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

Abstract

The invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern. The composition comprises the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a polymerization initiator; and (D) a boron compound having an absorption of h-rays and / or i-rays.

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 Art

[0002] [First Background Art]

[0003] Printed circuit boards are usually manufactured by photolithography. In photolithography, first, a photosensitive resin layer (a layer formed from a photosensitive resin composition) is formed on a substrate. Then, a photosensitive resin pattern (a resist pattern) is formed by exposing and developing the photosensitive resin layer. Next, after forming a conductor pattern through an etching process or a plating process, the resist pattern is removed, thereby forming a desired wiring pattern on the substrate.

[0004] In photolithography, as a method for forming a photosensitive resin layer on a substrate, the following are generally used:

[0005] A method of coating a solution of a photosensitive resin composition on a substrate and drying it; or

[0006] A method of laminating a photosensitive resin layer in a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer) on a substrate.

[0007] In the manufacturing process of printed circuit boards, the method using a photosensitive resin laminate among the above is mostly adopted. In the method using a photosensitive resin laminate, the good sensitivity of the photosensitive resin layer and the flexibility of the resist pattern are likely to affect the productivity and resolution of the wiring pattern.

[0008] Here, Patent Document 1 discloses an example of using tributylphenyl borate as a chain transfer agent. Patent Document 2 discloses an example of using a borate having various cations as a coinitiator of an initiator system containing an amine and hexaarylbisimidazole (HABI). Patent Document 3 discloses an example of using an organic boron compound having a specified structure as a radical generator.

[0009] [Related Background Art]

[0010] Printed circuit boards are usually manufactured by photolithography. In photolithography, first, a photosensitive resin layer (a layer containing a photosensitive resin composition) is formed on a substrate. Then, a resin pattern (a resist pattern) is formed by exposing and developing the photosensitive resin layer. Next, after forming a conductor pattern through an etching process or a plating process, the resist pattern is removed, thereby forming a desired wiring pattern on the substrate.

[0011] In photolithography, as a method for forming a photosensitive resin layer on a substrate, the following are generally used:

[0012] A method of coating a solution of a photosensitive resin composition on a substrate and drying it; or

[0013] A method of laminating a photosensitive resin layer in a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer) on a substrate.

[0014] In the manufacturing process of electronic devices, such as the manufacturing process of printed circuit boards, the method of using a photosensitive resin laminate among the above is mostly adopted.

[0015] In recent years, with the miniaturization / high density of electronic devices, the formation of finer wirings than before has been required. In the formation of wirings using a photosensitive resin laminate, a photosensitive resin laminate capable of forming a resist pattern with excellent resolution and high adhesion to a substrate is required.

[0016] Patent Document 4 describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an anthracene-based sensitizer. Among them, the binder polymer contains polymer (a), and the polymer (a) contains (meth)acrylic acid hydroxyalkyl ester units and contains 40 mass% or more of styrene or styrene derivative units. In addition, Patent Document 4 describes a photosensitive resin laminate having a support and a photosensitive resin layer formed using the above photosensitive resin composition.

[0017] Prior Art Documents

[0018] Patent Documents

[0019] Patent Document 1: Japanese Patent No. 4156069

[0020] Patent Document 2: Japanese Patent No. 3674336

[0021] Patent Document 3: Japanese Unexamined Patent Application Publication No. 4-271352

[0022] Patent Document 4: International Publication No. 2021 / 193232 Summary of the Invention

[0023] Problems to be Solved by the Invention

[0024] [Problem 1]

[0025] However, in each of the above materials of Patent Documents 1 and 2, in addition to the boron compound, it is necessary to additionally add an aromatic onium salt and a near-infrared dye as sensitizers, which may be an obstacle from the viewpoint of achieving good sensitivity of the photosensitive resin material.

[0026] In recent years, as the productivity and resolution of wiring patterns have been required to increase, from the viewpoint of flexibility, there is room for further improvement in the resist patterns obtained from the above materials of Patent Documents 1, 2, and 3, respectively.

[0027] Therefore, the present inventors focused on compounds in boron compounds that absorb light of a specified exposure wavelength, and found that a photosensitive resin composition contains such a compound.

[0028] An object of the present invention is to provide a photosensitive resin laminate, a photosensitive resin composition capable of realizing the photosensitive resin laminate, and a method for forming a resist pattern, which can achieve 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 specified exposure wavelength and causing the boron compound to absorb light of the exposure wavelength.

[0029] [Related Problems]

[0030] Here, in the photosensitive resin composition described in Patent Document 1, from the viewpoints of resolution and adhesion, the polymer (a) contains 40% by mass or more of styrene or styrene derivative units. On the other hand, from the viewpoints of developability and flexibility of the cured film, there is room for research on the photosensitive resin composition described in Patent Document 1 and the photosensitive resin laminate having a photosensitive resin layer obtained by using the same.

[0031] An object of the present invention is to provide a photosensitive resin composition that is excellent in all of resolution, adhesion, developability, and flexibility of the cured film. In addition, an object of the present invention is to provide a photosensitive resin laminate and a method for forming a resist pattern obtained by using the photosensitive resin composition, and a method for forming a wiring board.

[0032] [Solutions to the Problems]

[0033] [Solutions to "First Problem"]

[0034] One embodiment of the present invention is as follows. [1]

[0036] A photosensitive resin composition comprising the following components:

[0037] (A) An alkali-soluble polymer;

[0038] (B) A compound having an ethylenically unsaturated double bond;

[0039] (C) A polymerization initiator; and

[0040] (D) A boron compound that absorbs h-rays and / or i-rays. [2]

[0042] A photosensitive resin composition comprising the following components:

[0043] (A) An alkali-soluble polymer;

[0044] (B) A compound having an ethylenically unsaturated double bond; and

[0045] (C) A polymerization initiator;

[0046] The photosensitive resin composition contains a boron compound that absorbs h-rays and / or i-rays as component (D),

[0047] The aforementioned component (B) contains a bifunctional compound having 2 ethylenically unsaturated bonds in 1 molecule. [3]

[0049] The photosensitive resin composition according to item 1 or 2, wherein the aforementioned boron compound is a compound having a carbon (C)-boron (B) bond. [4]

[0051] The photosensitive resin composition according to any one of items 1 to 3, wherein the aforementioned component (D) contains a compound selected from the following general formula:

[0052] R 2 -B(OH) 2 ;

[0053] R 3 -B(OR 1 ) 2 ;

[0054] R 4 -B(NR 5 2 ) 2 ; and

[0055] R 6 -B(OH)(OR 7 );

[0056] (In the formula, R 1 to R 7 are monovalent organic groups, and multiple R 1 and R 5 that can exist in 1 molecule may be the same or different optionally.) The compound shown, and,

[0057] At least one compound selected from the group consisting of the compound shown by the following general formula (3).

[0058]

[0059] (In the formula, R 8is a monovalent organic group, R 9 is a divalent organic group.) [5]

[0061] The photosensitive resin composition according to any one of Items 1 to 4, wherein, in the aforementioned component (D), having absorption of h-rays and / or i-rays means that, as measured by the following method, there is a wavelength with an absorbance (A3) of 0.008 or more in the range of 400 to 410 nm and / or 350 to 370 nm.

[0062] (1) Prepare a toluene solution with a concentration of 5 ppm of the compound to be measured. Use a quartz cell with a light path length of 10 mm that transmits light on both sides, and measure the absorbance with a spectrophotometer. Read the absorbance values obtained every 1 nm. Treat the read values as the absorbance (A1);

[0063] (2) Measure the absorbance of toluene alone by the same method as in the aforementioned (1). Read the absorbance values obtained every 1 nm. Treat the read values as the absorbance (A2); and

[0064] (3) Subtract the aforementioned absorbance (A2) at the same wavelength from the aforementioned absorbance (A1) to obtain a subtracted value (A1 - A2) every 1 nm. Treat this subtracted value (A1 - A2) as the absorbance (A3) at 5 ppm in the toluene solution. [6]

[0066] The photosensitive resin composition according to any one of Items 1 to 5, wherein, in the aforementioned component (D), having absorption of h-rays and / or i-rays means that, as measured by the following method, the absorbance (A3) is 0.008 or more at at least one of 405 nm and 365 nm.

[0067] (4) Prepare a toluene solution with a concentration of 5 ppm of the compound to be measured. Use a quartz cell with a light path length of 10 mm that transmits light on both sides, and measure the absorbance with a spectrophotometer. Read the absorbance values obtained every 1 nm. Treat the read values as the absorbance (A1);

[0068] (5) Measure the absorbance of toluene alone by the same method as in the aforementioned (1). Read the absorbance values obtained every 1 nm. Treat the read values as the absorbance (A2); and

[0069] (6) Subtract the aforementioned absorbance (A2) at the same wavelength from the aforementioned absorbance (A1) to obtain a subtracted value (A1 - A2) every 1 nm. Treat this subtracted value (A1 - A2) as the absorbance (A3) at 5 ppm in the toluene solution. [7]

[0071] The photosensitive resin composition according to any one of Items 1 to 6, wherein the component (D) includes at least one compound selected from the group consisting of the following general formulas:

[0072] R 2 -B(OH) 2 ; and

[0073] R 3 -B(OR 1 ) 2 ;

[0074] (In the formula, R 1 to R 3 represent monovalent organic groups, and the plurality of R 1 that may be present in one molecule may be the same or different.) [8]

[0076] The photosensitive resin composition according to Item 4 or 7, wherein the monovalent organic group is 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, an arbitrary substituent containing a saturated or unsaturated heterocyclic group, or a substituent formed by substituting a hydrogen atom in these groups with a halogen atom.

[0077] 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]

[0079] The photosensitive resin composition according to any one of Items 1 to 8, wherein the component (D) includes a compound having an anthracene skeleton.

[10]

[0081] The photosensitive resin composition according to any one of Items 1 to 9, wherein the component (D) includes a compound having a pyrazoline skeleton.

[11]

[0083] The photosensitive resin composition according to any one of Items 1 to 10, wherein the component (D) includes a compound having at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, benzophenone, oxazole, and ;

[12]

[0085] The photosensitive resin composition according to any one of Items 1 to 11, wherein the component (D) is a compound having a boron atom directly bonded to an anthracene skeleton.

[13]

[0087] The photosensitive resin composition according to any one of Items 1 to 12, wherein the component (D) contains 10-phenyl-9-anthracene boronic acid.

[14]

[0089] The photosensitive resin composition according to Item 2, wherein the component (B) contains a compound having a bisphenol A skeleton as the bifunctional compound.

[15]

[0091] The photosensitive resin composition according to any one of Items 1 to 14, wherein the component (A) contains 2-hydroxyethyl (meth)acrylate as a comonomer component.

[16]

[0093] The photosensitive resin composition according to Item 2, wherein the component (B) further contains a hindered amine compound in addition to the bifunctional compound.

[17]

[0095] The photosensitive resin composition according to any one of Items 1 to 16, comprising:

[0096] The component (A): 10 to 90% by mass,

[0097] The component (B): 5 to 70% by mass,

[0098] The component (C): 0.01 to 20% by mass, and

[0099] The component (D): 0.01 to 20% by mass.

[18]

[0101] The photosensitive resin composition according to any one of Items 1 to 17, wherein the ratio (B / A) of the total mass of the component (B) to the total mass of the component (A) is 1 / 3.0 to 1 / 0.5.

[19]

[0103] A photosensitive resin laminate having: a support, and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of Items 1 to 18.

[20]

[0105] The photosensitive resin laminate according to Item 19, wherein the photosensitive resin laminate further has a protective layer on the side of the photosensitive resin layer opposite to the support,

[0106] The protective layer is a film of polyethylene terephthalate or a film of biaxially oriented polypropylene.

[21]

[0108] The photosensitive resin laminate according to Item 20, wherein the protective layer has a release layer on its surface.

[22]

[0110] A method for forming a resist pattern, comprising the following steps:

[0111] A laminating step of laminating the photosensitive resin layer in the photosensitive resin laminate according to any one of Items 19 to 21 on a substrate;

[0112] An exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate; and

[0113] A developing step of removing the unexposed portion of the photosensitive resin layer.

[23]

[0115] The method for forming a resist pattern according to Item 22, wherein the component (D) is a compound that absorbs h-rays,

[0116] In the exposure step, the photosensitive resin layer is exposed to light having a wavelength of 400 to 410 nm.

[24]

[0118] The method for forming a resist pattern according to Item 22, wherein the component (D) is a compound that absorbs i-rays,

[0119] In the exposure step, the photosensitive resin layer is exposed to light having a wavelength of 350 to 370 nm.

[25]

[0121] A method for forming a wiring board, comprising the following steps:

[0122] A step of forming a resist pattern on a substrate using the photosensitive resin laminate according to any one of Items 20 to 24;

[0123] A step of etching or plating the substrate on which the resist pattern is formed to form a conductor pattern; and

[0124] A step of peeling the resist pattern from the substrate.

[0125] [Solution for solving "associated problems"]

[0126] The associated mode of the present invention is as described below.

[0127] [1A]

[0128] A photosensitive resin composition, comprising the following components:

[0129] (A) An alkali-soluble polymer;

[0130] (B) A compound having an ethylenically unsaturated bond; and

[0131] (C) A polymerization initiator,

[0132] The foregoing component (A) contains a copolymer (A-1),

[0133] The foregoing copolymer (A-1) has at least structural units derived from the following components,

[0134] (a1) (Meth)acrylic acid;

[0135] (a2) A styrene derivative; and

[0136] (a3) A hydroxyalkyl (meth)acrylate,

[0137] The proportion of the structural units derived from the foregoing component (a1) is 15 to 26% by mass,

[0138] The proportion of the structural units derived from the foregoing component (a2) is 30 to 70% by mass,

[0139] The proportion of the structural units derived from the foregoing component (a3) is 15 to 35% by mass, and

[0140] The glass transition temperature (Tg) calculated based on the Fox equation is 100 °C or lower.

[0141] [2A]

[0142] The photosensitive resin composition according to Item 1A, wherein the proportion of the structural units derived from the foregoing component (a1) in the foregoing copolymer (A-1) is 25% by mass or less.

[0143] [3A]

[0144] The photosensitive resin composition according to Item 1A or 2A, wherein the foregoing copolymer (A-1) contains a structural unit derived from methacrylic acid as the foregoing component (a1).

[0145] [4A]

[0146] The photosensitive resin composition according to Item 3A, wherein the proportion of the structural units derived from methacrylic acid in the foregoing copolymer (A-1) is 15 to 25% by mass.

[0147] [5A]

[0148] The photosensitive resin composition according to Item 1A or any one of Items 1A to 4A, wherein the proportion of the structural units derived from the foregoing component (a3) is 16% by mass or more.

[0149] [6A]

[0150] The photosensitive resin composition according to any one of Items 1A to 5A, wherein the copolymer (A-1) further has a structural unit derived from the following component:

[0151] (a4) an (alkyl) acrylate represented by the following general formula (I);

[0152]

[0153] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 3 or more carbon atoms.)

[0154] In the copolymer (A-1),

[0155] the proportion of the structural unit derived from the component (a2) is 30 to 60% by mass, and

[0156] the proportion of the structural unit derived from the component (a4) is 1% to 15% by mass.

[0157] [7A]

[0158] The photosensitive resin composition according to Item 6A, wherein the aforementioned R 2 represents an alkyl group having 3 to 12 carbon atoms.

[0159] [8A]

[0160] The photosensitive resin composition according to Item 6A or 7A, wherein the component (a4) includes 2-ethylhexyl (meth)acrylate.

[0161] [9A]

[0162] The 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.

[0163] [10A]

[0164] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 9A, wherein, based on all solid components of the photosensitive resin composition, it contains 10% by mass or more of the copolymer (A-1).

[0165] [11A]

[0166] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 10A, wherein, based on all solid components of the photosensitive resin composition, it contains 30% by mass or more of the copolymer (A-1).

[0167] [12A]

[0168] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 11A, wherein the component (B) contains a bis(meth)acrylate having a bisphenol A skeleton.

[0169] [13A]

[0170] The photosensitive resin composition according to Item 12A, wherein, based on all solid components of the photosensitive resin composition, it contains 20% by mass or more of the bis(meth)acrylate having a bisphenol A skeleton.

[0171] [14A]

[0172] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 13A, wherein the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {(content of component (A)) / (content of component (B))} is 1.40 or more.

[0173] [15A]

[0174] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 14A, wherein the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {(content of component (A)) / (content of component (B))} is 1.50 or more.

[0175] [16A]

[0176] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 15A, wherein the component (C) contains a compound having a biimidazole structure.

[0177] [17A]

[0178] The photosensitive resin composition according to any one of Items 1A to 5A and 6A to 16A, which further contains a sensitizer, and the sensitizer contains 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.

[0179] [18A]

[0180] The photosensitive resin composition according to Item 17A, wherein the sensitizer contains a compound having a skeleton derived from an anthracene derivative.

[0181] [19A]

[0182] The photosensitive resin composition according to Item 17A or 18A, wherein the sensitizer contains at least one compound selected from the group consisting of 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid.

[0183] [20A]

[0184] A photosensitive resin laminate having: a support, and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of Items 1A to 5A and 6A to 19A.

[0185] [21A]

[0186] The photosensitive resin laminate according to Item 20A, wherein the diameter of the following smallest mandrel obtained by the following method is 8 mm or less.

[0187] (1) After forming the photosensitive resin layer on the flexible substrate, exposing it with an energy of 15 steps of the residual steps of a Stouffer (Stouffer Industries) 41-step exposure meter at a size of 1 inch in width and 250 mm in length, thereby obtaining a cured film on the substrate.

[0188] (2) Using an aqueous solution of 1 mass% Na 2 CO 3 at 30 °C, developing the exposed substrate for a time twice the shortest development time.

[0189] (3) Washing the developed substrate for a time twice the shortest development time.

[0190] (4) Cutting the washed substrate into a width of 1.2 inches with the cured photosensitive resin layer of 1 inch width located at the center in the width direction, thereby obtaining a sample.

[0191] (5) Conducting a mandrel test on the sample by the method based on the cylindrical mandrel method JIS K5600-5-1.

[0192] (6) Determining the diameter of the smallest mandrel in which no cracks are confirmed in the cured film, or the diameter of the smallest mandrel in which no peeling of the cured film from the substrate is confirmed.

[0193] [22A]

[0194] The photosensitive resin laminate according to Item 20A or 21A, wherein the photosensitive resin laminate further has a protective layer on the side of the photosensitive resin layer opposite to the support,

[0195] The aforementioned protective layer is a film of polyethylene terephthalate (PET) or a film of biaxially oriented polypropylene (OPP).

[0196] [23A]

[0197] The photosensitive resin laminate according to Item 22A, wherein the aforementioned protective layer has a release layer on its surface.

[0198] [24A]

[0199] A method for forming a resist pattern, which comprises the following steps:

[0200] A laminating step of laminating the aforementioned photosensitive resin layer in the photosensitive resin laminate according to any one of Items 20A to 23A on a substrate;

[0201] An exposure step of exposing the photosensitive resin layer of the aforementioned photosensitive resin laminate; and

[0202] A developing step of removing the unexposed portion of the aforementioned photosensitive resin layer.

[0203] [25A]

[0204] A method for forming a wiring board, which comprises the following steps:

[0205] A step of forming a resist pattern on a substrate using the photosensitive resin laminate according to any one of Items 20A to 23A;

[0206] A step of etching or plating the substrate on which the resist pattern is formed to thereby form a conductor pattern; and

[0207] A step of peeling the aforementioned resist pattern from the substrate.

[0208] Effects of the Invention

[0209] [Effects of "First Invention"]

[0210] According to the present invention, it is possible to provide a photosensitive resin laminate that takes into account both the good sensitivity of the photosensitive resin layer and the high flexibility of the resist pattern, a photosensitive resin composition that can realize the photosensitive resin laminate, and a method for forming a resist pattern.

[0211] [Effects of "Related Mode"]

[0212] According to the related mode of the present invention, it is possible to provide a photosensitive resin composition that can form a photosensitive resin layer (resist) having all excellent resolution, adhesion, developability, and flexibility of the cured film.

[0213] In addition, according to the association method of the present invention, a photosensitive resin laminate having the photosensitive resin layer, a method for forming a resist pattern, and a method for forming a wiring board can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0214] Figure 1 It is a top view showing the configuration of a drawn pattern related to this embodiment.

[0215] Figure 2 It is a top view showing the configuration of a drawn pattern related to this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0216] Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[0217] The present invention is not limited to this embodiment, and various modifications can be made and implemented within the scope of its gist.

[0218] In this specification, when there are multiple structures indicated by the same symbol in the same chemical formula, as long as there is no particular limitation, these structures can be selected independently of each other, and furthermore, they may be the same or different from each other optionally. When there are multiple structures indicated by the same symbol in different chemical formulas, as long as there is no particular limitation, these structures can also be selected independently of each other, and furthermore, they may be the same or different from each other optionally. In this specification, various measurements are carried out based on the methods described in the examples unless otherwise specified. In this specification, the upper limit value or the lower limit value within the numerically described range in stages can be replaced with the upper limit value or the lower limit value within the corresponding other numerically described range in stages, and furthermore, it can also be replaced with the corresponding value described in the examples.

[0219] In this specification, “(meth)acrylic acid” means “acrylic acid” and / or “methacrylic acid”, “(meth)acrylate” means “acrylate” and / or “methacrylate”, and “(meth)acryloyl” means “acryloyl” and / or “methacryloyl”. A “compound containing a (meth)acryloyl group” is, for example, referred to as a “(meth)acrylate compound”. In this specification, regarding “processes”, not only cases where they are independent processes are included, but also cases where they cannot be clearly distinguished from other processes are included in this term as long as the functions of these processes can be achieved. For the sake of further clarity, in the content shown in the drawings, the scale, shape, and length are sometimes exaggerated.

[0220] In this specification, “derivative” includes not only compounds derived from a 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 as the parent compound.

[0221] [Embodiment of "First Invention"]

[0222] [Photosensitive resin composition]

[0223] The photosensitive resin composition of this embodiment contains the following components:

[0224] (A) Alkali-soluble polymer;

[0225] (B) Compound having an ethylenically unsaturated double bond;

[0226] (C) Initiator; and

[0227] (D) Boron compound having absorption for h-ray and / or i-ray (hereinafter sometimes simply referred to as "boron compound").

[0228] Thereby, a photosensitive resin laminate capable of achieving both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern can be provided.

[0229] In one mode, the photosensitive resin composition of this embodiment contains the following components:

[0230] (A) Alkali-soluble polymer;

[0231] (B) Compound having an ethylenically unsaturated double bond; and

[0232] (C) Polymerization initiator;

[0233] The photosensitive resin composition contains a boron compound having absorption for h-ray and / or i-ray as component (D),

[0234] (B) Component contains a bifunctional compound having 2 ethylenically unsaturated bonds in one molecule.

[0235] In this specification, the following terms are defined as follows.

[0236] "h-ray" refers to light having a wavelength of 400 - 410 nm, and in one mode, refers to light having a wavelength of 405 nm.

[0237] "i-ray" refers to light having a wavelength of 350 - 370 nm, and in one mode, refers to light having a wavelength of 365 nm.

[0238] "Having absorption" means that the absorbance at 5 ppm in toluene solution is 0.008 or more. Regarding "having absorption", the absorbance is measured according to the following (1) - (5). The measurement of the absorbance is carried out at room temperature (25 °C). The measurement can be carried out in the same manner in the examples.

[0239] (1) Prepare a toluene solution with a concentration of 5 ppm of the compound to be measured. For this toluene solution, use a quartz cell (S15-UV-10 manufactured by Tokyo Glass Kikai Co., Ltd.) with a light path length of 10 mm, that is, an internal dimension of 10 mm in the advancing direction of the irradiated light, and measure the absorbance with a spectrophotometer (U-3010 manufactured by Hitachi High-Technologies Corporation). Read the obtained absorbance values every 1 nm. Treat the read values as absorbance (A1).

[0240] The above-mentioned "toluene solution with a concentration of 5 ppm" can accept a toluene solution with a concentration of approximately 5 ppm. Specifically, it can be a toluene solution with a concentration of 4.90 - 5.10 ppm. At this time, the absorbances (A1) and (A3) at 5 ppm in the following toluene solution are obtained by converting to the absorbance value at a concentration of 5 ppm.

[0241] (2) Measure the absorbance of toluene alone by the same method as in the above (1). Read the obtained absorbance values every 1 nm. Treat the read values as absorbance (A2).

[0242] (3) Subtract the above absorbance (A2) at the same wavelength from the above absorbance (A1). Thus, the subtracted value (A1 - A2) is obtained every 1 nm. Treat the obtained value as the absorbance (A3) at 5 ppm in the toluene solution.

[0243] (4) In the absorbance (A3) obtained every 1 nm, when there is a wavelength with an absorbance of 0.008 or more in the range of 400 - 410 nm, it is treated as "absorbing h-rays". Similarly, in the absorbance (A3) obtained every 1 nm, when there is a wavelength with an absorbance of 0.008 or more in the range of 350 - 370 nm, it is treated as "absorbing i-rays".

[0244] In addition, as measured in the examples, the case where the value of the absorbance (A3) at 405 nm is 0.008 or more can be treated as "absorbing h-rays", and the case where the value of the absorbance (A3) at 365 nm is 0.008 or more can be treated as "absorbing i-rays".

[0245] In the photosensitive resin composition of the present embodiment, by containing the component (D) together with the above components (A) to (C), the component (D) suitably exhibits a sensitizing function with respect to a specified exposure wavelength (h-ray and / or i-ray) used in photolithography. Therefore, from the viewpoint of achieving good sensitivity of the photosensitive resin layer, the content of other sensitizers that may be obstructive can be reduced. Therefore, by using the photosensitive resin composition of the present embodiment, a photosensitive resin layer having good sensitivity can be obtained.

[0246] Moreover, it has generally been considered difficult to achieve both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern. For example, from the viewpoint of achieving good sensitivity of the photosensitive resin layer, although a resin design that is suitably crosslinked during the exposure process in photolithography is preferred, there is a tendency for the flexibility of the photosensitive resin layer, and thus the flexibility of the resist pattern, to be lost due to the progress of crosslinking.

[0247] In contrast, in the photosensitive resin composition of the present embodiment, by containing the component (D) together with the above components (A) to (C), it is possible to achieve both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern.

[0248] The achievement of good sensitivity of the photosensitive resin layer is related to the shortening of the exposure time, and thus to the improvement of the productivity of the wiring pattern. In addition, the achievement of high flexibility of the resist pattern is related to the suppression of resist pattern defects, and thus to the improvement of the resolution of the wiring pattern. Therefore, by using the photosensitive resin composition of the present embodiment, it is also possible to meet the expectations for the improvement of the productivity and resolution of the wiring pattern of a printed wiring board produced by photolithography.

[0249] The photosensitive resin composition of the present embodiment preferably contains:

[0250] (A) component: 10 to 90% by mass,

[0251] (B) component: 5 to 70% by mass,

[0252] (C) component: 0.01 to 20% by mass, and

[0253] (D) component: 0.01 to 20% by mass.

[0254] Thereby, it is easy to suitably exhibit the function as a photosensitive resin composition, and as a result, it is easy to exhibit the effects of the present invention.

[0255] Hereinafter, each component constituting the present embodiment will be described.

[0256] <(A) Component: Alkali-Soluble Polymer>

[0257] (A) component is an alkali-soluble polymer, that is, a polymer soluble in an alkaline solution. In one embodiment, the (A) component is a polymer soluble in an alkali developer.

[0258] From the viewpoint of suitably exhibiting alkali solubility, the (A) component preferably has a carboxyl group. Further, from the same viewpoint, the (A) component preferably has an acid value of 50 to 600 mgKOH. The acid value of the (A) component may be 60 mgKOH or more or 80 mgKOH or more, and may be 500 mgKOH or less or 400 mgKOH or less.

[0259] The weight-average molecular weight (Mw) of the (A) component 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. By making the Mw of the (A) component be above the above lower limit value, it is easy to uniformly maintain the thickness of the photosensitive resin layer. Further, by making the Mw of the (A) component be below the above upper limit value, it is easy to ensure the developability of the photosensitive resin layer. The ratio of the above Mw to the number-average molecular weight (Mn) of the (A) component, that is, the polydispersity (Mw / Mn), is preferably 1.0 to 6.0.

[0260] When the (A) component contains a plurality of alkali-soluble polymers, the "Mw of the (A) component" means the overall Mw of the (A) component calculated from the mass ratio of each alkali-soluble polymer and the Mw of each alkali-soluble polymer.

[0261] Similarly, when the (A) component contains a plurality of alkali-soluble polymers, the "Mn of the (A) component" means the overall Mn of the (A) component calculated from the mass ratio of each alkali-soluble polymer and the Mn of each alkali-soluble polymer.

[0262] The content of the (A) component in the photosensitive resin composition (based on the total amount of the solid components of the photosensitive resin composition. Hereinafter, the same applies to each contained component unless otherwise specified) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass. From the viewpoint of maintaining the alkali developability of the photosensitive resin layer, the content of the (A) component is preferably above the above lower limit value, and from the viewpoint of the resist pattern being easily flexible, it is preferably below the above upper limit value.

[0263] The (A) component is preferably a copolymer containing at least one of the following first monomers as a copolymerization monomer component. The (A) component is more preferably a copolymer containing at least one of the following first monomers and at least one of the following second monomers as copolymerization monomer components.

[0264] (A) component, the first monomer, and the second monomer may each be used alone in one kind or in combination of two or more kinds.

[0265] (The first monomer)

[0266] The first monomer is a carboxylic acid or acid anhydride having a polymerizable unsaturated group in the 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 them, from the viewpoint of alkali developability, (meth)acrylic acid is preferred, and methacrylic acid is more preferred. Since methacrylic acid has relatively high hydrophobicity, by using it, in addition to the above, it is also easy to improve the resolution of the resist pattern.

[0267] From the viewpoints of excellent adhesion and resolution, etc., the copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all copolymer monomer components. From the same viewpoints, the above copolymerization ratio is more preferably 15% by mass or more, further preferably 20% by mass or more, and additionally, more preferably 45% by mass or less, further preferably 40% by mass or less.

[0268] (The second monomer)

[0269] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include aromatic monomers, (meth)acrylic acid alkyl esters, conjugated diene compounds, polar monomers, and crosslinkable monomers.

[0270] Examples of the aromatic monomer include (meth)acrylic acid benzyl ester, phenoxy polyethylene glycol (meth)acrylate, divinylbenzene, and styrene derivatives (styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, etc.).

[0271] (Meth)acrylic acid alkyl ester is a concept including both linear alkyl esters and cyclic alkyl esters. Specifically, examples of (meth)acrylic acid alkyl ester include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid tert-butyl ester, (meth)acrylic acid pentyl ester, (meth)acrylic acid hexyl ester, (meth)acrylic acid heptyl ester, (meth)acrylic acid octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid lauryl ester, (meth)acrylic acid n-tetradecyl ester, (meth)acrylic acid stearyl ester, and (meth)acrylic acid cyclohexyl ester.

[0272] As conjugated diene compounds, for example, 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, 3-butyl-1,3-octadiene can be cited.

[0273] As polar monomers, for example, hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, pentenol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide, N-hydroxymethyl (meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloracrylonitrile, α-cyanoethyl acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate can be cited.

[0274] As crosslinkable monomers, for example, trimethylolpropane triacrylate can be cited.

[0275] In addition, from the viewpoint of improving the adhesion and resolution of the resist pattern, the second monomer is preferably a monomer having an aromatic hydrocarbon group. As the aromatic hydrocarbon group, for example, substituted or unsubstituted phenyl; substituted or unsubstituted aralkyl can be cited. As the aralkyl, for example, benzyl etc. can be cited. Especially from the same viewpoint, the second monomer is preferably benzyl (meth)acrylate, styrene derivative, more preferably styrene.

[0276] The copolymerization ratio of the monomer having an aromatic hydrocarbon group is preferably 10% by mass or more, more preferably 25% by mass or more, further preferably 40% by mass or more, based on the total mass of all copolymer monomer components. In addition, it is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less.

[0277] In addition, from the viewpoint of improving the adhesion and resolution of the resist pattern, the second monomer is preferably 2-hydroxyethyl (meth)acrylate, more preferably 2-hydroxyethyl methacrylate (HEMA).

[0278] In one mode of the second monomer, the following modes are all included:

[0279] The mode containing a monomer having an aromatic hydrocarbon group;

[0280] The mode containing 2-hydroxyethyl (meth)acrylate; and

[0281] The mode containing both a monomer having an aromatic hydrocarbon group and 2-hydroxyethyl (meth)acrylate.

[0282] (A) The synthesis method of the component may have the following steps: In a solution obtained by diluting the above-described single or multiple monomers with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, a radical polymerization initiator is appropriately added, and heating and stirring are performed. The above synthesis method may have a step of synthesizing while dropping a part of the mixture into the reaction solution. The above synthesis method may have a step of further adding a solvent after the reaction is completed to adjust to a desired concentration. The synthesis method may be a method based on bulk polymerization, suspension polymerization, or emulsion polymerization in addition to the method based on solution polymerization.

[0283] <Component (B): A compound having an ethylenically unsaturated bond>

[0284] Component (B) is a compound having an ethylenically unsaturated bond in its structure. Such component (B) is polymerizable. Component (B) may be used alone as one kind, or two or more kinds may be used in combination.

[0285] Component (B) preferably contains a compound having two ethylenically unsaturated bonds in one molecule (a bifunctional compound). Compared with a compound having three or more ethylenically unsaturated bonds in one molecule (a polyfunctional compound), the bifunctional compound can easily inhibit the entanglement between molecules. Therefore, by including the bifunctional compound as component (B), a desired fluidity can be imparted to the photosensitive resin composition. In this case, a photosensitive resin laminate having a support and a photosensitive resin layer with high flatness can be obtained, which can effectively inhibit defects in the wiring pattern.

[0286] In addition, by using a photosensitive resin composition containing a bifunctional compound as component (B), an appropriate softness can be easily imparted to the photosensitive resin layer. The photosensitive resin layer having appropriate softness has good followability to the substrate, so that a gap is not easily generated between the photosensitive resin layer and the substrate during lamination.

[0287] Furthermore, compared with a compound having one ethylenically unsaturated bond in one molecule (a monofunctional compound), the bifunctional compound has excellent crosslinking efficiency in the exposure process. In addition, compared with the polyfunctional compound, the bifunctional compound can inhibit excessive crosslinking in the exposure process, and can further impart appropriate softness to the photosensitive resin layer after exposure. Therefore, through the above components (A) to (D), the softness of the resist pattern can be ensured, and the expectation for improving the resolution of the wiring pattern can also be met.

[0288] Component (B) may include: a compound having one ethylenically unsaturated bond in one molecule; a compound having three ethylenically unsaturated bonds; a compound having four ethylenically unsaturated bonds; a compound having five ethylenically unsaturated bonds; and a compound having six or more ethylenically unsaturated bonds. That is, component (B) may include a monofunctional compound and / or a polyfunctional compound. In component (B), the total mass of the above bifunctional compounds may be more than the total mass of the monofunctional compounds and the polyfunctional compounds.

[0289] The bifunctional compound is preferably a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure, more preferably a compound having a bisphenol A structure. Thus, the effects of the present invention can be easily exerted. For the above compounds, based on the total amount of the photosensitive composition components, it may contain 5% by mass or more, or 10% by mass or more, and in addition, it may contain 60% by mass or less, 55% by mass or less, or 50% by mass or less.

[0290] It should be noted that the hydrogenated bisphenol A structure is a structure obtained by hydrogenating bisphenol A.

[0291] Examples of component (B) include:

[0292] The di(meth)acrylate of a polyalkylene glycol obtained by adding an average of 1 to 15 moles of an alkylene oxide to each end of bisphenol A;

[0293] The tri(meth)acrylate of a polyalkylene triol obtained by adding an average of 3 to 25 moles of an alkylene oxide to trimethylolpropane;

[0294] Glycerol;

[0295] Trimethylolpropane;

[0296] Pentaerythritol;

[0297] Diglycerol;

[0298] Bis-trimethylolpropane;

[0299] A compound obtained by converting an alcohol obtained by adding a polyalkylene oxide to an isocyanurate ring or the like or by subjecting it to ε-caprolactone modification into a (meth)acrylate;

[0300] A compound obtained by directly reacting an alcohol obtained by adding a polyalkylene oxide to an isocyanurate ring or the like or by subjecting it to ε-caprolactone modification with (meth)acrylic acid without using an alkylene oxide or ε-caprolactone for modification;

[0301] The tetra(meth)acrylate of a polyol obtained by adding an average of 4 to 35 moles of an alkylene oxide to pentaerythritol;

[0302] A hexa(meth)acrylate of a polyol obtained by adding an average of 4 to 30 moles of an alkylene oxide to dipentaerythritol.

[0303] As the above alkylene oxide, ethylene oxide (EO), propylene oxide (PO), etc. are preferred.

[0304] In addition, the component (B) preferably contains a hindered amine compound. Thereby, residues after the stripping of the resist pattern are less likely to occur.

[0305] In this specification, the "hindered amine compound" is, for example, the following general formula:

[0306]

[0307] (In the formula, R 1 each independently represents an alkyl group having 1 or more carbon atoms, and R 2 represents hydrogen or an alkyl group having 1 or more carbon atoms. The number of carbon atoms of R 1 and R 2 can each independently be 10 or less.)

[0308] Regarding the content of the hindered amine compound, based on the total amount of the photosensitive composition components, it may contain 1% by mass or more, 3% by mass or more, or 5% by mass or more. In addition, it may contain 20% by mass or less, 15% by mass or less, or 10% by mass or less, or may be 0% by mass.

[0309] The hindered amine compound sometimes belongs to a compound having 1 ethylenically unsaturated bond. Regarding the content of the compound having 1 ethylenically unsaturated bond (excluding the hindered amine compound when the hindered amine compound belongs to a compound having 1 ethylenically unsaturated bond), based on the total amount of the photosensitive composition components, it may contain 20% by mass or less, 10% by mass or less, 5% by mass or less, or may be 0% by mass.

[0310] Specifically, as one mode of the component (B), for example, the following can be cited:

[0311] Dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of EO to both ends of bisphenol A;

[0312] Dimethacrylate of polyethylene glycol obtained by adding an average of 2 moles of EO to both ends of bisphenol A;

[0313] Tetramethacrylate obtained by adding an average of 9 moles of EO to pentaerythritol;

[0314] Tetramethacrylate obtained by adding an average of 15 moles of EO to pentaerythritol;

[0315] The hexamethacrylate of polyethylene glycol obtained by adding an average of 13 moles of EO to dipentaerythritol;

[0316] The dimethacrylate of polyethylene glycol obtained by adding an average of 2 moles of EO to both ends of hydrogenated bisphenol A;

[0317] 1,2,2,6,6-pentamethylpiperidyl methacrylate; etc.

[0318] 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 still more preferably 35 to 60% by mass based on the total amount of the photosensitive composition components. From the viewpoints of preventing poor curing of the photosensitive resin layer and suppressing the delay of the development time, the content of component (B) is preferably not less than the above lower limit value. In addition, from the viewpoint of improving the removability of the resist pattern, it is preferably not more than the above upper limit value.

[0319] The ratio (B / A) of the total mass of component (B) to the total mass of component (A) is preferably 1 / 3.0 to 1 / 0.5 (for example, 0.33 to 2.0). Thereby, it is easy to suitably exhibit the function as a photosensitive resin composition, and as a result, it is easy to exhibit the effects of the present invention. From the same viewpoint, the above ratio (B / A) is more preferably 1 / 2.5 to 1 / 0.7 (for example, 0.40 to 1.4).

[0320] <(C) component: polymerization initiator>

[0321] Component (C) is a compound capable of initiating the polymerization of component (B). Component (C) is preferably a photopolymerization initiator, and more preferably includes a compound that generates free radicals by actinic rays and thereby initiates the polymerization of component (B).

[0322] 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, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoate compounds, oxime ester compounds, acridine compounds, and halogen compounds.

[0323] Examples of the hexaarylbiimidazole compound include dimers of compounds having a lophine structure (lophine dimer), that is, dimers of 2,4,5-triaryl imidazole and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, etc.

[0324] Examples of the lophen dimer include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (alias: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole.

[0325] From the viewpoints of excellent high sensitivity, resolution, and adhesion, the component (C) preferably contains a lophen dimer. Among them, the component (C) more preferably contains the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole, the dimer of 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole, and the dimer of 2-(p-methoxyphenyl)-4,5-diphenylimidazole, and further preferably contains the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole.

[0326] As quinone compounds, for example, 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-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone can be cited.

[0327] As aromatic ketone compounds, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4-methoxy-4'-dimethylaminobenzophenone can be cited. Aromatic ketone compounds sometimes function as a photoinitiator by being used alone, and also sometimes function as a sensitizer when used in combination with other photoinitiators.

[0328] As acetophenone compounds, for example, 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-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1 can be cited. As commercially available products of acetophenone compounds, for example, Irgacure series (manufactured by BASF: Irgacure-907, Irgacure-369, Irgacure-379, etc.) can be cited.

[0329] As acylphosphine oxide compounds, for example, 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide can be cited. As commercially available products of acylphosphine oxide compounds, for example, Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by BASF) can be cited.

[0330] As benzoin compounds and benzoin ether compounds, for example, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin can be cited.

[0331] As dialkyl ketal compounds, for example, benzil dimethyl ketal, benzil diethyl ketal can be cited.

[0332] As thioxanthone compounds, for example, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone can be cited.

[0333] Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4-(dimethylamino)benzoate.

[0334] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione 2-O-benzoyl oxime and 1-phenyl-1,2-propanedione 2-(O-ethoxycarbonyl)oxime. Examples of commercially available products of the oxime ester compound include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF).

[0335] Examples of the acridine compound include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine.

[0336] Examples of the halogen compound include bromopentane, bromoisopentane, bromoisobutene, bromoethylene, benzhydryl bromide, benzyl bromide, dibromomethane, tribromomethyl phenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodo-isobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, a chlorotriazine compound, and a diallyl iodonium compound.

[0337] The content of the 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 the component (C) within the above range, sufficient sensitivity is easily obtained, and thus high resolution is easily achieved.

[0338] From the viewpoint of excellent sensitivity, the component (C) preferably contains a thiophene dimer. When the photosensitive resin composition contains a thiophene dimer as the component (C), the content of the thiophene dimer is preferably 3.0 to 10% by mass, more preferably 4.0 to 9.0% by mass, and further preferably 5.0 to 8.0% by mass based on the total solid content of the photosensitive resin composition. By adjusting the content of the component (C) within the above range, sufficient sensitivity is easily obtained, and thus high resolution is easily achieved.

[0339] <(D) component: a boron compound that absorbs h-rays and / or i-rays>

[0340] (D) component contains a boron compound that absorbs h-rays and / or i-rays.

[0341] The boron compound as the component (D) is excited by h-rays and / or i-rays to generate the movement of -(negative) electrons to the component (C). Thereby, a sensitizing function can be exhibited. In addition, in the boron compound that becomes a radical cation by the movement of - electrons to the component (C), the substituent on boron cleaves and functions as a polymerization initiation species. By using the photosensitive resin composition of the present embodiment containing such a boron compound that exhibits a sensitizing function, a photosensitive resin layer with good sensitivity can be obtained.

[0342] The boron compound as the component (D) preferably has a wavelength at which the absorbance (A3) value at 5 ppm in a toluene solution measured by the above method is 0.008 or more in the range of 400 to 410 nm or in the range of 350 to 370 nm. By making the absorbance (A3) value the above lower limit value or more, the boron compound is easily excited, and thus the sensitizing function is easily exhibited. In addition, from the viewpoint of more suitably exhibiting the sensitizing function, the absorbance (A3) value is more preferably 0.010 or more, and further preferably 0.012 or more.

[0343] The upper limit of the absorbance (A3) value can be 0.500 or less, can be 0.400 or less, and can be 0.300 or less. By making the absorbance value the above upper limit value or less, even when the component (D) is contained in a sufficient amount to exhibit the sensitizing function, the transmittance of the photosensitive resin composition is easily ensured, and thus it is not likely to have an adverse effect on the curing of the photosensitive resin composition during exposure.

[0344] In the case of exposure using a mercury lamp, the absorbance (A3) value under h-rays (405 nm) and / or i-rays (365 nm) is preferably 0.008 or more, more preferably 0.010 or more, and further preferably 0.012 or more.

[0345] When exposing with exposure light of either 350 to 370 nm or 400 to 410 nm, it is preferable to have a wavelength at which the absorbance (A3) value is 0.008 or more in the corresponding wavelength region. On the other hand, in the other wavelength region, the absorbance (A3) value is not limited.

[0346] For example, in the case of exposure using light having a wavelength near h-rays, it is preferable to have a wavelength at which the absorbance (A3) value is 0.008 or more in the range of 400 to 410 nm. At this time, in 350 to 370 nm, it is not necessary to have a wavelength at which the absorbance (A3) value is 0.008 or more.

[0347] In addition, for example, in the case of performing exposure using light having a wavelength near the i-ray, it is preferable to have a wavelength in the range of 350 to 370 nm and having an absorbance (A3) value of 0.008 or more. At this time, in the range of 400 to 410 nm, it is not necessary to have a wavelength with an absorbance (A3) value of 0.008 or more.

[0348] In addition, in the boron compound as the component (D), since boron is a Lewis acid, there will be an interaction different from a covalent bond (bonding between Lewis acid and Lewis base) with a Lewis base. At this time, the bonding between the Lewis acid and the Lewis base is relatively easy to reorganize. Even if the resist pattern is subjected to external stress, since the bonding between the Lewis acid and the Lewis base in the resist pattern is relatively easy to reorganize, it is easy to deform softly in response to the external stress. Therefore, it is easy to suppress the breakage of the resist pattern.

[0349] The boron compound is preferably a compound represented by the following general formula:

[0350] B-R 1 R 2 R 3 ···(1)

[0351] By appropriately selecting R 1 ~R 3 in the general formula (1), it is easy to appropriately realize a boron compound having absorption for h-ray and / or i-ray.

[0352] R 1 ~R 3 in the aforementioned general formula (1) may each independently be at least one selected from the group consisting of a monovalent organic group, an alkoxy group (-OR 4 ; R 4 is a hydrocarbon group having 1 to 10 carbon atoms), an alkylamino group (-NR 5 R 6 ; R 5 and R 6 are each independently 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 a saturated or unsaturated ring can be formed by a plurality of R 1 ~R 3 .

[0353] Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkanoyl group, an arbitrary substituent having a ring structure having 3 to 20 carbon atoms, or a group obtained by substituting a hydrogen atom in these groups with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.

[0354] Examples of the aforementioned arbitrary substituent having a ring structure having 3 to 20 carbon atoms include benzoyl group, an aryl group having 6 to 20 carbon atoms, etc.

[0355] R in the aforementioned general formula (1) 1 ~R 3 may each independently be a group having a heterocycle, and may be a group containing a heteroatom (such as nitrogen, oxygen, sulfur) and having a saturated or unsaturated ring.

[0356] R 1 ~R 3 may form a saturated or unsaturated ring. This ring may contain a heteroatom.

[0357] The halogen in the aforementioned monovalent organic group may be, for example, fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0358] According to the above, the effects of the present invention can be easily exerted.

[0359] Among them, it is more preferable that at least one of R 1 ~R 3 is an alkoxy group or a hydroxyl group. Thereby, the effects of the present invention can be easily exerted.

[0360] R 1 ~R 3 When at least one of them is an alkoxy group or a hydroxyl group, R 1 ~R 3 that is not an alkoxy group or a hydroxyl group may be hydrogen.

[0361] Examples of the boron compound represented by the above general formula (1) include organic boric acid ((boronic acid)), organic boronic ester (boronic ester), borate ester, cycloboroxane, dialkylborinic acid ester (borinic acid ester), etc. Among them, from the viewpoint of the flexibility of the resist pattern, organic boric acid, organic boronic ester, and cycloboroxane are preferred.

[0362] Organic boric acid can be represented in the form of R-B(OH) 2 .

[0363] Organic boronic ester can be represented in the form of R-B(OH)(OR a ), R-B(OR a ), 2 , or R-BO 2 R b .

[0364] Borate ester can be represented in the form of B(OH) 2 (OR a ), B(OH)(OR a ), 2 , or B(OR a ). 3 .

[0365] The dialkyl borate can be represented by R 2 B-OR a in the following manner.

[0366] In the above formula, R and R a can each independently be the aforementioned monovalent organic group, and R b can be a divalent organic group. In the formula, when there are multiple Rs, and when there are multiple Rs a , the multiple Rs can be different from each other. Additionally, it goes without saying that the multiple Rs a can also be different from each other.

[0367] As the divalent organic group, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferred.

[0368] In one embodiment, the boron compound can be R-(NR a 2 ) 2 or a compound represented by the formula R-B(OR a )(NR a 2 ) (in the above formula, R and R a can each independently be the aforementioned monovalent organic group).

[0369] Here, the boron compound preferably contains at least one boron moiety selected from the group consisting of the following general formulas:

[0370] *-B(OH) 2 ;

[0371] *-B(OR 1 ) 2 ;

[0372] *-B(NR 1 2 ) 2 ;

[0373] *-B(OH)(OR 1 ); or

[0374] at least one boron moiety selected from the group consisting of the following general formula (2).

[0375]

[0376] (In the formula, R 1 each independently represents the aforementioned monovalent organic group, R 2 represents a divalent organic group, and * represents the bonding site to various skeletons.)

[0377] The boron compound of this embodiment includes a compound formed by replacing any hydrogen atom in such a boron moiety with various skeletons.

[0378] Specifically, as the boron compound, preferably selected from the following general formulas:

[0379] R 2 -B(OH) 2

[0380] R 3 -B(OR 1 ) 2

[0381] R 4 -B(NR 5 2 ) 2

[0382] R 6 -B(OH)(OR 7 )

[0383] (In the formula, R 1 ~R 7 are monovalent organic groups, and multiple R 1 and R 5 present in one molecule can be the same or different optionally); and

[0384] at least one compound selected from the group consisting of the compounds represented by the following general formula (3)

[0385] .

[0386]

[0387] (In the formula, R 8 is a monovalent organic group, and R 9 is a divalent organic group.)

[0388] In one aspect, the boron compound can be a compound having multiple borons in one molecule. As the compound having multiple borons in one molecule, for example, diorganoboric acid, diorganoborate, etc. can be cited.

[0389] Diorganoboric acid can be represented in the form of R(B(OH) 2 ) 2 .

[0390] Diorganoborate can be represented in the form of B 2 (OR a ) 4 , or R(B(OR a ) 2 ) 2 .

[0391] In the above formula, R and R a can each independently be the aforementioned monovalent organic group. In the formula, when there are multiple Rs a , it goes without saying that the multiple Rs a can be different from each other.

[0392] Including the above, a boron compound having a hydrocarbon group can be treated as an organoboron compound. Among boron compounds having a hydrocarbon group, for a compound that absorbs h-rays and / or i-rays and has a carbon (C)-boron (B) bond, free radical cations are generated by exciting electrons with h-rays and / or i-rays, and then the C-B bond between carbon (C) and boron (B) cleaves, thereby generating a new polymerization end. Therefore, a compound that absorbs h-rays and / or i-rays and has a carbon (C)-boron (B) bond not only has good sensitization but also functions as a polymerization initiator, and thus it is easy to realize a photosensitive resin layer with better sensitivity.

[0393] In one aspect, the boron compound can have a specified skeleton. As the specified skeleton, a skeleton having an aromatic ring and / or a skeleton having a heteroatom is preferred. By having these skeletons, the boron compound is easily excited by h-rays and / or i-rays, and good sensitivity of the photosensitive resin composition can be easily obtained.

[0394] Regarding the skeleton that the boron compound can have, for example, it preferably has a skeleton derived from at least one selected from the group consisting of pyrazoline, anthracene, naphthalene, triarylamine, oxazole, N-aryl-α-amino acid, aromatic ketone derivative, dialkylaminobenzoate, and . Among them, from the viewpoint of sensitivity, the boron compound more preferably has a skeleton derived from anthracene and / or pyrazoline.

[0395] As the boron compound having the above skeleton, examples include compounds in which any hydrogen atom in pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives, dialkylaminobenzoate derivatives, and derivatives, etc. is replaced by the above boron moiety.

[0396] The boron compound can include a compound having multiple above boron moieties in the above skeleton, and the multiple above boron moieties that can be present in the same compound can be the same or different optionally.

[0397] As pyrazoline derivatives, examples 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, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-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, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline.

[0398] As anthracene derivatives, examples 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-dipentyoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenyl)-10-bromoanthracene, 9-(4-biphenyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene, 9-(3-bromophenyl)-10-phenylanthracene. Among them, from the viewpoint of sensitivity, an organic boronic acid having a 10-phenyl-9-anthracene skeleton (10-phenyl-9-anthracene boronic acid) is preferred.

[0399] As naphthalene derivatives, examples thereof 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(isobutoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, 1,4-bis(n-heptyloxy)naphthalene, 1,4-bis(n-octyloxy)naphthalene, 1,4-bis(2-ethylhexyloxy)naphthalene, 1,4-bis(n-nonyloxy)naphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethoxynaphthalene, 1,4-diglycidoxynaphthalene, 1,4-bis(2-methylglycidoxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, 2-(2-hydroxyethoxy)naphthalene, and the like. Among them, as the naphthalene derivative, 1,4-diethoxynaphthalene is preferred.

[0400] As oxazole derivatives, examples thereof include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole, 2-[4-(1,3-benzoxazol-2-yl)naphthalen-1-yl]-1,3-benzoxazole.

[0401] As N-aryl-α-amino acid derivatives, examples thereof 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-phenyld-leucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, N-(n-propyl)-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, N-(o-chlorophenyl)glycine, and the like.

[0402] As aromatic ketone derivatives, benzophenone derivatives can be cited. Specifically, for example, the following can be cited:

[0403] Alkyl benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone;

[0404] Benzophenone compounds having halogen atoms such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone;

[0405] Benzophenone compounds substituted with a carboxyl group or an alkoxycarbonyl group such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid, or its tetramethyl ester; etc.

[0406] In addition, as aromatic ketone derivatives, benzophenone derivatives substituted with an alkylamino group can also be exemplified. Specifically, for example, the following can be exemplified:

[0407] 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;

[0408] 4-methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, etc.

[0409] In one embodiment, the boron compound is preferably a compound having the following skeleton together with the above skeleton or independently of the above skeleton. As this skeleton, for example, at least one skeleton selected from the group consisting of pyrene, coumarin, and triarylamine can be exemplified. Thus, it is advantageous from the viewpoint of sensitivity.

[0410] In one embodiment, as the component (D), the following can be exemplified:

[0411] 10-phenyl-9-anthraceneboronic acid,

[0412] 4,4,5,5-tetramethyl-2-(10-phenylanthracen-9-yl)-1,3,2-dioxaborolane,

[0413] [10-[4-(naphthalen-1-yl)phenyl]anthracen-9-yl]boronic acid, and

[0414] 2-ethyl-4-methylimidazolium tetraphenylborate, etc.

[0415] The component (D) is a boron compound that absorbs h-rays and / or i-rays.

[0416] That is, the component (D) is any one of the following:

[0417] A boron compound that absorbs h-rays but does not absorb i-rays,

[0418] A boron compound that does not absorb h-rays but absorbs i-rays, and

[0419] A boron compound that absorbs h-rays and also absorbs i-rays.

[0420] Among them, the boron compound of component (D) preferably absorbs at least h-rays.

[0421] Based on the total mass of component (A), the content of component (D) is preferably 0.01 to 2.0% by mass, more preferably 0.3 to 1.5% by mass.

[0422] Component (D) can be used alone as one kind, or two or more kinds can be used in combination. Component (D) can also contain other boron compounds different from the boron compounds described in this embodiment (boron compounds that do not belong to the boron compounds described in this embodiment).

[0423] Based on the total mass of component (D), the other boron compounds (boron compounds that do not belong to the boron compounds described in this embodiment) can be 20% by mass or less, can be 10% by mass or more, can also be 1% by mass or less, and further, can be 0% by mass.

[0424] <(E) component: other components>

[0425] The photosensitive resin composition can contain components other than the above components (A) to (D) as needed. As other components, for example, colorants, leuco dyes, basic dyes (dyes other than leuco dyes), colorants, antioxidants, stabilizers, plasticizers, other sensitizers (sensitizers other than component (D) above) can be mentioned. Other components can be used alone as one kind, or two or more kinds can be used in combination.

[0426] As colorants, examples include magenta, phthalocyanine green, auramine base, pararosaniline, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green (for example, AIZEN (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, diamond green (for example, AIZEN (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (for example, OPLAS GREEN533 manufactured by Orient Chemical Industries, Ltd.), 1,4-bis(butylamino)anthraquinone (for example, OIL BLUE 2N manufactured by Orient Chemical Industries, Ltd.), 1,4-bis(isopropylamino)-9,10-anthraquinone (for example, OIL BLUE630 manufactured by Orient Chemical Industries, Ltd.), etc.

[0427] The content of the colorant is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 2% by mass based on the total mass of the photosensitive resin composition.

[0428] Examples of the leuco dye include leuco crystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.

[0429] The content of the leuco dye is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass based on the total mass of the photosensitive resin composition.

[0430] Examples of the basic dye include basic green 1 [CAS No. (the same hereinafter): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), magenta [632-99-5], methyl violet [603-47-4], methyl green [82-94-0], victoria blue B [2580-56-5], basic blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], etc.

[0431] The content of the basic dye is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and still more preferably 0.04 to 1% by mass based on the total mass of the photosensitive resin composition.

[0432] Examples of the antioxidant include triphenyl phosphite (e.g., manufactured by ADEKA Corporation, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA Corporation, trade name 2112), tris(monononylphenyl) phosphite (e.g., manufactured by ADEKA Corporation, trade name: 1178), bis(monononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA Corporation, trade name: 329K).

[0433] The content of the antioxidant is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass based on the total mass of the photosensitive resin composition.

[0434] Examples of the stabilizer include at least one of a radical inhibitor and an epoxyalkane compound having a glycidyl group.

[0435] As a radical polymerization inhibitor, for example, 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-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], aluminum salt of nitrosophenylhydroxylamine (for example, aluminum salt added with 3 moles of nitrosophenylhydroxylamine), diphenylnitrosamine, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, diol ether diamine tetraacetic 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, ammonium salt of N-nitroso-N-phenylhydroxylamine, ammonium salt of N-nitroso-N(1-naphthyl)hydroxylamine, etc. can be used.

[0436] As the epoxy alkane compound having a glycidyl group, for example, neopentyl glycol diglycidyl ether (for example, Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2 mole adduct diglycidyl ether (for example, Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.

[0437] The total content of the radical polymerization inhibitor and the epoxy alkane 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.

[0438] As other sensitizers, sensitizers other than the above component (D) can be mentioned. Therefore, other sensitizers do not contain the above boron part, for example.

[0439] As other sensitizers (sensitizers other than the above component (D)) in the photosensitive resin composition, 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, dialkylaminobenzoate derivatives can be mentioned. Derivatives.

[0440] Regarding specific examples of various derivatives, as described in the item of the component (D), as one mode of other sensitizers, for example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, coumarin (for example, coumarin 102), etc. can be cited.

[0441] 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. It is preferably 0.8% by mass or less, more preferably 0.3% by mass or less. The content of other sensitizers may also be 0% by mass. When used in combination with the above-mentioned component (D), the content (% by mass) of other sensitizers is preferably 2 times or less, more preferably 1.7 times or less, compared with the content of the above-mentioned component (D).

[0442] In addition, as other components, carboxybenzotriazoles can be cited. The content of carboxybenzotriazoles 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.

[0443] [Embodiments of "Related Inventions"]

[0444] Hereinafter, embodiments of the mode related to the present invention will be described. The effects exhibited by this embodiment are the effects related to the effects of the present invention.

[0445] In one mode, unless otherwise specified,

[0446] "Adhesion" means the adhesion performance of the resist pattern to the substrate;

[0447] "Resolution" means the resolution performance of the resist pattern;

[0448] "Developability" means the developability of the photosensitive resin layer (resist);

[0449] "Flexibility of the cured film" means the flexibility of the photosensitive resin layer (resist), particularly the photosensitive resin layer cured by exposure.

[0450] [First Embodiment]

[0451] [Photosensitive Resin Composition]

[0452] One mode of this embodiment is a photosensitive resin composition.

[0453] This photosensitive resin composition contains the following components:

[0454] (A) An alkali-soluble polymer;

[0455] (B) A compound having an ethylenically unsaturated bond; and

[0456] (C) Polymerization initiator,

[0457] The aforementioned component (A) contains copolymer (A-1),

[0458] The aforementioned copolymer (A-1) has at least structural units derived from the following components:

[0459] (a1) (Meth)acrylic acid;

[0460] (a2) Styrene derivative; and

[0461] (a3) Hydroxyalkyl (meth)acrylate,

[0462] The proportion of the structural units derived from the aforementioned component (a1) is 15 to 26% by mass,

[0463] The proportion of the structural units derived from the aforementioned component (a2) is 30 to 70% by mass,

[0464] The proportion of the structural units derived from the aforementioned component (a3) is 15 to 35% by mass, and

[0465] The glass transition temperature (Tg) calculated based on the Fox equation is 100 °C or lower.

[0466] According to this photosensitive resin composition, a photosensitive resin layer (resist) excellent in all of resolution, adhesion, developability, and flexibility of the cured film can be formed. In addition, according to this photosensitive resin composition, a photosensitive resin laminate having the photosensitive resin layer and a method for forming an anti-etching pattern can be provided.

[0467] The inventors of the present invention have found that by adopting one aspect of the present invention, a photosensitive resin composition capable of forming a photosensitive resin layer (resist) excellent in all of resolution, adhesion, developability, and flexibility of the cured film can be obtained. Here, in the exposure process, the photosensitive resin layer is cured. On the other hand, a specified flexibility is required for the cured photosensitive resin layer (cured film), and one aspect of the present invention can provide a photosensitive resin layer (resist) excellent in the balance of the flexibility of the cured film itself (the balance between curing and flexibility).

[0468] In this specification, the above-mentioned (A) to (C) may sometimes be abbreviated as "(A) component" to "(C) component". The same applies to the following components other than the (A) to (C) components.

[0469] Each component and raw materials of each component can be used alone in one kind, or two or more kinds can be used in combination. In this specification, the "solid component" of the photosensitive resin composition refers to the components other than the solvent in the photosensitive resin composition.

[0470] Hereinafter, each component will be described.

[0471] <Component (A)>

[0472] 《Schematic Configuration》

[0473] Component (A) is a polymer soluble in an alkaline aqueous solution, and this polymer is, for example, a vinyl-based polymer containing a carboxyl group.

[0474] Component (A) preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent refers to the mass in grams of a base-soluble polymer having 1 equivalent of carboxyl groups. From the viewpoint of excellent resolution and adhesion, it is preferable to adjust the acid equivalent to 100 or more. From the viewpoint of excellent developability and peelability, it is preferable to adjust the acid equivalent to 600 or less. The acid equivalent can be measured using a titration device {for example, the Hiranuma Automatic Titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.}, and using 0.1 mol / L sodium hydroxide, by potentiometric titration. From the same viewpoints as above, the acid equivalent of component (A) is more preferably 250 to 450.

[0475] The weight average molecular weight (Mw) of component (A) is preferably 5,000 to 500,000. From the viewpoints of excellent adhesion, flexibility of the cured film, and edge fusion property, etc., it is preferable to adjust the weight average molecular weight (Mw) to 5,000 or more. From the viewpoint of easily preventing the polymer aggregates from growing due to the developer, and further from the viewpoint of easily preventing the reduction in the yield that may occur due to such aggregates during the formation of the circuit board, etc., it is preferable to adjust the weight average molecular weight (Mw) to 500,000 or less. Here, the edge fusion property is a property of suppressing the phenomenon that the photosensitive resin overflows from the end face of the roll when the photosensitive resin laminate is wound into a roll. The weight average molecular weight (Mw) of component (A) is more preferably 20,000 to 70,000, further preferably 30,000 to 50,000, and particularly preferably 35,000 to 45,000.

[0476] The polydispersity {weight average molecular weight (Mw) / number average molecular weight (Mn)} of component (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0477] Component (A) preferably has a monomer component containing a first monomer described later, and more preferably has a monomer component containing at least one of the first monomer and at least one of the second monomer described later.

[0478] The first monomer is an acidic monomer having a polymerizable unsaturated group in the molecule, for example, a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. As the first monomer, for example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semi-ester can be cited. Among them, (meth)acrylic acid is preferred.

[0479] Based on the total mass of all monomer components, the content of the first monomer is preferably 10 to 50% by mass. From the viewpoints of excellent adhesion and resolution, it is preferred to adjust the content of the first monomer to 10% by mass or more, more preferably 15% by mass or more, 18% by mass or more, 21% by mass or more, further preferably 23% by mass or more, and particularly preferably 25% by mass or more. From the viewpoints of excellent adhesion and resolution, it is preferred to adjust the content of the first monomer to 50% by mass or less, more preferably 35% by mass or less, 30% by mass or less, further preferably 29% by mass or less, and particularly preferably 27% by mass or less. When using two or more first monomers, it is preferred that the total of their respective contents is within the above range.

[0480] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, styrene derivatives, (meth)acrylate compounds having a hydroxyl group, (meth)acrylic acid alkyl esters, (meth)acrylate compounds having an alicyclic or aromatic ring, vinyl alcohol, vinyl acetate, and esters of (meth)acrylonitrile can be cited.

[0481] As styrene derivatives, for example, styrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and haloalkylstyrene can be cited.

[0482] As (meth)acrylate compounds having a hydroxyl group, for example, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, (meth)acrylic acid hydroxybutyl ester, and glycerol mono(meth)acrylate can be cited.

[0483] As (meth)acrylic acid alkyl esters, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid tert-butyl ester, (meth)acrylic acid pentyl ester, (meth)acrylic acid hexyl ester, (meth)acrylic acid heptyl ester, (meth)acrylic acid octyl ester, and (meth)acrylic acid 2-ethylhexyl ester can be cited.

[0484] Examples of the (meth)acrylate compound having an alicyclic or aromatic ring include benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and ethyl carbitol (meth)acrylate.

[0485] In the present embodiment, one kind of the component (A) may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the molecular weight and polydispersity of the monomers in the plurality of components (A) are preferably selected such that the weighted average when treated with the content ratio as the weight falls within the above range.

[0486] The synthesis of the component (A) is preferably carried out by appropriately mixing a radical polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile in a solution obtained by diluting the above-described single or plural monomers with a solvent such as acetone, methyl ethyl ketone, and isopropyl alcohol, and then heating and stirring. Sometimes, a part of the mixture is dropped into the reaction solution while carrying out the synthesis. In addition, sometimes a solvent is further added after the reaction is completed and adjusted to a desired concentration. As the synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used. In addition, sometimes the synthesis is carried out by living radical polymerization.

[0487] Based on the total solid content of the photosensitive resin composition, the content of the component (A) may be 30% by mass or more, may be 35% by mass or more, may be 40% by mass or more, or may be 45% by mass or more. From the viewpoint of appropriately exerting the effects of the present invention, based on the total solid content of the photosensitive resin composition, the content of the component (A) is preferably 50% by mass or more, more preferably 55% by mass or more. In addition, the content is 70% by mass or less, may be 65% by mass or less, or may be 60% by mass or less.

[0488] In order to obtain a photosensitive resin composition having excellent desired properties, it is preferable to control the mass ratio of the component (A) to the component (B) {(component (A) / component (B)); sometimes abbreviated as "A / B".}. If the value of A / B is controlled to be large, it is likely to be advantageous from the viewpoints of excellent resolution and adhesion. In addition, if the value of A / B is controlled to be small, it is likely to be advantageous from the viewpoints of excellent developability and flexibility of the cured film. A / B can be controlled by adjusting the feeding ratio of the component (A) to the component (B) when preparing the photosensitive resin composition. A / B can be analyzed from the photosensitive resin layer by a specified method, and the value obtained therefrom is based on the above feeding ratio during the preparation of the photosensitive resin composition.

[0489] The analysis of the value of A / B can be performed, for example, by the following steps:

[0490] (1) After dissolving the photosensitive resin layer in a good solvent, a poor solvent for only the component (A) is added dropwise, whereby the component (A) is separated by reprecipitation, and then the mass of the component (A) obtained by reprecipitation is measured.

[0491] (2) For other components such as initiators, quantification is performed using GC-MS or the like, and then the content of components other than the component (A) and the component (B) is measured, whereby the mass of the component (B) is indirectly obtained, and the value of A / B is calculated therefrom.

[0492] By controlling the value of A / B to 1.30 or more, the photosensitive resin composition of the present embodiment can easily provide a photosensitive resin layer that satisfies developability, resolution, adhesion, and flexibility of the cured film at a high level. From the same viewpoint, the value of A / B is more preferably 1.40 or more, and further preferably 1.50 or more. The upper limit of the value of A / B can be, for example, 2.50 or less.

[0493] When the component (A) contains a large amount of styrene as a monomer component, the resolution and adhesion of the photosensitive resin composition containing the component (A) are likely to be excellent. For a photosensitive resin composition containing a large amount of a copolymer containing styrene as a monomer component in order to suitably exhibit this effect, when the content of the component (A) in the composition is increased (for example, A / B is 1.30 or more), the cured film and the resist pattern become hard and are likely to become brittle. Therefore, it is generally considered difficult to form a fine resist pattern, and the adhesion is also likely to deteriorate. On the other hand, according to the present embodiment, even when using a photosensitive resin composition containing a large amount of a copolymer containing styrene as a monomer component, a photosensitive resin layer (resist) having excellent flexibility of the cured film itself can be provided. Because it is such a photosensitive resin composition, by controlling the value of A / B to 1.30 or more, it is easy to provide a photosensitive resin layer that satisfies developability, resolution, adhesion, and flexibility of the cured film at a high level.

[0494] In the present disclosure, when the component (A) contains a plurality of copolymers, the glass transition temperature Tg of the component (A) is represented in the form of its weight average Tg total of.

[0495] The weight average Tg total is a value obtained by the following formula.

[0496] Tg total = Σ i (W i × Tg i ) / W total

[0497] (wherein, W i is the solid weight of each alkali-soluble polymer, and Tg i is the glass transition temperature (Tg) of each alkali-soluble polymer calculated by the Fox equation, and W total is the total solid weight of each alkali-soluble polymer.)

[0498] From the viewpoints of excellent developability and flexibility of the cured film, the value of this Tg total is preferably 100 °C or lower. From the same viewpoints as above, Tg total is more preferably 99 °C or lower, and even more preferably 95 °C or lower. From the viewpoint of easy control of edge fusion, 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.)

[0499] 《Copolymer (A-1)》

[0500] Component (A) contains copolymer (A-1),

[0501] and the aforementioned copolymer (A-1) has at least structural units derived from the following components:

[0502] (a1) (Meth)acrylic acid;

[0503] (a2) Styrene derivative; and

[0504] (a3) Hydroxyalkyl (meth)acrylate,

[0505] The proportion of the structural units derived from the aforementioned component (a1) is 15 to 26% by mass,

[0506] The proportion of the structural units derived from the aforementioned component (a2) is 30 to 70% by mass,

[0507] The proportion of the structural units derived from the aforementioned component (a3) is 15 to 35% by mass, and

[0508] The glass transition temperature (Tg) calculated based on the Fox equation is 100 °C or lower.)

[0509] From the viewpoint of excellent flexibility of the cured film, 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.)

[0510] From the viewpoint of appropriately exerting the effects of the present invention, based on the total solid content of the photosensitive resin composition, the content of the copolymer (A-1) is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 45% by mass or more.

[0511] From the viewpoint of appropriately exerting the effects of the present invention, relative to the whole of the component (A), the content of the copolymer (A-1) is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 80% by mass or more.

[0512] 《Glass transition temperature (Tg)》

[0513] From the viewpoints of excellent developability and flexibility of the cured film, the glass transition temperature (Tg) of the copolymer (A-1) calculated based on the Fox equation is 100 °C or lower. From the same viewpoints as above, Tg is preferably 99 °C or lower, and further preferably 95 °C or lower. From the viewpoint of easily controlling the edge fusion property, Tg is preferably 50 °C or higher, more preferably 70 °C or higher, further preferably 80 °C, and particularly preferably 85 °C or higher.

[0514] Tg is the temperature at which the ratio of the free volume in the total volume of the polymer starts 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, there is a tendency that the higher the Tg of the polymer, the smaller the free volume, and conversely, the lower the Tg, the larger the free volume. Therefore, 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.

[0515] For a copolymer composed of n kinds of monomers, the Fox equation for calculating the Tg (K: Kelvin) of the copolymer is represented by the following formula.

[0516]

[0517] {In the formula, Tg i (K: Kelvin) is the glass transition temperature of the homopolymer composed of each monomer, and c i is the copolymerization ratio of each monomer}

[0518] In this specification, as the Tg value of the homopolymer composed of the monomers forming the alkali-soluble polymer, the literature value (edited by Brandrup, J. and Immergut, E. H., Polymer handbook, Third edition, John wiley&sons, 1989, Chapter VI “GLASS transition temperatures of polymers”, p209) is used. It should be noted that an example of the glass transition temperature (Tg i ) of the homopolymer composed of each monomer is as described below.

[0519] [Table 1]

[0520]

[0521] The mechanism by which it is speculated that this embodiment can suitably exhibit all performances in terms of resolution, developability, adhesion, and flexibility of the cured film is as follows.

[0522] When the component (A) contains a copolymer containing a relatively large amount (30 to 70% by mass) of structural units derived from the component (a2), the resolution and adhesion of the obtained photosensitive resin composition are likely to be excellent. On the other hand, since the component (a2) has high hydrophobicity, it is necessary to improve the developability of the obtained photosensitive resin composition. In addition, the photosensitive resin layer obtained by using the photosensitive resin composition containing this copolymer is likely to become a hard and brittle cured film after exposure, so it is necessary to improve the flexibility of the cured film.

[0523] Therefore, usually, the developability of the photosensitive resin composition is supplemented by containing a large amount of the component (a1) having a carboxyl group. However, the photosensitive resin layer obtained from the photosensitive resin composition containing this copolymer containing a large amount of the component (a1) is still likely to become a hard cured film after exposure. That is, from the viewpoint of the flexibility of the cured film, the content of the component (a1) in the copolymer is preferably as small as possible. Since the component (a3) has a hydroxyl group, it shows high hydrophilicity. Therefore, by containing a copolymer in which the copolymerization ratio of the component (a3) is adjusted to a large amount of 15% by mass or more in the photosensitive resin composition, even if the copolymerization ratio of the component (a1) in the copolymer is set to 26% by mass or less, a photosensitive resin composition capable of forming a photosensitive resin layer with excellent developability can be obtained.

[0524] In the photosensitive resin composition, on the basis of making the contents of the aforementioned components (a1) to (a3) within the ranges specified in this application, further, by adjusting the Tg of the copolymer to 100 °C or lower, a photosensitive resin layer capable of forming a cured film with excellent flexibility can be obtained.

[0525] Therefore, in the photosensitive resin composition, by containing a copolymer in which the copolymerization ratio and Tg of the components (a1) to (a3) are adjusted to the ranges specified in the present application, a photosensitive resin layer excellent in all properties of resolution, developability, adhesion, and flexibility of the cured film can be obtained.

[0526] 《Component (a1)》

[0527] (a1) component may contain only either methacrylic acid or acrylic acid, may contain only either one, may contain both, or may contain only both. In the case where (a1) component contains only both methacrylic acid and acrylic acid, the copolymerization ratio of (a1) component is determined by the sum of the copolymerization ratio of methacrylic acid and the copolymerization ratio of acrylic acid.

[0528] Based on the total mass of all the structural units of copolymer (A-1), the proportion of the structural units derived from (a1) component is 15 to 26% by mass. From the viewpoint of excellent developability and resolution, it is preferred to adjust this proportion to 15% by mass or more. From the viewpoints of controlling the glass transition temperature (Tg) of the photosensitive resin layer within a moderate range and the flexibility of the cured film, it is preferred to adjust this proportion to 26% by mass or less. This proportion is more preferably 17 to 25% by mass, and further preferably 18 to 23% by mass.

[0529] From the viewpoint of excellent resolution, (a1) component preferably contains methacrylic acid. In this case, the copolymerization ratio of methacrylic acid is preferably 50% by mass or more, more preferably 75% by mass or more, further preferably 90% by mass or more, and may also be 100% with respect to all of (a1) component. When (a1) component contains methacrylic acid, the copolymerization ratio of methacrylic acid is preferably 15 to 25% by mass, and preferably 17 to 23% by mass.

[0530] 《Component (a2)》

[0531] Examples of (a2) component include styrene, oxy styrene, hydroxy styrene, acetoxystyrene, alkylstyrene, and haloalkylstyrene. Among them, (a2) component preferably contains styrene.

[0532] Based on the total mass of all the structural units of copolymer (A-1), the proportion of the structural units derived from (a2) component is 30 to 70% by mass. From the viewpoints of excellent resolution and adhesion, it is preferred to adjust this proportion to 30% by mass or more. From the viewpoints of excellent developability and flexibility of the cured film, it is preferred to adjust this proportion to 70% by mass or less. This proportion is preferably 30 to 60% by mass, and more preferably 35 to 50% by mass.

[0533] (Component (a2) may contain only one compound. Additionally, it may also contain two or more compounds. When component (a2) contains two or more compounds, the copolymerization ratio of component (a2) is determined by the sum of the copolymerization ratios of each compound.)

[0534] 《Component (a3)》

[0535] (Component (a3) is a compound in which a hydrogen atom of an alkyl group of an (alkyl) acrylate is substituted with a hydroxyl group. Examples of such a compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Among them, from the viewpoint of excellent developability, component (a3) preferably contains 2-hydroxyethyl (meth)acrylate.)

[0536] Based on the total mass of all the structural units of copolymer (A-1), the proportion of the structural units derived from component (a3) is 15 to 35% by mass. From the viewpoint of balancing developability and the flexibility of the cured film, it is preferably adjusted to 15% by mass or more. From the viewpoint of excellent resolution and adhesion, it is preferably adjusted to 35% by mass or less. This proportion is preferably 20 to 30% by mass, more preferably 23 to 27% by mass.)

[0537] (Component (a3) may contain only one compound. Additionally, it may also contain two or more compounds. When component (a3) contains two or more compounds, the copolymerization ratio of component (a3) is determined by the sum of the copolymerization ratios of each compound.)

[0538] 《Component (a4)》

[0539] In addition to the structural units derived from the above-mentioned components (a1) to (a3), copolymer (A-1) may also contain structural units derived from the following component (a4) that is different from the above-mentioned components (a1) to (a3).)

[0540] As component (a4), for example, it is preferably:

[0541] (a4) An (alkyl) acrylate represented by the following general formula (I).

[0542]

[0543] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 3 or more carbon atoms.)

[0544] Generally, the glass transition temperature Tgi of the homopolymer of component (a4) is lower than the glass transition temperature Tg of the homopolymer of component (a1), component (a2), or component (a3))i , Therefore, by using such a component (a4), it is easy to adjust the glass transition temperature Tg of the copolymer (A-1) to a lower level.

[0545] As the component (a4), preferably, in the above general formula (I), R 2 is a compound having an alkyl group with 3 to 12 carbon atoms. Examples of such a compound include propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and nonyl (meth)acrylate. Among them, as the component (a4) represented by the above formula (I), more preferably, R 2 is a compound having an alkyl group with 4 to 10 carbon atoms, and still more preferably, it is a compound having an alkyl group with 6 to 9 carbon atoms. As such a compound, 2-ethylhexyl (meth)acrylate is particularly preferred.

[0546] Based on the total mass of all the structural units of the copolymer (A-1), the proportion of the structural units derived from the component (a4) is preferably 1 to 15% by mass. From the viewpoints of easily reducing the Tg of the copolymer (A-1) and excellent flexibility of the cured film, this proportion is preferably 1% by mass or more. On the other hand, since the component (a4) contains an unsaturated hydrocarbon group without a hydrophilic group, it has high hydrophobicity. Furthermore, since the component (a4) does not have an aromatic ring, it is preferable to achieve a balance with the component (a2) having an aromatic ring incorporated into the polymer main chain. In this case, from the viewpoints of excellent various properties (such as resolution, adhesion, and developability), this proportion is preferably 15% by mass or less. This proportion is more preferably 5 to 13% by mass, and still more preferably 8 to 12% by mass.

[0547] 《Monomers Other than Components (a1) to (a4)》

[0548] The copolymer (A-1) may contain monomers other than the components (a1) to (a4) as copolymerization components. The monomers other than the components (a1) to (a4) are the first monomers other than (a1), or the second monomers other than the components (a2) to (a4). Examples thereof include compounds that are not among the components (a1) to (a4) among the compounds exemplified as the above first monomers and the compounds exemplified as the second monomers.

[0549] When the copolymer (A-1) has the first monomers other than the component (a1), from the viewpoint of excellent flexibility of the cured film, the copolymerization proportion of the first monomers as a whole {including the component (a1)} is preferably 26% by mass or less, and more preferably 25% by mass or less. The copolymerization proportion of the first monomers other than the component (a1) may be 0% by mass.

[0550] When the copolymer (A-1) has a second monomer other than the components (a2) to (a4), from the viewpoint of easily exerting the effects of the present invention, the copolymerization ratio of this monomer component is preferably 20% by mass or less, more preferably 10% by mass or less. The copolymerization ratio of the second monomer other than the components (a2) to (a4) can be 0% by mass.

[0551] <Component (B)>

[0552] Component (B) is a compound having an ethylenically unsaturated bond. Component (B) may have at least 1 ethylenically unsaturated bond in one molecule. From the viewpoint of obtaining a photosensitive resin layer having appropriate flexibility, component (B) preferably contains a compound having 2 ethylenically unsaturated bonds in one molecule. From the viewpoint of excellent crosslinking efficiency in the exposure step, component (B) may further contain a compound having 3 ethylenically unsaturated bonds in one molecule, and may further contain a compound having 4, 5, or 6 ethylenically unsaturated bonds in one molecule.

[0553] From the viewpoint of excellent resolution, the content of the compound having 2 ethylenically unsaturated bonds in one molecule in component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more with respect to the whole of component (B). This content may be 100% by mass with respect to the whole of component (B), or may be less than 100% by mass.

[0554] When component (B) contains a compound having 3 or more ethylenically unsaturated bonds in one molecule, from the viewpoints of excellent adhesion and developability, the content of the compound having 3 or more ethylenically unsaturated bonds in one molecule is preferably 30% by mass or less, and may also be 20% by mass or less with respect to the whole of component (B). In addition, this content may be 1% by mass or more, and may be 5% by mass or more with respect to the whole of component (B).

[0555] Component (B) preferably contains a (meth)acrylate compound, and from the viewpoint of obtaining a photosensitive resin layer having appropriate flexibility, more preferably contains a (meth)acrylate compound having 2 or more functional groups (a compound having 2 or more (meth)acryloyl groups in one molecule). Regarding component (B), the case where "(meth)acrylate compound has n (meth)acryloyl groups in one molecule" is, for example, referred to as "n-functional". For example, regarding component (B), the cases where there are 1, 2, 3, 4, 5, or 6 ethylenically unsaturated bonds in one molecule are respectively referred to as "1-functional (or monofunctional)", "2-functional", "3-functional", "4-functional", "5-functional", or "6-functional".

[0556] When the component (B) contains a (meth)acrylate compound, from the viewpoint of excellent crosslinking efficiency in the exposure step, it may contain only a bifunctional (meth)acrylate compound, or may contain a bifunctional (meth)acrylate compound and a (meth)acrylate compound having a functionality of 3 or more. The component (B) may contain, together with the bifunctional (meth)acrylate compound and / or the (meth)acrylate compound having a functionality of 3 or more, or independently of these compounds, a tetrafunctional, pentafunctional, or hexafunctional (meth)acrylate compound, for example.

[0557] When the component (B) contains a (meth)acrylate compound, from the viewpoints of excellent resolution and flexibility of the cured film, the content of the bifunctional (meth)acrylate compound is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, based on the total amount of the component (B). In addition, this content may be 100% by mass or less than 100% by mass based on the total amount of the component (B).

[0558] When the component (B) contains a (meth)acrylate compound having a functionality of 3 or more, from the viewpoints of excellent adhesion and developability, the content of the (meth)acrylate compound having a functionality of 3 or more is preferably 30% by mass or less, and may be 20% by mass or less, based on the total amount of the component (B). In addition, this content may be 1% by mass or more, and may be 5% by mass or more, based on the total amount of the component (B).

[0559] Examples of the bifunctional (meth)acrylate compound include dialkyl (meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylate, tricyclodecane di(meth)acrylate, bisphenol A-based di(meth)acrylate, and hydrogenated bisphenol A-based di(meth)acrylate.

[0560] Examples of the polyalkylene glycol di(meth)acrylate include compounds represented by the following general formula (II).

[0561]

[0562] (In the formula, R 1 are each independently a hydrogen atom or a methyl group, X 1 O and Y 1 O are each independently an oxyalkylene group having 2 to 4 carbon atoms, m1, m2, and n1 are each independently an integer of 0 to 40, m1 + m2 is 1 to 40, and n1 is 0 to 20.)

[0563] Examples of the bisphenol A-based di(meth)acrylate include compounds represented by the following general formula (III).

[0564]

[0565] (wherein, R 2 is independently a hydrogen atom or a methyl group, X 2 O and Y 2 O are independently an oxyethylene group or an oxypropylene group, m3, m4, n2 and n3 are independently integers from 0 to 40, m3 + m4 is from 1 to 40, and n2 + n3 is from 0 to 20)

[0566] It should be noted that the number of structural units of the oxyethylene group or the oxypropylene group represents an integer value in a single molecule and represents a rational number as an average value in an aggregate of multiple molecules.

[0567] Examples of the bis(meth)acrylate having a hydrogenated bisphenol A structure include compounds obtained by subjecting the aromatic ring of the compound represented by the above formula (III) to addition hydrogenation.

[0568] Examples of the compound represented by the above formula (II) include those in which R 1 = methyl, m1 + m2 = 6 (average value), n1 = 12 (average value), X 1 O = oxyethylene group, and Y 1 O = oxypropylene group (manufactured by Resonac Co., Ltd., product name "FA-024M"), etc.

[0569] Examples of the compound represented by the above formula (III) include BPE-200 (wherein, R 2 = methyl, X 2 O = oxyethylene group, m3 + m4 = 4, and n2 = n3 = 0), BPE-500 (wherein, R 2 = methyl, X 2 O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), BPE-900 (wherein, R 2 = methyl, X 2 O = oxyethylene group, m3 + m4 = 17, and n2 = n3 = 0) (above, manufactured by Shin-Nakamura Chemical Co., Ltd., product name), FA-321M (wherein, R 2 = methyl, X 2 O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), FA-P321M (wherein, R 2 = methyl, X 2 O = oxypropylene group, m3 + m4 = 10, and n2 = n3 = 0) (above, manufactured by Resonac Co., Ltd., product name), FA-P323M (wherein, R 2 = methyl, X 2O = oxypropylene group, m3 + m4 = 30, and n2 = n3 = 2) (above, manufactured by Resonac, product name), etc.

[0570] From the viewpoint of excellent resolution, the component (B) preferably contains bis(meth)acrylate having a bisphenol A structure and / or bis(meth)acrylate having a hydrogenated bisphenol A structure as the bifunctional (meth)acrylate compound. Based on the total amount of the component (B), it is preferably contained in an amount of 20% by mass or more of this compound, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0571] In addition, based on all solid components of the photosensitive resin composition, it is preferably contained in an amount of 10% by mass or more of this compound, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more.

[0572] Examples of commercially available bifunctional (meth)acrylate compounds include: NK ESTER (registered trademark) A-HD-N, the same series A-NOD-N, the same series A-DOD-N, the same series A-NPG, the same series 701A, the same series A-200, the same series A-400, the same series A-600, the same series A-1000, the same series APG-200, the same series APG-400, the same series APG-700, the same series A-PTMG65, the same series A-DCP, the same series ABE-300, the same series A-BPE-4, the same series A-BPE-10, the same series A-BPE-20, the same series HD-N, the same series NOD-N, the same series DOD-N, the same series NPG, the same series 701, the same series 2G, the same series 3G, the same series 4G, the same series 9G, the same series 14G, the same series 23G, the same series 9PG, the same series DCP, the same series BPE-80N, the same series BPE-100, the same series BPE-200, the same series BPE-500, the same series BPE-900, the same series BPE-1300N, NKOLIGO (registered trademark) UA-4200, the same series UA-160TM, the same series UA-290TM, the same series UA-W2A, the same series UA-4400, the same series UA-122P, the same series U-200PA (all of the above are manufactured by Shin-Nakamura Chemical Co., Ltd.), LIGHTACRYLATE (registered trademark) 3EG-A, the same series 4EG-A, the same series 9EG-A, the same series 14EG-A, the same series PTMGA-250, the same series NP-A, the same series MPD-A, the same series 1.6HX-A, the same series 1.9ND-A, DCP-A of the same series, BP-4EAL of the same series, BP-4PA of the same series, HPP-A of the same series, Light Ester G-201P (above, manufactured by Kyoeisha Chemical Co., Ltd.), FANCRYL (registered trademark) FA-124AS, FA-023M of the same series, FA-121M of the same series, FA-124M of the same series, FA-125M of the same series, FA-129AS of the same series, FA-137M of the same series, FA-220M of the same series, FA-222A of the same series, FA-240A of the same series, FA-240M of the same series, FA-320M of the same series, FA-3218M of the same series, FA-321A of the same series, FA-321M of the same series, FA-324A of the same series, FA-731A of the same series, FA-P240A of the same series, FA-P270A of the same series, FA-PTG9A of the same series, FA-PTG9M of the same series, FA-PTG28A of the same series, FA-PTG49A of the same series (above, manufactured by Resonac Corporation), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYLPEG200DMA (above, manufactured by Daicel allnex), 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 (above, manufactured by Arkema), KAYARAD (registered trademark) NPGDA, PEG400DA of the same series, FM-400 of the same series, R-167 of the same series, HX-220 of the same series, HX-620 of the same series, R-551 of the same series, R-712 of the same series, R-604 of the same series, R-684 of the same series (above, manufactured by Nippon Kayaku Co., Ltd.), etc.

[0573] Examples of the (meth)acrylate compound having three or more functional groups include trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, diglycerol tetra(meth)acrylate, bis-trimethylolpropane (tetra / penta / hexa)(meth)acrylate, triglycerol penta(meth)acrylate, dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and the like.

[0574] The (meth)acrylate compound having three or more functional groups may be a compound obtained by forming a (meth)acrylate from an alcohol having three or more groups capable of adding an epoxyalkyl group in the molecule as a central skeleton and adding an epoxyalkyl group (such as epoxyethyl, epoxypropyl, and epoxybutyl) thereto. Examples of such a compound include epoxyalkane-modified trimethylolpropane tri(meth)acrylate, epoxyalkane-modified glycerol tri(meth)acrylate, epoxyalkane-modified isocyanuric acid tri(meth)acrylate, epoxyalkane-modified pentaerythritol (tri / tetra)(meth)acrylate, epoxyalkane-modified diglycerol tetra(meth)acrylate, epoxyalkane-modified bis-trimethylolpropane (tetra / penta / hexa)(meth)acrylate, epoxyalkane-modified triglycerol penta(meth)acrylate, epoxyalkane-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and the like.

[0575] From the viewpoint of excellent developability, the (meth)acrylate compound having three or more functional groups preferably contains epoxyalkane-modified pentaerythritol (tri / tetra)(meth)acrylate and / or epoxyalkane-modified dipentaerythritol (tri / tetra)(meth)acrylate.

[0576] Specific examples of such a compound include:

[0577] tetramethacrylate obtained by adding an average of 9 moles of epoxyethyl groups to pentaerythritol;

[0578] tetramethacrylate obtained by adding an average of 15 moles of epoxyethyl groups to pentaerythritol;

[0579] hexaacrylate of polyethylene glycol obtained by adding an average of 13 moles of epoxyethyl groups to dipentaerythritol; and the like.

[0580] Examples of commercially available products of (meth)acrylate compounds having three or more functional groups include: NK ESTER (registered trademark) A-TMPT, the same series A-TMPT-9EO, the same series AT-20E, the same series A-GLY-3E, the same series A-GLY-9E, the same series A-GLY-20E, the same series A-9300, the same series A-9200YN, the same series A-TMM-3, the same series A-TMM-3L, the same series A-TMM-3LM-N, the same series A-TMMT, the same series ATM-35E, the same series AD-TMP, the same series A-DPH, the same series A-9550, the same series A-DPH-12E, the same series TPOA-50, NK OLIGO (registered trademark) UA-7100, the same series UA-1100H, the same series U-6LPA, the same series UA-33H, the same series U-10HA, the same series U-10PA, the same series U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), LIGHT ACRYLATE (registered trademark) TMP-A, cPE-3A, the same series PE-4A, the same series DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (manufactured by Resonac Corporation), TMPTA, EBECRYL 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel allnex), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema), KAYARAD (registered trademark) GPO-303, the same series TMPTA, the same series THE-330, the same series TPA-330, the same series PET-30, the same series T-1420(T), the same series RP-1040, the same series DPHA, the same series DPEA-12, the same series D-310, the same series DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0581] Component (B) may contain a hindered amine compound. Thereby, residues after stripping of the resist pattern are less likely to occur. Examples of the hindered amine compound include the compounds represented by the following general formula (IV).

[0582]

[0583] (In the formula, R 1 each independently represents an alkyl group having 1 or more carbon atoms, and R 2 represents hydrogen or an alkyl group having 1 or more carbon atoms, and R 1 and R 2 each independently have 10 or less carbon atoms.)

[0584] Examples of the compound represented by the general formula (IV) include 1,2,2,6,6-pentamethylpiperidyl methacrylate.

[0585] Based on the total solid content of the photosensitive resin composition, the content of the hindered amine compound may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may also be 20% by mass or less, 15% by mass or less, 10% by mass or less, or 0% by mass.

[0586] The hindered amine compound sometimes belongs to a compound having one ethylenically unsaturated bond. Regarding the content of the compound having one ethylenically unsaturated bond (excluding the hindered amine compound when the hindered amine compound belongs to the compound having one ethylenically unsaturated bond), based on the total solid content of the photosensitive composition components, it may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 0% by mass.

[0587] Based on the total solid content of the photosensitive resin composition, the content of the component (B) is preferably 10 to 50% by mass. From the viewpoints of preventing poor curing of the photosensitive resin layer and suppressing the delay of the development time, this content is preferably 10% by mass or more. In addition, from the viewpoint of improving the developability of the resist pattern, it is preferably 50% by mass or less. From the same viewpoints, this content is more preferably 20 to 45% by mass, and further preferably 25 to 40% by mass.

[0588] Based on the total solid content of the photosensitive resin composition, the total content of the component (A) and the component (B) is preferably 85% by mass or more, and more preferably 90% by mass or more. By making this content within the above range, it is easier to suitably exhibit the effects of the present invention that are easily exerted by the component (A) and the component (B).

[0589] The total content of the component (A) and the component (B) may be 99% by mass or less, or may also be 95% by mass or less.

[0590] <(Component (C))>

[0591] (The component (C) is a polymerization initiator. The component (C) is preferably a photopolymerization initiator that generates free radicals by actinic rays and thereby initiates the polymerization of the component (B). The component (C) preferably contains a compound having a benzimidazole structure.)

[0592] As the component (C), for example, hexarylimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoate compounds, oxime ester compounds, acridine compounds, and halogen compounds can be cited.

[0593] As the hexarylimidazole compounds, for example, dimers of compounds having a lophine structure (lophine dimers), namely: dimers of 2,4,5-triaryl imidazoles and 2,2’,5-tri-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4’,5’-diphenyl benzimidazole, etc. can be cited.

[0594] As the lophine dimers, for example, dimers of 2-(o-chlorophenyl)-4,5-diphenyl imidazole (alias: 2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-1,2’-biimidazole), 2,2’-bis-(2-fluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3-difluoromethylphenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,4-difluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,5-difluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,6-difluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4-trifluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,5-trifluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,6-trifluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,4,5-trifluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,4,6-trifluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,5-tetrafluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,6-tetrafluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole, and 2,2’-bis-(2,3,4,5,6-pentafluorophenyl)-4,4’,5,5’-tetra-(3-methoxyphenyl)-biimidazole can be cited.

[0595] From the viewpoints of excellent high sensitivity, resolution, and adhesion, component (C) preferably contains thiophene dimers. Among them, component (C) more preferably contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and further preferably contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0596] Examples of the quinone compound 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-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0597] Examples of the aromatic ketone compound include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. The aromatic ketone compound sometimes functions as a photopolymerization initiator when used alone, and sometimes functions as a sensitizer when used in combination with other photopolymerization initiators.

[0598] Examples of the acetophenone compound 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-acetone-1. Commercially available products of the acetophenone compound include, for example, the Irgacure series (manufactured by BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0599] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Commercially available products of the acylphosphine oxide compound include, for example, Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by BASF).

[0600] As benzoin compounds and benzoin ether compounds, for example, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin can be cited.

[0601] As dialkyl ketal compounds, for example, benzil dimethyl ketal and benzil diethyl ketal can be cited.

[0602] As thioxanthone compounds, for example, 2,4 - diethylthioxanthone, 2,4 - diisopropylthioxanthone, and 2 - chlorothioxanthone can be cited.

[0603] As dialkyl aminobenzoate compounds, for example, ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl - p - dimethylaminobenzoate, and 2 - ethylhexyl 4 - (dimethylamino)benzoate can be cited.

[0604] As oxime ester compounds, for example, 1 - phenyl - 1,2 - propanedione - 2 - O - benzoyl oxime and 1 - phenyl - 1,2 - propanedione - 2 - (O - ethoxycarbonyl)oxime can be cited. As commercially available products of oxime ester compounds, for example, CGI - 325, Irgacure - OXEO1, and Irgacure - OXEO2 (manufactured by BASF Corporation, etc.) can be cited.

[0605] As acridine compounds, for example, 1,7 - bis(9,9’ - acridinyl)heptane and 9 - phenylacridine can be cited.

[0606] As halogen compounds, for example, bromopentane, bromoisopentane, bromoisobutene, bromoethylene, benzhydryl bromide, benzyl bromide, dibromomethane, tribromomethyl phenyl sulfone, carbon tetrabromide, tris(2,3 - dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodo - isobutane, 1,1,1 - trichloro - 2,2 - bis(p - chlorophenyl)ethane, chlorotriazine compounds, and diallyl iodonium compounds can be cited.

[0607] Based on the total solid content of the photosensitive resin composition, the content of component (C) is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass. When the photosensitive resin composition contains a thiophene dimer as component (C), based on the total solid content of the photosensitive resin composition, the content of the thiophene dimer is preferably 3.0 to 10% by mass, more preferably 4.0 to 9.0% by mass, and further preferably 5.0 to 8.0% by mass. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, and thus high resolution can be easily achieved.

[0608] <(D) Component: Sensitizer>

[0609] From the viewpoint of excellent sensitivity and resolution, the photosensitive resin composition preferably further contains (D) a sensitizer. The component (D) promotes the photopolymerization reaction by transferring the energy obtained from its own absorbed light to the initiator. The "(D) component" referred to in the present embodiment (the embodiment of the "related invention") may be different from the "(D) component" referred to in the above [the embodiment of the "first invention"].

[0610] Examples of the 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. Among them, the component (D) preferably contains pyrazoline derivatives and anthracene derivatives.

[0611] Examples of the pyrazoline derivative 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, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-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 them, as the pyrazoline derivative, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred.

[0612] As anthracene derivatives, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenyl)-10-bromoanthracene, 9-(4-biphenyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene, and 9-(3-bromophenyl)-10-phenylanthracene can be cited. Among them, as anthracene derivatives, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred.

[0613] As naphthalene derivatives, for example, 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(isobutoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, 1,4-bis(n-heptyloxy)naphthalene, 1,4-bis(n-octyloxy)naphthalene, 1,4-bis(2-ethylhexyloxy)naphthalene, 1,4-bis(n-nonyloxy)naphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethoxynaphthalene, 1,4-diglycidoxynaphthalene, 1,4-bis(2-methylglycidoxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, and 2-(2-hydroxyethoxy)naphthalene can be cited. Among them, as naphthalene derivatives, 1,4-diethoxynaphthalene is preferred.

[0614] As oxazole derivatives, for example, 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazol-2-yl)naphthalen-1-yl]-1,3-benzoxazole can be cited.

[0615] As N-aryl-α-amino acid derivatives, for example, 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, N-(n-propyl)-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, N-(o-chlorophenyl)glycine, etc. can be mentioned.

[0616] As aromatic ketone derivatives substituted with alkylamino, benzophenone derivatives can be mentioned. As benzophenone derivatives, for example,

[0617] Alkylbenzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone;

[0618] Benzophenone compounds having a halogen atom such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone;

[0619] Benzophenone compounds substituted with a carboxyl group or an alkoxycarbonyl group such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester;

[0620] Bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, and preferably 4,4'-bis(dialkylamino)benzophenone compounds;

[0621] 4-methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, etc.

[0622] In one mode, the component (D) may contain a compound having the following skeleton together with the above-mentioned skeleton or having the following skeleton independently of the above-mentioned skeleton. As such a skeleton, for example, at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, oxazole, and is mentioned. Thus, it is likely to be advantageous from the viewpoint of sensitivity.

[0623] In one mode, the component (D) may contain a boron compound that absorbs h-rays and / or i-rays. As the boron compound that absorbs h-rays and / or i-rays, it is at least one compound selected from the group consisting of pyrazoline derivatives, anthracene derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives, and aromatic ketone derivatives substituted with alkylamino, and preferably a compound containing at least one boron moiety selected from the group consisting of the following general formulas.

[0624] *-BH 2

[0625] *-B(OH) 2

[0626] *-B(OR 1 ) 2

[0627] *-B(OH)(OR 1 )

[0628] (In the formula, each R 1 independently represents a monovalent organic group, and * represents the bonding site to various skeletons.)

[0629] As such a compound, for example, boric acids having a pyrazoline skeleton, an anthracene skeleton, and an oxazole skeleton are mentioned. Among them, as such a compound, an organic boric acid having a 10-phenyl-9-anthracene skeleton (10-phenyl-9-anthracene boric acid) is preferred.

[0630] In the above boron compound that absorbs h-rays and / or i-rays, the definitions of "h-rays", "i-rays", and "having absorption" are the same as those in [the embodiment of "the first invention"].

[0631] Based on the total mass of the component (A), the content of the component (D) is preferably 0.01 to 2.0% by mass, more preferably 0.3 to 1.5% by mass.

[0632] <(Component (E): Other components)>

[0633] The photosensitive resin composition may contain components other than the above components (A) to (D) {component (E): other components} as needed. Examples of the component (E) include colorants, leuco dyes, basic dyes (dyes other than leuco dyes), antioxidants, stabilizers, and the like.

[0634] (Colorant)

[0635] Examples of the colorant include magenta, phthalocyanine green, auramine, pararosaniline, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green {e.g., AIZEN (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.}, basic blue 20, diamond green {e.g., AIZEN (registered trademark) 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 Industries, Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industries, Ltd.), 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OIL BLUE 630 manufactured by Orient Chemical Industries, Ltd.).

[0636] Based on the total solid content of the photosensitive resin composition, the content of the colorant is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 2% by mass.

[0637] (Leuco dye)

[0638] Examples of the leuco dye include leuco crystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.

[0639] Based on the total solid content of the photosensitive resin composition, the content of the leuco dye is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass.

[0640] (Basic dye)

[0641] As basic dyes (dyes other than leuco dyes), for example, basic green 1 [CAS number (the same hereinafter): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), magenta [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] (for example, Aizen Victoria Pure Blue BOH, trade name, Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], etc. can be cited.

[0642] Based on the total solid content of the photosensitive resin composition, the content of the basic dye is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and still more preferably 0.04 to 1% by mass.

[0643] (Antioxidant)

[0644] As antioxidants, for example, triphenyl phosphite (for example, manufactured by Asahi Denka Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, manufactured by ADEKA Corporation, trade name 2112), tris(monononylphenyl) phosphite (for example, manufactured by ADEKA Corporation, trade name: 1178), bis(monononylphenyl)-dinonylphenyl phosphite (for example, manufactured by Asahi Denka Co., Ltd., trade name: 329K) can be cited.

[0645] Based on the total mass of the photosensitive resin composition, the content of the antioxidant is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass.

[0646] (Stabilizer)

[0647] As stabilizers, for example, at least one of a radical inhibitor and an epoxyalkane compound having a glycidyl group can be cited.

[0648] As radical polymerization inhibitors, examples 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-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], aluminum salt of nitrosophenylhydroxylamine (e.g., aluminum salt added with 3 moles of nitrosophenylhydroxylamine), diphenylnitrosamine, hydroquinone, N-nitrosodiphenylamine, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, diol ether diamine tetraacetic 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, ammonium salt of N-nitroso-N-phenylhydroxylamine, ammonium salt of N-nitroso-N(1-naphthyl)hydroxylamine, etc. Among them, as radical polymerization inhibitors, p-methoxyphenol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, phenothiazine, and triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] are preferred.

[0649] As epoxyalkane compounds having glycidyl groups, examples include neopentyl glycol diglycidyl ether (e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mole adduct diglycidyl ether (e.g., Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (e.g., Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.).

[0650] The total content of the radical polymerization inhibitor and the epoxyalkane 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.

[0651] (Other optional components)

[0652] As other components, carboxybenzotriazoles can be cited. The content of carboxybenzotriazoles 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.

[0653] [For preparing a formulation liquid (coating liquid) of the photosensitive resin composition]

[0654] By mixing a photosensitive resin composition with a solvent, a preparation liquid for preparing the photosensitive resin composition can be prepared. Examples of the solvent include:

[0655] ketones such as acetone and methyl ethyl ketone (MEK);

[0656] alcohols such as methanol, ethanol, and isopropyl alcohol.

[0657] The photosensitive resin composition and the solvent are preferably mixed such that the viscosity of the preparation liquid is 500 to 4000 mPa·sec at 25°C.

[0658] In addition, 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.

[0659] Regarding the [embodiment of the "Related Invention"], in the photosensitive resin laminate obtained using the photosensitive resin composition,

[0660] the diameter of the following smallest mandrel obtained by the following method is preferably 8 mm or less.

[0661] (1) After forming the aforementioned photosensitive resin layer on a flexible substrate, exposure is performed at an energy with a remaining grade of 15 on a Stouffer (Stouffer Industries) 41-step step tablet, and in a size of 1 inch in width and 250 mm in length, thereby obtaining a cured film on the aforementioned substrate.

[0662] (2) Using a 1 mass% Na 2 CO 3 aqueous solution, the exposed substrate is developed for a time twice the shortest development time.

[0663] (3) The developed substrate is washed with water for a time twice the shortest development time.

[0664] (4) The substrate after washing is cut into a width of 1.2 inches such that the cured photosensitive resin layer with a width of 1 inch is located at the center in the width direction, thereby obtaining a sample.

[0665] (5) A mandrel test based on the method of the cylindrical mandrel method JIS K5600-5-1 is performed on the aforementioned sample.

[0666] (6) The diameter of the smallest mandrel in which no crack is confirmed in the aforementioned cured film or the diameter of the smallest mandrel in which no peeling of the aforementioned cured film from the substrate is confirmed is obtained.

[0667] Furthermore, the diameter of the smallest mandrel is more preferably 6 mm or less. In particular, the formability of independent fine lines of the photosensitive resin laminate capable of achieving both adhesion and flexibility of the cured film is excellent.

[0668] [Elements common to both the embodiment of the "First Invention" and the embodiment of the "Related Invention"]

[0669] Hereinafter, for the elements common to the above [embodiment of the "First Invention"] and the above [embodiment of the "Related Invention"], for convenience, they are collectively described herein.

[0670] 〔Photosensitive Resin Laminate〕

[0671] The photosensitive resin laminate has, for example, a support and a photosensitive resin layer obtained from a photosensitive resin composition. From the viewpoint of easily and significantly exhibiting 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 use.

[0672] <Support>

[0673] The support is preferably a transparent film that transmits light emitted from an exposure light source. Examples of the support 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 can be stretched films used as needed. The support can be one layer or multiple layers.

[0674] When exposing the photosensitive resin layer through the support, the thickness of the support is related to the transmission distance of the exposure light source. Therefore, when the thickness of the support is thin, it is beneficial for image formability and is also economically advantageous. On the other hand, considering the function of maintaining strength, it is preferably 5 to 50 μm, more preferably 10 to 30 μm. In addition, the haze of the support is preferably 5 or less.

[0675] <Photosensitive Resin Layer>

[0676] The thickness of the photosensitive resin layer is preferably 3 to 100 μm, more preferably 10 to 50 μm, and further preferably 15 to 50 μm. The thinner the thickness of the photosensitive resin layer, the easier it is to improve the resolution, and the thicker the film, the easier it is to improve the film strength. Therefore, the thickness of the photosensitive resin layer can be appropriately selected according to the field and use of the photosensitive resin laminate, etc.

[0677] <Protective Layer>

[0678] The photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin layer opposite to the support. Examples of the protective layer include polyethylene film, polypropylene film, polyethylene terephthalate film, and polyester film. These films may be stretched films used as needed. The protective layer may be one layer or multiple layers.

[0679] 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 from the photosensitive resin laminate. From this viewpoint, as the protective layer, a film of polyethylene terephthalate (PET) or biaxially stretched polypropylene (OPP) is preferred.

[0680] The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm. In particular, when the protective layer is a film of polyethylene terephthalate (PET) or biaxially stretched polypropylene (OPP), the thickness is preferably 5 to 100 μm, more preferably 8 to 50 μm, and further preferably 10 to 30 μm.

[0681] The protective layer preferably has a release layer on its surface. Thereby, it is easy to appropriately peel the protective film from the photosensitive resin layer. The release layer can be classified into, for example, silicone compounds and non-silicone compounds. The release layer may have an antistatic function, that is, it can be an antistatic layer. In this case, static electricity between the photosensitive resin layer and the protective film can be prevented, so it is easier to appropriately peel the protective film from the photosensitive resin layer. In one embodiment, the protective layer is preferably a PET film having an antistatic function.

[0682] Examples of the silicone compound include:

[0683] A condensation reaction type silicone resin formed by reacting polydimethylsiloxane with terminal silanol groups at both ends with polymethylhydrosiloxane or polymethylmethoxysiloxane;

[0684] An addition reaction type silicone resin formed by reacting a dimethylsiloxane / methylvinylsiloxane copolymer or a dimethylsiloxane / methylhexenylsiloxane copolymer with polymethylhydrosiloxane;

[0685] A UV-curable or electron beam-curable silicone resin formed by curing acrylic silicone and epoxy group-containing silicone with ultraviolet rays or electron beams;

[0686] 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).

[0687] As non-silicone compounds, for example, alkyd (or also called alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins can be cited.

[0688] The thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and still more preferably 0.01 to 0.5 μm. If the thickness is below the above upper limit value, the appearance of the coating film after peeling the protective layer is likely to be good, and in addition, the coating film is likely to be sufficiently cured. On the other hand, when the thickness is above the above lower limit value, sufficient releasability is easily ensured.

[0689] 〔Method for producing a photosensitive resin laminate〕

[0690] A photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support. One example of the production method is as follows. First, a preparation liquid (coating liquid) of the photosensitive resin composition is prepared as described above. Then, the preparation liquid is applied to the support using a bar coater or a roll coater and dried, thereby forming a photosensitive resin layer on the support. Then, a protective layer can be laminated on the photosensitive resin layer as needed, thereby producing a photosensitive resin laminate.

[0691] 〔Method for forming an etching pattern and method for forming a wiring pattern〕

[0692] Embodiments of the "first invention" and embodiments of the "related invention" each include a method for forming an etching pattern using a photosensitive resin composition.

[0693] This method has the following steps:

[0694] A lamination step (lamination step) of laminating the photosensitive resin layer in the photosensitive resin laminate on a substrate;

[0695] An exposure step (exposure step) of exposing the photosensitive resin layer of the laminated photosensitive resin laminate; and

[0696] A step of removing the unexposed portion of the photosensitive resin layer (development step).

[0697] Another mode of the above embodiment is a method for forming a wiring pattern.

[0698] This method is a wiring pattern forming method having the following steps:

[0699] A step of etching (etching step) and a peeling step of the substrate on which an etching pattern is formed by the above method after performing plating treatment as needed.

[0700] Hereinafter, an example of a method for forming a resist pattern and a wiring pattern will be described.

[0701] <Lamination process>

[0702] In the lamination process, specifically, after peeling the protective film from the photosensitive resin laminate, the resist layer is heat-pressed onto the substrate surface using a laminator, and lamination is performed one or more times. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc., and a copper-clad laminate is preferred. As needed, for example, the substrate can be cleaned with an aqueous solution of about 10% by mass of H 2 SO 4 to planarize the substrate. The heating temperature during lamination is usually 40 to 160°C, more preferably 80 to 120°C. Heat-pressing can be performed by using a laminator equipped with rollers, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition through the rollers several times. Heat-pressing can be performed under a reduced-pressure environment as needed. In addition, heat-pressing can be performed two or more times, whereby it is easy to improve the adhesion of the obtained resist pattern to the substrate. When performing heat-pressing two or more times, a two-stage laminator equipped with double rollers can be used, or the laminate of the substrate and the photosensitive resin layer can be repeatedly passed through the rollers.

[0703] <Exposure process>

[0704] In the exposure process, an exposure machine such as a contact aligner, a mirror projector, or a stepper is used to expose the resist layer through a patterned photomask or reticle or directly using an ultraviolet light source, etc. The exposure process can be performed after peeling the support film as needed, or through the support film. When performing exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and it can also be measured using a light meter. In the exposure process, direct imaging exposure can also be performed. In direct imaging exposure, instead of using a photomask, exposure is performed on the substrate through a direct drawing device. As the light source, a semiconductor laser or an ultra-high-pressure mercury lamp with a wavelength of 350 nm to 410 nm is used. When controlling the drawn pattern by a computer, the exposure amount is determined by the exposure light source illuminance and the substrate moving speed.

[0705] In the above-described embodiments, when exposing using only light having a wavelength in the vicinity of h-rays (i.e., 400 to 410 nm), the boron compound (D) that absorbs h-rays and / or i-rays preferably absorbs h-rays. When exposing using only light having a wavelength in the vicinity of i-rays (i.e., 350 to 370 nm), the boron compound (D) that absorbs h-rays and / or i-rays preferably absorbs i-rays. In these cases, there is no limitation on the absorbance in the other wavelength region. When exposing using exposure light having both a wavelength in the vicinity of h-rays and a wavelength in the vicinity of i-rays, the boron compound (D) that absorbs h-rays and / or i-rays only needs to absorb at least one of h-rays and i-rays.

[0706] In the above-described embodiments,

[0707] When the aforementioned boron compound (D) that absorbs h-rays and / or i-rays absorbs h-rays, the exposure light in the exposure step preferably has a wavelength in the vicinity of h-rays;

[0708] When the aforementioned boron compound (D) that absorbs h-rays and / or i-rays absorbs i-rays, the exposure light in the exposure step preferably has a wavelength in the vicinity of i-rays.

[0709] That is, it is preferable that the above boron compound is a compound that absorbs h-rays, and

[0710] In the exposure step, the photosensitive resin layer is exposed using light including a wavelength of 400 to 410 nm. Additionally,

[0711] It is preferable that the above boron compound is a compound that absorbs i-rays, and

[0712] In the exposure step, the photosensitive resin layer is exposed using light including a wavelength of 350 to 370 nm.

[0713] The exposure method used in the exposure step is preferably at least one method selected from projection exposure method, proximity exposure method, contact exposure method, direct imaging exposure method, and electron beam direct drawing method, and more preferably performed by a projection exposure method or a direct imaging exposure method.

[0714] <Heating step>

[0715] A heating step may be provided between the exposure step and the development step. The heating temperature is preferably 30 to 200 °C, more preferably 30 to 150 °C, and further preferably 35 to 120 °C. By performing this heating step, the resolution and adhesion can be improved. Heating can be performed using a heating furnace, constant temperature bath, hot plate, hot air dryer, infrared dryer, hot roller, etc. in a hot air, infrared, or far-infrared manner. The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0716] The elapsed time from the exposure step to the heating step, more precisely, the elapsed time from the moment when exposure stops to the moment when heating starts, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The elapsed time from the start of heating to the moment when heating stops is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0717] <Developing step>

[0718] In the developing step, a developing apparatus is used to remove the unexposed portion of the exposed resist layer with a developer to form a resist pattern. After exposure, when there is a support film on the resist layer, the support film is removed. Then, a developer containing an aqueous alkali solution is used to develop and remove the unexposed portion to obtain a resist pattern. As a developing method for developing the exposed (irradiated) resist layer, any method can be selected from known photoresist developing methods, such as spin spray method, paddle method, dipping method with ultrasonic treatment, etc.

[0719] For the aqueous alkali solution as the developer, preferably Na 2 CO 3 、K 2 CO 3 and aqueous solutions such as tetramethylammonium hydroxide. The aqueous alkali solution is selected according to the characteristics of the resist layer, and usually an aqueous solution of Na 2 CO 3 with a concentration of 0.2% to 2% by mass is used. A surfactant, an antifoaming agent, and a small amount of organic solvent for promoting development can be added to the aqueous alkali solution. The temperature of the developer in the developing step is preferably kept constant in the range of 20 to 40°C.

[0720] In the developing step, a water washing step for removing the developer contained in the resist pattern after development is preferably included. As the washing water, in addition to pure water, industrial water, etc., it can be selected according to the characteristics of the resist layer, but in order to improve the resolution and the shape of the resist pattern, a polyvalent metal salt such as MgSO 4 with a concentration of 0.001% to 1% by mass can also be added. The temperature of the washing water in the water washing step is preferably kept constant in the range of 20 to 40°C.

[0721] A resist pattern is obtained through the above steps. If necessary, heat treatment can also be further performed at 60 to 300°C for 1 to 120 minutes. By performing this heat treatment, the chemical resistance of the resist pattern can be improved. The heat treatment can use a heating furnace using hot air, infrared rays or far-infrared rays.

[0722] In order to obtain a conductor pattern, the conductor pattern forming process may also be performed after the development process or the heating process. The conductor pattern forming process etches or plates a substrate on which a resist pattern is formed.

[0723] <Conductor pattern forming process>

[0724] The conductor pattern forming process is a process of forming a conductor pattern on the surface of a substrate (for example, a copper surface) on which a resist pattern is formed by development using a known etching method or plating method.

[0725] As a method for forming a conductor pattern based on the plating method, for example, it is as follows.

[0726] The substrate after the development process is immersed in an acidic degreasing bath such as a 1 to 50 mass% sulfuric acid aqueous solution at 20 to 60 °C for 1 to 60 minutes. After washing the immersed substrate with water, it is immersed in a sulfuric acid aqueous solution with a concentration of 1 to 50 mass% at room temperature for 1 to 60 minutes.

[0727] Prepare an aqueous solution with a concentration of 1 to 15 mass% of copper sulfate, 0.1 to 30 mass% of sulfuric acid, and 1 to 1000 ppm of hydrochloric acid. Then, add 0.01 to 40 ml / l and 1 to 200 ml / l of a brightening agent (in one method, Cupracid HL and Cupracid GS manufactured by ATOTECH Co., Ltd.) respectively to prepare a copper sulfate plating solution. Using the prepared copper sulfate plating solution, a conductor pattern is formed by plating for 1 to 300 minutes with a current application of 0.01 to 10 A using a Haring Cell uniform plating device (manufactured by Yamamoto Plating Tester Co., Ltd.). Although the thickness of the copper plating film also depends on the thickness of the resist pattern, it is preferably 1 μm or more and 2 μm or less than the thickness of the resist pattern (μm). In the present disclosure, the thickness of the resist pattern refers to the thickness of the resist layer.

[0728] As a method for forming a conductor pattern based on the etching method, for example, flash etching can be cited. In flash etching, a copper seed layer can be removed with a prescribed etching solution. As the etching solution, for example, a mixed etching solution of sulfuric acid and hydrogen peroxide water (manufactured by Ebara Corporation) can be cited, but it is not limited thereto.

[0729] [Manufacturing method of conductor pattern]

[0730] The manufacturing method of the conductor pattern is performed, for example, by using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern using the above-described resist pattern forming method, and then undergoing the conductor pattern forming process.

[0731] <Stripping process>

[0732] Furthermore, after manufacturing the conductor pattern by the above-described method for manufacturing a conductor pattern, a stripping process may be performed to strip the resist pattern from the substrate using an aqueous solution having a stronger alkalinity than the developer. By performing the stripping process, a wiring board (a printed wiring board in one embodiment) having a desired wiring pattern can be obtained.

[0733] The alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 20% by mass or an organic amine-based stripping solution is generally used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohols. 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.

[0734] 〔Method for manufacturing a wiring board〕

[0735] In one embodiment, the method for manufacturing a wiring board using the photosensitive resin laminate of the above-described embodiment includes the following steps:

[0736] A laminating step of laminating a photosensitive resin layer on a substrate;

[0737] An exposure step of exposing the photosensitive resin layer;

[0738] A developing step of developing and removing the unexposed portion of the photosensitive resin layer to form a resist pattern;

[0739] A conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed to form a conductor pattern; and

[0740] A stripping step of stripping the resist pattern from the substrate.

[0741] The steps included in the method for manufacturing a wiring board in the above-described embodiment, that is, the laminating step, the exposure step, the developing step, the conductor pattern forming step, and the stripping step are the same as those described above.

[0742] The photosensitive resin laminate in the above-described embodiment can be used for: manufacturing a printed wiring board; manufacturing a lead frame for mounting an IC chip; precision processing of a metal foil such as manufacturing a metal mask; manufacturing a package such as a ball grid array (BGA) or a chip scale package (CSP); manufacturing a tape substrate such as a chip on film (COF) or a tape automated bonding (TAB); manufacturing a semiconductor bump; and manufacturing a partition wall of a flat panel display such as an ITO electrode, an address electrode, or an electromagnetic wave shield.

[0743] Unless otherwise specified, the above various parameters are measured according to the measurement methods in the examples described later.

[0744] Examples

[0745] [Embodiment of "First Invention"]

[0746] Next, examples and comparative examples will be listed to more specifically explain this embodiment.

[0747] [Production of Samples for Evaluation]

[0748] Samples for evaluation are produced as described below.

[0749] [Production of Photosensitive Resin Laminate]

[0750] The components shown in the following table (the numbers of the respective components represent the compounding amounts (parts by mass) based on solid content) and ethanol measured so that the solid content concentration becomes 60% are stirred and mixed to obtain a formulation liquid for a photosensitive resin composition. The details of the components are shown in the following table. A 16-μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., QS71) is used as the support film, and the above formulation liquid is coated on its surface using a bar coater and dried in a dryer at 95°C for 2.5 minutes. Thus, a photosensitive resin layer with a thickness of 25 μm is formed on the support film. Next, a 19-μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "GF-818") as a protective layer is pasted on the side of the photosensitive resin layer opposite to the support film, thereby obtaining a photosensitive resin laminate.

[0751] [Flattening of Substrate]

[0752] The surface of a copper-clad laminate with a total thickness of 0.4 mm laminated with an 18-μm-thick rolled copper foil is cleaned with a 10% by mass H 2 SO 4 aqueous solution. The cleaned copper-clad laminate is used as a substrate for image evaluation (evaluation substrate).

[0753] [Lamination]

[0754] While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, it is laminated on the copper-clad laminate (evaluation substrate) preheated to 50°C from the photosensitive resin layer side using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700) at a roll temperature of 105°C. The air pressure is set to 0.35 MPa, and the lamination speed is set to 1.5 m / min.

[0755] [Exposure]

[0756] For the evaluation substrate after lamination for 2 hours, using a mask pattern for direct imaging (DI) exposure specified, and using a direct drawing exposure machine (FDi-3 manufactured by ORC Manufacturing Co., Ltd.), direct exposure is performed with exposure light having a wavelength of 401 nm. The exposure is performed using a Stouffer (Stouffer Industries) 41-step stepwise exposure meter as a mask, and the exposure amount is such that the highest remaining film step number during subsequent development is 15 steps.

[0757] <Heating>

[0758] The evaluation substrate after exposure for 1 minute is heated for 30 seconds using a forced-air constant-temperature thermostat (DKM600 manufactured by YAMATO Scientific Co., Ltd.) set at 60°C.

[0759] <Development>

[0760] The polyethylene terephthalate film (support film) is peeled off. Then, using an alkali developing machine (a developing machine for dry film manufactured by Fuji Kiko Co., Ltd.), a 1 mass% Na 2 CO 3 aqueous solution at 30°C is sprayed onto the photosensitive resin layer for a specified time to perform development. The spraying time is set to twice the shortest development time, and the time for post-development cleaning (water washing based on spraying) is set to twice the shortest development time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed portion is treated as the shortest development time. As described above, an anti-etching pattern is formed on the evaluation substrate.

[0761] Note that, according to the width of L (line width) / S (line pitch), anti-etching patterns having:

[0762] L / S = 10 μm / 10 μm;

[0763] L / S = 8 μm / 8 μm;

[0764] L / S = 5 μm / 5 μm;

[0765] are respectively formed on the evaluation substrate.

[0766] [Evaluation]

[0767] <Sensitivity>

[0768] Based on the exposure amount in the above exposure process, using a Stouffer (Stouffer Industries) 41-step stepwise exposure meter as a mask and with the highest remaining film step number during subsequent development being 15 steps, evaluation is performed according to the following criteria. The evaluation results are shown in the table below.

[0769] Good: The exposure amount for the highest residual film level of 15 levels is 45 mJ / cm 2 or less.

[0770] Fair: The exposure amount for the highest residual film level of 15 levels is greater than 45 mJ / cm 2 and is 55 mJ / cm 2 or less.

[0771] Passable: The exposure amount for the highest residual film level of 15 levels is greater than 55 mJ / cm 2 and is 65 mJ / cm 2 or less.

[0772] Not Passable: The exposure amount for the highest residual film level of 15 levels is greater than 65 mJ / cm 2 .

[0773] <Flexibility>

[0774] Using a microscope, observe the pattern parts of the above-mentioned resist patterns with L / S = 10 μm / 10 μm, 8 μm / 8 μm, and 5 μm / 5 μm that are fabricated, and evaluate according to the following criteria. The evaluation results are shown in the table below.

[0775] Good: In the resist pattern with L / S = 5 μm / 5 μm, the pattern does not bend or break.

[0776] Fair: In the resist pattern with L / S = 8 μm / 8 μm, the pattern does not bend or break (excluding the cases evaluated as "Good").

[0777] Passable: In the resist pattern with L / S = 10 μm / 10 μm, the pattern does not bend or break (excluding the cases evaluated as "Good" or "Fair").

[0778] Not Passable: In the resist pattern with L / S = 10 μm / 10 μm, the pattern bends or breaks.

[0779] <Followability>

[0780] Laminating a commercially available dry film resist (DFR) on a copper-clad laminate, after exposing and developing the photosensitive resin layer, performing copper etching and stripping of the DFR, a pit substrate with a circular depression having a diameter of 310 μm and a depth of about 10 μm is fabricated. Laminate the photosensitive resin laminates of the examples and comparative examples on this pit substrate according to the above lamination process. At this time, when the photosensitive resin layer does not fully follow, a gap is generated between the circular depression and the substrate. Calculate the average value at 10 diameters of this gap and evaluate according to the following criteria. If it is "Passable" or above, it is regarded as qualified.

[0781] Good: 100 um or less

[0782] Good: greater than 100 um and less than or equal to 150 um

[0783] Acceptable: greater than 150 um and less than or equal to 200 um

[0784] Unacceptable: greater than 200 um

[0785] <Wavelength Absorbency of Boron Compounds>

[0786] For 10-phenyl-9-anthraceneboronic acid and 9-anthraceneboronic acid respectively;

[0787] 9,10-dibutoxyanthracene, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butylphenyl)-pyrazoline, and coumarin 102,

[0788] According to the above (1) to (5), the absorbencies of h-rays and i-rays were measured. The results are shown in the following table. It should be noted that the wavelength absorbency of the boron compound can be treated as the wavelength absorbency of the photosensitive resin composition containing the boron compound.

[0789] [Table 2]

[0790] Table 2

[0791]

[0792] [Table 3]

[0793]

[0794] [Table 4]

[0795]

[0796] [Table 5]

[0797]

[0798] It can be confirmed from the above table that in the examples, qualified evaluation results were obtained for both sensitivity and flexibility. In contrast, in the comparative examples, at least one of sensitivity and flexibility was "unacceptable".

[0799] Reference Example 1 evaluated each property of a photosensitive resin composition containing a compound that does not absorb h-rays but absorbs i-rays as component (D). In Reference Example 1, which used component (D) that does not absorb h-rays but absorbs i-rays and was exposed with exposure light having a wavelength near h-rays, the sensitization function could not be suitably exerted.

[0800] The above describes the present embodiment. The present invention is not limited to this embodiment and can be appropriately modified without departing from the gist of the invention.

[0801] [Examples of "Association Modes"]

[0802] The present embodiment will be described in more detail while listing examples and comparative examples.

[0803] [Preparation of Samples for Evaluation]

[0804] [Synthesis of Component (A)]

[0805] The monomers (copolymerization components) shown in the following table and azobisisobutyronitrile were mixed in the compounding amounts (unit: parts by mass) shown in the following table to prepare solution (a). After charging 200 g of methyl ethyl ketone and 100 g of ethanol into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet tube, nitrogen was blown into the flask while stirring, and then the mixed solution in the flask was heated to 80°C. While keeping the dropping rate constant, 300 g of the above solution (a) was dropped into the above mixed solution in the flask over 4 hours, and then stirred at 80°C for 2 hours.

[0806] Next, 0.5 part by mass of azobisisobutyronitrile was dissolved in 50 parts by mass of a mixed solution of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol to prepare solution (b). While keeping the dropping rate constant, 50 g of the above solution (b) was dropped into the solution in the flask over 10 minutes, and then stirred at 80°C for 3 hours. After further heating the solution in the flask to 90°C over 30 minutes, it was kept at 90°C for 2 hours. Then, stirring was stopped and cooled to room temperature (25°C). Thus, solutions of alkali-soluble polymers A1-1 to A1-6, A2-1 to A2-5, and A3-1 to A3-5 were obtained. The glass transition temperatures (Tg) and weight-average molecular weights (Mw) of these alkali-soluble polymers are shown in the following table.

[0807] The weight-average molecular weight was measured by gel permeation chromatography (GPC) and then derived by conversion using a standard curve of standard polystyrene. The conditions of GPC are as follows.

[0808] (GPC Conditions)

[0809] Pump: PU-4580 manufactured by JASCO

[0810] Degasser: DG-2080-53

[0811] Column oven: CO-1560

[0812] Columns: A total of 4 columns manufactured by Shodex, KF-807×1, KF-806M×2, KF-802.5×1

[0813] Eluent: Tetrahydrofuran

[0814] Measured temperature: 40°C

[0815] Flow rate: 1.00 mL / min

[0816] Detector: RI-1530 manufactured by JASCO Corporation

[0817] <Manufacture of photosensitive resin laminate>

[0818] The components shown in the following table {the numbers of the respective components represent the compounding amounts (parts by mass) in terms of solid components.} and ethanol measured in such a manner that the solid component concentration becomes 60% were stirred and mixed so that the compounding amounts in terms of the solid components of the respective components became the compounding amounts shown in the following table, to obtain a formulation for a photosensitive resin composition. A 16-μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., QS71) was used as the support film, and the above formulation was coated on its surface using a bar coater and then dried in a dryer at 95°C for 2.5 minutes. Thus, a photosensitive resin layer with a thickness of 25 μm was formed on the support film. Thus, a photosensitive resin laminate was obtained.

[0819] Next, a 19-μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “GF-818”) as a protective layer was pasted on the side of the above photosensitive resin layer opposite to the support film, thereby obtaining a laminate. Here, the laminate of the support film, the photosensitive resin layer, and the protective film was treated as a photosensitive resin laminate.

[0820] <Flattening of substrate>

[0821] The surface of a copper-clad laminate with a total thickness of 0.4 mm having a 18-μm-thick rolled copper foil laminated thereon was prepared. And this surface was cleaned with a 10 mass% H 2 SO 4 aqueous solution and then with pure water. The cleaned copper-clad laminate was preheated to 50°C.

[0822] <Lamination>

[0823] While peeling off the protective film from the photosensitive resin laminate, using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700), the copper-clad laminate preheated to 50°C was laminated at a roll temperature of 105°C in such a manner that the photosensitive resin layer was in contact with the surface of the above copper-clad laminate. Thus, a substrate for evaluation was obtained. The air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0824] <Exposure>

[0825] For the evaluation substrate after 2 hours of lamination, a prescribed drawing pattern for direct imaging (DI) exposure is used, and direct exposure is performed using a direct drawing exposure machine (FDi-3 manufactured by ORC Manufacturing Co., Ltd.). The exposure is performed using a Stouffer (Stouffer Industries) 41-step exposure meter as a mask, and the exposure amount is such that the highest remaining film step during subsequent development is 15 steps.

[0826] <Heating>

[0827] The evaluation substrate after 2 minutes of exposure is heated for 30 seconds using a forced-air constant temperature thermostat (DKM600 manufactured by YAMATO Scientific Co., Ltd.) set at 70°C.

[0828] <Development>

[0829] The support film is peeled off from the evaluation substrate. Then, using an alkali developer (a developer for dry film manufactured by Fuji Kiko Co., Ltd.), a 1% by mass aqueous solution of Na 2 CO 3 at 30°C is sprayed onto the photosensitive resin layer for a specified time to perform development. Then, pure water is sprayed onto the photosensitive resin layer for a specified time to perform water washing. Thus, a resist pattern is obtained on the evaluation substrate.

[0830] [Evaluation]

[0831] <Developability>

[0832] The minimum time required to completely dissolve the photosensitive resin layer in the unexposed portion is defined as the "shortest development time", and the developability is evaluated by classifying this shortest development time as described below. When the shortest development time is short, it is easy to shorten the development time. In addition, when good results are obtained in the <Developability> evaluation, an improvement in productivity during the production of a wiring substrate can be expected.

[0833] (Evaluation Criteria)

[0834] Excellent (E): The shortest development time is 19 seconds or less.

[0835] Good (G): The shortest development time is greater than 19 seconds and 23 seconds or less.

[0836] Poor (P): The shortest development time is greater than 23 seconds.

[0837] <Resolution>

[0838] A drawing pattern with L / S of x / x {x = 5, 8, and 10 μm} (unit: μm) is used (refer to Figure 1), evaluate the resolution. That is, for the substrate that has undergone the above <levelling> and <lamination>, perform direct imaging exposure as described in the depicted pattern. Then, form a resist pattern by performing the above <heating> and <development>. It should be noted that in <development>, develop and wash with water for twice the time of the shortest development time.

[0839] Figure 1 It is a top view showing a configuration example of the depicted pattern.

[0840] In the figure, in the depicted area 100, the exposed area is indicated by the symbol 10, and the unexposed area (hatched area) is indicated by the symbol 1. The unexposed area 1 has a prescribed width and extends along the X direction, and a plurality of such unexposed areas 1 are arranged at a prescribed interval in the width direction (Y direction). In this embodiment, the unexposed area 1 is removed through the <development> process. Therefore, based on Figure 1 the depicted pattern, the photosensitive resin layer is exposed, and theoretically, it is expected to form a resist pattern corresponding to the width (S: line pitch) of the unexposed area 1 and the width (L: line width) of the exposed area 10, with an L / S.

[0841] Observe the substrate on which the resist pattern is formed with an optical microscope at a magnification of 200 times, and then evaluate according to the following criteria. It should be noted that if the unexposed portion of the resist is not sufficiently removed during the above <development>, resist residue may occur.

[0842] (Evaluation criteria)

[0843] Excellent (E):

[0844] No collapse, bending, or defect is confirmed in the resist pattern with L / S = 5 μm / 5 μm. Also, no resist residue is confirmed between the patterns with L / S = 5 μm / 5 μm.

[0845] Good (G):

[0846] No collapse, bending, or defect is confirmed in the resist pattern with L / S = 8 μm / 8 μm. Also, no resist residue is confirmed between the patterns with L / S = 8 μm / 8 μm (excluding the case of "excellent (E)" evaluation).

[0847] Acceptable (A):

[0848] No collapse, bending, or defect is confirmed in the resist pattern with L / S = 10 μm / 10 μm. Also, no resist residue is confirmed between the patterns with L / S = 10 μm / 10 μm (excluding the cases of "excellent (E)" or "good (G)" evaluation).

[0849] Unacceptable (P):

[0850] Collapse, bending, or defects were confirmed in the resist pattern with L / S = 10 μm / 10 μm. Alternatively, resist residue was confirmed between the patterns with L / S = 5 μm / 5 μm, 8 μm / 8 μm, or 10 μm / 10 μm.

[0851] <Adhesion>

[0852] Using a drawn pattern with L / S = x / 200 {x = 5, 8, and 10 μm} (unit: μm) (refer to Figure 2 ), the adhesion was evaluated. That is, for the substrate that has undergone the above <planarization> and <lamination>, the drawn pattern was used for exposure. Then, a resist pattern was formed by performing the above <heating> and <development>. It should be noted that during <development>, development and water washing were performed for twice the time of the shortest development time.

[0853] Figure 2 It is a top view showing a configuration example of the drawn pattern.

[0854] In the figure, in the drawing area 100A, the exposed area is denoted by the symbol 10, and the unexposed area (hatched area) is denoted by the symbol 1. The exposed area 10 has a predetermined width and extends along the x direction, and a plurality of the exposed areas 10 are arranged at a predetermined interval in the width direction (y direction). In this embodiment, the unexposed area 1 is removed through the <development> process, and thus, based on Figure 2 the drawn pattern, it is theoretically expected to form a resist pattern with L / S corresponding to the width (L: line width) of the exposed area 10 and the width (S: line pitch) of the unexposed area 1.

[0855] The substrate on which the resist pattern was formed was observed with an optical microscope at a magnification of 100 times, and then evaluated according to the following criteria.

[0856] (Evaluation Criteria)

[0857] Excellent (E):

[0858] No bending or defects were confirmed in the resist pattern with L / S = 5 μm / 200 μm.

[0859] Good (G):

[0860] No bending or defects were confirmed in the resist pattern with L / S = 8 μm / 200 μm (excluding the cases evaluated as "excellent (E)").

[0861] Acceptable (A):

[0862] No bending or defects were confirmed in the resist pattern with L / S = 10 μm / 200 μm (excluding the cases evaluated as "excellent (E)" or "good (G)").

[0863] Not acceptable (P):

[0864] In the resist pattern with L / S = 10 μm / 200 μm, bending or defects were confirmed.

[0865] <Flexibility of the cured film>

[0866] The above <lamination> was performed on a flexible substrate {NIKKAN INDUSTRIES, NIKKAFLEX F - 30VC125RC11(H)} cut into a size of 200 mm × 250 mm, and a photosensitive resin layer was formed on the substrate. Then, exposure was performed at an energy level corresponding to a remaining step of 15 on a Stouffer (Stouffer Industries) step - wedge with a width of 1 inch and a length of 250 mm. Further, after development and water washing were performed in accordance with the above <development> for twice the time of the shortest development time, the substrate was cut into a width of 1.2 inches such that the cured photosensitive resin layer with a width of 1 inch was located at the center in the width direction, thereby producing a sample.

[0867] The mandrel test (cylindrical mandrel method; a bending resistance test in accordance with JIS K5600 - 5 - 1 - 1999) was performed using the produced sample. Then, the minimum diameter of the mandrel in which no "cracks" or "peeling from the substrate" were confirmed in the cured film on the sample was determined, and based on this diameter, the flexibility was evaluated according to the following criteria. The smaller this value is, the higher the flexibility.

[0868] (Evaluation criteria)

[0869] Excellent (E):

[0870] The minimum diameter of the mandrel in which no "cracks" or "peeling from the substrate" were confirmed in the cured film is 6 mm or less.

[0871] Good (G):

[0872] The minimum diameter of the mandrel in which no "cracks" or "peeling from the substrate" were confirmed in the cured film is 8 mm or less (excluding the case of "excellent (E)" evaluation).

[0873] Not acceptable (P):

[0874] The minimum diameter of the mandrel in which no "cracks" or "peeling from the substrate" were confirmed in the cured film is 10 mm or more (excluding the cases of "excellent (E)" or "good (G)" evaluation).

[0875] The observations of "cracks" and "peeling from the substrate" are carried out visually. The case where cracks are observed in the cured film belongs to "cracks", and the case where the cured film is observed to peel from the substrate belongs to "peeling from the substrate". It should be noted that the case where "defects" are observed in the cured film is treated as a case included in "cracks".

[0876] [Table 6]

[0877]

[0878] [Table 7]

[0879]

[0880] [Table 8]

[0881] Table 8

[0882]

[0883] [Table 9]

[0884]

[0885] [Table 10]

[0886] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 A1-1 A1-2 A1-4 A1-5 A1-6 A1-7 A2-1 14 6 A2-2 14 A2-3 14 A2-4 14 A2-5 56 56 56 A3-1 17 17 17 17 A3-2 A3-3 24 24 24 24 38 A3-4 42 A3-5 12 9 B-1 19 19 19 19 9 26 26 26 B-3 4 B-4 4 4 4 4 6 6 6 B-5 2 2 2 2 15 15 2 2 2 B-6 9 9 B-7 1 1 1 1 1 B-8 10 10 10 10 7 C-1 4.1 4.1 4.1 4.1 4.6 4.6 4.1 4.1 4.1 D-1 0.7 D-2 0.35 0.35 0.35 0.35 0.29 0.25 0.35 D-3 0.4 D-4 E-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E-2 0.08 0.08 0.08 0.08 0.08 0.08 0.03 0.03 0.03 E-3 E-4 0.05 0.05 0.05 E-5 0.025 0.025 0.025 0.025 0.025 0.025 E-6 0.01 0.01 0.01 0.01 0.01 E-7 0.01 0.01 0.01 E-8 0.012 0.012 0.012 0.012 0.004 0.012 Total 95.08 95.08 95.08 95.08 93.50 94.48 96.04 96.09 96.39

[0887] [Table 11]

[0888]

[0889] [Table 12]

[0890]

[0891] Industrial Applicability

[0892] [Industrial Applicability of "First Invention"]

[0893] 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 wirings in printed circuit boards and the like. The photosensitive resin composition of the present invention can suitably obtain the above-mentioned photosensitive resin laminate that is industrially applicable. The method for forming an anti-etching pattern can be used in the process for forming a wiring pattern.

[0894] [Industrial Applicability of "Related Method"]

[0895] The photosensitive resin composition of the present invention can be used to form wirings in printed circuit boards and the like. By using the photosensitive resin composition of the present invention, the above-mentioned photosensitive resin laminate that can be industrially utilized can be suitably obtained. The method for forming an etching pattern of the present invention can be suitably used in the process for forming a wiring pattern.

[0896] Explanation of Reference Numerals

[0897] 1: Un-exposed area (un-exposed portion)

[0898] 10: Exposed area (exposed portion)

[0899] 100, 100A: Drawn area

[0900] L: Line width

[0901] S: Line pitch

Claims

1. A photosensitive resin composition, comprising the following components: (A) An alkali-soluble polymer; (B) A compound having an ethylenically unsaturated double bond; (C) A polymerization initiator; and (D) A boron compound that absorbs h-rays and / or i-rays.

2. A photosensitive resin composition, comprising the following components: (A) An alkali-soluble polymer; (B) A compound having an ethylenically unsaturated double bond; and (C) A polymerization initiator; The photosensitive resin composition contains a boron compound that absorbs h-rays and / or i-rays as component (D), and component (B) contains a bifunctional compound having 2 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 photosensitive resin composition according to claim 1 or 2, wherein component (D) contains at least one compound selected from the group consisting of 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 ) shown in the formula (a); and at least one compound selected from the group consisting of the compounds represented by the following general formula (3), wherein, R 1 ~R 7 is a monovalent organic group, and a plurality of R 1 and R 5 in one molecule may be the same or different optionally In the formula, R 8 is a monovalent organic group, and R 9 is a divalent organic group.

5. The photosensitive resin composition according to claim 1 or 2, wherein in component (D), the absorption of h-rays and / or i-rays means that, by the following method of measurement, there is a wavelength with an absorbance (A3) of 0.008 or more in the range of 400 - 410 nm and / or 350 - 370 nm, (1) Prepare a toluene solution with a concentration of 5 ppm of the compound to be measured, use a quartz cell with a path length of 10 mm that is transmissive on both sides, measure the absorbance with a spectrophotometer, read the absorbance values obtained every 1 nm, and treat the read values as absorbance (A1); (2) Measure the absorbance of toluene alone by the same method as in (1) above, read the absorbance values obtained every 1 nm, and treat the read values as absorbance (A2); and (3) Subtract the absorbance (A2) at the same wavelength from the absorbance (A1), obtain the subtracted value (A1 - A2) every 1 nm, and treat this subtracted value (A1 - A2) as the absorbance (A3) at 5 ppm in the toluene solution.

6. The photosensitive resin composition according to claim 1 or 2, wherein in component (D), the absorption of h-rays and / or i-rays means that, by the following method of measurement, the absorbance (A3) is 0.008 or more at at least one of 405 nm and 365 nm, (4) Prepare a toluene solution with a concentration of 5 ppm of the compound to be measured, use a quartz cell with a path length of 10 mm that is transmissive on both sides, measure the absorbance with a spectrophotometer, read the absorbance values obtained every 1 nm, and treat the read values as absorbance (A1); (5) Measure the absorbance of toluene alone by the same method as in (1) above, read the absorbance values obtained every 1 nm, and treat the read values as absorbance (A2); and (6) Subtract the absorbance (A2) at the same wavelength from the absorbance (A1), and obtain the subtracted value (A1 - A2) every 1 nm. Treat this subtracted value (A1 - A2) as the absorbance (A3) at 5 ppm in the toluene solution.

7. The photosensitive resin composition according to claim 1 or 2, wherein, the component (D) includes those selected from the following general formula: R 2 -B(OH) 2 ; and R 3 -B(OR 1 ) 2 at least one compound in the group consisting of In the formula, R 1 ~R 3 represents a monovalent organic group, and a plurality of R 1 which may be present in one molecule may be the same or different optionally.

8. The photosensitive resin composition according to claim 4, wherein, the monovalent organic group is 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, any substituent containing a saturated or unsaturated heterocyclic group, or a substituent formed by substituting a hydrogen atom in these groups with a halogen atom, 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 component (D) includes a compound having an anthracene skeleton.

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

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

12. The photosensitive resin composition according to claim 1 or 2, wherein, the 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 component (D) includes 10-phenyl-9-anthracene boronic acid.

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

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

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

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

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

5.

19. A photosensitive resin laminate, which has: a support, and a photosensitive resin layer obtained from the photosensitive resin composition according to claim 1 or 2.

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

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

22. A method for forming an etching pattern, comprising the following steps: a laminating step of laminating the photosensitive resin layer in the photosensitive resin laminate according to claim 19 on a substrate; an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate; and a developing step of removing the unexposed portion of the photosensitive resin layer.

23. The method for forming an etching pattern according to claim 22, wherein, the component (D) is a compound that absorbs h-rays, in the exposure step, the photosensitive resin layer is exposed using light having a wavelength of 400 to 410 nm.

24. The method for forming an etching pattern according to claim 22, wherein, the component (D) is a compound that absorbs i-rays, in the exposure step, the photosensitive resin layer is exposed using light having a wavelength of 350 to 370 nm.

25. A method for forming a wiring board, comprising the following steps: a step of forming an etching pattern on a substrate using the photosensitive resin laminate according to claim 20; a step of etching or plating the substrate on which the etching pattern is formed to thereby form a conductor pattern; and a step of peeling the etching pattern from the substrate.

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