TW202003238A - Laminate, laminate plate having conductor layer, printed circuit board, production methods therefor, and semiconductor package - Google Patents

Abstract

Provided are: a laminate such that conduction can easily occur between the front and the back despite having a glass substrate layer; a laminate plate having a conductor layer; a printed circuit board; production methods therefor; and a semiconductor package. Specifically, the laminate includes one or more thermosetting resin composition layers and one or more glass substrate layers, wherein at least one of the glass substrate layers has one or more glass through-holes, and there is a thermosetting resin composition layer on the wall surface of at least one of the glass through-holes.

Description

Laminated body, laminated board with conductor layer, printed wiring board, manufacturing method thereof, and semiconductor package

The present invention relates to a laminate, a laminate with a conductor layer, a printed wiring board, a manufacturing method thereof, and a semiconductor package.

In recent years, there has been an increasing demand for thinning and lightening of electronic equipment, and the thinning and high density of printed wiring boards and semiconductor packages are being promoted. In order to stably mount electronic components in response to thinning and higher density, it is important to suppress warpage generated during mounting. During mounting, one of the main causes of warpage in the semiconductor package is the difference in thermal expansion coefficient between the laminate used in the semiconductor package and the silicon wafer mounted on the surface of the laminate. Therefore, in the laminate for semiconductor packages, efforts are being made to make the thermal expansion rate close to that of silicon wafers, that is, to lower the thermal expansion rate. In addition, the low elasticity coefficient of the laminate also causes warpage. Therefore, in order to reduce warpage, it is also effective to make the laminate more elastic. As described above, in order to reduce the warpage of the laminate, it is effective to reduce the expansion ratio and increase the elasticity of the laminate.

Various methods have been studied to reduce the thermal expansion coefficient and increase the elasticity of the laminate, and it has been known to reduce the thermal expansion coefficient of the resin for the laminate and to increase the inorganic filler in the resin. In particular, the increase of the inorganic filler can be expected to reduce the thermal expansion rate, and the improvement of heat resistance and flame retardancy can also be expected (for example, refer to Patent Document 1). However, it is known that increasing the filling amount of the inorganic filler leads to a decrease in insulation reliability, insufficient adhesion between the resin and the wiring layer formed on the surface, and poor press-forming when manufacturing a laminate, and an increase in the filling of the inorganic filler There is a limit.

In addition, attempts have been made to achieve a low thermal expansion rate through the selection or improvement of resins. For example, a method of increasing the glass transition temperature (Tg) and reducing the thermal expansion rate by increasing the cross-linking density of the resin for wiring boards is known (for example, refer to Patent Document 2 and Patent Document 3). However, increasing the cross-link density shortens the molecular chain between functional groups, and shortening the molecular chain by more than a certain degree has a limit in terms of reaction, and also has a problem of reducing the resin strength. Therefore, there is also a limit to achieving a low thermal expansion rate by increasing the crosslink density. As described above, in the conventional laminates, the high thermal expansion rate and high elasticity are achieved by the high filling of inorganic fillers or the use of resins with low thermal expansion rates, but these methods are reaching the limit.

Under such circumstances, Patent Document 4 discloses that, for a laminated board that includes a glass substrate having a thermal expansion coefficient that substantially matches the thermal expansion coefficient of an electronic component such as a silicon wafer, and includes a resin cured layer and a glass substrate layer, By including the inorganic filler in the cured resin layer, a laminate having a low thermal expansion coefficient and a high elastic coefficient, which can suppress warpage and is less prone to cracking can be obtained. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2004-182851 Patent Document 2: Japanese Patent Laid-Open No. 2000-243864 Patent Document 3: Japanese Patent Laid-Open No. 2000-114727 Patent Literature 4: International Publication No. 2013/042748

[Problems to be solved by the invention]

However, in Patent Document 4, a resin film layer is laminated on a glass substrate to manufacture a laminate and a laminate. Since there is no glass through hole in the glass substrate [hereinafter sometimes referred to as TGV (Through Glass Via)], lamination cannot be performed. The wiring on the front and back of the board is conducted. In addition, even if a through hole is to be formed in the laminate board described in Patent Document 4 for conduction, the plating for the conductor layer will not adhere to the wall surface of the TGV opened on the glass substrate, so research is needed Other means.

In view of the above-mentioned current situation, an object of the present invention is to provide a laminate, a laminate with a conductor layer, a printed wiring board, a method for manufacturing the same, and a semiconductor package, which include a glass substrate layer but are easy to communicate with the front and back. [Means to solve the problem]

The present inventors repeatedly worked hard to solve the above-mentioned problems, and as a result, it was found that if it is a laminate including a glass substrate layer and using a glass substrate having a glass through-hole, a thermosetting is provided on the wall surface of the glass through-hole The laminate of the layer of the resin composition can solve the above problems. That is, the present invention provides the following [1] to [18].

[1] A layered body comprising one or more thermosetting resin composition layers and one or more glass substrate layers, wherein, At least one glass substrate layer of the glass substrate layer has one or more glass through-holes, and a wall surface of at least one glass through-hole in the glass through-hole has a thermosetting resin composition layer. [2] The laminate according to the above [1], wherein the glass substrate layer is in contact with at least one thermosetting resin composition layer, and the constituent material of the thermosetting resin composition layer penetrates through the glass The constituent materials of the thermosetting resin composition layer on the wall surface of the hole are the same. [3] The laminate according to the above [1] or [2], wherein the thermosetting resin composition layers are all layers containing a thermosetting resin composition, and the thermosetting resin composition contains (A) Epoxy resin and (B) Compound containing active ester group. [4] The laminate according to the above [3], wherein the (A) epoxy resin contains an epoxy resin having a structural unit derived from an alkylene glycol having 3 or more carbon atoms. [5] The laminate according to the above [4], wherein the alkanediol having 3 or more carbon atoms is hexanediol. [6] The laminate according to any one of the above [3] to [5], wherein the ester group derived from the (B) active type ester-containing compound in the thermosetting resin composition, The equivalent ratio (ester group/epoxy group) to the epoxy group derived from the (A) epoxy resin is 0.5 to 1.5. [7] The laminate according to any one of [3] to [6], wherein the thermosetting resin composition further contains (C) a curing accelerator. [8] The laminate according to any one of the above [1] to [7], wherein the thermosetting resin composition layer (wherein the thermosetting resin composition layer located on the wall surface of the glass through hole) Except) the surface roughness (Ra) is 0.2 μm or less. [9] The laminate according to any one of [3] to [8], wherein the thermosetting resin composition layer is a B-stage or C-stage transformation of the thermosetting resin composition Layer. [10] A laminate with a conductor layer formed by forming a conductor layer in the laminate as described in any one of [1] to [9] and existing in the glass through-hole The thermosetting resin composition layer on the wall surface also has a conductor layer. [11] A printed wiring board produced by circuit-processing the laminated board with a conductor layer as described in [10]. [12] A semiconductor package in which a semiconductor element is mounted on the printed wiring board as described in [11]. [13] A method for manufacturing a laminate, which is the method for manufacturing a laminate as described in any one of the above [1] to [9], It includes the step of applying the thermosetting resin composition to the glass substrate layer having glass through holes. [14] The method for manufacturing a laminate according to the above [13], wherein the method is selected from the group consisting of spin coating method, dip coating method, dip spin coating method, spray coating method, round spray coating method, Mist coating method, flow coating method, curtain coating method, roll coating method, blade coating method, blade coating method, air knife coating method, bar coating method, screen printing method, gravure printing method, The coating is performed by a method in the group consisting of lithography, flexography, and bristle coating. [15] The method for manufacturing a laminate according to the above [13] or [14], which further includes a step of thermally curing the applied thermosetting resin composition. [16] The method for manufacturing a laminate according to any one of the above [13] to [15], which further includes applying the applied thermosetting resin composition or the thermosetting thermosetting resin composition The step of irradiating the object with active energy rays. [17] A method for manufacturing a laminate with a conductor layer, comprising: a step of manufacturing a laminate by the method for manufacturing a laminate as described in any one of [13] to [16]; and The layered body is subjected to a plating process to form a conductor layer. [18] A method of manufacturing a printed wiring board, comprising: a step of manufacturing a laminate with a conductor layer by the method for manufacturing a laminate with a conductor layer as described in [17]; and forming the conductor layer Circuit steps. [Effect of invention]

According to the present invention, it is possible to provide a laminated body, a laminated board with a conductor layer, a printed wiring board, a method for manufacturing the same, and a semiconductor package, although the glass substrate layer is included but the conduction between the front and back is easy.

In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. In addition, the lower limit value and the upper limit value of the numerical range can be arbitrarily combined with the lower limit value or the upper limit value of the other numerical range. In addition, with respect to each component and material exemplified in the present specification, unless otherwise specified, one type may be used alone, or two or more types may be used in combination. In this specification, regarding the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it refers to the plurality of substances present in the composition Total measurement. All aspects described in this specification in any combination are included in the present invention.

[Laminate] The laminated body of the present invention will be described with reference to FIGS. 1 and 2. The laminated body of the present invention is as follows, It is a laminate including more than one thermosetting resin composition layer (1) and more than one glass substrate layer (2), wherein, At least one glass substrate layer (2) of the glass substrate layer (2) has one or more glass through-holes (4), and the wall surface of at least one glass through-hole in the glass through-hole has a thermosetting resin Composition layer (3). Hereinafter, the glass substrate layer and the thermosetting resin composition layer will be described in detail.

<Glass substrate layer> The glass substrate layer includes a glass substrate, that is, plate glass, and does not include a layer containing glass fibers. The glass substrate is not particularly limited, and examples thereof include alkali-free glass, soda lime glass, borosilicate glass, whiteboard glass, quartz glass, and Vycor glass. Among these, alkali-free glass is preferred. In the laminate of the present invention, at least one glass substrate in the glass substrate layer has one or more glass through holes (TGV). The TGV is a through hole formed by making a hole in a glass substrate, and its formation method is not particularly limited. For example, TGV can be set by laser, sand blast, drill, etc. The TGV is not particularly limited as long as its wall surface protrudes from the surface to the back of the glass substrate.

In the laminate of the present invention, at least one of the TGVs included in the glass substrate layer has a thermosetting resin layer described later on the wall surface. It is preferable that the wall surface of 80% or more of TGV in the TGV of the glass substrate layer has a thermosetting resin layer described later, and it is preferable that the wall surface of 90% or more of the TGV in the TGV of the glass substrate layer have the wall surface described later It is more preferable that the thermosetting resin layer has a thermosetting resin layer described later on all the wall surfaces of the TGV included in the glass substrate layer. The thickness of one glass substrate layer is not particularly limited, and from the viewpoint of thinning and weight reduction, it is preferably 1,000 μm or less, more preferably 800 μm or less, and further preferably 650 μm or less. The lower limit of the thickness of one glass substrate layer is not particularly limited, but it is usually 200 μm or more, or 300 μm or more. The laminate of the present invention includes more than one glass substrate layer, preferably 1 to 20 glass substrate layers, more preferably 1 to 10 glass substrate layers, and even more preferably 1 to 5 layers. The glass substrate layer preferably contains a glass substrate layer. However, the number of glass substrate layers is not limited to these.

In addition, the glass substrate layer is in contact with at least one thermosetting resin composition layer, and it is preferable that the constituent material of the thermosetting resin composition layer in contact and the configuration of the thermosetting resin composition layer located on the wall surface of the TGV The same material. On the other hand, they may be different constituent materials.

<Thermosetting resin composition layer> The thermosetting resin composition layer is not particularly limited as long as it contains a thermosetting resin-containing composition (ie, a thermosetting resin composition). From the viewpoint of adhesion to the conductor layer, the Preferably, the layer contains a thermosetting resin composition containing (A) an epoxy resin and (B) a compound containing an active ester group. In addition, the thermosetting resin composition preferably further contains (C) a curing accelerator.

The thermosetting resin composition layer may be a layer formed by the B stage of the thermosetting resin composition or may be a layer formed by the C stage, and is included in any aspect of the present invention. Here, B-staged means that the thermosetting resin composition is cured at 5% to 90%, and C-staged means that the thermosetting resin composition is cured at more than 90% (including 100%). The thermosetting resin composition B-staged is also called a semi-hardened state. In addition, the degree of curing of the thermosetting resin composition can be obtained from the reaction rate measured by a differential scanning calorimeter.

Hereinafter, each component contained in the thermosetting resin composition will be described in detail. (Thermosetting resin) The thermosetting resin composition contains thermosetting resin. As the thermosetting resin, from the viewpoint of productivity, a thermosetting resin that is thermosetting at a normal thermosetting temperature in the range of 150°C to 230°C is preferred. Examples of thermosetting resins include epoxy resins, cyanate ester compounds, bismaleimide compounds, bisallyl naldiimide resins, benzoxazine compounds, and bismaleimides. Addition reactants of imidate compounds and diamine compounds. Among these, an epoxy resin, an addition reaction product of a bismaleimide compound and a diamine compound, and a cyanate compound are preferred, and from the viewpoint of chemical resistance, an epoxy resin is more preferred.

The thermosetting resin composition preferably contains (A) an epoxy resin [hereinafter sometimes referred to as (A) component] and (B) a compound containing an active ester group [hereinafter sometimes referred to as (B) component] Appearance. It is also preferable that the thermosetting resin composition contains (A) epoxy resin and other hardeners.

((A) Epoxy resin) (A) The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule, and specific examples include cresol novolac epoxy resin, phenol novolac epoxy resin, and naphthalene Phenolic novolac epoxy resin, aralkyl novolac epoxy resin, biphenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin , Bisphenol T epoxy resin, bisphenol Z epoxy resin, tetrabromobisphenol A epoxy resin, biphenyl epoxy resin, tetramethyl biphenyl epoxy resin, triphenyl epoxy resin Resin, tetraphenyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene glycol aralkyl type epoxy resin, fluorene type epoxy resin, epoxy resin with dicyclopentadiene skeleton, skeleton Among them are epoxy resins and alicyclic epoxy resins with ethylenically unsaturated groups. From the viewpoint of insulation reliability and heat resistance, the component (A) may be used alone or in combination of two or more. From the viewpoint of heat resistance, an aromatic epoxy resin is preferred, and a phenol novolac epoxy resin is more preferred. As the (A) component, commercially available products can be used, and examples thereof include "jER828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation as a bisphenol A type epoxy resin, and Mitsubishi as a bisphenol F type epoxy resin. "JER806H" and "YL983U" manufactured by Chemical Co., Ltd.

From the viewpoint of flexibility, the component (A) preferably contains (A1) a structural unit having (preferably in the main chain) an alkylene glycol having 3 or more carbon atoms (hereinafter sometimes referred to as “AG Structural unit") epoxy resin, preferably (A1) epoxy resin with (preferably in the main chain) AG structural unit and (A2) epoxy resin without AG structural unit (eg phenol novolac) The aforementioned epoxy resins such as varnish-type epoxy resins) are used in combination. In the case of combined use, the content ratio of (A1) epoxy resin with (preferably in the main chain) AG structural unit to (A2) epoxy resin without AG structural unit [(A1)/(A2) ] (Mass ratio) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, more preferably 30/70 to 80/20, and further preferably 40/60 to 70/30, especially It is preferably 50/50 to 70/30, and most preferably 55/45 to 70/30. On the other hand, component (A) does not contain (A1) epoxy resins with (preferably in the main chain) AG structural units, while (A2) epoxy resins without AG structural units are also more good.

The carbon number of the alkanediol used to form the AG structural unit is preferably 3 to 15, more preferably 4 to 10, and still more preferably 5 to 8. Examples of the alkanediol include propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and decanediol. Among these, hexanediol is preferred, and 1,6-hexanediol is more preferred. These may be used alone or in combination of two or more. In addition, from the viewpoint of improving flexibility, it is preferable that the AG structural unit in the component (A) is two or more continuous and repeating.

（式中，(-R¹ -O-)表示源自碳數3以上的烷二醇的結構單元。R² 表示碳數1～10的二價脂肪族烴基。n表示1～15）As a specific example of the component (A) having the AG structural unit in the main chain, for example, an epoxy resin having a structural unit represented by the following general formula (1) can be cited. [Chemical 1]

(In the formula, (-R ¹ -O-) represents a structural unit derived from an alkylene glycol having 3 or more carbon atoms. R ² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. n represents 1 to 15)

The alkanediol used to form the structural unit derived from an alkanediol having 3 or more carbon atoms represented by (-R ¹ -O-) is the same as the alkanediol used to form the AG structural unit. And the better is also the same. The carbon number of the divalent aliphatic hydrocarbon group represented by R ² is preferably 1 to 5, and more preferably 1 to 4. Examples of the divalent aliphatic hydrocarbon group include an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, and the like. Among these, alkylene having 1 to 10 carbon atoms and alkylene having 2 to 10 carbon atoms are preferred. The alkylene group is preferably methylene, and the alkylene group is preferably isopropylene. n is preferably 2-10.

Among these epoxy resins, the component (A) is preferably a bisphenol A epoxy resin having a structural unit derived from diol in the main chain (that is, R ¹ in the general formula (1) is Hexanediol residue, R ² is isopropylidene compound).

The content of the component (A) in the thermosetting resin composition is relative to the total solids of the thermosetting resin composition from the viewpoint of adhesion to the conductor layer and the balance of various characteristics such as heat resistance. The component is preferably 10% by mass to 85% by mass, more preferably 30% by mass to 80% by mass, and still more preferably 45% by mass to 75% by mass. Here, the solid content in this embodiment refers to a component in a composition other than volatile substances such as water and a solvent described later. That is, the solid content is also included in a liquid state, a paste state, or a wax state at room temperature near 25°C, and does not necessarily mean that it is solid.

((B) Compounds containing active ester groups) (B) The compound containing an active type ester group is a compound containing an active type ester group, in other words, a compound having more than one ester group in one molecule and having a hardening effect of epoxy resin. The component (B) can function as a curing agent for the component (A). Examples of the component (B) include compounds that include one or more ester groups in one molecule and can harden the component (A). (B) One component may be used alone, or two or more components may be used in combination. Since the thermosetting resin composition contains the component (B), even if the surface roughness (Ra) of the thermosetting resin composition layer is small, the adhesion to the conductor layer tends to be good.

When the (A) component contains (A1) an epoxy resin having (preferably in the main chain) an AG structural unit, the thermosetting resin composition preferably contains the (B) component. On the other hand, when the (A) component does not contain (A1) an epoxy resin having (preferably in the main chain) an AG structural unit, and (A2) an epoxy resin not containing an AG structural unit, There is no particular limitation, and the thermosetting resin composition preferably contains another curing agent described later as the curing agent instead of the component (B).

Examples of the component (B) include ester compounds obtained from aliphatic carboxylic acids or aromatic carboxylic acids, and aliphatic hydroxy compounds or aromatic hydroxy compounds. Among these, from the viewpoint of improving solubility in organic solvents and compatibility with epoxy resins by including aliphatic chains, esters obtained from aliphatic carboxylic acids and aliphatic hydroxy compounds are preferred Compound. On the other hand, from the viewpoint that heat resistance can be improved by having an aromatic ring, an ester compound obtained from an aromatic carboxylic acid and an aromatic hydroxy compound is preferred. Examples of the ester compound obtained from an aromatic carboxylic acid and an aromatic hydroxy compound include a mixture of an aromatic carboxylic acid and an aromatic hydroxy compound as a raw material, and condensation of the carboxyl group of the aromatic carboxylic acid and the hydroxyl group of the aromatic hydroxy compound The aromatic ester obtained by the reaction, the aromatic carboxylic acid is substituted with aromatic compounds such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenylether, diphenylsulfonic acid, etc. An aromatic carboxylic acid composed of 2 to 4 hydrogen atoms, the aromatic hydroxy compound is a monohydric phenol obtained by replacing one hydrogen atom of the above-mentioned aromatic compound with a hydroxyl group, or substituted with a hydroxyl group Aromatic hydroxy compounds such as polyphenols with 2 to 4 hydrogen atoms of the aromatic compounds. These can also be obtained as commercially available products, for example: "EXB9451" (ester equivalent: about 220 g/eq), "EXB9460", "EXB9460S-65T" (ester equivalent: 223 g/eq), "HPC-8000-65T" (ester equivalent: 223 g/eq) (all made by DIC Corporation, trade name); "BPN80" (Mitsui Chemical Co., Ltd., trade name), etc.

The equivalent ratio (ester group/epoxy group) of the ester group derived from (B) component in the thermosetting resin composition and the epoxy group derived from (A) component is preferably 0.5 to 1.5, more preferably 0.7～1.3. When the equivalent ratio (ester group/epoxy group) is within the above range, the heat resistance and the glass transition temperature tend to become better.

The content of the component (B) in the thermosetting resin composition is preferably 5 mass% to 70 mass% relative to the total solid content of the thermosetting resin composition from the viewpoint of adhesion to the conductor layer %, more preferably 10% by mass to 60% by mass, and further preferably 20% by mass to 50% by mass.

(Other hardeners) When the component (A) does not contain (A1) an epoxy resin having (preferably in the main chain) an AG structural unit, but contains (A2) an epoxy resin not containing an AG structural unit, the thermosetting resin The composition preferably contains other hardeners instead of the component (B). As other hardeners, those known as epoxy resin hardeners can be used without particular limitation. As another hardener, it is preferable to use a hardener selected from the group consisting of phenol resin, acid anhydride, amine, hydrazide compound, dicyandiamide, cyanate resin, and the like. Among these, from the viewpoint of insulation reliability, a phenol resin is preferred.

The phenol resin is not particularly limited as long as it is a phenol resin having two or more phenolic hydroxyl groups in one molecule. Examples include: resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted bisphenol equal to a compound having two phenolic hydroxyl groups in one molecule; aralkyl type phenol resin ; Dicyclopentadiene phenol resin; triphenylmethane phenol resin; phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac resin, aminotriazine modified novolac Phenolic resins such as novolac-type phenol resins; Soluble phenol-type phenol resins; Copolymerized phenol resins of benzaldehyde-type phenols and aralkyl-type phenols; P-xylene and/or m-xylene modified phenol resins; Quality phenol resin; terpene modified phenol resin; dicyclopentadiene type naphthol resin; dicyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin; biphenyl type phenol resin, etc. One type of phenol resin may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of insulation reliability, a novolak type phenol resin is preferable, and a bisphenol A novolak resin is more preferable. As the phenol resin, a commercially available product can also be used, and for example, "YLH129" (bisphenol A novolak resin, manufactured by Mitsubishi Chemical Corporation, trade name, hydroxyl equivalent: 117 g/eq), etc. may be mentioned.

Examples of the acid anhydride include phthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetra Hydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3,6 -Tetrahydrophthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl-5-norbornene-2,3-dicarboxylic acid (methylhimic acid), etc. The acid anhydride may be used alone or in combination of two or more.

Examples of the amines include chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and diethylaminopropylamine; N-aminoethylpiperazine, and isophoronediamine And other cyclic aliphatic polyamines; m-xylenediamine and other aliphatic aromatic diamines; m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylbenzene and other aromatic amines; guanylurea Wait. One type of amine may be used alone, or two or more types may be used in combination. Examples of the hydrazide compound include adipic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, dodecanediohydrazide, isophthalic acid dihydrazide, and salicylic acid dihydrazide. Hydrazine, etc. The hydrazine compound may be used alone or in combination of two or more.

Examples of the cyanate resins include 2,2-bis(4-cyanooxyphenyl)propane, bis(4-cyanophenyl)ethane, and bis(3,5-dimethyl-4 -Cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanooxybenzene Group)-m-diisopropylbenzene, cyanate compound of phenol addition dicyclopentadiene polymer, phenol novolak type cyanate compound, cresol novolak type cyanate compound, etc. The cyanate resin may be used alone or in combination of two or more.

The equivalent ratio (functional group/epoxy group) of the functional group derived from the other hardener in the thermosetting resin composition and the epoxy group derived from the component (A) is preferably 0.2 to 1.5, more preferably It is 0.4 to 1.0, and more preferably 0.4 to 0.8. When the equivalent ratio (functional group/epoxy group) is within the above range, the heat resistance and the glass transition temperature tend to become better.

The content of the other curing agent in the thermosetting resin composition is preferably 5 to 60 mass% relative to the total solid content of the thermosetting resin composition from the viewpoint of adhesion to the conductor layer It is more preferably 10% by mass to 50% by mass, and still more preferably 10% by mass to 30% by mass.

((C) Hardening accelerator) As described above, the thermosetting resin composition preferably further contains (C) a hardening accelerator. Examples of hardening accelerators include (C1) imidazole compounds and derivatives [hereinafter sometimes referred to as (C1)]; (C2) phosphorus compounds [hereinafter sometimes referred to as (C2)]; tertiary amine compounds; Quaternary ammonium compounds, etc. From the viewpoint of promoting the hardening reaction, (C1) imidazole compounds and derivatives thereof, and (C2) phosphorus compounds are preferred.

From the viewpoint of storage stability and solder heat resistance, the thermosetting resin composition preferably uses the (C1) component as the (C) component. The derivative of the (C1) imidazole compound may be an imidazoline compound, or may be a potential imidazole compound by masking secondary amine groups with acrylonitrile, isocyanate, melamine, acrylate, or the like.

Examples of the imidazole compound and its derivatives include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 1,2- Dimethylimidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl 2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzene Bimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Alkyl imidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl- Imidazole compounds such as mesitazine; 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, 2-phenyl-4-methylimidazoline and other imidazoline compounds ; The addition reaction of the imidazole compound (preferably 1-cyanoethyl-2-phenylimidazole) and trimellitic acid; the addition reaction of the imidazole compound and isocyanuric acid; Addition reaction of imidazole compound (preferably 2-ethyl-4-methylimidazole) and diisocyanate compound (preferably hexamethylene diisocyanate); addition reaction of the imidazole compound with hydrobromic acid Things. The imidazole compound may be used alone or in combination of two or more. Among these, as the (C1) component, an addition reaction product of an imidazole compound (preferably 1-cyanoethyl-2-phenylimidazole) and trimellitic acid is preferred.

From the viewpoints of low reactivity at lower temperatures, storage stability, adhesion to the conductor layer, and solder heat resistance, the thermosetting resin composition preferably uses the (C2) component as (C) ingredient. As the component (C2), a general phosphorus-based compound used as a curing accelerator for epoxy resins can be used. Specific examples thereof include organic phosphine compounds such as triphenylphosphine and tributylphosphine; organic phosphite compounds such as trimethylphosphite and triethylphosphite; ethyltriphenylbromide Phosphonium compounds such as phosphonium, tetraphenylboronic acid tetraphenylphosphonium, etc. (C2) One component may be used alone, or two or more components may be used in combination. Among these, organic phosphine-based compounds are preferred.

Examples of the organic phosphine include trimethylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, triethylphosphine, ethyldiphenylphosphine, triphenylphosphine, Tri(4-methylphenyl)phosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(isopropylbenzene) Group) phosphine, tri(third butylphenyl) phosphine, tri(2,4-dimethylphenyl) phosphine, tri(2,6-dimethylphenyl) phosphine, tri(2,4,6 -Trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl ) Tertiary phosphines such as phosphines and tricyclohexylphosphines. Among these, as the (C2) component, triphenylphosphine is preferred.

The content of the (C) curing accelerator in the thermosetting resin composition is preferably 0.1 to 3 parts by mass, more preferably 0.3 to 2.5 parts by mass relative to (A) 100 parts by mass of the epoxy resin. Furthermore, it is preferably 0.5 to 2.0 parts by mass. If the content of the (C) component is 0.1 parts by mass or more, (A) the curing of the epoxy resin will become more sufficient and the heat resistance will tend to be good; if it is 3 parts by mass or less, there will be storage stability and B The ease of handling of the stepped thermosetting resin composition tends to increase.

((D) inorganic filler) The thermosetting resin composition may further contain (D) an inorganic filler [hereinafter sometimes referred to as (D) component], or may not contain it. Examples of (D) inorganic fillers include silicon dioxide, aluminum oxide, titanium oxide, mica, beryllium oxide, 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, talc, aluminum borate, silicon carbide, quartz powder, glass short fiber, glass fine powder and insulating glass Etc., preferably at least one selected from the group consisting of these. As glass, E glass, T glass, D glass, etc. are mentioned preferably. (D) One component may be used alone, or two or more components may be used in combination. Among these, from the viewpoint of dielectric characteristics, heat resistance, and low thermal expansion, silicon dioxide is preferred. Examples of the silicon dioxide include sedimentary silica with a high water content produced by a wet method, and dry-process silica produced by a dry method that hardly contains bound water or the like. The dry-process silicon dioxide is further classified into finely divided silicon dioxide, gas-phase silicon dioxide, molten spherical silicon dioxide, etc. according to the manufacturing method.

As the (D) component, a commercially available product can be used, and examples thereof include: "AEROSIL (registered trademark) R972" (made by AEROSIL) Co., Ltd. as fumed silica , Trade name, specific surface area: 110 m ² /g±20 m ² /g), "AEROSIL (registered trademark) R202" (made by Japan AEROSIL Co., Ltd., trade name , Specific surface area: 100 m ² /g), “PL-1” (manufactured by Fusang Chemical Industry Co., Ltd., trade name, 181 m ² /g), “PL-7” (manufactured by Fusang Chemical Industry Co., Ltd., product) Name, 36 m ² /g) etc.

When the thermosetting resin composition contains the component (D), the content of the thermosetting resin composition relative to the total solid content of the thermosetting resin composition is preferably 1% by mass to 10% by mass, more preferably 1% by mass to 7% The mass% is more preferably 1 mass% to 5 mass%. If the content of the component (D) is 10% by mass or less, the surface of the thermosetting resin composition layer becomes smooth, and the coating property to TGV tends to be good. From the viewpoint of applicability to TGV, the aspect in which the thermosetting resin composition does not contain the component (D) can also be said to be preferable.

(Other ingredients) The thermosetting resin composition may optionally further contain known thermoplastic resins, organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent light, as long as the effects of the present invention are not hindered. Brighteners, adhesive enhancers, etc. These may be used alone or in combination of two or more.

Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamidoamide resin, polyimide resin Acetyleneimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyether ether ketone (PEEK) resin, silicone resin, tetrafluoroethylene resin, etc. Among these, the polyamide resin is preferred. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. As the polyamide resin, a polybutadiene modified polyamide resin having a phenolic hydroxyl group is more preferred, and a structure derived from a diamine-derived structural unit and a phenolic hydroxyl group-containing dicarboxylic acid is more preferred. Units, structural units derived from dicarboxylic acids that do not contain phenolic hydroxyl groups, and structural units derived from polybutadiene having carboxyl groups at both ends. For the polybutadiene-modified polyamide resin having a phenolic hydroxyl group, the “phenolic hydroxyl-containing polybutadiene-modified polyamide resin (F)” described in Japanese Patent Laid-Open No. 2017-193693 can be used.

Examples of the organic filler include resin fillers including polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, and tetrafluoroethylene resin, and core-shell structure resin fillers. One type of organic filler may be used alone, or two or more types may be used in combination. Examples of the flame retardant include aromatic phosphate compounds, phosphazene compounds, phosphinate esters, metal salts of phosphinate compounds, red phosphorus, 9,10-dihydro-9-oxa-10 -Phosphorus phenanthrene-10-oxide and its derivatives, phosphorus-based flame retardants; guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate and other nitrogen-based flame retardants; contains bromine, chlorine, etc. Of halogen-containing flame retardants; antimony trioxide and other inorganic flame retardants. The flame retardant may be used alone or in combination of two or more.

Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers. Examples of antioxidants include hindered phenol antioxidants, hindered amine antioxidants, and the like. Examples of the photopolymerization initiator include benzophenones, benzoyl ketals, and thioxanthone-based photopolymerization initiators. Examples of the fluorescent whitening agent include fluorescent whitening agents of stilbene derivatives and the like. Examples of the adhesion promoter include urea compounds such as urea silane and the above-mentioned coupling agents. The ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, and adhesiveness enhancer may be used alone or in combination of two or more.

(Varnish) The thermosetting resin composition can be prepared in a varnish state in which each component is dissolved or dispersed in an organic solvent. That is, the thermosetting resin composition also includes a state of varnish. Examples of organic solvents used in varnishes include alcohol solvents such as methanol, ethanol, propanol, butanol, methylcellulose, butylcellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone, cyclohexanone; ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene Series solvents; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other nitrogen atom-containing solvents; dimethyl sulfoxide and other sulfur atom-containing solvents. These organic solvents may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellulol, propylene glycol monomethyl ether, and dimethylacetamide are preferred, From the viewpoint of low toxicity, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferred. The solid content concentration of the varnish is not particularly limited, but it is preferably 1% by mass to 60% by mass, more preferably 1% by mass to 30% by mass, further preferably 1% by mass to 20% by mass, and particularly preferably 1% by mass to 10% by mass, preferably 3% to 8% by mass. When the solid content concentration of the varnish is within the above range, the applicability to the glass substrate and the thermosetting resin composition to the wall surface of the TGV tend to be good. In addition, from the viewpoint of easily adjusting the thickness of the thermosetting resin composition layer formed by the spin coating method or the like, the viscosity of the varnish is preferably 1 cP to 1,000 cP. In addition, the method of measuring the viscosity is not particularly limited. For example, an EHD type rotary viscometer can be used for the measurement.

(Manufacturing method of thermosetting resin composition) The manufacturing method of the thermosetting resin composition is not particularly limited, and a conventionally known manufacturing method can be applied. For example, it can be manufactured by adding the components to the organic solvent, using a method selected from the group consisting of ultrasonic dispersion method, high-pressure conflicting dispersion method, high-speed rotation dispersion method, bead mill method, and high-speed The mixing method in the group consisting of the shearing dispersion method and the rotation revolution dispersion method is mixed. For mixing each component, a known mixing device such as a kneader, a ball mill, a bead mill, a three-roll mill, or a nanomizer can be used.

[Manufacturing method of laminate] The method for manufacturing a laminate of the present invention includes a step of applying a thermosetting resin composition to a glass substrate layer having a glass through-hole (TGV) [referred to as a coating step]. As described above, the glass substrate layer having TGV can be manufactured, for example, by providing TGV on the glass substrate by laser, sand blasting, drilling, or the like. As a method of installing the TGV, a commercially available laser device, sand blasting device, drilling machine, etc. can be used. Examples of commercially available laser devices include LC-2E21B/1C manufactured by Hitachi Via Mechanics Co., Ltd., ML605GTWII manufactured by Mitsubishi Electric Co., Ltd., and substrate openings manufactured by Panasonic Fusion Systems Co., Ltd. Use carbon dioxide gas laser processing machine, etc. As a commercially available sandblasting device, there can be mentioned a sandblasting device for fine processing such as the Elfo-blaster ELP-3MR manufactured by Elfotec Co., Ltd. In addition, as a commercially available drilling machine, a drilling machine for fine processing such as Android II manufactured by Lulu Industry Co., Ltd. may be mentioned.

(Coating step) The TGV-containing glass substrate layer obtained in this way is coated with the thermosetting resin composition. The coating method is not particularly limited. For example, it is preferably selected from the group consisting of spin coating method, dip coating method, dip spin coating method, spray coating method, circulating spray coating method, spray coating method, flow coating method, curtain coating method, and roller In the group consisting of coating method, blade coating method, blade coating method, air knife coating method, bar coating method, screen printing method, gravure printing method, lithography method, flexographic printing method and bristle coating Method. Among these coating methods, it is more preferable to use a method selected from the group consisting of a spin coating method, a dip coating method, and a dip spin coating method.

The coating conditions are not particularly limited. For example, if it is a spin coating method, it is preferably as follows: coating is performed under the conditions of preferably a rotation speed of 100 rpm to 5,000 rpm (more preferably a rotation speed of 250 rpm to 800 rpm) . Furthermore, in the case where the spin coating method is adopted, the spin coating device may use a common one including a turn table (turn table) and a vacuum flow path, and there is no particular limitation. The turn table supports the substrate to be coated and When rotating, the vacuum flow path is formed on the upper surface of the turntable to form a groove so that the base material can be adsorbed and held.

Since the thermosetting resin composition is applied to the glass substrate layer with TGV, the thermosetting resin composition not only adheres to the front and back of the glass substrate layer, but also allows the thermosetting resin composition to adhere to the wall surface of the TGV. After the coating step, it is preferable to place the glass substrate layer coated with the thermosetting resin composition under a reduced pressure environment (preferably under a vacuum), etc., as necessary, in order to remove excess heat at the TGV site The curable resin composition is removed. In addition, the method of setting to a reduced pressure environment is not specifically limited, For example, the method of vacuuming using a vacuum pump etc. is mentioned.

(Drying step) After the coating step, it is generally preferable to include a step of drying the applied thermosetting resin composition [referred to as a drying step]. By this drying step, the organic solvent in the thermosetting resin composition can be volatilized. The drying is preferably carried out at a temperature and time to such an extent that the thermosetting resin composition is not cured. For example, it is more preferable to set the thermosetting resin composition at 80°C to 150°C (preferably 80°C to 130 ℃, more preferably 80 ℃ ~ 120 ℃ temperature heating and drying for 1 minute to 30 minutes (preferably 3 minutes to 30 minutes, more preferably 5 minutes to 20 minutes) to make it semi-hardened (stage B ). By going through this drying step, a thermosetting resin composition layer can be formed on the front and back of the glass substrate layer and the wall surface of the TGV. If the heating and drying temperature is 80° C. or more and the drying time is 1 minute or more, the volatilization of the organic solvent proceeds sufficiently, and it is possible to suppress the occurrence of voids in the thermosetting resin composition layer. In addition, the drying conditions can be appropriately adjusted according to the types of components in the thermosetting resin composition, the mixing ratio, the thickness of the coating film, and the like.

The surface roughness (Ra) of the thermosetting resin composition layer (excluding the thermosetting resin composition layer located on the wall surface of the glass through-hole) formed in this way is preferably 0.2 μm or less, more preferably 0.1 μm the following. The lower limit of the surface roughness (Ra) is not particularly limited, but tends to be 0.03 μm or more. In addition, the surface roughness (Ra) is the value measured by the method described in the Example. In addition, the thickness of the formed thermosetting resin composition layer (excluding the thermosetting resin composition layer located on the wall surface of the glass through-hole) through the drying step is preferably 0.1 μm to 50 μm, It is more preferably 1 μm to 25 μm, further preferably 1 μm to 15 μm, and particularly preferably 2 μm to 10 μm.

(Thermal hardening step) The layered product of the present invention is preferably manufactured through a step of thermally curing the applied thermosetting resin composition layer. By this thermosetting step, the applied thermosetting resin composition can be hardened to be C-staged. The conditions of thermosetting are not particularly limited, for example, by applying the applied thermosetting resin composition at a temperature exceeding 150°C to 230°C (preferably exceeding 150°C to 220°C, more preferably exceeding 150°C to 200 Heating at a temperature of ℃, further preferably 155°C to 190°C for 10 minutes to 180 minutes (preferably 20 minutes to 120 minutes, more preferably 30 minutes to 90 minutes) to make the thermosetting resin composition layer sufficient Hardening (C staged). In the thermosetting step, from the viewpoint of preventing the generation of cracks, it is preferable to perform thermosetting in a state where the laminate is not pressurized, but it is not particularly limited thereto, and heating and pressing methods may also be used. Pressure is applied to sufficiently harden the thermosetting resin composition layer (C-stage).

(Step of irradiation with active energy rays) The layered product of the present invention is preferably produced by irradiating the applied thermosetting resin composition layer or the thermosetting thermosetting resin composition layer with active energy rays. Furthermore, it is preferable to pass through the active energy ray irradiation step after being sufficiently hardened through the thermal hardening step. With this active energy ray irradiation step, when a functional group is provided on the surface of the thermosetting resin composition layer, the functional group can be modified, and the adhesion to the conductor layer tends to be improved. Examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, ultraviolet rays, and X rays; and particle beams such as α rays, γ rays, and electron beams. Among these, ultraviolet rays are preferred. The wavelength of the active energy ray is preferably 450 nm or less, and more preferably, an ultraviolet lamp that emits light at 400 nm or less and further 250 nm or less is used. Examples of ultraviolet lamps include mercury short-arc lamps, low-pressure mercury lamps, high-pressure mercury lamps, capillary-type ultrahigh-pressure lamps, high-pressure lamps, and metal halide lamps. Among these, metal halide lamps having a wide ultraviolet wavelength over the entire area are preferred.

The irradiation of active energy rays is preferably carried out under an atmospheric pressure environment. The light quantity of the active energy rays is preferably 1,000 mJ/cm ² to 5,000 mJ/cm ² , and more preferably 2,000 mJ/cm ² to 4,000 mJ/cm ² . If the light amount of the active energy ray is 1,000 mJ/cm ² or more, there is a tendency that the adhesion to the conductor layer is sufficient even if the surface of the thermosetting resin composition layer is not treated with a roughening liquid, if it is 5,000 When mJ/cm ² or less, the adhesive force is easily expressed well, which is advantageous in terms of economy. Furthermore, the light quantity (mJ/cm ² ) is represented by “illuminance (mW/cm ² )×irradiation time (second)”. The temperature of the thermosetting resin composition layer at the time of active energy ray irradiation is preferably 50°C to 80°C.

[Laminate with conductor layer and method of manufacturing the same] A layered plate with a conductor layer can be manufactured through a step of forming a conductor layer (hereinafter sometimes referred to as conductor layer A) by subjecting the laminate of the present invention to a plating process. The laminate with a conductor layer of the present invention also has a conductor layer on the thermosetting resin composition layer present on the wall surface of the glass through-hole. Hereinafter, an aspect of the manufacturing method of the laminated board with a conductor layer of the present invention will be described. First, the laminate of the present invention is immersed in an aqueous solution of stannous chloride in hydrochloric acid to perform a neutralization treatment of the thermosetting resin composition layer, and then a plating catalyst imparting treatment to which palladium is adhered is performed. The plating catalyst application treatment can be performed by immersing in a palladium chloride-based plating catalyst solution, for example. Next, by immersing in the plating catalyst solution, an electroless plating layer having a thickness of 0.3 μm to 1.5 μm, for example, is deposited on the plating catalyst. As the electroless plating solution used in the electroless plating process, a known electroless plating solution can be used.

Before the plating treatment, it is preferable to include a treatment step of treating the surface of the thermosetting resin composition layer with an oxidizing roughening liquid. In the processing step, a roughening liquid may be used to remove stains generated at the bottom of the through hole, for example. Examples of the roughened liquid include chromium/sulfuric acid roughened liquid, alkaline permanganate roughened liquid (sodium permanganate roughened liquid, etc.), sodium fluoride/chromium/sulfuric acid roughened liquid, and the like. In addition, the treatment with the roughening liquid may be carried out after being immersed in a solvent, an alkaline liquid, or a mixture liquid of these (generally, a wetting liquid or a prepreg liquid). Examples of the solvent include alcohol-based solvents such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and isopropyl alcohol. In addition, the alkaline solution is not particularly limited as long as it shows basicity when dissolved in water, and examples thereof include sodium hydroxide solution and potassium hydroxide solution. Furthermore, it may be a mixed liquid obtained by mixing a solvent and an alkaline solution. Examples of the mixed liquid include sodium hydroxide and diethylene glycol monobutyl ether.

Preferably, it includes the step of performing electroplating on the conductor layer A formed as described above. Through this step, a metal layer can be provided on the conductor layer A to increase the thickness of the conductor layer. Examples of the conductor material used at this time include gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. It can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed of an alloy of two or more metals selected from the group (for example, an alloy of nickel and chromium, an alloy of copper and nickel, an alloy of copper and titanium, etc.) can be cited. This electroplating can be performed by a well-known method. The thickness of the entire conductor layer may be appropriately adjusted according to the desired configuration of the multilayer printed wiring board, and is usually 3 μm to 35 μm, more preferably 5 μm to 30 μm.

[Printed wiring board and its manufacturing method] The present invention also provides a printed wiring board formed by circuit-processing a laminated board with a conductor layer. For example, the printed wiring board of the present invention can be manufactured by patterning the conductor layer of the laminate with a conductor layer to form a circuit. As a method of patterning the conductor layer to form a circuit, a subtractive method (Subtractive Process), a full additive process (Full Additive Process), a semi-additive process (Semi Additive Process, SAP), an improved type can be used A well-known method such as a modified semi additive process (m-SAP).

[Semiconductor package] The present invention also provides a semiconductor package in which a semiconductor element is mounted on the printed wiring board of the present invention. The semiconductor package can be manufactured by mounting a semiconductor element such as a semiconductor wafer or a memory at a predetermined position on the multilayer printed wiring board, and sealing the semiconductor element with a sealing resin or the like. [Example]

Next, the present invention will be further described in detail by the following examples, but these examples do not limit the present invention. In addition, with respect to the laminate with conductor layers obtained in each example, the performance was measured and evaluated by the following method.

<Measurement and evaluation method> (1) Adhesive strength with conductor layer For the part of the conductor layer of the laminated board with a conductor layer obtained in each example, the unnecessary part was removed by etching, thereby forming a part with a width of 5 mm and a length of 100 mm, peeling off one end and clamping with a jig Hold, at room temperature, measure the load when peeling approximately 50 mm in the vertical direction.

(2) Surface roughness of the thermosetting resin composition layer on the copper-plated etching-removed surface (average surface roughness) The conductor layer of the laminated board with a conductor layer obtained in each example was subjected to etching treatment to remove copper, thereby preparing a test piece. The test piece was cut to about 2 mm square, and using the ultra-deep shape measuring microscope "VK-8500" manufactured by KEYENCE Co., Ltd., any three different points in the test piece Except for the thermosetting resin composition layer on the wall surface of the glass through-hole), the measurement is carried out under the conditions of a measurement length of 149 μm, a magnification of 2,000 times, and a resolution of 0.05 μm. The value obtained in the section is set as the surface roughness (Ra) of the insulating resin layer, and the average value at three places is calculated.

(3) Heat resistance of solder The laminate with a conductor layer obtained in each example was cut to 25 mm square, and then floated in a solder bath adjusted to 288°C±2°C, and the time until the expansion occurred (unit: second) was investigated.

(4) Observation of glass through-hole (TGV) In order to observe the surface of the TGV of the laminate with conductor layer obtained in each example, the laminate with conductor layer was scratched and cut with a glass cutter, and then a digital microscope "VHX-1000" (Kean Manufactured by Shishi Co., Ltd.), observe the penetration of the hole, and evaluate according to the following evaluation criteria. A: The plating is attached to the TGV evenly. C: The plating is not attached to TGV.

In addition, each component described in Table 1 will be described below. [(A) Epoxy resin] (A1): Epoxy resin having a structural unit derived from 1,6-hexanediol produced in Production Example 1 below (A2): Phenol novolac epoxy resin (made by DIC), epoxy equivalent: 188 g/eq) [(B) Compounds containing ester groups] (B1): Compound containing active ester group, "HPC-8000-65T" (made by DIC Corporation, trade name, ester equivalent: 223 g/eq) [Other hardeners] Phenol resin: bisphenol A novolak resin (Mitsubishi Chemical Co., Ltd., hydroxyl equivalent: 117 g/eq) [(C) Hardening accelerator] (C1): Imidazole derivative compound, trimellitic acid 1-cyanoethyl-2-phenylimidazolium (C2): Triphenylphosphine

[(D) Inorganic filler] (D1): Silicon dioxide (made by Japan Aerosil Co., Ltd., specific surface area: 110±20 m ² /g) [Thermoplastic resin] Polyamide resin: containing Phenolic hydroxyl-modified polybutadiene-modified polyamide "BPAM-155, manufactured by Nippon Kayaku Co., Ltd., trade name" [organic solvent] MEK: methyl ethyl ketone DMAc: dimethyl acetamide

<Production Example 1> Production of epoxy resin (A1) A flask equipped with a thermometer and a stirrer was charged with 228 g (1 mol) of bisphenol A and 1,6-hexanediol divinyl ether 170 g (1 mol), and the temperature was raised to 120 over 1 hour. After ℃, react at 120 ℃ for 6 hours to obtain 398 g of transparent semi-solid modified polyphenols. Next, put 398 g of the modified polyphenols, 925 g (10 mol) of epichlorohydrin, and 185 g of n-butanol into a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer. Dissolve. Thereafter, the temperature was raised to 65° C. while performing nitrogen purge, and the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of 49% by mass sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under these conditions. In the meantime, the distillate distilled by azeotrope was separated by a Dean-Stark trap, the aqueous phase was removed, and the reaction was carried out while returning the organic phase to the reaction system. Thereafter, the unreacted epichlorohydrin was distilled under reduced pressure to be distilled off. 1,000 g of methyl isobutyl ketone and 100 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Furthermore, 20 g of a 10% by mass sodium hydroxide aqueous solution was added to this solution, and after reacting at 80°C for 2 hours, it was washed repeatedly with water three times. Then, the system was dehydrated by azeotrope, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 425 g of transparent liquid epoxy resin (epoxy equivalent: 403 g/eq).

<Example 1> (1. Preparation of thermosetting resin composition) Each component described in Table 1 was mixed at the stated compounding amount to obtain a varnish (thermosetting resin composition). (2. Production of laminate) TGV was installed on the very thin glass substrate "OA-10G" (manufactured by Nippon Electric Glass Co., Ltd., trade name, thickness 500 μm) by sandblasting. The aperture of TGV is ϕ 250 μm (average), and it is set at intervals of 500 μm (average). To the glass substrate provided with TGV in this way, using a spin coater "SC-308S" (manufactured by Oshigane Co., Ltd.), by a spin coating method (spin coating conditions for the first time: 500 rpm- 30 seconds, second time: 600 rpm-10 seconds) while applying the varnish obtained by the method. Drying treatment was carried out at 100° C. for 10 minutes to be B-staged, thereby obtaining a laminate having a thermosetting resin composition layer with a thickness of 4 μm. Furthermore, the thermosetting resin composition layer was subjected to thermosetting treatment at 170°C for 60 minutes under hardening conditions. Then, using a conveyor-type ultraviolet irradiation device, a metal halide lamp (main wavelength: 365 nm) was used to measure the amount of light. The ultraviolet ray was irradiated so as to be 3,000 mJ/cm ² to obtain a laminate in which the thermosetting resin composition layer was C-staged. (3. Manufacture of laminate with conductor layer) As a pretreatment for electroless plating described later, an aqueous solution (diluent solution containing 200 mL/L of diethylene glycol monobutyl ether and 5 g/L of sodium hydroxide) ) After heating to 70°C, the laminate is immersed in this aqueous solution for 5 minutes. Next, in a conditioner liquid "CLC-601" (manufactured by Hitachi Chemical Co., Ltd., trade name), the substrate with an insulating resin layer was immersed at 60°C for 5 minutes, washed with water, and pre-dipped The liquid "Predip Neoganth B" (manufactured by Atotech Japan Co., Ltd., trade name) was immersed at room temperature for 2 minutes. Next, the laminated body is used as a catalyst for electroless plating "Activator Neoganth 834" (made by Atotech Japan Co., Ltd., trade name, alkali seeder) In the meantime, after immersion treatment at 35°C for 5 minutes, it was washed with water. Next, the laminate was placed in "Printganth MSK-DK plating solution" (made by Atotech Japan Co., Ltd., trade name) as an electroless copper plating solution at 35°C After immersion for 15 minutes, copper sulfate electrolytic plating was further performed. Thereafter, annealing treatment was performed at 170° C. for 30 minutes to form a plated conductor layer with a thickness of 20 μm on the surface of the thermosetting resin composition layer to obtain a laminate with a conductor layer. Using this laminated board with a conductor layer, each performance was evaluated according to the above method. The results are shown in Table 1.

<Example 2> In Example 1, the dip coating method was used instead of the spin coating method in the production of the laminate. Except for this, the same operation was carried out to obtain a laminate with a conductor layer, and each performance was evaluated. The results are shown in Table 1.

<Example 3 and Example 4> In Example 1, except that the components and blending amounts described in Table 1 were used, the same operation was performed to obtain a laminate with a conductor layer, and each performance was evaluated. The results are shown in Table 1.

<Example 5> In the preparation of the thermosetting resin composition of Example 2, the components and formulation amounts described in Table 1 are set, and the inorganic filler is formulated at the end, except that the same operation is performed to obtain thermosetting properties Resin composition. Next, in order to chemically roughen the thermosetting resin composition layer, an aqueous solution (pour solution) containing 200 mL/L of diethylene glycol monobutyl ether and 5 g/L of sodium hydroxide was heated to 80°C , Where the laminate is immersed for 5 minutes. Next, an aqueous solution (roughened liquid) containing 60 g/L of potassium permanganate and 40 g/L of sodium hydroxide was heated to 80°C, and the laminate was immersed in the aqueous solution for 10 minutes. Next, the substrate with the insulating resin layer was dipped in an aqueous solution as a neutralizing solution (tin (II) chloride 30 g/L, 98% by mass sulfuric acid 300 mL/L) at room temperature for 5 minutes Come to neutralize. Thereafter, the same operation as in Example 2 was carried out to obtain a laminate with a conductor layer, and each performance was evaluated. The results are shown in Table 1.

<Example 6> In Example 1, except that the ultraviolet irradiation lamp was changed from a metal halide lamp to a low-pressure mercury lamp UV ozone irradiation device (main wavelength 254 nm), the same operation was performed to obtain a laminate with a conductor layer And evaluate each performance. The results are shown in Table 1.

<Comparative Example 1> First, the varnish prepared in Example 1 was coated on a polyethylene terephthalate (PET) film and dried at 100° C. for 5 minutes, thereby obtaining a resin film with a thickness of 4 μm. Using a vacuum laminator, the resin film was attached to the glass substrate “OA-10G” under the conditions of 120° C. and 0.5 MPa, thereby producing a laminate (without TGV). The laminate was subjected to thermosetting treatment and ultraviolet irradiation in the same manner as in Example 1, whereby a laminate obtained by C-stage was obtained. For this laminate, the same TGV as in the example was set by the sand blast method, and then, a laminate with a conductor layer was manufactured in the same manner as in Example 1, and each of the resulting laminate with a conductor layer Performance evaluation. The results are shown in Table 1.

[Table 1]

As can be seen from Table 1, in the laminate with a conductor layer of the embodiment, the conductor layer is sufficiently present on the inner wall of the TGV, so that the front and back surfaces can be electrically connected. On the other hand, in the laminate with a conductor layer of the comparative example, there is no conductor layer on the inner wall of the TGV. Since the thermosetting resin composition layer exists on the inner wall of the TGV of the laminate used in the examples, it is presumed that the conductor layer is sufficiently attached to the thermosetting resin composition layer. In addition, the laminate with a conductor layer of the embodiment has a glass substrate layer, and therefore has low thermal expansion and a high elastic coefficient. Furthermore, it can be seen that the laminated plate with a conductor layer of the example has a low average surface roughness, but the adhesive strength between the thermosetting resin composition layer and the conductor layer is high. In addition, it is understood that the laminates with conductor layers of the examples are also excellent in solder heat resistance. [Industry availability]

The laminate of the present invention has low thermal expansion and a high coefficient of elasticity. Furthermore, it has excellent adhesion strength and heat resistance to the conductor layer, and can further realize the conduction of the front and back. Therefore, it can be preferably used in computers that process large amounts of data at high speed. , Printed circuit boards of electronic equipment used in information equipment terminals, etc.

1‧‧‧Glass substrate layer 2‧‧‧thermosetting resin composition layer 3‧‧‧The thermosetting resin composition layer on the wall surface of the glass through hole 4‧‧‧Glass through hole

FIG. 1 is a cross-sectional view of an example of the laminate of the present invention. 2 is a plan view of an example of the layered product of the present invention.

1‧‧‧Glass substrate layer

2‧‧‧thermosetting resin composition layer

3‧‧‧The thermosetting resin composition layer on the wall surface of the glass through hole

4‧‧‧Glass through hole

Claims (18)

A layered body comprising: More than one layer of thermosetting resin composition; and More than one glass substrate layer, At least one of the glass substrate layers of the glass substrate layer has one or more glass through-holes, and the wall surface of at least one of the glass through-holes has the thermosetting resin composition layer . The laminated body according to item 1 of the patent application scope, wherein the glass substrate layer is in contact with at least one of the thermosetting resin composition layers, and the constituent material of the thermosetting resin composition layer is located on the The constituent materials of the thermosetting resin composition layer on the wall surface of the glass through hole are the same. The laminate according to the first or second patent application, wherein the thermosetting resin composition layers are all layers containing a thermosetting resin composition, and the thermosetting resin composition contains (A ) Epoxy resin and (B) Compounds containing active ester groups. The laminate according to item 3 of the patent application range, wherein the (A) epoxy resin contains an epoxy resin having a structural unit derived from an alkylene glycol having 3 or more carbon atoms. The laminate as described in claim 4 of the patent application, wherein the alkanediol having a carbon number of 3 or more is hexanediol. The laminated body according to any one of claims 3 to 5, wherein the ester group derived from the (B) active ester group-containing compound in the thermosetting resin composition, The equivalent ratio (ester group/epoxy group) to the epoxy group derived from the (A) epoxy resin is 0.5 to 1.5. The laminate as described in any one of claims 3 to 6, wherein the thermosetting resin composition further contains (C) a hardening accelerator. The laminated body according to any one of claims 1 to 7, wherein the thermosetting resin composition layer (wherein the thermosetting resin composition located on the wall surface of the glass through-hole (Except for the object layer) The surface roughness (Ra) is 0.2 μm or less. The laminated body according to any one of claims 3 to 8, wherein the thermosetting resin composition layer is formed by B-stage or C-stage of the thermosetting resin composition Layer. A laminate with a conductor layer formed by forming a conductor layer on a laminate as described in any one of claims 1 to 9 and thermosetting on the wall surface of a glass through hole The conductive resin composition layer also has a conductor layer. A printed wiring board is obtained by circuit-processing a laminate board with a conductor layer as described in item 10 of the patent application. A semiconductor package in which a semiconductor element is mounted on a printed wiring board as described in item 11 of the patent application scope. A method for manufacturing a laminate, which is the method for manufacturing a laminate as described in any one of claims 1 to 9, It includes the step of applying the thermosetting resin composition to the glass substrate layer having glass through holes. The method for manufacturing a laminate according to item 13 of the patent application scope, wherein the method is selected from the group consisting of spin coating, dip coating, dip spin coating, spray coating, circulating spray coating, spray coating, and flow coating Method, curtain coating method, roll coating method, blade coating method, blade coating method, air knife coating method, bar coating method, screen printing method, gravure printing method, lithographic printing method, flexographic printing method and brush coating The coating is performed by a method in a group composed of cloth. The method for manufacturing a laminate according to item 13 or item 14 of the scope of patent application further includes the step of thermally curing the applied thermosetting resin composition. The method for manufacturing a laminate as described in any one of claims 13 to 15 further includes applying the thermosetting resin composition or the thermosetting thermosetting The step of irradiating the resin composition with active energy rays. A method for manufacturing a laminate with a conductor layer, which includes: The step of manufacturing the laminate by the method for manufacturing a laminate as described in any one of claims 13 to 16; and The step of performing a plating process on the laminate to form a conductor layer. A method for manufacturing a printed wiring board, including: A step of manufacturing a laminate with a conductor layer by the method for manufacturing a laminate with a conductor layer as described in item 17 of the scope of the patent application; and The step of forming a circuit on the conductor layer.

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