Photosensitive resin composition and method for producing the same

Abstract

To provide a photosensitive resin composition capable of realizing a photosensitive resin layer excellent in desired properties (particularly, sensitivity, resolution, and adhesion). 【Solution means】A photosensitive resin composition containing the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; and (D) a polymerization inhibitor, wherein the content of component (C) is 3.5% by mass or more based on the total solid content of the photosensitive resin composition, and component (D) is represented by the following general formula (I): JPEG2026060536000018.jpg2250 [In formula (I), R 1 represents a hydrocarbon group which may have a substituent, NHR 4 or NR 4 R 5 where R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.], a photosensitive resin composition containing a compound having a nitroso structure.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition and a method for producing the same.

Background Art

[0002] Printed wiring boards are generally manufactured using a photolithography process. Photolithography is a method of forming a desired wiring pattern on a substrate through the following steps. First, a coating film obtained using a photosensitive resin composition is formed on the substrate, and then a resist pattern is formed by exposure and development; next, a conductor pattern is formed on the substrate by etching or plating; and then, the wiring pattern is formed on the substrate by removing the resist pattern.

[0003] In recent years, with the miniaturization and high density of electronic devices, the formation of finer wiring than before has been required. Various photosensitive resin compositions have been studied for the formation of resist patterns or metal patterns using them. For example, in Patent Documents 1 to 3, photosensitive compositions containing a specific alkali-soluble polymer, a compound having an ethylenic unsaturated bond, a polymerization initiator, and a nitroso compound are described from the viewpoints of improving sensitivity, resolution, and adhesion.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, conventional photosensitive resin compositions, including those described in Patent Documents 1-3, still had room for improvement in terms of enhancing various properties.

[0006] Therefore, the object of this disclosure is to provide a photosensitive resin composition that can realize a photosensitive resin layer with excellent desired properties (particularly sensitivity, resolution, and adhesion). Another object of this disclosure is to provide a photosensitive resin laminate having a photosensitive resin layer, and a method for producing a photosensitive resin composition. [Means for solving the problem]

[0007] One aspect of the present invention is as follows: [1] The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having ethylenically unsaturated bonds; (C) polymerization initiator; and (D) A photosensitive resin composition comprising a polymerization inhibitor, The content of component (C) is 3.5% by mass or more relative to the total solid content of the photosensitive resin composition. The aforementioned component (D) is given by the following general formula (I): [ka] [In formula (I), R 1 This is a hydrocarbon group which may have substituents, NHR 4 or NR 4 R 5 Show, R 4 and R 5 Each of these is independently a hydrocarbon group which may have substituents. A photosensitive resin composition comprising a compound having a nitroso structure as shown. [2] The aforementioned component (D) is given by the following general formula (II): [ka] [In formula (II), R 2 and R 3Each of these is independently a hydrocarbon group which may have substituents. A photosensitive resin composition according to [1], comprising a nitrosamine compound represented by [1]. [3] The photosensitive resin composition according to [1] or [2], wherein the component (D) further comprises at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton. [4] The aforementioned component (A) includes copolymer (A-1), The copolymer (A-1) comprises at least the following components: (a1) (meth)acrylic acid; and (a2) Hydroxyalkyl (meth)acrylate; A photosensitive resin composition according to any one of [1] to [3], comprising a constituent unit derived from [1]. [5] A photosensitive resin composition according to any one of [1] to [4], wherein the absorbance at a wavelength of 405 nm per 1 μm of the photosensitive resin layer obtained using the above photosensitive resin composition is 0.004 to 0.0120. [6] The aforementioned component (C) is a biimidazole compound, and A photosensitive resin composition according to any one of [1] to [5], comprising at least one selected from the group consisting of pyrazoline derivatives and anthracene derivatives. [7] The photosensitive resin composition according to [6], wherein the (C) component comprises the biimidazole compound and the anthracene derivative. [8] A photosensitive resin composition according to any one of [1] to [7], comprising one or more of the above-mentioned (C) components, wherein the ratio of absorbance at a wavelength of 405 nm to a wavelength of 400 nm in an ethanol solution (A405nm / A400nm) is 0.5 or more. [9] The following components: (A) Alkali-soluble polymer; (B) Compounds having ethylenically unsaturated bonds; (C) polymerization initiator; and A method for producing a photosensitive resin composition, comprising a polymerization inhibitor (D), where the content of the component (C) is 3.5% by mass or more based on the total solid content of the photosensitive resin composition, and the component (D) is a compound represented by the following general formula (I): [Chemical formula] [In formula (I), R 1 represents a hydrocarbon group which may have a substituent, NHR 4 or NR 4 R 5 , R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.] and containing a compound having a nitroso structure represented by a method for producing a photosensitive resin composition.

[10] The component (D) is a compound represented by the following general formula (II): [Chemical formula] [In formula (II), R 2 and R 3 each independently represent a hydrocarbon group which may have a substituent.] The method for producing a photosensitive resin composition according to [9], containing a nitrosoamine compound represented by

[11] The method for producing a photosensitive resin composition according to [9] or

[10] , wherein the component (D) further contains at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton. [Advantages of the Invention]

[0008] The present invention provides a photosensitive resin composition capable of realizing a photosensitive resin layer with excellent desired properties (particularly sensitivity, resolution, and adhesion). Furthermore, the present invention provides a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, as well as a method for manufacturing a photosensitive resin composition and a method for forming a resist pattern. [Brief explanation of the drawing]

[0009] [Figure 1] This is a plan view showing the configuration of a drawing pattern related to this embodiment. [Figure 2] This is a plan view showing the configuration of a drawing pattern related to this embodiment. [Modes for carrying out the invention]

[0010] The embodiments of the present invention (hereinafter abbreviated as "these embodiments") will be described below. The present invention is not limited to these embodiments and can be implemented in various ways within the scope of its gist. In this specification, the upper and lower limits of each numerical range may be arbitrarily combined and may be replaced with the values ​​described in the examples. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylate" means "acrylate" or "methacrylate". Unless otherwise specified in this specification, various numerical values ​​and characteristics may be measured in accordance with the methods described in the examples.

[0011] In this embodiment, the photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a polymerization initiator, and (D) a polymerization inhibitor, and optionally a solvent and other components. Each component is described below. The photosensitive resin composition of this embodiment can be used as a negative-type photosensitive resin composition.

[0012] [Photosensitive resin composition] This embodiment comprises the following components: (A) Alkali-soluble polymer, (B) Compounds having an ethylenically unsaturated bond, (C) polymerization initiator, and (D) Polymerization inhibitors This is a photosensitive resin composition (hereinafter referred to as the photosensitive resin composition of this embodiment) that includes [the specified element].

[0013] In one embodiment, the photosensitive resin composition of this embodiment is (D) Component is given by the following general formula (I): [ka] [In formula (I), R 1 This is a hydrocarbon group which may have substituents, NHR 4 or NR 4 R 5 Show, R 4 and R 5 These are hydrocarbon groups, each of which may independently have substituents. This is a photosensitive resin composition containing a compound having a nitroso structure as shown.

[0014] The absorbance at a wavelength of 405 nm per 1 μm of the photosensitive resin layer obtained using the photosensitive resin composition of this embodiment is preferably 0.004 to 0.0120. The absorbance can be measured according to the method described in the examples.

[0015] The photosensitive resin layer obtained by exposing the photosensitive resin composition of this embodiment has a transmittance of 35% or more at a wavelength of 405 nm in a 25 μm layer, more preferably 50% or more, and even more preferably 60% or more. This makes it easier to achieve good adhesion (adhesion between the photosensitive resin layer and the substrate) and resolution. The transmittance can be measured according to the method described in the examples.

[0016] Components (A), (B), (C), and (D) can each be used individually or in combination of two or more. If the photosensitive resin composition of this embodiment contains other components besides components (A), (B), (C), and (D), such other components may also be used individually or in combination of two or more.

[0017] (A) Component: Alkali-soluble polymer Component (A) is an alkali-soluble polymer. In this disclosure, an alkali-soluble polymer is a polymer that can dissolve in an alkaline aqueous solution. Component (A) preferably has a carboxyl group, and from the viewpoint of exhibiting suitable alkali solubility, it is preferable to have an acid value of 50 to 600 mg KOH / g. The acid value of component (A) is preferably 50 mg KOH / g or more, more preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, particularly preferably 100 mg KOH / g or more, and most preferably 120 mg KOH / g or more. The acid value of component (A) is preferably 600 mg KOH / g or less, more preferably 500 mg KOH / g or less, even more preferably 400 mg KOH / g or less, particularly preferably 300 mg KOH / g or less, and most preferably 200 mg KOH / g or less.

[0018] The acid value of component (A) can be determined by the following method. (A) Weigh approximately 1 g of the sample of component (A) accurately, dissolve it in 100 mL of acetone, then perform a neutralization titration with a 1 mol / L potassium hydroxide solution, and determine the amount of potassium hydroxide solution added. The acid value of component (A) is given by the following formula: (A) The acid value of component (mgKOH / g) can be calculated by applying the amount of potassium hydroxide solution added to the formula: (A) = 56.1 × {Amount of 1 mol / L potassium hydroxide solution added (mL)} / {Mass of the accurately weighed sample (g)}. Neutralization titration can be performed, for example, using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

[0019] Component (A) preferably has repeating units comprising at least one selected from the "first monomers" described later, and more preferably has repeating units comprising both at least one selected from the "first monomers" and at least one selected from the "second monomers" described later. In one embodiment, component (A) includes a copolymer (A-1) having "first monomer" and "second monomer" as copolymer components. Furthermore, the proportion of monomeric components in component (A) is the copolymerization ratio when component (A) contains only one type of alkali-soluble polymer, and when two or more types of alkali-soluble polymers are used as component (A), it is the weighted average value of the copolymerization ratios, with the content ratio of each alkali-soluble polymer as the weight.

[0020] The weight-average molecular weight (Mw) of component (A) is preferably 10,000 to 60,000. A weight-average molecular weight of 60,000 or less is preferable from the viewpoint of achieving both flexibility and resolution of the resist pattern, more preferably 55,000 or less, and even more preferably less than 50,000 from the same viewpoint. From a similar viewpoint, it is preferable to have a weight-average molecular weight of 10,000 or more, more preferably 14,000 or more, and even more preferably 25,000 or more.

[0021] The polydispersity of component (A) {weight-average molecular weight of component (A) (Mw) / number-average molecular weight of component (A) (Mn)} is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0022] When using a mixture of two or more components (A), it is preferable that the molecular weight and polydispersity of the multiple (A) components be selected such that the weighted average value, when the content ratio is treated as the weight, falls within various ranges.

[0023] <First monomer (component a1)> The first monomer has a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. Among these, from the viewpoint of excellent adhesion and resolution, copolymer (A-1) preferably contains constituent units derived from (meth)acrylic acid as copolymer components, and more preferably contains constituent units derived from methacrylic acid. Regarding (meth)acrylic acid, "methacrylic acid" refers to the compound represented by the chemical formula C4H6O2, while "acrylic acid" refers to the compound represented by the chemical formula C3H4O2.

[0024] (A) The proportion of the first monomer (component a1) in component (A) is preferably 15 to 50% by mass, based on the total mass of all monomer components. A proportion of 15% by mass or more is preferred from the viewpoint of excellent adhesion and resolution, more preferably 20% by mass or more, even more preferably 22% by mass or more, and particularly preferred 24% by mass or more. A proportion of 50% by mass or less is preferred from the viewpoint of excellent adhesion and resolution, more preferably 35% by mass or less, even more preferably 30% by mass or less, particularly preferred 29% by mass or less, and most preferably 27% by mass or less.

[0025] <Second monomer (component a2)> The second monomer has at least one polymerizable unsaturated group in its molecule. Examples of second monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, and tetrahydrofurfuryl Examples include (meth)acrylates such as (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate; styrene derivatives such as methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile.

[0026] The proportion of the second monomer (component a2) in component (A) is preferably 50 to 85% by mass, based on the total mass of all monomer components. A proportion of 50% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, 60% by mass or more is more preferable, and 70% by mass or more is even more preferable. A proportion of 85% by mass or less is preferable from the viewpoint of excellent adhesion and resolution, and 75% by mass or less is even more preferable.

[0027] The second monomer may include a compound having a hydroxyl group. The proportion of the general compound in component (A) is preferably 1.0 to 25% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 6% by mass, based on the total mass of all monomer components. Controlling this proportion within the above range is preferable from the viewpoint of excellent adhesion and resolution.

[0028] Examples of compounds containing a hydroxyl group include hydroxyalkyl (meth)acrylates, specifically 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin-based (meth)acrylates (e.g., glycerin mono(meth)acrylate). Among these, 2-hydroxyethyl (meth)acrylate is preferred. These are relatively easy to obtain. Moreover, their developability and adhesion are easy to control, and therefore, it is easy to realize resist patterns with excellent properties. From the viewpoint of excellent adhesion and resolution, copolymer (A-1) preferably contains constituent units derived from hydroxyalkyl (meth)acrylate as copolymer components.

[0029] The second monomer preferably contains a compound having an aromatic ring. The proportion of this compound in component (A) is preferably 20 to 85% by mass, and more preferably 25 to 80% by mass, based on the total mass of all monomer components. From the viewpoint of excellent adhesion and resolution, the ratio is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more. From the viewpoint of excellent developability, the ratio is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less.

[0030] Examples of compounds having an aromatic ring include styrene, benzyl (meth)acrylate, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimers, styrene trimers and other styrene derivatives, and 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate. Among these, styrene and benzyl (meth)acrylate are preferred, and styrene is more preferred.

[0031] (A) The component may have a proportion of styrene-derived constituent units of 20% by mass or more, based on the total mass of all its monomer components. Here, the component (A) preferably has a proportion of styrene-derived constituent units of 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, based on the total mass of its total monomer components. This makes it easier to achieve the effects of this embodiment. The component (A) preferably has a proportion of styrene-derived constituent units of 85% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less, based on the total mass of its total monomer components.

[0032] The second monomer may contain a compound having an alicyclic ring. The proportion of this compound in component (A) is preferably 10 to 40% by mass, based on the total mass of all monomer components.

[0033] Examples of compounds having an alicyclic ring include (meth)acrylic acid esters having a group consisting of one cyclic hydrocarbon group such as a cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group, or a derivative thereof. Also, examples of (meth)acrylic acid esters having a group consisting of two or more cyclic hydrocarbon groups such as a dicyclopentanyl group, dicyclopentenyl group, adamantyl group, and isobornyl group, or a derivative thereof.

[0034] The second monomer may contain compounds other than those listed above. Examples of such compounds include (meth)acrylate alkyl esters other than those mentioned above (chain alkyl esters and cyclic alkyl esters), conjugated diene compounds other than those mentioned above, polar monomers other than those mentioned above (amino group-containing monomers, amide group-containing monomers, cyano group-containing monomers, and epoxy group-containing monomers, etc.), crosslinkable monomers other than those mentioned above, and acid anhydrides other than those mentioned above.

[0035] <(A) Synthesis> The synthesis of component (A) is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring. In some cases, the synthesis may be carried out by adding a portion of the mixture dropwise to the reaction solution, or after the reaction is complete, the solvent may be added to adjust to the desired concentration. In addition to solution polymerization, living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used as synthesis methods.

[0036] The content of component (A) may be 10% by mass or more, or 20% by mass or more, or 25% by mass or more, or 30% by mass or more, or 35% by mass or more, or 40% by mass or more, or 45% by mass or more, or 50% by mass or more, or 55% by mass or more, or 60% by mass or more, based on the total solid content mass of the photosensitive resin composition. Alternatively, the content of component (A) may be 90% by mass or less, or 80% by mass or less, or 70% by mass or less, or 60% by mass or less, or 50% by mass or less, based on the total solid content mass of the photosensitive resin composition.

[0037] (A) It is preferable to reduce the content of component to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to reduce the content to 10% by mass or more from the viewpoint of improving edge fusing resistance, that is, from the viewpoint of suppressing the leakage of the photosensitive resin layer from the film edge. Edge fusing resistance may be particularly required for rolls formed by winding a photosensitive resin laminate.

[0038] (B) Component: Compound containing an ethylenically unsaturated bond In this disclosure, component (B) is a compound having at least one ethylenically unsaturated bond in one molecule.

[0039] Component (B) preferably contains a compound having two or more ethylenically unsaturated bonds in one molecule. Component (B) may also contain a compound having three ethylenically unsaturated bonds in one molecule, or a compound having four, five, or six ethylenically unsaturated bonds in one molecule.

[0040] Component (B) preferably contains a compound containing a (meth)acryloyl group (hereinafter referred to as a (meth)acrylate compound), and more preferably contains a (meth)acrylate compound with two or more functionalities. In this disclosure, "monofunctional (meth)acrylate compound" means a compound having one or more (meth)acryloyl groups in one molecule.

[0041] Component (B) is preferably a (meth)acrylate compound. The (meth)acrylate compound may include, for example, a monofunctional (meth)acrylate compound, a bifunctional (meth)acrylate compound, and a trifunctional or more functional (meth)acrylate compound, from the viewpoint of adhesion and flexibility of the resist pattern, and may include, for example, a tetrafunctional, pentfunctional, or hexafunctional (meth)acrylate compound.

[0042] The number of functional groups in a compound having an ethylenically unsaturated bond may be, for example, monofunctional (hereinafter also referred to as monofunctional), two or more functional groups, three or more functional groups, four or more functional groups, five or more functional groups, six or more functional groups, three to ten functional groups, three to six functional groups, or four to six functional groups, or multiple types of compounds with different numbers of functional groups may be combined. In this disclosure, "number of functional groups" refers to the number of ethylenically unsaturated bonds per molecule of a compound, and is defined, for example, as the number of acryloyl groups per molecule in the case of an acrylate monomer, and as the number of methacryloyl groups per molecule in the case of a methacrylate monomer.

[0043] Monofunctional (meth)acrylate compounds include alkylene oxide-modified phenol (meth)acrylate, alkylene oxide-modified nonylphenol (meth)acrylate, alkylene oxide-modified 2-ethylhexyl (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 1-naphthalenemethyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, isoamyl ( Examples include meth)acrylate, hexyl(meth)acrylate, isodecyl(meth)acrylate, n-lauryl(meth)acrylate, tetradecyl(meth)acrylate, n-stearyl(meth)acrylate, isostearyl(meth)acrylate, behenyl(meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, isobolonyl(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, 1H,1H,5H-octafluoropentyl(meth)acrylate, and 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl(meth)acrylate.

[0044] Examples of bifunctional (meth)acrylate compounds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, ethoxylated propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycoxified (hydrogenated) bisphenol A di(meth)acrylate.

[0045] Commercially available bifunctional (meth)acrylate compounds include: For example, NK Ester® A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, NOD-N, DOD-N, NPG, 70 1. 2G, 3G, 4G, 9G, 14G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, NK O Rigo (registered trademark) UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA and EA-1020 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate® 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, 1.9ND-A, DCP-A, BP-4EAL, BP-4PA, HPP-A, Light Ester G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.) Funcryl® FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Resonac Co., Ltd.), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel Ornex Co., Ltd.) SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema Co., Ltd.) Examples include KAYARAD® NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0046] Examples of (meth)acrylate compounds with three or more functions include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0047] Furthermore, examples of trifunctional or more (meth)acrylate compounds include trimethylolpropane alkylene oxide-modified tri(meth)acrylate, glycerin alkylene oxide-modified tri(meth)acrylate, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0048] Commercially available (meth)acrylate compounds with three or more functionalities include: For example, NK Ester® A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, A-9550, A-DPH-12E, TPOA-50, NK Oligo® UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Light Acrylate® TMP-A, cPE-3A, cPE-4A, cPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.) FA-731A (manufactured by Resonac Corporation), TMPTA, EBECRYL 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel Ornex Co., Ltd.) SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema Co., Ltd.) Examples include KAYARAD® GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, and DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.).

[0049] The content of the trifunctional or more (meth)acrylate compound may be 0 to 50% by mass, 0 to 25% by mass, or 1 to 15% by mass, based on the total amount of component (B).

[0050] Specifically, examples of compounds that may be included in component (B) are as follows. However, the component (B) used in this embodiment is not limited to the following compounds. A polyethylene glycol dimethacrylate (product name "BPE-500") in which an average of 5 moles of EO are added to each end of a bisphenol A molecule. Hexamethacrylate of polyethylene glycol with a total of 13 moles of EO attached to the six ends of dipentaerythritol; Tetramethacrylate, in which an average of 9 moles of EO (electrolyte-containing polymer) is attached to each of the four ends of pentaerythritol; Dodecapropylene glycol dimethacrylate; Dimethacrylate of polyalkylene glycosides, in which an average of 2 moles of PO and an average of 6 moles of EO are attached to each end of bisphenol A; Epoxy acrylate (product name "EA-1020" above); 4-Nonylphenyl-heptaethylene glycol;-Dipropylene glycol acrylate; These include (where "EO" is an abbreviation for ethylene oxide, and "PO" is an abbreviation for propylene oxide).

[0051] (B) The content of component (B) is preferably 30% by mass or more, and preferably 35% by mass or more, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of sensitivity, tackiness, and followability. Furthermore, from the viewpoint of edge fusing resistance, tackiness, and resolution, it is preferably 50% by mass or less, preferably 45% by mass or less, and preferably 42% by mass or less.

[0052] From the viewpoint of edge fusing resistance, tackiness, and resolution, the content of component (B) relative to the content of component (A) in the photosensitive resin composition (i.e., content of component (B) / content of component (A)) is preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 or less, and preferably 1.1 or less. The lower limit is preferably 0.6 or more, preferably 0.7 or more, preferably 0.8 or more, preferably 0.9 or more, and preferably 1.0 or more.

[0053] The number of ethylenically unsaturated bonds per 100g of solids in the photosensitive resin composition is preferably controlled to 0.1 to 0.3 mol. Controlling it to 0.1 mol or more makes it easier to prevent the photosensitive resin component from eluting from the cured resist pattern during the water washing step after development, and consequently, to prevent contamination during the water washing step. Controlling it to 0.3 mol or less makes it easier to prevent the cured resist pattern from chipping and falling off during the water washing step after development, and consequently, to prevent contamination during the water washing step.

[0054] The number of ethylenically unsaturated bonds per 100g of solids in the photosensitive resin composition is preferably 0.1 mol or more, more preferably 0.11 mol or more, more preferably 0.12 mol or more, and more preferably 0.13 mol or more. It is also preferably 0.3 mol or less, preferably 0.28 mol or less, preferably 0.25 mol or less, preferably 0.22 mol or less, preferably 0.20 mol or less, preferably 0.18 mol or less, and preferably 0.15 mol or less.

[0055] (C) Ingredient: Polymerization initiator Component (C) is a polymerization initiator. A polymerization initiator is a compound that generates radicals when exposed to active light, thereby initiating the polymerization of compounds containing ethylenically unsaturated bonds. In one embodiment, the content of component (C) is 3.5% by mass or more relative to the total solid content of the photosensitive resin composition. In one embodiment, the content of component (C) in the photosensitive resin composition may be 3.5% by mass or more with respect to the total solid content of the photosensitive resin composition, preferably 4.0% by mass or more, more preferably 5.0% by mass or more, and even more preferably 6.0% by mass or more, with respect to the total solid content of the photosensitive resin composition. The effects of this embodiment are easily achieved when the content of component (C) is within a predetermined range. In another embodiment, the content of component (C) is 10% by mass or less, or 8.0% by mass or less, based on the total solid content of the photosensitive resin composition.

[0056] Examples of component (C) include biimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds.

[0057] Biimidazole compounds refer to compounds having a biimidazole structure, such as rofin dimers, i.e., dimers of 2,4,5-triarylimidazole. Examples of rophine dimers include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, and 2,4-bis-(o-chlorophenyl 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-di Fluorophenyl)-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-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-tri Fluorophenyl)-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,Examples include 3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0058] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that the (C) component contains a rofin dimer, and among these, it is more preferable that it contains a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0059] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0060] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0061] Examples of aromatic ketone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. 4,4'-bis(diethylamino)benzophenone is also an aromatic ketone compound, given its sensitizing effect and adhesion properties.

[0062] In this specification, "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraceneboronic acid. From the viewpoint of sensitization effect and adhesion, 10-phenyl-9-anthraceneboronic acid, 9,10-dibutoxyanthracene, and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0063] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0064] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0065] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0066] Examples of dialkylketal compounds include benzyldimethyl ketal and benzyldiethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0067] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0068] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0069] From the viewpoint of adhesion and rectangular resist pattern, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred as pyrazoline derivatives, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

[0070] Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0071] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diallylodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0072] (C) component preferably contains a biimidazole compound. When component (C) contains a biimidazole compound, the content of the biimidazole compound in the photosensitive resin composition is preferably 3.0% to 10% by mass, and more preferably 3.0% to 7.0% by mass, based on the total solid content mass of the photosensitive resin composition.

[0073] (C) Component may be used alone or in combination of two or more components. Component (C) preferably contains at least one selected from the group consisting of biimidazole compounds, pyrazoline derivatives, and anthracene derivatives, and more preferably contains biimidazole compounds and anthracene derivatives.

[0074] When component (C) contains a biimidazole compound, the content of component (C) other than the biimidazole compound in the photosensitive resin composition is preferably 0.01 to 3.0% by mass, more preferably 0.03 to 2.0% by mass, and particularly preferably 0.05 to 1.0% by mass, based on the total solid content mass in the photosensitive resin composition. By adjusting the content of component (C) within the above range, it is possible to achieve both sufficient sensitivity and ease of light transmission to the bottom of the photosensitive resin layer, thereby making it easier to achieve high resolution.

[0075] In one embodiment, component (C) has an absorbance ratio (A405nm / A400nm) of 0.5 or more for a wavelength of 405nm to a wavelength of 400nm in an ethanol solution. Examples of such component (C) include pyrazoline derivatives, among which 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred. The photosensitive resin composition of this embodiment is preferable because it contains such a component (C) because it reduces the influence of wavelength deviation in the exposure machine. The absorbance is measured using the following method. (C) Ethanol is added to component, and the concentration is 1.0 × 10 -5A mol / L sample solution was prepared. This sample solution was placed in a quartz cell with a path length of 1 cm, and the absorbance of the (C) component at wavelengths of 400 nm and 405 nm (A405 nm and A400 nm) was measured using an ultraviolet-visible-near-infrared spectrophotometer.

[0076] (D) Ingredient: Polymerization inhibitor Component (D) is a polymerization inhibitor. Component (D) is given by the following general formula (I): [ka] [In formula (I), R 1 This is a hydrocarbon group which may have substituents, NHR 4 or NR 4 R 5 Show, R 4 and R 5 Each of these is independently a hydrocarbon group which may have substituents. It includes compounds having a nitroso structure as shown.

[0077] In the above general formula (I), R 1 From the viewpoint of obtaining the effects of this embodiment more fully, A linear or branched saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms (e.g., a methyl group); Saturated or unsaturated monocyclic or polycyclic cyclic hydrocarbon groups (alicyclic hydrocarbon groups) having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); Aromatic monocyclic hydrocarbon groups having 6 to 20 carbon atoms (e.g., phenyl group, phenylene group, etc.); A condensed polycyclic aromatic hydrocarbon group having 10 to 20 carbon atoms (e.g., naphthyl group); NHR 4 and NR 4 R 5 Preferably, the group is one or more combinations selected from the group consisting of the following: R 4 and R 5 Each of them operates independently. A linear or branched saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms (e.g., a methyl group); Saturated or unsaturated monocyclic or polycyclic hydrocarbon groups (alicyclic hydrocarbon groups) having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); Aromatic monocyclic hydrocarbon groups with 6 to 20 carbon atoms (e.g., phenyl group, phenylene group, etc.); A condensed polycyclic aromatic hydrocarbon group having 10 to 20 carbon atoms (e.g., naphthyl group); It is preferable that the group is one or more combinations selected from the group consisting of the following. 1 , R 4 and R 5 It may be substituted with a group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, and halogen atoms. For example, halogen atoms include chlorine and bromine atoms.

[0078] In this disclosure, the cyclic hydrocarbon group may be a saturated or unsaturated alicyclic hydrocarbon group or an aromatic hydrocarbon group. In this disclosure, the chain hydrocarbon group may be saturated or unsaturated, and may be linear or branched. R 1 Examples include phenyl groups, naphthyl groups, and groups in which the hydrogen atoms of phenyl and naphthyl groups are substituted with substituents (e.g., amino groups, hydroxyl groups, thiol groups, and chloro groups). Among these, R 1 Preferred members include phenyl groups, naphthyl groups, and groups in which the hydrogen atoms of phenyl and naphthyl groups are substituted with amino or hydroxyl groups. Also, R 4 and R 5 Examples include alkyl groups, naphthyl groups, and phenyl groups having 1 to 10 carbon atoms, as well as groups in which the hydrogen atoms of alkyl groups, naphthyl groups, and phenyl groups having 1 to 10 carbon atoms are substituted with substituents (e.g., amino groups, hydroxyl groups, thiol groups, and chloro groups). Among these, R 4 and R 5 Preferably, alkyl groups having 1 to 10 carbon atoms and phenyl groups are used, and methyl groups and phenyl groups are more preferred.

[0079] The photosensitive resin composition of this embodiment contains component (D), which includes a compound having a nitroso structure represented by the above general formula (I), thereby providing excellent stability, sensitivity, and resolution.

[0080] In the photosensitive resin composition of this embodiment, component (D) is the following general formula (II): [ka] [In formula (II), R 2 and R 3 Each of these is independently a hydrocarbon group which may have substituents. It is preferable that the nitrosamine compound represented by [the formula shown] is included.

[0081] In the above general formula (II), R 2 and R 3 From the viewpoint of obtaining the effects of this embodiment more fully, R 2 and R 3 Each of them operates independently. A linear or branched saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms (e.g., a methyl group); Saturated or unsaturated monocyclic or polycyclic hydrocarbon groups (alicyclic hydrocarbon groups) having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); Aromatic monocyclic hydrocarbon groups with 6 to 20 carbon atoms (e.g., phenyl group, phenylene group, etc.); A condensed polycyclic aromatic hydrocarbon group having 10 to 20 carbon atoms (e.g., naphthyl group); It is preferable that the group is one or more combinations selected from the group consisting of the following. 2 and R 3 It may be substituted with a group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, and halogen atoms. For example, halogen atoms include chlorine and bromine atoms.

[0082] R 2 and R 3Examples include alkyl groups, naphthyl groups, and phenyl groups having 1 to 10 carbon atoms, as well as groups in which the hydrogen atoms of alkyl groups, naphthyl groups, and phenyl groups having 1 to 10 carbon atoms are substituted with substituents (e.g., amino groups, hydroxyl groups, thiol groups, and chloro groups). Among these, R 2 and R 3 Preferably, alkyl groups having 1 to 10 carbon atoms and phenyl groups are used, and methyl groups and phenyl groups are more preferred.

[0083] The photosensitive resin composition of this embodiment contains component (D), which includes the nitrosamine compound represented by the above general formula (II), and thus has excellent sensitivity, resolution, and adhesion.

[0084] Any compound having a nitroso structure represented by the above general formula (I) and any nitrosamine compound represented by the above general formula (II) can be used as component (D) without any particular limitations. Examples of component (D) include N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodipropylamine, N-nitrosodibutylamine, N-nitrosodiethanolamine, N-nitrosodiisopropanolamine, N-nitroso-N-methylaniline, N-nitrosodiphenylamine, N,N-diethyl-N-nitrosoaniline, 5-nitroso-8-quinolinol, 1-nitroso-2-naphthol, and 2-nitroso-1-naphthol, which may be used individually or in combination of two or more. Among these, N-nitrosodiphenylamine and 1-nitroso-2-naphthol are preferred from the viewpoint of resolution and adhesion.

[0085] Component (D) may further include, in addition to compounds having a nitroso structure represented by the above general formula (I) and nitrosamine compounds represented by the above general formula (II), at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton. The photosensitive resin composition of this embodiment is superior in resolution and adhesion because component (D) contains at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton.

[0086] Compounds selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having phenothiazine and phenoxazine skeletons include, for example, hydroquinone, catechol, 4-tert-butylcatechol, pyrogallol, gallic acid, methyl gallate, phenothiazine, and phenoxazine. Among these, 4-tert-butylcatechol and phenothiazine are preferred. These compounds may be used individually or in combination of two or more.

[0087] The total content of component (D) in the photosensitive resin composition is preferably 0.001 to 2% by mass, more preferably 0.01 to 1% by mass, and particularly preferably 0.02 to 0.5% by mass, relative to the total solid content in the photosensitive resin composition. From the viewpoint of imparting good resolution and adhesion to the photosensitive resin composition, the total content of component (D) in the photosensitive resin composition is preferably above the lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably below the upper limit.

[0088] <<Other ingredients>> The photosensitive resin composition may optionally contain antioxidants, leuco dyes, base dyes, color-developing dyes, plasticizers, hindered amine compounds, carboxybenzotriazoles, and the like.

[0089] Examples of antioxidants include triphenyl phosphite (e.g., ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., ADEKA, trade name: 2112), tris(mononylphenyl) phosphite (e.g., ADEKA, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., ADEKA, trade name: 329K).

[0090] The antioxidant content in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, relative to the total solid content in the photosensitive resin composition. From the viewpoint of exhibiting good color stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, the antioxidant content is preferably above the lower limit. On the other hand, from the viewpoint of exhibiting good color stability while suppressing the color development of the resist pattern and improving adhesion, it is preferably below the upper limit.

[0091] Examples of base dyes include Diamond Green [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsine [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2]. Among these, diamond green is preferred from the viewpoint of improving colorability, hue stability, and exposure contrast.

[0092] The base dye content in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and even more preferably 0.04 to 1% by mass, based on the total solid content mass in the photosensitive resin composition. From the viewpoint of obtaining good colorability, the base dye content is preferably above the lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably below the upper limit.

[0093] As for color-developing dyes, for example, combinations of leuco dyes and halogen compounds are known. Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leucocrystal violet], bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green], and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane. As a leuco dye, the above-mentioned leucocrystal violet, or what is called diamond green, may be used.

[0094] Examples of additives such as plasticizers include phthalate esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

[0095] Examples of hindered amine compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine, 2,2,6,6-tetramethylpiperidyl methacrylate, and 1,2,2,6,6-pentamethylpiperidyl methacrylate. From the viewpoint of improving the flexibility and peelability of the cured film after the crosslinking reaction, it is preferable that the hindered amine compound has a monofunctional polymerizable group, and 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are particularly preferred.

[0096] The ratio of the hindered amine compound to the total solid content of the photosensitive resin composition is preferably 0.001 to 10% by mass. From the viewpoint of excellent peelability, this ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, from the viewpoint of improving resolution, this ratio is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0097] Examples of carboxybenzotriazoles include carboxybenzotriazole (e.g., manufactured by Chiyoda Chemical, trade name: Thiolite F-888). The content of carboxybenzotriazoles is 0.01% by mass or more and 5% by mass or less, based on the total solid content of the photosensitive resin composition.

[0098] <<Formulation of photosensitive resin composition>> A preparation solution for producing a photosensitive resin composition can be prepared by adding a solvent to the photosensitive resin composition. Examples of solvents include ketones such as acetone and methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. The solvent can be added to the photosensitive resin composition so that the viscosity of the preparation solution is 500 to 4000 mPa·sec at 25°C. Viscosity is measured at 25°C using a Brookfield viscometer (Eikohsha, model number DVNext).

[0099] [Method for producing a photosensitive resin composition] A further embodiment of this embodiment is: The following components: (A) Alkali-soluble polymer; (B) Compounds having ethylenically unsaturated bonds; (C) polymerization initiator; and (D) A polymerization inhibitor; a method for producing a photosensitive resin composition (hereinafter referred to as the method for producing a photosensitive resin composition of this embodiment), The aforementioned component (D) is given by the following general formula (I): [ka] [In formula (I), R 1 This is a hydrocarbon group which may have substituents, NHR 4 or NR 4 R 5 Show, R 4 and R 5 Each of these is independently a hydrocarbon group which may have substituents. Includes compounds having a nitroso structure as shown, This is a method for producing a photosensitive resin composition. In one embodiment, the content of component (C) in the method for producing the photosensitive resin composition of this embodiment is 3.5% by mass or more relative to the total solid content of the photosensitive resin composition.

[0100] In one embodiment, component (D) relating to the method for producing the photosensitive resin composition of this embodiment is the following general formula (II): [ka] [In formula (II), R 2 and R 3 Each of these is independently a hydrocarbon group which may have substituents. The compound includes the nitrosamine compound represented by [ ].

[0101] In one embodiment, component (D) in the method for producing the photosensitive resin composition of this embodiment further comprises at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton. The components (A), (B), (C), and (D) in the method for producing the photosensitive resin composition of this embodiment are the same as described above.

[0102] [Photosensitive resin laminate] A further embodiment of this embodiment is: Support film and A photosensitive resin layer obtained by exposing the above photosensitive resin composition, It is a photosensitive resin laminate that has the following features.

[0103] The thickness of the photosensitive resin layer is preferably 3 to 100 μm, with a more preferable upper limit of 50 μm. Resolution tends to improve as the thickness of the photosensitive resin layer approaches 3 μm, and film strength tends to improve as it approaches 100 μm, so it can be appropriately selected depending on the application.

[0104] In this embodiment, the transmittance at a wavelength of 405 nm at a photosensitive resin layer thickness of 25 μm is preferably 35% or more, more preferably 50% or more, and even more preferably 60% or more. The transmittance at a wavelength of 405 nm in a photosensitive resin layer with a thickness of 25 μm can be controlled, for example, by the content and / or type of component (C). For example, the transmittance can be easily increased by reducing the content of component (C) and / or by using a component (C) with a low absorption coefficient at a wavelength of 405 nm.

[0105] Support film The support film is preferably a layer or film for supporting the photosensitive resin layer, and is transparent to allow active light to pass through.

[0106] Examples of films include transparent films made from synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Polyethylene terephthalate (PET), which has moderate flexibility and strength, is generally preferred. Among these, it is preferable to use a high-quality film with minimal internal impurities. Specifically, it is more preferable to use high-quality films such as PET films synthesized using titanium (Ti)-based catalysts, PET films with small lubricant diameters and low lubricant content, PET films containing lubricant on only one side, thin-film PET films, PET films with smoothing treatment on at least one side, or PET films with roughening treatment such as plasma treatment on at least one side. This makes it easier to improve the resolution of the photosensitive resin laminate. At least one side of the support film may be subjected to a smoothing process using a calender or the like.

[0107] The thickness of the support film is preferably 5 to 25 μm, and more preferably 6 to 20 μm. The thinner the support film, the fewer internal foreign matter particles there are, and therefore it is easier to prevent a decrease in resolution. If the film thickness is 5 μm or more, it is easier to prevent stretching deformation in the winding direction due to tension and tearing due to minute scratches during the coating and winding manufacturing process, and it is also easier to ensure the strength of the film, thus making it easier to prevent wrinkles during lamination.

[0108] The haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01% to 0.95%, from the viewpoint of improving the parallelism of the light rays irradiated onto the photosensitive resin layer, thereby making it easier to obtain high resolution after exposure and development of the photosensitive resin laminate.

[0109] ≪Protective Film≫ The photosensitive resin laminate may include a support film, a photosensitive resin layer, and a protective film. The protective film is laminated on the side of the photosensitive resin layer opposite the support film and functions as a cover for the photosensitive resin layer.

[0110] If the adhesion force between the photosensitive resin layer and the protective film is sufficiently smaller than the adhesion force between the photosensitive resin layer and the support film, the protective film can be easily peeled off the photosensitive resin layer. Examples of preferred protective films include polyethylene film, polypropylene film, stretched polypropylene film, and polyester film.

[0111] A release layer can be applied to the surface of the protective film to allow for easy peeling of the protective film from the photosensitive resin layer. Release layers are classified, for example, into silicone compounds and non-silicone compounds.

[0112] Examples of silicone compounds include condensation-type silicone resins obtained by reacting terminally silanol polydimethylsiloxane with polymethylhydrogensiloxane or polymethylmethoxysiloxane; Addition-type silicone resin obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; UV-curable or electron-beam-curable silicone resins, such as acrylic silicone and epoxy group-containing silicone, that are cured with ultraviolet light or electron beams; Examples of modified silicone resins include epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acrylic), phenol-modified silicone resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), and melamine-modified silicone resin (silicone melamine).

[0113] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0114] The thickness of the release layer is preferably 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 is below the above upper limit, the appearance of the coating film tends to be good, and the coating film is easier to cure sufficiently. On the other hand, if the thickness is above the above lower limit, it is easier to ensure sufficient release properties.

[0115] The thickness of the protective film is preferably 10 to 100 μm, and more preferably 10 to 50 μm. Examples of protective films include Alphan® EM-501, E-200, E-201F, FG-201, MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Trefan® KW37, 2578, 2548, 2500, YM17S, Therapiel® PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, SY (all manufactured by Toray Industries, Inc.), GF-18, GF-818, GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0116] [Method for manufacturing photosensitive resin laminates] A further aspect of this embodiment is a method for manufacturing a photosensitive resin laminate. A photosensitive resin laminate can be manufactured by laminating a photosensitive resin layer and, if necessary, a protective film onto a support film. A manufacturing method, for example, is as follows: A process to obtain a photosensitive resin composition preparation solution (coating solution) by mixing the photosensitive resin composition with a solvent that dissolves them. A process of applying a coating liquid to a support film using a bar coater or roll coater, and then drying it to form a photosensitive resin layer on the support film. If necessary, a step of laminating a protective film onto the photosensitive resin layer. It can have.

[0117] [Roll (Photosensitive resin roll)] A further embodiment of this invention is a photosensitive resin roll formed by winding a photosensitive resin laminate. The roll may or may not have a core material. The long photosensitive resin laminate may be wound around a core material, or it may be wound without a core material.

[0118] [Method for forming a resist pattern] A further embodiment of this embodiment is: A method for forming a resist pattern using the above-mentioned photosensitive resin laminate, The following steps: The process of laminating a photosensitive resin laminate onto a substrate (lamination process); A step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate (exposure step); and A step of developing the photosensitive resin layer after exposure (development step); This is a method for forming a resist pattern, including [a specific element].

[0119] <Lamination process> In the lamination process, after peeling off the protective film from the photosensitive resin laminate, the photosensitive resin layer is heat-pressed onto the surface of a support (e.g., a substrate) using a laminator, and laminated once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is, for example, 40°C to 160°C. Heat pressing can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and photosensitive resin layer through the rolls several times. Heat pressing can be performed under reduced pressure if desired.

[0120] <Exposure process> In the exposure process, the photosensitive resin layer is exposed to active light using an exposure machine. Exposure can be performed after removing the support film, if desired, or without removing the support film. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, which may be measured using a light meter. Direct imaging exposure may also be performed in the exposure process. In direct imaging exposure, exposure is performed directly on the substrate using a writing device without using a photomask. A semiconductor laser with a wavelength of 350 to 410 nm or an ultra-high pressure mercury lamp is used as the light source. When the writing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0121] The light irradiation method used in the exposure process is preferably at least one method selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and more preferably projection exposure or direct imaging exposure.

[0122] A heating step may be included between the exposure step and the development step. The heating temperature is preferably 30 to 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By performing the heating step, it is easier to improve resolution and adhesion. Examples of heating methods include heating furnaces using hot air, infrared rays, or far infrared rays, as well as constant temperature baths, hot plates, hot air dryers, infrared dryers, and hot rolls.

[0123] The elapsed time from the exposure process to the heating process, for example, the elapsed time from the point when exposure is stopped to the point when heating is started, is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds. The elapsed time from the start of heating to the point when heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.

[0124] <Developing process> In the development process, unexposed areas (non-pattern areas) of the photosensitive resin layer after exposure are removed using a developing device and developing solution. If there is a support film on the photosensitive resin layer after exposure, it is peeled off. Subsequently, the exposed areas are developed (removed) using a developing solution containing an alkaline aqueous solution, thereby obtaining a resist image (resist pattern).

[0125] Preferred alkaline aqueous solutions include aqueous solutions of Na2CO3, K2CO3, and tetramethylammonium hydroxide. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, for example, an aqueous solution of Na2CO3 with a concentration of 0.2 to 2% by mass. Surface surfactants, defoamers, small amounts of organic solvents to promote development may be mixed into the alkaline aqueous solution. The temperature of the developer solution during the development process is preferably maintained within the range of 20 to 40°C.

[0126] The development process preferably includes a step (washing step) in which, after developing (removing) the exposed area, the developer solution contained in the resist pattern is removed with washing water. The washing water is selected according to the characteristics of the photosensitive resin layer, such as pure water or industrial water, and may contain, for example, 0.001 to 1 mass% of a polyvalent metal salt such as MgSO4, from the viewpoint of improving resolution and the rectangularity of the resist pattern. The temperature of the washing water in the washing step is preferably maintained within the range of 20 to 40°C.

[0127] After obtaining the resist pattern, the process may optionally include a step of further heating it to 60°C to 300°C (heating step). This heating step makes it easier to improve the chemical resistance of the resist pattern. A heating furnace using hot air, infrared rays, or far-infrared rays can be used for the heating step.

[0128] [Manufacturing method for wiring boards] It is also possible to manufacture a wiring board using the photosensitive resin composition according to this embodiment. In one embodiment, the method for manufacturing a wiring board involves the following steps: A conductor pattern formation step involves etching or plating a substrate on which a resist pattern has been formed to form a conductor pattern; and A peeling process to remove the resist pattern from the substrate; Includes.

[0129] <Conductor pattern formation process> As described above, the substrate on which the resist pattern has been formed may be subjected to an etching or plating process (etching or plating process) if necessary. This makes it easier to form wiring patterns (conductor patterns) corresponding to the resist pattern on the substrate. In other words, a further aspect of this embodiment is a method for manufacturing a conductor pattern.

[0130] A method for manufacturing a conductor pattern involves, for example, using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern on the substrate by the above method, and then manufacturing the desired conductor pattern. An etching or plating process is then performed on the substrate surface (e.g., copper surface) that is exposed by developing (removing) the exposed area.

[0131] Etching is performed, for example, by spraying an etching solution onto the resist pattern and the substrate surface. Examples of etching methods include acid etching and alkaline etching. Examples of etching solutions include aqueous hydrochloric acid solution, aqueous ferric chloride solution, or mixtures thereof.

[0132] Plating is performed by developing (removing) the exposed substrate portion according to known plating methods, and then applying metal plating (for example, metal plating with copper sulfate plating solution) or solder plating to that portion.

[0133] <Peeling process> After manufacturing the conductor pattern using the method described above, a step (exfoliation step) may be performed to peel the resist pattern from the substrate using an aqueous solution that is more alkaline than the developer. This makes it possible to obtain a wiring board (for example, a printed circuit board) having the desired conductor pattern.

[0134] Examples of the alkaline aqueous solution used for stripping (hereinafter also referred to as "stripping solution") include an aqueous solution of 2-5% by mass of NaOH or KOH, or an organic amine-based stripping solution. A small amount of water-soluble solvent may be mixed into the stripping solution. Examples of water-soluble solvents include alcohols. The temperature of the stripping solution in the stripping process is preferably in the range of 40-70°C.

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

[0136] This embodiment will be described with reference to examples and comparative examples. This embodiment is not limited to the following examples. The examples and comparative examples were prepared by the following methods, and the physical properties of the examples and comparative examples were measured by the following methods.

[0137] [Examples 1-19 and Comparative Examples 1-4 (evaluation samples)] <Preparation of photosensitive resin composition and photosensitive resin laminate> The materials shown in Tables 1 and 2 were mixed according to the composition shown in Table 3 (wherein the numbers for each component indicate the amount (parts by mass) of solids). Ethanol was then added to achieve a solids concentration of 60% by mass, and the mixture was thoroughly stirred and mixed to obtain a preparation containing the photosensitive resin composition (Examples and Comparative Examples). As a support film, this mixture was uniformly applied to the surface of a 16 μm thick polyethylene terephthalate film (Toray Industries, Inc., QS71) using a bar coater, and dried in a 95°C dryer for 2 minutes and 30 seconds to form a 25 μm thick photosensitive resin layer. Next, a 19 μm thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) was laminated as a protective film onto the surface where the support film for the photosensitive resin layer was not laminated, to obtain a photosensitive resin laminate (Examples and Comparative Examples).

[0138] The weight-average molecular weight of component (A) was determined by measuring it using gel permeation chromatography (GPC) and then converting it using a calibration curve for standard polystyrene. The GPC conditions are as follows: (GPC conditions) Pump: JASCO PU-980 Columns: A total of 2 columns as follows Shodex KF-80Y / KF-806M Eluent: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: RI-1530, manufactured by JASCO Corporation In this specification, "weight-average molecular weight (Mw)" was measured according to the above method.

[0139] [Measurement and Evaluation] <Transmittance per 25 μm of photosensitive resin layer at a wavelength of 405 nm> After removing the protective film from the photosensitive resin laminate, the transmittance of the photosensitive resin layer at a wavelength of 405 nm was measured using a U-3010 spectrophotometer (manufactured by Hitachi High-Technologies Corporation), with a polyethylene terephthalate film (support film) as a reference. The measurement was performed with a slit of 4 nm and a scan speed of 600 nm / min.

[0140] <Absorbance per 1 μm of photosensitive resin layer at a wavelength of 405 nm> After removing the protective film from the photosensitive resin laminate, the absorbance of the photosensitive resin layer at a wavelength of 405 nm was measured using a U-3010 spectrophotometer (manufactured by Hitachi High-Technologies Corporation), with a polyethylene terephthalate film (support film) as a reference. The measurement was performed with a slit size of 4 nm and a scan speed of 600 nm / min. The absorbance per 1 μm thickness was obtained by dividing the absorbance of the photosensitive resin layer by the thickness of the photosensitive resin layer.

[0141] [Fabrication of evaluation boards] <Surface> As a substrate, a 0.4 mm thick copper-clad laminate was prepared by laminating 18 μm thick rolled copper foil. The surface was washed with a 10 mass% H2SO4 aqueous solution, and then washed with pure water.

[0142] <Laminate> The copper-clad laminate, which had undergone the surface preparation described above, was preheated to 50°C. Subsequently, while peeling off the polyethylene film (protective film) from the photosensitive resin laminate, the photosensitive resin laminate was laminated using a hot roll laminator (Asahi Kasei Corporation, AL-700) at a roll temperature of 105°C so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate, thereby fabricating an evaluation substrate. The air pressure during lamination was 0.35 MPa, and the lamination speed was 1.5 m / min.

[0143] <Exposure> Two hours after lamination, the evaluation substrate was exposed using a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.). The exposure was performed using a predetermined direct imaging (DI) exposure pattern.

[0144] <Heating> One minute after exposure, the evaluation substrate was heated for 30 seconds in a forced-air constant-temperature incubator (DKM600, manufactured by Yamato Scientific Co., Ltd.) set to 60°C.

[0145] <Developing> The polyethylene terephthalate film (support film) was peeled off the photosensitive resin layer to expose it. Then, using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., for dry film), a 1% by mass Na2CO3 aqueous solution at 30°C was sprayed onto the photosensitive resin layer (spray pressure 0.15 Pa), and development was carried out for a predetermined time.

[0146] In the following evaluations of adhesion and resolution, the development and exposure conditions were defined as follows.

[0147] <Developing conditions> An evaluation substrate was prepared after completing the lamination process described above. The development process was then performed without the exposure and heating processes described above, and the "shortest development time," which is the shortest time required for the photosensitive resin layer in the unexposed areas to completely dissolve, was measured. In the evaluation of adhesion, resolution, and optimal exposure described below, the time for developing spray and the time for rinsing with water after development were set to twice the shortest development time for each.

[0148] <Exposure conditions; optimal exposure> An evaluation substrate was prepared after completing the lamination process described above. Exposure was performed using a mask pattern (see Figure 1) with a line width (L) / space width (S) (hereinafter referred to as "L / S") of 8 / 8 (unit: μm). After the heating process described above, development was performed under the development conditions described above to form a pattern on the evaluation substrate. The line width of the formed pattern was measured using an observation image obtained at 100x magnification with an optical microscope. The exposure amount (unit: mJ) at which the line width was 8 μm was defined as the optimal exposure amount. A smaller value for the optimal exposure amount indicates higher sensitivity. Sensitivity is evaluated as follows: "Excellent" if the optimal exposure is 30mJ or more and 50mJ or less; "Good" if the optimal exposure is greater than 50mJ and 60mJ or less; and "Acceptable" if the optimal exposure is greater than 60mJ and 75mJ or less. In the resolution and adhesion evaluations below, the exposure was always set to the optimal exposure level.

[0149] [evaluation] <Adhesion> The evaluation was performed using a mask pattern (see Figure 1) with an L / S ratio of x / x (x = 1 to 15 (varying at 0.5 μm intervals)) (unit: μm). Specifically, the substrate that underwent the surface preparation and lamination processes described above was exposed to the optimal exposure using this mask pattern. Subsequently, a resist pattern was formed by performing the heating and development processes described above. This resist pattern was observed using an optical microscope at 100x magnification to obtain an image. In the observed image, the minimum line width in which the line portion (exposed portion) was formed without meandering or missing lines was defined as the adhesion line width (unit: μm). A smaller value indicates better adhesion.

[0150] Figure 1 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The unexposed area 1 has a predetermined width and extends in the X direction, and multiple such unexposed areas 1 are arranged in the width direction (Y direction) at predetermined intervals. In this embodiment, since the unexposed area 1 is removed after the <development> process, it is theoretically expected that by exposing the photosensitive resin layer based on the drawing pattern in Figure 1, a resist pattern with L / S corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0151] <Resolution> The evaluation was performed using a mask pattern (see Figure 2) with an L / S ratio of 3x / x (x = 1 to 15 (varying at 0.5 μm intervals)) (unit: μm). Specifically, a resist pattern was formed on a substrate that had undergone the above surface preparation and lamination processes by exposing it with the mask pattern at the optimal exposure dose, followed by the above heating and development conditions.

[0152] The resist pattern was observed using an optical microscope at 100x magnification to obtain an image. In the observed image, the minimum line width in which the line portions (exposed areas) did not show meandering or missing parts, and the space portions (unexposed areas) were removed without residue, was defined as the resolution line width (unit: μm). A smaller value indicates better resolution.

[0153] Figure 2 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100B, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The unexposed area 1 has a predetermined width and extends in the x direction, and multiple such unexposed areas 1 are arranged in the width direction (y direction) at predetermined intervals. By exposing the photosensitive resin layer based on the drawing pattern in Figure 2, it is theoretically expected that a resist pattern with L / S corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0154] The optimal exposure, adhesion, and resolution of Examples 1-11 and Comparative Examples 1-3 were evaluated using Evaluation A (balance between optimal exposure and adhesion) and Evaluation B (balance between optimal exposure and resolution). The value of evaluation A was defined as the optimal exposure value [mJ] × adhesion [μm]. The value of evaluation B was calculated as: optimal exposure value [mJ] × resolution [μm]. Grades A and B were evaluated according to the following criteria. Excellent: Both the A and B grade values ​​are 300 or less. Acceptable: Either the A or B rating value is between 300 and 350. Failure: Either the A or B rating value exceeds 350. Table 3-1 shows the evaluation results for optimal exposure, adhesion, and resolution for Examples 1-11 and Comparative Examples 1-3.

[0155] The optimal exposure, adhesion, and resolution of Examples 12-19 and Comparative Example 4 were evaluated using Evaluation A' (balance between optimal exposure and adhesion) and Evaluation B' (balance between optimal exposure and resolution). The value of evaluation A' was defined as the optimal exposure value [mJ] × adhesion [μm]. The value of evaluation B' was defined as the optimal exposure value [mJ] × resolution [μm]. Grades A' and B' were evaluated according to the following criteria. Excellent: Both the A' and B' ratings are 350 or less. Acceptable: Either the value of evaluation A' or B' is greater than 350 and 400 or less. Failure: Either the value of evaluation A' or B' exceeds 400. Table 3-2 shows the evaluation results for optimal exposure, adhesion, and resolution for Examples 12-19 and Comparative Example 4.

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3-1]

[0159] [Table 3-2]

[0160] The table above confirms that the example obtained better results compared to the comparative example in the evaluation items <sensitivity, adhesion, and resolution>. [Industrial applicability]

[0161] The present invention provides a photosensitive resin composition that enables the realization of a photosensitive resin layer with excellent desired properties (e.g., sensitivity, adhesion, and resolution). According to the photosensitive resin composition of the present invention, a photosensitive resin laminate with good sensitivity, adhesion, and resolution can be obtained. The present invention can be widely used in the resist pattern forming industry. [Explanation of Symbols]

[0162] 1: Unexposed area (unexposed portion) 10: Exposure area (exposure part) 100,100B:Drawing area L: Line S: Space

Claims

1. The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated bond; (C) polymerization initiator; and (D) A photosensitive resin composition comprising a polymerization inhibitor, The content of component (C) is 3.5% by mass or more relative to the total solid content of the photosensitive resin composition. The aforementioned component (D) is given by the following general formula (I): 【Chemistry 1】 [In formula (I), R １ This is a hydrocarbon group which may have substituents, NHR ４ Or NR ４ R ５ R ４ and R ５ Each of these is independently a hydrocarbon group which may have substituents. A photosensitive resin composition comprising a compound having a nitroso structure as shown.

2. The aforementioned component (D) is given by the following general formula (II): 【Chemistry 2】 [In formula (II), R ２ and R ３ Each of these is independently a hydrocarbon group which may have substituents. The photosensitive resin composition according to claim 1, comprising a nitrosamine compound represented by [the specified compound].

3. The photosensitive resin composition according to claim 1 or 2, wherein the component (D) further comprises at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton.

4. The aforementioned component (A) includes copolymer (A-1), The copolymer (A-1) comprises at least the following components: (a1) (meth)acrylic acid; and (a2) Hydroxyalkyl (meth)acrylate; A photosensitive resin composition according to claim 1 or 2, comprising a constituent unit derived from the above.

5. The photosensitive resin composition according to claim 1 or 2, wherein the absorbance at a wavelength of 405 nm per 1 μm of the photosensitive resin layer obtained using the above photosensitive resin composition is 0.004 to 0.0120.

6. The aforementioned component (C) is a biimidazole compound, and A photosensitive resin composition according to claim 1 or 2, comprising at least one selected from the group consisting of pyrazoline derivatives and anthracene derivatives.

7. The photosensitive resin composition according to claim 6, wherein the component (C) comprises the biimidazole compound and the anthracene derivative.

8. The photosensitive resin composition according to claim 6, comprising one or more of the above-mentioned component (C), wherein the ratio of absorbance at a wavelength of 405 nm to a wavelength of 400 nm in an ethanol solution (A405 nm / A400 nm) is 0.5 or more.

9. The following components: (A) Alkali-soluble polymer; (B) Compounds having an ethylenically unsaturated bond; (C) polymerization initiator; and (D) A method for producing a photosensitive resin composition comprising a polymerization inhibitor, The content of component (C) is 3.5% by mass or more relative to the total solid content of the photosensitive resin composition. The aforementioned component (D) is given by the following general formula (I): 【Transformation 3】 [In formula (I), R １ represents a hydrocarbon group which may have a substituent, NHR ４ or NR ４ R ５ ; R ４ and R ５ each independently represent a hydrocarbon group which may have a substituent.] Includes compounds having a nitroso structure as shown, A method for producing a photosensitive resin composition.

10. The aforementioned component (D) is given by the following general formula (II): 【Chemistry 4】 [In formula (II), R ２ and R ３ Each of these is independently a hydrocarbon group which may have substituents. A method for producing the photosensitive resin composition according to claim 9, comprising a nitrosamine compound represented by [the specified compound].

11. A method for producing a photosensitive resin composition according to claim 9 or 10, wherein the component (D) further comprises at least one compound selected from the group consisting of phenols having two or more phenolic hydroxyl groups, and compounds having a phenothiazine and phenoxazine skeleton.

Images