Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board

Abstract

The present invention provides a photosensitive resin composition having excellent via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, a photosensitive resin composition for forming photovias, and a photosensitive resin composition for an interlayer insulating layer. Furthermore, the present invention provides a photosensitive resin film and a photosensitive resin film for an interlayer insulating layer made of the above photosensitive resin composition. Additionally, the present invention provides a multilayer printed circuit board and a semiconductor package, and a method for manufacturing the above multilayer printed circuit board. Specifically, the above photosensitive resin composition is a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and (B) a photopolymerization initiator, wherein the photopolymerizable compound having an ethylenically unsaturated group (A) comprises (A1) a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group.

Description

Technology Field

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive resin film, a multilayer printed circuit board and a semiconductor package, and a method for manufacturing a multilayer printed circuit board. Background Technology

[0002] Recently, as electronic devices have become more miniaturized and high-performance, multilayer printed circuit boards are becoming more dense due to an increase in the number of circuit layers and the miniaturization of wiring. In particular, the high density of semiconductor package substrates, such as BGA (Ball Grid Array) and CSP (Chip Size Package) on which semiconductor chips are mounted, is prominent, and not only is wiring miniaturization required, but also thinning of insulating films and further reduction of the diameter of vias (also referred to as "via holes") for interlayer connections. Furthermore, with the thinning of insulating films in printed circuit boards, excellent electrical insulation reliability between layers [especially electrical insulation reliability after moisture absorption (HAST (High Accelerated Stress Test) resistance)] is also required.

[0003] As a method for manufacturing a printed circuit board, a method for manufacturing a multilayer printed circuit board by a build-up method (e.g., see Patent Document 1) in which an interlayer insulating layer and a conductor circuit layer are sequentially laminated to form a multilayer printed circuit board can be cited. In multilayer printed circuit boards, as circuits become miniaturized, a semi-additive process in which circuits are formed by plating is the mainstream.

[0004] In the conventional semi-additive process, for example, (1) a thermosetting resin film is laminated onto a conductor circuit, and the thermosetting resin film is cured by heating to form an "interlayer insulating layer." (2) Subsequently, vias for interlayer connection are formed by laser processing, and desmearing and oxidizing treatments are performed using alkali permanganate treatment, etc. (3) After that, electroless copper plating is performed on the substrate, and a copper circuit layer is formed by forming a pattern using a resist and then performing electrolytic copper plating. (4) Subsequently, the resist is peeled off, and a copper circuit can be formed by performing flash etching of the electroless layer.

[0005] As described above, laser processing is the mainstream method for forming vias in an interlayer insulating layer formed by curing a thermosetting resin film, but the small curing of vias by laser irradiation using a laser processing machine has reached its limit. In addition, when forming vias using a laser processing machine, it is necessary to form each via hole individually, and when it is necessary to provide a large number of vias due to high density, there is a problem that the formation of vias requires a long time and the manufacturing efficiency is poor.

[0006] Under these circumstances, as a method capable of forming multiple vias in batches, a method is proposed to form multiple small-diameter vias in batches by photolithography using a photosensitive resin composition containing (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound, wherein the content of (D) the inorganic filler is 10 to 80 mass% (see, for example, Patent Document 2). Prior art literature

[0007] Patent Document 1: Japanese Patent Publication No. JP7-304931 Patent Document 2: Japanese Patent Publication No. JP2017-116652 The problem to be solved

[0008] Patent Document 2 addresses the suppression of the decrease in adhesion strength with plated copper caused by using a photosensitive resin composition instead of a conventional thermosetting resin composition as a material for an interlayer insulating layer or a surface protective layer, and also addresses the resolution of vias and adhesion to silicon substrates and chip components, and states that these issues have been resolved. However, as wiring becomes even more miniaturized, and as the insulating film becomes thinner and via holes for interlayer connection become smaller, the demand for improvements in adhesion strength with plated copper and electrical insulation reliability is increasing. Therefore, there is room for new improvements in the photosensitive resin composition of Patent Document 2 regarding adhesion strength with plated copper and electrical insulation reliability.

[0009] Likewise, it is conceivable to use photosensitive resin compositions, which are the material of conventional solder resists, as the material of the interlayer insulating layer; however, since the interlayer insulating layer requires characteristics that were not necessary for solder resists (e.g., electrical insulation reliability between layers, adhesion strength with plated copper, high heat resistance capable of withstanding multiple heating cycles, high dimensional accuracy of via shapes, etc.), it is difficult to predict whether it will be suitable for practical use as an interlayer insulating layer, and it cannot be easily repurposed.

[0010] Furthermore, it was difficult to say that conventional photosensitive resin compositions possessed sufficient crack resistance to withstand reflow mounting.

[0011] Therefore, the objective of the present invention is to provide a photosensitive resin composition having excellent via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, a photosensitive resin composition for forming photovias, and a photosensitive resin composition for an interlayer insulating layer. Furthermore, the invention aims to provide a photosensitive resin film and a photosensitive resin film for an interlayer insulating layer made of the above photosensitive resin composition, a multilayer printed circuit board and a semiconductor package, and a method for manufacturing the above multilayer printed circuit board. means of solving the problem

[0012] The inventors, as a result of repeated research to solve the above problem, discovered that the problem can be solved by a photosensitive resin composition containing components (A) and (B) described below, wherein component (A) comprises "(A1) a photopolymerizable compound having an acidic substituent and a dicycloidal skeleton together with an ethylenically unsaturated group."

[0013] That is, the present invention relates to the following [1] to

[20] .

[0014] [1] A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group and (B) a photopolymerization initiator,

[0015] A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group, (A1) a photopolymerizable compound having an acidic substituent and a dicycloal skeleton together with an ethylenically unsaturated group.

[0016] [2] The photosensitive resin composition described in [1] comprises at least one selected from the group consisting of (A) a photopolymerizable compound having an ethylenically unsaturated group, (Ai) a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group, (Aii) a difunctional vinyl monomer having two polymerizable ethylenically unsaturated groups, and (Aiii) a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.

[0017] [3] A photopolymerizable compound having an acidic substituent and a cycloaliphatic backbone together with an ethylenically unsaturated group (A1), wherein the cycloaliphatic backbone is a cyclic cycloaliphatic backbone having 5 to 20 carbon atoms, the photosensitive resin composition described in [1] or [2].

[0018] [4] A photopolymerizable compound having an acidic substituent and a cycloaliphatic backbone together with an ethylenically unsaturated group (A1), wherein the cycloaliphatic backbone is composed of two or more rings, a photosensitive resin composition as described in [1] or [2].

[0019] [5] A photopolymerizable compound having an acidic substituent and a cycloaliphatic backbone together with an ethylenically unsaturated group (A1), wherein the cycloaliphatic backbone is composed of three or more rings, a photosensitive resin composition as described in [1], [2] or [4].

[0020] [6] A photopolymerizable compound having an acidic substituent and a cycloaliphatic backbone together with an ethylenically unsaturated group (A1), wherein the cycloaliphatic backbone is represented by the following general formula (a), a photosensitive resin composition described in any one of [1] to [5].

[0021]

[0022] (of general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any of the above alicyclic skeletons. 1is an integer between 0 and 6. * is a linkage site to another structure.)

[0023] [7] A photosensitive resin composition described in any one of [1] to [6], wherein the photopolymerizable compound having an acidic substituent and a cycloaliphatic skeleton together with the above (A1) ethylenically unsaturated group is represented by the following general formula (A-1).

[0024]

[0025] (of general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any point in the above alicyclic framework. R A2 represents an alkyl group having 1 to 12 carbon atoms. R A3 It is silver, an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least one R A3 is an organic group having an ethylenically unsaturated group and an acidic substituent. 1 is an integer from 0 to 6, m 2 is an integer from 0 to 3. n is from 0 to 10.)

[0026] [8] A photopolymerizable compound having an acidic substituent and a dicycloidal skeleton together with an ethylenically unsaturated group (A1), wherein the acidic substituent is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group, a photosensitive resin composition described in any one of [1] to [7].

[0027] [9] (C) A photosensitive resin composition described in any one of [1] to [8], further containing a thermosetting resin.

[0028]

[10] (D) A photosensitive resin composition described in any one of [1] to [9], further containing an elastomer.

[0029]

[11] A photosensitive resin composition described in any one of [1] to

[10] , wherein the above (D) elastomer comprises at least one selected from the group consisting of styrene-based elastomer, olefin-based elastomer, polyester-based elastomer, urethane-based elastomer, polyamide-based elastomer, acrylic-based elastomer and silicone-based elastomer.

[0030]

[12] (F) A photosensitive resin composition described in any one of [1] to

[11] , further containing an inorganic filler.

[0031]

[13] A photosensitive resin composition for forming photovias, comprising a photosensitive resin composition described in any one of [1] to

[12] above.

[0032]

[14] A photosensitive resin composition for an interlayer insulating layer, comprising a photosensitive resin composition described in any one of [1] to

[12] above.

[0033]

[15] A photosensitive resin film composed of a photosensitive resin composition described in any one of [1] to

[12] above.

[0034]

[16] A photosensitive resin film for an interlayer insulating layer, comprising a photosensitive resin composition described in any one of [1] to

[12] above.

[0035]

[17]

[0036] A multilayer film wiring board comprising an interlayer insulating layer formed using a photosensitive resin composition described in any one of [1] to

[12] above.

[0037]

[18]

[0038] A multilayer printed circuit board comprising an interlayer insulating layer formed using the photosensitive resin film described in

[15] above.

[0039]

[19]

[0040] A semiconductor package formed by mounting a semiconductor element on a multilayer printed circuit board as described in

[17] or

[18] above.

[0041]

[20]

[0042] A method for manufacturing a multilayer printed circuit board having the following processes (1) to (4).

[0043] Process (1): A process of laminating the photosensitive resin film described in

[15] above onto one side or both sides of a circuit board.

[0044] Process (2): A process of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in the above process (1).

[0045] Process (3): A process for roughening the above vias and the above interlayer insulation layer.

[0046] Process (4): A process of forming a circuit pattern on the interlayer insulation layer. Effects of the invention

[0048] According to the present invention, a photosensitive resin composition having excellent via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, a photosensitive resin composition for forming photovias, and a photosensitive resin composition for an interlayer insulating layer can be provided. In addition, a photosensitive resin film and a photosensitive resin film for an interlayer insulating layer made of the photosensitive resin composition can be provided, and a multilayer printed circuit board and a semiconductor package comprising an interlayer insulating layer formed using the photosensitive resin composition or the photosensitive resin film can be provided.

[0049] In addition, a method can be provided to efficiently manufacture a multilayer printed circuit board having high-resolution vias, high adhesion strength between the interlayer insulating layer and plated copper, and excellent electrical insulation reliability. The vias of the multilayer printed circuit board obtained by the manufacturing method of the present invention can be made smaller in diameter than vias formed by laser processing. Brief explanation of the drawing

[0050] [Fig. 1] This is a schematic diagram showing one aspect of the manufacturing process of a multilayer printed circuit board according to the present embodiment. Specific details for implementing the invention

[0051] In the 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. Additionally, the lower and upper limits of the numerical range may be arbitrarily combined with the lower or upper limits of other numerical ranges.

[0052] In addition, in this specification, the content of each component in the photosensitive resin composition refers to the content of the sum of the corresponding multiple types of substances present in the photosensitive resin composition, unless specifically determined otherwise, in cases where multiple types of substances corresponding to each component exist.

[0053] In this specification, "ring-forming carbon number" refers to the number of carbon atoms required to form a ring, and does not include the number of carbon atoms of the substituents on the ring. For example, for both the cyclohexane backbone and the methylcyclohexane backbone, the ring-forming carbon number is 6.

[0054] In addition, forms formed by arbitrarily combining the details described in this specification are also included in the present invention.

[0055] [Photosensitive resin composition, photosensitive resin composition for photovia formation and photosensitive resin composition for interlayer insulating layer]

[0056] A photosensitive resin composition according to one embodiment of the present invention (hereinafter simply referred to as this embodiment) is a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and (B) a photopolymerization initiator, wherein the photopolymerizable compound having (A) an ethylenically unsaturated group comprises (A1) a photopolymerizable compound having an acidic substituent and a cycloaliphatic backbone together with the ethylenically unsaturated group.

[0057] In addition, in this specification, the above components may each be referred to as component (A), component (B), component (A1), etc., and other components may be omitted in the same manner. In this specification, "resin component" refers to the above components (A) and (B), etc., and includes other components that may be included as needed (e.g., components (C), (D), (E), and (H), etc.), but does not include (F) inorganic filler and (G) pigment that may be included as needed, as described below. Also, "solid component" refers to a non-volatile component excluding volatile substances such as water and solvents included in the photosensitive resin composition, and represents a component that remains without volatilizing when the resin composition is dried, and also includes components that are liquid, syrup-like, and wax-like at room temperature around 25°C.

[0058] Since the photosensitive resin composition of the present embodiment is suitable for via formation by photolithography (also referred to as photovia formation), the present invention also provides a photosensitive resin composition for photovia formation. Furthermore, since the photosensitive resin composition of the present embodiment has excellent via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, and is useful as an interlayer insulating layer of a multilayer printed circuit board, the present invention also provides a photosensitive resin composition for an interlayer insulating layer. In this specification, when the term "photosensitive resin composition" is used, it includes a photosensitive resin composition for photovia formation and a photosensitive resin composition for an interlayer insulating layer.

[0059] In addition, the photosensitive resin composition of the present embodiment is useful as a negative-type photosensitive resin composition.

[0060] Below, each component that may contain a photosensitive resin composition is described in detail.

[0061] <(A) Photopolymerizable compound having an ethylenically unsaturated group>

[0062] The photosensitive resin composition of the present embodiment comprises a photopolymerizable compound having an ethylenically unsaturated group as component (A). Examples of the ethylenically unsaturated group having component (A) include a vinyl group, an allyl group, a propagyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, a (meth)acryloyl group, etc. As for the ethylenically unsaturated group, a (meth)acryloyl group is preferred.

[0063] The present invention comprises a photopolymerizable compound having an acidic substituent and an alicyclic skeleton, along with an ethylenically unsaturated group (A1) described below. By including the component (A) as the component (A1), a photosensitive resin composition is obtained that has excellent via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability.

[0064] The following describes the component (A1) in detail.

[0065] ((A1) Photopolymerizable compounds having acidic substituents and alicyclic skeletons along with ethylenically unsaturated groups)

[0066] (A1) The ethylenically unsaturated group having the component may be the same as the aforementioned ethylenically unsaturated group, and at least one selected from the group consisting of vinyl group, allyl group, propagyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group and (meth)acryloyl group is preferred, vinyl group, allyl group, (meth)acryloyl group is more preferred, and (meth)acryloyl group is more preferred.

[0067] (A1) As for the acidic substituents of the component, it is preferable to have one or more selected from the group consisting of, for example, carboxyl groups, sulfonic acid groups, phenolic hydroxyl groups, etc., and carboxyl groups are more preferable.

[0068] (A1) As for the cyclic framework of the component, a cyclic framework having 5 to 20 carbon atoms is preferred in terms of via resolution, adhesion strength with plated copper, crack resistance and electrical insulation reliability, a cyclic framework having 5 to 18 carbon atoms is more preferred, a cyclic framework having 6 to 18 carbon atoms is more preferred, a cyclic framework having 8 to 14 carbon atoms is particularly preferred, and a cyclic framework having 8 to 12 carbon atoms is most preferred.

[0069] In addition, the above-mentioned cyclic framework is preferably composed of two or more rings, more preferably two to four rings, and even more preferably three rings, in terms of via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability. Examples of cyclic frameworks with two or more rings include a norbornene framework, a decalin framework, a bicycloundecane framework, a saturated dicyclopentadiene framework, etc.

[0070] As for the above cyclic framework, a saturated dicyclopentadiene framework is preferred in terms of via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, and a cyclic framework (saturated dicyclopentadiene framework) represented by the following general formula (a) is more preferred.

[0071]

[0072] (of general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any of the above alicyclic skeletons. 1 is an integer from 0 to 6. * is a connection site to another structure.)

[0073] In general formula (a), R A1 Examples of the alkyl groups having 1 to 12 carbon atoms shown here include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, n-pentyl groups, etc. Among the alkyl groups, alkyl groups having 1 to 6 carbon atoms are preferred, alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl groups are even more preferred.

[0074] m 1 is an integer from 0 to 6, preferably an integer from 0 to 2, and more preferably 0.

[0075] m 1 If this is an integer from 2 to 6, multiple R A1 Each may be identical or different. Also, multiple R A1 The substitute may be placed on the same carbon atom or on different carbon atoms to the extent possible.

[0076] * is a bonding site to another structure and may be bonded to any one of the carbon atoms in the alicyclic skeleton, but it is preferable to be bonded to a carbon atom represented by 1 or 2 of the following general formula (a') and to a carbon atom represented by any one of 3 to 4.

[0077]

[0078] (of the general formula (a'), R A1 , m 1 and * are identical to those in general formula (a).

[0079] As for the (A1) component, an “(A1-1) acid-modified ethylenedimethyl group and alicyclic skeleton-containing epoxy derivative” is preferred, which is formed by reacting (a3) ​​a polybasic acid anhydride containing a saturated or unsaturated group with (a1) a compound modified in (a2) an organic acid containing an ethylenedimethyl group [hereinafter referred to as component (A')], which is capable of alkaline development and also has excellent via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability.

[0080] - (a1) Epoxy resin containing a cycloidal framework -

[0081] The above (a1) epoxy resin containing a cycloidal framework is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, a glycidyl ether type epoxy resin is preferred.

[0082] In the present invention, at least an epoxy resin having a cycloaliphatic framework is used as the epoxy resin. The cycloaliphatic framework is described in the same way as the cycloaliphatic framework of component (A1) described above, and the preferred embodiment is also the same.

[0083] (a1) As for the epoxy resin containing a cycloaliphatic framework, an epoxy resin represented by the following general formula (a1-1) is preferred. Additionally, an epoxy resin having a structural unit represented by the following general formula (a1-2) is also preferred.

[0084]

[0085] (of general formula (a1-1), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic framework. R A2 represents an alkyl group having 1 to 12 carbon atoms. m 1is an integer from 0 to 6, m 2 is an integer from 0 to 3. n is from 0 to 10.)

[0086]

[0087] (of general formula (a1-2), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any point in the above alicyclic framework. 1 is an integer from 0 to 6.

[0088] Among general formulas (a1-1) and (a1-2), R A1 is R in general formula (a) A1 It is identical to, and the desirable mode is also identical.

[0089] R in the general formula (a1-1) A2 Examples of the alkyl groups having 1 to 12 carbon atoms represented by α include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, n-pentyl groups, etc. Among the alkyl groups, alkyl groups having 1 to 6 carbon atoms are preferred, alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl groups are even more preferred.

[0090] m in general formulas (a1-1) and (a1-2) 1 is m in general formula (a) 1 It is identical to, and the desirable mode is also identical.

[0091] m in the general formula (a1-1) 2 is an integer from 0 to 3, preferably 0 or 1, and more preferably 0.

[0092] In general formula (a1-1), n ​​represents the number of repetitions of the structural unit within the parentheses and is 0 to 10. Typically, since epoxy resins are mixtures of different numbers of repetitions of the structural unit within the parentheses, in that case, n is expressed as the average value of the mixture. As for n, 2 to 10 is preferred.

[0093] (a1) As for the epoxy resin containing a cycloaliphatic framework, commercially available products may be used. Examples of commercially available products include XD-1000 (manufactured by Nippon Kayaku Kabushiki Kaisha, trade name), EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200HH, EPICLON HP-7200HHH (manufactured by DIC Corporation, trade name “EPICLON” is a registered trademark).

[0094] (a1) As the epoxy resin, an epoxy resin other than the epoxy resin having the above-mentioned alicyclic skeleton (hereinafter referred to as "other epoxy resin") may be used in combination. Examples of other epoxy resins include bisphenol-based epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolak type epoxy resins such as bisphenol A novolak type epoxy resin and bisphenol F novolak type epoxy resin; novolak type epoxy resins other than the above-mentioned bisphenol-based novolak type epoxy resins, such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, and biphenyl novolak type epoxy resin; phenol aral-kil type epoxy resin; phenyl aral-kil type epoxy resin; stilbene type epoxy resin; and naphthalene-skeleton-containing epoxy resins such as naphthalene type epoxy resin, naphthol novolak type epoxy resin, naphthol type epoxy resin, naphthol aral-kil type epoxy resin, and naphtylene ether type epoxy resin. Examples include biphenyl-type epoxy resin; xylylene-type epoxy resin; dihydroanthracene-type epoxy resin; aliphatic chain-type epoxy resin; rubber-modified epoxy resin, etc.

[0095] - (a2) Organic acids containing ethylenically unsaturated groups -

[0096] As for the above (a2) organic acid containing an ethylene unsaturated group, it is not particularly limited, but an ethylene unsaturated monocarboxylic acid is preferred. The ethylene unsaturated group is the same as described for the ethylene unsaturated group in the above (A1) component.

[0097] Examples of such monocarboxylic acids containing ethylenically unsaturated groups include, for instance, acrylic acid; acrylic acid derivatives such as dimers of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylic acid, cinnamic acid, crotonic acid, and α-cyanocinic acid; semi-ester compounds that are reaction products of a hydroxyl-containing acrylate and a dibasic acid anhydride; and semi-ester compounds that are reaction products of a monoglycidyl ether containing ethylenically unsaturated groups or a monoglycidyl ester containing ethylenically unsaturated groups and a dibasic acid anhydride. Among these, acrylic acid is preferred.

[0098] (a2) One type of ingredient may be used alone, or two or more types may be used in combination.

[0099] The above-mentioned semi-ester compound can be obtained, for example, by reacting a hydroxyl group-containing acrylate, an ethylenedimethyl group-containing monoglycidyl ether, or an ethylenedimethyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio.

[0100] (a2) Examples of hydroxyl group-containing acrylates, ethylenedimethyl unsaturated group-containing monoglycidyl ethers and ethylenedimethyl unsaturated group-containing monoglycidyl esters used in the synthesis of the above-mentioned semi-ester compound, which is an example of a component, include, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, glycidyl methacrylate, etc.

[0101] The dibasic acid anhydride used in the synthesis of the above-mentioned semi-ester compound may contain a saturated group or may contain an unsaturated group. Examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc.

[0102] Although not specifically limited, in the reaction between the above-mentioned component (a1) and the above-mentioned component (a2), it is preferable to react at a ratio where the amount of component (a2) is 0.6 to 1.05 equivalents relative to 1 equivalent of the epoxy group of component (a1), and it may also be reacted at a ratio where the amount is 0.8 to 1.0 equivalents. By reacting at such a ratio, photopolymerization is improved, that is, photosensitivity increases, and the resolution of the via tends to improve.

[0103] The above (a1) component and the above (a2) component can be dissolved in an organic solvent and reacted.

[0104] Examples of organic 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-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0105] In addition, it is preferable to use a catalyst to promote the reaction between the above-mentioned component (a1) and the above-mentioned component (a2). Examples of the catalysts include amine-based catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide; and phosphine-based catalysts such as triphenylphosphine. Among these, phosphine-based catalysts are preferred, and triphenylphosphine is more preferred.

[0106] The amount of catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the total of the above (a1) component and the above (a2) component. With the above amount, the reaction between the above (a1) component and the above (a2) component tends to be promoted.

[0107] In addition, it is desirable to use a polymerization inhibitor to prevent polymerization during the reaction. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.

[0108] When a polymerization inhibitor is used, the amount used is preferably 0.01 to 1 mass part, more preferably 0.02 to 0.8 mass parts, and even more preferably 0.05 to 0.5 mass parts, with respect to improving the storage stability of the composition, with respect to 100 mass parts of the total of the above (a1) component and the above (a2) component.

[0109] The reaction temperature between the above (a1) component and the above (a2) component is, in terms of productivity, preferably 60 to 150 ℃, more preferably 70 to 120 ℃, and even more preferably 80 to 110 ℃.

[0110] Thus, it is presumed that the component (A') formed by reacting the above component (a1) and the above component (a2) has a hydroxyl group formed by the reaction of the epoxy group of component (a1) and the carboxyl group of component (a2) at the ring-opening portion.

[0111] - (a3) ​​Polybasic acid anhydride -

[0113] The above (a3) ​​component may contain a saturated group or an unsaturated group. Examples of (a3) ​​components include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc. Among these, tetrahydrophthalic anhydride is preferably used from the perspective of via resolution.

[0114] It is presumed that by further reacting the (A') component obtained above with the (a3) ​​component containing saturated or unsaturated groups, the hydroxyl group of the (A') component (including the hydroxyl group originally present in the (a1) component) and the acid anhydride group of the (a3) ​​component are semi-esterified, resulting in an (A1-1) acid-modified ethylene-based unsaturated group and alicyclic backbone-containing epoxy derivative.

[0115] In the reaction between component (A') and component (a3), for example, by reacting component (a3) ​​with 0.1 to 1.0 equivalents for every 1 equivalent of a hydroxyl group in component (A'), the acid value of the (A1-1) acid-modified ethylenically unsaturated epoxy derivative containing a dicycloal framework can be adjusted.

[0116] (A1-1) The acid value of an acid-modified epoxy derivative containing an ethylenically unsaturated group and a dicycloal framework is preferably 20 to 150 mgKOH / g, more preferably 30 to 120 mgKOH / g, and even more preferably 40 to 100 mgKOH / g. If the acid value is 20 mgKOH / g or higher, the photosensitive resin composition tends to have excellent solubility in a diluted alkaline solution, and if it is 150 mgKOH / g or lower, the electrical properties of the cured film tend to improve.

[0117] The reaction temperature between component (A') and component (a3) ​​is, in terms of productivity, preferably 50 to 150 ℃, more preferably 60 to 120 ℃, and even more preferably 70 to 100 ℃.

[0118] In the above, the photopolymerizable compound having an acidic substituent and a cycloaliphatic skeleton together with the ethylenically unsaturated group (A1) is not particularly limited, but is preferably represented by the following general formula (A-1).

[0119]

[0120] (of general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic framework. R A2 represents an alkyl group having 1 to 12 carbon atoms. R A3 It is silver, an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least one R A3 is an organic group having an ethylenically unsaturated group and an acidic substituent. 1 is an integer from 0 to 6, m 2 is an integer from 0 to 3. n is from 0 to 10.)

[0121] R in the above general formula (A-1) A1 , R A2 , m 1 , m 2and n are identical to those in the above general formula (a1-1), and the preferred ones are also identical.

[0122] R A3 ...is the same as the definition above, but corresponds to the portion formed by the reaction of the glycidyl group in the general formula (a1-1) with the component (a2) and the component (a3), and is defined in a way that takes into account the fact that some of the glycidyl group remains unreacted. That is, R A3 The option "organic group having an ethylenically unsaturated group" is a group derived from (a2), and the "organic group having an ethylenically unsaturated group and an acidic substituent" is a group derived from components (a2) and (a3), and if components (a2) and (a3) ​​react with all glycidyl groups in the general formula (a1-1), R a3 The part that reacts only with the above (a2) component becomes an “organic group having an ethylenically unsaturated group and an acidic substituent,” but the part that does not react with either of the above (a2) and (a3) ​​components becomes a “glycidyl group.”

[0123] ((A1) Molecular weight of a photopolymerizable compound having an acidic substituent and a dicycloidal skeleton along with an ethylenically unsaturated group)

[0124] (A1) The weight average molecular weight (Mw) of the component is preferably 1,000 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 18,000. Within this range, the adhesion strength with plated copper, heat resistance, and electrical insulation reliability are improved. In particular, it is preferable that the weight average molecular weight (Mw) of the acid-modified ethylenedimethyl unsaturated group and alicyclic backbone-containing epoxy derivative (A1-1) be within the above range. Here, in this specification, the weight average molecular weight is a value measured using a calibration curve of standard polystyrene by gel permeation chromatography (GPC) (manufactured by Higashi Sokabushiki Kaisha), and more specifically, a value measured according to the method described below.

[0125] Method for Measuring Weight-Average Molecular Weight

[0126] The weight-average molecular weight was measured using the GPC measuring device and under the following measurement conditions, and the value converted using the calibration curve of standard polystyrene was taken as the weight-average molecular weight. In addition, for the preparation of the calibration curve, five sample sets ("PStQuick MP-H" and "PStQuick B", manufactured by Higashi Sokabushiki Kaisha) were used as standard polystyrene.

[0127] (GPC measuring device)

[0128] GPC Device: High-speed GPC device "HCL-8320GPC", detector is a differential refractometer or UV, manufactured by Higashi Sokabushiki Co., Ltd.

[0129] Column: Column TSKgel SuperMultipore HZ-H (Column length: 15 cm, Column inner diameter: 4.6 mm), Manufactured by Higashi Sokabushiki Co., Ltd.

[0130] (Measurement conditions)

[0131] Solvent: Tetrahydrofuran (THF)

[0132] Measured temperature: 40 ℃

[0133] Flow rate: 0.35 mL / min

[0134] Sample concentration: 10 mg / THF 5mL

[0135] Injection volume: 20 μL

[0136] ((A2-1) Acid-modified ethylenedimethyl unsaturated epoxy derivatives not containing a dicycloidal framework)

[0137] (A) As a photopolymerizable compound having an ethylenically unsaturated group, it may also be an embodiment comprising “(A2-1) an acid-modified ethylenically unsaturated group-containing epoxy derivative not containing an alicyclic skeleton” formed by reacting (a21) an epoxy resin (except that it does not contain an alicyclic skeleton) with (a22) an organic acid containing an ethylenically unsaturated group with (a23) a polybasic acid anhydride containing a saturated or unsaturated group.

[0138] The above (a21) epoxy resin is not particularly limited as long as it is an epoxy resin that does not contain a cycloaliphatic backbone, and examples include glycidyl ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, etc. Among these, a glycidyl ether type epoxy resin is preferred.

[0139] In addition, the above (a21) epoxy resin is classified into various epoxy resins depending on the difference in the main framework, and each of the above types of epoxy resins is further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolak type epoxy resins such as bisphenol A novolak type epoxy resin and bisphenol F novolak type epoxy resin; novolak type epoxy resins other than the above bisphenol-based novolak type epoxy resins, such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, and biphenyl novolak type epoxy resin; phenol aral-kil type epoxy resin; stilbene type epoxy resin; naphthalene-based skeleton-containing epoxy resins such as naphthalene type epoxy resin, naphthol novolak type epoxy resin, naphthol type epoxy resin, naphthol aral-kil type epoxy resin, and naphthylene ether type epoxy resin; biphenyl type epoxy resin; and biphenyl aral-kil type epoxy resin. They are classified into xylylene-type epoxy resins; dihydroanthracene-type epoxy resins; aliphatic chain-type epoxy resins; rubber-modified epoxy resins, etc. Among these, bisphenol-based novolak-type epoxy resins are preferred, and bisphenol F novolak-type epoxy resins are even more preferred.

[0140] The above (a22) ethylenedimethyl unsaturated group-containing organic acid and the above (a23) saturated or unsaturated group-containing polybasic acid anhydride are described in the same way as the above (a2) ethylenedimethyl unsaturated group-containing organic acid and the above (a3) ​​saturated or unsaturated group-containing polybasic acid anhydride, and the preferred embodiment is also the same.

[0141] Additionally, as a method for reacting the above (a23) component with the compound in which the above (a21) component is modified into the above (a22) component, a method of reacting the above (a3) ​​component with the compound in which the above (a1) component is modified into the above (a2) component may be referenced.

[0142] (A2-1) As for acid-modified ethylene unsaturated group-containing epoxy derivatives that do not contain a cycloaliphatic backbone, commercial products may be used. Examples of commercial products include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, UXE-3024, ZFR-1185, ZCR-1569H, ZXR-1807, ZCR-6000, ZCR-8000 (all manufactured by Nihon Kayaku Kabushiki Kaisha, trade names), UE-9000, UE-EXP-2810PM, UE-EXP-3045 (all manufactured by DIC Corporation, trade names).

[0143] (A) When the component contains both the above (A1-1) component and the above (A2-1) component, in terms of the balance of characteristics such as via resolution, adhesion strength with plated copper, crack resistance and electrical insulation reliability, the content ratio [(A1-1) / (A2-1)] of the (A1-1) component and the (A2-1) component is, in mass ratio, preferably 20 / 80 to 99 / 1, more preferably 50 / 50 to 99 / 1, even more preferably 60 / 40 to 99 / 1, particularly preferably 60 / 40 to 85 / 15, and most preferably 65 / 35 to 80 / 20.

[0144] ((A2-2) Styrene - Maleic acid resin)

[0145] (A) As a photopolymerizable compound having an ethylenically unsaturated group, a “(A2-2) styrene-maleic acid resin” such as a hydroxyethyl (meth)acrylate modified product of a styrene-maleic anhydride copolymer may be used in combination. The (A2-2) component does not contain a dicyclic skeleton. The (A2-2) component may be used alone or in combination of two or more types.

[0146] ((A2-3) Epoxy-based polyurethane resin)

[0147] In addition, as (A) a photopolymerizable compound having an ethylenically unsaturated group, a “(A2-3) epoxy-based polyurethane resin” obtained by reacting the (A’) component, which is a compound obtained by modifying the (a21) epoxy resin with (a22) an organic acid containing an ethylenically unsaturated group, with an isocyanate compound may be used in combination. The (A2-3) component does not contain a cycloaliphatic backbone. The (A2-3) component may be used alone or in combination of two or more types.

[0148] (Component (A) other than the above)

[0149] (A) As a photopolymerizable compound having an ethylenically unsaturated group, in order to increase chemical resistance after curing (exposure) and to increase the difference in developer resistance between the exposed and unexposed parts, it is preferable to have an embodiment comprising at least one selected from the group consisting of (Ai) a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group, (Aii) a difunctional vinyl monomer having two polymerizable ethylenically unsaturated groups, and (Aiii) a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups, and an embodiment comprising the above-mentioned (Aiii) component is more preferable. For components (Ai) to (Aiii), it is preferable that the molecular weight be 1,000 or less. However, in the present invention, the above-mentioned (Ai) to (Aiii) components do not include the above-mentioned (A1) component.

[0150] ((Ai) Monofunctional vinyl monomer)

[0151] Examples of monofunctional vinyl monomers having one polymerizable ethylenically unsaturated group include (meth)acrylic acid, (meth)acrylic acid alkyl esters, etc. 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, (meth)acrylic acid hydroxyethyl ester, etc. (Ai) The component may be used alone or two or more may be used in combination.

[0152] ((Aii) Difunctional vinyl monomer)

[0153] Examples of the above-mentioned difunctional vinyl monomers having two polymerizable 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, bisphenol A diglycidyl ether di(meth)acrylate, etc. (Aii) The component may be used alone or in combination of two or more types.

[0154] ((Aiii) Polyfunctional vinyl monomer)

[0155] The above-mentioned polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups includes, for example, a (meth)acrylate compound having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri(meth)acrylate; a (meth)acrylate compound having a skeleton derived from tetramethylolmethane, such as tetramethylolmethane tri(meth)acrylate or tetramethylolmethane tetra(meth)acrylate; a (meth)acrylate compound having a skeleton derived from pentaerythritol, such as pentaerythritol tri(meth)acrylate or pentaerythritol tetra(meth)acrylate; and a (meth)acrylate compound having a skeleton derived from dipentaerythritol, such as dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate. Examples include (meth)acrylate compounds having a backbone derived from ditrimethylolpropane, such as ditrimethylolpropane tetra(meth)acrylate; and (meth)acrylate compounds having a backbone derived from diglycerin. Among these, (meth)acrylate compounds having a backbone derived from dipentaerythritol are preferred, and dipentaerythritol penta(meth)acrylate is more preferred, from the perspective of increasing chemical resistance after curing (exposure) and increasing the difference in developer resistance between the exposed and unexposed parts. (Aiii) The component may be used as a single type or in combination of two or more types.

[0156] Here, the phrase "(meth)acrylate compound having a skeleton derived from XXX" (where XXX is a compound name) means an esterified product of XXX and (meth)acrylic acid, and the said esterified product also includes a compound modified with an alkyleneoxy group.

[0157] ((A) Content of ingredient)

[0158] (A) The content of the component is not particularly limited, but is preferably 5 to 60 mass%, more preferably 10 to 55 mass%, even more preferably 20 to 50 mass%, particularly preferably 25 to 50 mass%, and most preferably 30 to 45 mass% based on the total solid content of the photosensitive resin composition in terms of heat resistance, electrical properties and chemical resistance.

[0159] (A) As for the component, it is not particularly limited, but from the perspective of photosensitive properties, it is preferable to use the above (A1) component and the above (Aiii) component together. In this case, the content ratio [(A1) / (Aiii)] (mass ratio) of the above (A1) component and the above (Aiii) component is preferably 2 to 20, more preferably 2 to 15, even more preferably 2.5 to 10, and particularly preferably 3 to 8.

[0160] In addition, the content ratio of component (A1) to the total amount of component (A) is preferably 20 to 95 mass%, more preferably 40 to 90 mass%, even more preferably 55 to 90 mass%, and particularly preferably 70 to 90 mass%, in terms of via resolution, adhesion strength with plated copper, crack resistance and electrical insulation reliability.

[0161] <(B) Photopolymerization Initiator>

[0162] As for the component (B) used in this embodiment, there are no particular limitations as long as it is capable of polymerizing the component (A), and it can be appropriately selected from commonly used photopolymerization initiators.

[0163] (B) As components, benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, N,N-dimethylaminoacetophenone, etc.; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; thioxantones such as 2,4-dimethylthioxantone, 2,4-diethylthioxantone, 2-chlorothioxantone, 2,4-diisopropylthioxantone; ketal types such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, mihiller ketone, 4-benzoyl-4'-methyldiphenyl sulfide; Examples include acridins such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and oxime esters such as 1,2-octanedion-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]. Among these, acetophenones and thioxantones are preferred, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxantone are more preferred. Acetophenones have the advantage of being difficult to volatilize and difficult to generate as outgas, while thioxantones have the advantage of being photocurable even in the visible light range.

[0164] (B) The component may be used alone or in combination with two or more types. When two or more types are used in combination, it is preferable to use acetophenones and thioxantones together, and it is more preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxantone together.

[0165] ((B) Content of Component)

[0166] (B) The content of component (B) is not particularly limited, but is preferably 0.1 to 15 mass%, more preferably 0.15 to 5 mass%, even more preferably 0.2 to 1.5 mass%, and particularly preferably 0.2 to 0.8 mass% based on the total solid content of the photosensitive resin composition. If the content of component (B) is 0.1 mass% or more, the risk of the exposed area leaching out during development in the interlayer insulating layer formed using the photosensitive resin composition tends to be reduced, and if it is 15 mass% or less, the heat resistance tends to be improved.

[0167] <(B') Photopolymerization Initiation Agent>

[0168] The photosensitive resin composition of the present embodiment may contain a (B') photopolymerization initiator together with the above-mentioned (B) component. Examples of (B') photopolymerization initiator include tertiary amines such as N,N-dimethylaminobenzoate ethyl ester, N,N-dimethylaminobenzoate isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. The (B') component may be used alone or in combination of two or more types.

[0169] When the photosensitive resin composition of the present embodiment contains component (B'), the content thereof is preferably 0.01 to 20 mass%, more preferably 0.2 to 5 mass%, and even more preferably 0.3 to 2 mass% based on the total amount of resin components of the photosensitive resin composition. In addition, the photosensitive resin composition of the present embodiment does not have to contain component (B').

[0170] <(C) Thermosetting Resin>

[0171] The photosensitive resin composition of the present embodiment may also contain a thermosetting resin as component (C), and it is preferable that it does. In component (C), the component corresponding to component (A) above is not included, and in this respect, component (C) can be said not to have an ethylenically unsaturated group. In addition, a material having an epoxy group after satisfying the corresponding conditions is included in component (C).

[0172] By including (C) a thermosetting resin in the photosensitive resin composition of the present embodiment, there is a tendency for not only the adhesion strength with plated copper and insulation reliability to be improved, but also the heat resistance to be improved.

[0173] Examples of thermosetting resins include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxadine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triadine resin, melamine resin, etc. In addition, known thermosetting resins may be used without being particularly limited to these. Among these, epoxy resin is preferred.

[0174] (C) The ingredients may be used as a single type or in combination of two or more types.

[0175] As for the epoxy resin, it is preferable to be an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0176] In addition, epoxy resins are classified into various types based on differences in their main frameworks, and each of the above-mentioned types of epoxy resins is further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolak type epoxy resins such as bisphenol A novolak type epoxy resin and bisphenol F novolak type epoxy resin; novolak type epoxy resins other than the above-mentioned bisphenol-based novolak type epoxy resins, such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, and biphenyl novolak type epoxy resin; phenol aral-kil type epoxy resin; stilbene type epoxy resin; naphthalene-frame-containing epoxy resins such as naphthalene type epoxy resin, naphthol novolak type epoxy resin, naphthol type epoxy resin, naphthol aral-kil type epoxy resin, and naphthylene ether type epoxy resin; biphenyl type epoxy resin; phenyl aral-kil type epoxy resin; and xylylene type epoxy resin. It is classified into dihydroanthracene-type epoxy resin; dicyclopentadiene-type epoxy resin; alicyclic epoxy resin; heterocyclic epoxy resin; spiro-ring containing epoxy resin; cyclohexanedimethanol-type epoxy resin; trimethylol-type epoxy resin; aliphatic epoxy resin; rubber-modified epoxy resin; etc.

[0177] (C) The ingredients may be used as a single type or in combination of two or more types.

[0179] Among these, in particular, in terms of heat resistance, electrical insulation reliability and adhesion strength with plated copper, bisphenol-based epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, and cresol novolak-type epoxy resin are preferred, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and biphenyl-type epoxy resin are more preferred, bisphenol F-type epoxy resin and biphenyl-type epoxy resin are more preferred, and biphenyl-type epoxy resin is particularly preferred.

[0180] These may use commercially available products, for example, bisphenol A type epoxy resin ("jER828EL", "YL980" manufactured by Mitsubishi Chemica Co., Ltd.), bisphenol F type epoxy resin ("jER806H", "YL983U" manufactured by Mitsubishi Chemica Co., Ltd.), naphthalene type epoxy resin ("HP4032D", "HP4710" manufactured by DIC Corporation), naphthalene backbone-containing polyfunctional epoxy resin ("NC7000" manufactured by Nippon Kayaku Co., Ltd.), naphthol type epoxy resin ("ESN-475V" manufactured by Nittetsu Chemica & Materia Co., Ltd.), epoxy resin having a biphenyl structure ("NC3000H", "NC3500" manufactured by Nippon Kayaku Co., Ltd.), Mitsubishi Chemica Co., Ltd. Examples include "YX4000HK", "YL6121"), anthracene-type epoxy resin ("YX8800") manufactured by Mitsubishi Chemicaru Co., Ltd., glycerol-type epoxy resin ("ZX1542") manufactured by Nittetsu Chemicaru & Materia Co., Ltd., naphthylene ether-type epoxy resin ("EXA7311-G4") manufactured by DIC Corporation, cresol novolak-type epoxy resin ("EPICLON N-680") manufactured by DIC Corporation, etc.

[0181] In addition to the examples above, epoxy-modified polybutadiene may be used as the epoxy resin. In particular, regarding handling properties when manufacturing printed circuit boards, it is preferable to use a combination of an aromatic epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature as component (C). In this regard, it is preferable to use a combination of the epoxy resin (aromatic epoxy resin that is solid at room temperature) and the epoxy-modified polybutadiene (epoxy resin that is liquid at room temperature) as exemplified above. In this case, the content ratio of the two combined (aromatic epoxy resin that is solid at room temperature / epoxy resin that is liquid at room temperature) is, in mass ratio, preferably 95 / 5 to 60 / 40, more preferably 95 / 5 to 70 / 30, and even more preferably 90 / 10 to 75 / 25.

[0182] The above epoxy-modified polybutadiene preferably has hydroxyl groups at the molecular ends, more preferably has hydroxyl groups at both molecular ends, and even more preferably has hydroxyl groups only at both molecular ends. Additionally, there is no particular limitation on the number of hydroxyl groups of the above epoxy-modified polybutadiene as long as it is one or more, but preferably 1 to 5, more preferably 1 or 2, and even more preferably 2.

[0183] The above epoxy-modified polybutadiene is preferably an epoxy-modified polybutadiene represented by the following general formula (C-1) in terms of adhesion strength with plated copper, heat resistance, coefficient of thermal expansion, and flexibility.

[0184]

[0185] (In the above equation (C-1), a, b, and c represent the ratio of structural units within the parentheses, respectively, where a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.80, and also satisfy a + b + c = 1.00 and (a + c) > b. y represents the number of structural units within the parentheses and is an integer from 10 to 250.)

[0186] In the above general formula (C-1), the order of combination of each structural unit of the brackets is independent of order. That is, the structural unit indicated on the left, the structural unit indicated in the center, and the structural unit indicated on the right may be staggered, and if each is indicated as (a), (b), and (c), there may be various combination orders such as - [(a) - (b) - (c)] - [(a) - (b) - (c) -] -, - [(a) - (c) - (b)] - [(a) - (c) - (b) -] -, - [(b) - (a) - (c) -] -, - [(a) - (b) - (c)] - [(c) - (b) - (a) -] -, - [(a) - (b) - (a)] - [(c) - (b) - (c) -] -, - [(c) - (b) - (c)] - [(b) - (a) - (a) -] -, etc.

[0187] In terms of adhesion strength with plated copper, heat resistance, coefficient of thermal expansion, and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0.40 to 0.80. Also, in the same regard, y is preferably an integer from 30 to 180.

[0188] In the above general formula (C-1), commercially available epoxidized polybutadienes in which a = 0.20, b = 0.20, c = 0.60 and y = an integer from 10 to 250 include "EPOLEAD (registered trademark) PB3600" (manufactured by Daicel Co., Ltd.).

[0189] ((C) Content of Component)

[0190] When the photosensitive resin composition of the present embodiment contains component (C), the content thereof is not particularly limited, but is preferably 5 to 70 mass% based on the total solid content of the photosensitive resin composition, more preferably 5 to 40 mass%, even more preferably 7 to 30 mass%, and particularly preferably 10 to 20 mass%. If the content of component (C) is 5 mass% or more, sufficient crosslinking of the photosensitive resin composition can be obtained, and the adhesion strength with plated copper and electrical insulation reliability tend to improve. On the other hand, if it is 70 mass% or less, the resolution of the via tends to be good.

[0191] <(D) Elastomer>

[0192] The photosensitive resin composition of the present embodiment may contain an elastomer as component (D), and it is preferable to contain it. By including component (D), the photosensitive resin composition tends to have excellent via resolution, adhesion strength with plated copper, and electrical insulation reliability. In addition, component (D) also has the effect of suppressing the decrease in flexibility and adhesion strength with plated copper caused by internal distortion (internal stress) within the cured product due to the curing shrinkage of component (A).

[0193] (D) As for the component, an elastomer that is liquid at 25°C is preferred.

[0194] (D) One type of ingredient may be used alone, or two or more types may be used in combination.

[0195] Examples of elastomers include styrene-based elastomers, olefin-based elastomers, polyester-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, etc., and it is preferable to use at least one type selected from these. Such elastomers are composed of hard segment components and soft segment components, the former tending to contribute to heat resistance and strength, and the latter tending to contribute to flexibility and toughness.

[0196] (D) As for the component, among the examples above, it is preferable to include at least one selected from the group consisting of olefin elastomers, polyester elastomers, and urethane elastomers in terms of compatibility, solubility, and adhesion strength with plated copper, and it is more preferable to include a polyester elastomer. In addition, it is more preferable that the component (D) be at least one selected from the group consisting of olefin elastomers, polyester elastomers, and urethane elastomers, and it is particularly preferable that it be a polyester elastomer.

[0197] (Styrene-based elastomer)

[0198] Examples of the above styrene-based elastomers include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, etc. One type of styrene-based elastomer may be used alone, or two or more types may be used in combination.

[0199] Components constituting styrene-based elastomers include styrene; and styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene.

[0200] As for the styrene-based elastomer, it is preferable that the number average molecular weight is 1,000 to 50,000, and more preferable that it is 3,000 to 20,000.

[0201] In this specification, the number average molecular weight is a value obtained by standard polystyrene conversion using gel permeation chromatography (GPC) with tetrahydrofuran as a solvent.

[0202] For styrene-based elastomers, commercially available products may be used, including TUFPRENE, SOLPRENE T, ASAPRENE T, TUFTEC (all manufactured by Asahi Kasei Kabushiki Kaisha; "TUFPRENE," "ASAPRENE," and "TUFTEC" are registered trademarks), Elastomer AR (manufactured by Aaron Kasei Kabushiki Kaisha), KRATON G, CALIFLEX (all manufactured by Shell Japan, Inc.), JSR-TR, TSR-SIS, DYNARON (all manufactured by JSR Corporation), Denka STR (manufactured by Denka Corporation), QUINTAC (manufactured by Nihon Zeon Kabushiki Kaisha; "QUINTAC" is a registered trademark), and the TPE-SB series. Examples include (manufactured by Sumitomo Chemical Co., Ltd.), RABALON (manufactured by Mitsubishi Chemical Co., Ltd., "Rabalon" is a registered trademark), SEPTON, HYBRAR (both manufactured by Kuraray Co., Ltd., "SEPTON" and "HYBRAR" are registered trademarks), SUMIFLEX (manufactured by Sumitomo Bakelite Co., Ltd.), LEOSTOMER, ACTYMER (both manufactured by Riken Technos Co., Ltd., "LEOSTOMER" and "ACTYMER" are registered trademarks).

[0203] (Olefin elastomer)

[0204] The above olefin elastomer is, for example, a polymer or copolymer of an α-olefin having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 4-methylpentene. In addition, the olefin elastomer may have hydroxyl groups at the molecular ends, and it is preferable that it have hydroxyl groups at the molecular ends. One type of olefin elastomer may be used alone, or two or more types may be used in combination.

[0205] Suitable examples of olefin-based elastomers include polyethylene, polybutadiene, hydroxyl-containing polybutadiene, hydroxyl-containing polyisopropylene, ethylene-propylene copolymer (EPR), and ethylene-propylene-diene copolymer (EPDM). Additionally, copolymers of the above α-olefin having 2 to 20 carbon atoms with non-conjugated dienes having 2 to 20 carbon atoms, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and isoprene, may be used. Furthermore, carboxyl-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acnilonitrile copolymer may be used.

[0206] For the olefinic elastomer, it is preferable that the number average molecular weight is 1,000 to 5,000, and more preferable that it is 1,500 to 3,500.

[0207] For olefin-based elastomers, commercially available products may be used. Examples of commercially available products include MILASTOMER (Mitsui Kagaku Kabushiki Kaisha, trade name), EXACT (ExxonMobil, trade name), ENGAGE (Dow Chemical, trade name), Poly ip, Poly bd (Idemitsu Kosan Kabushiki Kaisha, trade name), hydrogenated styrene-butadiene rubber "DYNABON HSBR" (JSR Corporation, trade name), butadiene-acrylonitrile copolymer "NBR series" (JSR Corporation, trade name), butadiene-acrylonitrile copolymer with bicarboxyl groups modified "XER series" (JSR Corporation, trade name), and epoxidized polybutadiene, which is partially epoxidized polybutadiene, BF-1000. Examples include (manufactured by Nihon Soodakabushiki Kaisha, product name), PB-4700, PB-3600 (manufactured by Daicel Co., Ltd., product name), etc.

[0208] (Polyester-based elastomer)

[0209] Examples of the above polyester-based elastomers include those obtained by polycondensing a dicarboxylic acid or its derivative and a diol compound or its derivative. One type of polyester-based elastomer may be used alone, or two or more types may be used in combination.

[0210] Examples of the above dicarboxylic acids include, for instance, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aromatic dicarboxylic acids in which a hydrogen atom of the aromatic ring of the above aromatic dicarboxylic acid is substituted with a methyl group, an ethyl group, a phenyl group, etc.; aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as adipic acid, sebacic acid, and decanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for the dicarboxylic acid, it is also preferable to use a dimer acid derived from natural products in terms of adhesion to the substrate. One type of dicarboxylic acid may be used alone, or two or more types may be used in combination.

[0211] Examples of the above dicarboxylic acid derivatives include the anhydrous form of the above dicarboxylic acid.

[0212] Examples of the above 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 represented by the following general formula (D-1). One type of diol compound may be used alone, or two or more types may be used in combination.

[0213]

[0214] (Of general formula (D-1), X D1 represents C1- to C10 alkylene groups, C2- to C10 alkylidene groups, C4- to C8 cycloalkylene groups, and -O-, -S-, -SO2-. R D1 and R D2 Each represents, independently, a halogen atom or a carbon-1 to carbon-12 alkyl group. p and q are each independently integers from 0 to 4, and r is 0 or 1.)

[0215] Among general formula (D-1), X D1 Examples of the alkylene groups having 1 to 10 carbon atoms shown here include methylene groups, 1,2-dimethylene groups, 1,3-trimethylene groups, 1,4-tetramethylene groups, 1,5-pentamethylene groups, etc. Among the alkylene groups, alkylene groups having 1 to 3 carbon atoms are preferred, and methylene groups are more preferred, from the perspective of via resolution, adhesion strength with plated copper, and electrical insulation reliability.

[0216] X D1Examples of the alkylidene groups having 2 to 10 carbon atoms shown here include ethylidene groups, propylidene groups, isopropylidene groups, butylidene groups, isobutylidene groups, pentylidene groups, isopentylidene groups, etc. Among the alkylidene groups, the isopropylidene group is preferred from the perspective of via resolution, adhesion strength with plated copper, and electrical insulation reliability.

[0217] X D1 Examples of cycloalkylene groups having 4 to 8 carbon atoms that represent this include cyclopentylene groups, cyclohexylene groups, cyclooctylene groups, etc.

[0218] X D1 Among the above, an alkylene group having 1 to 10 carbon atoms and an alkylidene group having 2 to 10 carbon atoms are preferred, and a methylene group and an isopropylidene group are more preferred.

[0219] In general formula (D-1), R D1 and R D2 Examples of halogen atoms represented by fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0220] R D1 and R D2 Examples of the alkyl group having 1 to 12 carbon atoms represented by α include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, n-pentyl groups, etc. As for the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.

[0221] p and q are each independently integers from 0 to 4, and each is preferably 0 or 1.

[0222] r is 0 or 1, either of which is acceptable, but when r is 0, the structure is represented by the following general formula (D-1').

[0223]

[0224] (of the general formula (D-1'), XD1 , R D1 and p are identical to those in general formula (D-1), and the preferred mode is also identical.)

[0225] Examples of aromatic diols represented by the above general formula (D-1) include bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane, resorcinol, etc.

[0226] In addition, as a polyester-based elastomer, a multi-block copolymer may be used in which an aromatic polyester (e.g., polybutylene terephthalate) portion is used as the hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) portion is used as the soft segment component, and it is preferable to use such a multi-block copolymer. As for such multi-block copolymers, there are commercially available products of various grades depending on the type, ratio, and molecular weight of the hard and soft segments. Specifically, examples include "HYTREL" (registered trademark) (manufactured by Toyobo Chemical Co., Ltd.), "PELPRENE" (registered trademark) (manufactured by Toyobo Chemical Co., Ltd.), and "ESPEL" (registered trademark) (manufactured by Hitachi Chemical Co., Ltd.).

[0227] As for the polyester elastomer, it is preferable that the number average molecular weight is 900 to 30,000, more preferable that it is 1,000 to 25,000, and more preferable that it is 5,000 to 20,000.

[0228] Polyester-based elastomers may be commercially available, and commercially available products other than those mentioned above include, for example, TESLAC 2505-63 (manufactured by Hitachi Kasei Kabushiki Kaisha, "TESLAC" is a registered trademark).

[0229] (Urethane-based elastomer)

[0231] The above urethane-based elastomer preferably contains, for example, a hard segment composed of a short-chain diol and a diisocyanate, and a soft segment composed of a high-molecular (long-chain) diol and a diisocyanate. The urethane-based elastomer may be used alone or in combination of two or more types.

[0232] Examples of polymeric (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), poly(1,6-hexylene-neopentylene adipate), etc. The number average molecular weight of the polymeric (long-chain) diol is preferably 500 to 10,000.

[0233] Examples of short-chain diols include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, etc. The number average molecular weight of the short-chain diol is preferably 48 to 500.

[0234] As for the urethane-based elastomer, it is preferable that the number average molecular weight is 1,000 to 25,000, more preferable that it is 1,500 to 20,000, and more preferable that it is 2,000 to 15,000.

[0235] For urethane-based elastomers, commercially available products may be used, and examples of commercially available products include NIPPOLAN 3116 (manufactured by Tosoh Corporation, "NIPPOLAN" is a registered trademark), PANDEX T-2185, T-2983N (both manufactured by DIC Corporation), MIRACTRAN series (manufactured by Nippon Miractran Kabushiki Kaisha, "MIRACTRAN" is a registered trademark), and HITALOD series (manufactured by Hitachi Kasei Kabushiki Kaisha, "HITALOD" is a registered trademark).

[0236] (Polyamide elastomer)

[0237] Polyamide-based elastomers are broadly classified into two types: the polyether blockamide type, which uses polyamide in the hard segment and polyether in the soft segment; and the polyetherester blockamide type, which uses polyamide in the hard segment and polyester in the soft segment.

[0238] Specific examples of the above polyamide-based elastomer include, for instance, block copolymers in which polyamide is used as the hard segment component and polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, polymethacrylate, polyurethane, silicone rubber, etc. are used as the soft segment component. One type of polyamide-based elastomer may be used alone, or two or more types may be used in combination.

[0239] As for the polyamide-based elastomer, it is preferable that the number average molecular weight is 1,000 to 50,000, and more preferable that it is 2,000 to 30,000.

[0240] For polyamide-based elastomers, commercially available products may be used, and examples of commercially available products include UBE polyamide elastomer (manufactured by Ube Kosan Kabushiki Kaisha), DIAMIDE (manufactured by Daicel Ebonic Co., Ltd., "DIAMIDE" is a registered trademark), PEBAX (manufactured by Tore Kabushiki Kaisha), GRILON ELY (manufactured by EMS-CHEMIE Japan Co., Ltd., "GRILON" is a registered trademark), NOVAMID (manufactured by Mitsubishi Chemica Kabushiki Kaisha), and "GRILAX" (manufactured by Toyobo Oseki Kabushiki Kaisha, "GRILAX" is a registered trademark).

[0241] (Acrylic elastomer)

[0242] Examples of the above acrylic elastomers include copolymers of raw monomers having acrylic acid esters as the main component. Suitable examples of acrylic acid esters include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, etc. Additionally, as crosslinking point monomers, copolymers of glycidyl methacrylate, allyl glycidyl ether, etc. may be used, or copolymers of acrylonitrile, ethylene, etc. Specifically, examples include acrylonitrile-butyl acrylate copolymers, acrylonitrile-butyl acrylate-ethyl acrylate copolymers, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymers, etc. One type of acrylic elastomer may be used alone, or two or more types may be used in combination.

[0243] As for the acrylic elastomer, it is preferable that the number average molecular weight is 1,000 to 50,000, and more preferable that it is 2,000 to 30,000.

[0244] (Silicone-based elastomer)

[0245] The above silicone-based elastomer is an elastomer with organic polysiloxane as the main component, and is classified, for example, into polydimethylsiloxane-based elastomers, polymethylphenylsiloxane-based elastomers, polyphenylsiloxane-based elastomers, etc. One type of silicone-based elastomer may be used alone, or two or more types may be used in combination.

[0246] As for the silicone-based elastomer, it is preferable that the number average molecular weight is 1,000 to 50,000, and more preferable that it is 2,000 to 30,000.

[0247] Silicone-based elastomers may be commercially available, and examples of commercially available products include the KE series (manufactured by Shin-Etsu Kagaku Kogyo Kabushiki Kaisha), SE series, CY series, and SH series (all manufactured by Tore, Dako Oningu Kabushiki Kaisha).

[0248] (Other elastomers)

[0249] In addition, (D) may be an embodiment comprising at least one selected from the group consisting of polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyetheretherketone resin, tetrafluoroethylene resin, polyacrylonitrile resin, maleic anhydride modified polybutadiene, phenol modified polybutadiene and carboxy-modified polyacrylonitrile.

[0250] ((D) Content of Component)

[0251] When the photosensitive resin composition of the present embodiment contains component (D), the content thereof is preferably 0.5 to 20 mass%, more preferably 1 to 20 mass%, even more preferably 1 to 15 mass%, particularly preferably 1 to 10 mass%, and most preferably 1 to 6 mass% based on the total solid content of the photosensitive resin composition. If the content of component (D) is 0.5 mass% or more, the effect of improving adhesion strength with plated copper is sufficient, and the electrical insulation reliability tends to be even better. If the content of component (D) is 20 mass% or less, the resolution of vias, adhesion strength with plated copper, and electrical insulation reliability tend to be sufficient together.

[0252] <(E) Thermal polymerization initiator>

[0253] The photosensitive resin composition of the present embodiment may contain a thermal polymerization initiator as component (E). As for the thermal polymerization initiator, although not particularly limited, examples include hydroperoxides such as diisopropylbenzene hydroperoxide "PERCUMYL P" (product name, manufactured by Ilyu Co., Ltd. (hereinafter the same)), cumene hydroperoxide "PERCUMYL H", and t-butyl hydroperoxide "PERBUTYL H"; Dialkyl peroxides such as α,α-bis(t-butylperoxy-m-isopropyl)benzene "perbutyl P", dicumyl peroxide "percumyl D", 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane "perhexa 25B", t-butylcumyl peroxide "perbutyl C", di-t-butylperoxide "perbutyl D", 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3 "perhexane 25B", t-butylperoxy-2-ethylhexanoate "perbutyl O"; ketone peroxides; peroxyketals such as n-butyl 4,4-di-(t-butylperoxy)valerate "perhexa V"; diacyl peroxides; Examples include organic peroxides such as peroxydicarbonates; peroxyesters; and azo compounds such as 2,2'-azobis(isobutylonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile). Among these, dialkyl peroxides are preferred, and 2,5-dimethyl-2,5-bis(t-bitylperoxy)hexine-3 is more preferred, from the perspective that they do not inhibit photopolymerization and have a significant effect in improving the physical properties and characteristics of the photosensitive resin composition.

[0254] One type of thermal polymerization initiator may be used alone, or two or more types may be used in combination.

[0255] ((E) Content of ingredient)

[0256] When the photosensitive resin composition of the present embodiment contains component (E), the content is not particularly limited, but is preferably 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, and even more preferably 0.03 to 2 mass% based on the total amount of resin components of the photosensitive resin composition. If it is 0.01 mass% or more, it tends to be sufficiently heat-curable, and if it is 5 mass% or less, the photosensitive properties and heat resistance tend to be good.

[0257] <(F) Inorganic Filler>

[0258] The photosensitive resin composition of the present embodiment may contain an inorganic filler as the (F) component, and it is preferable that it contains an inorganic filler. By containing an inorganic filler, low thermal expansion can be achieved, and the risk of warping is reduced. In thermosetting resin compositions that have been conventionally used as interlayer insulation layers for multilayer printed circuit boards, low thermal expansion has been achieved by including an inorganic filler; however, when an inorganic filler is included in a photosensitive resin composition, it has been difficult to achieve low thermal expansion by including a large amount because the inorganic filler becomes an obstacle to phenomena that cause light scattering. Thus, regarding the inclusion of an inorganic filler, a new challenge exists for the photosensitive resin composition alone; however, the photosensitive resin composition of the present embodiment tends to have higher resolution of vias even when a large amount of inorganic filler is included. Therefore, the photosensitive resin composition of the present embodiment can achieve both low thermal expansion and high resolution of vias.

[0259] (F) As components, for example, silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), magnesium carbonate (MgCO3), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), mullite (3Al2O 3ㆍ Examples include (2SiO2), coredierite (2MgO·2Al2O3 / 5SiO2), talc (3MgO·4SiO2·H2O), aluminum titanate (TiO2·Al2O3), yttria-containing zirconia (Y2O3·ZrO2), barium silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), hydrotalcite, mica, calcined kaolin, carbon, etc. (F) For the component, one type may be used alone, or two or more types may be used in combination.

[0260] The average particle diameter of component (F) is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, even more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm, in terms of via resolution. Here, the average particle diameter of component (F) is the volume-average particle diameter 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 (or dissolved) 1,000 times in methyl ethyl ketone, and then, using a submicron particle analyzer (Beckman Coulter, Inc., trade name: N5), the particles dispersed in the solvent at a refractive index of 1.38 are measured in accordance with the international standard ISO 13321, and the particle diameter at 50% (volume basis) of the cumulative value in the particle size distribution is taken as the average particle diameter (volume-average particle diameter). In addition, the (F) component included in the photosensitive resin film and interlayer insulating layer formed on the carrier film can also be measured by using the submicron particle analyzer after diluting (or dissolving) it by 1,000 times (volume ratio) using a solvent as described above.

[0261] As for component (F), it is preferable to include silica for the sake of heat resistance and low thermal expansion, and it is more preferable to use silica. Additionally, component (F) may be surface-treated with alumina or an organic silane compound for the sake of improving the dispersibility of inorganic fillers in the photosensitive resin composition by preventing aggregation.

[0262] ((F) Content of ingredient)

[0263] When the photosensitive resin composition of the present embodiment contains component (F), the content thereof is not particularly limited, but is preferably 5 to 80 mass%, more preferably 15 to 60 mass%, even more preferably 25 to 55 mass%, and particularly preferably 30 to 50 mass% based on the total solid content of the photosensitive resin composition. If the content of component (F) is within the above range, mechanical strength, heat resistance, and via resolution, etc. can be improved.

[0264] <(G) Pigment>

[0265] The photosensitive resin composition of the present embodiment may contain a pigment as component (G) according to the desired color for adjusting the photosensitivity. As component (G), a coloring agent that produces the desired color may be appropriately selected and used, and known coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black may be preferably used.

[0266] ((G) Content of ingredient)

[0267] When the photosensitive resin composition of the present embodiment contains component (G), the content thereof is preferably 0.01 to 5 mass%, more preferably 0.03 to 3 mass%, and even more preferably 0.05 to 2 mass% based on the total amount of solids of the photosensitive resin composition, for the purpose of adjusting photosensitivity.

[0268] <(H) Curing Agent>

[0269] The photosensitive resin composition of the present embodiment may contain a curing agent to further improve various properties such as heat resistance, adhesion strength with plated copper, and chemical resistance. In particular, when the thermosetting resin (C) contains an epoxy resin, it is preferable to contain an epoxy resin curing agent as the curing agent.

[0270] (H) As components, for example, imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamins such as acetoguanamin, benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazides; their organic acid salts and / or epoxy adducts; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xyllyl-S-triazine; Tertiary amines such as trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, m-aminophenol, etc.; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac, etc.; organic phosphines such as tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, etc.; phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide, hexadecyl tributylphosphonium chloride, etc.; quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyl tributylammonium chloride, etc.; the above-mentioned polybasic acid anhydride; Examples include diphenyl iodinium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiopyrillium hexafluorophosphate.

[0271] Among these, polyamines are preferred, and melamine is more preferred, from the perspective of further improving properties such as heat resistance, adhesion strength with plated copper, and chemical resistance.

[0272] When the photosensitive resin composition of the present embodiment contains component (H), the content is preferably 0.01 to 20 mass%, more preferably 0.02 to 10 mass%, and even more preferably 0.03 to 3 mass% based on the total amount of resin components of the photosensitive resin composition.

[0273] Diluted solution

[0274] In the photosensitive resin composition of the present embodiment, a diluent may be used as needed. For example, organic solvents may be used as diluents. Examples of organic 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, propylene glycol monoethyl ether 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. One type of diluent may be used alone, or two or more types may be used in combination.

[0275] (Diluent content)

[0276] The content of the diluent can be appropriately selected so that the concentration of the total amount of solids in the photosensitive resin composition is preferably 40 to 90 mass%, more preferably 50 to 80 mass%, and even more preferably 55 to 65 mass%. By adjusting the amount of diluent used in this way, the coating properties of the photosensitive resin composition are improved, and it becomes possible to form a more precise pattern.

[0277] Other Additives

[0278] The photosensitive resin composition of the present embodiment may, if necessary, contain various known and commonly used additives such as polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as benton and montmorillonite; defoaming agents such as silicone-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; and silane coupling agents. In addition, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, phosphate compounds of antimony compounds and phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters may be included.

[0279] The photosensitive resin composition of the present embodiment can be obtained by kneading and mixing each component using a roll mill, a bead mill, etc.

[0280] Here, the photosensitive resin composition of the present embodiment may be used in a liquid form or in a film form.

[0281] When used in a liquid form, the application method of the photosensitive resin composition of the present embodiment is not particularly limited, but various application methods such as printing, spin coating, spray coating, jet dispensing, inkjet, and immersion coating may be used. Among these, printing and spin coating methods may be appropriately selected from the viewpoint of more easily forming the photosensitive layer.

[0282] In addition, when used in the form of a film, it can be used, for example, in the form of a photosensitive resin film described later; in this case, a photosensitive layer of a desired thickness can be formed by laminating it onto a carrier film using a laminator or the like. Furthermore, using it in the form of a film is preferable because it increases the manufacturing efficiency of multilayer printed circuit boards.

[0283] [Photosensitive resin film, photosensitive resin film for interlayer insulation layer]

[0284] The photosensitive resin film of the present embodiment is composed of the photosensitive resin composition of the present embodiment as a photosensitive layer that later becomes an interlayer insulating layer. The photosensitive resin film of the present embodiment may also be an embodiment in which a photosensitive resin film is formed on a carrier film.

[0285] The thickness of the photosensitive resin film (photosensitive layer) (thickness after drying) is not particularly limited, but from the perspective of thinning the multilayer printed circuit board, it is preferably 1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 5 to 40 μm.

[0286] The photosensitive resin film of the present embodiment is obtained by forming a photosensitive layer that later becomes an interlayer insulating layer by applying and drying the photosensitive resin composition of the present embodiment onto a carrier film, for example, using a known coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, or die coater.

[0287] Examples of carrier films include polyester films such as polyethylene terephthalate films and polybutylene terephthalate films; and polyolefin films such as polypropylene films and polyethylene films. The thickness of the carrier film may be appropriately selected in the range of 5 to 100 μm, but is preferably 5 to 60 μm, and more preferably 15 to 45 μm.

[0288] In addition, the photosensitive resin film of the present embodiment may be provided with a protective film on the side opposite to the side in contact with the carrier film among the surfaces of the photosensitive layer. As the protective film, for example, a polymer film such as polyethylene or polypropylene may be used. In addition, a polymer film identical to the carrier film described above may be used, or a different polymer film may be used.

[0289] The drying of the coating film formed by applying the photosensitive resin composition may be performed using a hot air dryer, a far-infrared dryer, or a near-infrared dryer. The drying temperature is preferably 60 to 150°C, more preferably 70 to 120°C, and even more preferably 80 to 100°C. In addition, the drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes. The content of residual diluent in the photosensitive resin film after drying is preferably 3 mass% or less, more preferably 2 mass% or less, and even more preferably 1 mass% or less, from the perspective of preventing diffusion of the diluent during the manufacturing process of a multilayer printed circuit board.

[0290] The photosensitive resin film of the present embodiment is suitable as an interlayer insulating layer of a multilayer printed circuit board because it is excellent in via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability. That is, the present invention also provides a photosensitive resin film for an interlayer insulating layer. In addition, the photosensitive resin film for an interlayer insulating layer is also referred to as an interlayer insulating photosensitive film.

[0291] [Multilayer Printed Circuit Board and Method of Manufacturing the Same]

[0292] The present invention also provides a multilayer printed circuit board comprising an interlayer insulating layer formed using the photosensitive resin composition or photosensitive resin film of the present embodiment. The multilayer printed circuit board of the present embodiment has a process for forming an interlayer insulating layer using the photosensitive resin composition of the present embodiment, and there are no particular limitations on the manufacturing method thereof; for example, it can be easily manufactured by the manufacturing method of the multilayer printed circuit board of the present embodiment below.

[0293] Hereinafter, as an example of a preferred embodiment of a method for manufacturing a multilayer printed circuit board, a method for manufacturing a multilayer printed circuit board using the photosensitive resin film (photosensitive resin film for an interlayer insulating layer) of the present embodiment will be explained with reference to FIG. 1.

[0294] A multilayer printed circuit board (100A) can be manufactured by a manufacturing method including, for example, the following processes (1) to (4).

[0295] Process (1): A process of laminating the photosensitive resin film of the present embodiment onto one side or both sides of a circuit board (hereinafter referred to as "laminating process (1)").

[0296] Process (2): A process for forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in Process (1) (hereinafter referred to as "photovia formation process (2)").

[0297] Process (3): A process for roughening the above vias and the above interlayer insulating layer (hereinafter referred to as the "roughening process (3)").

[0298] Process (4): A process for forming a circuit pattern on the interlayer insulating layer (hereinafter referred to as "circuit pattern forming process (4)").

[0299] (Laminate Process (1))

[0300] The lamination process (1) is a process of laminating a photosensitive resin film (photosensitive resin film for interlayer insulating layer) of the present embodiment onto one side or both sides of a circuit board (a substrate (101) having a circuit pattern (102)) using a vacuum laminator. Examples of vacuum laminators include a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressure laminator manufactured by Meiki Co., Ltd., a roll dry coater manufactured by Hitachi, Ltd., and a vacuum laminator manufactured by Hitachi Chemical Electronics Co., Ltd.

[0301] In cases where a protective film is provided on the photosensitive resin film, the protective film can be peeled off or removed, and then the photosensitive resin film can be laminated by pressing it onto the circuit board while applying pressure and heating so that it comes into contact with the circuit board.

[0302] The lamination can be carried out, for example, by preheating the photosensitive resin film and the circuit board as needed, and then pressing at a compression temperature of 70 to 130°C, a compression pressure of 0.1 to 1.0 MPa, and a reduced pressure of 20 mmHg (26.7 hPa) or less, but is not particularly limited to these conditions. In addition, the lamination method may be a batch method or a continuous method using rolls.

[0303] Finally, the photosensitive resin film (hereinafter referred to as the photosensitive layer) laminated on the circuit board is cooled to near room temperature and becomes an interlayer insulating layer (103). The carrier film may be peeled off at this point, or it may be peeled off after exposure as described later.

[0304] (Photovia formation process (2))

[0305] The photovia formation process (2) involves exposing at least a portion of a photosensitive resin film laminated on a circuit board to light, and then developing it. By exposure, the portion irradiated with active light is photocured to form a pattern. There are no particular restrictions on the exposure method; for example, a method of irradiating active light onto an image through a negative or positive mask pattern called artwork (mask exposure method) may be adopted, or a method of irradiating active light in the form of an image by direct drawing exposure methods such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method may be adopted.

[0306] Known light sources may be used as the light source for the active light. Specifically, light sources include gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and argon lasers; solid-state lasers such as YAG lasers; and semiconductor lasers that effectively emit ultraviolet or visible light. The exposure dose is appropriately selected depending on the light source used and the thickness of the photosensitive layer; for example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, for a photosensitive layer thickness of 1 to 100 μm, the exposure dose is typically 10 to 1,000 mJ / cm². 2 The degree is desirable, and 15 to 500 mJ / cm² 2 It is more desirable.

[0307] In the phenomenon, the uncured portion of the above photosensitive layer is removed from the substrate, and an interlayer insulating layer composed of a photocured material is formed on the substrate.

[0308] If a carrier film is present on the photosensitive layer, the carrier film is removed, and then the removal (development) of the unexposed portion is performed. There are wet development and dry development methods, and either may be adopted, but wet development is widely used, and wet development may also be adopted in this embodiment.

[0309] In the case of wet development, a developer corresponding to the photosensitive resin composition is used, and development is performed using a known development method. Examples of development methods include the dip method, battle method, spray method, blushing, slapping, scraping, and agitation immersion. Among these, the spray method is preferred from the perspective of improving resolution, and among spray methods, the high-pressure spray method is more preferred. Development may be performed using only one method, but may also be performed by combining two or more methods.

[0310] The composition of the developer is appropriately selected according to the composition of the photosensitive resin composition. Examples include alkaline aqueous solutions, water-based developers, and organic solvent-based developers, among which alkaline aqueous solutions are preferred.

[0311] In the photovia formation process (2), after exposure and development, 200 to 10,000 mJ / cm 2 Approximately (preferably 500 to 5,000 mJ / cm²) 2 The interlayer insulating layer may be further cured by performing post-UV curing with an exposure amount of ) and post-thermal curing at a temperature of about 60 to 250°C (preferably 120 to 200°C) as needed, and it is also desirable to do so.

[0312] In this manner, an interlayer insulating layer having vias (104) is formed. There are no particular restrictions on the shape of the vias. When described in terms of a single-sided shape, examples include a square or an inverted shape (where the upper side is longer than the lower side), and when described in terms of a shape viewed from the front (where the bottom of the via is visible), examples include a circle or a square. In this embodiment, the formation of vias by photolithography can form vias with an inverted cross-sectional shape (where the upper side is longer than the lower side), which is preferable because it increases the adhesion rotation of the plated copper to the via wall.

[0313] The size (diameter) of the via formed by this process can be 60 μm or less, and it is even possible to make it less than 40 μm or 30 μm or less, and it can be made smaller than the via size produced by laser processing. There is no particular limit on the lower limit of the size (diameter) of the via formed by this process, but it may be 15 μm or more, or 20 μm or more.

[0314] However, the size (diameter) of the via formed by this process is not necessarily limited to 60 μm or less, but may be, for example, about 200 μm or less, or may be arbitrarily selected from a range of, for example, 15 to 300 μm.

[0315] (Harmonization process (3))

[0316] The harmonization treatment process (3) performs harmonization treatment on the surface of the via and the interlayer insulating layer using a harmonization solution. In addition, if smear occurs during the photovia formation process (2), the smear can be removed with the harmonization solution. Harmonization treatment and smear removal can be performed simultaneously.

[0317] Examples of the above-mentioned compounding solutions include chromium / sulfuric acid compounding solution, alkaline permanganate compounding solution (e.g., sodium permanganate compounding solution, etc.), sodium fluoride / chromium / sulfuric acid compounding solution, etc.

[0318] By harmonization treatment, anchors of irregularities are formed on the surface of vias and interlayer insulating layers.

[0319] (Circuit pattern formation process (4))

[0320] The circuit pattern forming process (4) is a process of forming a circuit pattern on the interlayer insulating layer after the above-mentioned harmony treatment process (3).

[0321] From the perspective of fine wiring formation, it is preferable to perform the formation of the circuit pattern by a semi-additive process. Conductivity of the vias is achieved along with the formation of the circuit pattern by the semi-additive process.

[0322] In the semi-additive process, first, a seed layer (105) is formed by performing electroless copper plating treatment on the entire surface of the via bottom, via wall, and interlayer insulating layer after the above-mentioned harmonization treatment process (3) using a palladium catalyst, etc. The seed layer is intended to form a power supply layer for performing electrolytic copper plating, and is preferably formed with a thickness of about 0.1 to 2.0 μm. If the thickness of the seed layer is 0.1 μm or more, it tends to suppress the decrease in connection reliability during electrolytic copper plating, and if it is 2.0 μm or less, it does not need to increase the amount of etching when flash etching the seed layer between the wires, and it tends to suppress damage to the wires during etching.

[0323] The above electroless copper plating treatment is carried out by depositing metallic copper on the surface of vias and interlayer insulating layers through the reaction of copper ions and a reducing agent.

[0324] The above electroless plating method and the above electrolytic plating method are known methods and are not particularly limited, but the catalyst of the electroless plating process is preferably a palladium-tin mixed catalyst, and the primary particle diameter of the catalyst is preferably 10 nm or less. In addition, the plating composition of the electroless plating process preferably contains hypophosphate as a reducing agent.

[0325] Commercially available products can be used as electroless copper plating solutions. Examples of commercially available products include "MSK-DK" manufactured by Atotech Japan KK and the "THRU-CUP (registered trademark) PEA ver.4" series manufactured by C. Uyemura & Co., Ltd.

[0326] After performing the above electroless copper plating treatment, a dry film resist is heat-pressed onto the electroless copper plating using a roll laminator. The thickness of the dry film resist must be higher than the wiring height after electroplating copper, and in this regard, a dry film resist with a thickness of 5 to 30 μm is preferred. As the dry film resist, the "PHOTEC" series manufactured by Hitachi Chemical Company, Ltd. is used.

[0327] After heat-pressing the dry film resist, the dry film resist is exposed through a mask on which, for example, a desired wiring pattern is drawn. The exposure can be performed using the same apparatus and light source as that used when forming vias in the photosensitive resin film. After exposure, the carrier film on the dry film resist is peeled off, and development is performed using an alkaline aqueous solution to remove unexposed portions and form a resist pattern (106). Afterward, if necessary, the development residue of the dry film resist may be removed using plasma or the like.

[0328] After development, electroplating with copper is performed to form a copper circuit layer (107) and to perform via filling.

[0329] After electroplating copper, the dry film resist is stripped using an alkaline aqueous solution or an amine-based stripping agent. After stripping the dry film resist, the seed layer between the wires is removed (flash etching). Flash etching is performed using an acidic solution, such as sulfuric acid and hydrogen peroxide, and an oxidizing solution. Specifically, examples include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc. After flash etching, palladium or similar substances attached to the portion between the wires are removed as needed. The removal of palladium can preferably be performed using an acidic solution, such as nitric acid or hydrochloric acid.

[0330] After peeling off the above dry film resist or after the flash etching process, preferably, a post-baking treatment is performed. The post-baking treatment sufficiently heat-cures unreacted heat-curing components and thereby improves electrical insulation reliability, curing characteristics, and adhesion strength with plated copper. Although the heat-curing conditions vary depending on the type of resin composition, it is preferable that the curing temperature be 150 to 240°C and the curing time be 15 to 100 minutes. After the post-baking treatment, the manufacturing process of a printed circuit board by the general photo via method is completed, but depending on the number of interlayer insulation layers required, this process is repeated to manufacture the substrate. Then, preferably, a solder resist layer (108) is formed on the outermost layer.

[0331] Although a method for manufacturing a multilayer printed circuit board that forms vias using the photosensitive resin composition of the present embodiment has been described above, the photosensitive resin composition of the present embodiment is suitable for forming cavities for embedding chips or passive components, for example, because it has excellent pattern resolution. The cavity can be preferably formed, for example, by making the drawing pattern formed when exposing the photosensitive resin film to light to form a pattern in the description of the multilayer printed circuit board above such that a desired cavity can be formed.

[0332] In addition, the photosensitive resin composition of the present embodiment is also useful as a surface protective film such as a solder resist.

[0333] [Semiconductor Package]

[0334] The present invention also provides a semiconductor package formed by mounting a semiconductor device on a multilayer printed circuit board of the present embodiment. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor device, such as a semiconductor chip or memory, at a predetermined location on the multilayer printed circuit board of the present invention and encapsulating the semiconductor device with an encapsulation resin or the like.

[0335] Examples

[0336] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0337] In addition, the photosensitive resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were evaluated for their characteristics using the method shown below.

[0338] [1. Evaluation of Via Resolution]

[0339] (1-1) Manufacture of an evaluation laminate

[0340] A copper foil surface of a printed circuit board substrate (manufactured by Hitachi Kasei Ekabushiki Kaisha, product name "MCL-E-679"), in which a copper foil with a thickness of 12 μm is laminated onto a glass epoxy substrate, was treated with a harmonizing pretreatment solution (manufactured by MEC COMPANY LTD., product name "CZ-8100"), then washed and dried to obtain a printed circuit board substrate that has undergone harmonizing pretreatment. Subsequently, the protective film was peeled off from the carrier film and the photosensitive resin film with the protective film attached prepared in each example and comparative example, and the exposed photosensitive resin film was placed to be in contact with the copper foil of the printed circuit board substrate that has undergone harmonizing pretreatment. Then, a lamination treatment was performed using a press-type vacuum laminator (manufactured by Kabushiki Kaisha Mekise Ekasho, product name "MVLP-500"). In addition, the lamination conditions were set as follows: press hot plate temperature 70 ℃, vacuum pulling time 20 seconds, lamination press time 30 seconds, atmospheric pressure 4 kPa or less, and compression pressure 0.4 MPa. After lamination treatment, the mixture was left at room temperature for at least 1 hour to obtain an evaluation laminate in which a photosensitive resin film and a carrier film were laminated in this order on the copper foil surface of a substrate for a printed circuit board.

[0341] (1-2) Measurement of sensitivity of photosensitive resin film

[0342] After peeling and removing the carrier film of the evaluation laminate obtained above, a 41-step tablet was placed, and exposure was performed using a direct imaging exposure device "DXP-3512" (manufactured by Okusei Sakusho, Kabushiki Kaisha (ORC MANUFACTURING CO., LTD.)) which uses an ultra-high pressure mercury lamp as a light source. The exposure pattern used was a pattern in which dots were arranged in a grid (dot diameter : distance between dot centers = 1 : 2). The dot diameter was varied by engraving the diameter by 5 μm within the range of φ 30 to 100 μm.

[0343] After exposure, the mixture was left at room temperature for 30 minutes, and then the photosensitive resin composition of the unexposed area was spray-developed for 60 seconds using a 1 mass% aqueous sodium carbonate solution at 30°C. After development, the amount of exposure energy that makes the remaining glossy step number of a 41-step tablet 8.0 was used to determine the sensitivity of the photosensitive resin film (unit: mJ / cm²). 2 ...was set to ). Using a pattern exposed at this sensitivity, the resolution of vias installed on a photosensitive resin film was evaluated according to the following evaluation criteria.

[0344] (1-3) Evaluation of Resolution

[0345] The resolution was evaluated by exposing the photosensitive resin film measured in (1-2) above to an amount of exposure energy that results in a step number of 8.0, then spray developing, observing the via pattern using an optical microscope, and evaluating it according to the following criteria. The above state referred to as "opening" indicates a state in which the copper foil of the substrate for the printed circuit board can be identified when observing the via portion of the dot pattern using an optical microscope. A judgment of "A" indicates good characteristics.

[0346] A: The φ 60 μm via portion of the dot pattern is open.

[0347] B: The φ 60 μm via portion of the dot pattern is not open.

[0348] C: Did not photochemical.

[0349] [2. Adhesion strength with plated copper (Evaluation of peel strength)]

[0350] While peeling off the protective layer of the above photosensitive film, a press-type vacuum laminator (manufactured by Meiki Co., Ltd., product name "MVLP-500") was used on a copper-layered substrate with a thickness of 1.0 mm, and lamination was performed at a compression pressure of 0.4 MPa, a press plate temperature of 80 ℃, a vacuum dragging time of 25 seconds, a lamination press time of 25 seconds, and an atmospheric pressure of 4 kPa or less, and a laminate was obtained.

[0351] For the obtained laminate, a parallel light exposure unit with an ultra-high pressure mercury lamp as a light source (manufactured by Oukusei Esakusho Kabushiki Kaisha (ORC MANUFACTURING CO., LTD.), product name "EXM-1201") was used at 500 mJ / cm² 2 Full-surface exposure was performed. Subsequently, an ultraviolet exposure device was used at 2,000 mJ / cm². 2 A cured film was obtained on a copper-clad laminated substrate by exposing to light with an exposure amount and heating at 170°C for 1 hour.

[0352] Next, to chemically harmonize the surface of the cured product, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L and sodium hydroxide: 5 g / L was prepared as a swelling solution, heated to 70 ℃, and immersed for 10 minutes. Next, an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L was prepared as a harmonizing solution, heated to 70 ℃, and immersed for 15 minutes. Subsequently, an aqueous solution of neutralizing solution (tin chloride (SnCl2): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 ℃, and immersed for 5 minutes to reduce the potassium permanganate.

[0353] Next, the surface of the desmeared cured product was treated with an alkaline cleaner (Cleaner Securigant 902) at 60°C for 5 minutes and degreased. After cleaning, the desmeared cured product was treated with a pre-dip solution (Pre-dip Neogant B) at 23°C for 1 minute. Then, the cured product was treated with an activator solution (Activator Neogant 834) at 35°C for 5 minutes, and then treated with a reducing solution (Reducer Neogant WA) at 30°C for 5 minutes.

[0354] The laminate obtained in this way was placed in a chemical copper solution (Basic Printgant MSK-DK, Copper Printgant MSK, Stabilizer Printgant MSK), and electroless plating was performed until the plating thickness reached about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120°C for 30 minutes to remove residual hydrogen gas. Subsequently, copper sulfate electroplating was performed, and an annealing treatment was carried out at 180°C for 60 minutes to form a conductor layer with a thickness of 25 μm.

[0355] For the laminate in which the conductor layer was formed as described above, the vertical stripping strength at 23°C was measured in accordance with JIS C6481 (1996) and evaluated according to the following evaluation criteria.

[0356] A: The adhesion strength with plated copper was 0.40 kN / m or higher.

[0357] B: The adhesion strength with plated copper was less than 0.40 kN / m and greater than 0.30 kN / m.

[0358] C: The adhesion strength with plated copper was less than 0.30 kN / m.

[0359] [3. Evaluation of Electrical Insulation Reliability (HAST Resistance)]

[0360] In the above [2. Evaluation of adhesion strength (peel strength) with plated copper], the same operation was performed except that a conductor layer with a thickness of 35 μm was formed instead of a conductor layer with a thickness of 25 μm, and a laminate with a conductor layer formed was obtained.

[0361] The formed conductor layer was etched to form a circular electrode of φ6 mm. Subsequently, a photosensitive solder resist film "FZ-2700GA" (manufactured by Hitachi Kasei Kabushiki Kaisha, trade name) was formed on the electrode and the cured film with a layer thickness of 25 μm using a press-type vacuum laminator (manufactured by Kabushiki Kaisha Meikisei Sakusho, trade name "MVLP-500") with a compression pressure of 0.4 MPa, a press plate temperature of 80 ℃, a vacuum dragging time of 25 seconds, a lamination press time of 40 seconds, and an atmospheric pressure of 4 kPa or less, thereby obtaining an evaluation laminate.

[0362] For the evaluation laminate obtained as described above, a parallel light exposure machine using an ultra-high pressure mercury lamp as a light source (manufactured by Oukusei Esakusho Kabushiki Kaisha (ORC MANUFACTURING CO., LTD.), product name "EXM-1201") was used at 500 mJ / cm² 2 Full-surface exposure was performed at [location]. Subsequently, an ultraviolet exposure device was used at 2,000 mJ / cm² 2 A cured film was obtained by exposing to light with an exposure amount and heating at 160°C for 1 hour.

[0363] Next, wiring was performed such that the circular electrode became the positive electrode and the copper foil on the side forming the circular electrode of the copper-clad laminated substrate became the negative electrode, and the device was exposed for 200 hours under conditions of 135°C, 85%, and 5.5 V in a pressure cooker (model name "Unsaturated Super Accelerated Life Test Device PC-422RP", manufactured by Hirayama Manufacturing Corporation). The resistance value between the electrodes was measured and evaluated according to the following evaluation criteria.

[0364] A: Resistance value after 200 hours is 10 × 10 7 It was more than Ω.

[0365] B: Resistance value after 200 hours is 10 × 10 7 Ω or less, also, 10 × 10 6 It was more than Ω.

[0366] C: Resistance value after 200 hours is 10 × 10 6 It was less than Ω.

[0367] <Synthesization Example 1> Synthesis of Acid-Modified Ethyleneate Unsaturated Group and Alicyclic Backbone-Containing Epoxy Derivative 1 [(A1-1) Component]

[0368] 350 parts by mass of dicyclopentadiene-type epoxy resin ("XD-1000" manufactured by Nippon Kayaku Kabushiki Kaisha, epoxy equivalent weight 252 g / eq, softening point 74.2 °C, corresponding to component (a1) and represented by the general formula (a1-1) above. Number of ring-forming carbons of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to component (a2)), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were injected, and the mixture was dissolved by heating to 90 °C and stirring.

[0369] Next, the obtained solution was cooled to 60 °C, 2 parts by mass of triphenylphosphine were added, and the mixture was heated to 100 °C and reacted until the acid value of the solution became 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to component (a3)) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 °C and reacted for 6 hours.

[0370] Afterwards, by cooling to room temperature, an acid-modified dicyclopentadiene-type epoxy acrylate with a solid content of 73 mass% was obtained (corresponding to component (A1-1). Hereinafter referred to as "acid-modified ethylenedimethyl group and alicyclic skeleton-containing epoxy derivative 1").

[0371] <Synthesization Example 2> Synthesis of Acid-Modified Ethyleneate Unsaturated Group and Alicyclic Backbone-Containing Epoxy Derivative 2 [Component (A1-1)]

[0372] 350 parts by mass of dicyclopentadiene-type epoxy resin ("EPICLON (registered trademark) HP-7200" manufactured by DIC Corporation, epoxy equivalent weight 254 ~ 264 g / eq, softening point 56 ~ 66 ℃, corresponding to component (a1) and represented by the general formula (a1-1) above. Number of ring-forming carbons of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to component (a2)), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were injected, and the mixture was dissolved by heating to 90 ℃ and stirring.

[0373] Next, the obtained solution was cooled to 60 °C, 2 parts by mass of triphenylphosphine were added, and the mixture was heated to 100 °C and reacted until the acid value of the solution became 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to component (a3)) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 °C and reacted for 6 hours.

[0374] Afterwards, by cooling to room temperature, an acid-modified dicyclopentadiene-type epoxy acrylate with a solid content of 74 mass% was obtained (corresponding to component (A1-1). Hereinafter referred to as "acid-modified ethylenedimethyl group and alicyclic backbone-containing epoxy derivative 2").

[0375] <Synthesization Example 3> (A2-1) Synthesis of an acid-modified ethylenically unsaturated epoxy derivative not containing a dicycloidal framework

[0376] 350 parts by mass of bisphenol F novolak type epoxy resin ("EXA-7376" manufactured by DIC Co., Ltd., corresponding to component (a21), 70 parts by mass of acrylic acid (corresponding to component (a22)), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were injected and the mixture was dissolved by heating to 90°C and stirring.

[0377] Next, the obtained solution was cooled to 60 °C, 2 parts by mass of triphenylphosphine were added, and the mixture was heated to 100 °C and reacted until the acid value of the solution became 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to component (a23)) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 °C and reacted for 6 hours.

[0378] Afterwards, it was cooled to room temperature to obtain an acid-modified bisphenol F type epoxy acrylate with a solid content of 73 mass% (corresponding to component (A2-1). Hereinafter referred to as "acid-modified ethylenedimethyl unsaturated group-containing epoxy derivative 3").

[0379] <Examples 1–3, Comparative Examples 1–2>

[0380] (Preparation of photosensitive resin composition)

[0381] A photosensitive resin composition was prepared by mixing the composition and mixing amounts according to the formulations and amounts shown in Table 1, and by kneading in a three-roll mill. In each example, carbitol acetate was appropriately added to adjust the concentration, and a photosensitive resin composition with a solid content of 60 mass% was obtained.

[0382] (Production of photosensitive resin film)

[0383] A polyethylene terephthalate film (G2-25, manufactured by Tejin Kabushiki Kaisha, trade name) with a thickness of 25 μm was used as a carrier film, and the photosensitive resin composition prepared in each example was applied onto the carrier film such that the thickness after drying was 25 μm, and dried at 100°C for 10 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Subsequently, a biaxially stretched polypropylene film (MA-411, manufactured by Oji Futetsu Kabushiki Kaisha, trade name) was laminated as a protective film on the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film, and the carrier film and the protective film were laminated to produce a photosensitive resin film.

[0384] Each evaluation was performed according to the above method using the fabricated photosensitive resin film. The results are shown in Table 1.

[0385]

[0386] Each component used in each example is as follows.

[0387] (A) Component;

[0388] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 1 [(A1-1) component]: The one obtained in Synthesis Example 1 was used.

[0389] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 2 [(A1-1) component]: The one obtained in Synthesis Example 2 was used.

[0390] ㆍ Acid-modified ethylene-containing unsaturated group epoxy derivative 3 [(A2-1) component]: The one obtained in Synthesis Example 3 was used.

[0391] ㆍ Dipentaerythritol pentaacrylate [(Aiii) Ingredient]

[0392] (B) Component;

[0393] ㆍ Photopolymerization Initiator 1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, acetophenones

[0394] ㆍ Photopolymerization Initiator 2: 2,4-Diethylthioxanthone, Thioxantones

[0395] (C) Component;

[0396] ㆍ Biphenyl-type epoxy resin: "YX-4000" (Manufactured by Mitsubishi Chemicaru Kabushiki Kaisha, product name)

[0397] ㆍ Epoxidized Polybutadiene: "PB3600" (Manufactured by Daicel Chemical Co., Ltd., Trade Name)

[0398] (D) Component;

[0399] ㆍ Polyester: "ESPEL (Registered Trademark) 1108" (Manufactured by Hitachi Kasei Kabushiki Kaisha, Product Name)

[0400] (F) Component;

[0401] ㆍ Silica: "SFP-20M" (Manufactured by Denka Corporation, average particle size 0.3 μm, trade name)

[0402] In Table 1, it can be seen that Examples 1 to 3 showed excellent results in via resolution, adhesion strength with plated copper, and electrical insulation reliability. On the other hand, in Comparative Examples 1 and 2, which did not contain component (A1), the adhesion strength with plated copper and electrical insulation reliability were insufficient.

[0403] In addition, a photosensitive resin composition described below was prepared separately, and its resolution and crack resistance were evaluated according to the following method.

[0404] [4. Evaluation of Via Resolution]

[0405] (4-1) Manufacture of evaluation laminate

[0406] A printed circuit board substrate (manufactured by Hitachi Kasei Ekabushiki Kaisha, product name "MCL-E-679"), having a 12 μm thick copper foil laminated onto a glass epoxy substrate, had its copper foil surface polished with a fine-grained brush, rinsed with water, and dried to obtain a pre-treated printed circuit board substrate. Subsequently, the protective film was peeled off from the carrier film and the photosensitive resin film with the protective film attached prepared in each example and comparative example. The exposed photosensitive resin film was then placed in contact with the copper foil of the pre-treated printed circuit board substrate, and a lamination treatment was performed using a press-type vacuum laminator (manufactured by Meikise Ekabushiki Kaisha, product name "MVLP-500"). In addition, the lamination conditions were a press plate temperature of 70°C, a vacuum pulling time of 20 seconds, a lamination press time of 20 seconds, and an atmospheric pressure of 4 The pressure was set to kPa or less and the compression pressure to 0.4 MPa. After lamination treatment, the material was left at room temperature for at least 1 hour to obtain an evaluation laminate in which a photosensitive resin film and a carrier film were laminated in this order on the copper foil surface of a substrate for a printed circuit board.

[0407] (4-2) Measurement of sensitivity of photosensitive resin film

[0408] After peeling off and removing the carrier film of the evaluation laminate obtained above, a 41-step tablet was placed, and exposure was performed using a direct imaging exposure device "DXP-3512" (manufactured by Oku Seisakusho, Kabushiki Kaisha) using an ultra-high pressure mercury lamp as a light source. The exposure pattern used was a pattern in which squares were arranged in a grid (length of one side : distance between the centers of the squares = 1 : 2).

[0409] After exposure, the sample was left at room temperature for 30 minutes, the polyethylene terephthalate on the support was removed, and the photosensitive resin composition of the unexposed area was spray-developed for 60 seconds using a 1 mass% aqueous sodium carbonate solution at 30°C. After development, the amount of exposure energy at which the remaining glossy step number of a 41-step tablet becomes 10.0 was used to determine the sensitivity of the photosensitive resin film (unit: mJ / cm²). 2 ...was set to ). Using a pattern exposed at this sensitivity, the resolution of vias installed on a photosensitive resin film was evaluated according to the following evaluation criteria.

[0410] (4-3) Evaluation of Resolution

[0411] The resolution was evaluated by exposing the photosensitive resin film measured in (4-2) above to an amount of exposure energy that makes the sensitivity, i.e., the step number, 10.0, and then spray developing, observing the via pattern using an optical microscope, and evaluating it according to the following criteria. The state referred to as "aperture" above refers to a state in which the copper foil of the substrate for the printed circuit board can be identified when observing the via portion of the dot pattern using an optical microscope. A judgment of "A" indicates good characteristics.

[0412] A: The bottom dimension of a via pattern with a side of 60 μm is 50 μm or more.

[0413] B: The dimensions of the bottom of the via pattern of 60 μm side are 40 μm or more and less than 50 μm side.

[0414] C: The dimensions of the bottom of the via pattern of 60 μm side are 30 μm or more and less than 40 μm side.

[0415] [5. Evaluation of Crack Resistance]

[0416] An evaluation laminate made in the same manner as (4-1) above was exposed to an atmosphere of -65 ℃ for 15 minutes, then heated at a heating rate of 180 ℃ / min, and then exposed to an atmosphere of 150 ℃ for 15 minutes, and then heated at a heating rate of 180 ℃ / min. This thermal cycle was repeated 1,000 times.

[0417] Afterwards, the evaluation laminate was observed at any 10 locations of the openings of the square vias with a 2 mm angle using a metallographic microscope at a magnification of 100x, and the degree of cracking and delamination was evaluated according to the following evaluation criteria.

[0418] A: No cracks or peeling were observed at all.

[0419] B: Cracks and delamination were observed in 1 or 2 of the 10 locations.

[0420] C: Cracks and peeling were observed in 3 out of 10 locations.

[0421] D: Cracks and peeling were observed in 4 or more of the 10 locations.

[0422] <Synthesization Examples 4–5> Synthesis of Acid-Modified Ethyleneate Unsaturated Group and Alicyclic Backbone-Containing Epoxy Derivatives 4–5 [(A1-1) Component]

[0423] 350 parts by mass of dicyclopentadiene-type epoxy resin ("EPICLON (registered trademark) HP-7200" manufactured by DIC Corporation, epoxy equivalent weight 254 ~ 264 g / eq, softening point 56 ~ 66 ℃, corresponding to component (a1) and represented by the general formula (a1-1) above. Number of ring-forming carbons of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to component (a2)), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were injected, and the mixture was dissolved by reacting by heating to 90 ℃ and stirring.

[0424] Next, the obtained solution was cooled to 60°C, 2 parts by mass of triphenylphosphine were added, and the mixture was heated to 100°C and reacted until the acid value of the solution became 1 mgKOH / g. To the solution after the reaction, tetrahydrophthalic anhydride (corresponding to component (a3)) and carbitol acetate were added, heated to 80°C, and reacted for about 6 hours. In addition, the amount of tetrahydrophthalic anhydride used was adjusted so that the acid value of the resulting acid-modified dicyclopentadiene-type epoxyacrylate was 60 mgKOH / g and 80 mgKOH / g.

[0425] Afterwards, the mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene-type epoxy acrylate with a solid acid value of 60 mgKOH / g (corresponding to component (A1-1). Hereinafter referred to as "acid-modified epoxy derivative containing ethylenically unsaturated groups and alicyclic skeleton 4") and an acid-modified dicyclopentadiene-type epoxy acrylate with a solid acid value of 80 mgKOH / g (corresponding to component (A1-1). Hereinafter referred to as "acid-modified epoxy derivative containing ethylenically unsaturated groups and alicyclic skeleton 5").

[0426] <Synthesization Examples 6–8> Synthesis of Acid-Modified Ethyleneate Unsaturated Group and Alicyclic Framework-Containing Epoxy Derivatives 6–8 [(A1-1) Component]

[0427] 350 parts by mass of dicyclopentadiene-type epoxy resin (Nihon Kayaku Kabushiki Kaisha “XD-1000”, epoxy equivalent 252 g / eq, softening point 74.2 °C, corresponding to component (a1) and represented by the general formula (a1-1) above. Number of ring-forming carbons of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to component (a2)), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were injected, and the mixture was dissolved by heating to 90 °C and stirring.

[0428] Next, the obtained solution was cooled to 60°C, 2 parts by mass of triphenylphosphine were added, and the mixture was heated to 100°C and reacted until the acid value of the solution became 1 mgKOH / g. To the solution after the reaction, tetrahydrophthalic anhydride (corresponding to component (a3)) and carbitol acetate were added, heated to 80°C, and reacted for about 6 hours. In addition, the amount of tetrahydrophthalic anhydride used was adjusted so that the acid value of the resulting acid-modified dicyclopentadiene-type epoxyacrylate was 60 mgKOH / g, 80 mgKOH / g, and 100 mgKOH / g.

[0429] Afterwards, the mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene-type epoxy acrylate with a solid acid value of 60 mgKOH / g (corresponding to component (A1-1). Hereinafter referred to as "acid-modified epoxy derivative containing ethylenically unsaturated groups and alicyclic skeleton 6"), an acid-modified dicyclopentadiene-type epoxy acrylate with a solid acid value of 80 mgKOH / g (corresponding to component (A1-1). Hereinafter referred to as "acid-modified epoxy derivative containing ethylenically unsaturated groups and alicyclic skeleton 7"), and an acid-modified dicyclopentadiene-type epoxy acrylate with a solid acid value of 100 mgKOH / g (corresponding to component (A1-1). Hereinafter referred to as "acid-modified epoxy derivative containing ethylenically unsaturated groups and alicyclic skeleton 8").

[0430] <Synthesization Example 9> Synthesis of an acid-modified ethylenically unsaturated epoxy derivative not containing a dicycloidal framework

[0432] 682 parts by mass of oxazolidone ring-containing epoxy resin, 104 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 219 parts by mass of carbitol acetate were injected, and the mixture was dissolved by heating to 90°C and stirring.

[0433] Next, the obtained solution was cooled to 60°C, 4 parts by mass of triphenylphosphine were added, and the mixture was heated to 100°C and reacted until the acid value of the solution became 1 mgKOH / g. Tetrahydrophthalic anhydride and carbitol acetate were added to the solution after the reaction, and the mixture was heated to 80°C and reacted for about 6 hours, after which it was cooled to obtain an acid-modified ethylenedimethyl group-containing epoxy acrylate with a solid dispersion acid value of 80 mgKOH / g (corresponding to component (A2-1). Hereinafter referred to as "acid-modified ethylenedimethyl group-containing epoxy derivative 9").

[0434] <Examples 4–8, Comparative Example 3>

[0435] (Preparation of photosensitive resin composition)

[0436] A photosensitive resin composition was prepared by mixing the composition and mixing amounts according to the formulations shown in Table 2 and kneading them in a three-roll mill. In each example, propylene glycol monomethyl ether acetate was appropriately added to adjust the concentration, and a photosensitive resin composition with a solid content of 50 mass% was obtained.

[0437] (Production of photosensitive resin film)

[0438] A polyethylene terephthalate film (G2-25, manufactured by Teijin Corporation, trade name) with a thickness of 25 μm was used as a carrier film, and the photosensitive resin composition prepared in each example was applied onto the carrier film such that the thickness after drying was 25 μm. The film was then dried at 100°C for 10 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Subsequently, a biaxially stretched polypropylene film (MA-411, manufactured by Oji Futetsu Kabushiki Kaisha, trade name) was laminated as a protective film on the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film, and the carrier film and the protective film were laminated to produce a photosensitive resin film.

[0439] Using the fabricated photosensitive resin film, each evaluation was performed according to the above method. The results are shown in Table 2.

[0440]

[0441] Each component used in each example is as follows.

[0442] (A) Component;

[0443] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 4 [(A1-1) component]: The one obtained in Synthesis Example 4 was used.

[0444] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 5 [(A1-1) component]: The one obtained in Synthesis Example 5 was used.

[0445] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 6 [(A1-1) component]: The one obtained in Synthesis Example 6 was used.

[0446] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 7 [(A1-1) component]: The one obtained in Synthesis Example 7 was used.

[0447] ㆍ Acid-modified ethylene-unsaturated group and alicyclic backbone-containing epoxy derivative 8 [(A1-1) component]: The one obtained in Synthesis Example 8 was used.

[0448] ㆍ Acid-modified ethylene-containing unsaturated group epoxy derivative 9 [(A2-1) component]: The one obtained in Synthesis Example 9 was used.

[0449] ㆍ Dipentaerythritol pentaacrylate [(Aiii) Ingredient]

[0450] (B) Component;

[0451] ㆍ Photopolymerization Initiator 1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, acetophenones

[0452] ㆍ Photopolymerization Initiator 2: 2,4-Diethylthioxanthone, Thioxantones

[0453] (C) Component;

[0454] ㆍ Biphenyl-type epoxy resin: "YX-4000" (Manufactured by Mitsubishi Chemicaru Kabushiki Kaisha, product name)

[0455] ㆍ o-Cresol Novolak type epoxy resin: "EPICLON N-680" (Manufactured by DIC Co., Ltd., trade name)

[0456] (F) Component;

[0457] ㆍ Silica: "SFP-20M" (Manufactured by Denka Corporation, average particle size 0.3 μm, trade name)

[0458] (G) Component ;

[0459] ㆍ Pigment: CI Pigment Blue 15 (Phthalocyanine-based pigment, manufactured by Sanyo Shikiso Kabushiki Kaisha, trade name)

[0460] (H) component;

[0461] ㆍ Curing Agent 1: Finely ground melamine (Manufactured by Nissan Chemical Co., Ltd., Trade Name)

[0462] ㆍ Curing Agent 2: 2-ethyl-4-methylimidazole

[0463] In Table 2, it can be seen that Examples 4 to 8 showed excellent results in via resolution and crack resistance. On the other hand, in Comparative Example 3, which did not contain component (A1), via resolution and crack resistance were insufficient. Explanation of the symbols

[0464] 100A Multilayer Printed Circuit Board 102 Circuit Patterns 103 Interlayer insulation layer 104 Via (Via Hole) 105 Seed Floor 106 Resist Pattern 107 Copper circuit layer 108 solder resist layers

Claims

Claim 1 A photosensitive resin composition for forming photovias comprising (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting resin, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group comprises (A1) a photopolymerizable compound having an acidic substituent and an alicyclic backbone along with an ethylenically unsaturated group, and the (C) thermosetting resin comprises a biphenyl-type epoxy resin and an epoxy-modified polybutadiene, wherein the content ratio of the biphenyl-type epoxy resin and the epoxy-modified polybutadiene is 95:5 to 60:40 by mass. Claim 2 A photosensitive resin composition for forming a photovia according to claim 1, wherein the photopolymerizable compound having (A) an ethylenically unsaturated group further comprises at least one selected from the group consisting of (Ai) a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group, (Aii) a difunctional vinyl monomer having two polymerizable ethylenically unsaturated groups, and (Aiii) a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups. Claim 3 A photosensitive resin composition for forming photovias according to claim 1 or 2, wherein the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the (A1) ethylenically unsaturated group, wherein the alicyclic skeleton is a cyclic alicyclic skeleton having 5 to 20 carbon atoms. Claim 4 A photosensitive resin composition for forming photovias according to claim 1 or 2, wherein the photopolymerizable compound having an acidic substituent and an alicyclic backbone together with the (A1) ethylenically unsaturated group, wherein the alicyclic backbone consists of two or more rings. Claim 5 A photosensitive resin composition for forming photovias according to claim 1 or 2, wherein the photopolymerizable compound having an acidic substituent and an alicyclic backbone together with the (A1) ethylenically unsaturated group, wherein the alicyclic backbone is composed of three rings. Claim 6 A photosensitive resin composition for forming a photovia according to claim 1 or 2, wherein the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the (A1) ethylenically unsaturated group, wherein the alicyclic skeleton is represented by the following general formula (a). (of general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any of the above alicyclic skeletons. 1 is an integer between 0 and 6. * is a linkage site to another structure.) Claim 7 A photosensitive resin composition for forming a photovia according to claim 1 or 2, wherein the photopolymerizable compound having an acidic substituent and a dicycloidal framework together with the (A1) ethylenically unsaturated group is represented by the following general formula (A-1). (of general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any point in the above alicyclic framework. R A2 represents an alkyl group having 1 to 12 carbon atoms. R A3 It is silver, an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least one R A3 is an organic group having an ethylenically unsaturated group and an acidic substituent. 1 is an integer from 0 to 6, m 2 is an integer from 0 to 3. n is from 0 to 10.) Claim 8 A photosensitive resin composition for forming a photovia according to claim 1 or 2, wherein the photopolymerizable compound having an acidic substituent and a dicycloidal frame together with (A1) an ethylenically unsaturated group, the acidic substituent is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group. Claim 9 A photosensitive resin composition for forming a photovia according to claim 1 or 2, further comprising (D) an elastomer. Claim 10 A photosensitive resin composition for forming a photovia according to claim 9, wherein the (D) elastomer comprises at least one selected from the group consisting of a styrene-based elastomer, an olefin-based elastomer, a polyester-based elastomer, a urethane-based elastomer, a polyamide-based elastomer, an acrylic-based elastomer, and a silicone-based elastomer. Claim 11 A photosensitive resin composition for forming a photovia according to claim 1 or 2, further comprising (F) an inorganic filler. Claim 12 A photosensitive resin composition for forming photovias and for interlayer insulating layers, comprising the photosensitive resin composition for forming photovias described in claim 1 or 2. Claim 13 A photosensitive resin film for forming a photovia, comprising a photosensitive resin composition for forming a photovia as described in claim 1 or 2. Claim 14 A photosensitive resin film for forming photovias and for interlayer insulating layers, comprising a photosensitive resin composition for forming photovias as described in claim 1 or 2. Claim 15 A multilayer printed circuit board comprising an interlayer insulating layer formed using a photosensitive resin composition for forming photovias described in claim 1 or 2. Claim 16 A multilayer printed circuit board comprising an interlayer insulating layer formed using a photosensitive resin film for forming photovias as described in claim 13. Claim 17 A semiconductor package formed by mounting a semiconductor device on a multilayer printed circuit board as described in claim 15. Claim 18 A method for manufacturing a multilayer printed circuit board having the following processes (1) to (4). Process (1): A process of laminating a photosensitive resin film described in claim 13 onto one side or both sides of a circuit board. Process (2): A process of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in process (1). Process (3): A process of coarse-processing the vias and the interlayer insulating layer. Process (4): A process of forming a circuit pattern on the interlayer insulating layer.

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