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

Abstract

The present invention provides a photosensitive resin laminate that achieves both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern by using a boron compound that absorbs light of a predetermined exposure wavelength and causing the boron compound to absorb light of the exposure wavelength, as well as a photosensitive resin composition capable of realizing such a photosensitive resin laminate, and a method for forming a resist pattern. [Solution] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern. The following components: (A) Alkali-soluble polymers; (B) Compounds having ethylenically unsaturated double bonds; (C) Polymerization initiators; and (D) Boron compounds having absorption for h-rays and / or i-rays; Includes.

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. [Background technology]

[0002] [First Background Technology] Printed circuit boards are generally manufactured using photolithography. In photolithography, a photosensitive resin layer (a layer formed from a photosensitive resin composition) is first formed on the substrate. Then, a photosensitive resin pattern (resist pattern) is formed by exposing and developing the photosensitive resin layer. Subsequently, a conductor pattern is formed through etching or plating, and then the resist pattern is removed to form the desired wiring pattern on the substrate.

[0003] In photolithography, the method for forming a photosensitive resin layer on a substrate is generally: A method of applying a solution of a photosensitive resin composition onto a substrate and drying it; or A method for laminating a photosensitive resin layer onto a substrate in a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer); The following methods are employed. In the manufacturing process of printed circuit boards, the method using a photosensitive resin laminate is often adopted. In the method using a photosensitive resin laminate, the good sensitivity of the photosensitive resin layer and the flexibility of the resist pattern tend to be factors that affect the productivity and resolution of the wiring pattern.

[0004] Here, Patent Document 1 discloses an example in which triphenylbutyl borate is used as a chain transfer agent. Patent Document 2 discloses an example in which borate salts having various cations are used as coinitiators in an initiator system containing an amine and hexaarylbisimidazole (HABI). Patent Document 3 discloses an example in which an organoboron compound of a predetermined structure is used as a radical generator.

[0005] [Related background technologies] Printed circuit boards are generally manufactured using photolithography. In photolithography, a photosensitive resin layer (a layer containing a photosensitive resin composition) is first formed on the substrate. Then, a resin pattern (resist pattern) is formed by exposing and developing the photosensitive resin layer. After forming a conductor pattern by etching or plating, the resist pattern is removed to form the desired wiring pattern on the substrate.

[0006] In photolithography, a method for forming a photosensitive resin layer on a substrate is: A method of applying a solution of a photosensitive resin composition onto a substrate and drying it; or A method for laminating a photosensitive resin layer onto a substrate in a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer); This is the most commonly adopted method. In the manufacturing process of electronic devices, for example, in the manufacturing process of printed circuit boards, the method using a photosensitive resin laminate is often adopted.

[0007] 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. For the formation of wiring using photosensitive resin laminates, there is a need for photosensitive resin laminates that offer excellent resolution and the ability to form resist patterns with high adhesion to the substrate.

[0008] Patent Document 4 describes a photosensitive resin composition comprising a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an anthracene-based sensitizer, wherein the binder polymer comprises polymer (a), and polymer (a) comprises hydroxyalkyl (meth)acrylate units and contains 40% by mass or more of styrene or styrene derivative units. Patent Document 4 also describes a photosensitive resin laminate comprising a support and a photosensitive resin layer formed using the above photosensitive resin composition. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Patent No. 4156069 [Patent Document 2] Patent No. 3674336 [Patent Document 3] Japanese Patent Application Publication No. 4-271352 [Patent Document 4] International Publication No. 2021 / 193232 [Overview of the project] [Problems that the invention aims to solve]

[0010] [First challenge] However, in the materials described in Patent Documents 1 and 2, it was necessary to separately add aromatic onium salts and near-infrared dyes as sensitizers in addition to the boron compound, which sometimes hindered the achievement of good sensitivity in the photosensitive resin material.

[0011] Furthermore, in recent years, there has been a demand for improved productivity and resolution of wiring patterns. In addition, the resist patterns obtained from the materials described in Patent Documents 1, 2, and 3 each had room for further improvement in terms of flexibility.

[0012] Therefore, the inventors focused on boron compounds that absorb light at a predetermined exposure wavelength, and discovered that such compounds can be incorporated into a photosensitive resin composition.

[0013] The object of the present invention is to provide a photosensitive resin laminate that achieves both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern by using a boron compound that absorbs light of a predetermined exposure wavelength and causing the boron compound to absorb light of the exposure wavelength, as well as a photosensitive resin composition that can realize such a photosensitive resin laminate, and a method for forming a resist pattern.

[0014] [Related Issues] In the photosensitive resin composition described in Patent Document 1, polymer (a) contains 40% by mass or more of styrene or styrene derivative units, from the viewpoint of resolution and adhesion. On the other hand, the photosensitive resin composition described in Patent Document 1, and the photosensitive resin laminate having a photosensitive resin layer obtained using it, had room for improvement in terms of developability and flexibility of the cured film.

[0015] The object of the present invention is to provide a photosensitive resin composition that is excellent in resolution, adhesion, developability, and flexibility of the cured film. Another object of the present invention is to provide a photosensitive resin laminate obtained using such a photosensitive resin composition, a method for forming a resist pattern, and a method for forming a wiring board. [Means for solving the problem]

[0016] [Means for solving the "first challenge"] One embodiment of the present invention is as follows: [1] The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; (C) polymerization initiator; and (D) Boron compounds that absorb to the h-ray and / or i-ray; A photosensitive resin composition containing [a specific substance]. [2] The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; and (C) Polymerization initiator; A photosensitive resin composition comprising, (D) Component includes a boron compound that absorbs to h-rays and / or i-rays, The aforementioned component (B) is a photosensitive resin composition comprising a difunctional compound having two ethylenically unsaturated bonds in one molecule. [3] The photosensitive resin composition according to item 1 or 2, wherein the boron compound is a compound having a carbon (C)-boron (B) bond. [4] The component (D) is represented by the following general formula: R 2 -B(OH)2; R 3 -B(OR 1 )2; R 4 -B(NR 5 2)2; and R 6 -B(OH)(OR 7 ); (In the formula, R 1 ~R 7 are monovalent organic groups, and a plurality of R 1 and R 5 present in one molecule may be the same or different.) a compound represented by, and the following general formula (3):

Chemical formula

[10] The (D) component is a photosensitive resin composition according to any one of items 1 to 9, comprising a compound having a pyrazoline skeleton.

[11] The aforementioned component (D) is, A photosensitive resin composition according to any one of items 1 to 10, comprising a compound having at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, benzophenone, oxazole, and chrysene.

[12] The photosensitive resin composition according to any one of items 1 to 11, wherein the (D) component is a compound having a boron atom directly bonded to an anthracene skeleton.

[13] The photosensitive resin composition according to any one of items 1 to 12, wherein the (D) component comprises 10-phenyl-9-anthraceneboronic acid.

[14] The photosensitive resin composition according to item 2, wherein component (B) comprises a compound having a bisphenol A skeleton as the bifunctional compound.

[15] The photosensitive resin composition according to any one of items 1 to 14, wherein the (A) component comprises hydroxyethyl (meth)acrylate as a comonomer component.

[16] The photosensitive resin composition according to item 2, wherein component (B) further comprises a hindered amine compound in addition to the bifunctional compound.

[17] The above-mentioned component (A): 10-90% by mass, Component (B): 5 to 70% by mass, Component (C): 0.01 to 20% by mass, and Component (D): 0.01~20% by mass A photosensitive resin composition according to any one of items 1 to 16, including the following:

[18] The photosensitive resin composition according to any one of items 1 to 17, wherein the ratio (B / A) of the total mass of component (B) to the total mass of component (A) is 1 / 3.0 to 1 / 0.5.

[19] A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from any one of the photosensitive resin compositions described in item 1 to 18.

[20] The photosensitive resin laminate further comprises a protective layer on the side of the photosensitive resin layer opposite to the support, The photosensitive resin laminate according to item 19, wherein the protective layer is a film of polyethylene terephthalate or a film of biaxially oriented polypropylene. [twenty one] The photosensitive resin laminate according to item 20, wherein the protective layer comprises a release layer on its surface. [twenty two] A lamination step of laminating the photosensitive resin layer in the photosensitive resin laminate described in any one of items 19 to 21 onto a substrate, An exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and A method for forming a resist pattern, comprising a developing step of removing the unexposed portion of the photosensitive resin layer. [twenty three] The aforementioned component (D) is a compound that absorbs on the h line, The method for forming a resist pattern according to item 22, wherein in the exposure step, the photosensitive resin layer is exposed with light including a wavelength of 400 to 410 nm. [twenty four] The aforementioned component (D) is a compound that absorbs at the i-ray, The method for forming a resist pattern according to item 22, wherein in the exposure step, the photosensitive resin layer is exposed with light containing a wavelength of 350 to 370 nm. [twenty five] A step of forming a resist pattern on a substrate using a photosensitive resin laminate described in any one of items 20 to 24, A step of forming a conductive pattern on a substrate on which the resist pattern has been formed by etching or plating, The process of peeling the resist pattern from the substrate, A method for forming a wiring board, including the method described above.

[0017] [Means for solving related issues] The embodiments relating to the present invention are as follows: [1A] The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having ethylenically unsaturated bonds; and (C) Polymerization initiator; A photosensitive resin composition comprising, The aforementioned component (A) includes copolymer (A-1), The copolymer (A-1) comprises at least the following components: (a1) (meth)acrylic acid; (a2) Styrene derivatives; and (a3) Hydroxyalkyl (meth)acrylate; It has constituent units derived from, The proportion of constituent units derived from component (a1) is 15 to 26% by mass, The proportion of constituent units derived from component (a2) is 30 to 70% by mass, The proportion of constituent units derived from component (a3) ​​is 15 to 35% by mass, and The glass transition temperature (Tg) calculated based on Fox's formula is 100°C or less. Photosensitive resin composition. [2A] The photosensitive resin composition according to item 1A, wherein the proportion of constituent units derived from component (a1) in the copolymer (A-1) is 25% by mass or less. [3A] The copolymer (A-1) is a photosensitive resin composition according to item 1A or 2A, wherein the (a1) component includes a constituent unit derived from methacrylic acid. [4A] The photosensitive resin composition according to item 3A, wherein the proportion of constituent units derived from methacrylic acid in the copolymer (A-1) is 15 to 25% by mass. [5A] A photosensitive resin composition according to item 1A or any one of items 1A to 4A, wherein the proportion of constituent units derived from the above-mentioned component (a3) ​​is 16% by mass or more. [6A] The copolymer (A-1) further comprises the following components: (a4) The following general formula (I): [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 3 or more carbon atoms.) Alkyl (meth)acrylate represented by; It has constituent units derived from, In the copolymer (A-1), The proportion of constituent units derived from component (a2) is 30 to 60% by mass, and A photosensitive resin composition according to any one of items 1A to 5A, wherein the proportion of constituent units derived from the above-mentioned component (a4) is 1% by mass to 15% by mass. [7A] The photosensitive resin composition according to item 6A, wherein R2 represents an alkyl group having 3 to 12 carbon atoms. [8A] The photosensitive resin composition according to item 6A or 7A, wherein the (a4) component comprises 2-ethylhexyl (meth)acrylate. [9A] A photosensitive resin composition according to any one of items 1A to 5A and 6A to 8A, wherein the weight-average molecular weight of the copolymer (A-1) is 30,000 or more and 50,000 or less. [10A] A photosensitive resin composition according to any one of items 1A to 5A and 6A to 9A, comprising 10% by mass or more of the copolymer (A-1) based on the total solid content of the photosensitive resin composition. [11A] A photosensitive resin composition according to any one of items 1A to 5A and 6A to 10A, comprising 30% by mass or more of the copolymer (A-1) based on the total solid content of the photosensitive resin composition. [12A] The photosensitive resin composition according to any one of items 1A to 5A and 6A to 11A, wherein the (B) component comprises a di(meth)acrylate having a bisphenol A skeleton. [13A] The photosensitive resin composition according to item 12A, comprising 20% ​​by mass or more of the di(meth)acrylate having the bisphenol A skeleton, based on the total solid content of the photosensitive resin composition. [14A] The photosensitive resin composition according to any one of items 1A to 5A and 6A to 13A, wherein the ratio of the content of component (A) to the content of component (B) {content of component (A) / content of component (B)} is 1.40 or more. [15A] The photosensitive resin composition according to any one of items 1A to 5A and 6A to 14A, wherein the ratio of the content of component (A) to the content of component (B) {content of component (A) / content of component (B)} in the photosensitive resin composition is 1.50 or more. [16A] The (C) component is a photosensitive resin composition according to any one of items 1A to 5A and 6A to 15A, comprising a compound having a biimidazole structure. [17A] Furthermore, Sensitizer A photosensitive resin composition according to any one of items 1A to 5A and 6A to 16A, wherein the sensitizer comprises a compound having at least one skeleton selected from the group consisting of skeletons derived from pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, and oxazole derivatives. [18A] The photosensitive resin composition according to item 17A, comprising a compound having a skeleton derived from an anthracene derivative as the sensitizer. [19A] The photosensitive resin composition according to item 17A or 18A, wherein the sensitizer comprises at least one compound selected from the group consisting of 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid. [20A] A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from any one of the photosensitive resin compositions described in items 1A to 5A and 6A to 19A. [21A] The following method; (1) After forming the photosensitive resin layer on a flexible substrate, a cured film is obtained on the substrate by exposing it to a size of 1 inch in width and 250 mm in length with an energy amount such that 15 steps remain on a Stuffer Industries 41-step tablet. (2) The exposed substrate is developed using a 1% by mass Na2CO3 aqueous solution at 30°C for twice the minimum development time. (3) After development, the substrate is washed with water for twice the minimum development time. (4) After washing the substrate with water, a sample is obtained by cutting it to a width of 1.2 inches so that the 1-inch wide cured photosensitive resin layer is in the center in the width direction. (5) Cylindrical mandrel method A mandrel test in accordance with the method of JIS K5600-5-1 is performed on the sample. (6) Determine the smallest mandrel diameter at which no cracks are observed in the cured film, or the smallest mandrel diameter at which no peeling of the cured film from the substrate is observed. A photosensitive resin laminate according to item 20A, wherein the minimum mandrel diameter determined by the method is 8 mm or less. [22A] The photosensitive resin laminate comprises a protective layer on the side of the photosensitive resin layer opposite to the support, The photosensitive resin laminate according to item 20A or 21A, wherein the protective layer is a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film. [23A] The photosensitive resin laminate according to item 22A, wherein the protective layer comprises a release layer on its surface. [24A] A lamination step of laminating the photosensitive resin layer in the photosensitive resin laminate described in any one of items 20A to 23A onto a substrate; An exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate; and A developing step to remove the unexposed portion of the photosensitive resin layer; A method for forming a resist pattern, comprising the characteristics of a resist pattern. [25A] A step of forming a resist pattern on a substrate using a photosensitive resin laminate described in any one of items 20A to 23A, A step of forming a conductive pattern on a substrate on which a resist pattern has been formed by etching or plating, The process of peeling the resist pattern from the substrate, A method for forming a wiring board, including the method described above. [Effects of the Invention]

[0018] [Effects of the "First Invention"] According to the present invention, it is possible to provide a photosensitive resin laminate that achieves both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern, a photosensitive resin composition that can realize such a photosensitive resin laminate, and a method for forming a resist pattern.

[0019] [Effects of "related aspects"] According to embodiments of the present invention, a photosensitive resin composition is available that can form a photosensitive resin layer (resist) that is excellent in resolution, adhesion, developability, and flexibility of the cured film. Furthermore, according to embodiments related to the present invention, it is possible to provide a photosensitive resin laminate having the photosensitive resin layer, a method for forming a resist pattern, and a method for forming a wiring board. [Brief explanation of the drawing]

[0020] [Figure 1] A plan view showing the configuration of a drawing pattern related to this embodiment. [Figure 2] A plan view showing the configuration of a drawing pattern related to this embodiment. [Modes for carrying out the invention]

[0021] Embodiments of the present invention will be described below with reference to the drawings. The present invention is not limited to this embodiment, and can be implemented with various modifications within the scope of its gist.

[0022] In this specification, if there are multiple structures represented by the same reference numeral in the same formula, unless otherwise specified, each structure may be selected independently and may be identical or different from one another. Similarly, if there are multiple structures represented by the same reference numeral in different formulas, unless otherwise specified, each structure may be selected independently and may be identical or different from one another. In this specification, various measurements are performed according to the methods described in the examples unless otherwise specified. In this specification, upper or lower limits in numerical ranges described in steps may be replaced by upper or lower limits in other numerical ranges described in steps, and further, by the corresponding values ​​described in the examples.

[0023] In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic," "(meth)acrylate" means "acrylate" and / or "methacrylate," and "(meth)acryloyl" means "acryloyl" and / or "methacryloyl." A "(meth)acryloyl group compound" is referred to, for example, as a "(meth)acrylate compound." In this specification, "process" is included in the term if it is an independent process, or even if it is not clearly distinguishable from other processes, as long as the function of the process is achieved. In the drawings, scale, shape and length may be exaggerated for further clarity.

[0024] In this specification, "derivative" includes not only compounds derived from the parent compound (compounds other than the parent compound), but also the parent compound itself. Therefore, for example, "styrene derivative" includes not only compounds derived from styrene (compounds other than styrene), but also styrene itself, which is the parent compound.

[0025] [Embodiment of the "First Invention"] [Photosensitive resin composition] The photosensitive resin composition of this embodiment is The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; (C) Initiator; and (D) Boron compounds that absorb h-rays and / or i-rays (hereinafter sometimes simply referred to as "boron compounds"); Includes. According to this, it is possible to provide a photosensitive resin laminate that achieves both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern.

[0026] In one embodiment, the photosensitive resin composition of this embodiment is The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; and (C) Polymerization initiator; A photosensitive resin composition comprising, (D) Component includes a boron compound that absorbs to h-rays and / or i-rays, Component (B) contains a difunctional compound having two ethylenically unsaturated bonds in one molecule.

[0027] In this specification, the following terms are defined as follows: "H-line" refers to light with a wavelength of 400-410 nm, and in one embodiment, it refers to light with a wavelength of 405 nm. "i-line" refers to light with a wavelength of 350-370 nm, and in one embodiment, it refers to light with a wavelength of 365 nm. "Having absorbance" means that the absorbance at 5 ppm in a toluene solution is 0.008 or higher. Regarding "having absorbance," the absorbance is measured according to (1) to (5) below. The absorbance measurement is performed at room temperature (25°C). The same measurement method can be used in the examples.

[0028] (1) Prepare a toluene solution of the compound to be measured at a concentration of 5 ppm. Measure the absorbance of this toluene solution using a spectrophotometer (Hitachi High-Technologies U-3010) with a two-sided transparent quartz cell (Tokyo Glass Instruments S15-UV-10) having a path length of 10 mm, i.e., an inner dimension of 10 mm in the direction of light propagation. Read the absorbance values ​​at 1 nm intervals. Treat the read values ​​as absorbance (A1). The above "toluene solution with a concentration of 5 ppm" is acceptable if it is a toluene solution with a concentration of approximately 5 ppm, specifically a toluene solution with a concentration of 4.90 to 5.10 ppm. In that case, the absorbances (A1) and (A3) at 5 ppm for the toluene solution below are calculated using values ​​converted to absorbances at a concentration of 5 ppm.

[0029] (2) Using the same method as in (1) above, measure the absorbance of toluene alone and read the obtained absorbance values ​​at 1 nm intervals. Treat the read values ​​as absorbance (A2). (3) Subtract the absorbance (A2) at the same wavelength from the absorbance (A1) above. This will give you the subtracted value (A1-A2) for every 1 nm. Treat the obtained value as the absorbance (A3) at 5 ppm in the toluene solution. (4) In the absorbance obtained at 1 nm intervals (A3), if there is a wavelength in the range of 400 to 410 nm where the absorbance is 0.008 or higher, it shall be treated as having "absorption on the h line". Similarly, in the absorbance obtained at 1 nm intervals (A3), if there is a wavelength in the range of 350 to 370 nm where the absorbance is 0.008 or higher, it shall be treated as having "absorption on the i line".

[0030] Furthermore, as measured in the examples, a value of 0.008 or higher for the absorbance (A3) at 405 nm may be treated as "having absorption in the h-line," and a value of 0.008 or higher for the absorbance (A3) at 365 nm may be treated as "having absorption in the i-line."

[0031] In the photosensitive resin composition of this embodiment, by including component (D) along with components (A) to (C) above, component (D) exhibits a suitable sensitizing function for predetermined exposure wavelengths (h-line and / or i-line) used in photolithography. Therefore, the content of other sensitizers that may hinder the achievement of good sensitivity in the photosensitive resin layer can be reduced. Thus, by using the photosensitive resin composition of this embodiment, a photosensitive resin layer with good sensitivity can be obtained.

[0032] Furthermore, it was generally recognized that achieving both good sensitivity in the photosensitive resin layer and high flexibility in the resist pattern was difficult. For example, from the viewpoint of achieving good sensitivity in the photosensitive resin layer, a resin design that crosslinks suitably during the exposure process in photolithography is preferable, but as crosslinking progresses, the flexibility of the photosensitive resin layer, and consequently the flexibility of the resist pattern, tends to be lost. In contrast, the photosensitive resin composition of this embodiment, by including component (D) along with components (A) to (C) above, makes it possible to achieve both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern.

[0033] Achieving good sensitivity in the photosensitive resin layer is related to shortening exposure time, and consequently to improving the productivity of wiring patterns. Furthermore, achieving high flexibility in the resist pattern is related to suppressing resist pattern defects, and consequently to improving the resolution of the wiring pattern. Therefore, by using the photosensitive resin composition of this embodiment, it is possible to meet expectations for improved productivity and resolution of wiring patterns in printed circuit boards manufactured by photolithography.

[0034] The photosensitive resin composition of this embodiment is (A) Component: 10~90% by mass, (B) Component: 5~70% by mass, (C) Components: 0.01-20% by mass, and (D) Component: 0.01~20% by mass It is preferable that it contains [a certain component]. This makes it easier for the photosensitive resin composition to exhibit its function favorably, and as a result, the effects of the present invention are easily achieved. The following describes each component that constitutes this embodiment.

[0035] <(A) Component: Alkali-soluble polymer> Component (A) is an alkali-soluble polymer, that is, a polymer soluble in alkaline solutions. In one embodiment, component (A) is a polymer soluble in alkaline developer.

[0036] From the viewpoint of exhibiting suitable alkali solubility, component (A) preferably has a carboxyl group. Also, from the same viewpoint, component (A) preferably has an acid value of 50 to 600 mg KOH. The acid value of component (A) may be 60 mg KOH or more or 80 mg KOH or more, and may be 500 mg KOH or less or 400 mg KOH or less.

[0037] The weight-average molecular weight (Mw) of component (A) is preferably 3,000 or more, 5,000 or more, 7,000 or more, 10,000 or more, 12,000 or more, or 15,000 or more, and preferably 500,000 or less, 200,000 or less, 100,000 or less, 70,000 or less, or 65,000 or less. When the Mw of component (A) is above the lower limit, it is easier to maintain a uniform thickness of the photosensitive resin layer. Also, when the Mw of component (A) is below the upper limit, it is easier to ensure the developability of the photosensitive resin layer. The polydispersity (Mw / Mn), which is the ratio of the above Mw to the number-average molecular weight (Mn) of component (A), is preferably 1.0 to 6.0.

[0038] If component (A) contains multiple alkali-soluble polymers, "Mw of component (A)" means the total Mw of component (A) calculated from the mass ratio of each alkali-soluble polymer and the Mw of each alkali-soluble polymer. Similarly, if component (A) contains multiple alkali-soluble polymers, "Mn of component (A)" means the total Mn of component (A), calculated from the mass ratio of each alkali-soluble polymer and the Mn of each alkali-soluble polymer.

[0039] The content of component (A) in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition; the same applies to each component unless otherwise specified) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass. From the viewpoint of maintaining the alkali developability of the photosensitive resin layer, the content of component (A) is preferably above the lower limit, and from the viewpoint of the resist pattern being easily flexible, it is preferably below the upper limit.

[0040] Component (A) is preferably a copolymer containing at least one of the following first monomers as a comonomer component. Component (A) is more preferably a copolymer containing at least one of the following first monomers and at least one of the following second monomers as comonomer components. (A) Component, the first monomer, and the second monomer may each be used individually or in combination of two or more.

[0041] (First monomer) The first monomer is a carboxylic acid or acid anhydride having a polymerizable unsaturated 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 alkali developability. Since methacrylic acid has relatively high hydrophobicity, using it makes it easier to improve the resolution of the resist pattern in addition to the above.

[0042] The copolymerization ratio of the first monomer is preferably 10 to 50% by mass, based on the total mass of all comonomer components, from the viewpoint of excellent adhesion and resolution. From the same viewpoint, the copolymerization ratio is more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0043] (Second monomer) The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include aromatic monomers, alkyl (meth)acrylates, conjugated diene compounds, polar monomers, and crosslinkable monomers.

[0044] Examples of aromatic monomers include benzyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, divinylbenzene, and styrene derivatives (styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, etc.).

[0045] Alkyl (meth)acrylates are a concept that encompasses both linear alkyl esters and cyclic alkyl esters. Specifically, examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0046] Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.

[0047] Examples of polar monomers include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and pentenol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol (meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate; and epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate.

[0048] Examples of crosslinkable monomers include trimethylolpropane triacrylate.

[0049] Furthermore, the second monomer is preferably a monomer having an aromatic hydrocarbon group, from the viewpoint of improving the adhesion and resolution of the resist pattern. Examples of aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. Examples of aralkyl groups include benzyl groups. In particular, from the same viewpoint, the second monomer is preferably benzyl (meth)acrylate, a styrene derivative, and more preferably styrene.

[0050] The copolymerization ratio of monomers having aromatic hydrocarbon groups is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, based on the total mass of all comonomer components, and also preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0051] Furthermore, the second monomer is preferably 2-hydroxyethyl (meth)acrylate, and more preferably 2-hydroxyethyl methacrylate (HEMA), from the viewpoint of improving the adhesion and resolution of the resist pattern.

[0052] One aspect of the second monomer is: Embodiments comprising monomers having aromatic hydrocarbon groups; Embodiments comprising 2-hydroxyethyl (meth)acrylate; and Embodiments comprising both a monomer having an aromatic hydrocarbon group and 2-hydroxyethyl (meth)acrylate; This includes all of the following.

[0053] The synthesis method for component (A) may include the step of adding an appropriate amount of a radical polymerization initiator 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. The above synthesis method may include the step of adding a portion of the mixture dropwise to the reaction solution while synthesizing. The above synthesis method may include the step of adding more solvent after the reaction is complete to adjust to the desired concentration. The synthesis method may be by bulk polymerization, suspension polymerization, or emulsion polymerization, in addition to the solution polymerization method.

[0054] <(B) Component: Compound containing an ethylenically unsaturated bond> Component (B) is a compound having an ethylenically unsaturated bond in its structure. Such component (B) is polymerizable. Component (B) may be used alone or in combination of two or more types.

[0055] Component (B) preferably contains a compound having two ethylenically unsaturated bonds in one molecule (a difunctional compound). Difunctional compounds are more likely to suppress intermolecular entanglement than compounds having three or more ethylenically unsaturated bonds in one molecule (a polyfunctional compound). Therefore, by including a difunctional compound as component (B), the desired fluidity can be imparted to the photosensitive resin composition. In this case, a photosensitive resin laminate having a support and a highly flat photosensitive resin layer can be obtained, which is likely to be effective in suppressing defects in the wiring pattern. In addition, by using a photosensitive resin composition containing a difunctional compound as component (B), it is easier to impart appropriate flexibility to the photosensitive resin layer. A photosensitive resin layer with appropriate flexibility has good conformability to the substrate, making it less likely for gaps to form between the layer and the substrate during lamination. Furthermore, difunctional compounds exhibit superior crosslinking efficiency in the exposure process compared to compounds containing one ethylenically unsaturated bond in a single molecule (monofunctional compounds). In addition, difunctional compounds can suppress excessive crosslinking during the exposure process compared to polyfunctional compounds, thereby imparting appropriate flexibility to the photosensitive resin layer after exposure. Therefore, the above components (A) to (D) ensure the flexibility of the resist pattern and also meet expectations for improved resolution of the wiring pattern.

[0056] Component (B) may include compounds having one ethylenically unsaturated bond in one molecule; compounds having three; compounds having four; compounds having five; and compounds having six or more. That is, component (B) may include monofunctional compounds and / or polyfunctional compounds. In component (B), the total mass of the difunctional compounds may be greater than the total mass of the monofunctional compounds and polyfunctional compounds.

[0057] The bifunctional compound is preferably a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure, and more preferably a compound having a bisphenol A structure. This makes it easier to achieve the effects of the present invention. The above compound may be present in an amount of 5% by mass or more, or 10% by mass or more, based on the total amount of photosensitive composition components, and may also be present in an amount of 60% by mass or less, 55% by mass or less, or 50% by mass or less. The hydrogenated bisphenol A structure is obtained by hydrogenating bisphenol A.

[0058] (B) For example, component B is: Di(meth)acrylates of polyalkylene glycols, in which an average of 1 to 15 moles of alkylene oxide are added to each end of bisphenol A; Tri(meth)acrylates of polyalkylentriols obtained by adding an average of 3 to 25 moles of alkylene oxide to trimethylolpropane; Glycerin; Trimethylolpropane; Pentaerythritol; Diglycerin; Ditrimethylolpropane; Compounds obtained by adding a polyalkylene oxide group to an isocyanurate ring or the like, or by modifying an alcohol with ε-caprolactone, and then converting that alcohol to a (meth)acrylate; Compounds obtained by directly reacting an alcohol, which is acquired by adding a polyalkylene oxide group to an isocyanurate ring or the like, or by ε-caprolactone modification, with (meth)acrylic acid without modification with an alkylene oxide group or ε-caprolactone; Tetra(meth)acrylates of polyols obtained by adding an average of 4-35 moles of alkylene oxide to pentaerythritol; Hexa(meth)acrylates of polyols obtained by adding an average of 4-30 moles of alkylene oxide to dipentaerythritol; We can list some examples. The alkylene oxides mentioned above are preferably ethylene oxide (EO) and propylene oxide (PO).

[0059] Furthermore, it is preferable that component (B) contains a hindered amine compound. This reduces the likelihood of residue being generated after the resist pattern is removed.

[0060] In this specification, "hindered amine compound" means, for example, the following general formula: [ka] (In the formula, R1 independently represents an alkyl group having 1 or more carbon atoms, and R2 represents hydrogen or an alkyl group having 1 or more carbon atoms. The number of carbon atoms in R1 and R2 may be 10 or less, independently.)

[0061] The hindered amine compound content may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total amount of photosensitive composition components, and may also be 20% by mass or less, 15% by mass or less, or 10% by mass or less, or even 0% by mass.

[0062] Hindered amine compounds may be compounds that have one ethylenically unsaturated bond. The content of compounds that have one ethylenically unsaturated bond (excluding hindered amine compounds if they are compounds that have one ethylenically unsaturated bond) may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 0% by mass, based on the total amount of photosensitive composition components.

[0063] Specifically, one embodiment of component (B) is, for example, Dimethacrylate of polyethylene glycol, in which an average of 5 moles of EO are added to each end of bisphenol A; Dimethacrylate of polyethylene glycol, in which an average of 2 moles of EO are added to each end of bisphenol A; Tetramethacrylate obtained by adding an average of 9 moles of EO to pentaerythritol; Tetramethacrylate obtained by adding an average of 15 moles of EO to pentaerythritol; Hexamethacrylate of polyethylene glycol obtained by adding an average of 13 moles of EO to dipentaerythritol; Dimethacrylate of polyethylene glycol obtained by adding an average of 2 moles of EO to each end of hydrogenated bisphenol A; 1,2,2,6,6-Pentamethylpiperidyl methacrylate; These are some examples.

[0064] The content of component (B) in the photosensitive resin composition is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and even more preferably 35 to 60% by mass, based on the total amount of components in the photosensitive composition. From the viewpoint of preventing curing defects in the photosensitive resin layer and suppressing delays in development time, the content of component (B) is preferably above the lower limit. From the viewpoint of improving the removeability of the resist pattern, it is preferably below the upper limit.

[0065] The ratio of the total mass of component (B) to the total mass of component (A) (B / A) is preferably 1 / 3.0 to 1 / 0.5 (for example, 0.33 to 2.0). This ratio allows the photosensitive resin composition to function well and, as a result, the effects of the present invention are easily achieved. From a similar viewpoint, the above ratio (B / A) is more preferably 1 / 2.5 to 1 / 0.7 (for example, 0.40 to 1.4).

[0066] <(C) Component: Polymerization initiator> Component (C) is a compound capable of initiating the polymerization of component (B). Component (C) is preferably a photopolymerization initiator and more preferably contains a compound that generates radicals upon exposure to active light, thereby initiating the polymerization of component (B).

[0067] Examples of component (C) include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, and halogen compounds.

[0068] Examples of hexaarylbiimidazole compounds include dimers of compounds having a rophine structure (rophine dimers), namely, dimers of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole. Examples of rophine dimers include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-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, and 2,2'-bis-(2,4 -Difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole , 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetraki Examples include su-(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.

[0069] From the viewpoint of excellent sensitivity, resolution, and adhesion, component (C) preferably contains a rofin dimer. In particular, component (C) more preferably contains a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, a 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, or a 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and even more preferably contains a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0070] 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.

[0071] Examples of aromatic ketone compounds include benzophenone, Michlaz ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. Aromatic ketone compounds may function as photoinitiators when used alone, and may also function as sensitizers when used in combination with other photoinitiators.

[0072] 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 BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0073] 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 BASF).

[0074] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. 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.

[0075] 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 BASF).

[0076] Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine.

[0077] 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.

[0078] The content of component (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to achieve high resolution.

[0079] From the viewpoint of having excellent sensitivity, it is preferable that component (C) contains a rofin dimer. When the photosensitive resin composition contains a rofin dimer as component (C), the rofin dimer content is preferably 3.0 to 10% by mass, more preferably 4.0 to 9.0% by mass, and even more preferably 5.0 to 8.0% by mass, based on the total solid content of the photosensitive resin composition. By adjusting the content of component (C) within the above range, it becomes easier to obtain sufficient sensitivity, and thus easier to achieve high resolution.

[0080] <(D) Component: Boron compound that absorbs h-rays and / or i-rays> Component (D) contains a boron compound that absorbs for h-rays and / or i-rays. The boron compound as component (D) is excited by the h-line and / or i-line, resulting in negative electron transfer to component (C). This exhibits a sensitizing function. In addition, the boron compound, which has become a radical cation due to the negative electron transfer to component (C), functions as a polymerization initiator species as the substituent on the boron cleaves. By using the photosensitive resin composition of this embodiment, which contains a boron compound that exhibits a sensitizing function in this way, a photosensitive resin layer with good sensitivity can be obtained.

[0081] The boron compound as component (D) preferably has a wavelength such that the absorbance (A3) value at 5 ppm in a toluene solution measured by the above method in the range of 400 to 410 nm or 350 to 370 nm is 0.008 or higher. When the absorbance (A3) value is above this lower limit, the boron compound is easily excited, and therefore the sensitizing function is easily exhibited. Furthermore, from the viewpoint of more favorably exhibiting the sensitizing function, the absorbance (A3) value is more preferably 0.010 or higher, and even more preferably 0.012 or higher.

[0082] The upper limit of the absorbance value (A3) may be 0.500 or less, 0.400 or less, or 0.300 or less. By keeping the absorbance value below this upper limit, it is easier to ensure the transmittance of the photosensitive resin composition even when a sufficient amount of component (D) is included to exert its sensitizing function, and therefore, it is less likely to adversely affect the curing of the photosensitive resin composition during exposure.

[0083] When performing exposure using a mercury lamp, the absorbance (A3) value at the h line (405 nm) and / or the i line (365 nm) is preferably 0.008 or higher, more preferably 0.010 or higher, and even more preferably 0.012 or higher.

[0084] When exposed to exposure light in either the 350-370 nm or 400-410 nm range, it is preferable that the absorbance (A3) value in the corresponding wavelength range is 0.008 or higher. On the other hand, the absorbance (A3) value in the other wavelength range is not limited. For example, when exposure is performed with light having a wavelength near the h-line, it is preferable to have wavelengths in the range of 400 to 410 nm in which the absorbance (A3) value is 0.008 or higher. In this case, for 350 to 370 nm, it is not necessarily required to have wavelengths in which the absorbance (A3) value is 0.008 or higher. Furthermore, for example, when exposed with light having a wavelength near the i-line, it is preferable to have wavelengths in the range of 350 to 370 nm in which the absorbance (A3) value is 0.008 or higher. In this case, for 400 to 410 nm, it is not necessarily required to have wavelengths in which the absorbance (A3) value is 0.008 or higher.

[0085] Furthermore, in the boron compound as component (D), since boron is a Lewis acid, an interaction different from a covalent bond (a Lewis acid-Lewis base bond) occurs between boron and the Lewis base. In this case, rearrangement of the Lewis acid-Lewis base bond is relatively easy. Even if the resist pattern is subjected to external stress, the rearrangement of the Lewis acid-Lewis base bond in the resist pattern is relatively easy, so it is easy to deform flexibly in response to external stress, and therefore, fracture of the resist pattern is easily suppressed.

[0086] Boron compounds are represented by the following general formula: BR 1 R 2 R 3 ... (1) It is preferable that the compound is represented by the formula (1). 1 ~R 3 By selecting the appropriate element, it is easier to realize boron compounds that have absorption for the h-line and / or i-line.

[0087] In the above general formula (1), R 1 ~R 3 These are, independently, a monovalent organic group and an alkoxy group (-OR). 4 ;R 4 (Carbon 1-10 hydrocarbon group), alkylamino group (-NR) 5 R 6 ;R 5 and R 6 Each of these may be at least one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group (-OH), hydrogen, and a halogen, and multiple R 1 ~R 3 This may form a saturated or unsaturated ring.

[0088] Examples of monovalent organic groups include alkyl groups having 1 to 20 carbon atoms, alkanoyl groups, any substituents including a ring structure having 3 to 20 carbon atoms, or groups in which the hydrogen atoms in these groups are substituted with halogen atoms or alkoxy groups having 1 to 10 carbon atoms. Examples of substituents containing the aforementioned ring structure with 3 to 20 carbon atoms include benzoyl groups and aryl groups with 6 to 20 carbon atoms.

[0089] In the above general formula (1), R 1 ~R 3 Each of these groups may independently be a heterocyclic group, and may be a saturated or unsaturated ring group containing a heteroatom (e.g., nitrogen, oxygen, sulfur). R 1 ~R 3 These may form saturated or unsaturated rings. Such rings may contain heteroatoms. The halogen in the monovalent organic group may be, for example, fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). As a result, the effects of the present invention are easily achieved.

[0090] Among them, R 1 ~R 3 It is more preferable that at least one of these is an alkoxy group or a hydroxyl group. This makes it easier to achieve the effects of the present invention. R 1 ~R 3 If at least one of them is an alkoxy group or a hydroxyl group, then R that is not an alkoxy group or a hydroxyl group 1 ~R 3 It can be hydrogen.

[0091] Examples of boron compounds represented by the above general formula (1) include boronic acid, boronic acid ester, boric acid ester, boroxine, and boric acid ester. Among these, boronic acid, boronic acid ester, and boroxine are preferred from the viewpoint of the flexibility of the resist pattern.

[0092] Boronic acids may be represented in the form of RB(OH)2. Boronic acid esters are RB(OH)(OR a ), RB(OR a )2, or R-BO2R b It may be expressed in the manner of: Boric acid esters are B(OH)2(OR a), B(OH)(OR a )2, or B(OR a )This may be represented in the manner of 3. The poric acid ester is R2B-OR a It may be expressed in the manner of: In the above formula, R and R a Each of these may independently be the aforementioned monovalent organic group, R b R may be a divalent organic group. In the formula, if there are multiple Rs, or R a If there are multiple Rs, the multiple Rs may be different from each other, and the multiple Rs a It goes without saying that they can be different from one another. Preferred divalent organic groups are alkyl groups having 1 to 20 carbon atoms and aryl groups having 6 to 20 carbon atoms.

[0093] In one embodiment, the boron compound is R-(NR a 2) 2 or RB (OR a )(NR a The compound may be represented in the embodiment of 2) (wherein R and R a Each of these may independently be the aforementioned monovalent organic group.

[0094] Here, the boron compound is given by the following general formula: *-B(OH)2; *-B(OR 1 )2; *-B(NR 1 2)2; *-B(OH)(OR 1 ); or, The following general formula (2): [ka] (In the formula, R 1 Each of these independently represents the aforementioned monovalent organic group, R 2 (where * indicates a divalent organic group, and * indicates a bonding site with various skeletons.) It is preferable that the compound contains at least one boron moiety selected from the group consisting of the following. The boron compounds of this embodiment include compounds in which such a boron moiety is substituted with any hydrogen atom in various skeletons.

[0095] Specifically, boron compounds include those with the following general formula: R 2 -B(OH)2 R 3 -B(OR 1 )2 R 4 -B(NR 5 2)2 R 6 -B(OH)(OR 7 ) (In the formula, R 1 ~R 7 R is a monovalent organic group and can have multiple R groups present in a single molecule. 1 , and R 5 They may be the same or different. ); and, The following general formula (3): [ka] (In the formula, R 8 is a monovalent organic group, R 9 ( is a divalent organic group.) Compounds represented by ; Preferably, the compound includes at least one compound selected from the group consisting of the following:

[0096] In one embodiment, the boron compound may be a compound having multiple boron atoms in a single molecule. Examples of compounds having multiple boron atoms in a single molecule include diboronic acid and diboronic acid esters. Diboronic acid may be represented in the form R(B(OH)2)2. Diboronic acid ester is B2(OR a )4, or R(B(OR a )2)2 may be expressed in the manner of 2. In the above formula, R and R a Each of these may independently be the aforementioned monovalent organic group. In the formula, R a If multiple Ra It goes without saying that they can be different from one another.

[0097] Boron compounds having hydrocarbon groups, including those mentioned above, can be treated as organoboron compounds. Among boron compounds having hydrocarbon groups, those that absorb h-rays and / or i-rays and have a carbon(C)-boron(B) bond excite electrons with the h-rays and / or i-rays, generating radical cations, and the CB bond between carbon(C) and boron(B) cleaves, creating new polymerization ends. Therefore, compounds that absorb h-rays and / or i-rays and have a carbon(C)-boron(B) bond not only have good sensitizing properties but also function as polymerization initiators, making it easier to realize photosensitive resin layers with better sensitivity.

[0098] In one embodiment, the boron compound may have a predetermined skeleton. Preferably, the predetermined skeleton is a skeleton having an aromatic ring and / or a skeleton having a heteroatom. Having these skeletons makes the boron compound easily excited by h-rays and / or i-rays, making it easier to obtain good sensitivity for the photosensitive resin composition.

[0099] The boron compound may have a skeleton that is preferably derived from at least one selected from the group consisting of pyrazoline, anthracene, naphthalene, triarylamine, oxazole, N-aryl-α-amino acid, aromatic ketone derivative, dialkylaminobenzoic acid ester, and chrysene. In particular, from the viewpoint of sensitivity, the boron compound is more preferably derived from anthracene and / or pyrazoline.

[0100] Examples of boron compounds having the above-mentioned skeleton include compounds in which any hydrogen atom in a compound such as pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives, dialkylaminobenzoic acid ester derivatives, and chrysene derivatives is substituted for the boron portion. The boron compound may include a compound having a plurality of the boron parts in the above-mentioned skeleton, and the plurality of boron parts that may exist in the same compound may be the same or different.

[0101] Examples of pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)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, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxy Examples include phenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline.

[0102] Examples of anthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9- Examples include chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenylyl)-10-bromoanthracene, 9-(4-biphenylyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene, and 9-(3-bromophenyl)-10-phenylanthracene. Among these, boronic acids having a 10-phenyl-9-anthracene skeleton (10-phenyl-9-anthraceneboronic acid) are preferred from the viewpoint of sensitivity.

[0103] Examples of naphthalene derivatives include 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-propoxynaphthalene, 1-butoxynaphthalene, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-bis(n-butoxy)naphthalene, 1,4-bis(i-butoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, and 1,4-bis(n-heptyloxy)naphthalene. Examples include 1,4-bis(n-octyloxy)naphthalene, 1,4-bis(2-ethylhexyloxy)naphthalene, 1,4-bis(n-nonyloxy)naphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,4-bis(2-methylglycidyloxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, and 2-(2-hydroxyethoxy)naphthalene. Among these, 1,4-diethoxynaphthalene is preferred as the naphthalene derivative.

[0104] Examples of oxazole derivatives include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazole-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazole-2-yl)naphthalene-1-yl]-1,3-benzoxazole.

[0105] Examples of N-aryl-α-amino acid derivatives include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-(n-propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, and N-(n-pro Examples include N-(n-butyl)-N-(p-tolyl)glycine, N-(n-butyl)-N-(p-tolyl)glycine, N-methyl-N-(p-chlorophenyl)glycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(n-propyl)-N-(p-chlorophenyl)glycine, N-methyl-N-(p-bromophenyl)glycine, N-ethyl-N-(p-bromophenyl)glycine, N-(n-butyl)-N-(p-bromophenyl)glycine, N,N'-diphenylglycine, N-methyl-N-(p-iodophenyl)glycine, N-(p-bromophenyl)glycine, N-(p-chlorophenyl)glycine, and N-(o-chlorophenyl)glycine.

[0106] Examples of aromatic ketone derivatives include benzophenone derivatives. Specifically, for example, Alkylbenzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone; Benzophenone compounds having halogen atoms, such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone; Examples include benzophenone compounds substituted with a carboxyl group or an alkoxycarbonyl group, such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid, or its tetramethyl ester; and so on. Furthermore, aromatic ketone derivatives include benzophenone derivatives substituted with alkylamino groups. Specifically, for example, Bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dihydroxyethylamino)benzophenone, among which 4,4'-bis(dialkylamino)benzophenone compounds are preferred; 4-Methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, etc. These are some examples.

[0107] In one embodiment, the boron compound is preferably a compound having the following skeleton together with or separately from the above skeleton. Examples of such skeletons include at least one skeleton selected from the group consisting of at least one skeleton selected from the group consisting of pyrene, coumarin, and triarylamine. This is advantageous in terms of sensitivity.

[0108] In one embodiment, component (D) is: 10-phenyl-9-anthraceneboronic acid, 4,4,5,5-Tetramethyl-2-(10-phenylanthracene-9-yl)-1,3,2-dioxaborolane, [10-[4-(naphthalene-1-yl)phenyl]anthracene-9-yl]boronic acid, and 2-ethyl-4-methylimidazolium tetraphenylborate, Examples include the following.

[0109] Component (D) is a boron compound that absorbs for the h-ray and / or i-ray. In other words, component (D) is, A boron compound that absorbs to the h-ray but not to the i-ray. A boron compound that does not absorb the h-ray but absorbs the i-ray, and A boron compound that absorbs both h-rays and i-rays. It is one of the following. However, it is preferable that the boron compound of component (D) has absorption for the h line at least.

[0110] The content of component (D) is preferably 0.01 to 2.0% by mass, and more preferably 0.3 to 1.5% by mass, based on the total mass of component (A).

[0111] Component (D) may be used alone or in combination of two or more. Component (D) may include other boron compounds (boron compounds that do not fall under the boron compounds described in this embodiment) in addition to the boron compounds described in this embodiment.

[0112] Other boron compounds (boron compounds not included in the boron compounds described in this embodiment) may be present in amounts of 20% by mass or less, 10% by mass or more, 1% by mass or less, or 0% by mass, based on the total mass of component (D).

[0113] <(E) Ingredients: Other ingredients> The photosensitive resin composition may optionally contain components other than those listed in (A) to (D) above. Examples of other components include colorants, leuco dyes, base dyes (dyes other than leuco dyes), colorants, antioxidants, stabilizers, plasticizers, and other sensitizers (sensitizers other than those listed in (D) above). These other components may be used individually or in combination of two or more.

[0114] Examples of colorants include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green (e.g., Eisen® MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20, Diamond Green (e.g., Eisen® DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLAS GREEN 533 manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industry Co., Ltd.), and 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OIL BLUE 630 manufactured by Orient Chemical Industry Co., Ltd.).

[0115] The colorant content is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.5 to 2% by mass, based on the total mass of the photosensitive resin composition.

[0116] Examples of leuco dyes include leucocrystal violet ("tris[4-(dimethylamino)phenyl]methane") and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.

[0117] The leuco dye content is preferably 0.01 to 2% by mass, and more preferably 0.1 to 1.5% by mass, based on the total mass of the photosensitive resin composition.

[0118] Examples of base dyes include Basic Green 1 [CAS number (same below): 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].

[0119] The base dye content 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 mass of the photosensitive resin composition.

[0120] Examples of antioxidants include triphenyl phosphite (e.g., ADEKA Corporation, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., ADEKA Corporation, trade name: 2112), tris(mononylphenyl) phosphite (e.g., ADEKA Corporation, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., ADEKA Corporation, trade name: 329K).

[0121] The antioxidant content is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, based on the total mass of the photosensitive resin composition.

[0122] Examples of stabilizers include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group.

[0123] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salts (e.g., aluminum salts with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosoamine. Examples of commonly used compounds include methyl phosphate, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0124] 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.).

[0125] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group is preferably 0.001 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive resin composition.

[0126] Other sensitizers include those other than component (D) above. Therefore, other sensitizers do not contain, for example, the boron portion. Other sensitizers in the photosensitive resin composition (sensitizers other than component (D) above) include, for example, pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives substituted with alkylamino groups, dialkylaminobenzoic acid ester derivatives, and chrysene derivatives.

[0127] Specific examples of various derivatives are as described in section (D), and other embodiments of sensitizers include, for example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, coumarin (e.g., coumarin 102), etc.

[0128] The content of other sensitizers is preferably 2% by mass or less, more preferably 1.5% by mass or less, based on the total mass of the photosensitive resin composition. Preferably 0.8% by mass or less, more preferably 0.3% by mass or less. The content of other sensitizers may be 0% by mass. When used in combination with component (D) above, the content (by mass) of other sensitizers is preferably 2 times or less, and more preferably 1.7 times or less, compared to the content of component (D) above.

[0129] Other components include carboxylbenzotriazoles. The content of carboxylbenzotriazoles is, for example, 0.01% by mass or more, and 5% by mass or less, based on the total mass of the photosensitive resin composition.

[0130] [Embodiments of the "Related Inventions"] Hereinafter, embodiments related to the present invention will be described. The effects achieved by such embodiments are effects related to the effects of the present invention. In one aspect, unless otherwise specified, "Adhesion" refers to the adhesion performance between the resist pattern and the substrate; "Resolution" refers to the resolution performance of the resist pattern; "Developability" refers to the development performance of the photosensitive resin layer (resist); "Flexibility of the cured film" refers to the flexibility performance of the photosensitive resin layer (resist), particularly the photosensitive resin layer cured by exposure; Each means.

[0131] [First Embodiment] [Photosensitive Resin Composition] One aspect of this embodiment is a photosensitive resin composition. Such a photosensitive resin composition contains the following components: (A) Alkali-soluble polymer; (B) A compound having an ethylenically unsaturated bond; and (C) A polymerization initiator; It is a photosensitive resin composition containing the component (A) contains a copolymer (A-1), the copolymer (A-1) has at least the following components: (a1) (Meth) acrylic acid; (a2) A styrene derivative; and (a3) Hydroxyalkyl (meth) acrylate; has structural units derived from the proportion of the structural units derived from the component (a1) is 15 to 26% by mass, the proportion of the structural units derived from the component (a2) is 30 to 70% by mass, the proportion of the structural units derived from the component (a3) is 15 to 35% by mass, and the glass transition temperature (Tg) calculated based on Fox's formula is 100 °C or lower, It is a photosensitive resin composition. According to such a photosensitive resin composition, it is possible to form a photosensitive resin layer (resist) that is excellent in all aspects of resolution, adhesion, developability, and flexibility of the cured film. Furthermore, according to such a photosensitive resin composition, it is possible to provide a photosensitive resin laminate having the photosensitive resin layer and a method for forming a resist pattern.

[0132] The present inventors have found that by adopting one aspect of the present invention, a photosensitive resin composition can be obtained that can form a photosensitive resin layer (resist) that is excellent in resolution, adhesion, developability, and flexibility of the cured film. Here, while the photosensitive resin layer is cured in the exposure process, the cured photosensitive resin layer (cured film) is required to have a certain degree of flexibility. One aspect of the present invention can provide a photosensitive resin layer (resist) that is also excellent in the balance of flexibility of the cured film itself (balance between curing and flexibility).

[0133] In this specification, components (A) to (C) above may be simply referred to as "component (A)" to "component (C)". The same applies to the other components described later, in addition to components (A) to (C). Each component, and the raw materials for each component, may be used individually or in combination of two or more. In this specification, "solids" of the photosensitive resin composition means the components of the photosensitive resin composition other than the solvent. The following explains each component.

[0134] <(A) component> ≪Schematic configuration≫ Component (A) is a polymer soluble in an alkaline aqueous solution, and such polymer is, for example, a vinyl polymer containing a carboxyl group. Component (A) preferably contains a carboxyl group and has an acid equivalent of 100 to 600. Acid equivalent refers to the mass in grams of an alkali-soluble polymer having 1 equivalent of a carboxyl group. Adjusting the acid equivalent to 100 or more is preferable from the viewpoint of excellent resolution and adhesion. Adjusting the acid equivalent to 600 or less is preferable from the viewpoint of excellent developability and peelability. The acid equivalent may be measured using a titration apparatus {for example, a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.} and 0.1 mol / L sodium hydroxide by potentiometric titration. From the same viewpoint as above, the acid equivalent of component (A) is more preferably 250 to 450.

[0135] The weight-average molecular weight (Mw) of component (A) is preferably 5,000 to 500,000. Adjusting the weight-average molecular weight (Mw) to 5,000 or more is preferable from the viewpoint of superior performance in areas such as adhesion, flexibility of the cured film, and edge fusing. Adjusting the weight-average molecular weight (Mw) to 500,000 or less is preferable from the viewpoint of making it easier to prevent polymer aggregates from becoming larger due to the developing solution, and consequently from the viewpoint of making it easier to prevent yield reduction that may occur due to such aggregates during circuit board formation, etc. Here, edge fusing refers to the ability to suppress the phenomenon of the photosensitive resin layer protruding from the end face of the roll when the photosensitive resin laminate is wound into a roll shape. The weight-average molecular weight (Mw) of component (A) is more preferably 20,000 to 70,000, even more preferably 30,000 to 50,000, and particularly preferably 35,000 to 45,000.

[0136] (A) The polydispersity of component {weight-average molecular weight (Mw) / number-average molecular weight (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.

[0137] Component (A) preferably has a monomer component consisting of a first monomer described later, and more preferably has a monomer component consisting of at least one of the first monomers and at least one of the second monomers described later.

[0138] The first monomer is an acidic monomer having a polymerizable unsaturated group in its molecule, such as a carboxylic acid or acid anhydride having one polymerizable unsaturated group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred.

[0139] The content of the first monomer is preferably 10 to 50% by mass, based on the total mass of all monomer components. Adjusting the content of the first monomer to 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, more preferably 15% by mass or more, 18% by mass or more, 21% by mass or more, even more preferably 23% by mass or more, and particularly preferable 25% by mass or more. Adjusting the content of the first monomer to 50% by mass or less is preferable from the viewpoint of excellent adhesion and resolution, more preferably 35% by mass or less, 30% by mass or less, even more preferably 29% by mass or less, and particularly preferable 27% by mass or less. When two or more types of first monomers are used, it is preferable that the sum of their respective contents is within the above range.

[0140] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include styrene derivatives, (meth)acrylate compounds having a hydroxyl group, alkyl (meth)acrylates, (meth)acrylate compounds having an alicyclic or aromatic ring, vinyl alcohol, vinyl acetate, and esters of (meth)acrylonitrile.

[0141] Examples of styrene derivatives include styrene, oxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene.

[0142] Examples of the (meth)acrylate compound having a hydroxy group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate.

[0143] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0144] Examples of the (meth)acrylate compound having an alicyclic or aromatic ring include benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and ethyl carbitol (meth)acrylate.

[0145] In the present embodiment, the component (A) can be used alone or in combination of two or more. When two or more are used in combination, it is preferable that the molecular weight and polydispersity of the monomers in the plurality of components (A) are selected so that the weighted average value when the content ratio is treated as a weight falls within the above range.

[0146] The synthesis of component (A) is preferably carried out by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, and isopropanol, mixing appropriate amounts of benzoyl peroxide and a radical polymerization initiator such as azoisobutyronitrile into the solution, 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. In addition, after the reaction is complete, the solvent may be further added to adjust to the desired concentration. Besides solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods. Furthermore, synthesis may be carried out by living radical polymerization.

[0147] The content of component (A) may be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more, based on the total solid content of the photosensitive resin composition. From the viewpoint of suitably exhibiting the effects of the present invention, the content of component (A) is preferably 50% by mass or more, and more preferably 55% by mass or more, based on the total solid content of the photosensitive resin composition. Furthermore, the content may be 70% by mass or less, 65% by mass or less, or 60% by mass or less.

[0148] To obtain a photosensitive resin composition with desirable properties, it is preferable to control the mass ratio of component (A) and component (B) {(A) component / (B) component} (sometimes abbreviated as "A / B") within a predetermined range. Controlling the A / B value to a large extent tends to be advantageous in terms of resolution and adhesion, while controlling the A / B value to a small extent tends to be advantageous in terms of developability and flexibility of the cured film. A / B can be controlled by adjusting the charging ratio of component (A) and component (B) when preparing the photosensitive resin composition. A / B can be analyzed from the photosensitive resin layer by a predetermined method, and the value obtained therefrom is based on the charging ratio at the time of preparation of the photosensitive resin composition. The analysis of the A / B value involves, for example, the following steps; (1) After dissolving the photosensitive resin layer in a good solvent, a poor solvent for component (A) is added dropwise to separate component (A) by reprecipitation, and the mass of component (A) obtained by reprecipitation is measured. (2) Other components such as initiators are quantified individually using GC-MS, etc., and the mass of component (B) is indirectly determined by measuring the content of components other than (A) and (B), and the A / B value is calculated from this. This can be done by [method].

[0149] The photosensitive resin composition of this embodiment makes it easier to provide a photosensitive resin layer that satisfies high levels of developability, resolution, adhesion, and flexibility of the cured film by controlling the A / B value to 1.30 or higher. From a similar viewpoint, the A / B value is more preferably 1.40 or higher, and even more preferably 1.50 or higher. The upper limit of the A / B value may be, for example, 2.50 or lower.

[0150] When component (A) contains a large amount of styrene as a monomer component, a photosensitive resin composition containing such component (A) tends to have excellent resolution and adhesion. In order to suitably exhibit this effect, when the content of component (A) in a photosensitive resin composition containing a copolymer with a large amount of styrene as a monomer component is increased (for example, A / B is 1.30 or more), the cured film and resist pattern tend to become hard and brittle. Therefore, it was generally understood that it becomes difficult to form fine resist patterns, and the adhesion tends to deteriorate. On the other hand, according to this embodiment, it is possible to provide a photosensitive resin layer (resist) that is excellent in terms of the flexibility of the cured film itself, even when using a photosensitive resin composition containing a copolymer with a large amount of styrene as a monomer component. Precisely because of this type of photosensitive resin composition, by controlling the A / B value to 1.30 or more, it becomes easier to provide a photosensitive resin layer that satisfies high levels of developability, resolution, adhesion, and flexibility of the cured film.

[0151] In this disclosure, if component (A) contains multiple copolymers, the glass transition temperature Tg of component (A) is the weight-average Tg. total It is expressed as follows. The average weight Tg total The formula is as follows: Tg total = Σ i (W i×Tg i ) / W total (where W i is the solid weight of each alkali-soluble polymer, and Tg i is the glass transition temperature (Tg) determined by the Fox equation for each alkali-soluble polymer, and W total is the total solid weight of each alkali-soluble polymer.) is a value determined according to This Tg total value is preferably 100 °C or lower from the viewpoints of excellent developability and flexibility of the cured film. Tg total is more preferably 99 °C or lower and even more preferably 95 °C or lower from the same viewpoints as above. Tg total is preferably 50 °C or higher, more preferably 70 °C or higher, even more preferably 80 °C, and particularly preferably 85 °C or higher from the viewpoint of easy control of edge fusion properties.

[0152] ≪Copolymer (A-1)≫ Component (A) contains copolymer (A-1), and the copolymer (A-1) has at least the following components: (a1) (Meth)acrylic acid; (a2) A styrene derivative; and (a3) Hydroxyalkyl (meth)acrylate; has structural units derived from the proportion of the structural units derived from component (a1) is 15 to 26% by mass, the proportion of the structural units derived from component (a2) is 30 to 70% by mass, the proportion of the structural units derived from component (a3) is 15 to 35% by mass, and the glass transition temperature (Tg) calculated based on the Fox equation is 100 °C or lower.

[0153] The weight-average molecular weight (Mw) of copolymer (A-1) is preferably 20,000 to 70,000, more preferably 30,000 to 50,000, and even more preferably 35,000 to 45,000, from the viewpoint of excellent flexibility of the cured film.

[0154] From the viewpoint of suitably exhibiting the effects of the present invention, the content of copolymer (A-1) is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more, based on the total solid content of the photosensitive resin composition.

[0155] From the viewpoint of suitably exhibiting the effects of the present invention, the content of copolymer (A-1) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, relative to the total amount of component (A).

[0156] ≪Glass transition temperature (Tg)≫ In copolymer (A-1), the glass transition temperature (Tg), calculated based on Fox's formula, is 100°C or lower, from the viewpoint of excellent developability and flexibility of the cured film. From the same viewpoint as above, Tg is preferably 99°C or lower, and more preferably 95°C or lower. From the viewpoint of easily controlling edge fusing properties, Tg is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C, and particularly preferably 85°C or higher.

[0157] Tg is the temperature at which the ratio of free volume in the total volume of the polymer begins to increase rapidly. It is considered that at temperatures above Tg, the free volume increases in proportion to the temperature difference from Tg. Therefore, under the same temperature conditions, the higher the Tg of the polymer, the smaller the free volume tends to be, and conversely, the lower the Tg, the larger the free volume tends to be. For this reason, it is considered that the cured film of the photosensitive resin layer obtained from the photosensitive resin composition with a high Tg tends to have low flexibility, and the cured film of the photosensitive resin layer obtained from the photosensitive resin composition with a low Tg tends to have high flexibility.

[0158] For a copolymer composed of n kinds of monomers, Fox's equation for calculating the Tg (K: Kelvin) of the copolymer is the following equation:

Equation

[0159] In this specification, as the value of Tg of the homopolymer composed of the monomers forming the alkali-soluble polymer, the literature value (edited by Brandrup, J. Immergut, E. H., Polymer handbook, Third edition, John wiley & sons, 1989, Chapter VI “GLASS transition temperatures of polymers”, p209) is used. An example of the glass transition temperature (Tg i ) of the homopolymer composed of each monomer is as follows.

[0160]

Table 1

[0161] The mechanism by which this embodiment can suitably exhibit all performance characteristics regarding resolution, developability, adhesion, and flexibility of the cured film is presumed to be as follows. When component (A) contains a copolymer that includes a relatively large amount (30-70% by mass) of constituent units derived from component (a2), the resulting photosensitive resin composition tends to have excellent resolution and adhesion. On the other hand, because component (a2) is highly hydrophobic, it becomes necessary to improve the developability of the resulting photosensitive resin composition. Furthermore, since the photosensitive resin layer obtained using the photosensitive resin composition containing the copolymer tends to become a hard and brittle cured film after exposure, it becomes necessary to improve the flexibility of the cured film.

[0162] Therefore, it is common to supplement the developability of a photosensitive resin composition by including a large amount of component (a1) which has a carboxyl group. However, a photosensitive resin layer obtained from a photosensitive resin composition containing a copolymer with a large amount of component (a1) still tends to harden into a hard film after exposure. In other words, from the viewpoint of the flexibility of the cured film, it is better to have a low content of component (a1) in the copolymer. Component (a3) ​​has a hydroxyl group and therefore exhibits high hydrophilicity. Therefore, by including a copolymer in which the copolymerization ratio of component (a3) ​​is adjusted to a large amount of 15% by mass or more in the photosensitive resin composition, it is possible to obtain a photosensitive resin composition that can form a photosensitive resin layer with excellent developability even if the copolymerization ratio of component (a1) in the copolymer is 26% by mass or less. In a photosensitive resin composition, in addition to setting the content of components (a1) to (a3) ​​within the range specified in this application, further adjusting the Tg of the copolymer to 100°C or less makes it possible to obtain a photosensitive resin layer capable of forming a cured film with excellent flexibility. Therefore, by including a copolymer in the photosensitive resin composition in which the copolymerization ratio of components (a1) to (a3) ​​and Tg are adjusted to the range specified in this application, a photosensitive resin layer can be obtained that is excellent in all aspects of performance, including resolution, developability, adhesion, and flexibility of the cured film.

[0163] (a1) Ingredients Component (a1) may contain either methacrylic acid or acrylic acid, consist of either one or both, or consist of both. If component (a1) consists of only methacrylic acid and acrylic acid, the copolymerization ratio of component (a1) is determined by the sum of the copolymerization ratio of methacrylic acid and the copolymerization ratio of acrylic acid.

[0164] The proportion of constituent units derived from component (a1) is 15 to 26% by mass, based on the total mass of all constituent units of copolymer (A-1). Adjusting this proportion to 15% by mass or more is preferable from the viewpoint of excellent developability and resolution. Adjusting this proportion to 26% by mass or less is preferable from the viewpoint of controlling the glass transition temperature (Tg) of the photosensitive resin layer within an appropriate range and from the viewpoint of the flexibility of the cured film. The proportion is more preferably 17 to 25% by mass, and even more preferably 18 to 23% by mass.

[0165] (a1) Component preferably contains methacrylic acid from the viewpoint of excellent resolution. In this case, the copolymerization ratio of methacrylic acid is preferably 50% by mass or more, more preferably 75% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass, relative to the total of component (a1). If component (a1) contains methacrylic acid, the copolymerization ratio of methacrylic acid is preferably 15 to 25% by mass, and preferably 17 to 23% by mass.

[0166] ≪(a2) component≫ Examples of component (a2) include styrene, oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene. Among these, component (a2) preferably contains styrene.

[0167] The proportion of constituent units derived from component (a2) is 30 to 70% by mass, based on the total mass of all constituent units of copolymer (A-1). Adjusting this proportion to 30% by mass or more is preferable from the viewpoint of excellent resolution and adhesion. Adjusting this proportion to 70% by mass or less is preferable from the viewpoint of excellent developability and flexibility of the cured film. The proportion is preferably 30 to 60% by mass, and more preferably 35 to 50% by mass.

[0168] (a2) Component may consist of only one compound or may contain two or more compounds. If component (a2) contains two or more compounds, the copolymerization ratio of component (a2) is determined by the sum of the copolymerization ratios of the individual compounds.

[0169] ≪(a3) component≫ Component (a3) ​​is a compound in which the hydrogen atom of the alkyl group of an alkyl(meth)acrylate is replaced with a hydroxyl group. Examples of such compounds include hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and hydroxybutyl(meth)acrylate. Among these, component (a3) ​​is preferably hydroxyethyl(meth)acrylate from the viewpoint of excellent developability.

[0170] The proportion of constituent units derived from component (a3) ​​is 15 to 35% by mass, based on the total mass of all constituent units of copolymer (A-1). Adjusting this proportion to 15% by mass or more is preferable from the viewpoint of achieving both developability and flexibility of the cured film. Adjusting this proportion to 35% by mass or less is preferable from the viewpoint of excellent resolution and adhesion. The proportion is preferably 20 to 30% by mass, and more preferably 23 to 27% by mass.

[0171] (a3) Component may consist of only one compound, or it may contain two or more compounds. If component (a3) ​​contains two or more compounds, the copolymerization ratio of component (a3) ​​is determined by the sum of the copolymerization ratios of the individual compounds.

[0172] ≪(a4) component≫ The copolymer (A-1) may further contain, in addition to the constituent units derived from the above components (a1) to (a3), constituent units derived from component (a4) below, which are different from the above components (a1) to (a3).

[0173] (a4) For example, the components are: (a4) The following general formula (I): [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 3 or more carbon atoms.) Alkyl (meth)acrylates represented by are preferred. Generally, the glass transition temperature Tg of the homopolymer of component (a4) i The glass transition temperature Tg of the homopolymer of components (a1), (a2), and (a3) ​​is i Because it is lower than that, using such a (a4) component makes it easier to adjust the glass transition temperature Tg of copolymer (A-1) to a lower level.

[0174] As component (a4), compounds in which R2 is an alkyl group having 3 to 12 carbon atoms in the above general formula (I) are preferred. Examples of such compounds include propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and nonyl (meth)acrylate. Among these, as component (a4) represented by the above formula (I), compounds in which R2 is an alkyl group having 4 to 10 carbon atoms are more preferred, and compounds in which R2 is an alkyl group having 6 to 9 carbon atoms are even more preferred. As such compounds, 2-ethylhexyl (meth)acrylate is particularly preferred.

[0175] The proportion of constituent units derived from component (a4) is preferably 1 to 15% by mass, based on the total mass of all constituent units of copolymer (A-1). From the viewpoint of easily lowering the Tg of copolymer (A-1) and having excellent flexibility of the cured film, the proportion is preferably 1% by mass or more. On the other hand, component (a4) has an unsaturated hydrocarbon group that does not have a hydrophilic group, and therefore has high hydrophobicity. Furthermore, since component (a4) does not have an aromatic ring, it is preferable to balance it with component (a2) which has an aromatic ring component incorporated into the polymer main chain. In this case, from the viewpoint of having excellent various properties (e.g., resolution, adhesion, and developability), the proportion is preferably 15% by mass or less. The proportion is more preferably 5 to 13% by mass, and even more preferably 8 to 12% by mass.

[0176] <<Monomers other than components (a1)~(a4)>> Copolymer (A-1) may contain monomers other than components (a1) to (a4) as copolymer components. Monomers other than components (a1) to (a4) are a first monomer other than (a1) and a second monomer other than components (a2) to (a4). Examples include compounds exemplified as the first monomer and compounds exemplified as the second monomer that do not fall under components (a1) to (a4).

[0177] When copolymer (A-1) contains a first monomer other than component (a1), from the viewpoint of excellent flexibility of the cured film, the copolymerization ratio of the entire first monomer {including component (a1)} is preferably 26% by mass or less, and more preferably 25% by mass or less. The copolymerization ratio of the first monomer other than component (a1) may be 0% by mass.

[0178] When copolymer (A-1) has a second monomer other than components (a2) to (a4), from the viewpoint of easily achieving the effects of the present invention, the copolymerization ratio of the monomer component is preferably 20% by mass or less, and more preferably 10% by mass or less. The copolymerization ratio of the second monomer other than components (a2) to (a4) may be 0% by mass.

[0179] <(B) component> Component (B) is a compound having an ethylenically unsaturated bond. Component (B) may have at least one ethylenically unsaturated bond per molecule. From the viewpoint of obtaining a photosensitive resin layer with appropriate flexibility, it is preferable that component (B) contains a compound having two ethylenically unsaturated bonds per molecule. From the viewpoint of excellent crosslinking efficiency in the exposure process, component (B) may further contain a compound having three ethylenically unsaturated bonds per molecule, or a compound having four, five, or six ethylenically unsaturated bonds per molecule.

[0180] The content of a compound having two ethylenically unsaturated bonds in one molecule in component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total content of component (B), from the viewpoint of excellent resolution. The content may be 100% by mass or less than 100% by mass relative to the total content of component (B).

[0181] When component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule, from the viewpoint of excellent adhesion and developability, the content of the compound having three or more ethylenically unsaturated bonds in one molecule is preferably 30% by mass or less, and may be 20% by mass or less, relative to the total amount of component (B). Furthermore, the content may be 1% by mass or more, and may be 5% by mass or more, relative to the total amount of component (B).

[0182] Component (B) preferably contains a (meth)acrylate compound, and more preferably contains a bifunctional (meth)acrylate compound (a compound having two or more (meth)acryloyl groups in one molecule) from the viewpoint of obtaining a photosensitive resin layer with appropriate flexibility. With respect to component (B), "the (meth)acrylate compound having n (meth)acryloyl groups in one molecule" is referred to as, for example, "n-functional." For example, with respect to component (B), having one, two, three, four, five, or six ethylenically unsaturated bonds in one molecule is referred to as "monofunctional (or monofunctional)," "difunctional," "trifunctional," "tetrafunctional," "pentafunctional," or "hexafunctional," respectively.

[0183] If component (B) contains a (meth)acrylate compound, from the viewpoint of excellent crosslinking efficiency in the exposure process, it may contain only a bifunctional (meth)acrylate compound, or it may contain a bifunctional (meth)acrylate compound and a trifunctional or higher (meth)acrylate compound. Component (B) may contain, together with or separately from the bifunctional (meth)acrylate compound and / or the trifunctional or higher (meth)acrylate compound, for example, a tetrafunctional, pentfunctional, or hexafunctional (meth)acrylate compound.

[0184] If component (B) contains a (meth)acrylate compound, the content of the bifunctional (meth)acrylate compound is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total component (B), from the viewpoint of excellent resolution and flexibility of the cured film. Furthermore, the content may be 100% by mass or less than 100% by mass relative to the total component (B).

[0185] When component (B) contains a trifunctional or higher (meth)acrylate compound, from the viewpoint of excellent adhesion and developability, the content of the trifunctional or higher (meth)acrylate compound is preferably 30% by mass or less, and may be 20% by mass or less, relative to the total of component (B). Furthermore, the content may be 1% by mass or more, and may be 5% by mass or more, relative to the total of component (B).

[0186] Examples of bifunctional (meth)acrylate compounds include alkyl di(meth)acrylates, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylates, tricyclodecanol di(meth)acrylates, di(meth)acrylates having a bisphenol A structure, and di(meth)acrylates having a hydrogenated bisphenol A structure.

[0187] As for polyalkylene glycol di(meth)acrylate, the following general formula (II): [ka] (In the formula, R 1 Each of these is independently a hydrogen atom or a methyl group, and X 1 O and Y 1 Each O is independently an oxyalkylene group having 2 to 4 carbon atoms, m1, m2, and n1 are independently integers from 0 to 40, m1 + m2 is from 1 to 40, and n1 is from 0 to 20. Examples of compounds represented by [the formula shown] are given.

[0188] Di(meth)acrylates having a bisphenol A structure include the following general formula (III): [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 compounds represented by [the formula shown]. Note that the number of structural units of an oxyethylene group or oxypropylene group is an integer value in a single molecule, and a rational number (the average value) in a collection of multiple molecules.

[0189] Di(meth)acrylates having a hydrogenated bisphenol A structure include compounds in which hydrogen is added to the aromatic ring of the compound represented by formula (III) above.

[0190] The compound represented by the above formula (II) is, in the formula, R 1 =methyl group, m1+m2=6 (average), n1=12 (average), X 1 O = oxyethylene group, and Y 1 Examples include compounds where O = oxypropylene group (manufactured by Resonaq, product name "FA-024M").

[0191] The compound represented by the above formula (III) is BPE-200 (wherein R 2 =methyl group, X 2 O = oxyethylene group, m3 + m4 = 4, and n2 = n3 = 0), BPE-500 (in the formula, R 2 =methyl group, X 2 O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), BPE-900 (in the formula, R 2 =methyl group, X 2 O = oxyethylene group, m3 + m4 = 17, and n2 = n3 = 0) (The above is a product name manufactured by Shin Nakamura Chemical Industry Co., Ltd.), FA-321M (In the formula, R 2 =methyl group, X 2 O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), FA-P321M (in the formula, R 2 =methyl group, X 2 O = oxypropylene group, m3 + m4 = 10, and n2 = n3 = 0) (The above is a product name from Resonaq Corporation), FA-P323M (In the formula, R 2 =methyl group, X 2 Examples include O = oxypropylene group, m3 + m4 = 30, and n2 = n3 = 2 (all manufactured by Resonaq, product name).

[0192] Component (B) preferably contains, from the viewpoint of excellent resolution, a difunctional (meth)acrylate compound, specifically a di(meth)acrylate having a bisphenol A structure and / or a di(meth)acrylate having a hydrogenated bisphenol A structure. The compound is preferably present in an amount of 20% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on the total amount of component (B). Furthermore, the compound is preferably present in an amount of 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on the total solid content of the photosensitive resin composition.

[0193] 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 14. G, 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 Resonaq), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel Ornex), 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), 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.).

[0194] Examples of (meth)acrylate compounds with three or more functions include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, diglycerin (tetra)(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, triglycerin (penta)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0195] The trifunctional or more (meth)acrylate compound may be a compound obtained by forming a (meth)acrylate from an alcohol having three or more groups in which alkylene oxide groups can be added to the molecule as a central skeleton, to which alkylene oxide groups (e.g., ethylene oxide group, propylene oxide group, and butylene oxide group) are added, and (meth)acrylic acid. Examples of such 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, diglycerin alkylene oxide-modified tetra(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, triglycerin alkylene oxide-modified penta(meth)acrylate, and alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0196] As a trifunctional or more (meth)acrylate compound, it is preferable to include alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate and / or alkylene oxide-modified dipentaerythritol (tri / tetra)(meth)acrylate from the viewpoint of excellent developability. Specific embodiments of the compound include: Tetramethacrylate obtained by adding an average of 9 moles of ethylene oxide groups to pentaerythritol; Tetramethacrylate obtained by adding an average of 15 moles of ethylene oxide groups to pentaerythritol; Hexamethacrylate of polyethylene glycol obtained by adding an average of 13 moles of ethylene oxide groups to dipentaerythritol; These are some examples.

[0197] 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 (all manufactured by Resonac Corporation), TMPTA, EBECRYL 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel Ornex), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema), 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.).

[0198] Component (B) may contain a hindered amine compound. This reduces the amount of residue generated after the resist pattern is removed. Examples of hindered amine compounds include the following general formula (IV): [ka] (In the formula, R1 independently represents an alkyl group having 1 or more carbon atoms, R2 represents hydrogen or an alkyl group having 1 or more carbon atoms, and the number of carbon atoms in R1 and R2 is independently 10 or less.) Examples of compounds represented by general formula (IV) include 1,2,2,6,6-pentamethylpiperidyl methacrylate.

[0199] The hindered amine compound content may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total solid content of the photosensitive resin composition, and may also be 20% by mass or less, 15% by mass or less, 10% by mass or less, or 0% by mass.

[0200] Hindered amine compounds may be compounds that have one ethylenically unsaturated bond. The content of compounds that have one ethylenically unsaturated bond (excluding the hindered amine compound if it is a compound that has one ethylenically unsaturated bond) may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 0% by mass, based on the total solid content of the photosensitive resin composition.

[0201] The content of component (B) is preferably 10 to 50% by mass, based on the total solid content of the photosensitive resin composition. From the viewpoint of preventing curing defects in the photosensitive resin layer and suppressing delays in development time, the content is preferably 10% by mass or more. From the viewpoint of improving the developability of the resist pattern, 50% by mass or less is preferred. From the same viewpoint, the content is more preferably 20 to 45% by mass, and even more preferably 25 to 40% by mass.

[0202] The total content of component (A) and component (B) is preferably 85% by mass or more, and more preferably 90% by mass or more, based on the total solid content of the photosensitive resin composition. When the content is within the above range, the effects of the present invention, which are easily exerted by component (A) and component (B), are more favorably exhibited. The total content of component (A) and component (B) may be 99% by mass or less, and 95% by mass or less.

[0203] <(C) component> Component (C) is a polymerization initiator. Preferably, component (C) is a photopolymerization initiator that generates radicals upon exposure to active light, thereby initiating the polymerization of component (B). Preferably, component (C) contains a compound having a biimidazole structure.

[0204] Examples of component (C) include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, and halogen compounds.

[0205] Examples of hexaarylbiimidazole compounds include dimers of compounds having a rophine structure (rophine dimers), namely, dimers of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole. Examples of rophine dimers include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-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, and 2,2'-bis-( 2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole Examples include kiss-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakiss-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakiss-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakiss-(3-methoxyphenyl)-biimidazole.

[0206] From the viewpoint of excellent sensitivity, resolution, and adhesion, component (C) preferably contains a rofin dimer. In particular, component (C) more preferably contains a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, a 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, or a 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and even more preferably contains a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0207] 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.

[0208] Examples of aromatic ketone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. Aromatic ketone compounds function as photoinitiators when used alone, but may also function as sensitizers when used in combination with other photoinitiators.

[0209] 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0210] 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 (both manufactured by BASF) and Irgacure-819 (both manufactured by BASF).

[0211] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. 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.

[0212] 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 BASF). Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine. 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.

[0213] The content of component (C) is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. If the photosensitive resin composition contains a rofin dimer as component (C), the content of the rofin dimer is preferably 3.0 to 10% by mass, more preferably 4.0 to 9.0% by mass, and even more preferably 5.0 to 8.0% by mass, based on the total solid content of the photosensitive resin composition. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to achieve high resolution.

[0214] <(D) Ingredient: Sensitizer> The photosensitive resin composition preferably further contains a sensitizer (D) from the viewpoint of excellent sensitivity and resolution. Component (D) promotes the photopolymerization reaction by transferring the energy it obtains from absorbing light to the initiator. The "component (D)" referred to in this embodiment ([Embodiment of the "Related Invention"]) may be different from the "component (D)" referred to in the above [Embodiment of the "First Invention"].

[0215] Examples of component (D) include pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives, and aromatic ketone derivatives substituted with alkylamino groups. In particular, component (D) preferably includes pyrazoline derivatives and anthracene derivatives.

[0216] Examples of pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazole-2-yl)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, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxy Examples include phenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline. Among the pyrazoline derivatives, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred.

[0217] Examples of anthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9- Examples include lolo-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenylyl)-10-bromoanthracene, 9-(4-biphenylyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene, and 9-(3-bromophenyl)-10-phenylanthracene. Among these, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred as anthracene derivatives.

[0218] Examples of naphthalene derivatives include 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-propoxynaphthalene, 1-butoxynaphthalene, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-bis(n-butoxy)naphthalene, 1,4-bis(i-butoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, and 1,4-bis(n-heptyloxy)naphthalene. Examples include 1,4-bis(n-octyloxy)naphthalene, 1,4-bis(2-ethylhexyloxy)naphthalene, 1,4-bis(n-nonyloxy)naphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,4-bis(2-methylglycidyloxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, and 2-(2-hydroxyethoxy)naphthalene. Among these, 1,4-diethoxynaphthalene is preferred as the naphthalene derivative.

[0219] Examples of oxazole derivatives include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazole-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazole-2-yl)naphthalene-1-yl]-1,3-benzoxazole.

[0220] Examples of N-aryl-α-amino acid derivatives include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-(n-propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, and N-(n-propyl Examples include N-(n-butyl)-N-(p-tolyl)glycine, N-(n-butyl)-N-(p-tolyl)glycine, N-methyl-N-(p-chlorophenyl)glycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(n-propyl)-N-(p-chlorophenyl)glycine, N-methyl-N-(p-bromophenyl)glycine, N-ethyl-N-(p-bromophenyl)glycine, N-(n-butyl)-N-(p-bromophenyl)glycine, N,N'-diphenylglycine, N-methyl-N-(p-iodophenyl)glycine, N-(p-bromophenyl)glycine, N-(p-chlorophenyl)glycine, and N-(o-chlorophenyl)glycine.

[0221] Examples of aromatic ketone derivatives substituted with alkylamino groups include benzophenone derivatives. Benzophenone derivatives include, for example, Alkylbenzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone; Benzophenone compounds having halogen atoms, such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone; Benzophenone compounds substituted with a carboxyl group or an alkoxycarbonyl group, such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid, or its tetramethyl ester; Bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dihydroxyethylamino)benzophenone, preferably 4,4'-bis(dialkylamino)benzophenone compounds; 4-Methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, etc. These are some examples.

[0222] In one embodiment, component (D) may include a compound having the following skeleton, either together with or separately from the above skeleton. Examples of such skeletons include at least one selected from the group consisting of pyrene, coumarin, triarylamine, oxazole, and chrysene. This is likely to be advantageous from the viewpoint of sensitivity.

[0223] In one embodiment, component (D) may include a boron compound having absorption for the h-line and / or i-line. The boron compound having absorption for the h-line and / or i-line is at least one compound selected from the group consisting of pyrazoline derivatives, anthracene derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives, and alkylamino group-substituted aromatic ketone derivatives, preferably the following general formula: *-BH2 *-B(OH)2 *-B(OR 1 )2 *-B(OH)(OR 1 ) (In the formula, R 1 Each of these independently represents a monovalent organic group, and * indicates a bonding site with various skeletons. It is a compound containing at least one boron moiety selected from the group consisting of the following. Examples of this type of compound include boronic acids having a pyrazoline skeleton, anthracene skeleton, and oxazole skeleton. Among these, boronic acids having a 10-phenyl-9-anthracene skeleton (10-phenyl-9-anthraceneboronic acid) are preferred.

[0224] In the boron compounds having absorption for the h-line and / or i-line described above, the definitions of "h-line," "i-line," and "having absorption" are the same as those in the [Embodiment of the First Invention].

[0225] The content of component (D) is preferably 0.01 to 2.0% by mass, and more preferably 0.3 to 1.5% by mass, based on the total mass of component (A).

[0226] <(E) Ingredients: Other ingredients> The photosensitive resin composition may optionally contain components other than those listed above (A) to (D) {(E): other components}. Examples of component (E) include colorants, leuco dyes, base dyes (dyes other than leuco dyes), antioxidants, and stabilizers.

[0227] (Coloring agent) Examples of colorants include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green (e.g., Eisen® MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20, Diamond Green (e.g., Eisen® DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLAS GREEN 533 manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industry Co., Ltd.), and 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OIL BLUE 630 manufactured by Orient Chemical Industry Co., Ltd.).

[0228] The colorant content is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.5 to 2% by mass, based on the total solid content of the photosensitive resin composition.

[0229] (Leuco dye) Examples of leuco dyes include leucocrystal violet ("tris[4-(dimethylamino)phenyl]methane") and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.

[0230] The leuco dye content is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, based on the total solid content of the photosensitive resin composition.

[0231] (Base dye) Examples of base dyes (dyes other than leuco dyes) include Basic Green 1 [CAS number (same below): 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].

[0232] The base dye content 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 of the photosensitive resin composition.

[0233] (Antioxidant) Examples of antioxidants include triphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA Corporation, trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by ADEKA Corporation, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 329K).

[0234] The antioxidant content is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, based on the total mass of the photosensitive resin composition.

[0235] (Stabilizer) Examples of stabilizers include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group.

[0236] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salts (e.g., aluminum salts with 3 moles of nitrosophenylhydroxylamine added), and diphthol. Examples of such agents include phenylnitrosamines, hydroquinones, N-nitrosodiphenylamines, phenothiazines, N-phenylnaphthylamines, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. Among these, p-methoxyphenol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, phenothiazines, and triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] are preferred as radical polymerization inhibitors.

[0237] 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.).

[0238] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group is preferably 0.001 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total solid content of the photosensitive resin composition.

[0239] (Other optional components) Other components include carboxylbenzotriazoles. The content of carboxylbenzotriazoles is, for example, 0.01% by mass or more, and 5% by mass or less, based on the total solid content of the photosensitive resin composition.

[0240] [Formulated solution (coating solution) for preparing a photosensitive resin composition] A preparation solution for producing a photosensitive resin composition can be made by mixing a photosensitive resin composition with a solvent. Examples of solvents include: Ketones such as acetone and methyl ethyl ketone (MEK); Alcohols such as methanol, ethanol, and isopropyl alcohol; For example, it is preferable to mix the photosensitive resin composition and the solvent so that the viscosity of the prepared solution is 500 to 4000 mPa·sec at 25°C.

[0241] A photosensitive resin laminate obtained using the photosensitive resin composition of the embodiment of the "First Invention" and the embodiment of the "Related Invention" is also another embodiment of the present invention.

[0242] With respect to the [Embodiment of the Related Invention], in a photosensitive resin laminate obtained using a photosensitive resin composition, The following method; (1) After forming the photosensitive resin layer on a flexible substrate, a cured film is obtained on the substrate by exposing it to a size of 1 inch in width and 250 mm in length with an energy amount such that 15 steps remain on a Stuffer Industries 41-step tablet. (2) The exposed substrate is developed using a 1% by mass Na2CO3 aqueous solution at 30°C for twice the minimum development time. (3) After development, the substrate is washed with water for twice the minimum development time. (4) After washing the substrate with water, a sample is obtained by cutting it to a width of 1.2 inches so that the 1-inch wide cured photosensitive resin layer is in the center in the width direction. (5) Cylindrical mandrel method A mandrel test in accordance with the method of JIS K5600-5-1 is performed on the sample. (6) Determine the smallest mandrel diameter at which no cracks are observed in the cured film, or the smallest mandrel diameter at which no peeling of the cured film from the substrate is observed. It is preferable that the minimum mandrel diameter determined by the method is 8 mm or less. Furthermore, it is more preferable that the minimum mandrel diameter is 6 mm or less. In particular, a photosensitive resin laminate that can achieve both adhesion and flexibility of the cured film is likely to have excellent ability to form independent fine lines.

[0243] [Elements that may be common to both the embodiment of the "first invention" and the embodiment of the "related invention"] For convenience, the elements that may be common to the above-mentioned [Embodiment of the "First Invention"] and the above-mentioned [Embodiment of the "Related Invention"] are summarized below.

[0244] [Photosensitive resin laminate] The photosensitive resin laminate comprises, for example, a support and a photosensitive resin layer obtained from a photosensitive resin composition. From the viewpoint of significantly enhancing the effects of the present invention, the photosensitive resin laminate is preferably a dry film resist. It can also be understood that the photosensitive resin composition is preferably for dry film resist applications.

[0245] <Support> The support is preferably a transparent film that transmits light emitted from an exposure light source. Examples of supports include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as needed. The support may be single-layer or multi-layer.

[0246] When exposing a photosensitive resin layer via a support, the thickness of the support is related to the transmission distance of the exposure light source. Therefore, a thinner support is advantageous for image formation and also economically advantageous. On the other hand, considering the function of maintaining strength, the thickness is preferably 5 to 50 μm, more preferably 10 to 30 μm. In addition, the haze of the support is preferably 5 or less.

[0247] <Photosensitive resin layer> The thickness of the photosensitive resin layer is preferably 3 to 100 μm, more preferably 10 to 50 μm, and even more preferably 15 to 50 μm. The thinner the photosensitive resin layer, the easier it is to improve resolution, and the thicker the layer, the easier it is to improve film strength. Therefore, the thickness of the photosensitive resin layer can be appropriately selected depending on the field and application to which the photosensitive resin laminate is applied.

[0248] <Protective layer> The photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite to the support. Examples of protective layers include polyethylene film, polypropylene film, polyethylene terephthalate film, and polyester film. These films may be used in stretched form as needed. The protective layer may be a single layer or multiple layers.

[0249] The protective layer has appropriate adhesion. Preferably, the adhesion of the protective layer to the photosensitive resin layer is less than the adhesion of the support to the photosensitive resin layer, and the protective layer can be easily peeled off the photosensitive resin laminate. From this viewpoint, the protective layer is preferably a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film.

[0250] The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm. In particular, if the protective layer is a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film, its thickness is preferably 5 to 100 μm, more preferably 8 to 50 μm, and even more preferably 10 to 30 μm.

[0251] The protective layer preferably has a release layer on its surface. This makes it easier to peel the protective film from the photosensitive resin layer. The release layer is classified, for example, into silicone compounds and non-silicone compounds. The release layer may have an antistatic function, that is, it may be an antistatic layer. In this case, it is possible to prevent static charge buildup between the photosensitive resin layer and the protective film, making it easier to peel the protective film from the photosensitive resin layer. In one embodiment, the protective layer is preferably a PET film having an antistatic function.

[0252] Examples of silicone compounds include, A condensation-type silicone resin obtained by reacting terminally silanol polydimethylsiloxane with polymethylhydrogensiloxane or polymethylmethoxysiloxane; Addition-type silicone resin obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; UV-curable or electron-beam-curable silicone resins, such as acrylic silicone and epoxy group-containing silicone, that are cured with ultraviolet light or electron beams; 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); These are some examples.

[0253] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0254] 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 after peeling off the protective layer tends to be good, and the coating film tends to harden sufficiently. On the other hand, if the thickness is above the above lower limit, it tends to ensure sufficient release properties.

[0255] [Method for fabricating photosensitive resin laminates] A photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer onto a support. An example of the production method is as follows: First, a photosensitive resin composition solution (coating solution) is prepared as described above. Next, the solution is applied to the support using a bar coater or roll coater and dried to produce a photosensitive resin layer on the support. After that, a photosensitive resin laminate can be produced by laminating a protective layer onto the photosensitive resin layer as necessary.

[0256] [Method for forming resist patterns, and method for forming wiring patterns] The embodiments of the "First Invention" and the embodiments of the "Related Inventions" each include a method for forming a resist pattern using a photosensitive resin composition. The method involves the following steps: The lamination process (lamination process) in which a photosensitive resin layer in a photosensitive resin laminate is laminated onto a substrate, A process of exposing the photosensitive resin layer of a laminated photosensitive resin structure (exposure process), and A process to remove unexposed areas of the photosensitive resin layer (developing process), It has.

[0257] Another embodiment of the above-described embodiment is a method for forming a wiring pattern. The method involves the following steps: After the resist pattern is formed on the substrate using the above method, a plating process is performed as necessary, followed by an etching process (etching process) and a stripping process. This is a wiring pattern formation method having [a specific characteristic].

[0258] The following describes an example of a method for forming resist patterns and wiring patterns. <Lamination process> In the lamination process, specifically, after peeling off the protective film from the photosensitive resin laminate, the resist layer is heat-pressed onto the substrate surface using a laminator, and laminated once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO), with copper-clad laminates being preferred. If desired, the substrate may be cleaned with, for example, an aqueous H2SO4 solution with a concentration of about 10% by mass to prepare the substrate surface. The heating temperature during lamination is generally 40 to 160°C, more preferably 80 to 120°C. Heat pressing can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rolls several times. Heat pressing can be performed under reduced pressure if desired. Furthermore, heat pressing can be performed two or more times, which makes it easier to improve the adhesion of the resulting resist pattern to the substrate. When performing two or more crimping processes, a two-stage laminator equipped with two rolls may be used, and the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rolls.

[0259] <Exposure process> In the exposure process, the resist layer is exposed to ultraviolet light or the like, either through a patterned photomask or reticle, or directly, using an exposure machine such as a contact aligner, mirror projection machine, or stepper. The exposure process may be performed after peeling off the support film, or through the support film, as desired. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter. Direct imaging exposure may also be performed in the exposure process. In direct imaging exposure, the substrate is exposed directly by a drawing device without using a photomask. As the light source, a semiconductor laser with a wavelength of 350 nm to 410 nm or an ultra-high pressure mercury lamp is used. 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.

[0260] In the above embodiments, when exposure is performed only with light near the h-line (i.e., 400-410 nm), it is preferable that the boron compound having absorption for the (D)h-line and / or i-line has absorption for the h-line, and when exposure is performed only with light near the i-line (i.e., 350-370 nm), it is preferable that the boron compound having absorption for the (D)h-line and / or i-line has absorption for the i-line. In these cases, the absorbance in the other wavelength range is not limited. When exposure is performed with exposure light having both wavelengths near the h-line and wavelengths near the i-line, it is sufficient that the boron compound having absorption for the (D)h-line and / or i-line has absorption for at least one of the h-line and i-line.

[0261] In the above embodiment, If the boron compound having absorption for the (D)h line and / or i line has absorption for the h line, the exposure light in the exposure step preferably has a wavelength near the h line. If the boron compound having absorption for the (D)h line and / or i line has absorption for the i line, it is preferable that the exposure light in the exposure step has a wavelength near the i line. In other words, the boron compound mentioned above is a compound that absorbs the h-ray, In the exposure process, it is preferable to expose the photosensitive resin layer with light containing wavelengths of 400 to 410 nm, and also, The above boron compound is a compound that absorbs i-rays, In the exposure process, it is preferable to expose the pre-photosensitive resin layer with light containing wavelengths of 350 to 370 nm.

[0262] The exposure method used in the exposure process is preferably at least one method selected from projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and is more preferably performed by projection exposure or direct imaging exposure.

[0263] <Heating process> A heating step may be included between the exposure step and the development step. The heating temperature is preferably 30 to 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By performing this heating step, it is possible to improve resolution and adhesion. For heating, a heating furnace using hot air, infrared rays, or far infrared rays, a constant temperature bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, etc., can be used. The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0264] The elapsed time from the exposure process to the heating process, or more precisely, 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.

[0265] <Developing process> In the development process, unexposed areas of the resist layer after exposure are removed using a developing device and a developing solution to form a resist pattern. If a support film is present on the resist layer after exposure, the support film is removed. Subsequently, the unexposed areas are developed and removed using a developing solution consisting of an alkaline aqueous solution to obtain a resist pattern. As a development method for developing the resist layer after exposure (irradiation), any method can be selected and used from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment.

[0266] As the alkaline aqueous solution used as the developer, aqueous solutions of Na2CO3, K2CO3, and tetramethylammonium hydroxide are preferred. The alkaline aqueous solution is selected according to the characteristics of the resist layer, but an aqueous solution of Na2CO3 with a concentration of 0.2% to 2% by mass is generally used. Surface surfactants, defoamers, and small amounts of organic solvents to promote development may be added to the alkaline aqueous solution. The temperature of the developer solution during the development process is preferably kept constant within the range of 20 to 40°C.

[0267] The development process preferably includes a water washing step to remove the developer solution contained in the resist pattern after development. The washing water can be pure water, industrial water, or other water selected according to the characteristics of the resist layer, but a polyvalent metal salt such as MgSO4 at a concentration of 0.001 to 1% by mass may be added to improve resolution and the shape of the resist pattern. The temperature of the washing water in the water washing step is preferably kept constant within the range of 20 to 40°C.

[0268] The resist pattern can be obtained through the above process, but if desired, a further heat treatment can be performed at 60-300°C for 1-120 minutes. This heat treatment can improve the chemical resistance of the resist pattern. For the heat treatment, a heating furnace using hot air, infrared rays, or far-infrared rays can be used.

[0269] To obtain a conductive pattern, a conductive pattern formation step may be performed after the development step or heating step, in which the substrate on which the resist pattern has been formed is etched or plated.

[0270] <Conductor pattern formation process> The conductor pattern formation process is a process of forming a conductor pattern on a substrate surface (for example, a copper surface) on which a resist pattern has been formed by development, using a known etching method or plating method.

[0271] Examples of methods for forming conductor patterns by plating include the following: After the development process, the substrate is immersed in an acidic degreasing bath such as a 1-50% by mass sulfuric acid aqueous solution at 20-60°C for 1-60 minutes. After rinsing the immersed substrate with water, it is immersed in a 1-50% by mass sulfuric acid aqueous solution at room temperature for 1-60 minutes.

[0272] An aqueous solution containing 1-15% by mass of copper sulfate, 0.1-30% by mass of sulfuric acid, and 1-1000 ppm of hydrochloric acid is prepared. Then, a brightener (in one embodiment, Caparacid HL and Caparacid GS manufactured by Attec Co., Ltd.) is added at concentrations of 0.01-40 ml / l and 1-200 ml / l, respectively, to prepare a copper sulfate plating solution. Using the prepared copper sulfate plating solution, a conductor pattern is formed by plating with a Harling cell uniform plating apparatus (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.) at an applied current of 0.01-10 A for 1-300 minutes. The thickness of the copper plating film depends on the thickness of the resist pattern, but is preferably 1 μm or more and the thickness of the resist pattern (μm) - 2 μm or less. In this disclosure, the thickness of the resist pattern refers to the thickness of the resist layer.

[0273] One method for forming conductive patterns by etching is flash etching. In flash etching, the copper seed layer can be removed with a predetermined etching solution. Examples of etching solutions include, but are not limited to, a mixed etching solution of sulfuric acid and hydrogen peroxide (manufactured by Ebara Electric Industries, Ltd.).

[0274] [Method for manufacturing conductor patterns] The method for manufacturing the conductor pattern is, for example, to use a metal plate or a metal film insulating plate as a substrate, to form a resist pattern using the resist pattern formation method described above, and then to go through a conductor pattern formation step.

[0275] <Peeling process> Furthermore, after manufacturing the conductor pattern using the method described above, a peeling step may be performed to peel the resist pattern from the substrate using an aqueous solution that is more alkaline than the developer. By performing the peeling step, a wiring board (in one embodiment, a printed wiring board) having a desired wiring pattern can be obtained.

[0276] The alkaline aqueous solution used for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, but an aqueous solution of NaOH or KOH with a concentration of 2% to 20% by mass, or an organic amine-based stripping solution, is generally used. A small amount of water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohol. The temperature of the stripping solution in the stripping process is preferably in the range of 40 to 70°C, and the immersion time of the stripping solution is preferably 1 to 60 minutes.

[0277] [Manufacturing method for wiring boards] A method for manufacturing a wiring board using the photosensitive resin laminate according to the above embodiment involves the following steps in one embodiment: Lamination process for depositing a photosensitive resin layer onto a substrate; Exposure process for exposing a photosensitive resin layer; A developing process in which unexposed portions of a photosensitive resin layer are developed and removed to form a resist pattern; 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. The steps included in the manufacturing method of the wiring board according to the above embodiment—the lamination step, exposure step, development step, conductor pattern formation step, and peeling step—are the same as described above.

[0278] The photosensitive resin laminate in the above embodiment can be used for the manufacture of printed circuit boards; lead frames for mounting IC chips; precision metal foil processing such as metal masks; packaging such as ball grid arrays (BGAs) and chip-size packages (CSPs); tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); semiconductor bumps; and partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.

[0279] Unless otherwise specified, the various parameters mentioned above are measured in accordance with the measurement methods described in the examples below. [Examples]

[0280] [Examples of the "First Invention"] Next, this embodiment will be described in more detail with reference to examples and comparative examples.

[0281] [Preparation of evaluation samples] The evaluation samples were prepared as follows:

[0282] <Fabrication of photosensitive resin laminates> The components shown in the table below (the numbers for each component indicate the amount (parts by mass) as solid content) and ethanol measured to a solid content concentration of 60% were stirred and mixed to obtain a formulation for a photosensitive resin composition. Details of the components are shown in the table below. A 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., QS71) was used as a support film, and the above formulation was applied to its surface using a bar coater and dried in a 95°C dryer for 2.5 minutes. This formed a 25 μm thick photosensitive resin layer on the support film. Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818"), which served as a protective layer, was attached to the side of the photosensitive resin layer opposite the support film to obtain a photosensitive resin laminate.

[0283] <Surface preparation of the circuit board> The surface of a 0.4 mm thick copper-clad laminate, constructed by laminating 18 μm rolled copper foil, was washed with a 10 mass% H2SO4 aqueous solution. The washed copper-clad laminate was used as a substrate for image quality evaluation (evaluation substrate).

[0284] <Laminate> While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, it was laminated from the photosensitive resin layer side onto a copper-clad laminate (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 set to 0.35 MPa and the lamination speed to 1.5 m / min.

[0285] <Exposure> Two hours after lamination, evaluation substrates were directly exposed to 401 nm wavelength exposure light using a direct imaging (DI) exposure mask pattern with a direct writing exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.). The exposure was performed at an exposure level that resulted in a maximum of 15 layers of residual film when exposed using a Stuffer Industries 41-step tablet as a mask and subsequently developed.

[0286] <Heating> 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.

[0287] <Developing> The polyethylene terephthalate film (support film) was peeled off. Then, development was performed by spraying a 1% by mass Na2CO3 aqueous solution at 30°C onto the photosensitive resin layer using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., for dry film) for a predetermined time. The spraying time was set to twice the minimum development time, and the washing time after development (water rinsing by spraying) was also set to twice the minimum development time. At this time, the shortest time required for the unexposed areas of the photosensitive resin layer to completely dissolve was treated as the minimum development time. Based on the above, a resist pattern was prepared on an evaluation substrate.

[0288] Furthermore, depending on the width of L (line) / S (space), L / S = 10 μm / 10 μm; L / S = 8μm / 8μm; L / S = 5μm / 5μm; Resist patterns having the specified characteristics were fabricated on evaluation substrates.

[0289] [evaluation] <Sensitivity> In the exposure process described above, the following criteria were used to evaluate the exposure amount at which the maximum number of remaining film layers after exposure using a Stuffer Industries 41-step step tablet as a mask and subsequent development resulted in 15 layers. The evaluation results are shown in the table below. Excellent: The exposure dose at which the maximum number of remaining film stops is 15 stops is 45 mJ / cm². 2 below. Good: The exposure dose at which the maximum number of remaining film stops is 15 is 45 mJ / cm². 2 Exceeding 55 mJ / cm², 2 below. Possible: The exposure dose at which the maximum number of remaining film stops is 15 stops is 55 mJ / cm². 2 Exceeding 65 mJ / cm² 2 below. Not possible: The exposure dose at which the maximum remaining film stage is 15 stages is 65 mJ / cm². 2 It exceeds.

[0290] <Flexibility> The resist patterns fabricated above, specifically those with L / S ratios of 10 μm / 10 μm, 8 μm / 8 μm, and 5 μm / 5 μm, were observed under a microscope and evaluated according to the following criteria. The evaluation results are shown in the table below. Excellent: The resist pattern has a L / S ratio of 5μm / 5μm, and there are no breaks or defects in the pattern. Good: The resist pattern has a L / S ratio of 8μm / 8μm, and there are no breaks or defects in the pattern (except in cases where the rating is "Excellent"). Acceptable: Resist pattern with L / S = 10 μm / 10 μm, with no breaks or defects in the pattern (except in cases where the rating is "Excellent" or "Good"). Unacceptable: The resist pattern has a L / S ratio of 10 μm / 10 μm, and the pattern has folds or defects.

[0291] <Followability> A pit substrate was fabricated by laminating a commercially available dry film resist (DFR) onto a copper-clad laminate, exposing the photosensitive resin layer to light, developing it, etching the copper, and removing the DFR, thereby creating a circular depression with a diameter of 310 μm and a depth of approximately 10 μm. The photosensitive resin laminates of the examples and comparative examples were then laminated onto this pit substrate according to the above lamination process. If the photosensitive resin layer did not follow the shape sufficiently, a gap would form between the circular depression and the substrate. The average value of 10 points in the diameter of this gap was calculated and evaluated according to the following criteria. A result of "acceptable" or higher was considered acceptable. Excellent: 100um or less Good: Over 100um and under 150um Possible: more than 150um but less than 200um Impossible: over 200um

[0292] <Wavelength absorption properties of boron compounds> 10-phenyl-9-anthraceneboronic acid, and 9-anthraceneboronic acid; 9,10-Dibutoxyanthracene, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and coumarin 102; For each of these, the absorption for the h-ray and i-ray was measured according to (1) to (5) above. The results are shown in the table below. Note that the wavelength absorption of a boron compound can be treated as the wavelength absorption of the photosensitive resin composition containing that boron compound.

[0293] [Table 2]

[0294] [Table 3]

[0295] [Table 4]

[0296] [Table 5]

[0297] As can be seen from the table above, the examples obtained passing evaluation results for both sensitivity and flexibility. In contrast, the comparative examples received a failing grade for at least one of the two, sensitivity or flexibility.

[0298] Reference Example 1 evaluates the performance of a photosensitive resin composition containing a compound as component (D) that does not absorb on the h-line but does absorb on the i-line. In Reference Example 1, where component (D) that does not absorb on the h-line but does absorb on the i-line was used, and the material was exposed with exposure light having a wavelength near the h-line, the sensitizing function was not adequately exhibited.

[0299] The present invention has been described above. The present invention is not limited to this embodiment and can be modified as appropriate without departing from the spirit of the invention.

[0300] [Examples of "Related Embodiments"] This embodiment will be described in more detail with reference to examples and comparative examples.

[0301] [Preparation of evaluation samples] <(A) Synthesis> Solution (a) was prepared by mixing the monomers (copolymer components) shown in the table below and azobisisobutyronitrile in the amounts (unit: parts by mass) shown in the table below. 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. Nitrogen gas was then blown into the flask while stirring, and the mixture in the flask was heated to 80°C. 300 g of solution (a) was added to the mixture in the flask dropwise over 4 hours at a constant dropping rate, and then the mixture was stirred at 80°C for 2 hours.

[0302] Next, solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol. 50 g of solution (b) was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, and then stirred at 80°C for 3 hours. The solution in the flask was further heated to 90°C over 30 minutes, and then kept at 90°C for 2 hours. After that, stirring was stopped and the solution was cooled to room temperature (25°C). This yielded solutions of alkali-soluble polymers A1-1 to A1-6, A2-1 to A2-5, and A3-1 to A3-5. The glass transition temperatures (Tg) and weight-average molecular weights (Mw) of these alkali-soluble polymers are shown in the table below.

[0303] The weight-average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a calibration curve for standard polystyrene. The GPC conditions are as follows. (GPC conditions) Pump: JASCO PU-4580 Degasser: DG-2080-53 Column Oven: CO-1560 Columns: A total of 4 columns, all manufactured by Shodex: KF-807 x 1, KF-806M x 2, KF-802.5 x 1 Eluent: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 1.00mL / min Detector: RI-1530, manufactured by JASCO Corporation

[0304] <Fabrication of photosensitive resin laminates> A preparation for a photosensitive resin composition was obtained by mixing the components shown in the table below (the numbers for each component indicate the amount of solids (parts by mass)) with ethanol measured to a solid content concentration of 60%, so that the amount of each component as solids matches the amount shown in the table below. A 16 μm thick polyethylene terephthalate film (Toray Industries, Ltd., QS71) was used as a support film, and the above preparation was applied to its surface using a bar coater, and then dried in a 95°C dryer for 2.5 minutes. This formed a 25 μm thick photosensitive resin layer on the support film. A photosensitive resin laminate was obtained.

[0305] Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818"), which serves as a protective layer, was attached to the side of the photosensitive resin layer opposite the support film to obtain a laminate. Here, the laminate of the support film, photosensitive resin layer, and protective film was referred to as a photosensitive resin laminate.

[0306] <Surface preparation of the circuit board> A copper-clad laminate with a total thickness of 0.4 mm was prepared by laminating rolled copper foil with a thickness of 18 μm. This surface was then washed with a 10 mass% H2SO4 aqueous solution, and subsequently washed with pure water. The washed copper-clad laminate was preheated to 50°C.

[0307] <Laminate> While peeling off the protective film from the photosensitive resin laminate, the copper-clad laminate, preheated to 50°C, was laminated using a hot roll laminator (Asahi Kasei AL-700) at a roll temperature of 105°C, so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. This obtained an evaluation substrate. The air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0308] <Exposure> Two hours after lamination, evaluation substrates were directly exposed using a direct imaging (DI) exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined direct imaging (DI) exposure pattern. Exposure was performed using a Stuffer Industries 41-step tablet as a mask, and the exposure amount was set to the maximum number of remaining film steps after development to 15.

[0309] <Heating> Two minutes after exposure, the evaluation substrate was heated for 30 seconds in a forced-air constant-temperature incubator (Yamato Scientific Co., Ltd., DKM600) set to 70°C.

[0310] <Developing> The support film was peeled off the evaluation substrate. Then, development was performed by spraying a 1% by mass Na2CO3 aqueous solution at 30°C onto the photosensitive resin layer using an alkaline developer (Fuji Kiko Co., Ltd., dry film developer) for a predetermined time. After that, the photosensitive resin layer was washed by spraying it with pure water for a predetermined time. This obtained a resist pattern on the evaluation substrate.

[0311] [evaluation] <Developability> The shortest time required for the photosensitive resin layer in the unexposed area to completely dissolve was defined as the "minimum development time," and the developability was evaluated by ranking this minimum development time as follows. A short minimum development time makes it easier to shorten the development time, and a good result in the <developability> evaluation is expected to improve productivity during the manufacturing of wiring boards. (Evaluation Criteria) Excellent (E): The minimum development time is 19 seconds or less. Good (G): The minimum development time is between 19 seconds and 23 seconds. Unacceptable (P): Minimum development time exceeds 23 seconds.

[0312] <Resolution> Resolution was evaluated using drawing patterns (see Figure 1) with L / S of x / x {x = 5, 8, and 10 μm} (unit: μm). Specifically, direct imaging exposure was performed on the substrate that had undergone the above-mentioned <surface preparation> and <lamination> according to the drawing pattern. Subsequently, a resist pattern was formed by performing the above-mentioned <heating> and <development>. In the <development> stage, development and washing were performed for twice the minimum development time.

[0313] Figure 1 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The unexposed area 1 has a predetermined width and extends in the X direction, and multiple such unexposed areas 1 are arranged in the width direction (Y direction) at predetermined intervals. In this embodiment, since the unexposed area 1 is removed through the <development> process, it is theoretically expected that by exposing the photosensitive resin layer based on the drawing pattern in Figure 1, a resist pattern with L / S corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0314] The substrates on which the resist pattern was formed were observed with an optical microscope at a magnification of 200x and evaluated according to the following criteria. Note that residual resist may occur if the unexposed portions of the resist are not sufficiently removed during the development process described above. (Evaluation Criteria) Yu(E) : No tilting, bending, or defects are observed in the L / S=5μm / 5μm resist pattern. Furthermore, no residual resist is observed between the L / S=5μm / 5μm patterns. Good (G): No tilting, bending, or defects are observed in the L / S=8μm / 8μm resist pattern. Furthermore, no residual resist is observed between L / S=8μm / 8μm patterns (except in cases of "Excellent (E)" evaluation). Possible (A): No tilting, bending, or defects are observed in the L / S = 10 μm / 10 μm resist pattern. Furthermore, no residual resist is observed between L / S = 10 μm / 10 μm patterns (except in cases of "Excellent (E)" or "Good (G)" evaluation). Not possible (P): In resist patterns with L / S = 10 μm / 10 μm, tilting, bending, or defects are observed. Alternatively, residual resist is observed between patterns with L / S = 5 μm / 5 μm, 8 μm / 8 μm, or 10 μm / 10 μm.

[0315] <Adhesion> Adhesion was evaluated using a drawing pattern (see Figure 2) with L / S = x / 200 {x = 5, 8, and 10 μm} (unit: μm). Specifically, the substrate that had undergone the above-mentioned <surface preparation> and <lamination> was exposed using the drawing pattern. Subsequently, the above-mentioned <heating> and <development> were performed to form a resist pattern. In the <development> stage, development and washing were performed for twice the minimum development time.

[0316] Figure 2 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100A, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The exposed area 10 has a predetermined width and extends in the x direction, and multiple such exposed areas 10 are arranged in the width direction (y direction) at predetermined intervals. In this embodiment, since the unexposed area 1 is removed through the <development> process, theoretically, based on the drawing pattern in Figure 2, it is expected that a resist pattern with L / S corresponding to the width of the exposed area 10 (L: line) and the width of the unexposed area 1 (S: space) will be formed.

[0317] The substrates on which the resist pattern was formed were observed with an optical microscope at a magnification of 100x, and then evaluated according to the following criteria. (Evaluation Criteria) Yu(E) : No breaks or defects were observed in the resist pattern with L / S = 5 μm / 200 μm. Good (G): No breaks or defects were observed in the resist pattern with L / S = 8 μm / 200 μm (except in cases where the rating is "Excellent (E)"). Possible (A): No breaks or defects are observed in the resist pattern with L / S = 10 μm / 200 μm (except in cases where the rating is "Excellent (E)" or "Good (G)"). Not possible (P): Folds or defects are observed in the resist pattern with L / S = 10 μm / 200 μm.

[0318] <Flexibility of the hardened film> A flexible substrate {NIKKAFLEX F-30VC1 25RC11(H)} cut to a size of 200mm x 250mm was laminated as described above, and a photosensitive resin layer was formed on the substrate. Next, exposure was performed to a size of 1 inch wide and 250mm long using an energy level that resulted in 15 remaining steps on a Stuffer Industries 41-step tablet. Furthermore, development and washing were performed according to the above description for twice the minimum development time, and then the substrate was cut to a width of 1.2 inches so that the 1-inch wide hardened photosensitive resin layer was centered in the width direction, thereby producing a sample.

[0319] A mandrel test (cylindrical mandrel method; a bending resistance test in accordance with JIS K5600-5-1-1999) was performed using the prepared samples. Subsequently, the smallest mandrel diameter in which no cracks or delamination from the substrate were observed in the cured film on the sample was determined, and the flexibility was evaluated based on this diameter according to the following criteria. A smaller value indicates higher flexibility. (Evaluation Criteria) Yu(E) : The smallest mandrel diameter that showed no "cracking" or "peeling from the substrate" in the cured film was 6 mm or less. Good (G): No cracks or peeling from the substrate were observed in the cured film, and the smallest mandrel diameter was 8 mm or less (except in cases of an "Excellent (E)" rating). Not possible (P): No cracks or peeling from the substrate were observed in the cured film, and the smallest mandrel diameter was 10 mm or larger (except in cases where the rating was "Excellent (E)" or "Good (G)").

[0320] Observations for "cracking" and "peeling from the substrate" were made by visual inspection. "Cracking" refers to the presence of cracks in the cured film, while "peeling from the substrate" refers to the presence of peeling of the cured film from the substrate. Furthermore, "chips" in the cured film were included in the category of "cracking."

[0321] [Table 6]

[0322] [Table 7]

[0323] [Table 8]

[0324] [Table 9]

[0325] [Table 10]

[0326] [Table 11]

[0327] [Table 12] [Industrial applicability]

[0328] [Industrial applicability of the "first invention"] The photosensitive resin laminate of the present invention has good sensitivity and excellent flexibility. Therefore, it can be suitably used as a photosensitive resin laminate for forming wiring in printed circuit boards and the like. The photosensitive resin composition of the present invention can suitably produce the above-mentioned photosensitive resin laminate that can be used industrially. The resist pattern formation method of the present invention can be used as a process for forming wiring patterns.

[0329] [Industrial applicability of "related aspects"] The photosensitive resin composition of the present invention can be used to form wiring in printed circuit boards and the like. By using the photosensitive resin composition of the present invention, industrially usable photosensitive resin laminates can be suitably obtained. The resist pattern formation method of the present invention can be suitably used in the process of forming wiring patterns. [Explanation of symbols]

[0330] 1: Unexposed area (unexposed portion) 10: Exposure area (exposure part) 100,100A: Drawing area L: Line S: Space

Claims

1. The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; (C) polymerization initiator; and (D) Boron compounds that absorb to the h-ray and / or i-ray; A photosensitive resin composition containing [a specific substance].

2. The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; and (C) Polymerization initiator; A photosensitive resin composition comprising, (D) Component includes a boron compound that absorbs to h-rays and / or i-rays, The aforementioned component (B) is a photosensitive resin composition comprising a difunctional compound having two ethylenically unsaturated bonds in one molecule.

3. The photosensitive resin composition according to claim 1 or 2, wherein the boron compound is a compound having a carbon (C)-boron (B) bond.

4. The aforementioned component (D) is given by the following general formula: R ２ -B(OH) ２ ; R ３ -B(OR １ ) ２ ; R ４ -B(NR ５ ２ ) ２ ; and R ６ -B(OH)(OR ７ ); (In the formula, R １ ~R ７ R is a monovalent organic group and can have multiple R groups present in a single molecule. １ , and R ５ (They may be the same or different.) Compounds represented by, And, the following general formula (3): 【Chemistry 1】 (In the formula, R ８ is a monovalent organic group, R ９ ( is a divalent organic group.) Compounds represented by ); The photosensitive resin composition according to claim 1 or 2, comprising at least one compound selected from the group consisting of the following.

5. In the above component (D), Absorption with respect to the h-line and / or i-line means the following method: (1) Prepare a toluene solution of the compound to be measured at a concentration of 5 ppm. Measure the absorbance using a spectrophotometer with a two-sided transmission quartz cell having a path length of 10 mm, and read the obtained absorbance values ​​at 1 nm intervals. Treat the read values ​​as absorbance (A1). (2) Using the same method as in (1) above, measure the absorbance of toluene alone and read the obtained absorbance values ​​at 1 nm intervals. Treat the read values ​​as absorbance (A2); and (3) Subtract the absorbance (A2) at the same wavelength from the absorbance (A1) to obtain the subtracted value (A1-A2) at 1 nm intervals. Treat this subtracted value (A1-A2) as the absorbance (A3) at 5 ppm in the toluene solution; The photosensitive resin composition according to claim 1 or 2, wherein there exists a wavelength in the range of 400 to 410 nm and / or 350 to 370 nm in which the absorbance (A3) is 0.008 or greater, as measured by [method / function].

6. In the above component (D), Absorption with respect to the h-line and / or i-line means the following method: (4) Prepare a toluene solution of the compound to be measured at a concentration of 5 ppm, and measure the absorbance using a spectrophotometer with a two-sided transmission quartz cell with a path length of 10 mm, reading the obtained absorbance values ​​at 1 nm intervals. Treat the read values ​​as absorbance (A1); (5) Using the same method as in (1) above, measure the absorbance of toluene alone and read the obtained absorbance values ​​at 1 nm intervals. Treat the read values ​​as absorbance (A2); and (6) Subtract the absorbance (A2) at the same wavelength from the absorbance (A1) to obtain the subtracted value (A1-A2) at 1 nm intervals. Treat this subtracted value (A1-A2) as the absorbance (A3) at 5 ppm in the toluene solution; The photosensitive resin composition according to claim 1 or 2, wherein the absorbance (A3) is 0.008 or higher at at least one of 405 nm and 365 nm, as measured by [method / tool].

7. The aforementioned component (D) is given by the following general formula: R ２ -B(OH) ２ ; and R ３ -B(OR １ ) ２ ; (In the formula, R １ ~R ３ This represents a monovalent organic group and can contain multiple R groups within a single molecule. １ (They may be the same or different.) The photosensitive resin composition according to claim 1 or 2, comprising at least one compound selected from the group consisting of the following.

8. The monovalent organic group is any substituent including an alkyl group having 1 to 20 carbon atoms, an alkanoyl group, a benzoyl group, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated or unsaturated heterocyclic group, or a substituent in which a hydrogen atom in any of these groups is replaced by a halogen atom. The photosensitive resin composition according to claim 4, wherein the divalent organic group is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

9. The photosensitive resin composition according to claim 1 or 2, wherein the (D) component comprises a compound having an anthracene skeleton.

10. The photosensitive resin composition according to claim 1 or 2, wherein the (D) component comprises a compound having a pyrazoline skeleton.

11. The aforementioned component (D) is, A photosensitive resin composition according to claim 1 or 2, comprising a compound having at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, benzophenone, oxazole, and chrysene.

12. The photosensitive resin composition according to claim 1 or 2, wherein component (D) is a compound having a boron atom directly bonded to an anthracene skeleton.

13. The photosensitive resin composition according to claim 1 or 2, wherein the (D) component comprises 10-phenyl-9-anthraceneboronic acid.

14. The photosensitive resin composition according to claim 2, wherein the component (B) comprises a compound having a bisphenol A skeleton as the bifunctional compound.

15. The photosensitive resin composition according to claim 1 or 2, wherein the (A) component comprises hydroxyethyl (meth)acrylate as a comonomer component.

16. The photosensitive resin composition according to claim 2, wherein component (B) further comprises a hindered amine compound in addition to the bifunctional compound.

17. The above-mentioned component (A): 10 to 90% by mass, Component (B): 5 to 70% by mass, Component (C): 0.01 to 20% by mass, and Component (D): 0.01 to 20% by mass A photosensitive resin composition according to claim 1 or 2, comprising the above.

18. The photosensitive resin composition according to claim 1 or 2, wherein the ratio of the total mass of component (B) to the total mass of component (A) (B / A) is 1 / 3.0 to 1 / 0.

5.

19. A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition described in claim 1 or 2.

20. The photosensitive resin laminate further comprises a protective layer on the side of the photosensitive resin layer opposite to the support, The photosensitive resin laminate according to claim 19, wherein the protective layer is a polyethylene terephthalate film or a biaxially oriented polypropylene film.

21. The photosensitive resin laminate according to claim 20, wherein the protective layer has a release layer on its surface.

22. A lamination step of laminating the photosensitive resin layer in the photosensitive resin laminate according to claim 19 onto a substrate, An exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and A method for forming a resist pattern, comprising a developing step of removing the unexposed portion of the photosensitive resin layer.

23. The aforementioned component (D) is a compound that absorbs on the h line, The method for forming a resist pattern according to claim 22, wherein in the exposure step, the photosensitive resin layer is exposed with light including a wavelength of 400 to 410 nm.

24. The aforementioned component (D) is a compound that absorbs on the i-line, The method for forming a resist pattern according to claim 22, wherein in the exposure step, the photosensitive resin layer is exposed with light including a wavelength of 350 to 370 nm.

25. A step of forming a resist pattern on a substrate using the photosensitive resin laminate described in claim 20, A step of forming a conductive pattern on a substrate on which the resist pattern has been formed by etching or plating, The process of peeling the resist pattern from the substrate, A method for forming a wiring board, including the method described above.

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