making it possible to obtain a photosensitive resin laminate suitable for plating processes that form, for example, metal pillars. The thickness of the photosensitive resin layer may be 200 μm or more, 300 μm or more, or 400 μm or more. The upper limit of the thickness T of the photosensitive resin layer is not limited, but for example, it can be 1000 μm or less, 800 μm or less, or 500 μm or less.

[0117] For measuring the thickness T of the photosensitive resin layer, devices such as the FT-A series contact-type continuous thickness gauge manufactured by Fujiwork Corporation, the VL-50 series dot-type thickness gauge manufactured by Mitutoyo Corporation, and the AccureX series non-contact inline thickness gauge manufactured by Hutech Corporation can be used. Furthermore, as a method for measuring the thickness T of the photosensitive resin layer using the aforementioned devices, the thickness can be calculated by measuring the total thickness of the photosensitive resin laminate and taking the difference between that thickness and the thickness of other parts of the photosensitive resin laminate, such as the support film and protective film. In this case, it is preferable to measure the thickness at 10 or more points in the width direction of the photosensitive resin laminate and use the average value as the thickness T.

[0118] From the viewpoint of press flow control and storage stability, the value of the following formula: (percentage of organic solvent content S (mass%) in the photosensitive resin layer / thickness T (μm) of the photosensitive resin layer) × 100 is preferably 2 or less, more preferably 1 or less, particularly preferably 0.75 or less, and most preferably 0.5 or less.

[0119] <Optical Properties> When the absorbance at a wavelength of 630 nm per 1 μm of film thickness of the photosensitive resin layer according to this disclosure increases, the dye pigment develops color and absorbs light, reducing sensitivity and making it difficult for the photopolymerization initiator to decompose. The absorbance (A) of the photosensitive resin layer at a wavelength of 630 nm is preferably 3 or less, more preferably 2.5 or less, even more preferably 2 or less, and particularly preferably 1 or less. In particular, it is preferable for the photosensitive resin layer to contain a leuco dye as a dye from the viewpoint of improving the contrast between the exposed and unexposed areas and from the viewpoint of improving sensitivity by having a part of it contribute to the reaction during exposure. However, since leuco dyes tend to develop color easily, when the photosensitive resin layer contains a leuco dye as a dye, it is especially important to adjust the absorbance (A) at a wavelength of 630 nm to 3 or less. Means for making the absorbance (A) of a photosensitive resin layer containing a leuco dye at a wavelength of 630 nm 3 or less include, for example, drying at a drying temperature of 130°C or less for a drying time of 1 minute or more and 20 minutes or less, or drying at a drying temperature exceeding 100°C for a drying time of less than 40 minutes. In particular, when forming a relatively thick photosensitive resin layer such as one with a thickness of 200 μm or more, it is possible to control the proportion S of the (D) organic solvent content in the photosensitive resin layer to 0.01% by mass to 3% by mass, while also making the absorbance (A) at a wavelength of 630 nm 3 or less, by performing the drying as described later for a film thickness of 200 μm or more, or by performing the drying under the conditions described in the examples. This makes it easier to suppress the color development of leuco dyes, even under strict drying conditions.

[0120] <Support Film> A transparent support film that transmits light emitted from the exposure light source is desirable. Examples of support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can also be used in stretched form as needed.

[0121] The haze of the support film is preferably 5% or less, more preferably 1% or less, even more preferably 0.5% or less, and most preferably 0.3% or less. A thinner support film is advantageous in terms of image formation and cost-effectiveness, but considering the function of maintaining strength, a thickness of 10 μm or more is preferable. Furthermore, if the thickness of the photosensitive resin layer is 80 μm or more or 200 μm or more, that is, if the photosensitive resin layer is a thick film, a thicker support film is preferable from the viewpoint of film thickness stability during coating, that is, the thickness of the support film is preferably 20 μm or more, more preferably 50 μm or more, even more preferably 75 μm or more, and most preferably 100 μm or more. From the viewpoint of slitting processability, the thickness of the support film may be 500 μm or less.

[0122] Furthermore, the thickness of the support film may be 10% or more of the thickness of the photosensitive resin layer, and may also be 20% or more.

[0123] <Protective Layer> The photosensitive resin laminate may have a protective layer (in one embodiment, a protective film) on the surface opposite to the support film of the photosensitive resin layer. The protective layer plays a role in protecting the photosensitive resin layer. Preferably, the protective layer has appropriate adhesion to the photosensitive resin layer. That is, it is preferable that the adhesion of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesion of the support film to the photosensitive resin layer, so that the protective layer can be easily peeled off the photosensitive resin laminate. As the protective layer, for example, polyethylene film, polypropylene film, or a film with excellent peelability as shown in Japanese Patent Publication No. 59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 to 50 μm.

[0124] 《Method for Manufacturing a Photosensitive Resin Laminate》 The photosensitive resin laminate of this disclosure can be manufactured by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film. The manufacturing of the photosensitive resin laminate of this disclosure includes, for example, the steps of: obtaining a photosensitive resin composition preparation (coating solution) by mixing a photosensitive resin composition with a solvent that dissolves them (in one embodiment, an organic solvent); applying the coating solution to a support film; forming a photosensitive resin layer on the support film by drying the coating solution; and, if necessary, laminating a protective film onto the photosensitive resin layer.

[0125] Known methods can be used for lamination. For example, each component used in the photosensitive resin layer is mixed with a solvent to dissolve them and obtain a homogeneous solution (coating solution). Examples of solvents include ketones such as toluene, methyl ethyl ketone (MEK), and acetone; alcohols such as methanol, ethanol, and isopropanol; and methyl cellosolve, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and tetrahydrofuran. The amount of solvent is preferably such that the viscosity of the coating solution is 500 to 6,000 mPa·s at 25°C. The viscosity was measured at 25°C using an E-type viscometer (Endo Kagaku Co., Ltd., model number TV-100). The coating solution is applied to a support film and then dried to remove the solvent from the photosensitive resin layer, thereby forming a photosensitive resin layer on the support film. Known methods can be used for application, for example, by using a bar coater or a roll coater.

[0126] Drying can be carried out using known methods, such as using a drying oven. The drying conditions should be such that the total content S (residual solvent amount) of the organic solvent in the photosensitive resin layer is 3% by mass or less, or preferably 2% by mass or less, or 1% by mass or less, or 0.5% by mass or less. Drying may be carried out only once, or after the first drying, it may be carried out multiple times under the same or different drying conditions as the first drying, or the film coated with the photosensitive resin composition liquid may be dried by transporting it in multiple drying ovens at different temperatures. In one embodiment, the drying conditions are a drying temperature of 40 to 130°C and a drying time of 1 to 60 minutes. For the film thickness of 100 μm or more, the drying temperature is preferably 90°C or higher; for the film thickness of 200 μm or more, the drying temperature is preferably 100°C or higher; and for the film thickness of 400 μm or more, the drying temperature is preferably 110°C or higher. For drying time, if the film thickness is 100 μm or more, the total drying time is preferably in the range of 3 minutes to 1 hour; if the film thickness is 200 μm or more, the total drying time is preferably in the range of 5 minutes to 1 hour; if the film thickness is 300 μm or more, the total drying time is preferably in the range of 10 minutes to 1 hour; and if the film thickness is 400 μm or more, the total drying time is preferably in the range of 15 minutes to 1 hour.

[0127] Since the photosensitive resin layer in this embodiment is a thick film, strong drying is preferred as a method for removing the solvent. However, this can be carried out as appropriate depending on the embodiment, and in detail, it can be carried out under the drying conditions described in the examples. For example, in the case of a photosensitive resin layer with a thickness of 120 μm, drying is performed for 5 minutes in a dryer preheated to 70°C, followed by drying for 10 minutes in a dryer at 90°C, so that the total percentage S (residual solvent amount) of organic solvent in the photosensitive resin layer becomes 0.5% by mass or less. Alternatively, for example, in the case of a photosensitive resin layer with a thickness of 340 μm, drying is performed for 12 minutes in a dryer preheated to 70°C, followed by drying for 40 minutes in a dryer at 100°C, so that the total percentage S (residual solvent amount) of organic solvent in the photosensitive resin layer becomes 0.5% by mass or less. Furthermore, for example, in the case of a photosensitive resin layer with a thickness of 450 μm, drying in a preheated dryer at 70°C for 15 minutes, followed by drying in a dryer at 120°C for 30 minutes, results in a total organic solvent content S (residual solvent amount) in the photosensitive resin layer being 0.5% by mass or less. Subsequently, if necessary, a protective layer can be laminated onto the photosensitive resin layer to produce a photosensitive resin laminate.

[0128] [Roll (Photosensitive Resin Roll)] A further embodiment of this embodiment is a photosensitive resin roll formed by winding a photosensitive resin laminate. The roll may or may not have a core material. A long photosensitive resin laminate may be wound around a core material, or it may be wound without a core material.

[0129] 《Method for forming resist patterns and metal pillars or semiconductor bumps》 A resist pattern can be formed using the photosensitive resin laminate of this disclosure. The resist pattern formation method may include: a step of laminating the photosensitive resin layer of the photosensitive resin laminate onto a substrate (laminating step); an exposure step of the laminated photosensitive resin laminate; a development step of developing the exposed photosensitive resin laminate to form a resist pattern (developing step); and optionally, a heating step of heating the obtained resist pattern.

[0130] Metal pillars or semiconductor bumps can be formed using a substrate on which a resist pattern has been formed. The method for forming metal pillars or semiconductor bumps may optionally include: a descam and pre-plating treatment step; a step of forming metal pillars or semiconductor bumps by metal plating or solder plating the substrate on which the resist pattern has been formed (plating step); an optional step of etching the substrate on which the resist pattern has been formed (etching step); and an optional step of peeling the resist pattern from the substrate (peeling step).

[0131] The following describes a series of methods for forming resist patterns and metal pillars or semiconductor bumps using a photosensitive resin laminate and a sputtered copper thin film as a substrate.

[0132] (1) Lamination process: For example, while peeling off the protective layer of the photosensitive resin laminate, the laminate is pressed onto a substrate such as a sputtered copper thin film using, for example, a hot roll laminator. The sputtered copper thin film is preferably a copper sputtered silicon wafer in which a copper layer has been formed on a silicon wafer using a sputtering apparatus.

[0133] (2) Exposure process The exposure process may be, for example: a process of exposing the photosensitive resin layer of a photosensitive resin laminate laminated on the substrate to a mask film having a desired wiring pattern while the mask film is in close contact with the photosensitive resin layer, a process of exposing the desired wiring pattern by direct imaging exposure, or a process of exposing the photosensitive resin layer by projecting the image of a photomask through a lens.

[0134] (3) Development process After the exposure process, the support film on the photosensitive resin layer is peeled off, and the unexposed areas (in the case of negative type) or exposed areas (in the case of positive type) are developed and removed using an alkaline aqueous developer to form a resist pattern on the substrate. As the alkaline aqueous solution, Na ２ CO ３ _K ２ CO ３Alternatively, an aqueous solution of tetramethylammonium hydroxide (TMAH) can be used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a concentration of about 0.2 to 2% by mass and a temperature of about 20°C to 40°C with Na ２ CO ３ It is preferable to use an aqueous solution.

[0135] The conditions for the exposure and / or development process may be determined according to the desired shape of the metal pillar or semiconductor bump. For example, in the case of forming metal pillars such as metal cylinders or polygonal prism patterns, the exposure and / or development process may be carried out in such a way that a hole-type resist pattern can be formed in which the ratio of the hole diameter to the film thickness of more than 100 μm is relatively high.

[0136] (4) Heating step If desired, the formed resist pattern may be further heated for 1 minute to 5 hours at, for example, about 50°C to 300°C. By performing this heating step, the adhesion and chemical resistance of the resulting cured resist pattern can be further improved. For heating in this case, for example, a heating furnace using a hot plate, hot air, infrared rays, or far infrared rays can be used.

[0137] (5) Descam and pre-plating treatment If desired, the substrate on which the resist pattern has been formed may be subjected to plasma treatment and / or immersion treatment to perform descam and pre-plating treatment.

[0138] (6) A conductor pattern can be manufactured by copper plating or solder plating the substrate surface exposed by the plating process development (for example, the copper surface of a sputtered copper thin film). The plating solution is preferably a copper sulfate plating solution.

[0139] (7) Peeling step After that, the laminate can be treated with an aqueous solution having a stronger alkalinity than the developer to peel off the resist pattern from the substrate. Examples of peeling solutions include an aqueous solution of an alkaline component with a concentration of about 2 to 5% by mass and a temperature of about 40°C to 70°C; an aqueous solution of NaOH or KOH; dimethyl sulfoxide (DMSO); tetramethylammonium hydroxide (TMAH); a mixture of DMSO and TMAH; SPR920 (product name); R-101 (product name); and a peeling solution that does not contain DMSO (hereinafter referred to as "DMSO-free peeling solution"). Among these, a DMSO-free peeling solution is preferred from the viewpoint of the effects of the photosensitive resin laminate according to this disclosure and from the viewpoint of reducing environmental burden. A DMSO-free peeling solution may contain one or more of the above components other than DMSO.

[0140] The photosensitive resin laminates, resist patterns, metal pillars, and semiconductor bumps described above can be used, for example, in the formation of semiconductor packages and wafer-level packages (WLPs).

[0141] [Examples 1-20 and Comparative Examples 1-3] <Preparation of Photosensitive Resin Laminates> The materials shown in Tables 1 and 2 were mixed in the composition shown in Table 3 (however, the numbers for each component indicate the amount (parts by mass) of solids). Methyl ethyl ketone was then added in an amount measured to a solids concentration of 64% by mass, and the mixture was thoroughly stirred and mixed to obtain a coating solution for the photosensitive resin composition. The obtained coating solution was uniformly applied to the surface of a 16 μm thick polyethylene terephthalate film (Toray Industries, Inc., FB-40) as a support film using a bar coater to form a photosensitive resin layer. The film was dried in a dryer under the drying conditions described in Table 4 to form a dried photosensitive resin layer. The drying conditions described in Table 4 were performed as follows: Drying condition 1: drying temperature 1 and drying time 1, followed by Drying condition 2: drying temperature 2 and drying time 2. The thickness (T) of the photosensitive resin layer after drying is shown in Table 4. The thickness (T) of the photosensitive resin layer after drying was measured using a dot-type thickness gauge (product name: dot-type VL-50B, manufactured by Mitutoyo Co., Ltd.).

[0142] A photosensitive resin laminate was obtained by laminating a 19 μm thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) as a protective film onto a surface that did not have a support film laminated on it.

[0143] [Measurement and Evaluation] <Absorbance of the photosensitive resin layer at a wavelength of 630 nm> After peeling off the protective film of the above photosensitive laminate, the absorbance of the photosensitive resin layer at a wavelength of 630 nm was measured using a U-3010 spectrophotometer (manufactured by Hitachi High-Technologies Corporation) with polyethylene terephthalate film (PET film) as a reference. The measurement was performed with a slit of 4 nm and a scan speed of 600 nm / min.

[0144] <Evaluation criteria for absorbance of photosensitive resin layer at a wavelength of 630 nm> Absorbance of 1 or less: Excellent Absorbance greater than 1 and 2 or less: Good Absorbance greater than 2 and 3 or less: Acceptable

[0145] <Measurement of residual solvent amount> The photosensitive resin layer, obtained by peeling off the protective film and support film from the photosensitive resin laminate, was subjected to gas chromatography to measure the amount of residual solvent in the photosensitive resin layer. The method for preparing the sample for measurement and the measurement conditions for gas chromatography are as follows.

[0146] (Preparation of sample for measurement) 1.0 g of the photosensitive resin layer was dissolved in 10.0 g of cyclohexanone, and then 2 g of the internal standard sample solution was added to prepare the sample for measurement.

[0147] (Preparation of internal standard solution) 0.3 g of propylene glycol monomethyl ether was dissolved in 94.5 g of cyclohexanone to prepare the internal standard solution.

[0148] <Measurement Conditions> Measuring device: GC / MS Agilent 6890, Agilent Column: Capillary column DB-1 Dimethylpolysiloxane (Column length 10 m, column inner diameter 0.15 mm, column film thickness 1.2 μm) Carrier gas: Helium 5.0 mL / min Injection temperature: 200 °C Detection temperature: 250 °C Oven temperature: Heating from 40 °C to 260 °C (20 °C / min) Detector: Flame ionization detector (FID) Sample injection volume: 1.0 μL Calibration curves were created for each solvent contained in the photosensitive resin layer, and the content (mass %) of each solvent in the photosensitive resin layer was determined. The sum of these was taken as the amount of remaining solvent.

[0149] <Minimum Development Time> A polyethylene film (protective film) was peeled off a 6-inch silicon wafer from a photosensitive resin laminate, and the substrate, preheated to 70°C, was laminated using an air damper type hot roll laminator (Taisei Laminator Co., Ltd., VA-400III) at a roll temperature of 70°C. The air pressure was set to 0.20 MPa and the lamination speed to 0.18 m / min. The support film was peeled off the substrate, and then 1 mass% Na was processed using a spin developer (Takizawa Sangyo Co., Ltd., spin developer AD-1200). ２ CO ３ The aqueous solution was sprayed onto the photosensitive resin layer at a liquid temperature of 30°C and a flow rate of 200 mL / min, and spray development was performed. For each experimental example, the shortest time required for the unexposed photosensitive resin layer to completely dissolve under the above conditions was defined as the "minimum development time."

[0150] <Evaluation Substrate> <Substrate> As the substrate, a 6-inch silicon wafer was prepared by forming a copper layer with a thickness of 2000 angstroms (Å) on it using a sputtering apparatus (L-440S-FHL) manufactured by Canon Anelva Corporation (copper sputtered silicon wafer).

[0151] <Lamination> While peeling the polyethylene film from the photosensitive resin laminate, the substrate, preheated to 70°C, was laminated using an air damper type hot roll laminator (Taisei Laminator Co., Ltd., VA-400III) at a roll temperature of 70°C. The air pressure was set to 0.20 MPa and the lamination speed to 0.18 m / min.

[0152] <Exposure> A glass chromium mask was prepared with a circular hole pattern (for photosensitive materials, a pattern where the outside of the circle is exposed and the inside is not) arranged in 5 μm increments, ranging in diameter from 10 μm to 200 μm. The substrate after the above <Lamination> was exposed using this glass chromium mask and an Ultratech Prisma ghi stepper (manufactured by Ultratech) as the exposure machine. The illuminance measured on the substrate surface was 2400 mW / cm². ２ That was the case.

[0153] <Development> After the above <exposure>, the PET film is peeled off as a support film from the substrate, and then 1 mass% Na is developed using a spin developer (Takizawa Sangyo Co., Ltd. spin developer AD-1200). ２ CO ３ An aqueous solution was sprayed onto the photosensitive resin layer at a liquid temperature of 30°C and a flow rate of 200 mL / min (spray development). For each experimental example, the development time was set to twice the previously determined minimum development time. After development, water was sprayed onto the photosensitive resin layer (water wash spray). The conditions and time for the water wash spray were set in the same way as for the development spray.

[0154] [Evaluation Method] <Sensitivity and Resolution> The resist pattern formed after the above <exposure> and <development> was observed at 10x magnification using an optical microscope, and sensitivity and resolution were evaluated based on the smallest mask size in which the empty areas (unexposed areas) were completely removed without residue. Patterns exposed at multiple exposure levels were observed, and the exposure level in which the smallest mask size circular hole was resolved was defined as the "optimal exposure level," and the mask size at this point was used to evaluate "resolution." Smaller values ​​for both the optimal exposure level and mask size indicate better sensitivity and resolution. The evaluation criteria for sensitivity and resolution under these evaluation conditions are as follows.

[0155] (When the thickness T of the photosensitive resin layer is 100 μm or more and less than 200 μm: Examples 1 to 3 and Comparative Example 1) <Sensitivity evaluation criteria> Optimal exposure dose is 200 mJ / cm ２ More than 300mJ / cm ２ The following is an example of an optimal exposure dose: 300 mJ / cm². ２ Ultra: OK <Resolution Evaluation Criteria> Diameter of circular hole in mask size is 50 μm or less: OK Diameter of circular hole in mask size is greater than 50 μm: Unacceptable

[0156] (When the thickness T of the photosensitive resin layer is 200 μm or more and less than 250 μm: Examples 4 to 6) <Sensitivity evaluation criteria> Optimal exposure dose is 200 mJ / cm ２ More than 300mJ / cm ２ The following is an example of an optimal exposure dose: 300 mJ / cm². ２ Ultra: OK <Resolution Evaluation Criteria> Diameter of circular hole in mask size is 70 μm or less: OK Diameter of circular hole in mask size is greater than 70 μm: Not OK

[0157] (When the thickness T of the photosensitive resin layer is 250 μm or more and less than 300 μm: Example 18) <Sensitivity evaluation criteria> Optimal exposure dose is 300 mJ / cm ２ 350mJ / cm or more ２ The following is the optimal exposure dose: 350 mJ / cm². ２ Ultra: OK <Resolution Evaluation Criteria> Diameter of circular hole in mask size is 90 μm or less: OK Diameter of circular hole in mask size is greater than 90 μm: Not OK

[0158] (When the thickness T of the photosensitive resin layer is 300 μm or more and less than 400 μm: Examples 7-9, Examples 14-17 and Comparative Example 2) <Sensitivity evaluation criteria> Optimal exposure dose is 400 mJ / cm ２ The following is an example of an optimal exposure dose of 400 mJ / cm². ２ Super 600mJ / cm ２ The following is an example of an optimal exposure dose: 600 mJ / cm². ２ Super 700mJ / cm ２ The following: Acceptable <Resolution evaluation criteria> Diameter of circular hole in mask size is 150 μm or less: Acceptable Diameter of circular hole in mask size is greater than 150 μm: Not acceptable

[0159] (When the thickness T of the photosensitive resin layer is 400 μm or more: Examples 10-13, Examples 19-20 and Comparative Example 3) <Sensitivity evaluation criteria> Optimal exposure dose is 1000 mJ / cm ２ The following is an example of an optimal exposure dose of 1000 mJ / cm². ２ Super 1500mJ / cm ２ Below: The optimal exposure dose is 1500 mJ / cm². ２ Super 2000mJ / cm ２ The following: Acceptable <Resolution evaluation criteria> Diameter of circular hole in mask size is 180 μm or less: Acceptable Diameter of circular hole in mask size is greater than 180 μm: Not acceptable

[0160] <Press Flow> A photosensitive resin laminate was cut into 2.5 cm squares, the protective film was removed, and it was placed in the center of a 10 cm square PET film. A hydraulic press heated to 40°C applied a force of 100 kg for 5 minutes. After that, the width of the photosensitive resin layer overhang was measured in four directions (8 points in total), and the average value was calculated. This test was performed with n=2, and the average value for n=2 was calculated. This average value was used as the press flow test value, and the value obtained by dividing this value by the thickness of the photosensitive resin layer (press flow test value (μm) / thickness T (μm) of the photosensitive resin layer) was evaluated according to the following criteria. The smaller this value, the lower the fluidity of the photosensitive resin layer, which means that the photosensitive resin laminate has excellent suppression of film leakage when in a roll state and excellent storage stability, and thus good performance. <Evaluation Criteria for Storage Stability> Press flow test value / photosensitive resin layer thickness T value less than 10: Excellent Press flow test value / photosensitive resin layer thickness T value 10 or more and 20 or less: Good Press flow test value / photosensitive resin layer thickness T value greater than 20 and 25 or less: Acceptable Press flow test value / photosensitive resin layer thickness T value greater than 25: Unacceptable

[0161] [Example 19] The total residual solvent content S in the photosensitive resin layer prepared in Example 19 was 1.80% by mass (MEK 0.80% by mass and toluene 1.00% by mass), the absorbance of the photosensitive resin layer at a wavelength of 630 nm was >3.0, and the optimal exposure dose was 1500 mJ / cm². ２ The resolution was 180 μm, the press flow test value was 6000 μm, and the value of the press flow test value / thickness T of the photosensitive resin layer was 13.

[0162] [Example 20] The total residual solvent content in the photosensitive resin layer prepared in Example 20 was 1.60% by mass (MEK 0.70% by mass and ethanol 0.90% by mass), the absorbance of the photosensitive resin layer at a wavelength of 630 nm was >3.0, and the optimal exposure dose was 1500 mJ / cm². ２ The resolution was 160 μm, the press flow test value was 5500 μm, and the value of the press flow test value / thickness T of the photosensitive resin layer was 12.

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Claims

1. A photosensitive resin laminate comprising a support film and a photosensitive resin layer containing a photosensitive resin composition, wherein the thickness T of the photosensitive resin layer is 200 μm or more, and the photosensitive resin composition comprises, with respect to the total solid content mass of the photosensitive resin composition: (A) 30% to 70% by mass of an alkali-soluble polymer; (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond; (C) 0.01% to 20% by mass of a photopolymerization initiator; and (D) an organic solvent; wherein the proportion S of the content of the (D) organic solvent contained in the photosensitive resin layer is 0.01% to 3% by mass, and the proportion of the (D) organic solvent contained in the photosensitive resin layer that has a boiling point of 100°C or less is 50% by mass or more.

2. The photosensitive resin laminate according to claim 1, wherein the proportion S of the organic solvent content contained in the photosensitive resin layer is 0.01% by mass to 2% by mass.

3. The photosensitive resin laminate according to claim 1, wherein the proportion S of the organic solvent content contained in the photosensitive resin layer is 0.01% by mass to 1% by mass.

4. The photosensitive resin laminate according to claim 1, wherein the value of the formula: (percentage S of organic solvent content in the photosensitive resin layer / thickness T of the photosensitive resin layer) × 100 is 1 or less.

5. The photosensitive resin laminate according to claim 1, wherein the thickness T of the photosensitive resin layer is 270 μm or more.

6. The photosensitive resin laminate according to claim 4, wherein the value of the formula: (S / T) × 100 is 0.75 or less.

7. The photosensitive resin laminate according to claim 4, wherein the value of the formula: (S / T) × 100 is 0.5 or less.

8. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin layer further comprises a leuco dye.

9. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the absorbance of the photosensitive resin layer at a wavelength of 630 nm is 3 or less.

10. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the absorbance of the photosensitive resin layer at a wavelength of 630 nm is 2 or less.

11. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the photosensitive resin composition contains (E) a thermal polymerization inhibitor.

12. The photosensitive resin laminate according to claim 11, wherein the content of (E) the thermal polymerization inhibitor is 0.01% by mass to 5% by mass with respect to the total solid content mass of the photosensitive resin composition.

13. The photosensitive resin laminate according to claim 11, wherein the (E) thermal polymerization inhibitor contains an amine compound.

14. The photosensitive resin laminate according to claim 11, wherein the (E) thermal polymerization inhibitor contains an aromatic amine compound.

15. The photosensitive resin laminate according to claim 11, wherein the (E) thermal polymerization inhibitor contains a secondary amine compound.

16. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the proportion of organic solvents with a boiling point of 80°C or lower among the (D) organic solvents contained in the photosensitive resin layer is 50% by mass or more.

17. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the (D) organic solvent contained in the photosensitive resin layer contains toluene, and the toluene content is 0.5% by mass or less.

18. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the (D) organic solvent contained in the photosensitive resin layer contains ethanol, and the ethanol content is 0.5% by mass or less.

19. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the (D) organic solvent contained in the photosensitive resin layer contains acetone and / or methyl ethyl ketone, and the total content of acetone and / or methyl ethyl ketone is 3.0% by mass or less.

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