JP-2026076190-A - Photosensitive resin composition, photosensitive resin laminate, and method for forming a resist pattern

JP2026076190AJP 2026076190 AJP2026076190 AJP 2026076190AJP-2026076190-A

Abstract

[Problem] 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. [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 and/or i lines; Includes. [Selection Diagram] Figure 1

Inventors

亀山奈央
西本秀昭
松本克久
松尾裕樹

Assignees

旭化成株式会社

Dates

Publication Date: 20260511
Application Date: 20251226
Priority Date: 20221021

Claims (20)

The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; (C) polymerization initiators; and (D) boron compounds having absorption for h-rays and/or i-rays; A photosensitive resin composition containing [a specific substance].
The following ingredients: (A) Alkali-soluble polymers; (B) Compounds having an ethylenically unsaturated double bond; and (C) Polymerization initiators; 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.
The photosensitive resin composition according to claim 1 or 2, wherein the boron compound is a compound having a carbon (C)-boron (B) bond.
The aforementioned component (D) is given by the following general formula: R 2 -B(OH) 2 ; R 3 -B(OR 1 ) 2 ; R4 -B( NR52 ) 2 ; and R6 -B(OH ) ( OR7 ); (In the formula, R1 to R7 are monovalent organic groups, and the multiple R1 and R5 groups that may exist in a single molecule may be the same or different.) Compounds represented by, And, the following general formula (3): Compounds represented by the formula (wherein R8 is a monovalent organic group and R9 is a divalent organic group); The photosensitive resin composition according to claim 1 or 2, comprising at least one compound selected from the group consisting of the following.
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 value at 1 nm intervals. Treat the read value 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].
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 value at 1 nm intervals. Treat the read value 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].
The aforementioned component (D) is given by the following general formula: R2 -B(OH) 2 ; and R3 -B( OR1 ) 2 ; (In the formula, R1 to R3 represent monovalent organic groups, and the multiple R1 groups that may exist in a single molecule 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.
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.
The photosensitive resin composition according to claim 1 or 2, wherein component (D) comprises a compound having an anthracene skeleton.
The photosensitive resin composition according to claim 1 or 2, wherein component (D) comprises a compound having a pyrazoline skeleton.
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.
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.
The photosensitive resin composition according to claim 1 or 2, wherein component (D) comprises 10-phenyl-9-anthraceneboronic acid.
The photosensitive resin composition according to claim 2, wherein component (B) comprises a compound having a bisphenol A skeleton as the bifunctional compound.
The photosensitive resin composition according to claim 1 or 2, wherein component (A) comprises hydroxyethyl (meth)acrylate as a comonomer component.
The photosensitive resin composition according to claim 2, wherein component (B) further comprises a hindered amine compound in addition to the bifunctional compound.
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.
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.
A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition described in claim 1 or 2.
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.

Description

This invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern. [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. In photolithography, the method for forming a photosensitive resin layer on a substrate is generally: A method of coating a solution of a photosensitive resin composition onto a substrate and drying it; or a method of laminating a photosensitive resin layer on 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. 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. [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. 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 of laminating a photosensitive resin layer on 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. 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. In 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. Patent Document 4 describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an anthracene-based sensitizer, wherein the binder polymer contains polymer (a), and polymer (a) contains 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-described photosensitive resin composition. Patent No. 4156069Patent No. 3674336Japanese Patent Application Publication No. 4-271352International Publication No. 2021/193232 A plan view showing the configuration of a drawing pattern related to this embodiment.A plan view showing the configuration of a drawing pattern related to this embodiment. 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. In this specification, if multiple structures represented by the same reference numeral exist in the same formula, unless otherwise specified, these structures may be selected independently and may be identical or different from one another. Similarly, if multiple structures represented by the same reference numeral exist in different formulas, unless otherwise specified, these structures may be selected independently and may be identical or different from one another. In this specification, various measurements are performed according to the methods d