Photosensitive resin composition, photosensitive element, printed wiring board, and method for producing printed wiring board

Abstract

To provide a photosensitive resin composition capable of forming a permanent resist excellent in insulation reliability, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board.SOLUTION: The photosensitive resin composition according to the present disclosure includes (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) an isocyanate group-containing silane compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition for permanent resist, a photosensitive element, a printed wiring board, and a method for producing a printed wiring board. [Background technology]

[0002] In the field of printed wiring boards, permanent resists are formed on printed wiring boards. The permanent resists have the role of preventing corrosion of the conductor layers and maintaining electrical insulation between the conductor layers when the printed wiring board is in use. In recent years, permanent resists have also come to function as solder resist films that prevent solder from adhering to unnecessary portions of the conductor layers of the printed wiring board in processes such as flip-chip mounting and wire bonding mounting of semiconductor elements on the printed wiring board via solder.

[0003] Conventionally, permanent resists have been produced by screen printing using a thermosetting resin composition or by a photographic method using a photosensitive resin composition. For example, in flexible wiring boards using mounting methods such as FC (Flip Chip), TAB (Tape Automated Bonding), and COF (Chip On Film), a thermosetting resin paste is screen printed and thermally cured to form a permanent resist, except for the IC chip, electronic components, or LCD (Liquid Crystal Display) panel and connection wiring pattern area (see, for example, Patent Document 1).

[0004] In semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) mounted on electronic components, it is necessary to remove the permanent resist from the bonding area in order to (1) flip-chip mount a semiconductor element onto the semiconductor package substrate via solder, (2) wire-bond the semiconductor element to the semiconductor package substrate, and (3) solder-bond the semiconductor package substrate to a motherboard. A photographic method is used to form an image on the permanent resist. This method involves applying a photosensitive resin composition, drying it, and then selectively irradiating it with actinic rays such as ultraviolet light to harden it, and then removing only the unirradiated areas by development to form an image. Because of its ease of operation and its suitability for mass production, the photographic method is widely used in the electronic materials industry for forming images on photosensitive materials (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-198105 [Patent Document 2] Japanese Patent Application Publication No. 11-240930 Summary of the Invention [Problem to be solved by the invention]

[0006] In response to the increasing density of printed wiring boards, even higher performance is being demanded of permanent resists, and in particular, there is a demand for further improvement in insulation reliability.

[0007] An object of the present disclosure is to provide a photosensitive resin composition capable of forming a permanent resist with excellent insulation reliability, a photosensitive element and a printed wiring board using the photosensitive resin composition, and a method for producing a printed wiring board. [Means for solving the problem]

[0008] One aspect of the present disclosure relates to the following photosensitive resin composition, photosensitive element, printed wiring board, and method for producing a printed wiring board. [1] A photosensitive resin composition for permanent resist, comprising (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) an isocyanate group-containing silane compound. [2] The photosensitive resin composition according to the above [1], wherein the (D) isocyanate group-containing silane compound does not have a blocked isocyanate group. [3] The photosensitive resin composition according to [1] or [2] above, wherein the content of the (D) isocyanate group-containing silane compound is 9.5 parts by mass or less per 100 parts by mass of the (A) acid-modified vinyl group-containing resin. [4] The photosensitive resin composition according to any one of the above [1] to [3], further comprising (E) an inorganic filler. [5] The photosensitive resin composition according to any one of the above [1] to [4], further comprising (F) a thermosetting resin. [6] The photosensitive resin composition according to any one of the above [1] to [5], further comprising (G) an elastomer. [7] The photosensitive resin composition according to any one of the above [1] to [6], further comprising (H) a curing accelerator. [8] A photosensitive element comprising a support film and a photosensitive layer formed on the support film, wherein the photosensitive layer contains the photosensitive resin composition according to any one of [1] to [7] above. [9] A printed wiring board comprising a permanent resist containing a cured product of the photosensitive resin composition according to any one of [1] to [7] above.

[10] A method for producing a printed wiring board, comprising the steps of: forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of [1] to [7] above; exposing and developing the photosensitive layer to form a resist pattern; and curing the resist pattern to form a permanent resist.

[11] A method for manufacturing a printed wiring board, comprising the steps of: forming a photosensitive layer on a substrate using the photosensitive element described in [8] above; exposing and developing the photosensitive layer to form a resist pattern; and hardening the resist pattern to form a permanent resist. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a photosensitive resin composition capable of forming a permanent resist with excellent insulation reliability, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view that schematically illustrates a photosensitive element according to this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, one embodiment of the present disclosure will be specifically described, but the present disclosure is not limited thereto. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified, or unless they are clearly considered essential in principle. The same applies to numerical values ​​and their ranges, and they do not unduly limit the present disclosure.

[0012] In this disclosure, the term "layer" encompasses not only a structure with a shape formed over the entire surface when observed in a plan view, but also a structure with a shape formed only on a portion of the surface. In this disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In this disclosure, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit of a numerical range of a certain stage may be replaced with the upper or lower limit of a numerical range of another stage. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In this disclosure, "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.

[0013] In the present disclosure, the term "solid content" refers to the non-volatile content excluding volatile substances such as water and diluents contained in the photosensitive resin composition, and refers to the components that remain without evaporating or vaporizing when the resin composition is dried, and includes components that are liquid, syrup-like, or waxy at room temperature (25°C; the same applies hereinafter).

[0014] [Photosensitive resin composition] The photosensitive resin composition according to this embodiment contains (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) an isocyanate group-containing silane compound. The photosensitive resin composition according to this embodiment is a negative-type photosensitive resin composition, and a cured film of the photosensitive resin composition can be suitably used as a permanent resist. Each component contained in the photosensitive resin composition according to this embodiment will be described in detail below.

[0015] <Component (A): Acid-modified vinyl group-containing resin> The photosensitive resin composition according to this embodiment contains an acid-modified vinyl group-containing resin as component (A). The acid-modified vinyl group-containing resin is not particularly limited as long as it has a vinyl bond, which is a photopolymerizable ethylenically unsaturated bond, and an alkali-soluble acidic group.

[0016] Examples of the group having an ethylenically unsaturated bond contained in component (A) include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. Among these, from the viewpoints of reactivity and resolution, the group having an ethylenically unsaturated bond may be a (meth)acryloyl group. Examples of the acidic group contained in component (A) include a carboxy group, a sulfo group, and a phenolic hydroxyl group. Among these, from the viewpoint of resolution, the acidic group may be a carboxy group.

[0017] The component (A) may be an acid-modified vinyl group-containing epoxy derivative obtained by reacting a resin (A') (hereinafter referred to as "component (A')") obtained by reacting (a) an epoxy resin (hereinafter referred to as "component (a)") with (b) an ethylenically unsaturated group-containing organic acid (hereinafter referred to as "component (b)"), with (c) a saturated group- or unsaturated group-containing polybasic acid anhydride (hereinafter referred to as "component (c)").

[0018] Examples of acid-modified vinyl group-containing epoxy derivatives include acid-modified epoxy(meth)acrylates. Acid-modified epoxy(meth)acrylates are resins obtained by acid-modifying epoxy(meth)acrylate, which is a reaction product of components (a) and (b), with component (c). Examples of acid-modified epoxy(meth)acrylates include addition reaction products obtained by adding saturated or unsaturated polybasic acid anhydrides to esters obtained by reacting epoxy resins with vinyl group-containing monocarboxylic acids.

[0019] Examples of component (A) include an acid-modified vinyl group-containing resin (A1) (hereinafter referred to as "component (A1)") obtained by using a bisphenol novolac epoxy resin (a1) (hereinafter referred to as "epoxy resin (a1)") as component (a), and an acid-modified vinyl group-containing resin (A2) (hereinafter referred to as "component (A2)") obtained by using an epoxy resin (a2) other than epoxy resin (a1) (hereinafter referred to as "epoxy resin (a2)") as component (a). These may be used alone or in combination of two or more.

[0020] From the viewpoint of insulation reliability, the component (A) may consist solely of the component (A1). When the component (A1) and the component (A2) are used in combination as the component (A), the content of the component (A1) may be 60 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % or more, or 95 mass % or more, based on the total amount of the component (A), from the viewpoint of insulation reliability.

[0021] (Epoxy resin (a1)) Examples of the epoxy resin (a1) include epoxy resins having a structural unit represented by the following formula (I) or (II): The epoxy resin (a1) may be an epoxy resin having a structural unit represented by formula (I).

[0022] [ka]

[0023] In formula (I), R 11 represents a hydrogen atom or a methyl group, and multiple R 11 may be the same or different. 1 and Y 2 each independently represents a hydrogen atom or a glycidyl group, and Y 1 and Y 2 At least one of R is a glycidyl group. From the viewpoint of suppressing undercut and improving the linearity and resolution of the resist pattern contour, 11 may be a hydrogen atom, and from the viewpoint of further improving thermal shock resistance, Y 1and Y 2 may be a glycidyl group.

[0024] The number of structural units represented by formula (I) in the epoxy resin (a1) is 1 or more, and may be 10 to 100, 15 to 80, or 15 to 70. When the number of structural units is within the above range, it is easy to improve the linearity of the resist pattern contour, adhesion to the copper substrate, heat resistance, and electrical insulation. Here, the number of structural units represents an integer value in a single molecule, and represents a rational number that is an average value in an aggregate of multiple types of molecules. The same applies to the number of structural units in the following structural units.

[0025] [ka]

[0026] In formula (II), R 12 represents a hydrogen atom or a methyl group, and multiple R 12 may be the same or different. 3 and Y 4 each independently represents a hydrogen atom or a glycidyl group, and Y 3 and Y 4 At least one of R is a glycidyl group. From the viewpoint of suppressing undercut and improving the linearity and resolution of the resist pattern contour, 12 may be a hydrogen atom, and from the viewpoint of further improving thermal shock resistance, Y 3 and Y 4 may be a glycidyl group.

[0027] The number of structural units represented by formula (II) in the epoxy resin (a1) is 1 or more, and may be 10 to 100, 15 to 80, or 15 to 70. When the number of structural units is within the above range, it becomes easier to improve the linearity of the resist pattern contour, adhesion to a copper substrate, and heat resistance.

[0028] In formula (II), R 12 is a hydrogen atom, and Y 3 and Y 4The epoxy resin in which R is a glycidyl group is commercially available as the EXA-7376 series (trade name, manufactured by DIC Corporation). 12 is a methyl group, and Y 3 and Y 4 Epoxy resins in which the carboxyl group is a glycidyl group are commercially available as the EPON SU8 series (trade name, manufactured by Westlake).

[0029] (Epoxy resin (a2)) The epoxy resin (a2) is not particularly limited as long as it is an epoxy resin different from the epoxy resin (a1), but from the viewpoint of suppressing the occurrence of undercut and improving the linearity of the resist pattern contour, adhesion to the copper substrate, and resolution, it may be at least one selected from the group consisting of novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenolmethane type epoxy resins, and biphenyl type epoxy resins.

[0030] Examples of novolac-type epoxy resins include epoxy resins having a structural unit represented by the following formula (III). Examples of bisphenol A-type epoxy resins or bisphenol F-type epoxy resins include epoxy resins having a structural unit represented by the following formula (IV). Examples of triphenolmethane-type epoxy resins include epoxy resins having a structural unit represented by the following formula (V). Examples of biphenyl-type epoxy resins include epoxy resins having a structural unit represented by the following formula (VI).

[0031] As the epoxy resin (a2), a novolac epoxy resin having a structural unit represented by the following formula (III) may be used. An example of a novolac epoxy resin having such a structural unit is a novolac epoxy resin represented by the following formula (III').

[0032] [ka]

[0033] In formulas (III) and (III'), R 13 represents a hydrogen atom or a methyl group, and Y 5 represents a hydrogen atom or a glycidyl group, and Y 5 In formula (III'), n1 is a number of 1 or more, and at least one of R 13 and Y 5 and may be the same or different. From the viewpoint of suppressing the occurrence of undercut and improving the linearity and resolution of the resist pattern contour, R 13 may be a hydrogen atom.

[0034] In formula (III'), Y is a hydrogen atom. 5 and a glycidyl group, Y 5 From the viewpoint of suppressing the occurrence of undercut and improving the linearity and resolution of the resist pattern contour, the molar ratio of n1 to n2 may be 0 / 100 to 30 / 70 or 0 / 100 to 10 / 90. n1 is 1 or more, but may also be 10 to 200, 30 to 150, or 30 to 100. When n1 is within the above range, the linearity of the resist pattern contour, adhesion to a copper substrate, and heat resistance are likely to be improved.

[0035] Examples of the novolac epoxy resin represented by formula (III') include phenol novolac epoxy resin and cresol novolac epoxy resin. These novolac epoxy resins can be obtained, for example, by reacting a phenol novolac resin or a cresol novolac resin with epichlorohydrin using a known method.

[0036] Commercially available examples of the phenol novolac epoxy resin or cresol novolac epoxy resin represented by formula (III') include YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A, and YDPN-638 (all of which are product names manufactured by Nippon Steel Chemical & Material Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1027, and BREN-S (all of which are product names manufactured by Nippon Kayaku Co., Ltd.), and N-740, N-770, N-665, and N-673 (all of which are product names manufactured by DIC Corporation).

[0037] Examples of the epoxy resin (a2) include bisphenol A-type epoxy resins or bisphenol F-type epoxy resins having a structural unit represented by the following formula (IV): Epoxy resins having such a structural unit include bisphenol A-type epoxy resins or bisphenol F-type epoxy resins represented by the following formula (IV'):

[0038] [ka]

[0039] In formulas (IV) and (IV'), R 14 represents a hydrogen atom or a methyl group, and there are multiple R 14 may be the same or different, and Y 6 represents a hydrogen atom or a glycidyl group, and Y 6 In formula (IV'), n2 represents a number of 1 or more, and when n2 is 2 or more, a plurality of Y 6 may be the same or different.

[0040] From the viewpoint of suppressing the occurrence of undercut and improving the linearity and resolution of the resist pattern contour, R 14 may be a hydrogen atom, and from the viewpoint of further improving thermal shock resistance, Y 6may be a glycidyl group. n2 is 1 or greater, but may be 10 to 100, 10 to 80, or 15 to 60. When n2 is within the above range, the linearity of the resist pattern contour, adhesion to the copper substrate, and heat resistance are likely to be improved.

[0041] Y in formula (IV) 6 The bisphenol A type epoxy resin or bisphenol F type epoxy resin in which Y is a glycidyl group can be prepared by, for example, 6 is a hydrogen atom, the hydroxyl group (-OY 6 ) with epichlorohydrin.

[0042] To promote the reaction between hydroxyl groups and epichlorohydrin, the reaction may be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120° C. When the reaction temperature is within the above range, the reaction does not slow down too much, and side reactions can be suppressed.

[0043] Commercially available examples of the bisphenol A epoxy resin or bisphenol F epoxy resin represented by formula (IV') include jER807, jER825, jER827, jER828, jER834, jER1004F, jER1007FS, and jER1009F (all of which are product names manufactured by Mitsubishi Chemical Corporation), YD-8125, YDF-170, YDF-2001, YDF-2004, and YDF-8170C (all of which are product names manufactured by Nippon Steel Chemical & Material Co., Ltd.), and the like.

[0044] Examples of the epoxy resin (a2) include triphenolmethane-type epoxy resins having a structural unit represented by the following formula (V): Examples of the triphenolmethane-type epoxy resins having such a structural unit include triphenolmethane-type epoxy resins represented by the following formula (V'):

[0045] [ka]

[0046] In formulas (V) and (V'), Y 7 represents a hydrogen atom or a glycidyl group, and a plurality of Y 7 may be the same or different, and at least one Y 7 is a glycidyl group. In formula (V'), n3 is a number of 1 or more.

[0047] From the viewpoint of suppressing the occurrence of undercut and upper portion loss and improving the linearity and resolution of the resist pattern contour, Y 7 Y is a hydrogen atom in 7 and a glycidyl group, Y 7 The molar ratio of Y to Y may be 0 / 100 to 30 / 70. 7 At least one of these is a glycidyl group. n3 is 1 or greater, and may be 10 to 100, 15 to 80, or 15 to 70. When n3 is within the above range, the linearity of the resist pattern contour, adhesion to the copper substrate, and heat resistance are likely to be improved.

[0048] As the triphenolmethane type epoxy resin represented by formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

[0049] Examples of the epoxy resin (a2) include biphenyl-type epoxy resins having a structural unit represented by the following formula (VI): Examples of the biphenyl-type epoxy resins having such a structural unit include biphenyl-type epoxy resins represented by the following formula (VI'):

[0050] [ka]

[0051] In formulas (VI) and (VI'), Y 8represents a hydrogen atom or a glycidyl group, and a plurality of Y 8 may be the same or different, and at least one Y 8 is a glycidyl group. In formula (V'), n4 is a number of 1 or more.

[0052] As the biphenyl type epoxy resin represented by formula (VI'), for example, NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

[0053] The epoxy resin (a2) may contain at least one selected from the group consisting of novolac epoxy resins having a structural unit represented by formula (III), bisphenol A epoxy resins having a structural unit represented by formula (IV), and bisphenol F epoxy resins having a structural unit represented by formula (IV), or may contain a bisphenol F epoxy resin having a structural unit represented by formula (IV).

[0054] From the viewpoints of thermal shock resistance, warpage reduction, and resolution, a combination of component (A1) using a bisphenol novolac epoxy resin having a structural unit represented by formula (I) as component (a1) and component (A2) using a bisphenol A epoxy resin or bisphenol F epoxy resin having a structural unit represented by formula (IV) as component (a2) may be used.

[0055] (Ethylenically unsaturated group-containing organic acid (b)) Examples of component (b) include acrylic acid, acrylic acid derivatives such as acrylic acid dimers, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing (meth)acrylates and dibasic acid anhydrides, and half-ester compounds which are reaction products of vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides. Component (b) can be used alone or in combination of two or more.

[0056] The half-ester compound can be obtained, for example, by reacting a hydroxyl group-containing (meth)acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride.

[0057] Examples of hydroxyl group-containing (meth)acrylates, vinyl group-containing monoglycidyl ethers, and vinyl group-containing monoglycidyl esters include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycidyl (meth)acrylate.

[0058] Examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0059] In the reaction between component (a) and component (b), the ratio may be such that 0.6 to 1.05 equivalents of component (b) are used per equivalent of the epoxy groups in component (a), or 0.8 to 1.0 equivalents of component (b). Reaction at such a ratio tends to increase photosensitivity and result in excellent linearity of the resist pattern contour.

[0060] A polymerization inhibitor may be used in the reaction between component (a) and component (b) to prevent polymerization during the reaction. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol. One polymerization inhibitor may be used alone, or two or more polymerization inhibitors may be used in combination. From the viewpoint of improving stability, the amount of the polymerization inhibitor used may be 0.01 to 1 part by mass, 0.02 to 0.8 parts by mass, or 0.04 to 0.5 parts by mass per 100 parts by mass of the total of component (a) and component (b).

[0061] Component (A'), obtained by reacting components (a) and (b), has hydroxyl groups formed by a ring-opening addition reaction between the epoxy groups of component (a) and the carboxyl groups of component (b). By further reacting component (A') with component (c), an acid-modified vinyl-group-containing epoxy resin is obtained in which the hydroxyl groups of component (A') (including the hydroxyl groups originally present in component (a)) and the acid anhydride groups of component (c) are half-esterified.

[0062] (Polybasic acid anhydride (c)) Examples of component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, from the viewpoint of resolution, component (c) may be tetrahydrophthalic anhydride. Component (c) may be used alone or in combination of two or more.

[0063] If necessary, as component (a), for example, a hydrogenated bisphenol A type epoxy resin may be used in combination, or a styrene-maleic acid resin such as a hydroxyethyl (meth)acrylate modified product of a styrene-maleic anhydride copolymer may be used in combination.

[0064] In the reaction between component (A') and component (c), for example, the acid value of component (A) can be adjusted by reacting 0.1 to 1.0 equivalents of component (c) with 1 equivalent of hydroxyl groups in component (A').

[0065] The acid value of component (A) may be 30 to 150 mgKOH / g, 40 to 120 mgKOH / g, or 50 to 100 mgKOH / g. When component (A) has an acid value of 30 mgKOH / g or more, the photosensitive resin composition tends to have excellent solubility in dilute alkaline solutions. When component (A) has an acid value of 150 mgKOH / g or less, the electrical properties of the permanent resist are easily improved.

[0066] The weight average molecular weight (Mw) of component (A) is not particularly limited, and may be 3,000 to 30,000, 4,000 to 25,000, or 5,000 to 18,000, from the viewpoints of resolution, adhesion, heat resistance, and insulation reliability.

[0067] Mw can be measured by gel permeation chromatography (GPC). Mw can be measured, for example, under the following GPC conditions, and the value converted using a calibration curve of standard polystyrene can be used as Mw. The calibration curve can be created using a five-sample set ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) as standard polystyrene. GPC equipment: High-speed GPC equipment "HCL-8320GPC" (Tosoh Corporation) Detector: Differential refractometer or UV detector (Tosoh Corporation) Column: TSKgel SuperMultipore HZ-H column (column length: 15 cm, column inner diameter: 4.6 mm) (manufactured by Tosoh Corporation) Eluent: tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35mL / min Sample concentration: 10 mg / 5 mL of THF Injection volume: 20μL

[0068] From the viewpoint of the heat resistance, electrical properties, and chemical resistance of the permanent resist, the content of the component (A) may be 10% by mass or more, 15% by mass or more, 20% by mass or more, or 23% by mass or more, and may be 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 28% by mass or less, based on the total solid content of the photosensitive resin composition.

[0069] <(B) Component: Photopolymerizable compound> The photosensitive resin composition according to this embodiment contains a photopolymerizable compound (excluding the above-described component (A)) as component (B). Component (B) is not particularly limited as long as it is a compound having a functional group exhibiting photopolymerizability. Examples of the functional group exhibiting photopolymerizability include groups having an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group.

[0070] Examples of component (B) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; mono- or di(meth)acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol; (meth)acrylamide compounds such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; hexanediol, trimethylolpropane, pentaerythritol, and ditrimethylolpropane. Examples of the (B) component include polyhydric (meth)acrylates of polyhydric alcohols such as dipentaerythritol and tris-hydroxyethyl isocyanurate, or their ethylene oxide or propylene oxide adducts; (meth)acrylate compounds of ethylene oxide or propylene oxide adducts of phenolic compounds such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth)acrylate. The (B) component can be used singly or in combination of two or more.

[0071] From the viewpoint of achieving even better insulation reliability, component (B) may contain a (meth)acrylic compound having a (meth)acryloyl group. The (meth)acrylic compound may be a monofunctional (meth)acrylic compound or a polyfunctional (meth)acrylic compound. A "monofunctional (meth)acrylic compound" refers to a compound in which the total number of acryloyl groups and methacryloyl groups in one molecule is 1, and a "polyfunctional (meth)acrylic compound" refers to a compound in which the total number of acryloyl groups and methacryloyl groups in one molecule is 2 or more. From the viewpoint of achieving even better insulation reliability, the (meth)acrylic compound may contain a tetrafunctional or higher (meth)acrylic compound. Examples of tetrafunctional or higher (meth)acrylic compounds include pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, and propoxylated dipentaerythritol hexa(meth)acrylate.

[0072] The content of component (B) may be 1 mass % or more, 5 mass % or more, or 8 mass % or more, or 30 mass % or less, 20 mass % or less, or 15 mass % or less, based on the total solid content in the photosensitive resin composition. When the content of component (B) is 1 mass % or more, the exposed area is less likely to dissolve during development, and when it is 30 mass % or less, heat resistance is more easily improved.

[0073] <Component (C): Photopolymerization initiator> The photosensitive resin composition according to this embodiment contains a photopolymerization initiator as component (C). The component (C) is not particularly limited as long as it can polymerize the photopolymerizable compound as component (B). The component (C) can be used alone or in combination of two or more.

[0074] Examples of component (C) include acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, and N,N-dimethylaminoacetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; and thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. benzophenone compounds such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone (Michler's ketone), and 4-benzoyl-4'-methyldiphenyl sulfide; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime].

[0075] Component (C) may contain at least one compound selected from the group consisting of an acetophenone compound, a thioxanthone compound, a benzophenone compound, an oxime ester compound, and an acylphosphine oxide compound. Component (C) can be selected depending on the desired performance. Component (C) may contain an acetophenone compound, a thioxanthone compound, or an acylphosphine oxide compound from the viewpoint of improving solder heat resistance, an acylphosphine oxide compound from the viewpoint of improving the curability of the bottom portion by photobleaching, or an acetophenone compound from the viewpoint of being less likely to volatilize and generate outgassing.

[0076] When the component (C) contains an acylphosphine oxide compound, the content of the acylphosphine oxide compound may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on the total amount of the component (C), from the viewpoint of resolution.

[0077] The content of component (C) may be 0.01 mass% or more, 0.05 mass% or more, 0.10 mass% or more, or 0.15 mass% or more, or may be 5.0 mass% or less, 1.0 mass% or less, 0.5 mass% or less, 0.3 mass% or less, or 0.2 mass% or less, based on the total solid content of the photosensitive resin composition. When the content of component (C) is 0.01 mass% or more, the exposed area is less likely to dissolve during development, and when it is 5.0 mass% or less, a decrease in heat resistance is more easily suppressed.

[0078] <Component (D): Isocyanate group-containing silane compound> The photosensitive resin composition according to this embodiment includes an isocyanate group-containing silane compound as component (D). Component (D) is a silane compound having an isocyanate group (NCO group). By including component (D), the photosensitive resin composition according to this embodiment can improve the hydrophobicity of the permanent resist by reacting the isocyanate group of component (D) with the hydroxyl group of component (A) or the like, thereby forming a permanent resist with excellent insulation reliability.

[0079] The number of isocyanate groups contained in component (D) may be 1 or 2 or more. The isocyanate groups contained in component (D) may be blocked or unblocked. Component (D) may be a silane compound without a blocked isocyanate group (hereinafter referred to as "component (d1)"), a silane compound with a blocked isocyanate group (hereinafter referred to as "component (d2)"), or a mixture thereof.

[0080] Component (D) is commercially available. Examples of commercially available products of component (d1) include KBE-9007N (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) and (3-isocyanatopropyl)trimethoxysilane (product name, manufactured by Tokyo Chemical Industry Co., Ltd.). Examples of commercially available products of component (d2) include X-12-1308ES and X-12-1293 (product names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0081] From the viewpoint of achieving better insulation reliability, the component (D) may contain a compound represented by the following formula (1).

[0082] [ka]

[0083] In formula (1), R 1 , R 2 and R 3 each independently represents an alkoxy group having 1 to 2 carbon atoms (for example, a methoxy group or an ethoxy group), and R 4 represents an alkylene group having 1 to 10 carbon atoms (for example, an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 1 to 3 carbon atoms). 1 , R 2 and R 3 may be the same or different. 1 , R 2 , R 3 and R 4 The hydrogen atoms in R may be substituted. 1 , R 2 and R 3may be a methoxy group or an ethoxy group, and R 4 may be an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 3 carbon atoms (for example, a propylene group).

[0084] Examples of the compound represented by formula (1) include 3-isocyanatopropyltriethoxysilane and (3-isocyanatopropyl)trimethoxysilane.

[0085] From the viewpoint of achieving better insulation reliability, the content of component (D) may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 1.5 parts by mass or more, 2.0 parts by mass or more, 2.6 parts by mass or more, 2.8 parts by mass or more, or 3.0 parts by mass or more, or may be 9.5 parts by mass or less, 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, or 6.5 parts by mass or less, relative to 100 parts by mass of component (A). From the viewpoint of achieving better insulation reliability, the content of component (D) may be 0.05% by mass or more, 0.10% by mass or more, 0.30% by mass or more, or 0.50% by mass or more, or may be 8.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 2.5% by mass or less, or 2.0% by mass or less, based on the total solid content of the photosensitive resin composition.

[0086] <Component (E): Inorganic filler> The photosensitive resin composition according to this embodiment may further contain an inorganic filler as component (E). Component (E) may be a filler that has not been surface-treated, or may be a surface-treated filler. The surface-treated filler can be obtained by treating the surface of the inorganic filler with a surface treatment agent. Treating the surface of the inorganic filler improves the adhesive strength with component (A) at the filler interface, thereby improving the heat resistance and thermal shock resistance of the permanent resist. One type of surface-treated filler may be used alone, or two or more types may be used in combination.

[0087] Examples of inorganic fillers include silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), magnesium carbonate (MgCO3), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), and spinel (MgO·Al2O3 Examples of inorganic fillers include silica, mullite (3Al2O3·2SiO2), cordierite (2MgO·2Al2O3 / 5SiO2), talc (3MgO·4SiO2·H2O), aluminum titanate (TiO2·Al2O3), yttria-containing zirconia (Y2O3·ZrO2), barium silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), hydrotalcite, mica, calcined kaolin, and carbon (C). The inorganic filler may contain silica to improve heat resistance, or barium sulfate or a combination of silica and barium sulfate to improve heat resistance and adhesive strength.

[0088] Examples of surface treatment agents include organic zirconium compounds, organic titanium compounds, organic aluminum compounds, and organic silane compounds (excluding the above-mentioned component (D)). The method for surface treatment of the inorganic filler is not particularly limited. Surface-treated fillers can also be purchased as commercially available products.

[0089] Examples of organic zirconium compounds include zirconium tetrapropoxide, zirconium tetrabutoxide, normal propyl zirconate, normal butyl zirconate, and zirconium tetraacetylacetonate. Examples of organic titanium compounds include tetraethyl orthotitanate, tetrakis(2-ethylhexyl) orthotitanate, tetraisopropyl titanate, tetra normal butyl titanate, and titanium acetylacetonate. Examples of organic aluminum compounds include aluminum sec-butoxide. Examples of organic silane compounds include epoxy silane compounds, amino silane compounds, mercapto silane compounds, (meth)acryl silane compounds, vinyl silane compounds, alkyl silane compounds, fluorene skeleton-containing silane compounds, and benzotriazole group-containing silane compounds.

[0090] The elemental composition of aluminum on the surface of an inorganic filler that has been surface-treated with an organoaluminum compound can be appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. The elemental composition of silicon on the surface of an inorganic filler that has been surface-treated with an organosilane compound can be appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. The elemental composition of carbon on the surface of an inorganic filler can be appropriately selected from 10 to 30 atomic %, 15 to 25 atomic %, or 18 to 23 atomic %. These elemental compositions can be measured using XPS (X-ray photoelectric spectroscopy).

[0091] Silica filler surface-treated with an organoaluminum compound or an organosilane compound may be produced by treating the Adma Fine Silica series manufactured by Admatech Co., Ltd. with the above-mentioned organoaluminum compound or organosilane compound. Barium sulfate surface-treated with an organoaluminum compound or an organosilane compound is commercially available under the trade name "BFN40DC" manufactured by Nippon Solvay Co., Ltd.

[0092] From the viewpoint of resolution, the average particle size of component (E) may be 0.01 to 5 μm, 0.05 to 3 μm, 0.1 to 2 μm, or 0.15 to 1 μm. The average particle size of component (E) is the average particle size in a state where it is dispersed in the photosensitive resin composition, and is a value obtained by measurement according to the following procedure.

[0093] The photosensitive resin composition was diluted 1000 times with a solvent (methyl ethyl ketone), and the particle size distribution of the particles dispersed in the solvent was measured using a submicron particle analyzer (Beckman Coulter, Inc., product name "N5") at a refractive index of 1.38 in accordance with the international standard ISO 13321. The particle size at 50% cumulative (volume basis) in the particle size distribution was taken as the average particle size. The component (E) contained in the photosensitive layer formed using the photosensitive resin composition and its cured film could also be measured using the same procedure.

[0094] The content of the component (E) may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more, and may be 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the total solid content of the photosensitive resin composition.

[0095] <(F) Component: Thermosetting resin> The photosensitive resin composition according to this embodiment may contain a thermosetting resin as component (F). Use of component (F) can improve the heat resistance, adhesiveness, and chemical resistance of a cured film (permanent resist) formed from the photosensitive resin composition. The component (F) may be used alone or in combination of two or more.

[0096] Examples of component (F) include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins.

[0097] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, hydantoin type epoxy resins, triglycidyl isocyanurate, and bixylenol type epoxy resins.

[0098] The content of the component (F) may be 2 to 30 mass%, 5 to 25 mass%, or 8 to 20 mass%, based on the total solid content of the photosensitive resin composition. When the content of the component (F) is within the above range, the heat resistance of the formed cured film can be further improved while maintaining good developability.

[0099] <Component (G): Elastomer> The photosensitive resin composition according to this embodiment may further contain an elastomer as component (G). Adding component (G) to the photosensitive resin composition can suppress a decrease in flexibility and adhesive strength due to strain (internal stress) inside the resin caused by cure shrinkage of component (A). In other words, the flexibility and adhesive strength of the permanent resist formed from the photosensitive resin composition can be improved.

[0100] Examples of component (G) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and silicone-based elastomers. Component (G) may contain a thermoplastic elastomer. Thermoplastic elastomers are composed of a hard segment component that contributes to heat resistance and strength, and a soft segment component that contributes to flexibility and toughness. Among these, olefin-based elastomers, polyester-based elastomers, and acrylic elastomers are preferred, and from the viewpoint of resolution, olefin-based elastomers are more preferred. Component (G) can be used alone or in combination of two or more types.

[0101] The content of component (G) may be 0.5 parts by mass or more, 1.0 parts by mass or more, 2.0 parts by mass or more, or 3.0 parts by mass or more, and may be 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less, per 100 parts by mass of component (A). By keeping the content of component (G) within the above range, unexposed areas of the photosensitive layer become more easily eluted in a developer, and the elastic modulus of the permanent resist at high temperatures tends to be lower.

[0102] <Component (H): Curing accelerator> The photosensitive resin composition according to this embodiment may further contain a curing accelerator as the component (H).

[0103] Examples of component (H) include imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazides; organic acid salts or epoxy adducts thereof; amine complexes of boron trifluoride; and triazine derivatives such as ethyldiamino-s-triazine, 2,4-diamino-s-triazine, and 2,4-diamino-6-xylyl-s-triazine. From the viewpoint of insulation reliability, component (H) may include at least one selected from the group consisting of melamine and dicyandiamide.

[0104] From the viewpoint of achieving better insulation reliability, the content of the component (H) may be 0.02 mass % or more, 0.05 mass % or more, or 0.08 mass % or more, and may be 10 mass % or less, 5 mass % or less, 1 mass % or less, or 0.5 mass % or less, based on the total solid content of the photosensitive resin composition.

[0105] <Other ingredients> The photosensitive resin composition according to this embodiment may be mixed with a diluent such as an organic solvent to adjust the viscosity. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate.

[0106] When a diluent is used, the content of the diluent in the photosensitive resin composition may be 10 to 50 mass %, 20 to 40 mass %, or 25 to 35 mass %. By setting the content of the diluent within the above range, the coatability of the photosensitive resin composition is improved.

[0107] The photosensitive resin composition according to this embodiment may further contain various additives as needed. Examples of additives include polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based antifoaming agents; silane coupling agents; flame retardants such as phosphorus-based phosphate compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters; and pigments such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, titanium oxide, carbon black, and naphthalene black. These may be used alone or in combination of two or more.

[0108] The photosensitive resin composition according to this embodiment can be prepared by uniformly mixing the above-mentioned components using a roll mill, a bead mill, or the like.

[0109] [Photosensitive element] The photosensitive element according to this embodiment includes a support film and a photosensitive layer containing the above-described photosensitive resin composition. FIG. 1 is a cross-sectional view schematically illustrating the photosensitive element according to this embodiment. As shown in FIG. 1, the photosensitive element 1 includes a support film 10 and a photosensitive layer 20 formed on the support film 10. The solid content of each component other than the volatile substance in the photosensitive layer 20 may be within the numerical range of the solid content of each component in the above-described photosensitive resin composition.

[0110] The photosensitive element 1 can be produced, for example, by applying the photosensitive resin composition according to this embodiment onto a support film 10 by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating, and then drying the coating to form a photosensitive layer 20.

[0111] Examples of the support film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, and polyolefin films such as polypropylene and polyethylene. The thickness of the support film may be, for example, 5 to 100 μm. The thickness of the photosensitive layer may be, for example, 10 to 50 μm, 15 to 40 μm, or 20 to 30 μm.

[0112] The coating film can be dried by hot air drying, far infrared drying, or near infrared drying. The drying temperature may be 60 to 120° C., 70 to 110° C., or 80 to 100° C. The drying time may be 1 to 60 minutes, 2 to 30 minutes, or 3 to 20 minutes.

[0113] The photosensitive element 1 may further include a protective film 30 on the photosensitive layer 20 to cover the photosensitive layer 20. The photosensitive element 1 may also have the protective film 30 laminated on the surface of the photosensitive layer 20 opposite to the surface that contacts the support film 10. The protective film 30 may be, for example, a polymer film such as polyethylene or polypropylene. The protective film may be the same film as the support film, or may be a different film.

[0114] [Printed wiring board] The printed wiring board according to this embodiment includes a permanent resist containing a cured product of the photosensitive resin composition according to this embodiment. Because the printed wiring board according to this embodiment includes a permanent resist containing a cured product of the photosensitive resin composition according to this embodiment, the printed wiring board according to this embodiment has excellent insulation reliability.

[0115] The method for producing a printed wiring board according to this embodiment includes the steps of forming a photosensitive layer on a substrate using the above-described photosensitive resin composition or the above-described photosensitive element, exposing and developing the photosensitive layer to form a resist pattern, and curing the resist pattern to form a permanent resist. An example of each step will be described below.

[0116] First, a metal-clad laminate such as a copper-clad laminate is prepared as a substrate, and a photosensitive layer is formed on the substrate. When a photosensitive resin composition is used, the photosensitive resin composition may be applied to the substrate by a method such as screen printing, spraying, roll coating, curtain coating, or electrostatic coating, and the resulting coating film may be dried at 60 to 110°C to form the photosensitive layer. The thickness of the coating film may be 10 to 200 μm, 15 to 150 μm, 20 to 100 μm, or 23 to 50 μm. When a photosensitive element is used, the photosensitive layer may be formed by thermally laminating the photosensitive layer of the photosensitive element onto the substrate using a laminator.

[0117] Next, a negative mask is brought into contact with the photosensitive layer directly or through a transparent film such as a support film, and the layer is exposed to actinic rays. The unexposed areas are then dissolved and removed with a developer to form a resist pattern. Examples of actinic rays include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being preferred. Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. The exposure dose is 10 to 2000 mJ / cm. 2 , 100-1500mJ / cm 2 , or 300 to 1000 mJ / cm 2The developing method may be, for example, a dipping method or a spraying method. As the developer, for example, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, or tetramethylammonium hydroxide may be used.

[0118] Next, the formed resist pattern is subjected to at least one of post-exposure and post-heating treatment to sufficiently harden it, thereby forming a permanent resist. The exposure dose of the post-exposure is 100 to 5000 mJ / cm 2 2 , 500~2000mJ / cm 2 , or 700 to 1500 mJ / cm 2 The heating temperature for post-heating may be 100 to 200°C, 120 to 180°C, or 135 to 165°C. The heating time for post-heating may be 5 minutes to 6 hours, 10 minutes to 3 hours, or 30 minutes to 2 hours. The thickness of the permanent resist may be 10 to 50 μm, 15 to 40 μm, or 20 to 30 μm.

[0119] The permanent resist according to this embodiment can be used as an interlayer insulating layer or a surface protective layer of a semiconductor element. A semiconductor element having an interlayer insulating layer or a surface protective layer formed from a cured film of the above-described photosensitive resin composition, and an electronic device including the semiconductor element can be produced. The semiconductor element may be, for example, a memory, a package, or the like having a multilayer wiring structure, a rewiring structure, or the like. Examples of electronic devices include mobile phones, smartphones, tablet terminals, personal computers, and hard disk suspensions. By providing a patterned cured film formed from the photosensitive resin composition according to this embodiment, semiconductor elements and electronic devices with excellent insulation reliability can be provided. [Example]

[0120] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0121] (Synthesis of component (A)) A flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with bisphenol F novolac epoxy resin (manufactured by DIC Corporation, trade name "EXA-7376"; in formula (II), Y 3 and Y 4 is a glycidyl group, R 12 350 parts by weight of bisphenol F novolac epoxy resin (epoxy equivalent: 186 g / eq) having a structure in which ⁻ is a hydrogen atom, 70 parts by weight of acrylic acid, 0.5 parts by weight of methylhydroquinone, and 120 parts by weight of carbitol acetate were charged and reacted with stirring at 90°C until the mixture was completely dissolved. The resulting solution was then cooled to 60°C, and 2 parts by weight of triphenylphosphine was added. The mixture was then reacted at 100°C until the acid value of the solution reached 1 mgKOH / g or less. To the reacted solution, 98 parts by weight of tetrahydrophthalic anhydride (THPAC) and 85 parts by weight of carbitol acetate were added and reacted at 80°C for 6 hours. The reaction solution was then cooled to room temperature to obtain a solution (solids concentration: 73% by weight) of THPAC-modified bisphenol F novolac epoxy acrylate (hereinafter sometimes referred to as "A-1") as component (A1).

[0122] The following materials were prepared as components (B) to (H). B-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA") C-1: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resins BV, trade name "Omnirad TPOH") C-2: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (manufactured by BASF Japan Ltd., trade name "Irgacure OXE02") C-3: 2,4-diethylthioxanthone (manufactured by IGM Resins BV, trade name "Omnirad DETX") D-1: 3-Isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBE-9007N") E-1: Silica filler (manufactured by Admatechs Co., Ltd., product name "SO-C2") E-2: Silica filler (manufactured by Admatechs Co., Ltd., product name "SO-C1") F-1: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "YL980") F-2: Phenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "RE-306") G-1: Epoxy-modified polybutadiene (manufactured by Daicel Corporation, product name "PB-3600") H-1: Melamine (Nissan Chemical Co., Ltd.)

[0123] [Photosensitive resin composition] The components were blended in the amounts (parts by mass, solid content equivalent) shown in Table 1 below and kneaded using a three-roll mill. Then, carbitol acetate was added so that the solid content concentration became 70% by mass, thereby obtaining a photosensitive resin composition.

[0124] [Photosensitive element] A 25 μm-thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "G2-25") was prepared as a support film. A solution prepared by diluting the photosensitive resin composition with methyl ethyl ketone was applied to the support film so that the thickness after drying was 25 μm. The solution was then dried at 75°C for 15 minutes using a hot air convection dryer to form a photosensitive layer. Next, a polyethylene film (manufactured by Tamapoly Co., Ltd., product name "NF-15") was attached as a protective film to the surface of the photosensitive layer opposite the side in contact with the support film, thereby obtaining a photosensitive element.

[0125] [Insulation reliability (HAST resistance)] Using a printed wiring board substrate (MCL-E-679FG, product name, manufactured by Resonac Corporation) in which 12 μm thick copper foil was laminated to a glass epoxy base material, interdigital electrodes with a line / space (wiring width / wiring spacing) of 14 μm / 14 μm were fabricated using the MSAP (Modified Semi-Additive Process) method, and this was used as the evaluation substrate.

[0126] The protective film was peeled off from the photosensitive element, and the exposed photosensitive layer was placed in contact with the interdigital electrodes on the evaluation substrate. The substrate was then laminated using a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., product name "MVLP-500") to obtain a laminate. The lamination conditions were a press hot plate temperature of 70°C, a vacuuming time of 20 seconds, a laminating press time of 20 seconds, an atmospheric pressure of 4 KPa or less, and a pressure of 0.4 MPa. The laminate was then left at room temperature for at least one hour, and then exposed to 500 mJ / cm using a direct imaging exposure device "DXP-3512" (manufactured by Oak Seisakusho Co., Ltd.) with an ultra-high pressure mercury lamp as a light source. 2 The entire surface of the photosensitive layer was exposed to an exposure dose of 2000 mJ / cm. Thereafter, the support film was peeled off from the photosensitive layer, and the layer was spray-developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at 30°C. Next, the developed photosensitive layer was exposed to an ultraviolet light exposure device at 2000 mJ / cm. 2 After post-exposure at an exposure dose of 1000 ppm, the substrate was heated at 170° C. for 1 hour to prepare a test piece having a cured film on the evaluation substrate.

[0127] The test piece was exposed to conditions of 130°C, 85% RH, and 15 V, and the change in the resistance value between the electrodes was measured. -6 The time when the resistance became Ω or less was taken as the time when copper migration occurred, and the insulation reliability was evaluated according to the following criteria. A: No copper migration occurred even after 200 hours. B: The time for which copper migration occurred was 100 hours or more but less than 200 hours. C: The time required for copper migration to occur was less than 100 hours.

[0128] [Table 1] [Explanation of symbols]

[0129] 1...photosensitive element, 10...support film, 20...photosensitive layer, 30...protective film.

Claims

1. A photosensitive resin composition for permanent resist, comprising (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) an isocyanate group-containing silane compound.

2. The photosensitive resin composition according to claim 1 , wherein the (D) isocyanate group-containing silane compound does not have a blocked isocyanate group.

3. 2. The photosensitive resin composition according to claim 1, wherein the content of the isocyanate group-containing silane compound (D) is 9.5 parts by mass or less relative to 100 parts by mass of the acid-modified vinyl group-containing resin (A).

4. The photosensitive resin composition according to claim 1 , further comprising (E) an inorganic filler.

5. The photosensitive resin composition according to claim 1 , further comprising (F) a thermosetting resin.

6. The photosensitive resin composition according to claim 1 , further comprising (G) an elastomer.

7. The photosensitive resin composition according to claim 1 , further comprising (H) a curing accelerator.

8. A support film and a photosensitive layer formed on the support film, A photosensitive element, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of claims 1 to 7.

9. A printed wiring board comprising a permanent resist comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 7.

10. forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 7; exposing and developing the photosensitive layer to form a resist pattern; hardening the resist pattern to form a permanent resist; A method for manufacturing a printed wiring board, comprising:

11. forming a photosensitive layer on a substrate using the photosensitive element of claim 8; exposing and developing the photosensitive layer to form a resist pattern; hardening the resist pattern to form a permanent resist; A method for manufacturing a printed wiring board, comprising:

Images