Laminate, printed circuit board, and semiconductor package

Abstract

Provided are: a laminate which contains two or more glass cloths and a cured product of a thermosetting resin composition and satisfies condition 1; a printed circuit board in which said laminate is used; and a semiconductor package. (Condition 1) When, from among two glass cloths in the laminate that are adjacent to one another in the thickness direction, the distance between surfaces thereof in the same thickness direction is defined as the inter-glass-cloth distance D12 (μm), and the thickness of the glass cloth which, from among the two adjacent cloths, is on the side in said same thickness direction is defined as the thickness T1 (μm), the average value R of the ratio [D12 × 100 / T1] of the inter-glass-cloth distance D12 (μm) to the thickness T1 (μm) in the laminate is 150-260%.

Description

Laminates, printed circuit boards, and semiconductor packages

[0001] This embodiment relates to laminates, printed circuit boards, and semiconductor packages.

[0002] Warping, which occurs during the manufacturing of semiconductor packages, can cause poor connections between semiconductor elements and printed circuit boards, and therefore must be suppressed. Warping occurs because the thermal expansion coefficient of the printed circuit board is greater than that of the semiconductor elements, resulting in stress generated by the thermal history during the mounting of the semiconductor elements. Therefore, to suppress warping, it is necessary to reduce the thermal expansion coefficient of the printed circuit board.

[0003] One method used to reduce the thermal expansion coefficient of printed circuit boards is to incorporate inorganic fillers into the insulating material contained in the printed circuit board (see, for example, Patent Document 1).

[0004] Japanese Patent Publication No. 2016-056367

[0005] However, increasing the density of inorganic fillers reduces the adhesion between the insulating material and the conductive layer formed on its surface, and can also cause defects in the lamination of the laminate. Therefore, there are limits to reducing the coefficient of thermal expansion by increasing the density of inorganic fillers.

[0006] In view of the current situation, this embodiment aims to provide a laminate with excellent low thermal expansion, conductor adhesion, and moldability, as well as a printed circuit board and a semiconductor package using the laminate.

[0007] The present inventors have conducted extensive research to solve the above problems and have found that the above problems can be solved by the following embodiment, and have completed this embodiment. That is, this embodiment relates to the following [1] to [7]. [1] A laminate containing two or more glass cloths and a cured product of a thermosetting resin composition, and satisfying the following condition 1. (Condition 1) In the laminate, the distance between two adjacent glass cloths in the thickness direction, between surfaces in the same thickness direction, is the glass cloth distance D １２ (μm), the thickness of the glass cloth on the same thickness direction side of the two adjacent glass cloths is defined as thickness T. １When [the thickness T is in μm], the distance D between the glass cloths in the laminate, with respect to the thickness T １ (μm), the ratio [D １２ × 100 / T １２ ] has an average value R of 150 to 260%. [2] The average value of the distance D between the glass cloths in the laminate １ (μm) is 3 to 200 μm, the laminate according to [1] above. [3] In the total amount of the laminate (however, when the laminate has a metal foil, excluding the mass of the metal foil), the content of the cured product of the thermosetting resin composition is 10 to 60% by mass, the laminate according to [1] or [2] above. [4] The basis weight of the glass cloth is 10 to 200 g / m １２ , the laminate according to any one of [1] to [3] above. [5] Further, having a metal foil, the laminate according to any one of [1] to [4] above. [6] A printed wiring board having the laminate according to any one of [1] to [5] above. [7] A semiconductor package having the printed wiring board according to [6] above and a semiconductor element. ２

[0008] According to the present embodiment, it is possible to provide a laminate excellent in low thermal expansion properties, conductor adhesion, and moldability, a printed wiring board using the laminate, and a semiconductor package.

[0009] Distance D between glass cloths １２ It is a schematic cross-sectional view of a laminate for explaining a method for measuring the distance D (μm) and the average ratio R.

[0010] In this specification, a numerical range indicated by using "~" represents a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. For example, the notation of the numerical range "X~Y" (X and Y are real numbers) means a numerical range that is X or more and Y or less. And the description "X or more" in this specification means X and numerical values exceeding X. Also, the description "Y or less" in this specification means Y and numerical values less than Y. The lower limit value and the upper limit value of the numerical ranges described in this specification can be arbitrarily combined with the lower limit value or the upper limit value of other numerical ranges, respectively. In the numerical ranges described in this specification, the lower limit value or the upper limit value of the numerical range may be replaced with the value shown in the examples.

[0011] Each component and material exemplified in this specification may be used alone or in combination of two or more, unless otherwise specified. In this specification, the content of each component in the thermosetting resin composition means the total amount of the plurality of substances present in the thermosetting resin composition when there are a plurality of substances corresponding to each component in the thermosetting resin composition, unless otherwise specified.

[0012] In this specification, "solid content" means components other than the solvent, and components that are liquid at 25°C are also regarded as solid content.

[0013] The expression "containing XX" described in this specification includes both the meaning of containing XX in a state where XX has reacted when XX can react, and simply containing XX.

[0014] The weight average molecular weight (Mw) in this specification means a value measured in terms of polystyrene by gel permeation chromatography (GPC; Gel Permeation Chromatography). Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in the examples.

[0015] In this specification, "resin component" means a resin and a compound that forms a resin by a curing reaction. Examples of resin components include thermosetting resins, thermoplastic resins, and the like.

[0016] In this specification, "semi-cured product" is synonymous with a thermosetting resin composition in the B-stage state as defined in JIS K 6800 (2006), and "cured product" is synonymous with a thermosetting resin composition in the C-stage state as defined in JIS K 6800 (2006).

[0017] The mechanism of action described herein is speculative and does not limit the mechanism by which the effects of this embodiment are achieved.

[0018] Embodiments that combine any combination of the information described herein are also included.

[0019] [Laminate] The laminate of this embodiment is a laminate containing two or more glass cloths and a cured product of a thermosetting resin composition, and satisfying the following condition 1. (Condition 1) In the laminate, the distance between two adjacent glass cloths in the thickness direction, and between the same thickness direction surfaces, is the glass cloth distance D １２ (μm), the thickness of the glass cloth on the same thickness direction side of the two adjacent glass cloths is defined as thickness T. １ When (μm), the thickness T in the laminate １ The distance D between the glass cloths relative to (μm) １２ (μm) ratio [D １２ ×100 / T １ The average R value for ] is between 150% and 260%.

[0020] In condition 1, the distance D between glass cloths １２ and thickness T １ The unit is μm, but the unit may be omitted in the following explanation as appropriate.

[0021] <Ratio [D １２ ×100 / T １ The average value R of ] in this embodiment is the above ratio [D １２ ×100 / T １The average value R (hereinafter also simply referred to as "average ratio R") of 150-260% results in excellent low thermal expansion, conductive adhesion, and moldability. Although the detailed reasons for this are unclear, it is presumed that when the average ratio R satisfies the above range, the balance between the volume of the layer containing glass cloth, which contributes to low thermal expansion, and the volume of the cured product of the thermosetting resin composition, which contributes to conductive adhesion and moldability, becomes suitable for exhibiting excellent low thermal expansion, conductive adhesion, and moldability.

[0022] The average ratio R is preferably 152 to 240%, more preferably 155 to 220%, even more preferably 160 to 200%, and particularly preferably 165 to 180%. When the average ratio R is above the lower limit, the conductor adhesion and moldability tend to be better. Also, when the average ratio R is below the upper limit, the low thermal expansion tend to be better.

[0023] (Distance between glass cloths D) １２ (Method for measuring the average ratio R) Below, referring to Figure 1, the distance between glass cloths D １２ The method for measuring the average ratio R will be explained. The distance between glass cloths D １２ This can be measured by observing the cross-section of the laminate. Figure 1 shows a schematic cross-sectional view of the laminate. In Figure 1, one direction in the thickness direction of the laminate is designated as direction X and the other as direction Y. Two adjacent glass cloths in the thickness direction are arbitrarily selected, and the glass cloth on the direction X side is designated as glass cloth 1, and the glass cloth on the direction Y side is designated as glass cloth 2. Next, the warp thread that is closest to direction X among the warp threads contained in glass cloth 1 is selected, and the tangent to this warp thread on the direction X side is drawn in the direction of the laminate surface, and this is line L corresponding to the direction X side surface of glass cloth 1. Ｘ１ Furthermore, the warp threads contained in the glass cloth 2 that are closest to the X direction are identified, and the tangent to the X direction of that warp thread is drawn in the direction of the laminate, and this is drawn as line L corresponding to the X direction surface of the glass cloth 2. Ｘ２ Let's assume that the line L of the glass cloth 1 determined above is correct. Ｘ１ and glass cloth 2 line L Ｘ２The perpendicular distance between them is defined as the distance between the surfaces of glass cloth 1 and glass cloth 2 in the same thickness direction, which is the distance between the glass cloths D. １２ This is calculated as follows. Also, the thickness of glass cloth 1 is given as thickness T. １ Thickness T １ Distance D between glass cloths １２ The ratio [D １２ ×100 / T １ The ratio [D] is calculated. The thickness of glass cloth 1 is determined as the perpendicular distance between the surfaces of glass cloth 1 before impregnation with the thermosetting resin composition, and can be measured in accordance with JIS R 3414:2012. Of the glass cloths contained in the laminate, all glass cloths except the one closest to direction Y are considered as glass cloth 1, and the above ratio [D] is calculated. １２ ×100 / T １ The following values ​​are calculated, and the average of these values ​​is taken as the average ratio R. Cross-sectional observation of the laminate can be performed, for example, by cutting the laminate to form a cross-section, and observing the cross-section with a scanning electron microscope (SEM) or the like. The observation magnification is not particularly limited as long as it is an observation magnification that allows the measurement described in the above procedure to be performed, but for example, it is 200 to 500 times.

[0024] In the laminate of this embodiment, the distance D between two glass cloths adjacent to each other in the thickness direction is １２ From the viewpoint of mechanical strength and high-density wiring of the laminate, the glass cloth distance D is preferably 3 to 200 μm, more preferably 15 to 150 μm, even more preferably 30 to 100 μm, and particularly preferably 50 to 70 μm. The laminate of this embodiment has the above glass cloth distance D １２ Preferably, the laminate contains at least two adjacent glass cloths within the range D, and all glass cloths included in the laminate of this embodiment are within the glass cloth-to-glass cloth distance D. １２ It is more preferable that it falls within the range.

[0025] Distance D between glass cloths in the laminate of this embodiment １２The average value is preferably 3 to 200 μm, more preferably 15 to 150 μm, even more preferably 30 to 100 μm, and particularly preferably 50 to 70 μm, from the viewpoint of mechanical strength of the laminate and high-density wiring. Distance between glass cloths in the laminate D １２ The average value is the "glass cloth distance D" mentioned above. １２ In the description of the method for measuring the average ratio R, the distance between glass cloths D is determined by considering all glass cloths except the one closest to direction Y as glass cloth 1. １２ It represents the average value.

[0026] <Cured product of thermosetting resin composition> The laminate of this embodiment contains a cured product of a thermosetting resin composition. The thermosetting resin composition is not particularly limited as long as it contains a thermosetting resin, and may contain thermoplastic resins, inorganic fillers, flame retardants, and other components as needed. The components contained in the thermosetting resin composition will be described below.

[0027] (Thermosetting resins) Examples of thermosetting resins include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, urea resins, and furan resins. Among these, maleimide resins, epoxy resins, and benzoxazine resins are preferred from the viewpoint of heat resistance and moldability. Thermosetting resins may be used individually or in combination of two or more types.

[0028] [Maleimide resin] Maleimide resins include one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins.

[0029] The maleimide resin having one or more N-substituted maleimide groups is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups. Examples of maleimide resins having one or more N-substituted maleimide groups include bis(4-maleimidophenyl)methane, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, aromatic bismaleimide resins having an indan skeleton, and biphenylaralkyl type maleimide resins. Among these, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is preferred.

[0030] As a derivative of the maleimide resin, an aminomaleimide resin having a structure derived from a maleimide resin having one or more N-substituted maleimide groups and a structure derived from a compound having two primary amino groups is preferred. The structure derived from a maleimide resin having one or more N-substituted maleimide groups and the structure derived from a compound having two primary amino groups include a structure formed by a Michael addition reaction between at least one N-substituted maleimide group from the N-substituted maleimide groups of the maleimide resin having one or more N-substituted maleimide groups and at least one primary amino group from the primary amino groups of the compound having two primary amino groups.

[0031] From the viewpoint of heat resistance, the content of structures derived from maleimide resin having one or more N-substituted maleimide groups in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 60 to 90% by mass. From the viewpoint of low thermal expansion, the content of structures derived from compounds having two primary amino groups in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 40% by mass. From the viewpoint of handling and moldability, the weight-average molecular weight (Mw) of the aminomaleimide resin is preferably 400 to 10,000, more preferably 1,000 to 5,000, and even more preferably 2,000 to 3,000.

[0032] Compounds having two primary amino groups include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and silicone compounds having two primary amino groups. Among these, silicone compounds having two primary amino groups are preferred. Hereinafter, an aminomaleimide resin having a structure derived from a maleimide resin having one or more N-substituted maleimide groups and a structure derived from a silicone compound having two primary amino groups will be referred to as a "siloxane-modified maleimide resin."

[0033] The primary amino group equivalent of the silicone compound having two primary amino groups is preferably 300 to 2,000 g / mol, more preferably 400 to 1,500 g / mol, and even more preferably 500 to 1,000 g / mol, from the viewpoint of the handlingability of the resulting siloxane-modified maleimide resin.

[0034] When the thermosetting resin composition contains maleimide resin, the maleimide resin content is preferably 20 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 85% by mass, based on the total amount of resin components (100% by mass) in the thermosetting resin composition, from the viewpoint of heat resistance, moldability, processability, and conductive adhesion.

[0035] [Epoxy resin] As the epoxy resin, a compound having two or more epoxy groups in one molecule is preferred. Epoxy resins can be classified into several categories, including bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; novolac-type epoxy resins such as bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl novolac type epoxy resin, and naphthol novolac type epoxy resin; aralkyl-type epoxy resins such as phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthol aralkyl type epoxy resin; stilbene-type epoxy resin; naphthylene ether-type epoxy resin; naphthalene-type epoxy resin; biphenyl-type epoxy resin; dihydroanthracene-type epoxy resin; epoxy resins containing a saturated dicyclopentadiene skeleton; cyclohexanedimethanol-type epoxy resin; spiro-ring-containing epoxy resin; heterocyclic epoxy resin; alicyclic epoxy resin; aliphatic chain-like epoxy resin; and rubber-modified epoxy resin. Among these, naphthalene-type epoxy resin is preferred.

[0036] When a thermosetting resin composition contains epoxy resin, the epoxy resin content is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 10% by mass, relative to the total amount of resin components (100% by mass) in the thermosetting resin composition, from the viewpoint of heat resistance, moldability, processability, and conductive adhesion.

[0037] [Benzoxazine Resin] As the benzoxazine resin, a compound having two or more benzoxazine rings in one molecule is preferred. In this embodiment, "benzoxazine resin" means a resin having at least one benzoxazine ring in its molecule. In this embodiment, "benzoxazine ring" means a ring structure in which one of the two double bonds in a six-membered oxazine ring containing one oxygen atom and one nitrogen atom is dihydrogenated, and the other double bond is fused to a benzene ring. Examples of benzoxazine resins include P-d type benzoxazine, F-a type benzoxazine, ALP-d type benzoxazine, T-ala type benzoxazine, etc. Among these, P-d type benzoxazine is preferred.

[0038] When a thermosetting resin composition contains benzoxazine resin, the benzoxazine resin content is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 10% by mass, based on the total amount of resin components (100% by mass) in the thermosetting resin composition, from the viewpoint of heat resistance, moldability, processability, and conductive adhesion.

[0039] The total content of thermosetting resin in the thermosetting resin composition is preferably 20 to 98% by mass, more preferably 50 to 97% by mass, even more preferably 70 to 96% by mass, and particularly preferably 90 to 95% by mass, based on the total solid content (100% by mass) of the thermosetting resin composition, from the viewpoint of heat resistance, moldability, processability, and conductive adhesion.

[0040] (Thermoplastic resin) Examples of thermoplastic resins include styrene resins, olefin resins, urethane resins, polyester resins, polyamide resins, acrylic resins, and silicone resins. Among these, acrylic resins are preferred. Thermoplastic resins may be used individually or in combination of two or more types.

[0041] From the viewpoint of moldability, the weight-average molecular weight (Mw) of the thermoplastic resin is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000, and even more preferably 500,000 to 1,000,000.

[0042] When a thermosetting resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 10% by mass, based on the total amount (100% by mass) of the resin components in the thermosetting resin composition, from the viewpoint of conductive adhesion and dielectric properties.

[0043] (Inorganic Fillers) Thermosetting resin compositions tend to exhibit better low thermal expansion and heat resistance when they contain inorganic fillers. One type of inorganic filler may be used alone, or two or more types may be used in combination.

[0044] Examples of inorganic fillers include silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, and silicon carbide. Among these, silica, alumina, mica, and talc are preferred from the viewpoint of low thermal expansion, heat resistance, and flame retardancy, silica and alumina are more preferred, and silica is even more preferred. As for silica, fused silica is preferred from the viewpoint of dispersibility and moldability.

[0045] Average particle size of inorganic filler (D ５０ The average particle size of the inorganic filler (D) is preferably 0.1 to 10 μm, more preferably 0.2 to 1 μm, and even more preferably 0.3 to 0.8 μm, from the viewpoint of dispersibility and fine wiring properties. ５０ The average particle size of an inorganic filler is the particle size at the point corresponding to 50% of the total volume when the cumulative frequency distribution curve by particle size is calculated with the total volume of particles set to 100%. The average particle size of an inorganic filler can be measured, for example, using a particle size distribution analyzer that employs laser diffraction scattering.

[0046] Examples of inorganic filler shapes include spherical and crushed forms. From the viewpoint of improving dispersibility and adhesion with organic components, the inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent.

[0047] When a thermosetting resin composition contains an inorganic filler, the amount of the inorganic filler is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, even more preferably 3 to 50% by mass, even more preferably 4 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 6 to 20% by mass, and particularly preferably 7 to 10% by mass, based on the total amount of solids (100% by mass) of the thermosetting resin composition. When the amount of inorganic filler is above the lower limit, the low thermal expansion and heat resistance tend to be better. Also, when the amount of inorganic filler is below the upper limit, the moldability and conductive adhesion tend to be better.

[0048] (Flame retardants) Examples of flame retardants include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, etc. Among these, phosphorus-based flame retardants are preferred. The phosphorus-based flame retardant may be an inorganic or organic phosphorus-based flame retardant. Examples of inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides; phosphoric acid; and phosphine oxide. Examples of organic phosphorus-based flame retardants include aromatic phosphate ester compounds, monosubstituted phosphonic acid diester compounds, disubstituted phosphinic acid ester compounds, metal salts of disubstituted phosphinic acid, organic nitrogen-containing phosphorus compounds, and cyclic organophosphorus compounds. A single flame retardant may be used alone, or two or more may be used in combination. When a thermosetting resin composition contains a flame retardant, the amount of the flame retardant is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 10% by mass, based on the total solid content (100% by mass) of the thermosetting resin composition, from the viewpoint of flame retardancy, moldability, and conductive adhesion.

[0049] (Other Components) The thermosetting resin composition may further contain, if necessary, other optional components such as resin materials other than the above components, curing accelerators, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, coupling agents, and other additives. Each of the other optional components may be used individually or in combination of two or more. The content of the above optional components in the thermosetting resin composition is not particularly limited and may be used as needed, within a range that does not impair the effects of this embodiment. Furthermore, the thermosetting resin composition may not contain the above optional components depending on the desired performance.

[0050] <Glass Cloth> The laminate of this embodiment contains two or more sheets of glass cloth. The two or more sheets of glass cloth may be one type used alone, or two or more types may be used in combination.

[0051] The glass cloth may be surface-treated with a coupling agent or mechanically opened, from the viewpoint of impregnation properties of the thermosetting resin composition.

[0052] Examples of glass fibers that make up glass cloth include E glass, D glass, T glass, S glass, and Q glass. Among these, Q glass is preferred from the viewpoint of low thermal expansion. SiO in glass fibers ２ The content of is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, from the viewpoint of low thermal expansion and elastic modulus.

[0053] From the viewpoint of the mechanical strength of the prepreg and the ability to achieve high-density wiring, the basis weight of the glass cloth is preferably 10 to 200 g / m². ２ More preferably 30 to 180 g / m² ２ More preferably 50 to 150 g / m² ２ , more preferably 70-120 g / m ２ Particularly preferably 80 to 100 g / m ２ That is the case.

[0054] The thickness of each glass cloth contained in the laminate of this embodiment is preferably 2 to 100 μm, more preferably 10 to 80 μm, even more preferably 20 to 60 μm, and particularly preferably 30 to 50 μm, from the viewpoint of the mechanical strength of the laminate and high-density wiring. The laminate of this embodiment preferably contains one or more glass cloths of the above thickness, more preferably two or more, and even more preferably all of the glass cloths contained in the laminate of this embodiment have a thickness within the above range.

[0055] The thickness T of the glass cloth in the laminate of this embodiment １ The average value of the glass cloth T in the laminate is preferably 2 to 100 μm, more preferably 10 to 80 μm, even more preferably 20 to 60 μm, and particularly preferably 30 to 50 μm, from the viewpoint of mechanical strength of the laminate and high-density wiring. １ The average value is the "glass cloth distance D" mentioned above. １２ In the description of the method for measuring the average ratio R, the thickness T is determined by taking all the glass cloths except the one closest to direction Y as glass cloth 1. １ It represents the average value.

[0056] <Metal Foil> The laminate of this embodiment may have metal foil. Examples of metals for the metal foil include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements. When the laminate of this embodiment has metal foil, it is preferable that the laminate has metal foil on one or both surfaces. Furthermore, the laminate of this embodiment may or may not have metal foil on surfaces other than the surface. The thickness of the metal foil can be a thickness generally used for laminates, for example, 1 to 200 μm.

[0057] <Laminate Structure> The laminate structure of this embodiment is not particularly limited, as long as it contains two or more glass cloths and a cured product of a thermosetting resin composition. In the laminate of this embodiment, if one layer formed from one glass cloth is considered one layer, the number of layers in the laminate of this embodiment is preferably 2 to 20 layers, more preferably 3 to 18 layers, even more preferably 4 to 17 layers, even more preferably 6 to 16 layers, even more preferably 8 to 15 layers, and particularly preferably 10 to 14 layers, from the viewpoint of the mechanical strength of the laminate, as well as miniaturization and processability of the laminate.

[0058] In the laminate of this embodiment, the content of cured thermosetting resin composition in the total amount of the laminate (excluding the mass of metal foil if the laminate has metal foil) is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 30% by mass. When the content of cured thermosetting resin composition is above the lower limit, conductive adhesion and moldability tend to be better. Also, when the content of cured thermosetting resin composition is below the upper limit, low thermal expansion tend to be better.

[0059] In the laminate of this embodiment, the glass cloth content in the total amount of the laminate (excluding the mass of the metal foil if the laminate contains metal foil) is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, even more preferably 60 to 80% by mass, and particularly preferably 70 to 75% by mass. When the glass cloth content is above the lower limit, the low thermal expansion properties tend to be better. Also, when the glass cloth content is below the upper limit, the conductive adhesion and moldability tend to be better.

[0060] In the laminate of this embodiment, the total content of the cured product of the thermosetting resin composition and the glass cloth in the total amount of the laminate (excluding the mass of the metal foil if the laminate has metal foil) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, particularly preferably 99 to 100% by mass, and may also be 100% by mass, from the viewpoint of low thermal expansion, conductive adhesion, and moldability.

[0061] In the laminate of this embodiment, the total content of glass cloth and inorganic filler in the total amount of the laminate (excluding the mass of metal foil if the laminate contains metal foil) is preferably 42 to 92% by mass, more preferably 52 to 87% by mass, even more preferably 62 to 82% by mass, and particularly preferably 72 to 77% by mass, from the viewpoint of low thermal expansion, conductive adhesion, and moldability.

[0062] The thickness of the laminate in this embodiment (excluding the thickness of the metal foil if the laminate has a metal foil) may be 0.2 to 5 mm, 0.3 to 3 mm, 0.4 to 2 mm, or 0.5 to 1.5 mm, depending on the application of the laminate.

[0063] <Method for Manufacturing Laminated Boards> The laminated board of this embodiment can be manufactured, for example, by laminating two or more prepregs containing a thermosetting resin composition and glass cloth, and then heat-pressure molding. Preferred embodiments of the thermosetting resin composition and glass cloth are as described above.

[0064] The prepreg used in the manufacturing method of the laminate in this embodiment is made by impregnating a glass cloth with a thermosetting resin composition. For example, it can be manufactured by impregnating a glass cloth with a varnish-like thermosetting resin composition, then heating and drying it at a temperature of 100 to 200°C for 1 to 30 minutes to partially cure it (B-stage).

[0065] Next, the obtained prepregs are stacked as appropriate to form the desired laminate, and the laminate of this embodiment can be manufactured by heating and pressing the layers with metal foil placed on one or both sides as needed. For heating and pressing, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, or an autoclave molding machine can be used. The conditions for heating and pressing can be, for example, a temperature of 100 to 300°C, a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0066] [Printed Wiring Board] The printed wiring board of this embodiment is a printed wiring board containing the laminate of this embodiment. The printed wiring board of this embodiment can be manufactured, for example, by forming conductive circuits on the surface of the laminate of this embodiment. Conductive circuits can be formed by known methods, and if the laminate of this embodiment has metal foil, the circuits may be formed on the metal foil, or the circuits may be formed by etching the metal foil and then plating. In addition, if necessary, multilayer printed wiring boards can be manufactured by forming through holes or blind via holes by drilling or laser processing, forming interlayer wiring by plating or conductive paste, etc.

[0067] [Semiconductor Package] The semiconductor package of this embodiment is a semiconductor package having the printed circuit board of this embodiment and semiconductor elements. The semiconductor package of this embodiment can be manufactured by mounting semiconductor elements, memory, etc., at predetermined positions on the printed circuit board of this embodiment.

[0068] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to the following examples.

[0069] In each example, the weight-average molecular weight (Mw) was measured by the following method: Gel permeation chromatography (GPC) was used to calculate the molecular weight from a calibration curve using standard polystyrene. The calibration curve was approximated by a cubic equation using standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The GPC measurement conditions are shown below. Equipment: Pump: L-6200 [Hitachi High-Technologies Corporation] Detector: L-3300 RI [Hitachi High-Technologies Corporation] Column Oven: L-655A-52 [Hitachi High-Technologies Corporation] Column: Guard column; TSK Guardcolumn HHR-L + Column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, product names) Column size: 6.0 × 40 mm (Guard column), 7.8 × 300 mm (column) Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL Injection volume: 20 μL Flow rate: 1.00 mL / min Measurement temperature: 40°C

[0070] [Distance between glass cloths D] １２ [Measurement of average ratio R] (1) Acquisition of cross-sectional SEM images of laminates Cross-sections were formed by cutting the laminates obtained in each example using a precision cutting machine. Next, the cross-sections of the formed laminates were treated with platinum deposition and used as test pieces for SEM observation. Cross-sectional SEM images were obtained by observing the cross-sections of the SEM observation test pieces obtained above at 150x magnification using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., product name: JSM-6010PLUS / LA) under conditions of an acceleration voltage of 10kV and secondary electron mode.

[0071] (2) Distance between glass cloths D １２ Measurement In the cross-sectional SEM image obtained above, the "distance between glass cloths D" １２ The glass cloth distance D is measured by the method described in "Method for measuring the average ratio R". １２The following was measured. Of the 10 glass cloths contained in the laminate, nine glass cloths were designated as glass cloth 1, excluding the one glass cloth furthest to the Y direction, and the distance D between each glass cloth was measured. １２ The following was calculated, where D is the distance between the glass cloths. １２ For each glass cloth, measurements were taken using cross-sectional SEM images of two fields of view, and these were averaged to obtain the value.

[0072] (3) Calculation of the average ratio R For each of the nine glass cloths mentioned above, the ratio [D １２ ×100 / T １ The following values ​​were calculated, and the average of these values ​​was defined as the average ratio R. Note that the thickness of glass cloth 1 was determined as the perpendicular distance between the surfaces of the glass cloth before impregnation with the resin composition.

[0073] Synthesis Example 1: Production of Siloxane-Modified Maleimide Resin A 2 L reaction vessel, capable of heating and cooling, equipped with a thermometer, stirrer, and moisture meter with reflux condenser, contained 100 g of diamine-modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A, amino group functional equivalent: 800 g / mol), 450 g of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 550 g of propylene glycol monomethyl ether. The mixture was then reacted at 120°C for 3 hours to produce a siloxane-modified maleimide resin. The weight-average molecular weight (Mw) of the obtained siloxane-modified maleimide resin was 2,500.

[0074] [Preparation of Thermosetting Resin Compositions] Production Examples 1-2 Each component listed in Table 1 was stirred and mixed with methyl ethyl ketone to prepare varnish-like thermosetting resin compositions A and B with a solid content concentration of 50% by mass. In Table 1, the unit of the amount of each component is parts by mass, and in the case of a solution, it means parts by mass on a solid content basis.

[0075]

[0076] The details of the epoxy resin and acrylic resin listed in Table 1 are as follows: • Epoxy resin: Naphthalene-type epoxy resin, manufactured by DIC Corporation, product name "EPICLON® HP-9500" • Acrylic resin: Weight-average molecular weight (Mw): 850,000

[0077] [Manufacturing of Laminates] Examples 1-2, Comparative Examples 1-2 (1) Preparation of Prepregs The thermosetting resin compositions shown in Table 2 were applied onto a PET film using a comma coater. Then, a resin film with a PET film was prepared by heating and drying at 130°C for 3 minutes. Next, glass cloth (IPC #2116, glass type: Q glass, basis weight: 86 g / m²) ２ A PET film-attached resin film (with a thickness of 39 μm) was placed on both sides so that the resin film side was in contact with the glass cloth, and then laminated using a vacuum laminating device. The vacuum laminating conditions were: heating plate temperature 130°C, pressing pressure 0.5 MPa, heating and pressing time 30 seconds, vacuum degree 100 kPa or less, and vacuum time 30 seconds.

[0078] (2) Preparation of copper-clad laminate Ten sheets of the prepreg obtained above were stacked, and 12 μm thick copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-M3-VLP-12") was placed above and below it so that the roughened surface was in contact with the prepreg. This laminate was heated and pressurized for 80 minutes at a temperature of 240°C and a pressure of 3.0 MPa to obtain a copper-clad laminate.

[0079] [Evaluation Method] Each evaluation was performed according to the method described below. The results are shown in Table 2. However, since the laminate produced in Comparative Example 2 had poor moldability and a good laminate could not be obtained, evaluations other than moldability were not performed.

[0080] (Measurement Method for Thermal Expansion Coefficient and Glass Transition Temperature) The copper foil on both sides of the copper-clad laminates obtained in each example was removed by etching to prepare 5 mm square test specimens. Next, the test specimens were mounted in a thermomechanical analyzer (TMA) (manufactured by T.A. Instruments Japan Co., Ltd., product name "Q400") in a direction that detects the displacement of the laminate in the X direction (plane direction), and thermomechanical analysis was performed twice consecutively by the compression method under the conditions of a temperature range of 30 to 260°C, a load of 5 g, and a heating rate of 10°C / min. The average thermal expansion coefficient from 30 to 260°C in the second measurement was taken as the thermal expansion coefficient. The glass transition temperature was the glass transition temperature obtained from the second thermomechanical measurement.

[0081] (Method for measuring copper foil peel strength) The copper foil from the copper-clad laminates obtained in each example was processed into a 5 mm wide straight line by etching and used as a test specimen. The formed straight line copper foil was attached to a small benchtop testing machine (manufactured by Shimadzu Corporation, product name "EZ-TEST") and the copper foil peel strength was measured by peeling it off in a 90° direction at 25°C. The pulling speed when peeling the copper foil was set to 50 mm / min.

[0082] (Method for measuring the modulus of elasticity at 30°C) Test specimens measuring 50 mm x 25 mm were prepared by removing the copper foil from the copper-clad laminates obtained in each example by immersing them in a copper etching solution. The bending modulus of elasticity in the X direction (plane direction) was measured at 30°C using a 5t Tensilon (manufactured by Orientec Co., Ltd.) under the conditions of a crosshead speed of 1 mm / min and a span distance of 20 mm.

[0083] (Method for evaluating solder heat resistance) Four evaluation boards were prepared for each example by cutting the copper-clad laminate obtained in each example to a size of 25 mm square. These evaluation boards were floated in a solder bath at 288°C for 10 minutes, and the appearance of the evaluation boards was visually observed to evaluate the solder heat resistance according to the following criteria. A: No blistering was observed in any of the four evaluation boards. C: Blistering was observed in one or more of the four evaluation boards.

[0084] (Method for evaluating moldability) The laminates obtained in each example were cut using a precision cutting machine to form cross-sections of the laminates. Next, the cross-sections were treated with platinum deposition to form test specimens. The cross-sections of the test specimens were observed using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., product name: JSM-6010PLUS / LA) under the conditions of an acceleration voltage of 10 kV, 500x magnification, and secondary electron mode, and the moldability was evaluated according to the following criteria. A: No voids were observed in the cross-section. C: Voids were observed in the cross-section.

[0085]

[0086] Table 2 shows that the laminates of Examples 1 and 2 of this embodiment exhibit excellent low thermal expansion, conductor adhesion, and moldability.

[0087] 1 Glass cloth 2 Glass cloth 10 Warp threads 20 Weft threads X One thickness direction of the laminate Y The other thickness direction of the laminate D １２ Distance L between glass cloths 1 and 2 Ｘ１ Line L corresponding to the X-side surface of glass cloth 1 Ｘ２ The line corresponding to the X-side surface of the glass cloth 2

Claims

1. A laminate containing two or more glass cloths and a cured product of a thermosetting resin composition, satisfying the following condition 1. (Condition 1) In the laminate, the distance between two adjacent glass cloths in the thickness direction, where the same thickness direction faces are defined as the glass cloth distance D. １２ (μm), the thickness of the glass cloth on the same thickness direction side of the two adjacent glass cloths is defined as thickness T. １ When (μm), the thickness T in the laminate １ The distance D between the glass cloths relative to (μm) １２ (μm) ratio [D １２ ×100 / T １ The average R value for ] is between 150% and 260%.

2. Distance D between glass cloths in the laminated plate １２ The laminate according to claim 1, wherein the average value of (μm) is 3 to 200 μm.

3. The laminate according to claim 1 or 2, wherein the content of cured product of the thermosetting resin composition in the total amount of the laminate (excluding the mass of the metal foil if the laminate has metal foil) is 10 to 60% by mass.

4. The basis weight of the glass cloth is 10 to 200 g / m². ２ The laminate according to claim 1 or 2.

5. The laminate according to claim 1 or 2, further comprising a metal foil.

6. A printed circuit board having the laminate according to claim 1 or 2.

7. A semiconductor package having a printed circuit board according to claim 6 and a semiconductor element.

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