Photosensitive resin composition, photosensitive element, and printed wiring board

Abstract

This photosensitive resin composition contains (A) acid-modified vinyl group-containing resin, (B) thermosetting resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) an inorganic filler. The (E) inorganic filler contains SiO2 or TiO2. The total content of SiO2 and TiO2 is 98 mass% or more with respect to the total amount of the (E) inorganic filler as 100 mass%, and the calcium concentration is less than 100 mass ppm, .

Description

Photosensitive resin composition, photosensitive element, and printed wiring board

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive element, and a printed wiring board.

[0002] As the performance of various electronic devices improves, the integration of semiconductors is becoming more and more advanced. Accordingly, permanent resists (solder resists) formed on printed wiring boards, semiconductor package substrates, etc. are required to have improved heat resistance and mechanical properties, as well as finer patterning.

[0003] It has been investigated to add inorganic substances having a size of about 10 to 5000 nm to photosensitive resin compositions used for forming solder resists in order to improve, for example, heat resistance and mechanical properties (see Patent Document 1).

[0004] JP 2010-145425 A

[0005] However, conventional solder resists leave inorganic residues after dry etching, necessitating a step of removing the inorganic residues, which tends to reduce manufacturing efficiency.

[0006] The present disclosure has been made in view of the above circumstances, and aims to provide a photosensitive resin composition and a photosensitive element that are less likely to leave inorganic residues after dry etching treatment. Another aim of the present disclosure is to provide a printed wiring board having a permanent resist containing a cured product of the photosensitive resin composition.

[0007] In order to solve the above problems, the present disclosure provides the following photosensitive resin composition, photosensitive element, and printed wiring board.

[0008] [1] A composition comprising (A) an acid-modified vinyl group-containing resin, (B) a thermosetting resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) an inorganic filler, wherein the inorganic filler (E) is SiO ２ or TiO ２ and the SiO ２ and the above TiO ２[2] A photosensitive resin composition in which the total content of the inorganic filler (E) is 98% by mass or more, based on 100% by mass of the total amount of the inorganic filler (E), and the calcium concentration is less than 100 ppm by mass. ２ The photosensitive resin composition according to [1] above, wherein the calcium concentration is 50 ppm by mass or less. [3] The photosensitive resin composition according to [1] or [2] above, wherein the calcium concentration is 50 ppm by mass or less. [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the content of the inorganic filler (E) is 5% by mass or more and 70% by mass or less, based on the total solid content of the photosensitive resin composition. [5] The photosensitive resin composition according to any one of [1] to [4] above, wherein the average particle size of the inorganic filler (E) is 100 μm or more and 550 μm or less. [6] A photosensitive element comprising, in this order, a support film, a photosensitive layer, and a protective film, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of [1] to [5] above. [7] A printed wiring board comprising a permanent resist comprising a cured product of the photosensitive resin composition according to any one of [1] to [5] above.

[0009] According to the present disclosure, it is possible to provide a photosensitive resin composition and a photosensitive element that are less likely to leave inorganic residues after dry etching treatment, and a printed wiring board having a permanent resist containing a cured product of the photosensitive resin composition.

[0010] Fig. 1 is a cross-sectional view schematically showing a photosensitive element according to the present embodiment. Fig. 2 is a view showing the results of electron microscopy of the etched surface of Example 1. Fig. 3 is a view showing the results of electron microscopy of the etched surface of Comparative Example 1. Fig. 4 is a view showing the results of electron microscopy of the etched surface of Comparative Example 4.

[0011] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, 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 function of the process is achieved. The term "layer" encompasses not only a structure that is formed over the entire surface when observed in a plan view, but also a structure that is formed only on a portion of the surface. Numerical ranges indicated using "to" indicate ranges that include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, 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. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples.

[0012] When referring to the amount of each component in a composition in this specification, if there are multiple substances corresponding to each component in the composition, the total amount of those multiple substances present in the composition is meant unless otherwise specified.

[0013] In this specification, "(meth)acrylate" means at least one of "acrylate" and its corresponding "methacrylate," and the same applies to other similar expressions such as (meth)acrylic acid and (meth)acryloyl. In this specification, "solid content" refers to the non-volatile content excluding volatile substances (water, solvent, etc.) contained in the photosensitive resin composition, and includes components that are liquid, syrup-like, or waxy at room temperature (around 25°C).

[0014] [Photosensitive Resin Composition] The photosensitive resin composition according to this embodiment contains (A) an acid-modified vinyl group-containing resin (hereinafter also referred to as "component (A)"), (B) a thermosetting resin (hereinafter also referred to as "component (B)"), (C) a photopolymerizable compound (hereinafter also referred to as "component (C)"), (D) a photopolymerization initiator (hereinafter also referred to as "component (D)"), and (E) an inorganic filler (hereinafter also referred to as "component (E)"), wherein the inorganic filler (E) is a SiO ２ or TiO ２ and the SiO ２ and the above TiO ２The total content of the inorganic filler (E) is 98% by mass or more, where the total amount of the inorganic filler (E) is 100% by mass, and the calcium concentration is less than 100 ppm by mass. The photosensitive resin composition according to this embodiment is a negative photosensitive resin composition, and a cured film of the photosensitive resin composition can be used as a permanent resist. Each component used in the photosensitive resin composition according to this embodiment will be described in more 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 that 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, a (meth)acryloyl group may be used from the viewpoint of reactivity and resolution. Examples of the acidic group contained in component (A) include a carboxy group, a sulfo group, and a phenolic hydroxyl group. Among these, a carboxy group may be used as the acidic group from the viewpoint of resolution.

[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) (hereinafter referred to as "epoxy resin (a2)") other than epoxy resin (a1) as component (a). These can be used alone or in combination of two or more.

[0020] (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).

[0021]

[0022] In formula (I), R １１ represents a hydrogen atom or a methyl group, and a plurality of 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 the occurrence of 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 １ and Y ２ may be a glycidyl group.

[0023] 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, the linearity of the resist pattern contour, adhesion to the copper substrate, heat resistance, and electrical insulation are easily improved. 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 hereinafter to the number of structural units in structural units.

[0024]

[0025] In formula (II), R １２ represents a hydrogen atom or a methyl group, and a plurality of 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 the occurrence of 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.

[0026] 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.

[0027] In formula (II), R １２ is a hydrogen atom, and Y ３ and Y ４ The 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 ４Epoxy resins in which the carboxyl group is a glycidyl group are commercially available as EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

[0028] (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 viewpoints 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 type 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.

[0029] Examples of novolac-type epoxy resins include epoxy resins having a structural unit represented by the following formula (III): Bisphenol A-type epoxy resins or bisphenol F-type epoxy resins include epoxy resins having a structural unit represented by the following formula (IV): Triphenolmethane-type epoxy resins include epoxy resins having a structural unit represented by the following formula (V): Biphenyl-type epoxy resins include epoxy resins having a structural unit represented by the following formula (VI):

[0030] The epoxy resin (a2) is preferably a novolac epoxy resin having a structural unit represented by the following formula (III): An example of a novolac epoxy resin having such a structural unit is a novolac epoxy resin represented by the following formula (III'):

[0031]

[0032] 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 At least one of n is a glycidyl group. １ is a number equal to or greater than 1, and a plurality of R １３ and Y ５From 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.

[0033] In formula (III′), Y is a hydrogen atom. ５ and Y, a glycidyl group 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 n to n may be 0 / 100 to 30 / 70 or 0 / 100 to 10 / 90. １ is 1 or more, but may be 10 to 200, 30 to 150, or 30 to 100. １ When the amount of the resist film falls within the above range, the linearity of the resist pattern contour, adhesion to the copper substrate, and heat resistance are likely to be improved.

[0034] 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.

[0035] Examples of the phenol novolac epoxy resin or cresol novolac epoxy resin represented by formula (III') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (all of which are trade names manufactured by Nippon Steel Chemical & Material Co., Ltd.), DEN-431, DEN-439 (all of which are trade names manufactured by The Dow Chemical Company), EOCN-120, EOCN- Commercially available examples include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, and BREN (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.), EPN-1138, EPN-1235, and EPN-1299 (all of which are trade names manufactured by BASF), and N-730, N-770, N-865, N-665, N-673, VH-4150, and VH-4240 (all of which are trade names manufactured by DIC Corporation).

[0036] The epoxy resin (a2) is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin having a structural unit represented by the following formula (IV): Epoxy resins having such a structural unit include, for example, bisphenol A type epoxy resins or bisphenol F type epoxy resins represented by the following formula (IV'):

[0037]

[0038] 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. ２ represents a number of 1 or more, and n ２ If there are two or more Y ６ may be the same or different, and at least one Y ６ is a glycidyl group.

[0039] 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 ６ may be a glycidyl group. ２ represents 1 or more, but may be 10 to 100, 10 to 80, or 15 to 60. ２ When the amount of the resist film falls within the above range, the linearity of the resist pattern contour, adhesion to the copper substrate, and heat resistance are likely to be improved.

[0040] 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, for example, ６ is a hydrogen atom, ６ ) with epichlorohydrin.

[0041] 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 become too slow, and side reactions can be suppressed.

[0042] Examples of commercially available bisphenol A epoxy resins or bisphenol F epoxy resins represented by formula (IV') include jER807, jER815, jER825, jER827, jER828, jER834, jER1001, jER1004, jER1007, and jER1009 (all of which are trade names manufactured by Mitsubishi Chemical Corporation), DER-330, DER-301, and DER-361 (all of which are trade names manufactured by The Dow Chemical Company), and YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (all of which are trade names manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0043] The epoxy resin (a2) is preferably a triphenolmethane-type epoxy resin having a structural unit represented by the following formula (V): An example of a triphenolmethane-type epoxy resin having such a structural unit is a triphenolmethane-type epoxy resin represented by the following formula (V'):

[0044]

[0045] 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. ３ indicates a number of 1 or more.

[0046] 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 Y, a glycidyl group ７The molar ratio of Y to Y may be 0 / 100 to 30 / 70. ７ At least one of the groups is a glycidyl group. ３ is 1 or more, but may be 10 to 100, 15 to 80, or 15 to 70. ３ When the amount of the resist film falls within the above range, the linearity of the resist pattern contour, adhesion to the copper substrate, and heat resistance are likely to be improved.

[0047] 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.

[0048] The epoxy resin (a2) is preferably a biphenyl-type epoxy resin having a structural unit represented by the following formula (VI): An example of a biphenyl-type epoxy resin having such a structural unit is a biphenyl-type epoxy resin represented by the following formula (VI'):

[0049]

[0050] In formulas (VI) and (VI′), Y ８ represents 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. ４ indicates a number of 1 or more.

[0051] As the biphenyl type epoxy resin represented by formula (VI'), for example, NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.), etc. are commercially available.

[0052] The epoxy resin (a2) is preferably 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), and more preferably bisphenol F epoxy resins having a structural unit represented by formula (IV).

[0053] From the viewpoints of thermal shock resistance, warpage reduction, and resolution, a combination of a component (A1) using a bisphenol novolac epoxy resin having a structural unit represented by the above formula (I) as the component (a1) and a component (A2) using a bisphenol A epoxy resin or bisphenol F epoxy resin having a structural unit represented by the formula (IV) as the component (a2) may be used.

[0054] (Ethylenically Unsaturated Group-Containing Organic Acid (b)) Examples of the 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. The component (b) can be used alone or in combination of two or more.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] In the reaction between component (a) and component (b), the reaction may be carried out in a ratio such that 0.6 to 1.05 equivalents of component (b) are used per equivalent of the epoxy groups in component (a), or in a ratio such that 0.8 to 1.0 equivalents of component (b) are used per equivalent of the epoxy groups in component (a). By carrying out the reaction in such a ratio, photosensitivity increases and the linearity of the resist pattern contour tends to be excellent.

[0059] The components (a) and (b) can be dissolved in an organic solvent and reacted. 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; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The organic solvents may be used alone or in combination of two or more.

[0060] A catalyst may be used to promote the reaction between component (a) and component (b). Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. The catalyst may be used alone or in combination of two or more.

[0061] From the viewpoint of promoting the reaction between the component (a) and the component (b), the amount of the catalyst used may be 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass relative to 100 parts by mass of the total of the component (a) and the component (b).

[0062] 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, relative to 100 parts by mass of the total of component (a) and component (b).

[0063] The reaction temperature between the components (a) and (b) may be 60 to 150°C, 80 to 120°C, or 90 to 110°C from the viewpoint of productivity.

[0064] 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.

[0065] (Polybasic Acid Anhydride (c)) Examples of the 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, tetrahydrophthalic anhydride is preferred from the viewpoint of resolution. The component (c) may be used alone or in combination of two or more.

[0066] The reaction temperature of the component (A') and the component (c) may be 50 to 150°C, 60 to 120°C, or 70 to 100°C from the viewpoint of productivity.

[0067] 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.

[0068] In the reaction of component (A') with 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 one equivalent of hydroxyl groups in component (A').

[0069] 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 the acid value of component (A) is 30 mgKOH / g or more, the photosensitive resin composition tends to have excellent solubility in a dilute alkaline solution. When the acid value of component (A) is 150 mgKOH / g or less, the electrical properties of the permanent resist are easily improved.

[0070] 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 electrical insulation.

[0071] 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 apparatus: High-speed GPC apparatus "HCL-8320GPC" (manufactured by Tosoh Corporation) Detector: Differential refractometer or UV detector (manufactured by Tosoh Corporation) Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm) (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran (THF) Measurement temperature: 40°C Flow rate: 0.35 mL / min Sample concentration: 10 mg / 5 mL THF Injection amount: 20 μL

[0072] From the viewpoint of improving the heat resistance, electrical properties, and chemical resistance of the permanent resist, the content of the component (A) in the photosensitive resin composition may be 20 to 80 mass %, 25 to 70 mass %, or 30 to 50 mass % based on the total solid content of the photosensitive resin composition.

[0073] When the component (A1) and the component (A2) are used in combination as the component (A), the total content of the components (A1) and (A2) in the component (A) may be 80 to 100 mass%, 90 to 100 mass%, 95 to 100 mass%, or 100 mass%, based on the total amount of the component (A), from the viewpoints of linearity of the resist pattern contour, resistance to electroless plating, and heat resistance. When the component (A1) or the component (A2) is used alone, the amount can also be appropriately selected from the above ranges.

[0074] When the component (A) is a combination of the component (A1) and the component (A2), the mass ratio (A1 / A2) thereof may be 20 / 80 to 90 / 10, 30 / 70 to 80 / 20, 40 / 60 to 75 / 25, or 50 / 50 to 70 / 30, from the viewpoints of linearity of the resist pattern contour, resistance to electroless plating, and heat resistance.

[0075] (Component (B): Thermosetting Resin) The photosensitive resin composition according to this embodiment contains a thermosetting resin as component (B). By using component (B), it is possible to improve the heat resistance, adhesiveness, chemical resistance, etc. of a cured film (permanent resist) formed from the photosensitive resin composition. The component (B) may be used alone or in combination of two or more.

[0076] Examples of component (B) 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.

[0077] 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, phenol 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.

[0078] The content of the component (B) 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 (B) is within the above range, the heat resistance of the formed cured film can be further improved while maintaining good developability.

[0079] (Component (C): Photopolymerizable Compound) The photosensitive resin composition according to this embodiment contains a photopolymerizable compound as component (C) from the viewpoint of improving chemical resistance after exposure and increasing the difference in developer resistance between exposed and unexposed areas. The component (C) is not particularly limited as long as it is a photopolymerizable compound having an ethylenically unsaturated group and no acidic group.

[0080] Examples of the component (C) include a photopolymerizable compound having one ethylenically unsaturated group, a photopolymerizable compound having two ethylenically unsaturated groups, and a photopolymerizable compound having three or more ethylenically unsaturated groups.

[0081] Examples of photopolymerizable compounds having one ethylenically unsaturated group include (meth)acrylic acid and (meth)acrylic acid alkyl esters. Examples of (meth)acrylic acid alkyl esters include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, and (meth)acrylic acid hydroxyethyl ester.

[0082] Examples of photopolymerizable compounds having two ethylenically unsaturated groups include polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloxypolyethoxypolypropoxyphenyl)propane, and bisphenol A diglycidyl ether di(meth)acrylate.

[0083] Examples of photopolymerizable compounds having three or more ethylenically unsaturated groups include (meth)acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a skeleton derived from tetramethylolmethane, such as tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from pentaerythritol, such as pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from dipentaerythritol, such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane, such as ditrimethylolpropane tetra(meth)acrylate; and (meth)acrylate compounds having a skeleton derived from diglycerin.

[0084] Among these, from the viewpoint of improving chemical resistance after exposure and increasing the difference in developer resistance between exposed and unexposed areas, (meth)acrylate compounds having a skeleton derived from dipentaerythritol are preferred, and dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are more preferred.

[0085] The content of the component (C) may be 1 to 20 mass %, 2 to 15 mass %, or 4 to 12 mass %, based on the total solid content of the photosensitive resin composition.

[0086] (Component (D): Photopolymerization Initiator) The photopolymerization initiator serving as component (D) is not particularly limited as long as it can polymerize component (A) or component (C). As component (D), one type may be used alone, or two or more types may be used in combination.

[0087] Examples of the component (D) include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 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-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, Acetophenone compounds such as N,N-dimethylaminoacetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal. benzophenone compounds such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer. imidazole compounds such as 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;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]; and tertiary amine compounds such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine.

[0088] The content of the component (D) in the photosensitive resin composition is not particularly limited, but may be 0.1 to 15 mass%, 0.15 to 10 mass%, or 0.2 to 5 mass%, based on the total solid content of the photosensitive resin composition.

[0089] (Component (E): Inorganic Filler) Component (E) is SiO ２ (silica, silicon dioxide) or TiO ２ (titanium dioxide), SiO ２ and TiO ２ In the photosensitive resin composition according to this embodiment, the component (E) is contained in an amount within the above range, so that the total amount of SiO is reduced during dry etching treatment after the formation of the solder resist. ２ and TiO ２ is removed as a gas through a chemical reaction, so inorganic residues are unlikely to be generated. ２ and TiO ２ When dry etching is performed with a gas species containing fluorine atoms, CO, CO ２ , NO, NO ２ , SiF ４ , TiF ４ and is removed as a gas.

[0090] From the viewpoint of making it more difficult to generate inorganic residues, SiO ２ and TiO ２The total content of the components (E) may be 98.5% by mass or more, 99% by mass or more, or 100% by mass, where the total amount of the component (E) is 100% by mass.

[0091] From the viewpoint of making it more difficult for inorganic residues to be generated, the component (E) is preferably SiO ２ may be.

[0092] The component (E) may contain an inorganic filler other than silicon dioxide and titanium dioxide. Examples of inorganic fillers other than silicon dioxide and titanium dioxide include alumina, tantalum oxide, zirconium oxide, silicon nitride, barium titanate, barium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, gallium oxide, spinel, mullite, cordierite, talc, aluminum titanate, yttria-containing zirconia, barium silicate, boron nitride, calcium carbonate, barium sulfate (BaSO ), and the like. ４ ), calcium sulfate, zinc oxide, magnesium titanate, hydrotalcite, mica, calcined kaolin, and carbon.

[0093] The component (E) may contain barium sulfate to improve the heat resistance and adhesive strength of the permanent resist. To improve the dispersibility of the inorganic filler, an inorganic filler that has been surface-treated in advance with alumina or an organic silane compound may be used.

[0094] The average particle size of component (E) may be 100 μm or more and 550 μm or less, 120 μm or more and 540 μm or less, or 140 μm or more and 530 μm or less. The average particle size of component (E) can be measured by laser diffraction.

[0095] The content of component (E) may be 5% by mass or more and 70% by mass or less, 6% by mass or more and 60% by mass or less, or 10% by mass or more and 50% by mass or less, based on the total solid content of the photosensitive resin composition. When the content of component (E) is within the above range, it is possible to improve the low thermal expansion coefficient, heat resistance, film strength, etc.

[0096] (Component (F): Pigment) The photosensitive resin composition of the present embodiment may further contain a pigment as component (F) from the viewpoint of improving the distinguishability or appearance of the production equipment. As component (F), a colorant that develops a desired color when concealing wiring, etc., can be used. Examples of component (F) include phthalocyanine blue (copper phthalocyanine), phthalocyanine green, iodine green, diazo yellow (pigment yellow 151), crystal violet, carbon black, and naphthalene black.

[0097] From the viewpoint of further concealing the wiring, the content of the component (F) may be 0.1 to 10 mass%, 0.15 to 8 mass%, or 0.2 to 5 mass%, based on the total amount of solids in the photosensitive resin composition.

[0098] (Other Components) The photosensitive resin composition according to this embodiment may further contain various additives as needed. Examples of the 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; and flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.

[0099] (Solvent) The photosensitive resin composition according to this embodiment contains a solvent for dissolving and dispersing each component, which makes it easy to apply the composition onto a substrate and allows a coating film of uniform thickness to be formed.

[0100] Examples of solvents 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; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The solvents may be used alone or in combination of two or more.

[0101] The amount of the solvent to be added is not particularly limited, but the ratio of the solvent in the photosensitive resin composition may be 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass.

[0102] The photosensitive resin composition of this embodiment has a calcium concentration of less than 100 ppm by mass. ２ The photosensitive resin composition of this embodiment reacts with the calcium hydroxide to form a salt such as calcium silicate. The formed salt such as calcium silicate becomes difficult to remove as an inorganic residue after dry etching. Since the calcium concentration of the photosensitive resin composition of this embodiment is less than 100 ppm by mass, calcium-derived salts are unlikely to be formed, and inorganic residues are unlikely to be generated after dry etching.

[0103] From the viewpoint of further reducing the generation of inorganic residues, the calcium concentration of the photosensitive resin composition may be 50 ppm by mass or less, 10 ppm by mass or less, or less than 10 ppm by mass.

[0104] The calcium concentration of the photosensitive resin composition can be measured by a conventional method, for example, by inductively coupled plasma optical emission spectroscopy (ICP-OES).

[0105] The photosensitive resin composition of this embodiment can be prepared by uniformly mixing the above-mentioned components using a roll mill, a bead mill, or the like.

[0106] [Photosensitive Element] The photosensitive element according to this embodiment includes a support film, a photosensitive layer containing the above-described photosensitive resin composition, and a protective film. Fig. 1 is a cross-sectional view schematically showing the photosensitive element according to this embodiment. As shown in Fig. 1, the photosensitive element 1 includes a support film 10, a photosensitive layer 20 formed on the support film 10, and a protective film 30 laminated on the photosensitive layer.

[0107] The photosensitive element 1 can be produced 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.

[0108] 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, 5 to 50 μm, 5 to 40 μm, or 10 to 30 μm. The surface roughness of the support film is not particularly limited, but the arithmetic mean roughness (Ra) may be 1000 nm or less, 500 nm or less, or 250 nm or less.

[0109] 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 5 to 20 minutes.

[0110] A protective film 30 is further provided on the photosensitive layer 20 to cover the photosensitive layer 20. As the protective film 30, for example, a polymer film such as polyethylene or polypropylene may be used.

[0111] According to the photosensitive element of this embodiment, since the photosensitive layer 20 contains the above-mentioned photosensitive resin composition, the adhesion (tack) between the photosensitive layer 20 and the protective film 30 can be reduced, and problems when peeling the protective film 30 from the photosensitive layer 20 can be suppressed.

[0112] [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.

[0113] The method for manufacturing a printed wiring board according to this embodiment includes the steps of forming a photosensitive layer on a substrate using a 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.

[0114] First, a substrate such as a copper-clad laminate is prepared, and a photosensitive layer is formed on the substrate. The photosensitive layer may be formed on the substrate by peeling off a protective film from a photosensitive element and laminating the photosensitive layer. Examples of methods for laminating the photosensitive layer include thermal lamination using a laminator.

[0115] Next, a negative film is brought into contact with the photosensitive layer directly or via a support film, and the layer is exposed to actinic rays. 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 ２ may be.

[0116] After exposure, the unexposed areas are removed with a developer to form a resist pattern. Examples of the developing method include dipping and spraying. Examples of the developer that can be used include aqueous alkali solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and tetramethylammonium hydroxide.

[0117] A patterned cured film (permanent resist) can be formed by subjecting the resist pattern to at least one of post-exposure and post-heating. The exposure dose of the post-exposure is 100 to 5000 mJ / cm. ２ , 500-2000mJ / cm ２ , or 700 to 1500 J / cm ２ The heating temperature of the post-heating may be 100 to 200° C., 120 to 180° C., or 135 to 165° C. The heating time of the post-heating may be 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.

[0118] The patterned cured film formed from the photosensitive resin composition 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 reliability can be provided.

[0119] The patterned cured film formed from the photosensitive resin composition according to this embodiment can be removed by etching. Dry etching is preferred as the etching method. A gas species containing fluorine atoms is preferred as the gas species used for dry etching. Since the patterned cured film is formed from the photosensitive resin composition according to this embodiment, when dry etching is performed with a gas species containing fluorine atoms, inorganic residues are unlikely to be generated.

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

[0121] [Preparation of Resin Composition for Resin Layer] The following materials were prepared.

[0122] Component (A): <Acid-Modified Vinyl Group-Containing Resin 1> Acid-modified vinyl group-containing resin 1 was obtained by the following procedure: 350 parts by mass of bisphenol F novolac epoxy resin (trade name "EXA-7376", manufactured by DIC Corporation), 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90°C, and stirred to react and completely dissolve the mixture.

[0123] Next, the obtained solution was cooled to 60° C., 2 parts by mass of triphenylphosphine was added, and the solution was heated to 100° C. and reacted until the acid value of the solution reached 1 mgKOH / g. To the reacted solution, 98 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate were added, and the solution was heated to 80° C. and reacted for 6 hours.

[0124] Thereafter, the mixture was cooled to room temperature to obtain an acid-modified vinyl group-containing epoxy derivative 1, which was an acid-modified bisphenol F novolac epoxy acrylate (acid-modified vinyl group-containing resin 1) having a solid content of 73 mass %.

[0125] <Acid-modified vinyl group-containing resin 2> Acid-modified vinyl group-containing resin 2 was obtained by the following procedure. An autoclave equipped with a thermometer, a nitrogen introducing device / alkylene oxide introducing device, and a stirrer was charged with 119.4 parts of a novolac cresol resin (trade name "Shonor CRG951", manufactured by Showa Denko K.K., OH equivalent: 119.4), 1.19 parts of potassium hydroxide, and 119.4 parts of toluene, and the system was purged with nitrogen while stirring, and heated to an elevated temperature. Next, 63.8 parts of propylene oxide was gradually added dropwise, and the temperature was raised to 125 to 132°C and 0 to 4.8 kg / cm. ２ The mixture was reacted at 100°C for 16 hours. The mixture was then cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize the potassium hydroxide, yielding a propylene oxide reaction solution of a novolak cresol resin with a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. This resin had an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

[0126] Next, 293.0 parts of the resulting propylene oxide reaction solution of the novolac cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were charged into a reactor equipped with a stirrer, thermometer, and air inlet tube. Air was blown in at a rate of 10 mL / min, and the mixture was stirred while reacting at 110°C for 12 hours. The water produced by the reaction was distilled off as an azeotrope with toluene, and 12.6 parts of water were distilled off. The mixture was then cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of 15% aqueous sodium hydroxide solution and then washed with water. The toluene was then distilled off while being replaced with 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate) using an evaporator, yielding a novolac acrylate resin solution.

[0127] Thereafter, 332.5 parts of the obtained novolac acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air-inlet tube, and while blowing air into the reaction mixture at a rate of 10 mL / min and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added thereto. The reaction was carried out at 95 to 101°C for 6 hours, and after cooling, a carboxy group-containing photosensitive resin solution (acid-modified vinyl group-containing resin 2) having an acid value of 88 mgKOH / g of the solid matter and a solid content of 70.9% was obtained.

[0128] Component (B): Thermosetting resin 1: phenol novolac type epoxy resin (trade name "RE-306", manufactured by Nippon Kayaku Co., Ltd.) Thermosetting resin 2: bisphenol F type epoxy resin (trade name "YX4000", manufactured by Mitsubishi Chemical Corporation) Component (C): dipentaerythritol hexaacrylate (DPHA) Component (D): photopolymerization initiator 1 (trade name "IRGACURE907", manufactured by BASF, α-acetophenone-based photopolymerization initiator) Photopolymerization initiator 2 (trade name "SBPI-799", manufactured by Nagase & Co., Ltd., thioxanthone-based polymerization initiator) Component (E): SiO ２ (Average particle size 500 nm) SiO ２ (Average particle size 300 nm) SiO ２ (Average particle size 180 nm) TiO ２ (Average particle size 100 nm) BaSO４ (average particle size 300 nm) Talc (average particle size 500 nm) Zirconium oxide (average particle size 100 nm) (F) component: Blue organic pigment (copper phthalocyanine) Yellow organic pigment (pigment yellow 151)

[0129] (Examples 1 to 9 and Comparative Examples 1 to 9) Each component was blended in the blending amount (parts by mass, solid content) shown in Table 1, and CaCl was added to achieve the calcium concentration shown in Table 1. ２ A water / ethanol mixed solution of the above was added and kneaded to prepare a photosensitive resin composition.

[0130] [Measurement of calcium concentration] The calcium concentration of the obtained photosensitive resin composition was measured by the following procedure: First, 0.3 g of the obtained photosensitive resin composition was weighed and placed in a 100 mL Teflon (registered trademark) container together with 9 mL of sulfuric acid (concentration: 98%) and 1 mL of hydrochloric acid (concentration: 37%). The Teflon container was then placed in a pressure-resistant sealed polypropylene container and then attached to a microwave decomposition device.

[0131] Next, the pressure-resistant sealed container was first microwave-heated at an output of 250 W for 5 minutes, then at an output of 400 W for 5 minutes, and then at an output of 500 W for 5 minutes, and then microwave-heated again at 250 W, 400 W, and 600 W in that order for 5 minutes each.The pressure-resistant sealed container was then removed from the apparatus and water-cooled for 15 minutes or more to obtain a decomposition sample.

[0132] After cooling with water, the resulting decomposed sample was diluted with water to a constant volume of 50 mL to obtain an aqueous solution of the decomposed sample. The calcium ion concentration of the resulting aqueous solution was measured by ICP-OES.

[0133] [Test for Confirmation of Inorganic Residue After Dry Etching] First, a 25 μm-thick polyethylene terephthalate film (manufactured by Teijin Limited, trade name "G2-25") was used as a support film, and the photosensitive resin composition prepared in each example was applied to the support film so that the film thickness after drying would be 25 μm. The composition was then dried for 10 minutes at 100° C. using a hot air convection dryer to form a photosensitive layer. Subsequently, a biaxially oriented polypropylene film (manufactured by Oji F-Tex Co., Ltd., trade name "MA-411") was laminated as a protective film to the surface of the photosensitive layer opposite the side in contact with the support film, to produce a photosensitive element having a laminated structure of the support film, photosensitive layer, and protective film.

[0134] Next, a 0.6 mm thick copper-clad laminate substrate (manufactured by Showa Denko Materials Co., Ltd., product name "MCL-E-679") was prepared, and the copper was removed with an aqueous solution of APS (ammonium persulfate). The protective film was peeled off and removed from the obtained photosensitive element, and the exposed photosensitive layer was laminated onto the copper-clad laminate substrate using a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., product name "MVLP-500") under predetermined lamination conditions (compression pressure: 0.4 MPa, press hot plate temperature: 80°C, evacuation time: 25 seconds, lamination press time: 25 seconds, air pressure: 4 kPa or less), to obtain a laminate for evaluation. Subsequently, the laminate was exposed to 300 mJ / cm using an ultraviolet exposure device. ２ After the exposure, the carrier film was peeled off and removed. ２ After the exposure, the laminate was heat-treated at 170° C. for 1 hour using a dryer to obtain a cured laminate.

[0135] Conductive grease was applied to the non-resist surface of the obtained cured laminate, and the laminate was placed on an 8-inch silicon wafer. The silicon wafer was placed in a vacuum chamber, the chamber was evacuated, and a fluorine-based gas species was introduced at a flow rate of 1.5 × 10 －６ m ３1 / s (90 sccm) and a voltage was applied to generate plasma, which was then used for etching. After etching, the laminate was removed from the silicon wafer, and the etched surface was observed under an electron microscope to check for the presence or absence of inorganic residues on the resist. The results are shown in Tables 1 and 2. <Evaluation criteria> A: No inorganic residues were observed. B: Inorganic residues were observed in some parts of the resist, but not on the entire surface. C: Inorganic residues were observed on the entire surface of the resist.

[0136]

[0137]

[0138] 2 to 4 are diagrams showing the results of electron microscope observation of the etched surfaces of Example 1, Comparative Example 1, and Comparative Example 4, respectively. As shown in Fig. 2, no inorganic residues are present on the etched surface of Example 1. On the other hand, as shown in Figs. 3 and 4, inorganic residues are present on the etched surfaces of Comparative Examples 1 and 4.

[0139] 1...photosensitive element, 10...support film, 20...photosensitive layer, 30...protective film

Claims

1. A composition comprising (A) an acid-modified vinyl group-containing resin, (B) a thermosetting resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) an inorganic filler, wherein the inorganic filler (E) is SiO ２ or TiO ２ The SiO ２ and the TiO ２ the total amount of the inorganic filler (E) being 100 mass %, and the calcium concentration is less than 100 ppm by mass.

2. The inorganic filler (E) is SiO ２ The photosensitive resin composition according to claim 1, wherein 3. The photosensitive resin composition according to claim 1, wherein the calcium concentration is 50 ppm by mass or less.

4. The photosensitive resin composition according to claim 1, wherein the content of the inorganic filler (E) is 5% by mass or more and 70% by mass or less based on the total solid content of the photosensitive resin composition.

5. The photosensitive resin composition according to claim 1, wherein the inorganic filler (E) has an average particle size of 100 μm or more and 550 μm or less.

6. A photosensitive element comprising a support film, a photosensitive layer, and a protective film in this order, wherein the photosensitive layer contains the photosensitive resin composition according to any one of claims 1 to 5.

7. A printed wiring board comprising a permanent resist containing a cured product of the photosensitive resin composition according to any one of claims 1 to 5.

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