Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, and like

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

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

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

[0002] Printed wiring boards are generally manufactured using a photolithography process. Photolithography is a method of forming a desired wiring pattern on a substrate by 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; then, a conductor pattern is formed on the substrate by etching or plating; and then, the resist pattern is removed to form a wiring pattern on the substrate.

[0003] In recent years, the miniaturization and increased density of electronic devices have led to a demand for the formation of finer wiring than ever before. Methods for manufacturing wiring boards that meet such demands include the modified semi-additive process (MSAP) and the semi-additive process (SAP). Known photosensitive resin compositions include those described in Patent Documents 1 to 4, for example.

[0004] International Publication No. 2021 / 193232 International Publication No. 2017 / 018053 International Publication No. 2015 / 098870 Japanese Patent Application Laid-Open No. 2007-79474

[0005] However, conventional photosensitive resin compositions such as those described in Patent Documents 1 to 4 still have room for improvement in terms of improving various properties.

[0006] Therefore, an object of the present disclosure is to provide a photosensitive resin composition capable of realizing a photosensitive resin layer excellent in desired properties. Another object of the present disclosure is to provide a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, and further to provide a method for producing a photosensitive resin composition and a method for forming a resist pattern.

[0007] One aspect of the present invention is as follows: [1] 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, wherein the components (A) and (B) both contain 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, and the component (C) contains 4.0 mass% or more of a biimidazole compound based on the total solid content of the photosensitive resin composition. [2] The photosensitive resin composition according to item 1, wherein the component (A) contains 51% by mass or more of structural units derived from styrene, based on the total mass of all monomer components, and the component (B) contains 70% by mass or more of a compound having a bisphenol A skeleton, based on the total amount of the component (B). [3] The photosensitive resin composition according to item 1 or 2, wherein the component (A) contains 55% by mass or more of structural units derived from styrene, based on the total mass of all monomer components. [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 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 a biimidazole 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 a biimidazole-based compound in an amount of 6.0% by mass or more, 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 a photosensitive resin layer obtained using the photosensitive resin composition has a transmittance of 45% or more at a wavelength of 365 nm at 25 μm. [8] The photosensitive resin composition according to item 7, wherein the transmittance is 60% or more. [9] A photosensitive resin laminate comprising: a support film; and a photosensitive resin layer containing the photosensitive resin composition according to any one of items 1 to 8.

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

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

[12] A method for producing 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, wherein both of the component (A) and the component (B) contain aromatic rings, and the component (A) has a proportion of the aromatic rings of 0.0045 mol / g or more, and the component (B) has a proportion of the aromatic rings of 0.0017 mol / g or more.

[13] A method for forming a resist pattern using the photosensitive resin laminate according to Item 9 or 10, comprising 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 photosensitive resin layer after exposure.

[0008] Aspects related to the present invention are as follows: [1A] 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, wherein the components (A) and (B) both contain aromatic rings, and 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. [2A] The photosensitive resin composition according to Item 1A, wherein the component (A) contains 51% by mass or more of structural units derived from styrene, based on the total mass of all monomer components; the component (B) contains 70% by mass or more of a compound having a bisphenol A skeleton, based on the total amount of the component (B); and the 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) contains 55% by mass or more of structural units derived from styrene, 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 component (B) contains 80% by mass or more of a compound having a bisphenol A skeleton, based on the total amount of the component (B). [5A] The photosensitive resin composition according to any one of Items 1A to 4A, wherein the component (C) contains 5.0% by mass or more of a biimidazole-based compound, based on the total solid content of the photosensitive resin composition. [6A] The photosensitive resin composition according to any one of Items 1A to 5A, wherein a photosensitive resin layer obtained using the photosensitive resin composition has a transmittance of 45% or more at a wavelength of 365 nm at a thickness of 25 μm. [7A] The photosensitive resin composition according to Item 6A, wherein the transmittance is 60% or more. [8A] A photosensitive resin laminate comprising: a support film; and a photosensitive resin layer comprising the photosensitive resin composition according to any one of Items 1A to 7A. [9A] The photosensitive resin laminate according to Item 8A, wherein the photosensitive resin layer has a transmittance of 45% or more at a wavelength of 365 nm at a thickness of 25 μm. [10A] A roll formed by winding the photosensitive resin laminate according to item 8A or 9A.[11A] A method for producing 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, wherein the components (A) and (B) both contain aromatic rings, and the component (A) contains component (A) such that a ratio of the aromatic rings is 0.0045 mol / g or more, and the component (B) contains component (B) such that a ratio of the aromatic rings is 0.0017 mol / g or more. [12A] A method for forming a resist pattern using the photosensitive resin laminate according to Item 8A or 9A, comprising the following steps: laminating the photosensitive resin laminate on a substrate; exposing the photosensitive resin layer in the laminated photosensitive resin laminate; and developing the photosensitive resin layer after exposure.

[0009] According to the present invention, it is possible to provide a photosensitive resin composition capable of realizing a photosensitive resin layer excellent in desired properties. Also, according to the present invention, it is possible to provide a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, and further to provide a method for producing a photosensitive resin composition and a method for forming a resist pattern.

[0010] Hereinafter, an embodiment of the present invention (hereinafter abbreviated as "the present embodiment") will be described. The present invention is not limited to this embodiment, and various modifications can be made within the scope of the gist thereof. In this specification, the upper and lower limits of each numerical range may be arbitrarily combined and may be replaced with 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". In this specification, various numerical values ​​and properties may be measured according to the methods described in the examples, unless otherwise specified.

[0011] [Photosensitive Resin Composition] This embodiment is 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, wherein the components (A) and (B) both contain aromatic rings, and 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. In particular, in the photosensitive resin composition of this embodiment, the component (A) contains a compound having a hydroxy group as a monomer component, and the component (C) contains 4.0 mass% or more of a biimidazole compound, based on the total solids content of the photosensitive resin composition.

[0012] The present inventors have focused on incorporating a predetermined proportion or more of aromatic rings into each of component (A) and component (B). When a resist pattern is formed by exposing and developing a photosensitive resin composition, the composition may remain on the resulting resist pattern. Therefore, in order to remove such residues (development residues), the resist pattern formed after development may be subjected to plasma treatment. In this regard, in this embodiment, the aromatic rings contained in component (A) and component (B) contribute to improving the chemical stability of the photosensitive resin layer, thereby 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, a photosensitive resin composition that satisfies the following conditions is likely to achieve the effects of this embodiment: the component (A) contains 51% by mass or more of structural units derived from styrene, based on the total mass of all monomer components; and the component (B) contains 70% by mass or more of a compound having a bisphenol A skeleton, based on the total amount of the component (B). Among compounds containing aromatic rings, styrene and compounds having a bisphenol A skeleton are likely to favorably improve plasma resistance. Furthermore, by using styrene and compounds having a bisphenol A skeleton, they can be favorably introduced into the photosensitive resin composition as the component (A) and the component (B), respectively. In a photosensitive resin composition, an increase in the proportion of aromatic rings tends to increase the resin viscosity, which tends to decrease the radical polymerization efficiency. In this case, it is possible to incorporate a large amount of a biimidazole compound, i.e., to prevent a decrease in sensitivity.

[0014] Furthermore, the photosensitive resin layer obtained by exposing the photosensitive resin composition to light preferably has a transmittance of 45% or more at a wavelength of 365 nm at 25 μm, and more preferably has a transmittance of 60% or more. This facilitates achieving good adhesion (adhesion between the photosensitive resin layer and the substrate). The combination of a sensitizer and a relatively large amount of a biimidazole-based compound facilitates preventing a decrease in sensitivity. On the other hand, reducing the amount of sensitizer is advantageous for improving transmittance, and it also facilitates designing a composition in which the amount of biimidazole-based compound is increased to compensate for the reduction in the sensitizer. The photosensitive resin composition of this embodiment has a wide range of compositional design options, i.e., it is possible to achieve both sensitivity and adhesion.

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

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

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

[0018] The component (A) preferably has a repeating unit containing at least one selected from the "first monomers" described below, and more preferably has a repeating unit containing both at least one selected from the "first monomers" and at least one selected from the "second monomers" described below. Furthermore, the proportion of the monomer components in the component (A) is the copolymerization ratio when only one alkali-soluble polymer is used as the component (A), and is a weighted average of the copolymerization ratios when two or more alkali-soluble polymers are used as the component (A), with the content ratio of each alkali-soluble polymer being used as the weight.

[0019] The proportion of aromatic rings in component (A) is 0.0045 mol / g or more. A proportion of aromatic rings of 0.0045 mol / g or more is preferable from the viewpoint of improving plasma resistance, and from the same viewpoint, 0.0050 mol / g or more is more preferable, 0.0053 mol / g or more is even more preferable, 0.0058 mol / g or more is particularly preferable, 0.0063 mol / g or more is even more preferable, and 0.0067 mol / g or more is most preferable. Furthermore, from the viewpoint of improving developability, the proportion of aromatic rings is preferably 0.0082 mol / g or less, more preferably 0.0077 mol / g or less, and more preferably 0.0067 mol / g or less. The aromatic rings may be derived from the first monomer, the second monomer, or both the first and second monomers. However, since it is easier to realize the desired component (A), it is preferable that the proportion of aromatic rings is derived from at least the second monomer. 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) based on 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 monomer).

[0020] The (A) component may have a proportion of styrene-derived structural units of 40% by mass or more, based on the total mass of all monomer components. Here, the (A) component preferably has a proportion of styrene-derived structural units of 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 the same viewpoint, the proportion of styrene-derived structural units is more preferably 52% by mass or more, 55% by mass or more, or 60% by mass or more, and even more preferably 65% ​​or more. The proportion of styrene-derived structural units 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 preferred from the standpoint of achieving both flexibility and resolution of the resist pattern, and from the same standpoint, a weight average molecular weight of 55,000 or less is more preferred, and a weight average molecular weight of less than 50,000 is even more preferred. From the same standpoint, a weight average molecular weight of 10,000 or more is preferred, a weight average molecular weight of 14,000 or more is more preferred, and a weight average molecular weight of 25,000 or more is even more preferred.

[0022] The polydispersity of component (A) {weight average molecular weight (Mw) of component (A) / number average molecular weight (Mn) of component (A)} 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 a mixture of two or more components is used as the component (A), the molecular weights and polydispersities of the multiple components (A) are preferably selected so that the weighted average values, when the content ratio is used as the weight, fall within the respective 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 half 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 a compound represented by the chemical formula C ４ H ６ O ２ "acrylic acid" means a compound represented by the chemical formula C ３ H ４ O ２ The compound represented by the formula:

[0025] 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, with 15% by mass or more being more preferred, 18% by mass or more being even more preferred, 21% by mass or more being even more preferred, 23% by mass or more being particularly preferred, and 24% by mass or more being most preferred. A proportion of 50% by mass or less is preferred from the viewpoint of excellent adhesion and resolution, with 35% by mass or less being more preferred, 30% by mass or less being even more preferred, 29% by mass or less being even more preferred, 27% by mass or less being particularly preferred, and 26% by mass or less being most preferred.

[0026] <Second Monomer> The second monomer has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, and tetrahydrofurfuryl. (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; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile.

[0027] The second monomer preferably includes 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, with 50% by mass or more being more preferred, 55% by mass or more being even more preferred, 60% by mass or more being even more preferred, and 65% by mass or more being particularly preferred. A proportion of 90% by mass or less is preferred from the viewpoint of excellent developability, with 80% by mass or less being more preferred.

[0028] Examples of compounds having an aromatic ring include styrene, benzyl (meth)acrylate, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene derivatives such as styrene dimer and styrene trimer, and 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate. Among these, styrene and benzyl (meth)acrylate are preferred, styrene is more preferred, and compounds containing both styrene and benzyl (meth)acrylate are even more preferred.

[0029] The second monomer may include 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 the compound having an alicyclic ring include (meth)acrylic acid esters having a group having one cyclic hydrocarbon group, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group, or a group consisting of a derivative thereof, and also include (meth)acrylic acid esters having a group having two or more cyclic hydrocarbon groups, such as a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, or an isobornyl group, or a group consisting of a derivative thereof.

[0031] The second monomer may include a compound having a hydroxy 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 preferred from the viewpoint of excellent adhesion and resolution.

[0032] Examples of compounds having a hydroxy group include hydroxyalkyl (meth)acrylates, specifically 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin-based (meth)acrylates (for example, glycerin mono(meth)acrylate). These are relatively easy to obtain. Furthermore, the developability and adhesion are easy to control, and therefore it is easy to realize a resist pattern with excellent properties.

[0033] The second monomer may be a compound other than those mentioned above, for example, a (meth)acrylic acid alkyl ester (a chain alkyl ester and a cyclic alkyl ester) other than those mentioned above, a conjugated diene compound other than those mentioned above, a polar monomer (an amino group-containing monomer, an amide group-containing monomer, a cyano group-containing monomer, an epoxy group-containing monomer, and the like) other than those mentioned above, a crosslinkable monomer other than those mentioned above, or an acid anhydride other than those mentioned above.

[0034] <Synthesis of Component (A)> Component (A) is preferably synthesized 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 of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the mixture. Synthesis may be performed while adding a portion of the mixture dropwise to the reaction solution, or after the reaction is completed, additional solvent may be added to adjust the concentration to the desired level. As a synthesis method, in addition to solution polymerization, living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used.

[0035] The content 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 mass of the photosensitive resin composition, or 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] It is preferable to set the content of component (A) to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the content to 10% by mass or more from the viewpoint of improving edge fuse resistance, that is, from the viewpoint of suppressing exudation of the photosensitive resin layer from the film edge. Note that edge fuse resistance is sometimes particularly required for rolls formed by winding a photosensitive resin laminate.

[0037] <Component (B): Compound Having an Ethylenically Unsaturated Bond> Component (B) is a compound having an ethylenically unsaturated bond. The proportion of aromatic rings in component (B) is 0.0017 mol / g or more. A proportion of aromatic rings of 0.0017 mol / g or more is preferable from the viewpoint of improving plasma resistance, and from the same viewpoint, the proportion is 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, the proportion is preferably 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. It is preferable that component (B) contains 61% by mass or more of a compound having a bisphenol A skeleton, based on the total amount of component (B). This makes it easier to achieve the effects of this embodiment. From the same viewpoint, the proportion of the compound having a bisphenol A skeleton is preferably 70% by mass or more, 75% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass. In this specification, the concept of "compound having a bisphenol A skeleton" also includes hydrogenated compounds having a bisphenol A skeleton, i.e., compounds having a hydrogenated bisphenol A skeleton.

[0038] Examples of compounds having a bisphenol A skeleton include compounds represented by the following general formula (I): (In the formula, R ２ are each independently a hydrogen atom or a methyl group, and X ２ O and Y ２ O are each independently an oxyethylene group or an oxypropylene group, m3, m4, n2, and n3 are each independently an integer of 0 to 40, m3+m4 is 1 to 40, and n2+n3 is 0 to 20.

[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 may further contain 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 bifunctional or higher functional (meth)acrylate compound. A "bifunctional or higher functional (meth)acrylate compound" refers to a compound having two or more (meth)acryloyl groups in one molecule.

[0041] The component (B) is preferably a (meth)acrylate compound. From the viewpoint of adhesion and flexibility of the resist pattern, the (meth)acrylate compound may include, for example, a bifunctional (meth)acrylate compound and a tri- or higher functional (meth)acrylate compound, such as a tetrafunctional, pentafunctional, 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 glycosylated (hydrogenated) bisphenol A di(meth)acrylate.

[0043] Commercially available bifunctional (meth)acrylate compounds include, for example, NK Ester (registered trademark) 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, and NOD-N. , DOD-N, NPG, 701, 2G, 3G, 4G, 9G, 14G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BP E-1300N, NK Oligo (registered trademark) UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA (manufactured by Shin-Nakamura Chemical Co., Ltd.), Litea Acrylate (registered trademark) 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.), Fancryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-12 9AS, 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 Allnex 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 of such polyglycerides 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 trifunctional or higher functional (meth)acrylate compounds 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 the trifunctional or higher functional (meth)acrylate compound include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, 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] Commercially available tri- or higher functional (meth)acrylate compounds include, for example, NK Ester (registered trademark) 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 (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) 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 Examples of such copolymers include TMPTMA (manufactured by Daicel Allnex Co., Ltd.), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, and SR9041 (manufactured by Arkema Co., Ltd.), KAYARAD (registered trademark) GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.).

[0047] The content of the tri- or higher functional (meth)acrylate compound may be 0 to 50 mass %, 0 to 25 mass %, or 1 to 15 mass %, based on the total amount of the component (B).

[0048] Specifically, compounds that may be contained in component (B) include: dimethacrylate of polyethylene glycol in which an average of 5 mol of EO has been added to each end of bisphenol A (the above-mentioned "FA-321M," product name); dimethacrylate of polyethylene glycol in which an average of 2 mol of EO has been added to each end of bisphenol A; dimethacrylate of polyalkylene glycol in which an average of 3 mol of EO has been added to each end of polypropylene glycol having an average of 12 PO repeating units per molecule ("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-mentioned "FA-321M" is a compound represented by R ２ = methyl group, X ２ It is expressed as follows: O = oxyethylene group, m3 + m4 = 10, n2 = n3 = 0.

[0049] The content of component (B) is preferably 30% by mass or more, and more preferably 35% by mass or more, based on the total solid mass of the photosensitive resin composition, from the viewpoints of sensitivity, tackiness, and followability, and is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 42% by mass or less, from the viewpoints of edge fuse resistance, tackiness, and resolution.

[0050] From the viewpoints of edge fuse resistance, tackiness, and resolution, the content of the component (B) relative to the content of the component (A) in the photosensitive resin composition (i.e., the content of the component (B) / the content of the 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 100 g 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 leaching out of the cured resist pattern in the water washing step after development, thereby preventing 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 in the water washing step after development, thereby preventing contamination during the water washing step.

[0052] The number of ethylenically unsaturated bonds per 100 g of solid content of 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, more preferably 0.13 mol or more, and 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] <Component (C): Photopolymerization Initiator> Component (C) is a photopolymerization initiator. Photopolymerization initiators generate radicals when exposed to actinic rays, which easily initiate polymerization of a compound having an ethylenically unsaturated bond. The component (C) may contain 3.5% by mass or more of a biimidazole-based 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-based compound, more preferably 4.2% by mass or more, even more preferably 5.0% by mass or more, particularly preferably 6.0% by mass 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 content of the biimidazole-based compound 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. The proportion of structural units derived from styrene in the component (A) may be 40 mass % or more based on the total mass of all monomer components.

[0054] Examples of the 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, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.

[0055] The biimidazole compound refers to a compound having a biimidazole structure, and examples thereof include lophine dimers, i.e., dimers of 2,4,5-triarylimidazole. Examples of lophine 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, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole. phenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl) )-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2, 2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,Examples of such compounds include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-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 viewpoints of high sensitivity, resolution, and adhesion, it is preferable that the component (C) contains a lophine dimer, and among these, it is more preferable that the component (C) 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 because of 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-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0059] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. From the viewpoints of sensitization effect and adhesion, examples of aromatic ketone compounds include 4,4'-bis(diethylamino)benzophenone.

[0060] In the present specification, the term "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 viewpoints 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. 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. Commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

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

[0064] Examples of dialkyl ketal compounds include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of dialkylaminobenzoate 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-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

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

[0067] From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives are preferably 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, or 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline.

[0068] Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[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 diaryliodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0070] The content of component (C) in the photosensitive resin composition is preferably 0.01 to 20 mass %, and more preferably 0.5 to 10 mass %, based on the total mass of solids in the photosensitive resin composition. By adjusting the content of component (C) within the above range, it is possible to obtain sufficient sensitivity while facilitating sufficient light transmission to the bottom of the photosensitive resin layer, thereby making it easier to achieve high resolution.

[0071] When the component (C) includes a biimidazole-based compound, the content of the component (C) other than the biimidazole-based compound in the photosensitive resin composition may be 0.001 to 2.0 mass%, or 0.01 to 2.0 mass%, based on the total mass of solids in the photosensitive resin composition. The upper limit of this content may be 1.0 mass%, preferably 0.1 mass%, more preferably 0.053 mass%, and even more preferably 0.031 mass%. By adjusting the content of the component (C) within the above range, it is possible to achieve both sufficient sensitivity and facilitate sufficient light transmission to the bottom of the photosensitive resin layer, thereby making it easier to achieve high resolution.

[0072] When the component (C) contains a biimidazole-based compound, the component (C) other than the biimidazole-based compound in the photosensitive resin composition is preferably an N-aryl-α-amino acid compound, a quinone compound, an aromatic ketone compound, an anthracene derivative, an acetophenone compound, an acylphosphine oxide compound, a benzoin compound, a benzoin ether compound, a dialkyl ketal compound, a thioxanthone compound, a dialkylaminobenzoic acid ester compound, an oxime ester compound, an acridine compound, a pyrazoline derivative, an N-arylamino acid ester compound, or a halogen compound, with aromatic ketone compounds, anthracene derivatives, and pyrazoline derivatives being particularly preferred. For details of these compounds, see the compounds exemplified in the section entitled "Component (C): Photopolymerization Initiator."

[0073] When the component (C) contains a sufficient amount of a biimidazole-based compound, for example, when the component (C) contains 6.0% by mass or more of a biimidazole-based compound, or when the component (C) contains 6.2% by mass or more of a biimidazole-based compound, the component (C) may not contain any other components than the biimidazole-based compound.

[0074] <Other Components> The photosensitive resin composition may contain, if desired, antioxidants, stabilizers, leuco dyes, base dyes, sensitizers, color-forming dyes, plasticizers, hindered amines, and the like.

[0075] Examples of the antioxidant include triphenyl phosphite (e.g., manufactured by ADEKA under the trade name of TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA under the trade name of 2112), tris(mononylphenyl) phosphite (e.g., manufactured by ADEKA under the trade name of 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA under the trade name of 329K).

[0076] The content of the antioxidant in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, based on the total solid content in the photosensitive resin composition. The content of the antioxidant is preferably equal to or greater than the lower limit described above, from the viewpoints of achieving good hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. On the other hand, the content of the antioxidant is preferably equal to or less than the upper limit described above, from the viewpoints of achieving good hue stability while suppressing the color development of the resist pattern and improving adhesion.

[0077] The stabilizer may be, for example, 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 salt (e.g., aluminum salt with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosamine. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred.

[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] The benzotriazoles are preferably compounds having a carboxy group, and examples thereof 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, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole are 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-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.).

[0082] The total content of the stabilizers in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total solid content in the photosensitive resin composition. The total content is preferably equal to or greater than the above lower limit from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably equal to or less than the above upper limit from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[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.), Fuchsin [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], Basic Yellow 2 [2465-27-2], etc. Among these, Diamond Green is preferred from the viewpoint of improving colorability, hue stability, and exposure contrast.

[0084] The content of the base dye in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total mass of solids in the photosensitive resin composition. From the viewpoint of obtaining good colorability, the content of the base dye is preferably equal to or greater than the above-mentioned lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the content is preferably equal to or less than the above-mentioned upper limit.

[0085] Known examples of color-forming dyes include combinations of leuco dyes and halogen compounds. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal 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, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane. Examples of leuco dyes that may be used include the aforementioned leuco crystal violet and those known as diamond green.

[0086] Examples of additives such as plasticizers include phthalate esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

[0087] Examples of the hindered amine compound 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 of the cured film after the crosslinking reaction and improving the releasability, 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 proportion of the hindered amine compound relative to the total solid mass of the photosensitive resin composition is preferably 0.001 to 10% by mass. From the viewpoint of excellent releasability, this proportion 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 proportion is preferably 5% by mass or less, more preferably 3% by mass or less, 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] <<Prepared Solution of Photosensitive Resin Composition>> A prepared solution for producing a photosensitive resin composition can be prepared by adding a solvent to the photosensitive resin composition. Examples of the solvent 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 prepared solution is 500 to 4000 mPa·sec at 25°C.

[0090] [Photosensitive Resin Laminate] A further aspect of the present embodiment is a photosensitive resin laminate comprising: a support film; and a photosensitive resin layer obtained by exposing the photosensitive resin composition.

[0091] The thickness of the photosensitive resin layer is preferably 3 to 100 μm, and more preferably 50 μm in upper limit. As the thickness of the photosensitive resin layer approaches 3 μm, the resolution is more likely to improve, and as the thickness approaches 100 μm, the film strength is more likely to improve. Therefore, the thickness can be appropriately selected depending on the application.

[0092] In this embodiment, the transmittance of the photosensitive resin layer at a wavelength of 365 nm when the layer is 25 μm thick 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 of the photosensitive resin layer at a wavelength of 365 nm when the layer is 25 μm thick 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 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 preferably transparent and transmits actinic rays.

[0094] Examples of films include transparent films made of 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 high-quality films with little internal foreign matter. Specifically, high-quality films include PET films synthesized using a titanium (Ti) catalyst, PET films with small diameters and low lubricant content, PET films containing lubricant on only one side of the film, thin-film PET films, PET films smoothed on at least one side, and PET films roughened on at least one side by plasma treatment or the like. This facilitates improving the resolution of the photosensitive resin laminate. At least one side of the support film may be smoothed using a calender or the like.

[0095] The thickness of the support film is preferably 5 to 25 μm, more preferably 6 to 20 μm. The thinner the support film, the fewer the number of internal foreign matter, and therefore the easier it is to prevent a decrease in resolution. A film thickness of 5 μm or more makes it easier to prevent stretching deformation in the winding direction due to tension and tearing due to minute scratches during the coating and winding manufacturing processes, and also makes it easier to ensure the strength of the film, 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 beam irradiated onto the photosensitive resin layer and 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 protective film in addition to the support film and the photosensitive resin layer. The protective film is laminated on the photosensitive resin layer on the side opposite to the support film, and functions as a cover for the photosensitive resin layer.

[0098] When the adhesive strength between the photosensitive resin layer and the protective film is sufficiently smaller than the adhesive strength between the photosensitive resin layer and the support film, the protective film can be easily peeled off from the photosensitive resin layer. Preferred examples of the protective film include polyethylene film, polypropylene film, oriented polypropylene film, and polyester film.

[0099] A release layer can be applied to the surface of the protective film so that the protective film can be easily peeled off from the photosensitive resin layer. Release layers are classified into silicone compounds and non-silicone compounds, for example.

[0100] Examples of silicone compounds include condensation reaction type silicone resins obtained by reacting polydimethylsiloxane having silanol ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; ultraviolet-curable or electron-beam-curable silicone resins obtained by curing acrylic silicone, epoxy group-containing silicone, or the like with ultraviolet light or electron beam; 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 film 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 film thickness is equal to or less than the upper limit, the coating film tends to have a good appearance and the coating film tends to be sufficiently cured. On the other hand, if the film thickness is equal to or greater than the lower limit, sufficient releasability tends to be ensured.

[0103] The thickness of the protective film is preferably 10 to 100 μm, more preferably 10 to 50 μm. Examples of the protective film include Alphan (registered trademark) EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Torayfan (registered trademark) KW37, 2578, 2548, 2500, and YM17S, Therapeel (registered trademark) PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, and SY (all manufactured by Toray Industries, Inc.), and GF-18, GF-818, and GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0104] [Method for Producing Photosensitive Resin Laminate] Another aspect of this embodiment is a method for producing a photosensitive resin laminate. The photosensitive resin laminate can be produced by laminating a photosensitive resin layer, and optionally a protective film, on a support film. The production method can include, for example, a step of mixing a photosensitive resin composition with a solvent that dissolves the photosensitive resin composition to obtain a photosensitive resin composition preparation (coating liquid), a step of applying the coating liquid to a support film using a bar coater or a roll coater and drying the coating liquid to form a photosensitive resin layer on the support film, and a step of laminating a protective film on the photosensitive resin layer, if necessary.

[0105] [Roll (Photosensitive Resin Roll)] Another aspect of this embodiment is a photosensitive resin roll formed by winding a photosensitive resin laminate. The roll may or may not have a core material. The long photosensitive resin laminate may be wound around a core material, or may be wound without a core material.

[0106] [Method for forming a resist pattern] A further aspect of the present embodiment is a method for forming a resist pattern using the above-described photosensitive resin laminate, the method comprising the following steps: a step of laminating the photosensitive resin laminate on a substrate (laminating step); a step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate (exposing step); and a step of developing the photosensitive resin layer after exposure (developing step).

[0107] <Lamination Step> In the lamination step, after peeling off the protective film from the photosensitive resin laminate, the photosensitive resin layer is laminated once or multiple times by heat and pressure bonding using a laminator onto the surface of a support (e.g., substrate). Examples of materials for the substrate 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 and pressure bonding can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rolls several times. Heat and pressure bonding can be performed in a reduced pressure environment, if desired.

[0108] <Exposure Step> In the exposure step, the photosensitive resin layer is exposed to actinic light using an exposure machine. The exposure can be carried out after peeling off the support film as desired, or can be carried out without peeling off the support film. When exposure is carried out through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, which may be measured using an actinometer. In the exposure step, direct imaging exposure may be carried out. In direct imaging exposure, exposure is carried out directly on the substrate using a drawing device without using a photomask. A semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm 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 step is preferably at least one method selected from the group consisting of a projection exposure method, a proximity exposure method, a contact exposure method, a direct imaging exposure method, and an electron beam direct writing method, and is more preferably a projection exposure method or a direct imaging exposure method.

[0110] A heating step may be performed 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 performing the heating step, it is easy to improve the resolution and adhesion. Examples of heating methods include a heating furnace using hot air, infrared, or far-infrared rays, as well as a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, and the like.

[0111] The time elapsed from the exposure step to the heating step, for example, the time elapsed from the time exposure is stopped to the time heating is started, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The time elapsed from the time heating is started to the time heating is stopped is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0112] <Developing Step> In the developing step, the unexposed areas (non-patterned areas) of the photosensitive resin layer after exposure are removed with a developer using a developing device. After exposure, if there is a support film on the photosensitive resin layer, this is peeled off. Next, the exposed areas are developed (removed) using a developer containing an alkaline aqueous solution, thereby obtaining a resist image (resist pattern).

[0113] The alkaline aqueous solution is Na ２ CO ３ , K. ２ CO ３ The alkaline aqueous solution is selected according to the properties of the photosensitive resin layer. For example, an aqueous solution of Na with a concentration of 0.2 to 2% by mass is preferable. ２ CO ３ The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent to accelerate development, etc. The temperature of the developer in the development step is preferably maintained within the range of 20 to 40°C.

[0114] The developing step preferably includes a step of developing (removing) the exposed area and then removing the developer contained in the resist pattern with washing water (water washing step). The washing water is selected according to the properties of the photosensitive resin layer, such as pure water or industrial water. For example, from the viewpoint of improving the resolution and rectangularity of the resist pattern, water containing 0.001 to 1 mass % of MgSO 4 may be used. ４ The temperature of the washing water in the washing step is preferably kept within the range of 20 to 40°C.

[0115] After obtaining the resist pattern, if desired, a step of heating the resist pattern at 60°C to 300°C (heating step) may be carried out. By carrying out this heating step, the chemical resistance of the resist pattern is easily improved. For the heating step, a heating furnace using hot air, infrared rays, or far infrared rays may be used.

[0116] [Method for Manufacturing a Wiring Board] A wiring board can also be manufactured using the photosensitive resin composition according to this embodiment. In one aspect, the method for manufacturing a wiring board includes the following steps: a conductive pattern forming step of etching or plating a substrate on which a resist pattern has been formed to form a conductive pattern; and a peeling step of peeling the resist pattern from the substrate.

[0117] <Conductive Pattern Forming Step> If necessary, the substrate on which the resist pattern has been formed as described above may be subjected to an etching or plating step (etching or plating step). This facilitates the formation of a wiring pattern (conductive pattern) corresponding to the resist pattern on the substrate. That is, another aspect of this embodiment is a method for producing a conductive pattern.

[0118] In a method for producing a conductor pattern, for example, a metal plate or a metal-coated insulating plate is used as a substrate, and a resist pattern is formed on the substrate by the above-mentioned method, followed by the production of a desired conductor pattern. The exposed portion is developed (removed) to expose the substrate surface (e.g., copper surface), which is then subjected to an etching or plating step.

[0119] The etching treatment is carried out, for example, by spraying an etching solution onto the resist pattern and the substrate surface. Examples of the etching method include acid etching and alkaline etching. Examples of the etching solution include an aqueous solution of hydrochloric acid, an aqueous solution of ferric chloride, or a mixture thereof.

[0120] The plating process is carried out in accordance with a known plating method by developing (removing) the exposed portion and then plating the exposed portion of the substrate with metal (for example, metal plating with a copper sulfate plating solution) or solder.

[0121] After the conductive pattern is formed by the above method, a step (stripping step) of stripping the resist pattern from the substrate using an aqueous solution having a stronger alkalinity than the developer may be performed, thereby obtaining a wiring board (e.g., a printed wiring board) having a desired conductive pattern.

[0122] Examples of the alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution") include a 2 to 5 mass % aqueous solution of NaOH or KOH, or an organic amine-based stripping solution. A small amount of a water-soluble solvent may be mixed into the stripping solution. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably within the range of 40 to 70°C.

[0123] The photosensitive resin laminate may be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGAs) and chip size packages (CSPs); the manufacture of tape substrates such as chip-on-film (COFs) and tape automated bonding (TABs); the manufacture of semiconductor bumps; and the manufacture of partition walls of flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.

[0124] The present embodiment will be described with reference to examples and comparative examples. The present 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] [Synthesis of Component (A)] 28 g of methacrylic acid, 52 g of styrene, and 20 g of 2-hydroxyethyl methacrylate (copolymerization component) were mixed with 0.8 g of azobisisobutyronitrile to prepare solution (a). 200 g of methyl ethyl ketone and 100 g of ethanol were placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and the mixture was stirred while blowing nitrogen gas into the flask and heated to 80°C. Solution (a) was added dropwise to the mixture in the flask at a constant dropping rate over 4 hours, and the mixture was then stirred at 80°C for 2 hours. Next, 0.5 g of azobisisobutyronitrile was dissolved in 50 g of a mixture of 30 g of methyl ethyl ketone and 20 g of ethanol to prepare solution (b). Solution (b) was added dropwise to the solution in the flask at a constant rate over 10 minutes, and the solution in the flask was then stirred at 80°C for 3 hours. The solution in the flask was then heated to 90°C over 30 minutes and maintained at 90°C for 2 hours. After this, 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 carrying out the same procedure while varying the amounts of monomers added to each copolymerization component in the blending amounts shown in Table 4. The weight-average molecular weights (Mw) of the resulting 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 calculated using a calibration curve of standard polystyrene. The GPC conditions are as follows: (GPC conditions) Pump: PU-980 manufactured by JASCO Corporation Column: Two columns (Shodex Corporation, KF-80Y / KF-806M) Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL / min Detector: RI-1530 manufactured by JASCO Corporation In this specification, "weight-average molecular weight (Mw)" and "polydispersity index (Mw / Mn)" are measured as described above.

[0127] [Evaluation Samples] <Photosensitive Resin Composition, Photosensitive Resin Laminate, etc.> The components shown in the tables (where the number for each component indicates the amount (parts by mass) of solids) and a solvent (ethanol) were stirred and mixed so that the solids content was 60 mass %, thereby obtaining preparations containing photosensitive resin compositions (Examples and Comparative Examples). The abbreviations in Tables 1 to 3 correspond to the names 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 was uniformly applied to the surface of the film using a bar coater, and then dried in a dryer at 95° C. for 3 minutes to form a photosensitive resin layer with a film thickness of 25 μm. This resulted in the production of photosensitive resin laminates (Examples and Comparative Examples).

[0129] Next, a 19 μm thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) was attached as a protective film to the surface of the photosensitive resin layer on the side on which the support film was not laminated. That is, a photosensitive resin laminate provided with a protective film was produced.

[0130] <Photosensitive Layer Transmittance> After peeling off the protective film from the photosensitive element, the transmittance of the photosensitive resin layer at a wavelength of 365 nm was measured using a spectrophotometer U-3010 (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 set to 4 nm and a scan speed set to 600 nm / min.

[0131] <Substrate for evaluation> A 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was prepared. The surface of the substrate was jet scrubbed using an abrasive (Ujiden Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa. The polished surface of the substrate was then scrubbed with 10% by mass H ２ SO ４ The substrate was washed with an aqueous solution and then with water, and the washed substrate was used as an evaluation substrate.

[0132] <Lamination> 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 (AL-700, manufactured by Asahi Kasei Corporation) 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> The evaluation substrate, two hours after lamination, was exposed using a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.). The exposure was performed using a predetermined imaging pattern for direct imaging (DI) exposure. Here, the evaluation substrate, one minute after exposure, was heated for 30 seconds in a constant temperature incubator with a fan (DKM600, manufactured by Yamato Scientific Co., Ltd.) set to 60°C.

[0134] <Development> The support film was peeled off from the photosensitive resin layer to expose the photosensitive resin layer. Thereafter, the photosensitive resin layer was developed with 1% by mass NaCl solution at 30°C using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer). ２ CO ３ The aqueous solution was sprayed onto the photosensitive resin layer for a predetermined time, thereby carrying out development. After development, the photosensitive resin layer was washed with water by spraying for a predetermined time. The development (spray) time and the water washing (spray) time were both twice the shortest development time. After development, a water washing spray was again carried out, and the time for this water washing spray was twice the shortest development time. At this time, the shortest time required for the unexposed portions 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 to an exposure amount that resulted in a maximum remaining film step number of 15 using a Stouffer 41-step tablet, and then developed. The photosensitive resin layer was then subjected to plasma treatment for 1000 seconds using a plasma etching device (EXAM manufactured by Shinko Seiki Co., Ltd.). The treatment here was carried out at an output of 133 W and O ２ 40cm of gas ３ / min, CF ４ 41cm of gas ３ The test was carried out at a speed of 1 / min and a pressure of 50 Pa.

[0136] Thereafter, 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 reference length of 100 μm, and the average value of these was calculated. The obtained average value was used as an index of plasma resistance and was evaluated according to the following criteria. If the photosensitive resin layer is damaged by plasma treatment, unevenness may occur on the surface, so the smaller the arithmetic mean roughness (Ra), the better the plasma resistance. Evaluation criteria: E: ◎ (extremely good) Arithmetic mean roughness (Ra) is less than 1.5 μm G: ○ (good) Arithmetic mean roughness (Ra) is 1.5 μm or more and less than 3.0 μm P: × (poor) Arithmetic mean roughness (Ra) is 3.0 μm or more

[0137] <Sensitivity> In the above <Exposure> step, a Stouffer 41-step tablet was used as a mask for exposure, and the exposure amount at which the maximum number of remaining film steps after subsequent development was 15 was determined. Evaluation was performed according to the determined exposure amount using the following criteria. The smaller the exposure amount value, the higher the sensitivity. Evaluation criteria: E: ◎ (very good) The exposure amount was 160 mJ / cm ２ Less than G: ○ (Good) The exposure amount was 160 mJ / cm ２ More than 200mJ / cm ２ P: × (poor) The exposure amount was less than 200 mJ / cm ２ End

[0138] <Adhesion> Evaluation was performed using a mask pattern with a line / space (L / S) of x / 3x (x = 1 to 20 (varying in 1 μm intervals), unit: μm). Specifically, the evaluation substrate after lamination was exposed to light using this mask pattern with a Stouffer 41-step step tablet at an exposure dose that resulted in a maximum remaining film step count of 15. This was then developed to form a resist pattern. This resist pattern was observed with an optical microscope at 50x magnification to obtain an observation image. In the observation image, the minimum line width formed without meandering or chipping of the line portion (exposed portion) was determined. The line width was used as an index of adhesion, and was evaluated according to the following criteria. The smaller the adhesion value, the better the adhesion. Evaluation criteria: E: ◎ (extremely good) Adhesion less than 6 μm G: ○ (good) Adhesion 6 μm or more but less than 9 μm P: × (poor) Adhesion 9 μm or more

[0139]

[0140]

[0141]

[0142]

[0143] In the table, "aromatic rings in component (A)" means the proportion of aromatic rings in component (A); "aromatic rings in component (B)" means the proportion of aromatic rings in component (B); "St / component (A)" means the proportion of structural units derived from styrene based on the total mass of all monomer components in component (A); "BisA / component (B)" means the proportion of compounds having a bisphenol A skeleton based on the total amount of component (B); and "component C-1 / composition" means the proportion of imidazole-based compounds based on the total amount of solids in the photosensitive resin composition.

[0144] It was confirmed from the above table that the Examples provided better results than the Comparative Examples in the evaluation item <plasma resistance>. The photosensitive resin laminates of the Examples could be wound up by a conventional method, i.e., the laminates could be suitably used to prepare rolls.

[0145] The present invention provides a photosensitive resin composition that can realize a photosensitive resin layer having excellent desired properties (e.g., plasma resistance). The photosensitive resin composition of the present invention can provide a photosensitive resin laminate that has good plasma resistance and may also have good sensitivity and adhesion. The present invention can be widely used in industries that form resist patterns.

Claims

1. 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, wherein the components (A) and (B) both contain aromatic rings, the ratio of the aromatic rings in the component (A) is 0.0045 mol / g or more, and the ratio 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, and the component (C) contains 4.0 mass% or more of a biimidazole compound based on the total solid content of the photosensitive resin composition.

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

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

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

5. The photosensitive resin composition according to claim 1, wherein the component (C) contains 5.0 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 the component (C) contains 6.0 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 a photosensitive resin layer of 25 μm obtained using said photosensitive resin composition has a transmittance of 45% or more at a wavelength of 365 nm.

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

9. A photosensitive resin laminate comprising: a support film; and a photosensitive resin layer containing the photosensitive resin composition according to any one of claims 1 to 8.

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 according to claim 9.

12. A method for producing 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, wherein the components (A) and (B) both contain aromatic rings, and the component (A) used has an aromatic ring ratio of 0.0045 mol / g or more, and the component (B) used has an aromatic ring ratio of 0.0017 mol / g or more.

13. A method for forming a resist pattern using the photosensitive resin laminate according to claim 9, comprising 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 photosensitive resin layer after exposure.

Images