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

Abstract

To provide a photosensitive resin composition capable of forming a permanent resist excellent in resolution and insulation reliability, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board.SOLUTION: A photosensitive resin composition according to one aspect of the present disclosure comprises (A) an acid-modified vinyl group-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, wherein the acid-modified vinyl group-containing resin (A) includes a reaction product of a compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group, and a compound having a functional group reactive with the hydroxyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, 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 the photographic method is easy to use and suitable for mass production, it 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 Laid-Open No. 2011-133851 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 (solder resists). In particular, requirements for the formation of fine patterns and insulation reliability are increasing year by year, making it important to achieve a high level of compatibility between these properties. However, permanent resists formed from conventional photosensitive resin compositions often have insufficient resolution during the formation of fine patterns, resulting in footing at openings and closure, and the resulting permanent resists may not be able to ensure sufficient insulation reliability, resulting in short circuits between wirings.

[0007] The present disclosure aims to provide a photosensitive resin composition capable of forming a permanent resist excellent in resolution and insulation reliability, a photosensitive element using the photosensitive resin composition, a printed wiring board, 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 comprising (A) an acid-modified vinyl group-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, wherein (A) the acid-modified vinyl group-containing resin comprises a reaction product of a compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group, and a compound having a functional group reactive with a hydroxyl group. [2] The photosensitive resin composition according to the above [1], wherein the compound having a functional group capable of reacting with a hydroxyl group has a Hansen solubility parameter difference with water of 30 to 50. [3] The photosensitive resin composition according to the above [1] or [2], wherein the compound having a functional group capable of reacting with a hydroxyl group is a monoisocyanate. [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group is an acid-modified vinyl group-containing epoxy derivative. [5] The photosensitive resin composition according to any one of the above [1] to [4], further comprising (E) an inorganic filler. [6] The photosensitive resin composition according to any one of the above [1] to [3], further comprising (F) a pigment. [7] 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 [6] above. [8] A printed wiring board comprising a permanent resist containing a cured product of the photosensitive resin composition according to any one of [1] to [6] above. [9] 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 [6] above; exposing and developing the photosensitive layer to form a resist pattern; and curing the resist pattern to form a permanent resist.

[10] 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 [7] 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 excellent in resolution and insulation reliability, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for producing 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] The present disclosure will be described in detail below. 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. 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 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 a value shown in the examples.

[0012] When referring to the amount of each component in a composition herein, if the composition contains multiple substances corresponding to each component, the total amount of those multiple substances present in the composition is used unless otherwise specified. In this specification, "(meth)acryloyl" refers to at least one of "acryloyl" and its corresponding "methacryloyl," and the same applies to other similar expressions such as "(meth)acrylic acid" and "(meth)acrylate." In this specification, "solid content" refers to the nonvolatile content of the photosensitive resin composition excluding volatile substances (water, solvent, etc.), and includes components that are liquid, syrup-like, or waxy at room temperature (around 25°C).

[0013] [Photosensitive resin composition] The photosensitive resin composition according to this embodiment contains (A) an acid-modified vinyl group-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, and the (A) acid-modified vinyl group-containing resin contains a reaction product of a compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group, and a compound having a functional group capable of reacting with a hydroxyl group.

[0014] 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 suitably used as a permanent resist. Hereinafter, each component used in the photosensitive resin composition according to this embodiment will be described in more detail.

[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). Component (A) includes a reaction product (hereinafter referred to as component (A2)) of a compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group (hereinafter referred to as component (A1)) with a compound having a functional group reactive with a hydroxyl group (hereinafter referred to as component (d)). In component (A2), at least some of the hydroxyl groups of the compound of component (A1) are protected by the compound of component (d).

[0016] The component (A1) is not particularly limited as long as it has a photopolymerizable ethylenically unsaturated bond, a hydroxyl group, and a carboxyl group. Examples of the group having an ethylenically unsaturated bond that the component (A1) has 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 is preferred from the viewpoints of reactivity and resolution.

[0017] The component (A1) is preferably an acid-modified vinyl group-containing epoxy derivative obtained by reacting (c) a saturated or unsaturated group-containing polybasic acid anhydride (hereinafter referred to as “component (c)”) with resin (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)”).

[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 the component (A1) include an acid-modified vinyl group-containing resin (A1-1) obtained by using a bisphenol novolac epoxy resin (a1) (hereinafter referred to as "epoxy resin (a1)") as the component (a), and an acid-modified vinyl group-containing resin (A1-2) obtained by using an epoxy resin (a2) (hereinafter referred to as "epoxy resin (a2)") other than the epoxy resin (a1) as the component (a).

[0020] Examples of the epoxy resin (a1) include bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, and bisphenol E novolac epoxy resins. The epoxy resin (a1) preferably has at least one structural unit selected from the structural units represented by the following formula (I) and the structural units represented by the following formula (II):

[0021] [ka]

[0022] In formulas (I) and (II), 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 is preferably a hydrogen atom, and from the viewpoint of further improving thermal shock resistance, Y 1 and Y 2 is preferably a glycidyl group.

[0023] The number of structural units represented by formula (I) or (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, 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 of a structural unit is an integer value in a single molecule, and is 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 of a structural unit hereinafter.

[0024] Bisphenol F novolac epoxy resins are commercially available, for example, as the EXA-7376 series (trade name, manufactured by DIC Corporation), and bisphenol A novolac epoxy resins are commercially available, for example, as the EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

[0025] The epoxy resin (a2) is not particularly limited as long as it is an epoxy resin different from the epoxy resin (a1). However, 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 is preferable that the epoxy resin (a2) be at least one selected from the group consisting of novolac-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, trisphenolmethane-type epoxy resins, and biphenyl-type epoxy resins.

[0026] 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).

[0027] 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'):

[0028] [ka]

[0029] In formulas (III) and (III'), R 13 represents a hydrogen atom or a methyl group, and Y5 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 From the viewpoint of suppressing the occurrence of undercut and improving the linearity and resolution of the resist pattern contour, R 13 is preferably a hydrogen atom.

[0030] 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.

[0031] 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.

[0032] 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 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).

[0033] Preferred 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, for example, bisphenol A-type epoxy resins or bisphenol F-type epoxy resins represented by the following formula (IV'):

[0034] [ka]

[0035] 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. 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, and at least one Y 6 is a glycidyl group.

[0036] From the viewpoint of suppressing the occurrence of undercut and improving the linearity and resolution of the resist pattern contour, R 14 is preferably a hydrogen atom, and from the viewpoint of further improving thermal shock resistance, Y 6 is preferably 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.

[0037] 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.

[0038] To promote the reaction between hydroxyl groups and epichlorohydrin, the reaction is preferably 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.

[0039] Commercially available examples of the bisphenol A epoxy resin or bisphenol F epoxy resin 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.).

[0040] The epoxy resin (a2) is preferably a trisphenolmethane type epoxy resin having a structural unit represented by the following formula (V): An example of a trisphenolmethane type epoxy resin having such a structural unit is a trisphenolmethane type epoxy resin represented by the following formula (V'):

[0041] [ka]

[0042] 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.

[0043] 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.

[0044] As the trisphenolmethane type epoxy resin represented by formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (all trade names, manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

[0045] 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'):

[0046] [ka]

[0047] 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. In formula (VI'), n4 is a number of 1 or more.

[0048] 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.) and the like are commercially available.

[0049] 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).

[0050] Examples of component (b) include acrylic acid, acrylic acid dimers, methacrylic acid, acrylic acid derivatives such as 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) may be used singly or in combination of two or more.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] In the reaction between component (a) and component (b), the ratio of component (b) is preferably 0.6 to 1.05 equivalents, and more preferably 0.8 to 1.0 equivalents, of component (b) per equivalent of epoxy groups in component (a). Reaction at such a ratio tends to increase photosensitivity and result in excellent linearity of the resist pattern contour.

[0055] 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.

[0056] 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.

[0057] The amount of 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 components (a) and (b), from the viewpoint of promoting the reaction between components (a) and (b).

[0058] 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 type of polymerization inhibitor may be used alone, or two or more types may be used in combination.

[0059] 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 the components (a) and (b).

[0060] 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.

[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 resin, component (A1), 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] 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, tetrahydrophthalic anhydride is preferred from the viewpoint of resolution. Component (c) may be used alone or in combination of two or more.

[0063] 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').

[0064] The reaction temperature between 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.

[0065] If necessary, a hydrogenated bisphenol A type epoxy resin may be used in part as component (a), or a styrene-maleic acid resin such as a hydroxyethyl (meth)acrylate modified styrene-maleic anhydride copolymer may be used in part.

[0066] The acid value of component (A1) is not particularly limited. From the viewpoint of improving the solubility of the unexposed area in an alkaline aqueous solution, the acid value of component (A1) may be 30 mgKOH / g or more, 40 mgKOH / g or more, or 50 mgKOH / g or more. From the viewpoint of improving the electrical properties of the cured film, the acid value of component (A) may be 150 mgKOH / g or less, 120 mgKOH / g or less, or 100 mgKOH / g or less.

[0067] The weight-average molecular weight (Mw) of the (A1) component is not particularly limited. From the viewpoint of improving the adhesion of the cured film, the Mw of the (A1) component may be 3,000 or more, 4,000 or more, or 5,000 or more. From the viewpoint of improving the resolution of the photosensitive layer, the Mw of the (A) component may be 30,000 or less, 25,000 or less, or 18,000 or less.

[0068] 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

[0069] The component (d) is not particularly limited as long as it is a compound that can serve as a protecting group for a hydroxyl group. Examples of the component (d) include monoisocyanates that can react with hydroxyl groups to form urethane bonds (hereinafter referred to as "component (d1)") and vinyl group-containing compounds or halogen compounds that can react with hydroxyl groups to form ether bonds (hereinafter referred to as "component (d2)").

[0070] Examples of the monoisocyanate of component (d1) include monoisocyanates having a (meth)acryloyl group, such as (meth)acryloyloxyethyl isocyanate and (meth)acryloyloxyethoxyethyl isocyanate; phenyl isocyanate, benzyl isocyanate, 4-methoxyphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2-biphenyl isocyanate, 1-naphthalene isocyanate, 2-phenylethyl isocyanate, 4-ethylphenyl isocyanate; Examples of the monoisocyanates include monoisocyanates having an aromatic ring, such as 4-butylphenyl isocyanate; monoisocyanates having an alkyl group, such as ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, heptyl isocyanate, hexyl isocyanate, octyl isocyanate, dodecyl isocyanate, and octadecyl isocyanate; and monoisocyanates having an alicyclic ring, such as 1-adamantyl isocyanate, cyclohexyl isocyanate, and cyclopentyl isocyanate.

[0071] Examples of the vinyl group-containing compound or halogen compound that is component (d2) include tetrahydropyran, chlorodimethyl ether, chlorodiethyl ether, chlorodimethyl sulfide, benzyl bromide, 4-methoxybenzyl chloride, and 2-methoxyethoxymethyl chloride.

[0072] The hydrophobicity of component (d) can be calculated by comparing the distance of the Hansen solubility parameter (HSP) in three-dimensional space coordinates, which is calculated from the energy due to intermolecular dispersion forces between water and component (d) (δD), the energy due to intermolecular dipole interactions (δP), and the energy due to intermolecular hydrogen bonds (δH). The hydrophobicity of component (d) corresponds to the hydrophobicity of the curable resin according to this embodiment.

[0073] Specific HSP distances between the HSP of component (d) and water calculated by Y-MB using HSPiP software are shown in Table 1. From the viewpoint of increasing the hydrophobicity of the curable resin, the HSP distance between component (d) and water may be 30 to 50, preferably 32 to 48, more preferably 34 to 46, and even more preferably 36 to 43.

[0074] [Table 1]

[0075] Component (A2) is obtained by reacting component (A1) with component (d). Component (A2) is an acid-modified vinyl group-containing resin in which at least a portion of the hydroxyl groups in component (A1) are protected with component (d). In the reaction between components (A1) and (d), for example, 0.1 to 2.0 equivalents of isocyanate groups in component (d1) are reacted with 1 equivalent of hydroxyl groups in component (A1), thereby increasing the hydrophobicity of the curable resin.

[0076] The likelihood of a urethane bond-forming reaction between the hydroxyl groups of component (A1) and the isocyanate groups of component (d1) depends on the structure of the isocyanate of component (d1). Generally, due to the electron-withdrawing properties of aromatic rings, isocyanates with aromatic rings tend to be highly reactive with hydroxyl groups, while isocyanates without aromatic rings tend to be less reactive with hydroxyl groups.

[0077] When using an isocyanate with low reactivity with hydroxyl groups, the reaction may be carried out in the presence of a catalyst. Examples of catalysts include tin-based catalysts such as dibutyltin laurate, amine-based catalysts such as triethylenediamine, carboxylate catalysts such as lead naphthenate, and trialkylphosphine catalysts such as triethylphosphine. The amount of catalyst used is approximately 10 to 1,000 ppm, preferably 100 to 200 ppm, based on the total amount of components (A1) and (d1).

[0078] A solvent may be added when reacting component (d). The amount of solvent added may be 10 to 100 parts by mass per 100 parts by mass of component (A1). Examples of the solvent include diethylene glycol monoethyl ether acetate.

[0079] The reaction temperature between component (A1) and component (d) may be 25 to 100°C, preferably 40 to 90°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C. The reaction time may be 0.5 to 15 hours. The reaction between component (A1) and component (d) can be carried out in air, but is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon.

[0080] Increasing the protection rate of the hydroxyl groups in component (A2) reduces the hydroxyl value, improving the hydrolysis resistance of component (A2). The hydroxyl value may be 50 mgKOH / g or less, 40 mgKOH / g or less, or 35 mgKOH / g or less. The hydroxyl value can be measured by potentiometric titration in accordance with JIS K0070.

[0081] From the viewpoint of further improving hydrolysis resistance, the protection rate of the hydroxyl groups in the component (A2) may be 30% or more, 40% or more, or 50% or more. 13 It can be calculated by measuring by C NMR or potentiometric titration.

[0082] The component (A) may contain the component (A1) together with the component (A2) from the viewpoints of suppressing the occurrence of undercuts and further improving adhesion to copper substrates, thermal shock resistance, and resolution.

[0083] When the component (A) is a combination of the components (A1) and (A2), the mass ratio of (A1 / A2) is not particularly limited, but 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 standpoint of improving the linearity of the resist pattern contour, the resistance to electroless plating, and the heat resistance.

[0084] The content of the component (A) in the photosensitive resin composition may be 20 to 70 mass%, 25 to 60 mass%, 28 to 55 mass%, or 30 to 50 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving the heat resistance, electrical properties, and chemical resistance of the permanent resist.

[0085] ((B) component: thermosetting resin) The photosensitive resin composition according to this embodiment uses a thermosetting resin as component (B), which can improve the heat resistance, adhesiveness, and chemical resistance 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.

[0086] 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.

[0087] 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.

[0088] The content of 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 component (B) is within the above range, good developability can be maintained while the heat resistance of the formed cured film can be further improved.

[0089] ((C) component: photopolymerizable compound) The photosensitive resin composition according to this embodiment contains a photopolymerizable compound as component (C). Component (C) 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. From the viewpoint of reactivity, component (C) may contain a compound having a (meth)acryloyl group.

[0090] Examples of component (C) include hydroxyalkyl (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; mono- or di(meth)acrylate compounds 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)acrylate compounds such as N,N-dimethylaminoethyl (meth)acrylate; hexanediol, trimethylolpropane, pentaerythritol, and ditrimethylolpropane. Examples of the (C) component include polyhydric (meth)acrylate compounds of polyhydric alcohols such as pantothenate, 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)acrylate compounds of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine (meth)acrylate. Component (C) can be used singly or in combination of two or more.

[0091] From the viewpoint of forming a permanent resist that exhibits higher resolution and a good resist pattern shape while also exhibiting excellent heat resistance and thermal shock resistance, the content of component (C) may be 1 to 15 mass%, 2 to 10 mass%, or 4 to 8 mass%, based on the total solid content of the photosensitive resin composition. When the content of component (C) is 1 mass% or more, photosensitivity is improved and exposed areas are less likely to dissolve during development, while when it is 15 mass% or less, the heat resistance of the permanent resist is more easily improved.

[0092] (Component (D): Photopolymerization initiator) The photosensitive resin composition according to this embodiment contains a photopolymerization initiator as component (D). The component (D) is not particularly limited as long as it can polymerize components (A) and (C). The component (D) may be used alone or in combination of two or more.

[0093] Examples of 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-[4-(methylthio)phenyl]-2-morpholino-1-propane, N,N ... acetophenone 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; benzo Benzophenone compounds such as phenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 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, 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;Examples of suitable oxime ester compounds include 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.

[0094] The content of component (D) is not particularly limited, and may be 0.2 to 15 mass%, 0.5 to 10 mass%, or 1 to 5 mass%, based on the total solid content of the photosensitive resin composition. When the content of component (D) is 0.2 mass% or more, the exposed area is less likely to dissolve during development, and when it is 15 mass% or less, it is easier to suppress a decrease in heat resistance.

[0095] (Component (E): inorganic filler) The photosensitive resin composition according to this embodiment may further contain an inorganic filler as component (E). By containing component (E), the adhesive strength and hardness of the permanent resist can be improved. The component (E) may be used alone or in combination of two or more.

[0096] Examples of inorganic fillers include silica, alumina, titania, tantalum oxide, zirconia, 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, calcium sulfate, zinc oxide, magnesium titanate, hydrotalcite, mica, calcined kaolin, and carbon.

[0097] The component (E) may contain silica from the viewpoint of improving the heat resistance of the permanent resist, or may contain barium sulfate from the viewpoint of improving the heat resistance and adhesive strength of the permanent resist, or may contain silica and barium sulfate. From the viewpoint of improving 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.

[0098] From the viewpoint of resolution, the average particle size of the inorganic filler may be 0.01 to 5.0 μm, 0.05 to 3.0 μm, 0.1 to 2.0 μm, or 0.15 to 1.0 μm.

[0099] The average particle size of component (E) is the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows: First, the photosensitive resin composition is diluted 1000 times with methyl ethyl ketone, and then the particles dispersed in the solvent are measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321 at a refractive index of 1.38, and the particle size at 50% cumulative value (volume basis) in the particle size distribution is taken as the average particle size.

[0100] The content of component (E) may be 5 to 70 mass%, 6 to 60 mass%, or 10 to 50 mass%, based on the total solid content of the photosensitive resin composition. When the content of component (E) is within the above range, the low thermal expansion coefficient, heat resistance, and film strength can be further improved.

[0101] When silica is used as component (E), the content of silica may be 5 to 60 mass%, 10 to 55 mass%, or 15 to 50 mass%, based on the total solid content of the photosensitive resin composition. When barium sulfate is used as component (E), the content of barium sulfate may be 5 to 30 mass%, 5 to 25 mass%, or 10 to 20 mass%, based on the total solid content of the photosensitive resin composition. When the contents of silica and barium sulfate are within the above ranges, the composition tends to have a low thermal expansion coefficient, excellent solder heat resistance, and excellent adhesive strength.

[0102] (Component (F): Pigment) The photosensitive resin composition according to this 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 (conductor pattern) or the like can be used. As component (F), one type may be used alone, or two or more types may be used in combination.

[0103] Examples of the component (F) include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

[0104] The content of the (F) component may be 0.01 to 5.0 mass%, 0.03 to 3.0 mass%, or 0.05 to 2.0 mass%, based on the total amount of solids in the photosensitive resin composition, from the viewpoint of making the manufacturing equipment easier to identify and further concealing the wiring.

[0105] (Component (G): Elastomer) The photosensitive resin composition according to this embodiment may further contain an elastomer as component (G). By containing component (G), it is possible to suppress a decrease in flexibility and adhesive strength caused by strain (internal stress) inside the resin due to cure shrinkage of component (A).

[0106] Examples of component (G) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers are composed of hard segment components that contribute to heat resistance and strength, and soft segment components that contribute to flexibility and toughness. Among these, olefin-based elastomers and polyester-based elastomers are preferred.

[0107] Examples of styrene-based elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, and styrene-ethylene-propylene-styrene block copolymers. In addition to styrene, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used as components constituting styrene-based elastomers.

[0108] Examples of olefin-based elastomers include ethylene-propylene copolymers, ethylene-α-olefin copolymers, ethylene-α-olefin-non-conjugated diene copolymers, propylene-α-olefin copolymers, butene-α-olefin copolymers, ethylene-propylene-diene copolymers, copolymers of non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and isoprene with α-olefins, epoxy-modified polybutadiene, and carboxylic acid-modified butadiene-acrylonitrile copolymers.

[0109] The epoxy-modified polybutadiene preferably has hydroxyl groups at the molecular terminals, more preferably at both molecular terminals, and even more preferably at only both molecular terminals. The number of hydroxyl groups that the epoxy-modified polybutadiene has may be one or more, preferably 1 to 5, more preferably 1 or 2, and even more preferably 2.

[0110] As the urethane-based elastomer, a compound composed of a hard segment made of a low molecular weight (short chain) diol and diisocyanate, and a soft segment made of a high molecular weight (long chain) diol and diisocyanate can be used.

[0111] Examples of short-chain diols include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48-500.

[0112] Examples of long-chain diols include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, poly(1,6-hexylene carbonate), and poly(1,6-hexylene-neopentylene adipate). The number-average molecular weight of the long-chain diol is preferably 500 to 10,000.

[0113] As the polyester elastomer, a compound obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof can be used.

[0114] Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The dicarboxylic acids can be used singly or in combination of two or more.

[0115] Examples of diol compounds include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols such as bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, and resorcinol.

[0116] Polyester elastomers can be multiblock copolymers that use aromatic polyesters (e.g., polybutylene terephthalate) as hard segment components and aliphatic polyesters (e.g., polytetramethylene glycol) as soft segment components. There are various grades of polyester elastomers that differ in the type, ratio, and molecular weight of the hard and soft segments.

[0117] Polyamide elastomers are broadly classified into two types: polyether block amides and polyether ester block amides, which use polyamides for the hard segments and polyethers or polyesters for the soft segments. Examples of polyamides include polyamide-6, polyamide-11, and polyamide-12. Examples of polyethers include polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene glycol.

[0118] The acrylic elastomer may be a compound containing a structural unit based on a (meth)acrylic acid ester as a main component. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. The acrylic elastomer may be a compound obtained by copolymerizing a (meth)acrylic acid ester with acrylonitrile, or may be a compound obtained by further copolymerizing a monomer having a functional group that serves as a crosslinking point. Examples of monomers having a functional group include glycidyl methacrylate and allyl glycidyl ether.

[0119] Examples of acrylic elastomers include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, methyl methacrylate-butyl acrylate-methacrylic acid copolymer, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer. As the acrylic elastomer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer or methyl methacrylate-butyl acrylate-methacrylic acid copolymer is preferred, and methyl methacrylate-butyl acrylate-methacrylic acid copolymer is more preferred.

[0120] Silicone elastomers are compounds primarily composed of organopolysiloxane. Examples of organopolysiloxane include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Silicone elastomers may be compounds in which a portion of an organopolysiloxane is modified with a vinyl group, an alkoxy group, or the like.

[0121] From the viewpoint of improving the adhesion of the cured film, the component (G) may contain a carboxylic acid-modified butadiene-acrylonitrile copolymer or a polyester-based elastomer having a hydroxyl group.

[0122] The amount of component (G) per 100 parts by mass of component (A) may be 2 to 40 parts by mass, 4 to 30 parts by mass, 6 to 20 parts by mass, or 10 to 15 parts by mass. When the amount of component (G) is within the above range, the elastic modulus of the cured film in high temperature ranges decreases, and the unexposed areas become more easily eluted in a developer.

[0123] (Other ingredients) The photosensitive resin composition according to this embodiment may further contain various additives as needed, such as 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.

[0124] (solvent) The photosensitive resin composition according to this embodiment contains a solvent for dissolving and dispersing each component, which makes it easy to apply onto a substrate and allows the formation of a coating film of uniform thickness.

[0125] 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. These solvents may be used alone or in combination of two or more.

[0126] 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 mass %, 20 to 40 mass %, or 25 to 35 mass %.

[0127] 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.

[0128] [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 showing 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.

[0129] 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.

[0130] 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 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.

[0131] The thickness of the photosensitive layer may be, for example, 5 to 50 μm, 5 to 40 μm, or 10 to 30 μm.

[0132] 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.

[0133] 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.

[0134] [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.

[0135] 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 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.

[0136] 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 by applying a photosensitive resin composition to the substrate and drying it. Examples of methods for applying the photosensitive resin composition include screen printing, spraying, roll coating, curtain coating, and electrostatic coating. 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 7 minutes, 1 to 6 minutes, or 2 to 5 minutes.

[0137] The photosensitive layer may be formed on the substrate by peeling off the protective film from the photosensitive element and laminating the photosensitive layer on the substrate. Examples of methods for laminating the photosensitive layer include thermal lamination using a laminator.

[0138] Next, a negative film is brought into contact with the photosensitive layer directly or via a support film, and 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.

[0139] 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.

[0140] 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 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 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.

[0141] 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 reliability can be provided. [Example]

[0142] The present disclosure will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0143] (Synthesis Example 1) A flask equipped with a stirrer, reflux condenser, and thermometer was charged with 350 parts by weight of bisphenol F novolac epoxy resin (manufactured by DIC Corporation, product name "EXA-7376," epoxy equivalent: 186), 70 parts by weight of acrylic acid, 0.5 parts by weight of methylhydroquinone, and 120 parts by weight of carbitol acetate. The mixture was heated and stirred at 90°C to completely dissolve the mixture. The resulting solution was then cooled to 60°C, 2 parts by weight of triphenylphosphine was added, and the mixture was heated to 100°C and reacted 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 the mixture was reacted at 80°C for 6 hours. The mixture was then cooled to room temperature to obtain a solution of acid-modified vinyl group-containing resin (A1-1) with a solids content of 73% by weight.

[0144] (Synthesis Example 2) A flask equipped with a stirrer and a thermometer was charged with 397.6 g of a solution of acid-modified vinyl group-containing resin (A1-1), and 0.8 g of a 10 mass % solution of dibutyltin dilaurate in ethyl acetate was added dropwise to the flask while stirring at 70°C under a nitrogen atmosphere. Next, 33.4 g of 2-methacryloyloxyethyl isocyanate (manufactured by Resonac Corporation, trade name "Karenz MOI") as component (d) was added dropwise to the flask, and the mixture was stirred at 70°C for 1 hour to obtain a solution of acid-modified vinyl group-containing resin (A2-1).

[0145] (Synthesis Example 3) To a flask equipped with a stirrer and a thermometer, 407.4 g of a propylene glycol monomethyl ether acetate solution of trisphenolmethane-type acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., product name "TCR-1348H") was added, and the mixture was stirred under a nitrogen atmosphere at 70° C. Next, 20.1 g of 2-methacryloyloxyethyl isocyanate was added dropwise to the flask, and the mixture was stirred at 70° C. for 30 minutes to obtain a solution of acid-modified vinyl group-containing resin (A2-2).

[0146] (Synthesis Example 4) To a flask equipped with a stirrer and a thermometer, 398.3 g of a propylene glycol monomethyl ether acetate solution of cresol novolac-type acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., product name "CCR-1235") was added, and the mixture was stirred under a nitrogen atmosphere at 70° C. Next, 19.8 g of 2-methacryloyloxyethyl isocyanate was added dropwise to the flask, and the mixture was stirred at 70° C. for 30 minutes to obtain a solution of acid-modified vinyl group-containing resin (A2-3).

[0147] (Synthesis Example 5) A solution of acid-modified vinyl group-containing resin (A2-4) was obtained in the same manner as in Synthesis Example 2, except that 25.9 g of phenyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) as component (d) was added dropwise to the flask and stirred at 70°C for 0.5 hours.

[0148] (Synthesis Example 6) A solution of acid-modified vinyl group-containing resin (A2-5) was obtained in the same manner as in Synthesis Example 2, except that 18.3 g of benzyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) as component (d) was added dropwise to the flask and stirred at 70°C for 1 hour.

[0149] (Synthesis Example 7) A solution of acid-modified vinyl group-containing resin (A2-6) was obtained in the same manner as in Synthesis Example 2, except that 20.7 g of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) as component (d) was added dropwise to the flask and stirred at 70°C for 3 hours.

[0150] (Synthesis Example 8) A solution of an acid-modified vinyl group-containing resin (A2-7) was obtained in the same manner as in Synthesis Example 2, except that 17.6 g of octyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) as component (d) was added dropwise to the flask and stirred at 70°C for 2.5 hours.

[0151] The following materials were prepared as components (A) to (F). A2-1: Acid-modified vinyl group-containing resin (A2-1) of Synthesis Example 2 A2-2: Acid-modified vinyl group-containing resin (A2-2) of Synthesis Example 3 A2-3: Acid-modified vinyl group-containing resin (A2-3) of Synthesis Example 4 A2-4: Acid-modified vinyl group-containing resin (A2-4) of Synthesis Example 5 A2-5: Acid-modified vinyl group-containing resin (A2-5) of Synthesis Example 6 A2-6: Acid-modified vinyl group-containing resin (A2-6) of Synthesis Example 7 A2-7: Acid-modified vinyl group-containing resin (A2-7) of Synthesis Example 8 A1-1: Acid-modified vinyl group-containing resin (A1-1) of Synthesis Example 1 A1-2: Trisphenolmethane-type acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., product name "TCR-1348H") B-1: Novolac-type multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "RE-306") B-2: Bisphenol A epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., product name "YD-8125") C-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "DPHA") D-1: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by IGM Resins BV, trade name "Omirad 907") D-2: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name "DETX-S") D-3: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (manufactured by BASF Japan Ltd., trade name "Irgacure OXE02") E-1: Silica (manufactured by Denka Co., Ltd., product name "SFP20M", average particle size: 0.3 μm) F-1: Phthalocyanine Green (manufactured by Sanyo Pigment Co., Ltd.)

[0152] [Photosensitive resin composition] The components were blended in the amounts (parts by mass, solid content equivalent) shown in Table 2 or Table 3 and kneaded using a three-roll mill. Then, carbitol acetate was added so that the solid content concentration became 70% by mass, thereby preparing a photosensitive resin composition.

[0153] [Photosensitive element] A 25 μm-thick polyethylene terephthalate film (manufactured by Toyobo Film Solutions Co., Ltd., product name "G2-25") was prepared as a support film. A solution prepared by diluting a photosensitive resin composition with methyl ethyl ketone was applied onto the support film so that the thickness after drying would be 25 μm, and the coating was dried at 75°C for 30 minutes using a hot air convection dryer to form a photosensitive layer. Next, a polypropylene film (manufactured by Oji F-Tex Co., Ltd., product name "Alphan MAM-430") 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.

[0154] (resolution) A 0.6 mm-thick copper-clad laminate substrate (manufactured by Resonac Corporation, product name "MCL-E-67") was prepared. While peeling and removing the protective film from the photosensitive element, a 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") at a pressure of 0.4 MPa, a press hot plate temperature of 80°C, a vacuuming time of 25 seconds, and a laminating press time of 25 seconds to obtain a laminate. Next, a negative mask having an opening pattern of a predetermined size (opening diameter size: 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 150, 200 μm) was attached to the support film of the laminate, and the photosensitive layer was exposed to light using an ultraviolet exposure device (manufactured by Oak Corporation, product name "EXM-1201") at an exposure dose equivalent to 13 steps of complete curing on a 41-step step tablet (manufactured by Resonac Corporation). Thereafter, the support film was peeled off from the photosensitive layer, and the layer was exposed to light using a 1% by mass aqueous solution of sodium carbonate for 60 seconds at 1.765 × 10 5 The developed photosensitive layer was then spray-developed at a pressure of 2000 mJ / cm 2 using an ultraviolet exposure device. 2 After that, the substrate was heated at 170°C for 1 hour to prepare a test piece 1 having a cured film with an opening pattern of a predetermined size formed on a copper-clad laminate substrate. The test piece 1 was observed using an optical microscope and evaluated according to the following criteria. A: The smallest opening diameter was 30 μm or less. B: The smallest opening diameter was more than 30 μm and 50 μm or less. C: The smallest opening diameter exceeded 50 μm.

[0155] (electrical insulation) Test piece 2 was prepared in the same manner as test piece 1, except that a bismaleimide triazine substrate on which interdigital electrodes (line / space = 10 μm / 10 μm) were formed was used instead of the copper-clad laminate substrate. Test piece 2 was then exposed to conditions of 135°C, 85%, and 5 V. Thereafter, the extent of migration in the permanent resist was observed using a metallurgical microscope at 100x magnification, and the electrical insulation was evaluated according to the following criteria. S: No migration occurs in the permanent resist even after 400 hours, and the resistance value is 10 -6 It never dropped below Ω. A: For 200 hours or more but less than 400 hours, no migration occurs in the permanent resist and the resistance value is 10 -6 It never dropped below Ω. B: 100 hours or more but less than 200 hours, no migration occurs in the permanent resist, and the resistance value is 10 -6 It never dropped below Ω. C: Migration occurs in the permanent resist within 100 hours, and the resistance value is 10 -6 It dropped below Ω.

[0156] [Table 2]

[0157] [Table 3] [Explanation of symbols]

[0158] 1...photosensitive element, 10...support film, 20...photosensitive layer, 30...protective film.

Claims

1. (A) an acid-modified vinyl group-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound; The photosensitive resin composition (A) includes a reaction product of a compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group, and a compound having a functional group reactive with a hydroxyl group.

2. 2. The photosensitive resin composition according to claim 1, wherein the compound having a functional group capable of reacting with a hydroxyl group has a Hansen solubility parameter difference with water of 30 to 50.

3. 2. The photosensitive resin composition according to claim 1, wherein the compound having a functional group capable of reacting with a hydroxyl group is a monoisocyanate.

4. 2. The photosensitive resin composition according to claim 1, wherein the compound having an ethylenically unsaturated group, a hydroxyl group, and a carboxyl group is an acid-modified vinyl group-containing epoxy derivative.

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

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

7. 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 6.

8. 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 6.

9. forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 6; 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:

10. forming a photosensitive layer on a substrate using the photosensitive element of claim 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:

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