Photosensitive resin composition and transfer film using photosensitive resin composition

Abstract

To provide a dry film resist which improves the yield of an object or a pattern formed by photolithography, a pattern forming method comprising the dry film resist or to provide a photosensitive resin laminate which is excellent in at least one of laminability, minimal development time, resolution, side edge amount, Cu defect, and development residue.SOLUTION: Provided is a dry film resist comprising a support film and a photosensitive resin composition layer on the support film, the photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound comprising an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a dye. The maximum point load in a specific puncture test is 70 gf or more. The component B contains a trifunctional or higher polyfunctional monomer and a bifunctional monomer, and / or when the acid value of the non-volatile component of the photosensitive resin composition is denoted as A (mgKOH / g) and the thickness of the photosensitive resin composition layer is denoted as T (μm), the ratio (A / T) of the acid value A to the thickness T is 5-90.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a dry film resist, a method for forming a resist pattern, a method for forming a wiring pattern, and the like. [Background technology]

[0002] Conventionally, photolithography has been used for the manufacture of printed wiring boards, precision machining of metals, etc. Photosensitive resin compositions used in photolithography are classified into negative-type compositions that dissolve and remove unexposed areas, and positive-type compositions that dissolve and remove exposed areas.

[0003] When applying a photosensitive resin composition onto a substrate in a photolithography method, (1) A method of applying a photoresist solution to a substrate and drying it, and (2) A method of laminating a photosensitive resin layer on a substrate using a photosensitive resin laminate in which a support, a layer containing a photosensitive resin composition (hereinafter also referred to as a "photosensitive resin layer"), and, if necessary, a protective layer are laminated in this order. In the manufacture of printed wiring boards, the latter method is often used.

[0004] A method for forming a pattern using the above-mentioned photosensitive resin laminate will be briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Then, 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. Then, the photosensitive resin layer is exposed to light through a photomask having a desired wiring pattern. Then, the support is peeled off from the exposed laminate, and the non-patterned portion is dissolved or dispersed and removed by a developer to form a resist pattern on the substrate.

[0005] Furthermore, a wiring pattern can be obtained by subjecting the substrate provided with the resist pattern to an etching process or a plating process such as copper plating or solder plating.

[0006] Various photosensitive resin compositions have been studied for forming resist patterns or wiring patterns. For example, Patent Documents 1 and 2 describe photosensitive resin compositions containing a specific alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

[0007] Patent Document 1 focuses on a photosensitive resin composition that is excellent in resist shape, minimum development time, and bleed-out properties, and on the formation of a resist pattern and a wiring board using the same.

[0008] Patent Document 2 discusses the adhesion of resist patterns, resolution, and suppression of the occurrence of resist tails in a projection exposure method.

[0009] For example, Patent Documents 3 to 5 disclose photosensitive resin compositions that contain a compound having polytetramethylene oxide as a structural unit, and thereby enable the formation of a resist pattern even with a low exposure dose, and provide a cured film that has excellent tent reliability and etching resistance. Furthermore, Patent Document 6 discloses a photosensitive resin composition that contains a compound having a polyalkylene oxide as a structural unit, and thereby is capable of forming a resist pattern even with a low exposure dose, and the formed cured film has excellent tent reliability and etching resistance. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Patent No. 6063200 [Patent Document 2] Patent No. 6432511 [Patent Document 3] International Publication No. 2015 / 174467 [Patent Document 4] JP 2018-31800 A [Patent Document 5] JP 2018-31799 A [Patent Document 6] Patent No. 6673196 Summary of the Invention [Problem to be solved by the invention]

[0011] There remains a demand for improving the yield of objects or patterns formed thereby in photolithography processes using photosensitive resin compositions.

[0012] In addition, conventional photosensitive resin compositions have not been able to provide sufficient properties in terms of lamination, minimum development time, resolution, side edge (SE) amount, Cu deficiency, and development residue. Furthermore, since some of these properties are considered to be difficult to achieve in combination, it has been desired to achieve a balance between various properties.

[0013] In view of the above circumstances, the present invention aims to provide a photosensitive resin composition capable of improving the yield of an object or pattern formed by a photolithography method, and a photosensitive resin laminate and a resist or wiring pattern forming method using the same, and / or to provide a photosensitive resin laminate excellent in at least one of lamination properties, minimum development time, resolution, side edge (SE) amount, Cu deficiency, and development residue. [Means for solving the problem]

[0014] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by specifying the composition of the photosensitive resin composition or the strength of the photosensitive resin composition measured by a unique test, and / or by specifying the relationship between the acid value of the non-volatile components of the photosensitive resin composition and the thickness of the photosensitive resin layer.

[0015] One embodiment of the present invention is illustrated below. (1) a support film; formed on the support film, (A) an alkali-soluble resin; (B) a photopolymerizable compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) a dye; and a layer containing a photosensitive resin composition comprising: The weight average molecular weight of the component (A), which is measured by gel permeation chromatography (GPC) and calculated using a calibration curve of polystyrene, is 60,000 or less; and The photosensitive resin composition is a dry film resist, which is a photosensitive resin composition having a maximum point load of 70 gf or more when a piercing test is performed in which a photosensitive resin layer containing the photosensitive resin composition is laminated to a thickness of 25 μm on a support to produce a photosensitive resin laminate, the photosensitive resin laminate is laminated on a copper-clad laminate substrate having a thickness of 1.6 mm and a through-hole with a diameter of 6 mm and having a copper foil with a thickness of 35 μm laminated thereon, the photosensitive resin laminate is exposed to light and developed to form a cured film, the support is peeled off from the cured film, and a cylinder having a diameter of 2.0 mm is pierced at a speed of 100 mm / min into a portion of the photosensitive resin layer corresponding to the center of the through-hole from the surface from which the support has been peeled off. (2) The dry film resist according to item 1, wherein the number of double bonds in the photosensitive resin composition is 1.50 mmol / g or more based on the solid content of the photosensitive resin composition. (3) The dry film resist according to item 1, wherein the photosensitive resin composition contains a polyfunctional monomer having three or more functional groups as the component (B). (4) The dry film resist according to item 1, wherein the photosensitive resin composition contains, as the component (B), (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group, which is a polyfunctional monomer having three or more functional groups. (5) The dry film resist according to item 4, wherein the photosensitive resin composition further contains, as the component (B), (B-iii) a (meth)acrylate compound having a skeleton derived from a bisphenol, which is a bifunctional monomer. (6) The dry film resist according to any one of items 1 to 5, wherein the photosensitive resin composition further contains a plasticizer. (7) The dry film resist according to any one of items 1 to 6, wherein the dye comprises a leuco dye. (8) The dry film resist according to any one of items 1 to 7, wherein the maximum point load is less than 250 gf. (9) a support film; and formed on the support film, (A) an alkali-soluble resin; (B) a photopolymerizable compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; and a layer containing a photosensitive resin composition comprising: The photosensitive resin composition contains, as the component (B), (B-ii) a compound having a dipentaerythritol-derived skeleton but not containing an alkylene oxide group, which is a trifunctional or higher polyfunctional monomer; A dry film resist comprising: (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol, which is a bifunctional monomer. (10) The dry film resist according to item 9, wherein a ratio of the (B-ii) / the (B-iii) is 10 to 80 mass %. (11) The dry film resist according to item 9 or 10, wherein the proportion of the (B-ii) and the (B-iii) in the component (B) is 50 mass % or more. (12) The dry film resist according to any one of items 9 to 11, further comprising, as the component (B), (Bi) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and including an alkylene oxide group. (13) The dry film resist according to any one of items 9 to 12, wherein the component (A) has a weight average molecular weight of 60,000 or less, as measured by gel permeation chromatography (GPC) and calculated using a calibration curve of polystyrene. (14) The dry film resist according to any one of items 9 to 13, wherein the photosensitive resin composition is a photosensitive resin composition having a maximum point load of 70 gf or more when a piercing test is performed in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a support to a thickness of 25 μm to prepare a photosensitive resin laminate, the photosensitive resin laminate is laminated on a copper-clad laminate substrate having a thickness of 1.6 mm and a through-hole having a diameter of 6 mm and a copper foil having a thickness of 35 μm, the photosensitive resin laminate is exposed to light and developed to form a cured film, the support is peeled off from the cured film, and a cylinder having a diameter of 2.0 mm is pierced at a speed of 100 mm / min into a portion of the photosensitive resin layer corresponding to the center of the through-hole from the surface from which the support has been peeled off. (15) The dry film resist according to any one of items 9 to 14, wherein the number of double bonds in the photosensitive resin composition is 1.50 mmol / g or more based on the solid content of the photosensitive resin composition. (16) The dry film resist according to any one of items 9 to 15, wherein the photosensitive resin composition further contains a plasticizer. (17) The dry film resist according to any one of items 9 to 16, wherein the dye comprises a leuco dye. (18) The dry film resist according to any one of items 9 to 17, wherein the maximum point load is less than 250 gf. (19) A step of laminating the dry film resist according to any one of items 1 to 18 onto a substrate; exposing the laminated dry film resist to light; and developing the exposed dry film resist A method for forming a resist pattern comprising the steps of: (20) A step of laminating the dry film resist according to any one of items 1 to 18 onto a substrate; exposing the laminated dry film resist; developing the exposed dry film resist to form a resist pattern; and A step of performing an etching or plating process on the substrate on which the resist pattern is formed. A method for forming a wiring pattern comprising:

[0016] Further aspects of the invention are illustrated below. (21) A photosensitive resin laminate comprising: a support; and a photosensitive resin composition layer formed on the support using a photosensitive resin composition comprising: (A) an alkali-soluble resin having no ethylenically unsaturated group in its main chain; (B) a photopolymerizable compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; A photosensitive resin laminate, characterized in that, when the acid value of the non-volatile component of the photosensitive resin composition is A [mgKOH / g] and the thickness of the photosensitive resin composition layer is T [μm], the ratio (A / T) of the acid value A to the thickness T is 5 or more and 90 or less. (22) The photosensitive resin laminate according to item 21, wherein the photosensitive resin composition further contains, as component (D), a compound having polytetramethylene oxide as a structural unit. (23) The photosensitive resin laminate according to item 21 or 22, wherein the photosensitive resin composition further contains a compound having a benzotriazole skeleton as a component (E). (24) The photosensitive resin laminate according to any one of items 21 to 23, wherein the photosensitive resin composition contains, as the component (B), a photopolymerizable compound having 4 or more functional ethylenically unsaturated bonds. (25) The photosensitive resin laminate according to item 22, wherein a ratio of the component (A) to the total of the component (B) and the component (D) [component (A) / (component (B)+component (D))] is greater than 0 and not greater than 1.4. (26) The photosensitive resin laminate according to any one of items 21 to 25, wherein the component (A) has a weight average molecular weight of 20,000 or more. (27) The photosensitive resin laminate according to any one of items 21 to 26, wherein the acid value (acid equivalent) of a non-volatile component of the photosensitive resin composition is greater than 0 and is not greater than 79.0. Effect of the Invention

[0017] According to the present invention, defects in a pattern formed using a photosensitive resin composition are suppressed, and therefore the yield of an object or pattern formed by a photolithography method can be improved, and / or a photosensitive resin laminate having excellent at least one of lamination properties, minimum development time, resolution, side edge (SE), Cu defects, and development residues can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, a detailed description will be given of an embodiment of the present invention (hereinafter, abbreviated as "embodiment"). Note that the present invention is not limited to the following embodiment, and can be modified in various ways within the scope of the present invention.

[0019] Also, in this specification, "(meth)acrylic" means acrylic or methacrylic, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate.

[0020] [One aspect of the present invention] <Photosensitive resin composition> One aspect of the present invention provides a photosensitive resin composition. The photosensitive resin composition comprises the following components: (A) an alkali-soluble resin; (B) a photopolymerizable compound having an ethylenically unsaturated bond; (C) a photopolymerization initiator; The photosensitive resin composition may contain, if desired, a dye (D) in addition to the components (A) to (C), and may also contain a plasticizer, an antioxidant, a stabilizer, and the like.

[0021] <First embodiment> The photosensitive resin composition according to the first embodiment is characterized in that it contains a dye (D) in addition to the components (A) to (C), and has a maximum point load of 70 gf or more measured when a puncture test described below is carried out.

[0022] (Puncture test) A support, a photosensitive resin composition, and a copper-clad laminate board having a 35 μm-thick copper foil laminated thereon, a thickness of 1.6 mm, and a through-hole with a diameter (φ) of 6 mm are prepared. A photosensitive resin layer containing the photosensitive resin composition is laminated on the support to a thickness of 25 μm to produce a photosensitive resin laminate, and the photosensitive resin laminate is laminated on the copper-clad laminate board, exposed to light, and developed to form a cured film. The support is then peeled off from the cured film, and a cylinder with a diameter (φ) of 2.0 mm is pierced at a speed of 100 mm / min into the part of the photosensitive resin layer corresponding to the center of the through-hole from the surface from which the support has been peeled off.

[0023] In the first embodiment, when the maximum point load of the cured film measured when the piercing test is performed is 70 gf or more, the resolution, side etch amount and peelability of the resist pattern formed by the photolithography method using the photosensitive resin composition are good, and the loss of the pattern is suppressed, so that the yield of the object or pattern formed by the photolithography method tends to be improved. Note that a more specific method for measuring the maximum point load by the piercing test will be described in detail in the examples described later.

[0024] Although the present inventors do not wish to be bound by theory, they thought that there is a correlation between the piercing strength of the cured film of the photosensitive resin composition during the piercing test and the damage to the metal substrate. In the first embodiment, a maximum point load of 70 gf or more during the piercing test was found as an index for suppressing damage to an object or wiring pattern formed by a photolithography method using a photosensitive resin composition and improving the yield. From the viewpoint of further improving the yield, the maximum point load during the piercing test is preferably 74 gf or more or 78 gf or more, and more preferably 85 gf or more. In addition, it is clear that the higher the upper limit value of the maximum point load during the piercing test, the more preferable it is based on common sense in this technical field, and it can be, for example, less than 250 gf, or 245 gf or less.

[0025] The maximum point load during the puncture test can be adjusted to within the numerical range described above, for example, by optimizing the composition of the photosensitive resin composition, using multiple components as component (B) in the photosensitive resin composition, blending two or more types of components or three or more types of components, or optimizing the types and blending ratios.

[0026] From the viewpoints of improving the resolution, side etch amount, and peelability of the resist pattern and suppressing defects in the pattern, the photosensitive resin composition according to the first embodiment preferably contains a trifunctional or higher polyfunctional monomer and / or a bifunctional monomer as component (B). From the same viewpoint, the trifunctional or higher polyfunctional monomer is preferably (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group, and the bifunctional monomer is preferably (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol.

[0027] Second embodiment The photosensitive resin composition according to the second embodiment contains, as the component (B): (Bi) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an alkylene oxide group; (B-ii) A compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group. The present invention is characterized in that it contains:

[0028] When the photosensitive resin composition according to the second embodiment contains both the component (Bi) and the component (B-ii) as the component (B), the resolution, side etch amount, piercing strength and peelability of the resist pattern formed by the photolithography method using the photosensitive resin composition are good, and pattern damage is suppressed, so that the yield of the object or pattern formed by the photolithography method tends to improve.

[0029] <Third embodiment> The photosensitive resin composition according to the third embodiment is characterized in that the component (B) is: As a trifunctional or higher polyfunctional monomer, (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group; As a bifunctional monomer, (B-iii) a (meth)acrylate compound having a skeleton derived from a bisphenol; The present invention is characterized in that it contains:

[0030] When the photosensitive resin composition according to the third embodiment contains, as the component (B), both the component (B-ii) which is a polyfunctional monomer having three or more functionalities, and the component (B-iii) which is a bifunctional monomer, the resolution, side etch amount, piercing strength, and peelability of the resist pattern formed by the photolithography method using the photosensitive resin composition are good, and pattern damage is suppressed, so that the yield of the object or pattern formed by the photolithography method tends to improve.

[0031] From the viewpoints of improving the resolution, side etch amount, piercing strength, and peelability of the resist pattern and suppressing damage to the pattern, the photosensitive resin composition according to the third embodiment preferably has a ratio of component (B-ii) / component (B-iii) of 10 to 80 mass%, and / or the ratio of components (B-ii) and (B-iii) in component (B) is preferably 50 mass% or more. From the same viewpoint, it is preferable that component (B) according to the third embodiment further contains component (Bi) described above in addition to components (B-ii) and (B-iii).

[0032] The features described above for the first, second and third embodiments can be combined or interchanged. The photosensitive resin compositions according to the first, second and third embodiments can be used for carrying out photolithography, preparing photosensitive resin laminates, forming wiring patterns for touch panels, and the like, and are preferably used for etching substrates such as copper-clad laminates and copper sputtered thin films. Hereinafter, each component contained in the photosensitive resin compositions according to the first, second and third embodiments will be described in order.

[0033] <(A) Alkali-soluble resin> The (A) alkali-soluble resin is a polymer that can be dissolved in an alkaline solution. The (A) alkali-soluble resin preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and is further preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. The (A) alkali-soluble resin may be thermoplastic.

[0034] The acid equivalent of the (A) alkali-soluble resin is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the developability and peelability of the photosensitive resin layer. The acid equivalent of the (A) alkali-soluble resin is more preferably 200 to 500, and even more preferably 250 to 450. In one embodiment of the present invention, the acid equivalent means the mass (grams) of a polymer having one equivalent of a carboxyl group in a molecule, and can be measured, for example, by potentiometric titration using an automatic titrator and a 0.1 mol / L aqueous sodium hydroxide solution.

[0035] The alkali-soluble resin (A) is represented by the following formula (I):

number

[0036] Glass transition temperature Tg i When calculating the glass transition temperature of a homopolymer consisting of a comonomer that forms the corresponding alkali-soluble resin, the value shown in "Polymer handbook, Third edition, John Wiley & Sons, 1989, p.209 Chapter VI 'Glass transition temperatures of polymers'" edited by Brandrup, J. Immergut, EH shall be used.

[0037] Tg of representative comonomers i are as follows (all literature values): Methacrylic acid: Tg=501K Benzyl methacrylate: Tg=327K Methyl methacrylate: Tg=378K Styrene: Tg=373K 2-Ethylhexyl acrylate: Tg=223K The glass transition temperature (Tg total The alkali-soluble resin exhibiting the above formula (I) is preferably a copolymer of an acid monomer and another monomer.

[0038] The glass transition temperature (Tg total There is no particular limitation on the lower limit of the glass transition temperature (Tg total ) may be 10°C or higher, 30°C or higher, 50°C or higher, or 70°C or higher.

[0039] On the other hand, the weight average molecular weight (Mw) of the component (A) of the above-mentioned (A) alkali-soluble resin is preferably 60,000 or less, as calculated by measuring at least the (A) component by gel permeation chromatography (GPC) and using a calibration curve of polystyrene. The Mw of the (A) alkali-soluble resin is preferably 60,000 or less from the viewpoint of solubility in a developer, and is preferably 5,000 or more from the viewpoints of maintaining a uniform thickness of a photosensitive resin laminate such as a dry film resist, tackiness, edge fuse property, cut chip property, etc. From such a viewpoint, the Mw of the (A) alkali-soluble resin is more preferably 10,000 or more and 55,000 or less. Furthermore, the dispersity (Mw / Mn) of the (A) alkali-soluble resin, which is the ratio of the above Mw to the number average molecular weight (Mn) of the (A) alkali-soluble resin, is preferably 1.0 to 6.0.

[0040] The alkali-soluble resin (A) is preferably obtained by polymerizing at least one kind of the first monomer described later, and more preferably obtained by copolymerizing at least one kind of the first monomer and at least one kind of the second monomer described later.

[0041] The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is particularly preferred.

[0042] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Of these, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene and benzyl (meth)acrylate are preferred.

[0043] Furthermore, from the viewpoint of improving the resolution of the resist pattern, it is preferable that the alkali-soluble resin (A) has an aromatic group on the side chain of its structure.

[0044] The (A) alkali-soluble resin having an aromatic group in the side chain can be prepared by using a compound having an aromatic group as the first monomer and / or the second monomer. Examples of the monomer having an aromatic group include benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, benzyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is more preferred.

[0045] The alkali-soluble resin (A) can be prepared by subjecting the above-mentioned first monomer and / or second monomer to a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0046] The content of (A) alkali-soluble resin in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. Hereinafter, the same applies to each component unless otherwise specified) is preferably in the range of 10% by mass to 90% by mass, more preferably in the range of 20% by mass to 80% by mass, and further preferably in the range of 30% by mass to 60% by mass. The content of (A) alkali-soluble resin is preferably 10% by mass or more from the viewpoint of maintaining the alkaline developability of the photosensitive resin layer, while on the other hand, it is preferably 90% by mass or less from the viewpoint of the resist pattern formed by exposure fully exhibiting the performance as a resist material.

[0047] <(B) Photopolymerizable compound having an ethylenically unsaturated group> The photopolymerizable compound having an ethylenically unsaturated group (B) is a compound having polymerizability due to the presence of an ethylenically unsaturated group in its structure. In the first, second and third embodiments, the photosensitive resin composition preferably contains a (meth)acrylate compound, more preferably a poly(meth)acrylate compound, as the component (B), and is represented by the following formula (II): [ka] {where, R 10 represents a hydrogen atom, a (meth)acryloyl group, or an alkylene oxide-modified (meth)acryloyl group, and contains at least four (meth)acryloyl groups in one molecule.} It is more preferable that the (meth)acrylate compound contains a dipentaerythritol-derived skeleton represented by the following formula:

[0048] In the general formula (II), the number of (meth)acryloyl groups in one molecule is 4 or more, and preferably 5 or 6, from the viewpoint of obtaining sufficient cured film strength, resist shape and resolution.10 The alkylene oxide-modified (meth)acryloyl group as the alkylene oxide-modified (meth)acryloyl group is, for example, modified with at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and is preferably modified with ethylene oxide and / or propylene oxide. Specifically, -(C 2 H 4 O) m -CO-CR=CH 2 {wherein R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30.}, -(C 3 H 6 O) n -CO-CR=CH 2 {wherein R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 30.}, -(C 2 H 4 O) m -(C 3 H 6 O) n -CO-CR=CH 2 In the formula, R represents a hydrogen atom or a methyl group, m represents an integer of 1 to 30, and n represents an integer of 1 to 30; 2 H 4 O) m and (C 3 H 6 O) n The arrangement of may be alternating, random or block.}, etc.

[0049] In the photosensitive resin composition according to the first embodiment, from the viewpoint of adjusting the maximum load at a point of the puncture test to 70 gf or more, the component (B) is: (Bi) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an alkylene oxide group; (B-ii) A compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group. It is preferred that the compound contains

[0050] The photosensitive resin composition according to the second embodiment contains, as the component (B), the following from the viewpoints of the resolution, side etch amount, piercing strength, and peelability of the resist cured film, the suppression of pattern defects, and the improvement of the yield: (Bi) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an alkylene oxide group; (B-ii) A compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group. Contains:

[0051] When the photosensitive resin composition contains both the (Bi) component and the (B-ii) component, the mass ratio of the two components, (Bi):(B-ii), is preferably 8:9 to 9:7 from the viewpoints of suppressing pattern defects, suppressing defects in the metal substrate, and improving yield.

[0052] In the first and second embodiments, in addition to the component (Bi) and the component (B-ii), from the viewpoint of the side etch amount and piercing strength of the resist pattern, it is preferable that the photosensitive resin composition contains (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol and containing an alkylene oxide group (excluding the component (Bi)).

[0053] From the viewpoints of the resolution of the resist pattern, the amount of side etching, removability, and suppression of pattern defects, the photosensitive resin composition related to the first embodiment preferably contains, as the component (B), one or both of a component (B-ii) which is a trifunctional or higher polyfunctional monomer and a component (B-iii) which is a bifunctional monomer.

[0054] From the viewpoints of the resolution of the resist pattern, the side etch amount, the piercing strength, the peelability, and the suppression of pattern damage, it is preferable that the photosensitive resin composition according to the third embodiment further contains a component (Bi) in addition to the components (B-ii) and (B-iii).

[0055] In the photosensitive resin composition, the mass ratio of the component (B-iii) to the total mass of the component (Bi) and the component (B-ii) is preferably 0.9 to 1.8, and more preferably 0.95 to 1.76, from the viewpoint of the maximum point load in a piercing test or the piercing strength of a resist pattern.

[0056] (Bi) The (meth)acrylate compound having a dipentaerythritol-derived skeleton and containing an alkylene oxide group can be, for example, a compound having at least four alkylene oxide-modified (meth)acryloyl groups in one molecule of general formula (II). From the viewpoint of the maximum point load in a piercing test or the piercing strength of a cured resist film, it is preferable that the compound has five and / or six alkylene oxide-modified (meth)acryloyl groups in one molecule of general formula (II).

[0057] With regard to the component (Bi), from the viewpoint of the maximum point load in a piercing test or the piercing strength of a cured resist film, the group R 10 The alkylene oxide-modified (meth)acryloyl group as -(C) is preferably modified with at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and hexylene oxide, and more preferably modified with ethylene oxide and / or propylene oxide; 2 H 4 O) m -CO-CR=CH 2 {wherein R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30.}, -(C 3 H 6 O) n -CO-CR=CH 2 {wherein R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 30.}, or -(C 2 H 4 O) m -(C 3 H 6 O) n -CO-CR=CH 2In the formula, R represents a hydrogen atom or a methyl group, m represents an integer of 1 to 30, and n represents an integer of 1 to 30; 2 H 4 O) m and (C 3 H 6 O) n The arrangement of may be alternating, random or block. 2 H 4 O) m -CO-CR=CH 2 {wherein R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30.} From the same viewpoint, in general formula (II), the repeat number m of ethylene oxide and the repeat number n of propylene oxide are each preferably within the range of 3 to 27, more preferably 6 to 21, and further preferably 9 to 16.

[0058] Specific examples of the (Bi) component are: Dipentaerythritol tetra(meth)acrylate of polyethylene glycol having an average of 3 to 27 moles of ethylene oxide added thereto; Dipentaerythritol penta(meth)acrylate of polyethylene glycol having an average of 3 to 27 moles of ethylene oxide added thereto; Dipentaerythritol hexa(meth)acrylate of polyethylene glycol having an average of 3 to 27 moles of ethylene oxide added thereto; Dipentaerythritol tetra(meth)acrylate of polyethylene glycol with an average of 3 to 27 moles of propylene oxide added thereto; Dipentaerythritol penta(meth)acrylate of polyethylene glycol having an average of 3 to 27 moles of propylene oxide added thereto; Dipentaerythritol hexa(meth)acrylate of polyethylene glycol with an average of 3 to 27 moles of propylene oxide added thereto; Dipentaerythritol tetra-, penta- or hexa(meth)acrylate of polyethylene glycol to which an average of 3 to 27 moles of ethylene oxide and an average of 3 to 27 moles of propylene oxide are alternately, randomly or block-added, Combinations of the compounds listed above, Among these, dipentaerythritol hexamethacrylate of polyethylene glycol having an average of 12 to 15 moles of ethylene oxide added thereto is preferred from the viewpoints of the resolution, side etch amount, piercing strength, and peelability of the resist cured film, as well as the suppression of pattern defects and the improvement of the yield.

[0059] (B-ii) The compound having a dipentaerythritol-derived skeleton but not containing an alkylene oxide group may be an alkylene oxide unmodified dipentaerythritol mono- or poly(meth)acrylate, and from the viewpoint of obtaining sufficient cured film strength, resist shape, and resolution, it is preferably an alkylene oxide unmodified dipentaerythritol poly(meth)acrylate.

[0060] The component (B-ii) is, for example, a compound represented by the general formula (II) represented by R 10 In terms of the maximum point load in a piercing test or the piercing strength of a cured resist film, R 10 The acryloyl group preferably has 4 or more, and more preferably 5 or 6, (meth)acryloyl groups as the acryloyl group.

[0061] When a penta(meth)acrylate having five (meth)acryloyl groups and a hexa(meth)acrylate having six (meth)acryloyl groups are used in combination as the component (B-ii), the mass ratio of the penta(meth)acrylate is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass or 30% by mass to 40% by mass, from the viewpoint of the maximum point load in a piercing test or the piercing strength of the cured resist film.

[0062] Specific examples of the component (B-ii) are: Dipentaerythritol mono(meth)acrylate, Dipentaerythritol di(meth)acrylate, Dipentaerythritol tri(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, a combination of at least two of the dipentaerythritol mono- or poly(meth)acrylates listed above, Among these, from the viewpoints of the resolution, side etch amount, piercing strength, and peelability of the resist cured film, as well as the suppression of pattern defects and the improvement of the yield, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is preferred, and the pentaacrylate mass ratio in the mixture is preferably 10 mass % or 30 mass % to 40 mass %.

[0063] (B-iii) A (meth)acrylate compound having a bisphenol-derived skeleton does not overlap with the component (Bi), and therefore does not contain a dipentaerythritol skeleton and preferably has a bisphenol-derived skeleton and a (meth)acryloyl group, and more preferably has a bisphenol-derived skeleton, an alkylene oxide group, and a (meth)acryloyl group.

[0064] The component (B-iii) is, for example, a compound represented by the following general formula (III): [ka] {where, X 1 ~X 8 are each independently a hydrogen atom or a halogen atom, and preferably X 1 ~X 8 are all hydrogen atoms, and R 6 and R 7 each independently represents a hydrogen atom or a methyl group; R 8 and R9 each independently represents an alkylene group having 2 to 6 carbon atoms; 5 and n 6 are each independently 0 or a positive integer, and n 5 +n 6 is between 0 and 20. The compound may be represented by the formula:

[0065] In the general formula (III), R 8 and R 9 The alkylene group having 2 to 6 carbon atoms as represented by is preferably an ethylene group, a propylene group, or a butylene group, and -(R 8 -O)- and -(R 9 Each --O)-- can be ethylene oxide, propylene oxide, butylene oxide, or a combination thereof.

[0066] In the general formula (III), preferred -(R 8 -O)- and -(R 9 -O)- is -(C 2 H 4 O)-, -(C 3 H 6 O)- or -(C 2 H 4 O) α -(C 3 H 6 O) β -{where α+β=n 5 or n 6 (C 2 H 4 O) α and (C 3 H 6 O) β The arrangement of may be alternating, random or block, and (C 2 H 4 O) α and (C 3 H 6 O) βAny of the groups may be on the quaternary carbon side. The component (B-iii) containing these divalent groups is preferred from the viewpoints of the resolution, side etch amount, penetration strength, and peelability of the cured resist film, as well as the suppression of pattern defects and the improvement of the yield. From the same viewpoint, in the general formula (III), n 5 and n 6 are each independently preferably a positive integer, more preferably an integer selected from 1 to 14, and n 5 +n 6 is preferably 2 to 20.

[0067] Specific examples of the (B-iii) component include a compound obtained by modifying bisphenol A with an alkylene oxide and introducing (meth)acryloyl groups at both ends, and a compound having (meth)acryloyl groups at both ends of bisphenol A. Examples of alkylene oxide modifications include ethylene oxide modifications, propylene oxide modifications, butylene oxide modifications, pentylene oxide modifications, and hexylene oxide modifications.

[0068] Specific examples of ethylene oxide modified bisphenol A having (meth)acryloyl groups at both ends are: Di(meth)acrylate of polyethylene glycol in which an average of 1 mole of ethylene oxide is added to each end of bisphenol A, Di(meth)acrylate of polyethylene glycol in which an average of 2 moles of ethylene oxide are added to each end of bisphenol A, Di(meth)acrylate of polyethylene glycol in which an average of 3 moles of ethylene oxide are added to each end of bisphenol A, Di(meth)acrylate of polyethylene glycol in which an average of 5 moles of ethylene oxide are added to each end of bisphenol A, These may be used alone or in combination of two or more. Among the (B-iii) components described above, from the viewpoints of resolution, side etch amount, piercing strength, and suppressed damage to the metal substrate, dimethacrylate of polyethylene glycol having an average of 5 moles of ethylene oxide added to each end of bisphenol A, dimethacrylate of polyethylene glycol having an average of 1 mole of ethylene oxide added to each end of bisphenol A, and bisphenol A dimethacrylate are preferred.

[0069] The photosensitive resin composition may contain, as an additional component (B), a photopolymerizable compound having an ethylenically unsaturated group other than the components (Bi) to (B-iii).

[0070] Specific examples of the additional (B) component include (meth)acrylate compounds other than the (Bi) to (B-iii) components, such as compounds obtained by converting alcohols obtained by adding polyalkylene oxide groups to glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, isocyanurate rings, etc., or modifying them with ε-caprolactone, into (meth)acrylates, or compounds obtained by reacting them directly with (meth)acrylic acid without modifying them with alkylene oxide groups or ε-caprolactone, etc. More specifically, triacrylate obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane, trimethacrylate obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane, ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, etc. can be used.

[0071] The content of the photopolymerizable compound having an ethylenically unsaturated group (B) in the photosensitive resin composition is preferably within the range of 5% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 30% by mass to 50% by mass. The content of the compound having an ethylenically unsaturated group (B) is preferably 5% by mass or more from the viewpoint of suppressing poor curing of the photosensitive resin layer and delay in development time, while it is preferably 70% by mass or less from the viewpoint of suppressing delay in peeling of the cured resist.

[0072] The total content of the (Bi) component and the (B-ii) component in the photosensitive resin composition is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 20% by mass. When the total content of the (Bi) component and the (B-ii) component is within the above numerical range, it tends to be easy to adjust the maximum point load in the piercing test, to suppress damage to the pattern or metal substrate, and to improve the yield.

[0073] When the photosensitive resin composition contains the (B-ii) component and the (B-iii) component, the ratio of the (B-ii) component / the (B-iii) component is preferably 10 to 80 mass%, more preferably 12 to 78 mass%. In addition, the ratio of the (B-ii) component and the (B-iii) component in the (B) component contained in the photosensitive resin composition is preferably 50 mass% or more, more preferably 55 mass% or more, and the upper limit of this ratio is not limited and may be, for example, 100 mass% or less or less than 100 mass%.

[0074] <(C) Photopolymerization initiator> The (C) photopolymerization initiator is a compound that generates radicals by actinic rays and can polymerize the (B) photopolymerizable compound having an ethylenically unsaturated group, etc. The photosensitive resin composition may contain (C) a photopolymerization initiator that is generally known in the art.

[0075] Examples of the (C) photopolymerization initiator include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.

[0076] Examples of the hexaarylbiimidazole compound include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, and 2,4,5-tris-(o-chlorophenyl)-diphenyl Biimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3 ,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,Examples of the imidazole include 2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoints of high sensitivity, resolution and adhesion.

[0077] Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. N-phenylglycine is particularly preferred because of its high sensitizing effect.

[0078] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0079] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, etc. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoints of use as a sensitizer and adhesion, 4,4'-bis(diethylamino)benzophenone is preferred.

[0080] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of commercially available acylphosphine oxide compounds include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

[0081] Examples of the benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0082] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

[0083] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, etc.

[0084] From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives are preferably 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.

[0085] Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0086] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds, with tribromomethylphenylsulfone being particularly preferred.

[0087] The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass. By adjusting the content of the (C) photopolymerization initiator within the above range, it is possible to obtain a photosensitive resin composition that has sufficient sensitivity, allows light to be sufficiently transmitted to the bottom of the resist, and has high resolution and is well balanced with the amount of side etching in the conductor pattern.

[0088] It is preferable to use a hexaarylbisimidazole compound as the (C) photopolymerization initiator. In this case, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass.

[0089] As the (C) photopolymerization initiator, it is preferable to use an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone in combination with a hexaarylbisimidazole compound. In this case, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.5 mass% or less, more preferably 0.01 mass% to 0.4 mass%, and the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1 mass% to 10 mass%, more preferably 0.5 mass% to 5 mass%.

[0090] <(D) Dye> The photosensitive resin composition preferably contains a dye as the component (D) in order to impart suitable color developability and excellent sensitivity characteristics to the cured resist film.

[0091] Examples of dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green], fuchsine, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, diamond green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), etc. Among these, leuco dyes such as diamond green and leuco crystal violet are preferred from the viewpoint of improving coloring properties, hue stability, and exposure contrast. These can be used alone or in combination of two or more.

[0092] The content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass, and further preferably in the range of 0.04% by mass to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good coloring properties, and on the other hand, is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. When the proportion of the dye used is set within this range, By setting the above, good color development and sensitivity can be achieved.

[0093] <Other ingredients> The photosensitive resin composition preferably contains additives such as a plasticizer, an antioxidant, and a stabilizer, if desired.

[0094] Examples of the plasticizer 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; sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate; phthalate esters such as diethyl phthalate; o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate, propylene glycol with propylene oxide added to both sides of bisphenol A, ethylene glycol with ethylene oxide added to both sides of bisphenol A, polyoxyethylene glyceryl ether, and polyoxypropylene glyceryl ether.

[0095] Among these, from the viewpoint of suppressing delay in stripping time, p-toluenesulfonic acid amide, polypropylene glycol having an average of 3 units of propylene oxide added to each end of bisphenol A, and polyoxypropylene glyceryl ether are preferred, and from the viewpoint of piercing strength of the resist pattern, solubility of the stripped piece, and plating resistance, polyoxypropylene glyceryl ether is more preferred, and polyoxypropylene glyceryl ether having a weight average molecular weight of 3,000 is even more preferred.

[0096] The content of the plasticizer in the photosensitive resin composition is preferably in the range of 0.1% by mass to 3% by mass, more preferably 0.15% by mass to 2% by mass. A content of 0.1% by mass or more is preferable from the viewpoints of suppressing delay in development time, imparting flexibility to the cured film, and facilitating adjustment of the maximum point load in the piercing test. On the other hand, a content of 3% by mass or less is preferable from the viewpoints of suppressing insufficient curing and edge fuse.

[0097] Examples of the antioxidant include triphenyl phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 2112), tris(mononylphenyl)phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 1178), bis(mononylphenyl)-dinonylphenyl phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 329K), etc. These may be used alone or in combination of two or more.

[0098] The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.8% by mass, more preferably in the range of 0.01% by mass to 0.3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of favorably expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, while it is preferably 0.8% by mass or less from the viewpoint of favorably expressing the hue stability while suppressing the color development of the resist pattern and improving adhesion.

[0099] The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group. These may be used alone or in combination of two or more.

[0100] Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenylnitrosamine, etc. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred. In addition, these can be used alone or in combination of two or more.

[0101] 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, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole. Among these, a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole is preferred. These can be used alone or in combination of two or more.

[0102] 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, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, etc. These may be used alone or in combination of two or more.

[0103] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

[0104] The total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.05 to 1% by mass. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0105] The number of double bonds in the photosensitive resin composition according to the first, second and third embodiments is preferably 1.50 mmol / g or more based on the solid content of the photosensitive resin composition. By setting the number of double bonds in such a range, the piercing strength or resolution of the coating film becomes good. On the other hand, if the number of double bonds in the photosensitive resin composition is excessively high, the storage stability of the composition may be impaired. In order to avoid this, the number of double bonds in the photosensitive resin composition is more preferably 4.00 mmol / g or less. The number of double bonds (the number of ethylenically unsaturated bonds) in the photosensitive resin composition can be adjusted by the blending ratio of the (B) component, the molecular weight of the (B) component, the number of functional groups of the (B) component, etc. in the photosensitive resin composition. That is, an embodiment in which the number of double bonds in the photosensitive resin composition is within the above range can be said to be a preferred embodiment in which the blending ratio of the (B) component, the molecular weight of the (B) component, the number of functional groups of the (B) component, etc. are suitably adjusted among the embodiments in which the maximum point load in the piercing test is within the above range. In such a preferred embodiment, the effects of the present invention are easily achieved.

[0106] [Another aspect of the present invention] Another aspect of the present invention provides a photosensitive resin laminate comprising a support and a photosensitive resin composition layer formed on the support using a photosensitive resin composition containing (A) an alkali-soluble resin not containing an ethylenically unsaturated group in its main chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. A photosensitive resin laminate according to another embodiment of the present invention is characterized in that, when the acid value of the non-volatile component of the photosensitive resin composition is A [mgKOH / g] and the thickness of the photosensitive resin composition layer is T [μm], the ratio of the acid value A to the thickness T (A / T) is 5 or more and 90 or less.

[0107] When the ratio (A / T) of the acid value A to the thickness T is less than 5 (e.g., 5.0), the minimum development time and resolution are insufficient. On the other hand, when the ratio (A / T) is greater than 90, the side etch (SE) and Cu deficiency are insufficient. When the ratio (A / T) is 5 or more and 90 or less, the photosensitive resin laminate is excellent in lamination properties, minimum development time, resolution, side edge (SE), Cu deficiency, and development residue. The ratio (A / T) is preferably 12 (e.g., 12.0) or more and less than 70, and more preferably 12 (e.g., 12.0) or more and less than 50.

[0108] In another embodiment of the present invention, the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition means the mass (grams) of a polymer having one equivalent of a carboxyl group in a molecule, and is a value calculated from a value measured using NMR. Specifically, it is a measured value measured according to the measurement method in the examples described later. Hereinafter, each component constituting the photosensitive resin composition layer will be described.

[0109] <(A) Alkali-soluble resin containing no ethylenically unsaturated group in the main chain> (A) Alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is a polymer that can be dissolved in an alkaline solution. Also, (A) Alkali-soluble resin not containing an ethylenically unsaturated group in the main chain preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and is even more preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. Furthermore, (A) Alkali-soluble resin not containing an ethylenically unsaturated group in the main chain can be thermoplastic.

[0110] The acid equivalent of the non-volatile components of the photosensitive resin composition containing (A) an alkali-soluble resin that does not contain an ethylenically unsaturated group in its main chain is preferably greater than 0. From the viewpoints of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and further from the viewpoints of the developability and peelability of the photosensitive resin layer, the acid equivalent of the non-volatile components of the photosensitive resin composition is preferably 79.0 or less.

[0111] In addition, the acid value (acid equivalent) of the non-volatile components of the photosensitive resin composition containing (A) an alkali-soluble resin that does not contain an ethylenically unsaturated group in its main chain is more preferably greater than 0 and not greater than 78.0, and even more preferably greater than 0 and not greater than 76.0.

[0112] The acid value in the above range corresponds to a so-called "low acid value" as compared with the prior art. In another embodiment of the present invention, in response to the recent demand for a thinner photosensitive resin layer, the "thinner photosensitive resin layer" and the "low acid value" are realized. In the past, it was known that one method to achieve high resolution (low SE) was to improve the hydrophobicity of the resist. However, improving the hydrophobicity of the resist reduces its solubility in the developer, which tends to lengthen the development time. In this regard, if the molecular weight of the resin is reduced in order to shorten the development time, Cu deficiency (film strength) can easily decrease. In contrast to these, in another embodiment of the present invention in which "a thinner photosensitive resin layer" and "a lower acid value" are achieved, it becomes easier to achieve a balance between the various effects.

[0113] (A) The alkali-soluble resin having no ethylenically unsaturated group in the main chain is represented by the following formula (I):

number

[0114] Glass transition temperature Tg i When calculating the glass transition temperature of a homopolymer consisting of a comonomer that forms the corresponding alkali-soluble resin, the value shown in "Polymer handbook, Third edition, John Wiley & Sons, 1989, p.209 Chapter VI 'Glass transition temperatures of polymers'" edited by Brandrup, J. Immergut, EH shall be used.

[0115] Tg of representative comonomers i are as follows (all literature values): Methacrylic acid: Tg=501K Benzyl methacrylate: Tg=327K Methyl methacrylate: Tg=378K Styrene: Tg=373K 2-Ethylhexyl acrylate: Tg=223K The glass transition temperature (Tg total The alkali-soluble resin exhibiting the above formula (I) is preferably a copolymer of an acid monomer and another monomer.

[0116] The glass transition temperature (Tg total There is no particular limitation on the lower limit of the glass transition temperature (Tg total ) may be 10°C or higher, 30°C or higher, 50°C or higher, or 70°C or higher.

[0117] The weight average molecular weight of the (A) alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably 5,000 to 500,000. The weight average molecular weight of the (A) alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably 5,000 or more from the viewpoint of maintaining the uniform thickness of the photosensitive resin laminate such as a dry film resist and obtaining resistance to a developer, while it is preferably 500,000 or less from the viewpoint of maintaining the developability of the photosensitive resin laminate such as a dry film resist. The weight average molecular weight (Mw) of the (A) alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is more preferably 10,000 to 200,000, and further preferably 20,000 to 100,000 or 23,000 to 50,000. Furthermore, the dispersity (Mw / Mn) of (A) the alkali-soluble resin not containing an ethylenically unsaturated group in its main chain, which is the ratio of the above Mw to the number average molecular weight (Mn) of (A) the alkali-soluble resin not containing an ethylenically unsaturated group in its main chain, is preferably 1.0 to 6.0.

[0118] (A) The alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably obtained by polymerizing at least one kind of the first monomer described later, and more preferably, (A) the alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is obtained by copolymerizing at least one kind of the first monomer with at least one kind of the second monomer described later.

[0119] The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, β-carboxyethyl (meth)acrylate, and maleic acid half ester. Among these, (meth)acrylic acid is particularly preferred.

[0120] Examples of the second monomer include unsaturated aromatic compounds (sometimes referred to as "aromatic monomers"), (meth)acrylic acid alkyl esters, (meth)acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, crosslinkable monomers, etc. Among these, from the viewpoint of improving the resolution of the resist pattern, unsaturated aromatic compounds are preferred.

[0121] Examples of the unsaturated aromatic compound include benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), etc. Among these, benzyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is more preferred.

[0122] The (meth)acrylic acid alkyl ester is a concept that encompasses both chain alkyl esters and cyclic alkyl esters, and specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.

[0123] Examples of (meth)acrylic acid aralkyl esters include benzyl (meth)acrylate, and examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Examples of polar monomers include hydroxy group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and penteneol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol (meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate; and epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate.

[0124] Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

[0125] (A) The alkali-soluble resin not containing an ethylenically unsaturated group in the main chain can be prepared by subjecting the above-mentioned first monomer and / or second monomer to a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0126] The content of (A) an alkali-soluble resin not containing an ethylenically unsaturated group in the main chain in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. Hereinafter, the same applies to each component unless otherwise specified) is preferably in the range of 10% by mass to 90% by mass, more preferably in the range of 20% by mass to 80% by mass, and further preferably in the range of 30% by mass to 60% by mass. The content of (A) an alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably 10% by mass or more from the viewpoint of maintaining the alkaline developability of the photosensitive resin layer, while on the other hand, it is preferably 90% by mass or less from the viewpoint of the resist pattern formed by exposure fully exhibiting the performance as a resist material.

[0127] <(B) Photopolymerizable compound having an ethylenically unsaturated bond> (B) The photopolymerizable compound having an ethylenically unsaturated bond is a compound that has polymerizability due to having an ethylenically unsaturated bond, specifically an ethylenically unsaturated group, in its structure. The photosensitive resin composition may have one or more ethylenic double bonds as component (B), and it is preferable to use a compound having two or more ethylenic double bonds.

[0128] Specifically, examples of the component (B) include di(meth)acrylates of polyalkylene glycols in which an average of 2 to 15 moles of alkylene oxide are added to both ends of bisphenol A, tri(meth)acrylates of polyalkylene triols in which an average of 3 to 25 moles of alkylene oxide are added to trimethylolpropane, polyalkylene oxide groups are added to glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and isocyanurate rings, and ε- Examples of such compounds include compounds obtained by converting the alcohol obtained by modifying the alcohol with caprolactone into a (meth)acrylate, compounds obtained by directly reacting the alcohol with (meth)acrylic acid without modifying the alcohol with an alkylene oxide group or ε-caprolactone, tetra(meth)acrylates of polyols in which an average of 4 to 35 moles of alkylene oxide are added to pentaerythritol, and hexa(meth)acrylates of polyols in which an average of 4 to 30 moles of alkylene oxide are added to dipentaerythritol. These compounds can be used alone or in combination of two or more.

[0129] The content of the photopolymerizable compound having an ethylenically unsaturated group (B) in the photosensitive resin composition is preferably within the range of 5% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 30% by mass to 50% by mass. The content of the compound having an ethylenically unsaturated group (B) is preferably 5% by mass or more from the viewpoint of suppressing poor curing of the photosensitive resin layer and delay in development time, while it is preferably 70% by mass or less from the viewpoint of suppressing delay in peeling of the cured resist.

[0130] <(C) Photopolymerization initiator> The (C) photopolymerization initiator is a compound that generates radicals by actinic rays and can polymerize the (B) photopolymerizable compound having an ethylenically unsaturated group, etc. The photosensitive resin composition may contain (C) a photopolymerization initiator that is generally known in the art.

[0131] Examples of the (C) photopolymerization initiator include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.

[0132] Examples of the hexaarylbiimidazole compound include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, and 2,4,5-tris-(o-chlorophenyl)-diphenyl Biimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3 ,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,Examples of the imidazole include 2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoints of high sensitivity, resolution and adhesion.

[0133] Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. N-phenylglycine is particularly preferred because of its high sensitizing effect.

[0134] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0135] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, etc. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoints of use as a sensitizer and adhesion, 4,4'-bis(diethylamino)benzophenone is preferred.

[0136] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of commercially available acylphosphine oxide compounds include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

[0137] Examples of the benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0138] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

[0139] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, etc.

[0140] From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives are preferably 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.

[0141] Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0142] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds, with tribromomethylphenylsulfone being particularly preferred.

[0143] The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass. By adjusting the content of the (C) photopolymerization initiator within the above range, it is possible to obtain a photosensitive resin composition that has sufficient sensitivity, allows light to be sufficiently transmitted to the bottom of the resist, and has high resolution and is well balanced with the amount of side etching in the conductor pattern.

[0144] It is preferable to use a hexaarylbisimidazole compound as the (C) photopolymerization initiator. In this case, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass.

[0145] As the (C) photopolymerization initiator, it is preferable to use an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone in combination with a hexaarylbisimidazole compound. In this case, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.5 mass% or less, more preferably 0.01 mass% to 0.4 mass%, and the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1 mass% to 10 mass%, more preferably 0.5 mass% to 5 mass%.

[0146] <(D) Compound Having Polytetramethylene Oxide as a Structural Unit> Since the compound having polytetramethylene oxide as a structural unit has high flexibility, it can impart moderate flexibility to the resist pattern to be formed. This makes it difficult for the resist film to be damaged by the process load, and therefore Cu damage can also be reduced. Furthermore, since the compound having polytetramethylene oxide as a structural unit has high hydrophobicity, it is possible to improve the resolution and reduce side etching by using it in a photosensitive resin laminate. For the above reasons, it is preferable to use a compound having polytetramethylene oxide as a structural unit.

[0147] Examples of compounds having polytetramethylene oxide as a structural unit include polytetramethylene glycol, polytetramethylene glycol dimethacrylate, polytetramethylene glycol diacrylate, 2,2-bis(4-((meth)acryloxypolytetramethyleneoxy)phenyl)propane, polytetramethylene glycol trimethylolpropane tri(meth)acrylate, and urethane reaction products of hydroxyethyl(meth)acrylate, polytetramethylene glycol, and a diisocyanate compound or a triisocyanate compound. Among these, polytetramethylene glycol dimethacrylate compounds are preferred. These may be used alone or in combination of two or more.

[0148] The total content of the compounds (D) having polytetramethylene oxide as a structural unit in the photosensitive resin composition is preferably in the range of 0.5% to 50% by mass, and more preferably in the range of 1 to 40% by mass, from the viewpoint of alkali developability.

[0149] <(E) Compounds Having a Benzotriazole Skeleton> The compound having a benzotriazole skeleton is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the compound having a benzotriazole skeleton include benzotriazoles and carboxybenzotriazoles.

[0150] 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, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole. Among these, a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole is preferred. These can be used alone or in combination of two or more.

[0151] 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, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, etc. These may be used alone or in combination of two or more.

[0152] The total content of the (E) compounds having a benzotriazole skeleton in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.05 to 1% by mass. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity and resolution of the photosensitive resin layer.

[0153] In the photosensitive resin composition, the ratio of component (A) to the total of components (B) and (D) [component (A) / (component (B)+component (D)] is preferably 1.4 or less. This improves the solubility in an alkaline aqueous solution and the mechanical strength of the resist film, and can improve the minimum development time and Cu deficiency. From the viewpoint of edge fusion resistance, the lower limit of the ratio is preferably 0.5 or more.

[0154] <Other ingredients> The photosensitive resin composition preferably contains additives, such as a coloring material such as a dye, an antioxidant, and a stabilizer, if desired.

[0155] Examples of dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green], fuchsine, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, diamond green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), etc. Among these, diamond green and leuco crystal violet are preferred from the viewpoint of improving coloring properties, hue stability, and exposure contrast. These can be used alone or in combination of two or more.

[0156] The content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass, and further preferably in the range of 0.04% by mass to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, while being preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0157] Examples of the antioxidant include triphenyl phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 2112), tris(mononylphenyl)phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 1178), bis(mononylphenyl)-dinonylphenyl phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 329K), etc. These may be used alone or in combination of two or more.

[0158] The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.8% by mass, more preferably in the range of 0.01% by mass to 0.3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of favorably expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, while it is preferably 0.8% by mass or less from the viewpoint of favorably expressing the hue stability while suppressing the color development of the resist pattern and improving adhesion.

[0159] The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors and alkylene oxide compounds having a glycidyl group. These may be used alone or in combination of two or more.

[0160] Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenylnitrosamine, etc. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred. In addition, these can be used alone or in combination of two or more.

[0161] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

[0162] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.05% by mass to 1% by mass. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0163] [Photosensitive resin composition mixture] A photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition of the present disclosure. Suitable solvents include, for example, ketones such as acetone and methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add the solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 mPa·sec to 4000 mPa·sec at 25°C.

[0164] [Photosensitive resin laminates, dry film resists and transfer films] A photosensitive resin laminate can be provided using the photosensitive resin composition or photosensitive resin composition preparation liquid of the present disclosure. The photosensitive resin laminate has a support film (support) and a layer containing the above-mentioned photosensitive resin composition formed on the support film. The photosensitive resin laminate may have a protective layer on the surface opposite to the support film side, if necessary. From the viewpoint of significantly exhibiting the effects of the present invention, the photosensitive resin laminate is preferably a dry film resist or a transfer film, and more preferably a dry film resist.

[0165] Among these, particularly preferred dry film resists from the viewpoints of suppressing pattern defects, improving the yield of formed objects or patterns formed by photolithography, and / or being excellent in at least one of lamination properties, minimum development time, resolution, side edge, Cu defects, and development residues are: A support film; formed on the support film, (A) an alkali-soluble resin, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) Dye, A photosensitive layer containing a composition comprising: and the component (B) has: (B-ii) a compound having a dipentaerythritol skeleton but no alkylene oxide group; (B-iii) a compound having a skeleton derived from bisphenol; In the (B) component, the (B-ii) and (B-iii) components are 50 mass% or more, and the ratio of the (B-ii) component / the (B-iii) component is 10 to 80 mass%. A particularly preferred dry film resist configuration can be combined with or compatible with a photosensitive resin laminate configuration in which the ratio (A / T) of the acid value A of the non-volatile component of the photosensitive resin composition to the thickness T of the photosensitive resin layer is within the numerical range of the present disclosure.

[0166] The supporting film is preferably transparent and transmits the light emitted from the exposure light source. Examples of such supporting 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 may be stretched as necessary.

[0167] The haze of the support film is preferably not more than 5. A thinner support film is more advantageous in terms of image formation and cost efficiency, but taking into consideration the function of maintaining strength, the thickness is preferably 10 μm to 30 μm.

[0168] The layer of the photosensitive resin composition described above (hereinafter also referred to as "photosensitive resin layer") may contain a photosensitive resin composition or may consist of a photosensitive resin composition. The film thickness of the layer of the photosensitive resin composition in the photosensitive resin laminate is preferably 0.5 μm to 25 μm, more preferably 1 μm to 25 μm, and even more preferably 1 μm to 20 μm, from the viewpoints of the resolution of the resist pattern, the side etch amount, the piercing strength, or the peelability. From the same viewpoint, the upper limit of the film thickness is particularly preferably 16 μm or less, and most preferably 10 μm or less.

[0169] An important characteristic of the protective layer used in the photosensitive resin laminate is that it has a suitable adhesive force. In other words, it is preferable that the adhesive force of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesive force of the support film to the photosensitive resin layer, and the protective layer can be easily peeled off from the photosensitive resin laminate. For example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, etc. can be used as the protective layer. In addition, a release layer that can be suitably used to peel off the protective film from the photoresist layer may be provided on one side of the protective layer film. The release layer is generally classified into silicone compounds and non-silicone compounds. Silicone compounds include condensation reaction type silicone resins obtained by reacting polydimethylsiloxane with silanol at both ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane, addition reaction type silicone resins obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane, ultraviolet curing type or electron beam curing type silicone resins obtained by curing acrylic silicone or epoxy group-containing silicone with ultraviolet or electron beam, and modified silicone resins such as epoxy modified silicone resins (silicone epoxy), polyester modified silicone resins (silicone polyester), acrylic modified silicone resins (silicone acrylic), phenol modified silicone resins (silicone phenol), alkyd modified silicone resins (silicone alkyd), melamine modified silicone resins (silicone melamine), etc. Non-silicone compounds include alkyd (or also called alkyd) resins, long chain alkyl resins, acrylic resins, polyolefin resins, etc. The thickness of the release layer is preferably in the range of 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. If the thickness exceeds 2 μm, the coating appearance may deteriorate or the coating may not be sufficiently cured, and if the thickness is less than 0.001 μm, sufficient release properties may not be obtained. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

[0170] [Method for producing photosensitive resin laminate] The photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film. A known method can be used as the method. For example, the photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent that dissolves them to form a uniform solution-like photosensitive resin composition preparation liquid (coating liquid). Next, the coating liquid is applied onto a support film (support) using a bar coater or roll coater, and then dried, so that the photosensitive resin layer can be laminated on the support film. If necessary, a protective layer can be laminated on the photosensitive resin layer to produce a photosensitive resin laminate.

[0171] [Method of forming resist pattern] Yet another aspect of the present invention is a method for producing a method for manufacturing a process comprising the steps of: A step of laminating the photosensitive resin laminate of the present disclosure onto a substrate (lamination step); A step of exposing the laminated photosensitive resin laminate to light (exposure step), and A step of developing the exposed photosensitive resin laminate (developing step) The present invention provides a method for forming a resist pattern, comprising the steps of:

[0172] [Wiring pattern formation method] Yet another aspect of the present invention is a method for producing a method for manufacturing a process comprising the steps of: A step of performing an etching or plating process on the substrate on which the resist pattern has been formed by the above-mentioned resist pattern forming method (etching or plating step). The present invention provides a method for forming a wiring pattern, comprising the steps of:

[0173] An example of a method for forming a resist and a wiring pattern using a photosensitive resin laminate and a substrate will be described below.

[0174] (Lamination process) In the lamination step, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off from the laminate, and then, for example, the photosensitive resin layer is laminated by heating and pressing onto the surface of the substrate using a laminator.

[0175] Examples of the material of the substrate used include copper (Cu), stainless steel (SUS), glass, indium tin oxide (ITO), flexible substrates laminated with a conductive thin film, etc. Examples of the conductive thin film include ITO, copper, copper-nickel alloy, silver, etc. Examples of the material constituting the flexible substrate include polyethylene terephthalate (PET), etc.

[0176] The substrate used may be in the form of a copper-clad laminate having copper wiring formed thereon, a substrate made of glass alone, or a transparent resin substrate having a transparent electrode (e.g., ITO, Ag nanowire substrate, etc.) or a metal electrode (e.g., Cu, Al, Ag, Ni, Mo, and alloys of at least two of these, etc.) formed thereon. The substrate used may have a through-hole to accommodate a multilayer substrate.

[0177] From the viewpoint of achieving a remarkable effect of the present invention, the substrate used is preferably a copper-clad laminate, and more preferably a copper-clad laminate having a thickness of 1.6 mm and a through-hole with a diameter of 6 mm, laminated with a copper foil having a thickness of 35 μm.

[0178] The photosensitive resin layer may be laminated on only one surface of the substrate, or may be laminated on both surfaces of the substrate as necessary. The heating temperature during lamination is preferably 40°C to 160°C, more preferably 80°C to 120°C. The heat-pressure bonding may be performed two or more times to improve the adhesion of the resulting resist pattern to the substrate. When performing the pressure bonding two or more times, a two-stage laminator equipped with two consecutive rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rolls to be pressure bonded.

[0179] (Exposure process) In the exposure step, the photosensitive resin layer is exposed using an exposure machine. From the viewpoint of the piercing strength of the resulting resist film, this exposure is preferably performed after peeling off the support from the photosensitive resin laminate. By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after going through the development step described below. The pattern exposure may be performed by either a method of exposure through a photomask or a method of maskless exposure.

[0180] When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using an actinometer. In maskless exposure, a photomask is not used, and exposure is performed directly on the substrate using a drawing device. As the light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, etc. are used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount can be determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0181] From the viewpoints of improving the resolution of the resist pattern, reducing the amount of side etching, and improving the yield of the resist or wiring pattern, it is preferable to carry out the exposure through a photomask.

[0182] (Development process) In the development step, the non-patterned portion of the photosensitive resin layer is removed with a developer consisting of an alkaline aqueous solution, and in the development step, the unexposed portion is dissolved and removed when a negative-type photosensitive resin composition is used, and in the development step, the exposed portion is dissolved and removed when a positive-type photosensitive resin composition is used, to obtain a resist pattern.

[0183] The alkaline aqueous solution may be, for example, Na 2 CO 3 , K 2 CO 3 The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, but it is preferable to use an aqueous solution of Na 2 CO3 It is preferable to use an aqueous solution. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, etc. may be mixed into the alkaline aqueous solution. The temperature of the developer in the development step is preferably kept constant within the range of 18°C ​​to 40°C.

[0184] If desired, after the development step, a heating step may be performed in which the obtained resist pattern is heated at 100° C. to 300° C. By carrying out this heating step, the chemical resistance of the resist pattern may be improved. For heating, a suitable type of heating furnace such as hot air, infrared, or far infrared can be used.

[0185] (etching or plating process) After forming a resist pattern by the above-mentioned method for forming a resist pattern, the substrate on which the resist pattern is formed is subjected to etching or plating treatment to form a wiring pattern on the substrate. From the viewpoint of achieving the effects of the present invention remarkably, it is preferable to perform at least an etching step.

[0186] The etching step can be carried out according to a known etching method, for example, by spraying an etching solution onto the resist pattern to etch the substrate surface not covered by the resist pattern. Examples of the etching method include acid etching and alkaline etching, and the etching is carried out by a method suitable for the photosensitive resin laminate used. The etching solution can be, for example, an aqueous hydrochloric acid solution, an aqueous ferric chloride solution, or a mixture thereof. The etching solution can also be sprayed.

[0187] The plating step can be carried out by plating the substrate surface exposed by development with a metal (eg, with a copper sulfate plating solution) or solder according to known plating methods.

[0188] After the etching step and / or plating step, the photosensitive resin laminate may be treated with an aqueous solution having a stronger alkalinity than the developer to peel off the resist pattern from the substrate. The peeling solution may be, for example, an aqueous solution of NaOH or KOH with a concentration of about 2% by mass to 5% by mass and a temperature of about 40° C. to 70° C.

[0189] The evaluation values ​​of the various parameters described above are, unless otherwise specified, measured values ​​measured in accordance with the measurement methods in the examples described below.

[0190] Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the spirit of the invention. EXAMPLES

[0191] The present invention will be specifically described below based on examples, but the present invention is not limited to these.

[0192] [One aspect of the present invention] <1. Preparation of photosensitive resin composition> A photosensitive resin composition was prepared by mixing a plurality of components according to the composition shown in Table 1 (where the number for each component indicates the amount (parts by mass) of the solid content).

[0193] The names of the components represented by the abbreviations in Table 1, the solvents used, etc. are shown in Table 2. The weight average molecular weight (Mw) shown in Table 2 means the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (Shodex STANDARD SM-105, manufactured by Showa Denko K.K.). The weight average molecular weight (Mw) and number average molecular weight (Mn) can be measured under the following conditions using a gel permeation chromatography manufactured by JASCO Corporation. Differential Refractometer: RI-1530 Pump: PU-1580 Degasser: DG-980-50 Column oven: CO-1560 Columns: KF-8025, KF-806M x 2, KF-807 Eluent:THF

[0194] <2. Production of photosensitive resin laminate> Ethanol as a solvent was added to the photosensitive resin composition until the solid content reached 58% by mass, and the mixture was stirred and mixed. The solution of the photosensitive resin composition obtained was uniformly applied to a polyethylene terephthalate film having a thickness of 25 μm (Toray FB-40; 16 μm polyethylene terephthalate film) using a bar coater, and dried for 5 minutes in a dryer at 95° C. to form a photosensitive resin layer (dry film) having a thickness of 5 μm to 25 μm. Next, a polyethylene film having a thickness of 33 μm (Tamapoly GF-858) was attached to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

[0195] <3. Preparation of evaluation board>

[0196] <Lamination> While peeling off the polyethylene film, the photosensitive resin laminate was laminated onto a PET substrate with a copper layer using a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Corporation) at a roll temperature of 105° C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.

[0197] <Exposure> The polyethylene terephthalate film, which is the support for the photosensitive resin layer, is peeled off from the laminated evaluation substrate, and the substrate is exposed to light at a dose of 120 mJ / cm using a chrome glass photomask and an exposure machine equipped with an ultra-high pressure mercury lamp (parallel light exposure machine (Oak Manufacturing Co., Ltd., HMW-801)). 2 The evaluation substrate was exposed to light at 1000 nm.

[0198] <Development> Using a Fuji Kiko Co., Ltd. developing device, a full cone type nozzle, 1% by weight Na at 30°C was sprayed at a spray pressure of 0.15 MPa. 2 CO 3The aqueous solution was sprayed onto the developed evaluation substrate for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. The minimum development time was determined as the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve, and the resist pattern was produced by developing the substrate for twice the minimum development time. The water washing step was carried out with a flat nozzle at a water washing spray pressure of 0.15 MPa for the same time as the development step.

[0199] <Etching> Using an etching device manufactured by Fuji Kiko Co., Ltd., the evaluation substrate after development was etched for 60 seconds with an aqueous solution containing hydrochloric acid at a concentration of 2% by mass and ferric chloride at a full cone type nozzle at a spray pressure of 0.15 MPa and a temperature of 30°C.

[0200] <Peeling> Using a peeling device manufactured by Fuji Kiko Co., Ltd., the etched evaluation substrate was treated with a 3% by mass NaOH aqueous solution for 30 seconds at a spray pressure of 0.15 MPa and a temperature of 50°C using a full cone type nozzle, and the resist pattern was peeled off and removed from the evaluation substrate.

[0201] <4. Evaluation method>

[0202] <Image quality evaluation> A photosensitive resin laminate with a photosensitive resin layer thickness of 5 μm was laminated onto a PET substrate with a copper layer by the method described in <Lamination> above, and the evaluation substrate was exposed to light 15 minutes later through a chrome glass mask having a line pattern with a 1:1 ratio of width between exposed and unexposed areas. Development was then performed for twice the minimum development time, and the minimum mask width at which a cured resist line was normally formed was taken as the resolution value, and the resolution was ranked as follows. The minimum mask width at which the cured resist pattern was normally formed without collapse or adhesion between cured resists was evaluated. ◎ (very good): The resolution value is 3μm or less; ○ (good): the resolution value is greater than 3 μm and less than or equal to 4 μm; × (bad): Resolution value exceeds 4 μm.

[0203] <Side etch (SE) amount> To evaluate the amount of side etching, a photosensitive resin laminate having a photosensitive resin layer thickness of 5 μm was laminated onto a PET substrate with a copper layer by the method described in the above <Lamination>, and then an evaluation substrate was used after 15 minutes had elapsed. The laminate evaluation substrate was exposed to a pattern of lines / spaces = 10 μm / 10 μm, and then developed by the method described above in <Development>. First, the resist top width Wr (μm) of the pattern was measured using an optical microscope. Next, the substrate having this line / space pattern was etched for 1.5 times the minimum etching time using a dip method in an aqueous solution containing 2% by mass of hydrochloric acid and 2% by mass of ferric chloride at a temperature of 30° C. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions. After the above etching, the cured film on the substrate was peeled off at 50° C. using a 3% by mass aqueous NaOH solution as a stripping solution, and the top width Wc (μm) of the obtained copper line pattern was measured using an optical microscope. And the formula: Side etch (μm) = (Wr-Wc)÷2 The amount of side etching was calculated and the amount of side etching was ranked as follows: ◎ (Very good): Side etch amount is 3 μm or less; ○ (Good): The amount of side etching is more than 3 μm and 3.5 μm or less; △ (Acceptable): The side etch amount is more than 3.5 μm and 4.0 μm or less; × (bad): The amount of side etching exceeds 4.0 μm.

[0204] <Puncture strength evaluation> The evaluation substrate was a 1.6 mm thick copper-clad laminate substrate with 35 μm copper foil laminated thereon, with 1,008 through holes of 6 mm diameter formed therein, and the surface was smoothed by surface treatment using a jet scrub polisher. After the surface was prepared, the polyethylene film of the photosensitive resin laminate, which had a photosensitive resin layer thickness of 25 μm, was peeled off and the substrate was laminated on both sides of the prepared substrate using a hot roll laminator (AL-70, manufactured by Asahi Kasei Corporation) under conditions of a roll temperature of 105°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min. The laminated substrate was exposed to light for 15 minutes at 120 mJ / cm using an exposure machine equipped with an ultra-high pressure mercury lamp (parallel light exposure machine (Oak Manufacturing Co., Ltd., HMW-801)). 2 The evaluation substrate was exposed to light at 40° C. and then developed by the method described above in <Development>. The developed substrate was conditioned overnight in a room at a temperature of 25° C. and a humidity of 50%. After standing, the polyethylene terephthalate film, which is the support of the photosensitive resin layer, was peeled off from the obtained substrate, and a 2.0 mm diameter cylinder was pierced at a speed of 100 mm / min into the part of the photosensitive resin layer corresponding to the center of the 6 mm diameter through hole from the surface where the support was peeled off, and the maximum point load was measured using a Tensilon (RTM-500 manufactured by Orientec Co., Ltd.). The maximum point load was measured at 10 points on the part of the photosensitive resin layer corresponding to the center of the 6 mm diameter through hole, and the average value of the top 5 points among them was taken as the maximum point load of the piercing test. The obtained maximum point load was evaluated according to the following criteria. ◎ (Very good): The puncture strength is 90gf or more; ○ (Good): The puncture strength is 80 gf or more and less than 90 gf; △ (Acceptable): The puncture strength is 70 gf or more and less than 80 gf; × (bad): The piercing strength is less than 70 gf.

[0205] <Copper (Cu) deficiency evaluation> To evaluate the amount of side etching, a photosensitive resin laminate having a photosensitive resin layer thickness of 5 μm was laminated onto a PET substrate with a copper layer by the method described in the above <Lamination>, and then an evaluation substrate was used after 15 minutes had elapsed. The laminate evaluation board was exposed to a line / space = 10 μm / 10 μm pattern, and then developed by the method described in <Development> above. Next, the board with this line / space pattern was etched by dip method in an aqueous solution containing 2 mass% hydrochloric acid and 2 mass% ferric chloride at a temperature of 30°C for 1.5 times the minimum etching time. Here, the minimum etching time refers to the minimum time required for the copper foil on the board to be completely dissolved and removed under the above conditions. After the above etching, the cured film on the substrate was peeled off at 50°C using a 3% by mass NaOH aqueous solution as a stripping solution, and the obtained copper line pattern was measured and observed by an optical microscope and ranked as follows. ◯: There is no defect on the copper line pattern, and the linearity is high. ×: Defects were present on the copper line pattern, and linearity was poor.

[0206] The evaluation results of Examples 1 to 13 and Comparative Examples 1 to 3 are also shown in Table 1. Comparing Examples 1 to 13 and Comparative Examples 1 to 3, it is considered that a photosensitive resin film having a piercing strength of 70 gf or more shows good results in suppressing copper (Cu) deficiency during etching.

[0207] [Table 1]

[0208] [Table 2]

[0209] [Another aspect of the present invention] <1. Preparation of photosensitive resin composition> Photosensitive resin compositions were prepared by mixing the compounds shown in Tables 3 to 5. The values ​​in Tables 3 to 5 are solid contents. The names of the components represented by the abbreviations in Tables 3 to 5, the solvents used, etc. are shown in Table 6.

[0210] The acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition is a value calculated from a value measured using NMR. In this example, the photosensitive resin composition was dissolved in THF, reprecipitated with n-hexane, separated into the precipitate and the solution, and the precipitate was dried. The precipitate was dissolved in deuterated acetone, 1 H-NMR measurement was carried out. From the obtained area ratio of each component, the integral value of each component in the precipitate was calculated, and the following formula was obtained: Weight ratio of methacrylic acid = (integral value of methacrylic acid) / (total integral value derived from precipitate components) The weight ratio (wt%) of methacrylic acid in the precipitate was calculated from the above. Furthermore, the following formula: Acid value of non-volatile component of photosensitive resin composition= {(weight ratio of methacrylic acid×1000×56 / 86)×weight of precipitate} / weight of photosensitive resin composition dissolved in THF The acid value of the non-volatile components of the photosensitive resin composition was calculated from the above. The above-mentioned method for calculating the acid value (acid equivalent) of the non-volatile component is an example in the case where the acid component contained in the alkali-soluble resin is methacrylic acid. On the other hand, even if the alkali-soluble resin contains an acid component other than methacrylic acid as the acid component, the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition can be measured according to the above-mentioned calculation method.

[0211] <2. Production of photosensitive resin laminate> Acetone solvent was added to the photosensitive resin composition until the solid content reached 58% by mass, and the mixture was thoroughly stirred and mixed. The solution of the photosensitive resin composition was uniformly applied to a 25 μm-thick polyethylene terephthalate film (Toray FB-40; 16 μm-thick polyethylene terephthalate film) as a support film (support) using a bar coater, and dried for 5 minutes in a dryer at 95° C. to form a photosensitive resin layer (dry film) with a thickness of 1 to 20 μm. Next, a 33 μm-thick polyethylene film (Tamapoly GF-858) was laminated on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. The film thickness of the photosensitive resin layer was measured using a film thickness meter (ID-C112B, Mitutoyo).

[0212] <3. Preparation of evaluation board> (laminate) While peeling off the polyethylene film from the photosensitive resin laminate, the laminate was laminated onto a PET substrate with a copper layer using a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Corporation) at a roll temperature of 105° C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.

[0213] (exposure) The support film was peeled off, and the evaluation substrate was exposed to light using a chrome glass photomask with an exposure machine having an ultra-high pressure mercury lamp (parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.)).

[0214] (developing) Using a Fuji Kiko Co., Ltd. developing device, a full cone type nozzle, 1% by weight Na at 23°C with a spray pressure of 0.15 MPa was used. 2 CO 3 The unexposed portion of the photosensitive resin layer was dissolved and removed by spraying the aqueous solution for 30 seconds. The washing step was performed using a flat nozzle at a water spray pressure of 0.15 MPa for the same time as the developing step.

[0215] (etching) Using an etching device manufactured by Fuji Kiko Co., Ltd., etching was performed with a full cone type nozzle at a spray pressure of 0.15 MPa, a temperature of 30°C, hydrochloric acid concentration of 2 mass%, and ferric chloride of 2 mass% for 60 s.

[0216] (peeling) Using a Fuji Kiko Co., Ltd. peeling device, the coating was treated with a full cone type nozzle at a spray pressure of 0.15 MPa and a temperature of 50°C for 30 seconds using a 3% by mass NaOH aqueous solution, which was then peeled off and removed.

[0217] <4. Evaluation method> (Image quality) A photosensitive resin laminate having a photosensitive layer thickness of 1 to 20 μm was laminated by the method described in (Lamination) above, and the evaluation board after 15 minutes was exposed through a chrome glass mask having a line pattern with a width ratio of exposed and unexposed areas of 1:1. Then, it was developed by the method described in (Development) above to prepare a resist pattern.

[0218] The minimum mask width at which the produced cured resist lines were normally formed was taken as the resolution value, and the resolution was ranked as follows: The minimum mask width at which the cured resist pattern was normally formed without collapse or adhesion between the cured resists was evaluated. ◎: The resolution value is 2 μm or less. ○: The resolution value is greater than 2 μm and equal to or less than 3 μm. ×: Resolution value exceeds 3 μm.

[0219] (Side Etch (SE) Amount) For the evaluation of the side etch amount, a photosensitive resin laminate having a photosensitive resin layer thickness of 1 to 20 μm was laminated onto a PET substrate with a copper layer by the method described above (Lamination), and then an evaluation substrate was used after 15 minutes had elapsed. The laminate evaluation substrate was exposed to a pattern with a line / space of 10 μm / 10 μm, and then developed by the method described above in (Development). The resist top width Wr (μm) of the pattern thus produced was measured using an optical microscope.

[0220] Next, the substrate having this line / space pattern was etched for 1.5 times the minimum etching time using a dip method in an aqueous solution containing 2% by mass of hydrochloric acid and 2% by mass of ferric chloride at a temperature of 30° C. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions. After the above etching, the cured film on the substrate was peeled off at 50° C. using a 3% by mass aqueous NaOH solution as a stripping solution, and the top width Wc (μm) of the obtained copper line pattern was measured using an optical microscope.

[0221] And the formula: Side etch (μm) = (Wr-Wc)÷2 The amount of side etching was calculated and the amount of side etching was ranked as follows: ⊚ (Very good): The amount of side etching is 2.5 μm or less. ◯ (Good): The amount of side etching is more than 2.5 μm and 3.0 μm or less. Δ (Acceptable): The amount of side etching is more than 3.0 μm and 3.5 μm or less. × (bad): The amount of side etching exceeds 3.5 μm.

[0222] (Copper (Cu) deficiency evaluation) For the evaluation of the side etch amount, a photosensitive resin laminate having a photosensitive resin layer thickness of 1 to 20 μm was laminated onto a PET substrate with a copper layer by the method described above (Lamination), and then an evaluation substrate was used after 15 minutes had elapsed. The laminate evaluation board was exposed to a line / space = 10 μm / 10 μm pattern, and then developed by the method described in (Development) above. Next, the board with this line / space pattern was etched by dip method in an aqueous solution containing 2 mass% hydrochloric acid and 2 mass% ferric chloride at a temperature of 30°C for 1.5 times the minimum etching time. Here, the minimum etching time refers to the minimum time required for the copper foil on the board to be completely dissolved and removed under the above conditions.

[0223] After the above etching, the cured film on the substrate was peeled off at 50°C using a 3% by mass NaOH aqueous solution as a stripping solution, and the obtained copper line pattern was measured and observed by an optical microscope and ranked as follows. ◯: There is no defect on the copper line pattern, and the linearity is high. △: There is a small defect on the copper line pattern, and linearity is slightly reduced. ×: Many defects were found on the copper line pattern, and linearity was reduced.

[0224] (minimum development time) A photosensitive resin laminate having a photosensitive layer thickness of 1 to 20 μm was laminated onto a copper-clad laminate substrate having a thickness of 0.4 mm and a copper foil having a thickness of 18 μm, by the method described above (Lamination), to obtain a laminate. After removing the support film laminated on the photosensitive layer, the laminate was spray-developed at 23° C. for a predetermined time using a 1.0% by mass aqueous solution of sodium carbonate.

[0225] The surface of the substrate after development was observed, and the time until no development residue remained was defined as the minimum development time, and was evaluated according to the following criteria. ◎ (Very good): The minimum development time is within 15 seconds. ○(Good): The minimum development time is within 20 seconds. △(Acceptable): The minimum development time is within 25 seconds. × (bad): The minimum developing time is within 30 seconds.

[0226] (Photosensitive layer development residue test) The photosensitive resin laminate having a photosensitive layer thickness of 1 to 20 μm was laminated onto a copper-clad laminate substrate having a thickness of 0.4 mm and a copper foil having a thickness of 18 μm, by the method described above in (Lamination), to obtain a laminate. 2 The substrate was stored for 3 hours under an atmospheric condition of 60°C. The substrate was taken out and the support film laminated on the photosensitive layer was removed, and then the substrate was spray-developed at 23°C for 1.2 times the minimum development time using a 1.0 mass% aqueous sodium carbonate solution. The substrate surface after development was observed, and the development residue was evaluated as follows. ◯: No development residue on the substrate surface. △: A small amount of development residue is generated on the substrate surface. ×: Development residue occurs on the substrate surface.

[0227] For each of the Examples and Comparative Examples, the composition of the photosensitive resin composition and the evaluation results for the laminate are shown in Tables 3 to 5. In addition, the names of the components represented by abbreviations in Tables 3 to 5, the solvents used, etc. are shown in Table 6.

[0228] [Table 3]

[0229] [Table 4]

[0230] [Table 5]

[0231] [Table 6]

[0232] As is clear from the table, in Comparative Examples 4 to 7, in which the ratio (A / T) of the acid value A to the thickness T is less than 5, the minimum development time and resolution were insufficient. In addition, in the case of a film thickness of 20 μm and 15 μm, the developability was not good at a development time of 30 seconds or more, so other items could not be evaluated. On the other hand, in Comparative Example 8, in which the ratio (A / T) is greater than 90, development is possible with a high acid value and without PTMG, but due to the high acid value and without PTMG, Cu deficiency, resolution, and side etch (SE) were insufficient. In particular, in the case of a thick film, the resolution is relatively good by setting the acid value to 90 mgKOH / g or more, but there was a tendency for the resolution to deteriorate when the film was made thin. In contrast, in the examples in which the ratio (A / T) of acid value A to thickness T is 5 or more and 90 or less, sufficiently good results were obtained in the minimum development time, resolution, side etch, Cu loss, and development residue tests. [Industrial Applicability]

[0233] The photosensitive resin composition, photosensitive resin laminate, and dry film resist according to the present invention suppress defects in patterns formed using them, and therefore improve the yield of objects or patterns formed by photolithography, and / or have excellent lamination properties, minimum development time, resolution, side edge (SE) amount, Cu defects, and development residues, and can be widely used in forming resist patterns or wiring patterns.

Claims

1. A photosensitive resin laminate comprising: a support; and a photosensitive resin composition layer formed on the support using a photosensitive resin composition comprising: (A) an alkali-soluble resin not containing an ethylenically unsaturated group in its main chain; (B) a photopolymerizable compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; A photosensitive resin laminate, characterized in that, when an acid value of a non-volatile component of the photosensitive resin composition is A [mg KOH / g] and a thickness of the photosensitive resin composition layer is T [μm], a ratio (A / T) of the acid value A to the thickness T is 5 or more and 90 or less.

2. 2. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin composition further contains, as a component (D), a compound having polytetramethylene oxide as a structural unit.

3. The photosensitive resin laminate according to claim 1 or 2, wherein the photosensitive resin composition further contains a compound having a benzotriazole skeleton as a component (E).

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B) is a photopolymerizable compound having 4 or more functional ethylenically unsaturated bonds.

5. 3. The photosensitive resin laminate according to claim 2, wherein a ratio of the component (A) to the sum of the component (B) and the component (D) [component (A) / (component (B)+component (D)] is greater than 0 and equal to or less than 1.

4.

6. 6. The photosensitive resin laminate according to claim 1, wherein the component (A) has a weight average molecular weight of 20,000 or more.

7. 7. The photosensitive resin laminate according to claim 1, wherein the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition is greater than 0 and not greater than 79.0.

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