Laminate, laminated board, printed wiring board, semiconductor package, interposer, and ball grid array substrate

Abstract

Provided is a laminate having high adhesion to a metal layer. Further provided are a laminated board, a printed wiring board, a semiconductor package, an interposer, and a ball grid array (BGA) substrate that are obtained using the laminate. The laminate includes a glass substrate having a through-hole, and has a layer of a resin composition on a surface of the glass substrate and a side wall of the through-hole. The resin composition contains (A) an epoxy resin having a biphenyl-diyl group and (B) an ester-based curing agent. The content of the component (A) is 10-80 mass% with respect to the total amount of the resin component.

Description

Laminate, laminate plate, printed wiring board, semiconductor package, interposer, and ball grid array substrate

[0001] The present disclosure relates to laminates, laminates, printed wiring boards, semiconductor packages, interposers, and ball grid array substrates.

[0002] Glass substrates with through electrodes have traditionally been used as interposer components. Glass substrates with through electrodes are typically manufactured by irradiating the glass substrate with light, such as ultraviolet light or laser light, to form multiple through holes (vias) in the glass substrate, followed by forming a copper plating layer on the top and bottom surfaces of the glass substrate and on the side walls of the through holes (see, for example, Patent Document 1). However, because the copper plating layer does not have very good adhesion to the glass substrate, the copper plating layer formed on the side walls of the through holes in the glass substrate tends to peel off easily. This is thought to be due to the following reasons. Through holes are typically formed by irradiating the glass substrate with laser light and then ablation processing the glass substrate. The surface of the through holes formed by this method is recooled after thermal melting by laser heating, resulting in a smooth surface with few irregularities. It is difficult to ensure sufficient adhesion between the copper plating layer formed on a smooth surface and the side walls of the through holes in the glass substrate. In other words, the surface condition of the through holes formed by this laser processing is thought to be a factor that leads to the peeling of the copper plating layer. In order to solve such problems, it has been proposed to dispose a resin layer on the side wall of the through-hole in the glass substrate (see Patent Document 2).

[0003] JP 2005-86026 A International Publication No. 2013 / 150940

[0004] However, after careful investigation, the inventors found that even in glass substrates in which a resin layer is disposed on the side walls of through holes, peeling of metal layers such as copper plating layers can occur, and that there is room for further improvement.

[0005] In view of the current situation, an object of the present disclosure is to provide a laminate having high adhesion to a metal layer, and to provide a laminate, a printed wiring board, a semiconductor package, an interposer, and a ball grid array (BGA) substrate obtained using the laminate.

[0006] The present inventors have conducted research to solve the above problems and have found that the above object can be achieved by the present embodiment. The present embodiment includes the following [1] to

[15] .

[0007] [1] A laminate including a glass substrate having a through hole, wherein a resin composition layer is formed on the surface of the glass substrate and on the sidewall of the through hole, the resin composition containing (A) an epoxy resin having a biphenyl-diyl group and (B) an ester-based curing agent, and the content of the component (A) is 10 to 80 mass% based on the total amount of the resin components. [2] The laminate according to [1] above, wherein the resin composition further contains or does not contain (C) an epoxy resin having an alkylene group having 3 or more carbon atoms. [3] The laminate according to [1] or [2] above, wherein the maximum diameter of the through hole is 5 to 200 μm. [4] The laminate according to any of [1] to [3] above, wherein the thickness of the resin composition layer is 0.01 to 100 μm. [5] The laminate according to any of [1] to [4] above, wherein the through hole is not filled with the resin composition layer. [6] The laminate according to any one of [1] to [5] above, wherein a plurality of through holes are present, and the shortest distance between the outer edges of the nearest through holes is 1 to 1,000 μm. [7] The laminate according to any one of [1] to [6] above, wherein the glass substrate has a thickness of 10 to 2,000 μm. [8] A method for producing the laminate according to any one of [1] to [7] above, by forming the laminate by a coating method or a dipping method using a glass substrate having through holes and a medium containing the resin composition. [9] The laminate according to any one of [1] to [7] above, which is for a printed wiring board.

[10] The laminate according to any one of [1] to [7] above, which is for an interposer or a ball grid array (BGA) substrate.

[11] A laminate plate comprising the laminate according to any one of [1] to [7] above and a metal layer.

[12] A printed wiring board comprising the laminate according to any one of [1] to [7] above.

[13] A semiconductor package having the printed wiring board according to

[12] above and a semiconductor element.

[14] An interposer having the laminate according to any one of [1] to [7] above.

[15] A ball grid array (BGA) substrate having the laminate according to any one of [1] to [7] above.

[0008] According to the present disclosure, it is possible to provide a laminate having high adhesion to a metal layer, and to provide a laminate, a printed wiring board, a semiconductor package, an interposer, and a ball grid array (BGA) substrate obtained using the laminate.

[0009] Fig. 2 is a perspective view of an example of a laminate in the present embodiment. Fig. 3 is an end view taken along line AA in Fig. 1. Fig. 4 is an end view of an example of a laminate in the present embodiment. Fig. 5 is an end view of another example of a laminate in the present embodiment.

[0010] In the numerical ranges described in this disclosure, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. Furthermore, the lower and upper limits of a numerical range can be arbitrarily combined with the lower or upper limit of another numerical range. In the expression "AA to BB," the numerical values ​​AA and BB at both ends are included as the lower and upper limits, respectively, within the numerical range. In this disclosure, for example, the expression "10 or more" means 10 and a numerical value greater than 10, and this also applies when the numerical values ​​are different. Furthermore, for example, the expression "10 or less" means a numerical value less than 10 and this also applies when the numerical values ​​are different.

[0011] Unless otherwise specified, each component and material exemplified in this disclosure may be used alone or in combination of two or more. In this disclosure, when a resin composition contains multiple substances corresponding to each component, the content of each component in the resin composition means the total amount of the multiple substances present in the resin composition, unless otherwise specified.

[0012] In the present disclosure, the term "resin component" refers to all components, excluding inorganic compounds, among the solid components constituting the resin composition. In the resin composition of the present disclosure, for example, component (A), component (A'), component (B), component (C), component (D), etc., correspond to the resin component. In the present disclosure, the term "solid content" refers to components other than the solvent, and components that are liquid at 25°C are also considered to be solids. The expression "containing XX" described in the present disclosure may mean that XX is contained in a reacted state if XX is reactive, or may simply mean that XX is contained as is, or may include both of these aspects. Furthermore, any combination of the items described in the present disclosure is also included in this embodiment.

[0013] [Laminate] The laminate of this embodiment is a laminate including a glass substrate having a through hole, and has a layer of a resin composition (hereinafter, sometimes referred to as a "resin layer") on the surface of the glass substrate and on the sidewalls of the through hole, the resin composition containing (A) an epoxy resin having a biphenyl-diyl group and (B) an ester-based curing agent, and the content of the component (A) is 10 to 80 mass% based on the total amount of the resin components. When a metal layer such as a copper plating layer is formed on the upper and lower surfaces of the glass substrate and on the sidewalls of the through hole, the resin composition containing the specific component significantly enhances adhesion between the glass substrate (strictly speaking, the resin layer) and the metal layer, making peeling of the metal layer less likely to occur. In the laminate of this embodiment, the resin layer is in a C-stage state. Here, in this disclosure, C-stage refers to the C-stage defined in JIS K6900 (1994).

[0014] An example of a laminate of this embodiment is shown in FIG. 1 . An end view taken along line A-A in FIG. 1 is shown in FIG. 2 . As shown in FIGS. 1 and 2 , the laminate 100 of this embodiment includes a glass substrate 110 having a first surface 112 and a second surface 114, and a resin layer 130. The glass substrate 110 has a plurality of through holes 120 that penetrate from the first surface 112 to the second surface 114. For example, in FIGS. 1 and 2 , the laminate 100 has a large number of through holes 120 arranged at equal intervals along the horizontal (X direction) and vertical (Y direction) directions.

[0015] As shown in FIG. 2 , each through hole 120 may have a substantially cylindrical shape in which the diameter of the opening at the first surface 112 of the glass substrate 110 is equal to the diameter of the opening at the second surface 114. Here, "substantially cylindrical" means a cylindrical shape from a macroscopic perspective. Alternatively, each through hole 120 may have a so-called tapered shape in which the diameter decreases from the first surface 112 to the second surface 114 of the glass substrate 110. The cross section of each through hole 120 perpendicular to the extension direction (Z direction) may be substantially circular, substantially elliptical, or some other shape. Here, "substantially circular" means a circular shape from a macroscopic perspective. Also, "substantially elliptical" means an elliptical shape from a macroscopic perspective.

[0016] In the laminate 100, a resin layer 130 is disposed on the first surface 112 and the second surface 114 of the glass substrate 110 and the sidewall 125 of the through-hole 120. More specifically, a resin layer 130B is disposed on the first surface 112 of the glass substrate 110, a resin layer 130C is disposed on the second surface 114, and a resin layer 130A is disposed on the sidewall 125 of the through-hole 120. By including the resin layer 130 formed from the resin composition described below, the metal layer (conductor circuit) described below is formed on the glass substrate 110 via the resin layer 130, improving adhesion. The resin layer 130 functions as a stress relief layer, effectively suppressing peeling. Furthermore, by including the resin layer 130 formed from the resin composition described below, the laminate 100 also has the effect of improving handleability. Furthermore, as shown in FIGS. 2 and 3, it is preferable that the end portions of the laminate 100 also have a resin layer 130. By providing the resin layer 130 also at the end of the laminate 100, the handling property tends to be further improved, and cracks caused by impacts during transportation or processing tend to be more easily suppressed.

[0017] Next, each component of the laminate 100 of this embodiment will be described. (Glass Substrate 110, Through Hole 120) The material of the glass substrate 110 is not particularly limited, and examples thereof include alkali-free glass, borosilicate glass, soda-lime glass, and aluminosilicate glass. The dimensions of the through hole 120 in the glass substrate 110 are not particularly limited. The maximum diameter of the through hole 120 may be 5 to 200 μm, 5 to 180 μm, 10 to 160 μm, 15 to 140 μm, 30 to 100 μm, 50 to 100 μm, 100 to 200 μm, 120 to 180 μm, or 130 to 170 μm. When the through hole 120 has a substantially elliptical cross section, the maximum diameter of the through hole 120 is the length of the major axis (major axis). The maximum diameter of the through holes can be observed and measured using an optical microscope or an electron microscope. The number of through holes 120 in the glass substrate 110 is not particularly limited. The glass substrate 110 has a plurality of the through holes, and the shortest distance between the outer edges of the closest through holes may be 1 to 1,000 μm, 5 to 500 μm, 10 to 300 μm, 10 to 230 μm, 50 to 230 μm, 100 to 230 μm, or 150 to 230 μm. The shortest distance between the outer edges of the closest through holes can be measured by observation using an optical microscope or an electron microscope. The thickness of the glass substrate may be 10 to 2,000 μm, 50 to 1,500 μm, 100 to 1,200 μm, 100 to 800 μm, or 150 to 500 μm. The through hole 120 may or may not be filled with the resin layer, but from the viewpoint of providing a metal layer in the through hole, it is preferable that the through hole 120 is not filled with the resin layer.

[0018] (Resin Layer 130) The resin layer 130 is composed of a resin layer 130B disposed on the first surface 112 of the glass substrate 110, a resin layer 130C disposed on the second surface 114, and a resin layer 130A disposed on the sidewall 125 of the through-hole 120. The resin layer 130 (resin layer 130A, resin layer 130B, and resin layer 130C) contains (A) an epoxy resin having a biphenyl-diyl group and (B) an ester-based curing agent, and the content of the component (A) is 10 to 80 mass% with respect to the total amount of the resin components. Furthermore, the resin layer 130 containing (A) an epoxy resin having a biphenyl-diyl group and (B) an ester-based curing agent may or may not further contain (C) an epoxy resin having an alkylene group having 3 or more carbon atoms. The resin layer 130 may further contain other components, as described below.

[0019] The thickness of the resin layer 130 is not particularly limited and may be 0.01 to 100 μm, 0.1 to 50 μm, 0.25 to 30 μm, or 0.5 to 20 μm. Note that the thickness of the resin layer 130A may differ between the thickness at the top and the thickness at the bottom in the Z-axis direction, but this difference is preferably 30 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 3 μm or less (however, all include 0 μm).

[0020] The laminate 100 of this embodiment has high adhesion to a metal layer described later, and is therefore useful for printed wiring boards. Furthermore, the laminate 100 of this embodiment has high adhesion to a metal layer described later, and is therefore useful for interposers or ball grid array (BGA) substrates.

[0021] Each component contained in the resin layer 130 will be described in detail below. <(A) Epoxy Resin Having Biphenyl-diyl Groups> (A) Epoxy resins having biphenyl-diyl groups are thermosetting resins that, upon thermal curing, form cured products that exhibit excellent heat resistance, mechanical strength, and adhesion to metal layers. In this embodiment, the term "biphenyl-diyl group" refers to a divalent group formed by removing two hydrogen atoms from the hydrogen atoms directly bonded to the aromatic rings constituting the biphenyl. The two aromatic rings constituting the biphenyl may or may not have a substituent. Examples of biphenyl-diyl groups include biphenyl-2,3'-diyl groups, biphenyl-2,4'-diyl groups, biphenyl-3,4'-diyl groups, and biphenyl-4,4'-diyl groups. Among these, biphenyl-4,4'-diyl groups are preferred. (A) Epoxy resins having biphenyl-diyl groups may be used alone or in combination.

[0022] The (A) epoxy resin having a biphenyl-diyl group may be a resin having a biphenyl-diyl group in the molecule and having two or more epoxy groups. Examples of the (A) epoxy resin having a biphenyl-diyl group include biphenyl aralkyl epoxy resins; biphenyl epoxy resins such as biphenol diglycidyl ether and tetramethylbiphenol diglycidyl ether. Among these, biphenyl aralkyl epoxy resins are preferred from the viewpoint of adhesion to the metal layer.

[0023] The biphenylaralkyl epoxy resin may contain a structure represented by the following general formula (A-1).

[0024] (In the formula, R Ａ１ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n Ａ１ is an integer from 0 to 3.)

[0025] R in the above general formula (A-1) Ａ１Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. In the above general formula (A-1), n Ａ１ may be an integer of 0 to 2, or may be 0. Ａ１ is an integer of 2 or more, a plurality of R Ａ１ They may be the same or different.

[0026] The epoxy resin containing the structure represented by the above general formula (A-1) may be an epoxy resin represented by the following general formula (A-2).

[0027] (In the formula, R Ａ１ and n Ａ１ is the same as in the general formula (A-1), and n Ａ２ is an integer from 1 to 10.

[0028] In the general formula (A-2), multiple R Ａ１ n or multiple n Ａ１ In the general formula (A-2), n may be the same or different. Ａ２ may be an integer of 1 to 10, may be an integer of 1 to 7, or may be an integer of 1 to 5.

[0029] From the viewpoint of adhesion to the metal layer, the epoxy equivalent of (A) the epoxy resin having a biphenyl-diyl group may be 150 to 400 g / eq, 200 to 350 g / eq, or 270 to 320 g / eq. The epoxy equivalent can be measured according to the method specified in JIS K7236 (2001).

[0030] The content of the epoxy resin (A) having a biphenyl-diyl group in the resin composition (or resin layer 130) is 10 to 80% by mass, preferably 15 to 75% by mass, more preferably 20 to 70% by mass, and even more preferably 25 to 65% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition (or resin layer 130), and may be 25 to 60% by mass or 25 to 55% by mass. When the content of the epoxy resin (A) having a biphenyl-diyl group is within the above range, heat resistance, moldability, and adhesion to a metal layer tend to be improved.

[0031] <(A') Epoxy Resin Other than Component (A)> The resin composition (or resin layer 130) may or may not contain (A') an epoxy resin other than component (A). Component (A') is a thermosetting resin that tends to form a cured product excellent in heat resistance, mechanical strength, and the like by thermal curing. Component (A') is preferably an epoxy resin having two or more epoxy groups per molecule. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, and the like. Among these, glycidyl ether type epoxy resins are preferred. Epoxy resins are classified into various epoxy resins based on differences in their main skeletons, and each of the above types of epoxy resins can be further classified into bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; alicyclic epoxy resins such as dicyclopentadiene-type epoxy resins; aliphatic linear epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, bisphenol F novolac-type epoxy resins, and phenol aralkyl novolac-type epoxy resins; stilbene-type epoxy resins; naphthalene-skeleton-containing epoxy resins such as naphthol novolac-type epoxy resins and naphthol aralkyl-type epoxy resins; xylylene-type epoxy resins; and dihydroanthracene-type epoxy resins. As component (A'), one type may be used alone, or two or more types may be used in combination.

[0032] From the viewpoint of adhesion to the metal layer, the epoxy equivalent of the component (A') may be 100 to 1,000 g / eq, 150 to 600 g / eq, or 200 to 400 g / eq.

[0033] The content of the epoxy resin (A') in the resin composition (or resin layer 130) is preferably 0 to 30 mass%, more preferably 0 to 15 mass%, even more preferably 0 to 10 mass%, particularly preferably 0 to 5 mass%, and particularly preferably 0 to 3 mass%, or even 0 mass%, relative to the total amount (100 mass%) of resin components in the resin composition (or resin layer 130). When the content of component (A') is within the above range, the effects of component (A) tend to be sufficiently exhibited.

[0034] <(B) Ester-based curing agent> The (B) ester-based curing agent has one or more ester groups capable of reacting with epoxy groups, and functions as a curing agent for the (A) biphenyl-diyl group-containing epoxy resin and as a curing agent for the (A') epoxy resin. The (B) ester-based curing agent is also sometimes called an active ester curing agent. One type of (B) ester-based curing agent may be used alone, or two or more types may be used in combination.

[0035] Examples of the (B) ester-based curing agent include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, ester compounds of heterocyclic hydroxy compounds, etc. Among these, phenol ester compounds, thiophenol ester compounds, and N-hydroxyamine ester compounds are preferred, and phenol ester compounds are more preferred.

[0036] The (B) ester-based curing agent is preferably a compound having two or more ester groups in one molecule, and more preferably one having two or more ester groups in one molecule, the two or more ester groups being ester groups formed from a polycarboxylic acid compound and a compound having a phenolic hydroxyl group. The ester group formed from a polycarboxylic acid compound and a compound having a phenolic hydroxyl group is an ester group formed by an esterification reaction (condensation reaction) between a carboxy group in the polycarboxylic acid compound and a phenolic hydroxyl group in the compound having a phenolic hydroxyl group.

[0037] Examples of polycarboxylic acid compounds include compounds having two or more aliphatic carboxy groups and compounds having two or more aromatic carboxy groups. Examples of compounds having two or more aliphatic carboxy groups include succinic acid, maleic acid, and itaconic acid. Examples of compounds having two or more aromatic carboxy groups include benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; benzenetricarboxylic acids such as trimesic acid; and benzenetetracarboxylic acids such as pyromellitic acid. Among these, from the viewpoints of heat resistance and dielectric properties, compounds having two or more aromatic carboxy groups or benzenedicarboxylic acids may be used. One type of polycarboxylic acid compound may be used alone, or two or more types may be used in combination.

[0038] Examples of compounds having a phenolic hydroxyl group include compounds having one phenolic hydroxyl group, compounds having two phenolic hydroxyl groups, and compounds having three or more phenolic hydroxyl groups. Examples of compounds having one phenolic hydroxyl group include monophenol compounds such as phenol, o-cresol, m-cresol, and p-cresol; mononaphthol compounds such as α-naphthol and β-naphthol; and hydroxybenzophenone. Examples of compounds having two phenolic hydroxyl groups include dihydroxybenzene compounds such as hydroquinone, resorcinol, and catechol; bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol S; dihydroxynaphthalene compounds such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; phenolphthalene; and dicyclopentadiene-type phenolic resins having two phenolic hydroxyl groups. Examples of the compound having three or more phenolic hydroxyl groups include trihydroxybenzophenone, benzenetriol, tetrahydroxybenzophenone, phenol novolac resin, phenol aralkyl resin, etc. The compound having a phenolic hydroxyl group may be used alone or in combination of two or more.

[0039] The ester-based curing agent (B) having an ester group formed from a polycarboxylic acid compound and a compound having a phenolic hydroxyl group may be one represented by the following general formula (B-1):

[0040] (In the formula, X Ｂ are each independently a residue of a polycarboxylic acid compound excluding two carboxy groups, and Y Ｂ are each independently a residue of a compound having two phenolic hydroxyl groups excluding the two phenolic hydroxyl groups. Ｂ are each independently a residue of a compound having one or two phenolic hydroxyl groups, excluding one phenolic hydroxyl group. Ｂ１ is an integer from 0 to 10.

[0041] n in the above general formula (B-1) Ｂ１ may be an integer of 0 to 5, may be an integer of 0 to 4, or may be an integer of 0 to 3.

[0042] From the viewpoint of adhesion to the metal layer, the ester equivalent of (B) the ester-based curing agent may be 100 to 300 g / eq, 150 to 270 g / eq, or 200 to 250 g / eq. The ester equivalent can be measured according to the method specified in JIS K0070 (1992).

[0043] The content of the (B) ester-based curing agent in the resin composition (or resin layer 130) is preferably 20 to 90 mass%, more preferably 20 to 80 mass%, even more preferably 25 to 70 mass%, and particularly preferably 30 to 60 mass%, relative to the total amount (100 mass%) of resin components in the resin composition (or resin layer 130), and may be 30 to 50 mass%, or may be 30 to 40 mass%. When the content of the (B) ester-based curing agent is within the above range, curability and adhesion to the metal layer tend to be better.

[0044] In the resin composition (or resin layer 130), the equivalent ratio [epoxy group / ester group] of the epoxy group derived from the epoxy resin to the ester group derived from the ester-based curing agent (B) is preferably 0.5 to 2.0, more preferably 0.75 to 1.75, and even more preferably 1.0 to 1.5, from the viewpoints of curability and adhesion to the metal layer.

[0045] <(C) Epoxy Resin Having an Alkylene Group Having 3 or More Carbon Atoms> The resin composition (or resin layer 130) may or may not further contain (C) an epoxy resin having an alkylene group having 3 or more carbon atoms. Examples of the (C) component include (C1) an epoxy resin having an alkylene group having 3 or more carbon atoms. However, the (C1) component is not included in the (A) component and the (A') component.

[0046] The component (C1) may be an epoxy resin having an alkylene group of 3 or more carbon atoms and two or more epoxy groups, an epoxy resin having two epoxy groups (bifunctional epoxy resin), or an epoxy resin having three or more epoxy groups (polyfunctional epoxy resin). The number of carbon atoms in the alkylene group having 3 or more carbon atoms in the component (C1) may be 3 to 10, 4 to 9, or 5 to 8, from the viewpoints of adhesion to the metal layer and heat resistance.

[0047] The alkylene group having 3 or more carbon atoms in the component (C1) may be a group derived from an alkylene glycol having 3 or more carbon atoms. The component (C1) may be an epoxy resin (hereinafter also referred to as "epoxy resin (C1a)") having a structure derived from an alkylene glycol having 3 or more carbon atoms and two glycidyl ether groups. Examples of alkylene glycols having 3 or more carbon atoms include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. The epoxy resin (C1a) may be an aliphatic epoxy resin in which two glycidyl ether groups are bonded to the alkylene group having 3 or more carbon atoms, or an aromatic epoxy resin in which a glycidyl ether group is bonded to an aromatic ring.

[0048] Examples of the epoxy resin (C1a) include a compound represented by the following general formula (C-1) and a compound represented by the following general formula (C-2).

[0049] (In the formula, X Ｃ are each independently a residue obtained by removing two phenolic hydroxyl groups from a polyfunctional phenol compound, and Y Ｃ is a residue obtained by removing two hydroxyl groups from an alkylene glycol having 3 or more carbon atoms, and n Ｃ１ is an integer from 1 to 5, n Ｃ２ is an integer from 1 to 5.

[0050] (In the formula, Y Ｃ is a residue obtained by removing two hydroxyl groups from an alkylene glycol having 3 or more carbon atoms, and n Ｃ３ is an integer from 1 to 15.

[0051] Examples of the polyfunctional phenol compound include bisphenol resins such as bisphenol A, bisphenol F, and bisphenol S; novolak resins such as phenol novolak, cresol novolak, bisphenol novolak, and bisphenol F novolak; catechol, biphenol, and dihydroxynaphthalene.

[0052] From the viewpoint of adhesion to the metal layer, the epoxy equivalent of the component (C1) may be 250 to 900 g / eq, 300 to 600 g / eq, or 350 to 550 g / eq.

[0053] (D) Curing Accelerator The resin composition (or resin layer 130) may further contain (D) a curing accelerator. By containing (D) a curing accelerator, the resin composition (or resin layer 130) tends to have improved curability, and to have better dielectric properties, heat resistance, and adhesion to the metal layer. One type of (D) curing accelerator may be used alone, or two or more types may be used in combination.

[0054] Examples of the (D) curing accelerator include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate-masked imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; and phosphorus-based compounds such as triphenylphosphine and quaternary phosphonium compounds which are addition reaction products of p-benzoquinone and tri-n-butylphosphine. peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); carboxylates of manganese, cobalt, zinc, and the like; and acidic catalysts such as p-toluenesulfonic acid. Among these, imidazole compounds and phosphorus-based compounds are preferred.

[0055] When the resin composition (or resin layer 130) contains a (D) curing accelerator, the content of the (D) curing accelerator may be 0.01 to 10% by mass, 0.1 to 7% by mass, or 0.5 to 5% by mass relative to the total amount (100% by mass) of the resin components in the resin composition (or resin layer 130). When the content of the (D) curing accelerator is equal to or greater than the above lower limit, a sufficient curing acceleration effect tends to be easily obtained. Furthermore, when the content of the (D) curing accelerator is equal to or less than the above upper limit, storage stability tends to be more easily improved.

[0056] <Other Optional Components> The resin composition (or resin layer 130) may further contain other optional components, as needed, such as curing agents other than the component (B), such as phenolic curing agents, amine curing agents, and acid anhydride curing agents; resin materials other than the above components, elastomers, inorganic fillers, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, silane coupling agents, organic solvents, and other additives. Each of these optional components may be used alone, or two or more may be used in combination. The content of the optional components in the resin composition (or resin layer 130) is not particularly limited, and they may be used as needed within a range that does not impair the effects of this embodiment. Furthermore, the resin composition (or resin layer 130) may not contain any of the optional components, depending on the desired performance.

[0057] As described above, the resin composition (or resin layer 130) may or may not contain an elastomer, as necessary. Examples of elastomers include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, silicone-based elastomers, and derivatives thereof. Among these, styrene-based elastomers are preferred. The styrene-based elastomer has a structural unit derived from a styrene-based compound (hereinafter also referred to as a "styrene-based unit"). Examples of the styrene-based compound include styrene; and alkyl-substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. The alkyl group of the alkyl-substituted styrene may have 1 to 5 carbon atoms, 1 to 3 carbon atoms, or even 1 or 2 carbon atoms. The styrene-based elastomer may contain a structural unit other than the styrene-based unit. Examples of structural units other than the styrene-based unit include a butadiene-derived structural unit, an isoprene-derived structural unit, a maleic acid-derived structural unit, and a maleic anhydride-derived structural unit. The butadiene-derived structural units and the isoprene-derived structural units may be hydrogenated. When hydrogenated, the butadiene-derived structural units become structural units in which ethylene units and butylene units are mixed, and the isoprene-derived structural units become structural units in which ethylene units and propylene units are mixed.

[0058] Examples of styrene-based elastomers include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and styrene-maleic anhydride copolymers. Examples of hydrogenated styrene-butadiene-styrene block copolymers include SEBS, which is obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and SBBS, which is obtained by partially hydrogenating the carbon-carbon double bonds at 1,2-bond sites in the butadiene block. Hydrogenated styrene-isoprene-styrene block copolymers are obtained as SEPS by hydrogenating the polyisoprene portion. Among these, SEBS and SEPS are preferred, with SEBS being more preferred, from the viewpoints of dielectric properties, adhesion to metal layers, heat resistance, glass transition temperature, and low thermal expansion. SEBS and SEPS may be modified with an acid anhydride such as maleic anhydride. The acid value of the SEBS modified with an acid anhydride and the acid value of the SEPS modified with an acid anhydride are not particularly limited, but are preferably 2 to 20 mg CH ３ ONa / g is preferred, 5 to 15 mg CH ３ ONa / g is more preferred, 7 to 13 mg CH ３ ONa / g is more preferable. Here, the acid value is determined by the acid value of sodium methoxide (CH ３ ONa) can be measured by titration.

[0059] When the resin composition (or resin layer 130) contains an elastomer, the content of the elastomer in the resin composition (or resin layer 130) is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 40% by mass, relative to the total amount (100% by mass) of resin components in the resin composition (or resin layer 130). It may be 20 to 40% by mass or 25 to 40% by mass. When the elastomer content is within the above range, adhesion to the metal layer tends to be improved. Furthermore, the elastomer content of the resin composition (or resin layer 130) may be less than 2% by mass, 1% or less by mass, or 0% by mass.

[0060] As described above, the resin composition (or resin layer 130) may or may not contain an inorganic filler, as necessary. Examples of inorganic fillers include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, molybdenum acid compounds, talc, aluminum borate, and silicon carbide.

[0061] The content of the inorganic filler in the resin composition (or resin layer 130) is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and still more preferably 0% by mass, relative to the total solid content (100% by mass) of the resin composition (or resin layer 130). When the content of the inorganic filler is equal to or less than the upper limit, the fine wiring properties and through-hole formability of the resin layer 130 are improved, and when a glass substrate is used as the substrate, the occurrence of cracks in the glass substrate can be suppressed.

[0062] (Method for Manufacturing Laminate 100) The method for manufacturing the laminate of this embodiment is not particularly limited, but may include a method of performing the following steps (a) to (b) in this order: (a) preparing a glass substrate having a first surface and a second surface, and having a plurality of through holes penetrating from the first surface to the second surface; (b) forming the resin layer on the side walls of the through holes.

[0063] (Regarding (a)) First, a glass substrate 110 having a first surface 112 and a second surface 114 is prepared. The glass substrate 110 is as described above. Next, a plurality of through holes 120 are formed in the prepared glass substrate 110. The through holes 120 have side walls 125. The method for forming the through holes 120 is not particularly limited, and known methods can be used. Note that when the diameter of each through hole 120 is to be minute (for example, 10 to 60 μm), the through holes 120 may be formed by laser ablation. The through holes 120 formed by laser ablation usually tend to have a tapered shape. Other methods for forming the through holes include drilling; etching such as hydrofluoric acid etching; and the like. Details of the through holes 120 are as described above.

[0064] (Regarding (b)) A resin layer 130 is formed on a glass substrate 110 having a through hole 120. Preferred methods for forming the resin layer 130 include dipping, coating, slit coating, and curtain coating, with dipping being more preferred. The "dipping" method refers to a method in which a glass substrate is immersed in a medium (here, a liquid or varnish) containing the raw materials for the resin layer, then pulled up and dried. The "coating" method refers to a method in which a medium (here, a liquid, varnish, or solid) containing the raw materials for the resin layer is applied to a glass substrate by spray coating, brush coating, or the like, and the applied medium is dried. In other words, the present disclosure also provides a method for manufacturing a laminate according to this embodiment, which includes forming the laminate by a coating or dipping method using the glass substrate having a through hole and a medium containing the raw materials for the resin layer. Note that if the through hole 120 is completely filled with the resin layer 130, it is preferable to perform a penetration treatment of the resin layer using ultraviolet light or laser light. The resin layer is preferably heat-cured (C-staged) by heat treatment at 150 to 230°C (more preferably 160 to 200°C) for 10 to 120 minutes (more preferably 30 to 90 minutes).

[0065] [Laminate] As shown in FIG. 3, a laminate 200 of this embodiment is a laminate having the laminate 100 and a metal layer 160 .

[0066] (Metal Layer 160) As shown in FIG. 3 , in one embodiment of the present invention, the metal layer 160 is composed of a metal layer 160A formed in the through-hole 120 of the glass substrate 110, a metal layer 160B covering the entire resin layer 130B on the first surface 112 of the glass substrate 110, and a metal layer 160C covering the entire resin layer 130C on the second surface 114 of the glass substrate 110. The metal layer 160A may be arranged so as not to fill the through-hole 120 as shown in FIG. 3 , or may be arranged so as to fill the through-hole 120 (not shown). The metal layer 160 may be configured to cover the entire resin layer 130. In another embodiment of the present invention, the metal layer 160 may have a circuit formed thereon. That is, as shown in FIG. 4 , another laminate of this embodiment is composed of a metal layer 160A formed in the through-hole 120 of the glass substrate 110, a metal layer 160B' covering at least a portion of the resin layer 130B on the first surface 112 of the glass substrate 110, and a metal layer 160C' covering at least a portion of the resin layer 130C on the second surface 114 of the glass substrate 110. The laminate 200 can electrically connect the first surface 112 of the glass substrate 110 and the second surface 114 of the glass substrate 110 via the through-hole 120. Because the metal layer 160 is in close contact with the glass substrate 110 with the resin layer 130 containing the specific component sandwiched therebetween, the metal layer 160 and the glass substrate 110 (strictly speaking, the resin layer 130) have high adhesion and are less likely to peel off.

[0067] The material of the metal layer 160 is not particularly limited as long as it is a metal or alloy having electrical conductivity. Examples of the material of the metal layer 160 include copper metal, copper alloy, zinc metal, and zinc alloy. The thickness of the metal layer 160 is not particularly limited and may be 0.1 to 50 μm, 0.5 to 40 μm, 1 to 35 μm, 2 to 30 μm, or 5 to 30 μm. Note that an insulating resin may be disposed between the metal layers 160.

[0068] (Method for manufacturing laminated plate 200) The method for manufacturing the laminated plate according to this embodiment is not particularly limited, but includes a method in which the following (c) is performed on the laminated body 100: (c) Placing a metal layer on the resin layer placed on the side wall of the through hole.

[0069] (Regarding (c)) A metal layer 160 is provided on the resin layer 130 of the laminate 100. The method for providing the metal layer 160 is not particularly limited, and examples thereof include plating. When the metal layer is a copper layer (copper plating layer), examples thereof include a method in which a copper seed layer is formed on the glass substrate 110 by electroless copper plating or copper sputtering, and then a copper electroplating layer is formed on the copper seed layer by copper electroplating. Details of the metal layer 160 are as described above.

[0070] [Printed Wiring Board] The printed wiring board of this embodiment has the laminate of this embodiment. It can also be said that the printed wiring board of this embodiment is a printed wiring board having the laminate of this embodiment. The printed wiring board of this embodiment can be produced by performing circuit formation processing by a known method using one or more members selected from the group consisting of the laminate of this embodiment and the laminate of this embodiment. Furthermore, a multilayer printed wiring board can also be produced by further performing multilayer adhesive processing as necessary.

[0071] [Semiconductor Package] The semiconductor package of this embodiment is a semiconductor package including the printed wiring board of this embodiment and a semiconductor element. The semiconductor package of this embodiment can be manufactured by mounting semiconductor elements such as semiconductor chips and memories at predetermined positions on the printed wiring board of this embodiment.

[0072] [Interposer, Ball Grid Array (BGA) Substrate] The laminate, laminate, or printed wiring board of this embodiment can be easily applied to an interposer or a ball grid array (BGA) substrate. Therefore, the present disclosure also provides an interposer or a ball grid array (BGA) substrate having the laminate, laminate, or printed wiring board of this embodiment. An interposer is a relay member located between a circuit element such as a semiconductor element and a mounting substrate, and is a substrate used to establish electrical continuity between the circuit element and the mounting substrate. A ball grid array (BGA) substrate is a substrate on which small ball-shaped electrodes made of solder are arranged in a grid pattern. Note that a ball grid array (BGA) substrate is a type of semiconductor package.

[0073] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0074] [1. Production of Resin Compositions] Examples 1 to 7, Comparative Examples 1 to 3: Each component listed in Table 1 was blended with cyclohexanone in the amounts listed in Table 1, and the blends were stirred and mixed at 25°C to prepare a varnish-like resin composition (solid content concentration: 5% by mass). In Table 1, the blend amount of each component is expressed in parts by mass, and in the case of a solution, it means parts by mass converted to solid content. [2. Production of Glass Substrate with Through Holes] Twenty-five through holes with a maximum diameter of 150 μm were formed at 200 μm intervals (shortest distance between outer edges) in alkali-free glass "OA-11G" (size: 50 mm x 50 mm, thickness: 300 μm) manufactured by Nippon Electric Glass Co., Ltd. by etching. [3. Production of Laminate] A glass substrate with through holes was immersed in a container containing the varnish-like resin composition prepared by the above method, thereby adhering the resin composition to the surface of the glass substrate with through holes and the side walls of the through holes, and then dried at 140°C for 10 minutes. The resin layer on the glass substrate was then thermally cured by heating at 180°C for 60 minutes to obtain a laminate having a resin layer. [4. Production of Laminated Plate] Using an ultraviolet irradiation device, the laminated plate was irradiated with ultraviolet light from a metal halide lamp (maximum wavelength 350 to 380 nm) at a light intensity of 3,000 mJ / cm. ２The laminate was irradiated so that the surface was treated. The surface-treated laminate was treated with a sweller solution "Swelling Dip Securigant P" (manufactured by Atotech Japan Co., Ltd.) at 70 ° C. for 5 minutes, then with a conditioner solution "Cleaner Securigant MVPF" (manufactured by Atotech Japan Co., Ltd.) at 60 ° C. for 4 minutes, and with a pre-dip solution "Pre-dip Neogant B" (manufactured by Atotech Japan Co., Ltd.) at 25 ° C. for 3 minutes. Subsequently, the laminate was treated with an activator solution "Activator Neogant 834 Conc" (manufactured by Atotech Japan Co., Ltd.) at 35 ° C. for 5 minutes, and then with an acid treatment solution "8% by mass hydrochloric acid" at 35 ° C. for 2 minutes. Thereafter, the laminate was treated with a reducer solution "Reducer Accelerator" (manufactured by Atotech Japan Co., Ltd.) at 30 ° C. for 7 minutes. Next, electroless plating was performed at 35 ° C. for 20 minutes using an electroless plating solution "Basic Prigant MV TP1" (manufactured by Atotech Japan Co., Ltd.). Thereafter, electroplating treatment was carried out using an electroplating solution "Cupracid HL" (manufactured by Atotech Japan Co., Ltd.) at 24°C and 1 A / dm ２ The laminate produced in the above 4. was subjected to electroplating at 24°C and 2 A / dm for 0.5 hours to form a plated copper (copper layer) on the resin layer. The thickness of the plated copper (copper layer) was 5 μm. [5. Evaluation of Adhesion to Copper Layer] The laminate produced in the above 4. was subjected to electroplating at 24°C and 2 A / dm ２ The resin layer was then formed on the glass substrate surface at 100°C for 1 hour, forming a 25 μm thick copper-plated layer (copper layer). A 5 mm wide, 50 mm long section was formed on a portion of the copper layer, and one end of the section was peeled off and held with a gripper. The adhesive strength was determined by measuring the load when the section was peeled off for approximately 50 mm in the vertical direction at room temperature, and this was used as an index of adhesion to the copper layer.

[0075]

[0076] The details of each material in Table 1 are as follows: [Component (A)] Epoxy resin 1: biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "NC-3000H")

[0077] [Comparative Components] Epoxy resin 2: dicyclopentadiene-type epoxy resin (manufactured by DIC Corporation, trade name "EPICLON (registered trademark) HP-7200L") Epoxy resin 3: dicyclopentadiene-type epoxy resin (manufactured by DIC Corporation, trade name "EPICLON (registered trademark) HP-7200HHH") Epoxy resin 4: naphthalene skeleton-containing epoxy resin (manufactured by DIC Corporation, trade name "HP-9500")

[0078] [Component (B)] Ester-based curing agent 1: an active ester compound containing a dicyclopentadiene-type diphenol structure (manufactured by DIC Corporation, trade name "HPC-8000L-65MT", ester equivalent: 223 g / eq) Ester-based curing agent 2: an active ester curing agent containing a naphthalene structure (manufactured by DIC Corporation, trade name "HPC-8150-62T", ester equivalent: 229 g / eq)

[0079] [Component (C)] Aromatic epoxy resin 1 having an alkylene group with 3 or more carbon atoms, component (C1) Aliphatic epoxy resin 2 having an alkylene group with 3 or more carbon atoms, component (C1)

[0080] [Other components] Elastomer 1: Maleic anhydride-modified styrene-based thermoplastic elastomer (maleic anhydride-modified SEBS), acid value 10 mg CH ３ ONa / g, styrene content 30% by mass

[0081] As can be seen from Table 1, the laminates produced in Examples 1 to 7 had higher adhesion to the copper layer than the laminates produced in Comparative Examples 1 to 3.

[0082] 110 Glass substrate 112 First surface 114 Second surface 120 Through hole 125 Side wall 130 Resin layer 130A Resin layer 130B Resin layer 130C Resin layer 160 Metal layer 160A Metal layer 160B Metal layer 160B' Metal layer 160C Metal layer 160C' Metal layer 200 Laminate

Claims

1. A laminate including a glass substrate having a through hole, wherein a layer of a resin composition is formed on the surface of the glass substrate and on the side walls of the through hole, the resin composition containing (A) an epoxy resin having a biphenyl-diyl group and (B) an ester-based curing agent, and the content of component (A) is 10 to 80 mass% of the total amount of resin components.

2. The laminate according to claim 1, wherein the resin composition further contains or does not contain (C) an epoxy resin having an alkylene group having 3 or more carbon atoms.

3. The laminate according to claim 1, wherein the maximum diameter of the through holes is 5 to 200 μm.

4. The laminate according to claim 1, wherein the thickness of the resin composition layer is 0.01 to 100 μm.

5. The laminate according to claim 1, wherein the through-holes are not filled with the layer of the resin composition.

6. The laminate according to claim 1, wherein a plurality of the through holes are present and the shortest distance between the outer edges of the nearest through holes is 1 to 1,000 μm.

7. The laminate according to claim 1, wherein the thickness of the glass substrate is 10 to 2,000 μm.

8. A method for producing a laminate according to claim 1, comprising forming the laminate by a coating method or a dipping method using the glass substrate having through holes and a medium containing the resin composition.

9. The laminate according to claim 1, which is for use in a printed wiring board.

10. The laminate of claim 1, which is for an interposer or a ball grid array (BGA) substrate.

11. A laminate plate comprising the laminate of claim 1 and a metal layer.

12. A printed wiring board comprising the laminate of claim 1.

13. A semiconductor package comprising the printed wiring board according to claim 12 and a semiconductor element.

14. An interposer comprising the laminate of claim 1.

15. A ball grid array (BGA) substrate having the laminate of claim 1.

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