Photosensitive resin composition, photosensitive resin laminate, and method for forming resist patterns, etc.

Abstract

The present disclosure pertains to a photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator. The component (A) and the component (B) both include aromatic rings. The proportion of the aromatic rings in the component (A) is 0.0045 mol / g or more, and the proportion of the aromatic rings in the component (B) is 0.0017 mol / g or more. The component (A) contains a compound having a hydroxy group as a monomer component. The component (C) contains a biimidazole-based compound in an amount of 4.0 mass% or more with respect to the total amount of solid content in the photosensitive resin composition.

Description

[Technical Field]

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

[0002] Printed circuit 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 finally, the wiring pattern is formed on the substrate by removing the resist pattern.

[0003] In recent years, with the miniaturization and increased density of electronic devices, there has been a demand for the formation of finer wiring than before. Methods for manufacturing wiring boards that can meet these requirements include MSAP (Modified Semi Additive Process) and SAP (Semi Additive Process). Known photosensitive resin compositions include, for example, those described in Patent Documents 1 to 4. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2021 / 193232 [Patent Document 2] International Publication No. 2017 / 018053 [Patent Document 3] International Publication No. 2015 / 098870 [Patent Document 4] Japanese Patent Publication No. 2007-79474 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, conventional photosensitive resin compositions, including those described in Patent Documents 1-4, 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 capable of realizing a photosensitive resin layer with excellent desired properties. Furthermore, the object of this disclosure is to provide a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, and further, a method for manufacturing a photosensitive resin composition and a method for forming a resist pattern. [Means for solving the problem]

[0007] One aspect of the present invention is as follows: [1] The following ingredients: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator, A photosensitive resin composition comprising, Both component (A) and component (B) contain an aromatic ring, Of the components (A) mentioned above, the proportion of the aromatic ring is 0.0045 mol / g or more, Of the components (B) mentioned above, the proportion of the aromatic ring is 0.0017 mol / g or more. The above component (A) contains a compound having a hydroxyl group as a monomer component, The above-mentioned component (C) contains 4.0% by mass or more of a biimidazole compound, based on the total solid content of the photosensitive resin composition. Photosensitive resin composition. [2] The aforementioned component (A) has a proportion of styrene-derived constituent units of 51% by mass or more, based on the total mass of all its monomeric components. The photosensitive resin composition according to item 1, wherein component (B) contains 70% by mass or more of a compound having a bisphenol A type skeleton, based on the total amount of component (B). [3] The photosensitive resin composition according to item 1 or 2, wherein the proportion of the structural unit derived from styrene is 55% by mass or more based on the total mass of all monomer components of the component (A). [4] The photosensitive resin composition according to any one of items 1 to 3, wherein the component (B) contains 80% by mass or more of a compound having a bisphenol A type skeleton based on the total amount of the component (B). [5] The photosensitive resin composition according to any one of items 1 to 4, wherein the component (C) contains 5.0% by mass or more of an imidazole-based compound based on the total solid content of the photosensitive resin composition. [6] The photosensitive resin composition according to any one of items 1 to 5, wherein the component (C) contains 6.0% by mass or more of an imidazole-based compound based on the total solid content of the photosensitive resin composition. [7] The photosensitive resin composition according to any one of items 1 to 6, wherein the transmittance at a wavelength of 365 nm in the photosensitive resin layer 25 μm obtained using the photosensitive resin composition is 45% or more. [8] The photosensitive resin composition according to item 7, wherein the transmittance is 60% or more. [9] A support film, A photosensitive resin layer containing the photosensitive resin composition according to any one of items 1 to 8, A photosensitive resin laminate comprising:

[10] The photosensitive resin laminate according to item 9, wherein the transmittance at a wavelength of 365 nm in the photosensitive resin layer at a thickness of 25 μm is 45% or more.

[11] A roll formed by winding the photosensitive resin laminate according to item 9 or 10.

[12] The following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, A method for producing a photosensitive resin composition, comprising: Both the component (A) and the component (B) contain an aromatic ring, Among the component (A), a component (A) in which the proportion of the aromatic ring is 0.0045 mol / g or more is used, and Among the component (B), a component (B) in which the proportion of the aromatic ring is 0.0017 mol / g or more is used. A method for producing a photosensitive resin composition.

[13] A method for forming a resist pattern using the photosensitive resin laminate according to item 9 or 10, comprising the following steps: The following steps: A step of laminating the photosensitive resin laminate on a substrate; A step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate; and A step of developing the exposed photosensitive resin layer. A method for forming a resist pattern including these steps.

[0008] Aspects related to the present invention are as follows. [1A] The following components: (A) An alkali-soluble polymer, (B) A compound having an ethylenically unsaturated bond, and (C) A photoinitiator, A photosensitive resin composition comprising: Both the component (A) and the component (B) contain an aromatic ring, Among the component (A), the proportion of the structural unit derived from styrene is 51% by mass or more based on the total mass of all monomer components, and Among the component (B), the proportion of the compound having a bisphenol A type skeleton is 70% by mass or more based on the total amount of the component (B), and A photosensitive resin composition. [2A] Among the component (A), the proportion of the structural unit derived from styrene is 51% by mass or more based on the total mass of all monomer components, Among the component (B), the proportion of the compound having a bisphenol A type skeleton is 70% by mass or more based on the total amount of the component (B), and The photosensitive resin composition described in item 1A, wherein component (C) contains 4.0% by mass or more of a biimidazole compound based on the total solid content of the photosensitive resin composition. [3A] The photosensitive resin composition according to item 1A or 2A, wherein the component (A) has a proportion of styrene-derived constituent units of 55% by mass or more, based on the total mass of all monomer components. [4A] The photosensitive resin composition according to any one of items 1A to 3A, wherein the (B) component contains 80% by mass or more of a compound having a bisphenol A type skeleton, based on the total amount of the (B) component. [5A] The (C) component is a photosensitive resin composition according to any one of items 1A to 4A, comprising 5.0% by mass or more of a biimidazole compound based on the total solid content of the photosensitive resin composition. [6A] A photosensitive resin composition according to any one of items 1A to 5A, wherein the transmittance at a wavelength of 365 nm in a 25 μm photosensitive resin layer obtained using the above photosensitive resin composition is 45% or more. [7A] The photosensitive resin composition described in item 6A, wherein the transmittance is 60% or more. [8A] Support film and A photosensitive resin layer comprising a photosensitive resin composition described in any one of items 1A to 7A, A photosensitive resin laminate comprising the following features. [9A] The photosensitive resin laminate according to item 8A, wherein the transmittance of the photosensitive resin layer at a wavelength of 365 nm at a thickness of 25 μm is 45% or more. [10A] A roll formed by winding a photosensitive resin laminate as described in item 8A or 9A. [11A] The following components: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator, A method for producing a photosensitive resin composition, comprising: Both component (A) and component (B) contain an aromatic ring, Using component (A) in which the proportion of the aromatic ring is 0.0045 mol / g or more, Of the aforementioned component (B), component (B) is used in which the proportion of the aromatic ring is 0.0017 mol / g or more. A method for producing a photosensitive resin composition. [12A] A method for forming a resist pattern using a photosensitive resin laminate described in item 8A or 9A, The following steps: A process of laminating a photosensitive resin laminate onto a substrate; A step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate; and A step of developing the photosensitive resin layer after exposure; A method for forming a resist pattern, including [a specific component]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive resin composition that can realize a photosensitive resin layer with excellent desired properties. Furthermore, according to the present invention, it is possible to provide a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, and furthermore, a method for manufacturing a photosensitive resin composition and a method for forming a resist pattern. [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] [Photosensitive resin composition] This embodiment comprises the following components: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator, A photosensitive resin composition comprising, Both component (A) and component (B) contain an aromatic ring, Of the components (A) mentioned above, the proportion of the aromatic ring is 0.0045 mol / g or more, Of the components (B) mentioned above, the proportion of the aromatic ring is 0.0017 mol / g or more. It is a photosensitive resin composition. In particular, the photosensitive resin composition of this embodiment is The (A) component contains a compound having a hydroxyl group as a monomer component, and the (C) component contains 4.0% by mass or more of a biimidazole compound based on the total solid content of the photosensitive resin composition.

[0012] The inventors focused on ensuring that component (A) and component (B) each contain an aromatic ring in a predetermined proportion or greater. In this process, when a resist pattern is formed by exposure and development of a photosensitive resin composition, some of the composition may remain on the resulting resist pattern. For this reason, plasma treatment may be performed on the resist pattern formed after development in order to remove such residues (development residue). In this embodiment, the aromatic rings contained in components (A) and (B), respectively, contribute to improving the chemical stability of the photosensitive resin layer, and consequently, to improving plasma resistance. The proportion of aromatic rings in component (A) may be 0.0082 mol / g or less, and the proportion of aromatic rings in component (B) may be 0.0056 mol / g or less.

[0013] In particular, the following: The aforementioned component (A) has a proportion of styrene-derived constituent units of 51% by mass or more, based on the total mass of all its monomeric components. The aforementioned component (B) contains 70% by mass or more of a compound having a bisphenol A type skeleton, based on the total amount of component (B). A photosensitive resin composition that satisfies the above conditions is likely to exhibit the effects of this embodiment. Among compounds containing aromatic rings, compounds having a styrene and bisphenol A type skeleton are particularly effective at improving plasma resistance. Furthermore, by using compounds having a styrene and bisphenol A type skeleton, they can be readily introduced into a photosensitive resin composition as components (A) and (B), respectively. In a photosensitive resin composition, an increase in the proportion of aromatic rings tends to increase the resin viscosity, which can easily reduce the radical polymerization efficiency. In this case, it becomes possible to incorporate a larger amount of biimidazole-based compounds, thereby suppressing the decrease in sensitivity.

[0014] Furthermore, it is preferable that the transmittance at a wavelength of 365 nm in the 25 μm photosensitive resin layer obtained by exposing the photosensitive resin composition is 45% or more, and preferably 60% or more. This makes it easier to achieve good adhesion (adhesion between the photosensitive resin layer and the substrate). The combination of a sensitizer and a relatively large amount of biimidazole compound makes it easier to prevent a decrease in sensitivity. On the other hand, reducing the sensitizer is advantageous for improving transmittance, and it is also easier to design a composition in which the amount of biimidazole compound is further increased by the amount of sensitizer reduced. The photosensitive resin composition of this embodiment has a wide range of compositional design possibilities, that is, it is possible to achieve both sensitivity and adhesion.

[0015] Components (A), (B), and (C) can each be used individually or in combination of two or more. If the photosensitive resin composition contains components other than components (A), (B), and (C), such other components may also be used individually or in combination of two or more.

[0016] (A) Component: Alkali-soluble polymer

[0017] Component (A) is an alkali-soluble polymer. Component (A) preferably has a carboxyl group and, from the viewpoint of suitably exhibiting alkali solubility, preferably has an acid value of 50 to 600 mg KOH / g. The acid value of component (A) may be 60 mg KOH / g or more, 80 mg KOH / g or more, 500 mg KOH / g or less, or 400 mg KOH / g or less.

[0018] 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. 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.

[0019] (A) The proportion of aromatic rings in component (A) is 0.0045 mol / g or more. Having a proportion of aromatic rings of 0.0045 mol / g or more is preferable from the viewpoint of improving plasma resistance, more preferably 0.0050 mol / g or more, even more preferably 0.0053 mol / g, particularly preferably 0.0058 mol / g or more, even more preferably 0.0063 mol / g or more, and most preferably 0.0067 mol / g or more. Furthermore, from the viewpoint of improving developability, it is preferable to have a proportion of 0.0082 mol / g or less, even more preferably 0.0077 mol / g or less, and even more preferably 0.0067 mol / g or less. The aromatic ring may originate from the first monomer, the second monomer, or both the first and second monomers. However, it is preferable that the proportion of the aromatic ring originates from at least the second monomer, as this facilitates the realization of the desired component (A). The proportion of aromatic rings in component (A) can be calculated by taking the weighted average of the proportion of aromatic rings contained in each monomer component in component (A) by the content of each monomer component in component (A). The proportion of aromatic rings contained in each monomer component in component (A) can be calculated by (number of aromatic rings contained in one monomer molecule / molecular weight of the monomer).

[0020] (A) The component may have a proportion of styrene-derived constituent units of 40% by mass or more, based on the total mass of all its monomer components. Here, it is preferable that the proportion of constituent units derived from styrene in component (A) is 51% by mass or more, based on the total mass of all monomer components. This makes it easier to achieve the effects of this embodiment. From a similar viewpoint, it is more preferable that the proportion of constituent units derived from styrene is 52% by mass or more, 55% by mass or more, and 60% by mass or more, and even more preferable that it is 65% or more. The proportion of constituent units derived from styrene may be 85% by mass or less.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] <First monomer> 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 semi-ester. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of excellent adhesion and resolution. 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.

[0025] (A) The proportion of the first monomer in component (A) is preferably 10 to 50% by mass, based on the total mass of all monomer components. A proportion of 10% by mass or more is preferred from the viewpoint of excellent adhesion and resolution, more preferably 15% by mass or more, even more preferably 18% by mass or more, even more preferably 21% by mass or more, particularly preferably 23% by mass or more, and most preferably 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, even more preferably 29% by mass or less, particularly preferably 27% by mass or less, and most preferably 26% by mass or less.

[0026] <Second monomer> 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.

[0027] The second monomer preferably contains a compound having an aromatic ring. The proportion of this compound in component (A) is preferably 45 to 90% by mass, based on the total mass of all monomer components. A proportion of 45% by mass or more is preferred from the viewpoint of excellent adhesion and resolution, 50% by mass or more is more preferred, 55% by mass or more is even more preferred, 60% by mass or more is even more preferred, and 65% by mass or more is particularly preferred. A proportion of 90% by mass or less is preferred from the viewpoint of excellent developability, and 80% by mass or less is even more preferred.

[0028] 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, styrene is more preferred, and it is even more preferable to contain both styrene and benzyl (meth)acrylate.

[0029] The second monomer may contain a compound having an alicyclic ring. The proportion of this compound in component (A) may be 10 to 40% by mass, based on the total mass of all monomer components.

[0030] 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.

[0031] The second monomer may contain a compound having a hydroxyl group. The proportion of this 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.

[0032] 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). 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.

[0033] The second monomer is a compound other than those mentioned above, for example, Other examples include alkyl (meth)acrylates (chain alkyl esters and cyclic alkyl esters) other than those mentioned above, 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, epoxy group-containing monomers, etc.), crosslinkable monomers other than those mentioned above, and acid anhydrides other than those mentioned above.

[0034] <(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.

[0035] The percentage of component (A) may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total solid content mass of the photosensitive resin composition. It may also be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0036] (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.

[0037] (B) Component: Compound containing an ethylenically unsaturated bond Component (B) is a compound having an ethylenically unsaturated bond. (B) The proportion of aromatic rings in component (B) is 0.0017 mol / g or more. Having a proportion of aromatic rings of 0.0017 mol / g or more is preferable from the viewpoint of improving plasma resistance, more preferably 0.0019 mol / g or more, even more preferably 0.0021 mol / g, particularly preferably 0.0022 mol / g or more, even more preferably 0.0025 mol / g or more, and most preferably 0.0030 mol / g or more. Furthermore, from the viewpoint of improving developability, it is preferable to have a proportion of 0.0056 mol / g or less, even more preferably 0.0025 mol / g or less, and even more preferably 0.0022 mol / g or less. The aforementioned component (B) preferably contains 61% by mass or more of a compound having a bisphenol A type skeleton, based on the total amount of component (B). This makes it easier to achieve the effects of this embodiment. From a similar viewpoint, it is more preferable that the proportion of the compound having a bisphenol A type skeleton be 70% by mass or more, 75% by mass or more, and 80% by mass or more, even more preferable that it be 90% by mass or more, and most preferable that it be 100% by mass. Furthermore, in this specification, the concept of "compound having a bisphenol A type skeleton" also includes compounds that have been hydrogenated, i.e., compounds having a hydrogenated bisphenol A type skeleton.

[0038] Examples of compounds having a bisphenol A type skeleton include the following general formula (I): General formula (I) [ka] (In the formula, R 2 Each of these is independently a hydrogen atom or a methyl group, and X 2 O and Y 2 Each O is independently an oxyethylene group or an oxypropylene group, and each m3, m4, n2, and n3 are independently integers between 0 and 40, with m3 + m4 being between 1 and 40, and n2 + n3 being between 0 and 20. Examples include bisphenol A type di(meth)acrylate, represented by [formula].

[0039] Component (B) preferably contains a compound having two or more ethylenically unsaturated bonds in one molecule. The photosensitive resin composition may further 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 functions. A "(meth)acrylate compound with two or more functions" means a compound having two or more (meth)acryloyl groups in one molecule.

[0041] (B) Component is preferably a (meth)acrylate compound. The (meth)acrylate compound may include, for example, 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] 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, and tetramethylene glycoxified (hydrogenated) bisphenol A di(meth)acrylate.

[0043] Examples of commercially available bifunctional (meth)acrylate compounds include 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, 701, 2G, 3G, 4G, 9G, and 14G. , 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, NK Oligo® UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA (all manufactured by Shin Nakamura Chemical Industry 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 (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, FA-240 A, 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 Corporation), 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.), KAYARAD (registered trademark) Examples include 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.).

[0044] Examples of (meth)acrylate compounds with three or more functionalities 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.

[0045] 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.

[0046] Examples of commercially available (meth)acrylate compounds with three or more functionalities include 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, and 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, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (manufactured by Resonac Co., Ltd.), 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.), KAYARAD (registered trademark) Examples include 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.).

[0047] The content of trifunctional or more (meth)acrylate compounds 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).

[0048] Specifically, compounds that may be included in component (B) are: A polyethylene glycol dimethacrylate (FA-321M, product name) with an average of 5 moles of EO added to each end of a bisphenol A molecule. Dimethacrylate of polyethylene glycol, in which an average of 2 moles of EO are added to each end of bisphenol A; Dimethacrylate of polyalkylene glycol, which has an average of 12 repeating PO units per molecule, with an average of 3 moles of EO added to each end; These include (where "EO" is an abbreviation for ethylene oxide, and "PO" is an abbreviation for propylene oxide). In relation to the compound represented by the above general formula (I), for example, the above "FA-321M" is R 2 =methyl group, X 2 It is represented as O = oxyethylene group, m3 + m4 = 10, n2 = n3 = 0.

[0049] (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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] (C) Ingredient: Photopolymerization initiator Component (C) is a photopolymerization initiator. Photopolymerization initiators generate radicals when exposed to active light, which facilitates the polymerization of compounds containing ethylenically unsaturated bonds. The component (C) may contain 3.5% by mass or more of a biimidazole compound, based on the total solid content of the photosensitive resin composition. Here, the component (C) preferably contains 4.0% by mass or more of a biimidazole compound, more preferably 4.2% by mass or more, even more preferably 5.0% by mass or more, particularly preferably 6.0% or more, and most preferably 6.2% by mass or more, based on the total solid content of the photosensitive resin composition. This makes it easier to achieve the effects of this embodiment. Furthermore, the percentage of the biimidazole compound content may be 10% by mass or less, or 8.0% by mass or less, based on the total solid content of the photosensitive resin composition. (A) The component may have a proportion of styrene-derived constituent units of 40% by mass or more, based on the total mass of all its monomer components.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0061] 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.).

[0062] 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).

[0063] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0064] 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.

[0065] 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).

[0066] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0067] As pyrazoline derivatives, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred from the viewpoint of adhesion and rectangularity of the resist pattern.

[0068] 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.

[0069] 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.

[0070] The photosensitive resin composition preferably contains 0.01 to 20% by mass of component (C), and more preferably 0.5 to 10% 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 with which light can be transmitted to the bottom of the photosensitive resin layer, thereby making it easier to achieve high resolution.

[0071] If component (C) contains a biimidazole compound, the content of component (C) other than the biimidazole compound in the photosensitive resin composition may be 0.001 to 2.0% by mass, or 0.01 to 2.0% by mass, based on the total solid content mass in the photosensitive resin composition. The upper limit of this content may be 1.0% by mass, preferably 0.1% by mass, more preferably 0.053% by mass, and even more preferably 0.031% by mass. 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.

[0072] When component (C) includes a biimidazole compound, preferred components of (C) in the photosensitive resin composition other than the biimidazole compound include 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, ester compounds of N-aryl amino acids, and halogen compounds. Among these, aromatic ketone compounds, anthracene derivatives, and pyrazoline derivatives are particularly preferred. For these compounds, you may refer to the examples of compounds listed in the section "Component (C): Photopolymerization Initiator".

[0073] If the aforementioned component (C) contains a sufficient amount of a biimidazole compound, for example, if it contains 6.0% by mass or more of a biimidazole compound, then it is not necessary to include any other component (C) besides the biimidazole compound.

[0074] <<Other ingredients>> The photosensitive resin composition may optionally contain antioxidants, stabilizers, leuco dyes, base dyes, sensitizers, color-developing dyes, plasticizers, hindered amines, etc.

[0075] 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).

[0076] 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.

[0077] Examples of stabilizers include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and alkylene oxide compounds having a glycidyl group.

[0078] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, 4-tert-butylcatechol, phenothiazine, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salts (e.g., aluminum salts to which 3 moles of nitrosophenylhydroxylamine are added), and diphenylnitrosamines. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salts to which 3 moles of nitrosophenylhydroxylamine are added are preferred.

[0079] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0080] Benzotriazoles are preferably compounds having a carboxyl group, and examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole. Among these, a 1:1 mixture of 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole, and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole is preferred.

[0081] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2 molar adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.).

[0082] The total content of stabilizers in the photosensitive resin composition is preferably 0.001 to 3% by mass, and more preferably 0.05 to 1% by mass, relative to the total solid content in the photosensitive resin composition. From the viewpoint of providing good storage stability to the photosensitive resin composition, the total 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.

[0083] 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.

[0084] 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.

[0085] As color-developing dyes, for example, combinations of leuco dyes and halogen compounds are known. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [leucocrystal violet] and tris(4-dimethylamino-2-methylphenyl)methane [leucomalachite green]. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane. As leuco dyes, the above-mentioned leucocrystal violet and what is called diamond green may be used.

[0086] 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.

[0087] 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.

[0088] 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. The above hindered amine compound may be used as a repeating unit in component (A).

[0089] <<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.

[0090] [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.

[0091] 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.

[0092] In this embodiment, the transmittance at a wavelength of 365 nm at a photosensitive resin layer thickness of 25 μm is preferably 45% or more, more preferably 59% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 78% or more. The transmittance at a wavelength of 365 nm in a photosensitive resin layer with a thickness of 25 μm can be controlled, for example, by the content and / or type of photopolymerization initiator. For example, the transmittance can be easily increased by reducing the content of the photopolymerization initiator and / or by using a photopolymerization initiator with a low absorption coefficient at a wavelength of 365 nm.

[0093] 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.

[0094] 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 usually preferred. Among these, it is preferable to use a high-quality film with fewer internal impurities. Specifically, it is more preferable to use a PET film synthesized using a titanium (Ti)-based catalyst, a PET film with small lubricant diameter and low content, a PET film containing lubricant on only one side, a thin-film PET film, a PET film with a smoothing treatment on at least one side, or a PET film with a 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.

[0095] 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.

[0096] 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.

[0097] ≪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.

[0098] 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. Suitable protective films include, for example, polyethylene film, polypropylene film, stretched polypropylene film, and polyester film.

[0099] 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.

[0100] Examples of silicone compounds include condensation reaction type silicone resins obtained by reacting terminally silanol polydimethylsiloxane with polymethylhydrogen siloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogen siloxane; UV-curable or electron-beam-curable silicone resins obtained by curing acrylic silicone and epoxy group-containing silicone with ultraviolet light or electron beams; and modified silicone resins such as 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).

[0101] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0102] 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.

[0103] 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.).

[0104] [Method for fabricating photosensitive resin laminates] A further aspect of this embodiment is a method for producing 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. For example, the manufacturing method 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.

[0105] [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.

[0106] [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].

[0107] <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 by 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.

[0108] <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 as desired, or it can be performed 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 drawing 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 drawing 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.

[0109] 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.

[0110] A heating step may be included between the exposure step and the development step. The heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By implementing 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, hot rolls, etc.

[0111] 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.

[0112] <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).

[0113] Preferred alkaline aqueous solutions include those containing Na2CO3, K2CO3, or 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 is used. 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.

[0114] 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.

[0115] 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.

[0116] [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.

[0117] <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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] <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.

[0122] 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.

[0123] Photosensitive resin laminates may be used in the manufacture of printed circuit boards; lead frames for IC chip mounting; 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]

[0124] 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.

[0125] [(A) Synthesis] Solution (a) was prepared by mixing 28 g of methacrylic acid, 52 g of styrene, and 20 g of 2-hydroxyethyl methacrylate (copolymer component) with 0.8 g of azobisisobutyronitrile. 200 g of methyl ethyl ketone and 100 g of ethanol were added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. The flask was then stirred while blowing nitrogen gas into it, and the temperature was raised to 80°C. Solution (a) was added to the mixture in the flask dropwise at a constant rate over 4 hours, and the mixture was stirred at 80°C for 2 hours. Next, solution (b) was prepared by dissolving 0.5 g of azobisisobutyronitrile in 50 g of a mixture of 30 g of methyl ethyl ketone and 20 g of ethanol. Solution (b) was added to the solution in the flask dropwise at a constant rate over 10 minutes, and the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the solution in the flask was heated to 90°C over 30 minutes, maintained at 90°C for 2 hours, then the stirring was stopped and the solution was cooled to room temperature (25°C). This yielded a solution of alkali-soluble polymer A-1. Alkali-soluble polymers A-1 to A-12 were obtained by changing the amount of monomers added for each copolymer component according to the formulations shown in Table 4 and performing the same procedure. The weight-average molecular weights (Mw) of the obtained alkali-soluble polymers A-1 to A-12 are shown in Table 4.

[0126] The weight-average molecular weight was measured by gel permeation chromatography (GPC) and then converted 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)" and "polydispersion (Mw / Mn)" are measured according to the above.

[0127] [Evaluation sample] <Photosensitive resin compositions and photosensitive resin laminates, etc.> The components shown in the table (where the numbers for each component indicate the amount (parts by mass) as solid content) and the solvent (ethanol) were stirred and mixed until the solid content was 60% by mass, thereby obtaining a formulation containing the photosensitive resin composition (Examples and Comparative Examples). The abbreviations listed in Tables 1 to 3 correspond to the names listed in Table 4.

[0128] A 16 μm thick polyethylene terephthalate film (QS-68, manufactured by Toray Industries, Inc.) was used as the support film. The above-mentioned preparation solution was uniformly applied to the surface of the film using a bar coater, and then dried in a 95°C dryer for 3 minutes to form a photosensitive resin layer with a thickness of 25 μm. This yielded photosensitive resin laminates (Examples and Comparative Examples).

[0129] Next, a 19 μm thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) was laminated as a protective film onto the surface of the photosensitive resin layer that did not have a support film attached. In other words, a photosensitive resin laminate with a protective film was fabricated.

[0130] <Photosensitive layer transmittance> After removing the protective film from the above-mentioned photosensitive element, the transmittance of the photosensitive resin layer at a wavelength of 365 nm was measured using a U-3010 spectrophotometer (manufactured by Hitachi High-Technologies Corporation) with a 16 μm thick polyethylene terephthalate film (support film, manufactured by Toray Industries, Inc., QS-68) as a reference. The measurement was performed with a slit of 4 nm and a scan speed of 600 nm / min.

[0131] <Evaluation board> A 0.4 mm thick copper-clad laminate was prepared by laminating 35 μm rolled copper foil. The surface of the substrate was then jet-scrubbed using an abrasive (manufactured by Uji Denki Kagaku Kogyo Co., Ltd., #400) at a spray pressure of 0.2 MPa. After polishing, the surface of the substrate was washed with a 10 mass% H2SO4 aqueous solution and then with water. The washed substrate was used as the evaluation substrate.

[0132] <Laminate> While peeling off the protective film from the photosensitive resin laminate, the photosensitive resin laminate was laminated onto an evaluation substrate preheated to 50°C using a hot roll laminator (Asahi Kasei Corporation, AL-700) at a roll temperature of 105°C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m / min.

[0133] <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. Here, the evaluation substrate, one minute after exposure, was heated for 30 seconds in a forced-air constant-temperature incubator (DKM600, manufactured by Yamato Scientific Co., Ltd.) set to 60°C.

[0134] <Developing> The support film was peeled off the photosensitive resin layer, exposing the layer. 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 for a predetermined time, thereby performing development. After development, the photosensitive resin layer was washed with water by spraying for a predetermined time. The development (spraying) time and the washing (spraying) time were both set to twice the shortest development time. After development, further washing with water spray was performed, and the washing time was set to twice the shortest development time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was treated as the "shortest development time".

[0135] [evaluation] <Plasma resistance> The photosensitive resin layer was exposed using a 41-step step tablet with an exposure dose that resulted in a maximum of 15 remaining layers. The developed photosensitive resin layer was then subjected to plasma etching for 1000 seconds using a plasma etching device (EXAM, manufactured by Shinko Seiki Co., Ltd.). The processing was performed with an output of 133W and 40cm³ of O2 gas. 3 / min, CF4 gas at 41cm 3 The test was performed at a rate of / min and a pressure of 50 Pa.

[0136] Subsequently, the arithmetic mean roughness (Ra) of the surface of the photosensitive resin layer was measured using a laser microscope (LEXT OLS4100, manufactured by Olympus Corporation). The arithmetic mean roughness (Ra) was measured at three different locations on the surface within a standard length of 100 μm, and the average value of these measurements was calculated. The resulting average value was used as an indicator of plasma resistance and evaluated according to the following criteria. Since plasma treatment can cause damage to the photosensitive resin layer, resulting in surface irregularities, a smaller arithmetic mean roughness (Ra) indicates better plasma resistance. Evaluation criteria: E: ◎ (Excellent) Arithmetic mean roughness (Ra) is less than 1.5 μm G: ○ (Good) The arithmetic mean roughness (Ra) is 1.5 μm or more and less than 3.0 μm P: × (Bad) The arithmetic mean roughness (Ra) is 3.0 μm or more

[0137] <Sensitivity> In the above <Exposure> process, exposure was performed using a 41-step stoper tablet as a mask, and the exposure amount at which the maximum remaining film step number became 15 steps when developed thereafter was determined. Based on the obtained exposure amount, evaluation was performed according to the following criteria. The smaller the value of the exposure amount, the higher the sensitivity. Evaluation criteria: E: ◎ (Extremely good) The above exposure amount is less than 160 mJ / cm 2 Less than G: ○ (Good) The above exposure amount is 160 mJ / cm or more 2 and less than 200 mJ / cm 2 P: × (Bad) The above exposure amount is 200 mJ / cm or more 2 More than

[0138] <Adhesion> Evaluation was performed using a mask pattern with a line / space (L / S) of x / 3x {x = 1 to 20 (changing at 1 μm intervals), unit: μm}. That is, the evaluation substrate after the above lamination was exposed with an exposure amount at which the maximum remaining film step number became 15 steps using the mask pattern and a 41-step stoper tablet, and then developed to form a resist pattern. By observing this resist pattern with an optical microscope at a magnification of 50 times, an observation image was obtained. In the observation image, the minimum line width formed without meandering and chipping in the line portion (exposed portion) was determined. This line width was treated as an index of adhesion and evaluated according to the following criteria. The smaller the value of the adhesion, the better the adhesion. Evaluation criteria: E: ◎ (Extremely good) Adhesion is less than 6 μm G: ○ (Good) Adhesion is 6 μm or more and less than 9 μm P: × (Bad) Adhesion is 9 μm or more

[0139]

Table 1

[0140] [Table 2]

[0141] [Table 3]

[0142] [Table 4]

[0143] In the table, "(A) Aromatic ring in component (A)" refers to the proportion of aromatic rings in component (A); "(B) Aromatic rings in component (B)" refers to the proportion of aromatic rings in component (B); "St / (A) component" is the proportion of constituent units derived from styrene, based on the total mass of all monomeric components of (A); "BisA / (B) component" refers to the proportion of compounds having a bisphenol A type skeleton, based on the total amount of component (B); "Component C-1 / Composition" refers to the proportion of imidazole compounds based on the total solid content of the photosensitive resin composition; Each has its own meaning.

[0144] The table above confirms that the example obtained better results in the evaluation item <plasma resistance> compared to the comparative example. Furthermore, the photosensitive resin laminate of the example could be wound by conventional methods; that is, a roll could be suitably manufactured using the laminate. [Industrial applicability]

[0145] The present invention provides a photosensitive resin composition that enables the realization of a photosensitive resin layer with excellent desired properties (e.g., plasma resistance). According to the photosensitive resin composition of the present invention, a photosensitive resin laminate can be obtained that exhibits good plasma resistance and, in some cases, good sensitivity and adhesion. The present invention can be widely used in industries that form resist patterns.

Claims

1. The following ingredients: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator, A photosensitive resin composition comprising, Both component (A) and component (B) contain an aromatic ring, Of the components (A) mentioned above, the proportion of the aromatic ring is 0.0045 mol / g or more, Of the components (B) mentioned above, the proportion of the aromatic ring is 0.0017 mol / g or more. The above component (A) contains a compound having a hydroxyl group as a monomer component, The above-mentioned component (C) contains 4.0% by mass or more of a biimidazole compound based on the total solid content of the photosensitive resin composition. Photosensitive resin composition.

2. The aforementioned component (A) has a proportion of styrene-derived constituent units of 51% by mass or more, based on the total mass of all its monomeric components. The photosensitive resin composition according to claim 1, wherein component (B) contains 70% by mass or more of a compound having a bisphenol A type skeleton, based on the total amount of component (B).

3. The photosensitive resin composition according to claim 1, wherein the proportion of constituent units derived from styrene is 55% by mass or more, based on the total mass of all monomeric components of component (A).

4. The photosensitive resin composition according to claim 3, wherein component (B) contains 80% by mass or more of a compound having a bisphenol A type skeleton, based on the total amount of component (B).

5. The photosensitive resin composition according to claim 1, wherein component (C) contains 5.0% by mass or more of a biimidazole compound based on the total solid content of the photosensitive resin composition.

6. The photosensitive resin composition according to claim 1, wherein component (C) contains 6.0% by mass or more of a biimidazole compound based on the total solid content of the photosensitive resin composition.

7. The photosensitive resin composition according to claim 1, wherein the transmittance at a wavelength of 365 nm in a 25 μm photosensitive resin layer obtained using the above photosensitive resin composition is 45% or more.

8. The photosensitive resin composition according to claim 7, wherein the transmittance is 60% or more.

9. Support film and A photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 8, A photosensitive resin laminate comprising the following features.

10. The photosensitive resin laminate according to claim 9, wherein the transmittance of the photosensitive resin layer at a wavelength of 365 nm at a thickness of 25 μm is 45% or more.

11. A roll formed by winding the photosensitive resin laminate described in claim 9.

12. The following components: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator, A method for producing a photosensitive resin composition, comprising: Both component (A) and component (B) contain an aromatic ring, Using component (A) in which the proportion of the aromatic ring is 0.0045 mol / g or more, Using component (B) in which the proportion of the aromatic ring is 0.0017 mol / g or more, The above component (A) contains a compound having a hydroxyl group as a monomer component, The aforementioned component (C) contains 4.0% by mass or more of a biimidazole compound, based on the total solid content of the photosensitive resin composition. A method for producing a photosensitive resin composition.

13. A method for forming a resist pattern using the photosensitive resin laminate described in claim 9, The following steps: A process of laminating a photosensitive resin laminate onto a substrate; A step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate; and A step of developing the photosensitive resin layer after exposure; A method for forming a resist pattern, including [a specific component].

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