WO2019112066A1 - プリプレグ、積層板、及びそれらの製造方法、並びにプリント配線板及び半導体パッケージ - Google Patents
プリプレグ、積層板、及びそれらの製造方法、並びにプリント配線板及び半導体パッケージ Download PDFInfo
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- WO2019112066A1 WO2019112066A1 PCT/JP2018/045309 JP2018045309W WO2019112066A1 WO 2019112066 A1 WO2019112066 A1 WO 2019112066A1 JP 2018045309 W JP2018045309 W JP 2018045309W WO 2019112066 A1 WO2019112066 A1 WO 2019112066A1
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- prepreg
- glass fiber
- laminate
- resin composition
- thermosetting resin
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Classifications
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- H—ELECTRICITY
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
- H05K3/4629—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating inorganic sheets comprising printed circuits, e.g. green ceramic sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0872—Prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3425—Printed circuits
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0275—Fibers and reinforcement materials
- H05K2201/0287—Unidirectional or parallel fibers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0275—Fibers and reinforcement materials
- H05K2201/0293—Non-woven fibrous reinforcement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/06—Thermal details
- H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
Definitions
- the present invention relates to a prepreg, a laminate, and a method of manufacturing the same, and a printed wiring board and a semiconductor package.
- the elastic modulus of the laminate also affects the warp, it is also effective to increase the elasticity of the laminate in order to reduce the warp of the semiconductor package. Therefore, in order to reduce the warpage of the laminate, it is necessary to increase the elasticity as well as increase the modulus of elasticity of the laminate.
- the high filling of the inorganic filler may cause a decrease in insulation reliability, a decrease in adhesion between the resin and the wiring layer formed on the surface, and a press forming defect at the time of laminate production.
- a resin having a low thermal expansion coefficient a resin whose thermal expansion coefficient is reduced by raising the glass transition temperature (Tg) by raising the crosslinking density with cyanate resin etc. may be mentioned, but the crosslinking density is raised with cyanate resin etc. In the case of this resin, the molecular chain between functional groups becomes short, which may cause a decrease in resin strength, so there is a limit to low thermal expansion.
- a glass fiber prepreg to be provided in a laminate is prepared by impregnating a glass fiber bundle formed of a large number of glass fiber filaments with a glass cloth woven as a warp and a weft with a thermosetting resin and semi-curing it. It is manufactured.
- the glass fiber content is 60% by weight or more and 75% by weight or less for the purpose of improving the dimensional stability, the thermal expansion coefficient and the surface smoothness.
- the unit weight of the glass fibers of each of the layers is composed of at least two layers, one in which the bundle extends in parallel in one direction and the other in which the glass fiber bundle extends in one direction substantially orthogonal to the one direction.
- the glass fiber prepreg (refer FIG. 7) whose 40 g / m ⁇ 2 > or less is known (refer patent document 2).
- the prepreg described in Patent Document 2 achieves thinning by using glass fiber filaments having a small fiber diameter and forming a glass fiber bundle with a small number of convergence, and further, the glass fiber content is relatively large.
- the upper limit of the glass fiber content in the prepreg is 75 wt% (59 volume% in terms of volume ratio), and from the viewpoint of warpage reduction, low thermal expansion and high elasticity The point is not enough, and further improvement is desired.
- the present invention has been made in view of the present situation, and low thermal expansion and high elasticity can be achieved without adopting a resin having high filling of the inorganic filler and / or low thermal expansion coefficient.
- Providing a prepreg whose warpage can be reduced, a method of producing the prepreg, a laminate comprising the prepreg, a method of producing the laminate, and a printed wiring board comprising the laminate and the printed wiring An object is to provide a semiconductor package in which a semiconductor element is mounted on a plate.
- the present invention relates to the following [1] to [15].
- a prepreg comprising a glass fiber and a thermosetting resin composition, wherein the prepreg comprises a layer in which a plurality of glass fiber filaments extend substantially in parallel in one direction.
- the content does not contain the glass fiber bundle in which 50 or more glass fiber filaments are collected, or the content is 10 volume% or less with respect to the total amount of glass fibers in the prepreg. Prepreg described in.
- thermosetting resin composition does not contain an inorganic filler, or the content thereof is 12 volume% or less in the thermosetting resin composition.
- a laminate comprising the prepreg according to any one of the above [1] to [6], which is a laminate A layer in which a plurality of glass fiber filaments extend substantially parallel to one direction, and a layer in which a plurality of glass fiber filaments extend substantially parallel to another direction different from the one direction And containing, laminated board.
- the laminated board according to the above [7] or [8] wherein in a cross section in the thickness direction of the laminated board, an upper part and a lower part are substantially plane symmetric from the center.
- a printed wiring board comprising the laminate according to any one of the above [7] to [10].
- a semiconductor package formed by mounting a semiconductor element on the printed wiring board according to the above [11].
- a method for producing a prepreg having the following steps. (1) Opening step of opening glass fiber bundles to form a plurality of glass fiber filaments. (2) A plurality of glass fiber filaments formed in the opening step are disposed extending substantially in parallel in one direction on the surface of the carrier material coated with the thermosetting resin composition on the surface, and a prepreg is obtained. Forming process.
- a method for producing a laminated board comprising the following steps. (1) Opening step of opening glass fiber bundles to form a plurality of glass fiber filaments. (2) A plurality of glass fiber filaments formed in the opening step are disposed extending substantially in parallel in one direction on the surface of the carrier material coated with the thermosetting resin composition on the surface, and a prepreg is obtained. Forming process. (3) Prepare two or more prepregs formed in the step (2), and in at least one pair of prepregs, extending directions of a plurality of glass fiber filaments in one prepreg and a plurality of the other prepregs Step of laminating so as to be different from the extending direction of the glass fiber filament and heating and pressing.
- a prepreg in which low thermal expansion and high elasticity can be achieved and therefore warpage can be reduced without employing a resin with high filling of inorganic filler and / or low thermal expansion coefficient. be able to.
- a method for producing the prepreg, a laminate comprising the prepreg, a method for producing the laminate, a printed wiring board comprising the laminate, and a semiconductor package having the semiconductor element mounted on the printed wiring board can be provided.
- the thickness of the prepreg and the laminate of the present invention can be reduced, which can contribute to thinning of the printed wiring board and the semiconductor package.
- FIG. 1 It is a conceptual diagram showing a glass fiber bundle and a plurality of glass fiber filaments after fiber opening. It is a conceptual diagram which shows the one aspect
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
- the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value or the upper limit value of another numerical range, respectively.
- each component, material, etc. illustrated in this specification may be used individually by 1 type, and may use 2 or more types together, unless it refuses.
- the aspect which combined the description item in this specification arbitrarily is altogether contained in this invention.
- the present invention will be described in detail with reference to the drawings as needed.
- the prepreg of the present invention is a prepreg comprising a glass fiber and a thermosetting resin composition, wherein the prepreg comprises a layer in which a plurality of glass fiber filaments extend substantially in parallel in one direction. is there.
- a prepreg generally refers to a thermosetting resin composition coated on a fiber substrate and semi-cured by heating and drying.
- the glass fibers used for the prepreg are glass fiber bundles in which a plurality of glass fiber filaments are converged with a bundling agent and twisted as necessary, and the glass fiber bundles are called raw yarn and are commercially available.
- the glass fibers present are also glass fiber bundles (see left in FIG. 1).
- substantially parallel is meant to include a completely parallel state and a substantially non-perfectly parallel state.
- opening method There is no restriction
- the fiber opening method not only the glass fiber opening method but also other fiber, for example, a carbon fiber opening method can be applied.
- the methods (a) to (c) may be in any combination, and any number may be combined.
- (A) As a method of rounding with a round bar for example, a method of passing fiber bundles through alternate upper and lower rolls and running between rolls while applying tension to the fiber bundles (see, for example, JP-A-60-9961) Can be adopted.
- (B) As a method of applying vibration for example, a method of bringing a fiber bundle into contact with a round bar vibrated by ultrasonic wave (see, for example, JP-A 01-282362), a transverse vibration roll vibrating in roll axial direction, A method (for example, see JP-A-2004-225222) or the like can be adopted in which a longitudinal vibration roll which vibrates up and down with respect to the traveling direction of the fiber bundle is used.
- a method of applying a fluid for example, a method of spraying a fluid such as water, a mixture of water and air, an organic solvent, etc. onto a fiber bundle (for example, JP-A-52-151362), toward a fiber bundle
- a fiber bundle is drawn out from a plurality of yarn supplying bodies and supplied, and the supplied fiber bundle is introduced into an air flow in a plurality of fluid passing portions.
- the fiber bundle is made to travel in the width direction while being bent by the action of air flow, and the moving fiber bundle is bent and extended locally at that time, and alternately repeated with tension, relaxation, tension, relaxation, ...
- a fiber-opening method see, for example, JP-A-2007-518890
- the opening method described in, for example, Japanese Patent No. 5553074 can also be adopted.
- a continuously moving fiber bundle is vibrated in the width direction of the fiber bundle, and / or of the fiber bundle.
- the fiber is opened using a longitudinal vibration applying roll that vibrates in a direction intersecting the traveling direction, and an air flow is blown to the surface on one side and the other side of the fiber bundle traveling surface to separate the fiber bundle and open it.
- the prepreg of the present invention is, in other words, a prepreg containing glass fibers and a thermosetting resin composition, and glass fibers obtained by opening glass fiber bundles extend substantially in parallel in one direction. It can be said that it is a prepreg containing a layer disposed in an existing manner. Glass fiber bundles may be opened separately one by one, or plural fibers may be opened together.
- the number of glass fiber bundles used is not particularly limited, and may be, for example, 100 to 15,000, 100 to 10,000, or 500 to 10,000. It may be 1,000 to 10,000, or 3,000 to 8,000.
- the spreading ratio is not particularly limited, but may be, for example, 1.2 to 5.0 times, 1.5 to 4.0 times, or 1.8 to 3.5 times.
- the opening ratio is an index of how much the glass fiber bundle has been opened.
- the temperature at the time of opening is not particularly limited, but usually, it is preferably 0 to 60 ° C., more preferably 5 to 45 ° C., still more preferably 10 to 40 ° C., and carrying out at normal temperature is particularly preferable.
- FIG. 2 shows a cross-sectional configuration of the prepreg 1 which is an embodiment of the present invention, and is in a state of being held by the base material 2.
- the carrier material 2 made of polyethylene film, polyethylene terephthalate film, release paper or copper foil is stuck on both sides.
- the carrier material 2 is copper foil, this can be used as copper foil for circuit formation, adhering to the prepreg 1.
- the prepreg 1 uniformly contains a plurality of glass fiber filaments in one layer, and from the viewpoint of low thermal expansion and high elasticity, for example, 50 or more glass fiber filaments are converged It is preferable that the glass fiber bundle is not contained, and if such a glass fiber bundle is contained, the content thereof is preferably 10% by volume or less, more preferably, to the total amount of glass fibers in the prepreg. It is 5% by volume or less, more preferably 2% by volume or less.
- the glass fiber bundle is not contained, and even if the glass fiber bundle is contained, its content is preferably 10% by volume or less based on the total amount of glass fibers in the prepreg. More preferably, it is 5 volume% or less, More preferably, it is 2 volume% or less.
- the fiber diameter (diameter) of the glass fiber filaments is preferably 3 to 50 ⁇ m, more preferably 3 to 40 ⁇ m, still more preferably 4 to 30 ⁇ m, particularly preferably 5 to 25 ⁇ m, most preferably 5 to 5 from the viewpoint of the filling property. It is 18 ⁇ m.
- the content of glass fiber can be 50 to 75% by volume, 60 to 75% by volume, or 65 to 75% by volume with respect to the entire prepreg. . Therefore, the abundance of glass fibers in the prepreg is high, low thermal expansion and high elasticity are achieved, and consequently, reduction of warpage is achieved. If the glass fiber content is 75% by volume or less based on the entire prepreg, the ratio of the thermosetting resin composition 4 does not become too low, and the glass fiber filaments 31 and 32 are fully impregnated. It is possible to suppress the occurrence of the sagging on the surface of the prepreg and the laminate without being used.
- the total content of the glass fiber and the inorganic filler is preferably in the above range.
- the content (volume ratio) of the glass fibers (and the inorganic filler) in the prepreg is not particularly limited, but can be determined, for example, by the following method.
- Inorganic component that is, glass fiber and inorganic filler optionally contained
- the mass ratio A of the resin component is determined, and the mass ratio B of the resin component in the prepreg is determined from the value.
- the volume of the inorganic component and the volume of the resin component are calculated from the mass ratio A, the density of the inorganic component, and the mass ratio B and the density of the resin component, and the volume ratio of the inorganic component is calculated from them. be able to.
- the thickness of a prepreg can be adjusted thinly.
- the thickness of the prepreg of the present invention may be 100 ⁇ m or less, 70 ⁇ m or less, or 50 ⁇ m or less.
- the thickness of the prepreg is preferably 30 to 80 ⁇ m, more preferably 35 to 70 ⁇ m, and still more preferably 35 to 65 ⁇ m.
- the prepreg may be used by stacking a plurality of sheets.
- thermosetting resin composition The prepreg of the present invention is, as described above, a prepreg comprising glass fibers and a thermosetting resin composition.
- the thermosetting resin composition is not particularly limited, and a known thermosetting resin composition used for a prepreg in the field of printed wiring boards can be used.
- the content thereof is preferably 12% by volume or less in the thermosetting resin composition. It is preferably at most 8 vol%, more preferably at most 5 vol%, particularly preferably at most 3 vol%.
- the content of glass fibers in the prepreg can be increased, low thermal expansion and high elasticity can be achieved even as a prepreg using a thermosetting resin composition which does not contain an inorganic filler or has a small content. Is achieved.
- thermosetting resin composition may contain are not particularly limited, and, for example, (A) thermosetting resin, (B) curing accelerator, (C) inorganic filler and D) Other additives and the like can be mentioned.
- A) As a thermosetting resin for example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene Resin, silicone resin, triazine resin, melamine resin etc. are mentioned. Moreover, it does not restrict
- the epoxy resin examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, ⁇ -naphthol / cresol novolac epoxy resin, bisphenol A Novolak epoxy resin, bisphenol F novolac epoxy resin, stilbene epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolmethane epoxy resin, biphenyl epoxy resin, xylylene epoxy resin, biphenyl aralkyl epoxy Resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and anthracene Diglycidyl ether compounds of polycyclic aromatics and the like, such as those in the phosphorus-containing epoxy resin obtained by introducing a phosphorus compound.
- the epoxy resin examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin,
- the maleimide compound etc. which have at least 2 N- substituted maleimide group in 1 molecule are mentioned, for example,
- This maleimide compound is at least selected from the group which consists of a monoamine compound and a diamine compound. It may be a reaction product with one kind.
- a known curing accelerator may be used depending on the type of the thermosetting resin (A).
- phosphorus compounds; imidazole compounds and derivatives thereof; tertiary amine compounds; quaternary ammonium compounds and the like can be mentioned.
- One of these may be used alone, or two or more may be used in combination.
- the inorganic filler (C) is not particularly limited, and examples thereof include silica, alumina, barium sulfate, talc, mica, kaolin, boehmite, beryllia, barium titanate, potassium titanate, strontium titanate, and titanium.
- Examples thereof include clays such as silicon nitride, boron nitride and calcined clay, glass powder, hollow glass beads and the like. One of these may be used alone, or two or more may be used in combination.
- thermosetting resin composition may contain an organic solvent, a dispersant and the like. However, since the organic solvent is volatilized by the drying step in producing the prepreg, the organic solvent tends not to remain substantially in the prepreg.
- the prepreg is generally used as a laminate by laminating a plurality of sheets and then heating and pressing.
- the laminate of the present invention is a laminate comprising the above-mentioned prepreg, and a layer in which a plurality of glass fiber filaments are arranged extending substantially in parallel to one direction is different from the one direction And a layer including a plurality of glass fiber filaments extending substantially in parallel extending in the other direction.
- the other one direction different from the one direction is the other one direction substantially orthogonal to the one direction.
- thermosetting resin composition 4 is present around these glass fiber filaments.
- substantially orthogonal is a meaning including a completely orthogonal state and a state which is not perfect but approximately orthogonal. In addition, even if there is a part that is generally orthogonal, and there are places that are not orthogonal to details, it is included in “substantially orthogonal” if it can be regarded as macroscopic orthogonal.
- the layer containing the glass fiber filament 31 and the layer containing the glass fiber filament 32 are similar in fiber diameter and length of each glass fiber filament, glass fiber content, etc., except that the direction of the glass fiber filament is different. It is equivalent and the volume ratio of glass fiber is substantially equal, whereby the dimensional change in the longitudinal and lateral directions of the laminated plate 5 is substantially equal.
- the upper part and the lower part are substantially plane-symmetrical from the center in the cross section in the thickness direction of the laminate.
- “generally plane symmetry” does not mean to obtain symmetry by focusing on the position of each glass fiber filament, and focusing on the arrangement direction of the glass fiber filaments, the upper part and the lower part from the center Means that it is in plane symmetry.
- the laminated board shown in FIG. 4 is plane-symmetrical in the upper part and the lower part from the center part shown in the figure, and is preferable from the viewpoint of warpage reduction.
- the laminated board shown in FIG. 5 is also preferable from the viewpoint of warpage reduction since the laminated board shown in FIG.
- the content of glass fiber can be 50 to 75% by volume with respect to the entire laminate (but excluding metal foil in the case of a laminate having metal foil).
- the volume may be 55 to 75% by volume, 60 to 75% by volume, or 65 to 75% by volume.
- the total content of the glass fiber and the inorganic filler is preferably in the above range.
- the laminate of the present invention includes a structure that can increase the content of glass fiber, and therefore, the flexural modulus at 25 ° C. can be 35 GPa or more. Depending on the content of glass fiber, it may be 40 GPa or more, 44 GPa or more, and 47 GPa or more.
- the upper limit of the flexural modulus at 25 ° C. is not particularly limited, it is usually 55 GPa or less, and may be 50 GPa or less.
- the flexural modulus is a value measured according to the method described in the examples.
- the present invention also provides a method for producing a prepreg having the following steps. (1) Opening step of opening glass fiber bundles to form a plurality of glass fiber filaments. (2) A plurality of glass fiber filaments formed in the opening step are disposed extending substantially in parallel in one direction on the surface of the carrier material coated with the thermosetting resin composition on the surface, and a prepreg is obtained. Step of Forming [hereinafter, referred to as Step (2). ].
- the glass fiber bundle is opened to form a plurality of glass fiber filaments.
- the opening method is not particularly limited as described above, and for example, the above-mentioned opening method can be adopted.
- the method of arranging a plurality of glass fiber filaments extending substantially in parallel in one direction on the surface of the carrier material coated with the thermosetting resin composition on the surface is not particularly limited.
- a plurality of glass fiber filaments obtained through the opening step may be aligned as they are on the surface of the carrier material as it is, or the plurality of glass fiber filaments obtained through the opening step may be wound once with a roll. It may be taken, cut if necessary, and then aligned on the surface of the carrier material.
- the present invention also provides a method for producing a laminate, which comprises the following steps. (1) Opening step of opening glass fiber bundles to form a plurality of glass fiber filaments. (2) A plurality of glass fiber filaments formed in the opening step are disposed extending substantially in parallel in one direction on the surface of the carrier material coated with the thermosetting resin composition on the surface, and a prepreg is obtained. Process to form [process (2)].
- process (3) Prepare two or more prepregs formed in the step (2), and in at least one pair of prepregs, extending directions of a plurality of glass fiber filaments in one prepreg and a plurality of the other prepregs Process of laminating so as to be different from the extending direction of the glass fiber filament and heating and pressing [hereinafter, may be referred to as process (3). ].
- the fiber opening step and the step (2) are as described in the method for producing a prepreg.
- the extending direction of the plurality of glass fiber filaments in one prepreg and the extending direction of the plurality of glass fiber filaments in the other prepreg are substantially orthogonal to each other.
- the aspect can be implemented by laminating two prepregs formed in the step (2) in different directions.
- the heating and pressurizing conditions may be ordinary manufacturing conditions of laminates, for example, using a multistage press, a multistage vacuum press, a continuous forming, an autoclave forming machine, etc. C., pressure 0.2 to 10 MPa, heating time 0.1 to 5 hours.
- the present invention also provides a printed wiring board comprising the laminate. More specifically, a metal-clad laminate is manufactured by preparing a plurality of the prepregs of the present invention and laminating and forming a metal foil such as copper or aluminum on one side or both sides of the metal-clad laminate, A printed wiring board can be manufactured by forming a wiring pattern on the foil.
- the metal foil is not particularly limited as long as it is used for an electrical insulating material application, but a copper foil is preferable.
- the method of forming the wiring pattern is not particularly limited, but a subtractive method, a full additive method, a semi additive method (SAP: semi additive process) or a modified semi additive method (m-SAP), etc. Methods known in the art.
- the present invention also provides a semiconductor package formed by mounting a semiconductor element on the printed wiring board.
- the semiconductor package can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board and sealing the semiconductor element with a sealing resin or the like.
- thermosetting resin composition 1 Production Example 1 (Production of Thermosetting Resin Composition 1) "NC-3000H” (trade name, manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin, addition reaction product of bismaleimide compound and diamine compound as maleimide resin, "G-8009L” (trade name, isocyanate mask as curing accelerator) Imidazole, Dai-ichi Kogyo Seiyaku Co., Ltd.), “Yoshinox BB” (trade name, 4,4′-Butylidenebis- (6-t-butyl-3-methylphenol), manufactured by Mitsubishi Chemical Corporation) as an antioxidant
- the mixture was mixed in a mixed solvent of methyl ethyl ketone and cyclohexanone to obtain a thermosetting resin composition 1 having a solid content concentration of 55% by mass.
- Example 1 Using a polyethylene terephthalate film with a thickness of 38 ⁇ m as a carrier material, the thermosetting resin composition 1 obtained in Production Example 1 is coated on the carrier material with a thickness of 12 ⁇ m, and a resin coated film 1 with a thickness of 12 ⁇ m It formed. Next, a glass fiber bundle, in which 6,000 glass fiber filaments having a fiber diameter (diameter) of 12 ⁇ m are gathered, is opened at an opening magnification of 3.2 times, and the glass fiber filaments obtained by opening are arranged side by side 300 mm The width was made and aligned on the resin coated film 1 having a thickness of 12 ⁇ m.
- Another resin-coated film 1 with a thickness of 12 ⁇ m was pasted thereon with the resin-coated surface down.
- the prepreg precursor thus obtained was B-staged at a pressure of 1 MPa, a temperature of 150 ° C., and a feed rate of 1 m / min using a heat roller to obtain a prepreg having a glass fiber content of 50% by volume.
- the eight prepregs prepared above are laminated as shown in FIG. 5, and using a vacuum press, the laminated plate is heated and pressurized under the conditions of a temperature rising rate of 3 ° C./min, holding at 245 ° C. for 85 minutes, and pressure 2 MPa. I got Each evaluation was performed according to the said method using the obtained laminated board. The results are shown in Table 1.
- Example 2 In Example 1, the thermosetting resin composition 1 obtained in Production Example 1 is coated on the carrier material with a thickness of 10 ⁇ m to form a resin-coated film 2 with a thickness of 10 ⁇ m, and this is used as a resin-coated film
- the same operation as in (1) was carried out except that the glass fiber bundle was opened at an opening ratio of 2.6 times to obtain a prepreg having a glass fiber content of 60% by volume.
- a laminate was produced in the same manner as in Example 1 using this prepreg.
- Each evaluation was performed according to the said method using the obtained laminated board. The results are shown in Table 1.
- Example 3 In Example 1, the thermosetting resin composition 1 obtained in Production Example 1 is coated on the carrier material with a thickness of 7 ⁇ m to form a resin coated film 3 with a thickness of 7 ⁇ m, which is used as a resin coated film The same operation as in Example 1 was repeated except that the glass fiber bundle was opened at an opening ratio of 2.0 times to obtain a prepreg having a glass fiber content of 70% by volume. A laminate was produced in the same manner as in Example 1 using this prepreg. Each evaluation was performed according to the said method using the obtained laminated board. The results are shown in Table 1.
- Comparative Example 1 Glass fiber (100 g / m 2 ) is used as the glass fiber, and after the thermosetting resin composition 1 obtained in Production Example 1 is impregnated and coated thereon, the glass fiber is heated and dried at 110 ° C. for 3 minutes. The prepreg having a content of 45% by volume was obtained. A laminate was produced in the same manner as in Example 1 using this prepreg. Each evaluation was performed according to the said method using the obtained laminated board. The results are shown in Table 1. In Table 1, the amount of warping produced in the laminate produced in Comparative Example 1 was used as a reference (100).
- Comparative example 2 According to the method described in Patent Document 2, a thickness of the thermosetting resin composition 1 is applied as it is without opening a glass fiber bundle in which 200 glass fiber filaments having a fiber diameter (diameter) of 5 ⁇ m are converged.
- the resin coating film 4 of 10.5 ⁇ m was aligned at a pitch of 0.5 mm.
- the resin-coated film 4 with a thickness of 10.5 ⁇ m was attached on top of the above with the resin-coated surface down, to obtain a prepreg containing a glass fiber bundle having a limit content of a level at which the occurrence of blistering occurs.
- the glass fiber content of the prepreg and the laminate can be increased, and the thermal expansion coefficient is low, and the bending elastic modulus is high and the elasticity is high, and the warpage is reduced.
- prepregs and laminates were obtained which were free of blisters.
- Comparative Example 1 in which plain weave glass cloth is used the content of glass fiber is only 45% by volume, and the thermal expansion coefficient is not reduced and the bending elastic modulus is also reduced. It became.
- thermosetting resin composition was changed by changing the type of thermosetting resin composition.
- thermosetting resin composition 2 (Production of Thermosetting Resin Composition 2; Resin Composition for Containing 5% by Volume of Inorganic Filler in Prepreg) "NC-7000L” (trade name, manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin, addition reaction product of bismaleimide compound and diamine compound as maleimide resin, "G-8009L” (trade name, isocyanate mask as curing accelerator) Imidazole, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., fused spherical silica (trade name, average particle diameter 0.5 ⁇ m, manufactured by Admatex Co., Ltd.) as an inorganic filler, “Yoshinox BB” as a antioxidant [trade name 4, 4′-Butylidenebis- (6-t-butyl-3-methylphenol), manufactured by Mitsubishi Chemical Corporation, is mixed in a mixed solvent of methyl ethyl ketone and cyclohexanone to obtain a thermo
- thermosetting resin composition 3 (Production of Thermosetting Resin Composition 3; Resin Composition for Containing 10% by Volume of Inorganic Filler in Prepreg) "NC-7000L” (trade name, manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin, addition reaction product of bismaleimide compound and diamine compound as maleimide resin, "G-8009L” (trade name, isocyanate mask as curing accelerator) Imidazole, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., fused spherical silica (trade name, average particle diameter 0.5 ⁇ m, manufactured by Admatex Co., Ltd.) as an inorganic filler, “Yoshinox BB” as a antioxidant [trade name 4, 4′-Butylidenebis- (6-t-butyl-3-methylphenol), manufactured by Mitsubishi Chemical Corporation, is mixed in a mixed solvent of methyl ethyl ketone and cyclohexanone to obtain a thermosetting
- thermosetting resin composition 4 (Production of Thermosetting Resin Composition 4; Resin Composition for Containing 25% by Volume of Inorganic Filler in Prepreg) "NC-7000L” (trade name, manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin, addition reaction product of bismaleimide compound and diamine compound as maleimide resin, "G-8009L” (trade name, isocyanate mask as curing accelerator) Imidazole, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., fused spherical silica (trade name, average particle diameter 0.5 ⁇ m, manufactured by Admatex Co., Ltd.) as an inorganic filler, “Yoshinox BB” as a antioxidant [trade name 4, 4′-Butylidenebis- (6-t-butyl-3-methylphenol), manufactured by Mitsubishi Chemical Corporation, is mixed in a mixed solvent of methyl ethyl ketone and cyclohexanone to obtain a thermosetting
- Example 4 Using a 38 ⁇ m thick polyethylene terephthalate film as a carrier material, the thermosetting resin composition 2 obtained in Production Example 2 is coated on the carrier material with a thickness of 10 ⁇ m, and a resin coated film 2 with a thickness of 10 ⁇ m It formed. Next, a glass fiber bundle, in which 6,000 glass fiber filaments having a fiber diameter (diameter) of 12 ⁇ m are gathered, is opened at an opening magnification of 2.6 times, and the glass fiber filaments obtained by opening are arranged side by side 300 mm The width was made and aligned on the resin coated film 2 with a thickness of 10 ⁇ m.
- Example 5 the thermosetting resin composition 3 obtained in Production Example 3 is applied on the carrier material to a thickness of 10 ⁇ m to form a resin-coated film 3 having a thickness of 10 ⁇ m, and this is used as a resin-coated film
- the operation was carried out in the same manner except that it was used instead of 2, to obtain a prepreg having a glass fiber content of 60% by volume (the total content of the glass fiber and the inorganic filler was 70% by volume).
- a laminate was produced in the same manner as in Example 4 using this prepreg.
- Each evaluation was performed according to the said method using the obtained laminated board. The results are shown in Table 2.
- Example 5 a plain weave glass cloth (100 g / m 2 ) is used as the glass fiber, and the thermosetting resin composition 4 obtained in Production Example 4 is impregnated in a plain weave glass cloth instead of the thermosetting resin composition 3 After processing, heat drying at 110 ° C. for 3 minutes is carried out in the same manner except that a prepreg having a glass fiber content of 45% by volume (total content of glass fiber and inorganic filler 70% by volume) is obtained. A laminate was made.
- the total content of the glass fiber and the inorganic filler in the laminate is 70% by volume, which is the same as the total content of the glass fiber and the inorganic filler in the laminate produced in Example 5;
- Each evaluation was performed according to the said method using the obtained laminated board. The results are shown in Table 2.
- Comparative example 4 In Comparative Example 3, the same operation is performed except that the coating amount of the thermosetting resin composition 4 is reduced, and the content of the glass fiber is 60% by volume (the total content 85 of the glass fiber and the inorganic filler) In the same manner as in Comparative Example 3, a laminated board was produced. An attempt was made to reduce warpage by increasing the total content of glass fiber and inorganic filler in the laminate relative to Comparative Example 3 (70% by volume) to reduce warpage. Was observed.
- the glass fiber content of the prepreg and the laminate can be increased, and the thermal expansion coefficient is low, and the bending elastic modulus is high and the elasticity is high, and the warpage is reduced.
- the glass fiber content is only 45% by volume, and it can be said that the thermal expansion coefficient is not reduced, and the reduction of the generated warp has become an issue.
- the flexural modulus also decreased.
- Comparative Example 4 in which the glass fiber content was increased to improve warpage in Comparative Example 3, a large amount of blistering occurred on the surface of the laminate.
- the prepreg and the laminate of the present invention are compatible with low thermal expansion and high elasticity, and warpage is reduced, and thus they are useful as printed wiring boards for electronic devices.
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Abstract
Description
実装時、半導体パッケージに生じるそりの主な原因の1つが、半導体パッケージに使われている積層板と当該積層板の表面に実装されるシリコンチップとの熱膨張率差である。そのため、半導体パッケージ用積層板においては、熱膨張率をシリコンチップの熱膨張率に近づける、すなわち低熱膨張率化する努力が行われている。また、積層板の弾性率もそりに影響するため、半導体パッケージのそりを低減するには積層板を高弾性化することも有効である。従って、積層板のそりを低減するためには、積層板の低膨張率化と共に高弾性化する必要がある。
[1]ガラス繊維及び熱硬化性樹脂組成物を含有してなるプリプレグであって、複数のガラス繊維フィラメントが一方向に略平行に延在して配置された層を含有するプリプレグ。
[2]ガラス繊維フィラメントが50本以上集束したガラス繊維束を含有しないか、又は含有していてもその含有量がプリプレグ中のガラス繊維全量に対して10体積%以下である、上記[1]に記載のプリプレグ。
[3]ガラス繊維の含有量がプリプレグ全体に対して50~75体積%である、上記[1]又は[2]に記載のプリプレグ。
[4]ガラス繊維の含有量がプリプレグ全体に対して60~75体積%である、上記[1]~[3]のいずれかに記載のプリプレグ。
[5]前記熱硬化性樹脂組成物が無機充填材を含有しないか、又は含有していてもその含有量が、熱硬化性樹脂組成物中、12体積%以下である、上記[1]~[4]のいずれかに記載のプリプレグ。
[6]厚みが100μm以下である、上記[1]~[5]のいずれかに記載のプリプレグ。
[7]上記[1]~[6]のいずれかに記載のプリプレグを含有してなる積層板であって、
複数のガラス繊維フィラメントが一方向に略平行に延在して配置された層と、前記一方向とは異なる他の一方向に複数のガラス繊維フィラメントが略平行に延在して配置された層とを含有する、積層板。
[8]前記一方向とは異なる他の一方向が、前記一方向と略直交する他の一方向である、上記[7]に記載の積層板。
[9]前記積層板の厚さ方向の断面において、中心から上部と下部とが略面対称になっている、上記[7]又は[8]に記載の積層板。
[10]25℃における曲げ弾性率が35GPa以上である、上記[7]~[9]のいずれかに記載の積層板。
[11]上記[7]~[10]のいずれかに記載の積層板を含有してなるプリント配線板。
[12]上記[11]に記載のプリント配線板に半導体素子を搭載してなる半導体パッケージ。
[13]下記工程を有する、プリプレグの製造方法。
(1)ガラス繊維束を開繊して複数のガラス繊維フィラメントを形成する、開繊工程。
(2)熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に、前記開繊工程で形成した複数のガラス繊維フィラメントを一方向に略平行に延在して配置し、プリプレグを形成する工程。
[14]下記工程を有する、積層板の製造方法。
(1)ガラス繊維束を開繊して複数のガラス繊維フィラメントを形成する、開繊工程。
(2)熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に、前記開繊工程で形成した複数のガラス繊維フィラメントを一方向に略平行に延在して配置し、プリプレグを形成する工程。
(3)前記工程(2)によって形成されたプリプレグ2枚以上を準備し、少なくとも1対のプリプレグにおいて、一方のプリプレグ中の複数のガラス繊維フィラメントの延在方向と、他方のプリプレグ中の複数のガラス繊維フィラメントの延在方向とが異なるように積層し、加熱加圧する工程。
[15]一方のプリプレグ中の複数のガラス繊維フィラメントの延在方向と、他方のプリプレグ中の複数のガラス繊維フィラメントの延在方向とが略直交する、上記[14]に記載の積層板の製造方法。
本発明のプリプレグ及び積層板は厚みを薄くできるため、プリント配線板及び半導体パッケージの薄型化に寄与し得る。
また、本明細書に例示する各成分及び材料等は、特に断らない限り、1種を単独で使用してもよいし、2種以上を併用してもよい。なお、本明細書における記載事項を任意に組み合わせた態様は、全て本発明に含まれる。
以下、必要に応じて図面を参照しながら本発明について詳述する。
本発明のプリプレグは、ガラス繊維及び熱硬化性樹脂組成物を含有してなるプリプレグであって、複数のガラス繊維フィラメントが一方向に略平行に延在して配置された層を含有するプリプレグである。ここでプリプレグとは、一般的に、熱硬化性樹脂組成物を繊維基材に塗工し、加熱乾燥を行うことによって半硬化したものをいう。
通常、プリプレグに用いられるガラス繊維は、複数のガラス繊維フィラメントが集束剤で集束され、必要に応じて撚りが加わったガラス繊維束であり、当該ガラス繊維束が原糸と呼ばれ、市販されているガラス繊維もガラス繊維束(図1の左参照)である。糸切れ等による毛羽立ちなどを避けるため、当該ガラス繊維束の状態のままプリプレグの製造に使用することが常識であるが、本発明のプリプレグでは、当該ガラス繊維束をあえて開繊した複数のガラス繊維フィラメント(図1の右参照)を用いる。
本発明者等の検討によって、本発明のプリプレグであれば、プリプレグ内のガラス繊維の含有量及び後述する積層板内のガラス繊維の含有量を大幅に高められることが判明した。このような結果となった正確な理由は明らかではないが、ガラス繊維束は集束剤で束ねられているために、その集束材の体積分のロスがあること、及び、束ねられているために所定の大きさを要しており、単位体積当たりに存在させられる量に限界があると考えられるが、開繊して得られたガラス繊維フィラメントを一方向に略平行に延在して配置させることによってそれらの問題が解決したためと推察する。
本明細書において、略平行とは、完全に平行である状態と、完全ではなくともおおよそ平行である状態とを含む意味である。また、全体的におおよそ平行と言える状態を示し、細部に平行ではない所があったとしても、巨視的に平行であれば、「略平行」に含まれる。
前記開繊方法に特に制限はなく、公知の開繊方法を採用できる。例えば、(a)丸棒でしごく方法、(b)振動を与える方法、(c)流体を当てる方法等からなる群から選択される少なくとも1種を利用した開繊方法を採用できる。開繊方法としては、ガラス繊維の開繊方法のみならず、他の繊維、例えば炭素繊維の開繊方法を応用することもできる。前記方法(a)~(c)は、任意の組み合わせが可能であり、任意の数を組み合わせてもよい。
(b)振動を与える方法としては、例えば、超音波によって振動させた丸棒に繊維束を接触させる方法(例えば、特開平01-282362号公報参照)、ロール軸方向に振動する横振動ロール及び/又は繊維束の進行方向に対して上下に振動する縦振動ロールを用いて開繊する方法(例えば、特開2004-225222号公報参照)などを採用できる。
(c)流体を当てる方法としては、例えば、水、水と空気との混合物、有機溶媒等の流体を繊維束に吹き付ける方法(例えば、特開昭52-151362号公報)、繊維束に向けて空気流を噴出させる方法(例えば、特開昭57-77342号公報)、複数の給糸体からそれぞれ繊維束を引き出して供給し、供給された繊維束を複数の流体通流部において気流内に走行させて気流の作用により繊維束を撓ませながら幅方向に開繊させ、その際に移動する繊維束を局部的に屈伸させて、緊張、弛緩、緊張、弛緩、・・・と交互に反復的に張力変化させる開繊方法(例えば、特表2007-518890号公報参照)等を採用できる。他にも、例えば特許第5553074号公報に記載の開繊方法を採用することもできる。
ガラス繊維束は、1本ずつ別々に開繊してもよいし、複数本をまとめて開繊してもよい。
使用するガラス繊維束の集束数に特に制限はないが、例えば、100~15,000本であってもよく、100~10,000本であってもよく、500~10,000本であってもよく、1,000~10,000本であってもよく、3,000~8,000本であってもよい。
開繊倍率に特に制限はないが、例えば、1.2~5.0倍であってもよく、1.5~4.0倍であってもよく、1.8~3.5倍であってもよい。該開繊倍率は、ガラス繊維束をどの程度開繊したかの指標となる。
開繊する際の温度に特に制限はないが、通常、好ましくは0~60℃、より好ましくは5~45℃、さらに好ましくは10~40℃であり、常温にて実施することが特に好ましい。
図2が示す様に、プリプレグ1は、複数のガラス繊維フィラメントを1層中に万遍なく含有しており、低熱膨張化及び高弾性化の観点から、例えばガラス繊維フィラメントが50本以上集束したガラス繊維束を含有していないことが好ましく、また、もしそのようなガラス繊維束を含有していてもその含有量はプリプレグ中のガラス繊維全量に対して好ましくは10体積%以下、より好ましくは5体積%以下、さらに好ましくは2体積%以下である。特に、低熱膨張化及び高弾性化の観点から、100本以上集束したガラス繊維束を含有していないことが好ましく、200本以上集束したガラス繊維束を含有していないことが好ましく、500本以上集束したガラス繊維束を含有していないことが好ましく、また、もしこれらのガラス繊維束を含有していてもその含有量はプリプレグ中のガラス繊維全量に対して、それぞれ、好ましくは10体積%以下、より好ましくは5体積%以下、さらに好ましくは2体積%以下である。
なお、プリプレグ中のガラス繊維(及び無機充填材)の含有量(体積比率)は、特に制限されるものではないが、例えば、次の方法によって求めることができる。プリプレグを600~650℃で加熱して得られる固形分(残渣)の質量を加熱前のプリプレグの質量で割ることにより、無機成分(つまりガラス繊維及び必要に応じて含有している無機充填材)の質量比率Aを求め、且つ、その値からプリプレグ中の樹脂成分の質量比率Bを求める。前記質量比率Aと前記無機成分の密度、及び前記質量比率Bと前記樹脂成分の密度から、前記無機成分の体積と前記樹脂成分の体積を算出し、それらから前記無機成分の体積比率を算出することができる。
本発明のプリプレグは、前述の通り、ガラス繊維及び熱硬化性樹脂組成物を含有してなるプリプレグである。
熱硬化性樹脂組成物については、特に制限されるものではなく、プリント配線板の分野においてプリプレグに使用される公知の熱硬化性樹脂組成物を使用することができる。
本発明のプリプレグにおいては、前記熱硬化性樹脂組成物が無機充填材を含有しないか、又は含有していてもその含有量を、熱硬化性樹脂組成物中、好ましくは12体積%以下、より好ましくは8体積%以下、さらに好ましくは5体積%以下、特に好ましくは3体積%以下とすることができる。本発明では、プリプレグ中のガラス繊維の含有量を高めることができるため、無機充填材を含有しないか又は含有量の少ない熱硬化性樹脂組成物を用いたプリプレグとしても、低熱膨張化及び高弾性化が達成される。
(A)熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂及びメラミン樹脂等が挙げられる。また、特にこれらに制限されず、公知の熱硬化性樹脂を使用できる。これらは、1種を単独で使用してもよいし、2種以上を併用することもできる。
前記エポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、α-ナフトール/クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールFノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物、これらにリン化合物を導入したリン含有エポキシ樹脂などが挙げられる。
前記不飽和イミド樹脂としては、例えば、1分子中に少なくとも2個のN-置換マレイミド基を有するマレイミド化合物等が挙げられ、該マレイミド化合物は、モノアミン化合物及びジアミン化合物からなる群から選択される少なくとも1種との反応物であってもよい。
(D)その他の添加剤としては、特に制限されるものではないが、例えば、有機充填材、難燃剤、熱可塑性樹脂、熱可塑性エラストマ、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び接着性向上剤等からなる群から選択される少なくとも1種を使用できる。
また、前記熱硬化性樹脂組成物は、有機溶剤、分散剤等を含有していてもよい。但し、プリプレグを作製する際の乾燥工程によって有機溶媒は揮発するため、プリプレグ中には有機溶媒が実質的に残存していない傾向にある。
前記プリプレグは、通常、複数枚積層してから加熱加圧することによって、積層板として用いられる。特に、本発明の積層板は、前記プリプレグを含有してなる積層板であって、複数のガラス繊維フィラメントが一方向に略平行に延在して配置された層と、前記一方向とは異なる他の一方向に複数のガラス繊維フィラメントが略平行に延在して配置された層とを含有する、積層板である。
ここで、本発明においては、前記一方向とは異なる他の一方向が、前記一方向と略直交する他の一方向であることが好ましい。具体的には、図3に示す本発明の一態様を示す積層板5は、複数の縦方向ガラス繊維フィラメント31が紙面の前後方向に略平行に延在して配置された1つの層と、前記縦方向ガラス繊維フィラメント31と略直交する方向に横方向ガラス繊維フィラメント32が略平行に延在して配置されたもう一つの層から形成されており、好ましい態様の1つである。これらのガラス繊維フィラメントの周囲には、熱硬化性樹脂組成物4が存在する。ここで、略直交するとは、完全に直交する状態と、完全ではなくともおおよそ直交する状態とを含む意味である。また、全体的におおよそ直交と言える状態を示し、細部に直交していない所があったとしても、巨視的に直交しているとみなせれば、「略直交」に含まれる。
ガラス繊維フィラメント31を含有する層とガラス繊維フィラメント32を含有する層とは、ガラス繊維フィラメントの方向が異なること以外は、各ガラス繊維フィラメントの繊維径及び長さ、並びにガラス繊維含有量等はほぼ同等であって、ガラス繊維の体積比率がほぼ等しくなっており、これによって、積層板5の縦横の寸法変化はほぼ等しくなっている。
本発明の積層板は、ガラス繊維の含有量を高められる構造を含んでおり、そのため、25℃における曲げ弾性率は35GPa以上になり得る。ガラス繊維の含有量によっては、40GPa以上にもなり、44GPa以上にもなり、47GPa以上にもなる。25℃における曲げ弾性率の上限に特に制限はないが、通常、55GPa以下であり、50GPa以下であってもよい。
なお、曲げ弾性率は実施例に記載の方法に従って測定した値である。
本発明は、下記工程を有するプリプレグの製造方法も提供する。
(1)ガラス繊維束を開繊して複数のガラス繊維フィラメントを形成する、開繊工程。
(2)熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に、前記開繊工程で形成した複数のガラス繊維フィラメントを一方向に略平行に延在して配置し、プリプレグを形成する工程[以下、工程(2)と称することがある。]。
前記工程(2)において、熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に複数のガラス繊維フィラメントを一方向に略平行に延在して配置する方法に特に制限はなく、開繊工程を経て得られた複数のガラス繊維フィラメントをそのままキャリア材の当該表面上に引き揃えて配置してもよいし、開繊工程を経て得られた複数のガラス繊維フィラメントを一旦ロールで巻き取り、必要に応じて切断してから、キャリア材の当該表面上引き揃えて配置してもよい。
本発明は、下記工程を有する積層板の製造方法も提供する。
(1)ガラス繊維束を開繊して複数のガラス繊維フィラメントを形成する、開繊工程。
(2)熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に、前記開繊工程で形成した複数のガラス繊維フィラメントを一方向に略平行に延在して配置し、プリプレグを形成する工程[工程(2)]。
(3)前記工程(2)によって形成されたプリプレグ2枚以上を準備し、少なくとも1対のプリプレグにおいて、一方のプリプレグ中の複数のガラス繊維フィラメントの延在方向と、他方のプリプレグ中の複数のガラス繊維フィラメントの延在方向とが異なるように積層し、加熱加圧する工程[以下、工程(3)と称することがある。]。
前記工程(3)では、一方のプリプレグ中の複数のガラス繊維フィラメントの延在方向と、他方のプリプレグ中の複数のガラス繊維フィラメントの延在方向とを略直交させることが好ましい。例えば、前記工程(2)によって形成されたプリプレグ2枚を、向きを変えて積層させることで、当該態様を実施できる。
工程(3)において、加熱加圧の条件は、通常の積層板の製造条件を採用すればよく、例えば、多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度100~260℃、圧力0.2~10MPa、加熱時間0.1~5時間という条件で製造することができる。
本発明は、前記積層板を含有してなるプリント配線板も提供する。より具体的には、本発明のプリプレグ複数枚を準備し、その片面又は両面に、銅、アルミニウム等の金属箔を配置した構成で積層成形することにより、金属張積層板を製造し、前記金属箔に配線パターンを形成することにより、プリント配線板を製造することができる。なお、金属箔は、電気絶縁材料用途で用いるものであれば特に制限されないが、銅箔が好ましい。配線パターンの形成方法としては特に限定されるものではないが、サブトラクティブ法、フルアディティブ法、セミアディティブ法(SAP:Semi Additive Process)又はモディファイドセミアディティブ法(m-SAP:modified Semi Additive Process)等の公知の方法が挙げられる。
本発明は、前記プリント配線板に半導体素子を搭載してなる半導体パッケージも提供する。半導体パッケージは、前記プリント配線板の所定の位置に半導体チップ、メモリ等の半導体素子を搭載し、封止樹脂等によって半導体素子を封止することによって製造できる。
なお、以下の実施例で得られた積層板について、以下の方法で物性又は特性を測定及び評価した。
各例で得た積層板から40mm×25mmの評価基板を切り出し、株式会社オリエンテック製の5トンテンシロンを用い、25℃、クロスヘッド速度1mm/min、スパン間距離20mmで曲げ弾性率(GPa)を測定した。
各例で作製した積層板を目視によって観察し、下記評価基準に従って評価した。
A:全くカスレが観察されない。
B:少しだけカスレが観察される。
C:カスレが多く観察される。
各例で製造した積層板に銅箔を配置した銅張積層板を作製し、得られた銅張積層板を評価基板とした。該評価基板から、40×40mm角の試験片を切り出した。その基板の上に20×20mm半導体シリコン基板を接着し、そり測定用基板を作製した。
基板のそりはシャドーモアレ装置(サーモレイPS-200、AKROMETRIX社製)を用いて測定した。測定条件は、25℃から260℃まで昇温し、その後25℃まで冷却したときのそり量を測定し、比較例1において得られたそり量を基準(100)としたときの値を算出した。
エポキシ樹脂として「NC-3000H」(商品名、日本化薬株式会社製)、マレイミド樹脂としてビスマレイミド化合物とジアミン化合物との付加反応物、硬化促進剤として「G-8009L」(商品名、イソシアネートマスクイミダゾール、第一工業製薬株式会社製)、酸化防止剤として「ヨシノックスBB」(商品名、4,4’-ブチリデンビス-(6-t-ブチル-3-メチルフェノール)、三菱ケミカル株式会社製)をメチルエチルケトン及びシクロヘキサノン混合溶媒中で混合し、固形分濃度55質量%の熱硬化性樹脂組成物1を得た。
キャリア材として厚さ38μmのポリエチレンテレフタレートフィルムを使用し、製造例1で得た熱硬化性樹脂組成物1を厚み12μmで前記キャリア材上に塗工し、厚さ12μmの樹脂塗工フィルム1を形成した。
次いで、繊維径(直径)12μmのガラス繊維フィラメントが6,000本集束したガラス繊維束を開繊倍率3.2倍に開繊し、開繊して得られたガラス繊維フィラメントを横に並べて300mm幅にし、前記厚さ12μmの樹脂塗工フィルム1上に引き揃えた。その上にもう一枚の前記厚さ12μmの樹脂塗工フィルム1を、樹脂塗工面を下にして貼り付けた。
こうして得られたプリプレグ前駆体について、熱ローラーを使用し、圧力1MPa、温度150℃、送り速度1m/分でBステージ化することによって、ガラス繊維の含有量が50体積%のプリプレグを得た。
上記で作製したプリプレグ8枚を図5が示す様に積層し、真空プレスを使用し、昇温速度3℃/分、245℃で85分保持、圧力2MPaの条件で加熱加圧することによって積層板を得た。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表1に示す。
実施例1において、製造例1で得た熱硬化性樹脂組成物1を厚み10μmで前記キャリア材上に塗工して厚さ10μmの樹脂塗工フィルム2を形成し、これを樹脂塗工フィルム1の代わりに用い、且つ、ガラス繊維束を開繊倍率2.6倍に開繊したこと以外は同様にして操作を行い、ガラス繊維の含有量が60体積%のプリプレグを得た。該プリプレグを用いて、実施例1と同様にして積層板を作製した。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表1に示す。
実施例1において、製造例1で得た熱硬化性樹脂組成物1を厚み7μmで前記キャリア材上に塗工して厚さ7μmの樹脂塗工フィルム3を形成し、これを樹脂塗工フィルム1の代わりに用い、且つ、ガラス繊維束を開繊倍率2.0倍に開繊したこと以外は同様にして操作を行い、ガラス繊維の含有量が70体積%のプリプレグを得た。該プリプレグを用いて、実施例1と同様にして積層板を作製した。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表1に示す。
ガラス繊維として平織ガラスクロス(100g/m2)を用い、これに製造例1で得た熱硬化性樹脂組成物1を含浸塗工した後、110℃で3分加熱乾燥することにより、ガラス繊維の含有量が45体積%であるプリプレグを得た。該プリプレグを用いて、実施例1と同様にして積層板を作製した。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表1に示す。なお、表1では、比較例1で作製した積層体に生じたそり量を基準(100)とした。
特許文献2に記載の方法に準拠して、繊維径(直径)5μmのガラス繊維フィラメントが200本集束したガラス繊維束を開繊せずにそのまま熱硬化性樹脂組成物1が塗工された厚さ10.5μmの樹脂塗工フィルム4上にピッチ0.5mmで引き揃えた。その上に前記の厚さ10.5μmの樹脂塗工フィルム4を、樹脂塗工面を下にして貼り付け、カスレが生じ始める程度の限界含有量のガラス繊維束を含有させたプリプレグを得た。
熱ローラーを使用し、圧力1MPa、温度150℃、送り速度1m/分でBステージ化したところ、ガラス繊維の含有量が59体積%のプリプレグとなった。
上記で作製したプリプレグ8枚を図8が示す様に積層し、真空プレスを使用し、昇温速度3℃/分、245℃で85分保持、圧力2MPaの条件で加熱加圧することによって積層板を得た。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表1に示す。
一方、平織ガラスクロスを用いた比較例1では、ガラス繊維の含有率が45体積%にしかならず、低熱膨張率化されていないと共に、曲げ弾性率も低くなり、且つ、発生したそりの低減が課題となった。さらに、比較例2のように、特許文献2に記載の方法に準拠して作製したプリプレグではカスレを最低限に抑えようとしたものの、多量のカスレが発生してしまい、且つ、そのときのガラス繊維の含有率は59体積%までにしか高められず、低熱膨張率化には限界があると共に、曲げ弾性率は35GPaであって、そりの低減効果には改善の余地があると言える。
エポキシ樹脂として「NC-7000L」(商品名、日本化薬株式会社製)、マレイミド樹脂としてビスマレイミド化合物とジアミン化合物との付加反応物、硬化促進剤として「G-8009L」(商品名、イソシアネートマスクイミダゾール、第一工業製薬株式会社製)、無機充填材として溶融球状シリカ(商品名、平均粒子径0.5μm、株式会社アドマテックス製)、酸化防止剤として「ヨシノックスBB」[商品名、4,4’-ブチリデンビス-(6-t-ブチル-3-メチルフェノール)、三菱ケミカル株式会社製]をメチルエチルケトン及びシクロヘキサノン混合溶媒中で混合し、固形分濃度55質量%の熱硬化性樹脂組成物2を得た。
エポキシ樹脂として「NC-7000L」(商品名、日本化薬株式会社製)、マレイミド樹脂としてビスマレイミド化合物とジアミン化合物との付加反応物、硬化促進剤として「G-8009L」(商品名、イソシアネートマスクイミダゾール、第一工業製薬株式会社製)、無機充填材として溶融球状シリカ(商品名、平均粒子径0.5μm、株式会社アドマテックス製)、酸化防止剤として「ヨシノックスBB」[商品名、4,4’-ブチリデンビス-(6-t-ブチル-3-メチルフェノール)、三菱ケミカル株式会社製]をメチルエチルケトン及びシクロヘキサノン混合溶媒中で混合し、固形分濃度55質量%の熱硬化性樹脂組成物3を得た。
エポキシ樹脂として「NC-7000L」(商品名、日本化薬株式会社製)、マレイミド樹脂としてビスマレイミド化合物とジアミン化合物との付加反応物、硬化促進剤として「G-8009L」(商品名、イソシアネートマスクイミダゾール、第一工業製薬株式会社製)、無機充填材として溶融球状シリカ(商品名、平均粒子径0.5μm、株式会社アドマテックス製)、酸化防止剤として「ヨシノックスBB」[商品名、4,4’-ブチリデンビス-(6-t-ブチル-3-メチルフェノール)、三菱ケミカル株式会社製]をメチルエチルケトン及びシクロヘキサノン混合溶媒中で混合し、固形分濃度55質量%の熱硬化性樹脂組成物4を得た。
キャリア材として厚さ38μmのポリエチレンテレフタレートフィルムを使用し、製造例2で得た熱硬化性樹脂組成物2を厚み10μmで前記キャリア材上に塗工し、厚さ10μmの樹脂塗工フィルム2を形成した。
次いで、繊維径(直径)12μmのガラス繊維フィラメントが6,000本集束したガラス繊維束を開繊倍率2.6倍に開繊し、開繊して得られたガラス繊維フィラメントを横に並べて300mm幅にし、前記厚さ10μmの樹脂塗工フィルム2上に引き揃えた。その上にもう一枚の前記厚さ10μmの樹脂塗工フィルム2を、樹脂塗工面を下にして貼り付けた。
こうして得られたプリプレグ前駆体について、熱ローラーを使用し、圧力1MPa、温度150℃、送り速度1m/分でBステージ化することによって、ガラス繊維の含有量が60体積%(ガラス繊維と無機充填材の合計含有量65体積%)のプリプレグを得た。
上記で作製したプリプレグ8枚を図5が示す様に積層し、真空プレスを使用し、昇温速度3℃/分、245℃で85分保持、圧力2MPaの条件で加熱加圧することによって積層板を得た。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表2に示す。
実施例4において、製造例3で得た熱硬化性樹脂組成物3を厚み10μmで前記キャリア材上に塗工して厚さ10μmの樹脂塗工フィルム3を形成し、これを樹脂塗工フィルム2の代わりに用いたこと以外は同様にして操作を行い、ガラス繊維の含有量が60体積%(ガラス繊維と無機充填材の合計含有量70体積%)のプリプレグを得た。該プリプレグを用いて、実施例4と同様にして積層板を作製した。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表2に示す。
実施例5において、ガラス繊維として平織ガラスクロス(100g/m2)を用い、熱硬化性樹脂組成物3の代わりに製造例4で得た熱硬化性樹脂組成物4を平織ガラスクロスに含浸塗工した後、110℃で3分加熱乾燥することにより、ガラス繊維の含有量が45体積%(ガラス繊維と無機充填材の合計含有量70体積%)のプリプレグを得たこと以外は同様にして積層板を作製した。
積層板中のガラス繊維及び無機充填材の合計含有量は70体積%であり、実施例5において作製した積層板中のガラス繊維及び無機充填材の合計含有量と同じであるが、積層体にそり(表2では、比較例3における積層体のそり量を基準(100)とした。)が生じ、これを低減することが本発明の課題となった。
得られた積層板を用いて、前記方法に従って各評価を行った。結果を表2に示す。
比較例3において、熱硬化性樹脂組成物4の塗工量を減らしたこと以外は同様にして操作を行い、ガラス繊維の含有量が60体積%(ガラス繊維と無機充填材の合計含有量85体積%)のプリプレグを得、比較例3と同様にして積層板を作製した。
積層板中のガラス繊維及び無機充填材の合計含有量を、比較例3(70体積%)に対して増量して低熱膨張化させることによってそりの低減を試みた結果、積層板の表面に多量のカスレが観察された。
一方、平織ガラスクロスを用いた比較例3では、ガラス繊維の含有率が45体積%にしかならず、低熱膨張率化されていないと言え、且つ、発生したそりの低減が課題となった。また、曲げ弾性率も低下した。比較例3におけるそりを改善すべくガラス繊維の含有量を増大させた比較例4では、積層板の表面に多量のカスレが生じた。
2 キャリア材
3 ガラス繊維フィラメント
4 熱硬化性樹脂組成物
5 積層板
31 縦方向ガラス繊維フィラメント
32 横方向ガラス繊維フィラメント
Claims (15)
- ガラス繊維及び熱硬化性樹脂組成物を含有してなるプリプレグであって、複数のガラス繊維フィラメントが一方向に略平行に延在して配置された層を含有するプリプレグ。
- ガラス繊維フィラメントが50本以上集束したガラス繊維束を含有しないか、又は含有していてもその含有量がプリプレグ中のガラス繊維全量に対して10体積%以下である、請求項1に記載のプリプレグ。
- ガラス繊維の含有量がプリプレグ全体に対して50~75体積%である、請求項1又は2に記載のプリプレグ。
- ガラス繊維の含有量がプリプレグ全体に対して60~75体積%である、請求項1~3のいずれか1項に記載のプリプレグ。
- 前記熱硬化性樹脂組成物が無機充填材を含有しないか、又は含有していてもその含有量が、熱硬化性樹脂組成物中、12体積%以下である、請求項1~4のいずれか1項に記載のプリプレグ。
- 厚みが100μm以下である、請求項1~5のいずれか1項に記載のプリプレグ。
- 請求項1~6のいずれか1項に記載のプリプレグを含有してなる積層板であって、
複数のガラス繊維フィラメントが一方向に略平行に延在して配置された層と、前記一方向とは異なる他の一方向に複数のガラス繊維フィラメントが略平行に延在して配置された層とを含有する、積層板。 - 前記一方向とは異なる他の一方向が、前記一方向と略直交する他の一方向である、請求項7に記載の積層板。
- 前記積層板の厚さ方向の断面において、中心から上部と下部とが略面対称になっている、請求項7又は8に記載の積層板。
- 25℃における曲げ弾性率が35GPa以上である、請求項7~9のいずれか1項に記載の積層板。
- 請求項7~10のいずれか1項に記載の積層板を含有してなるプリント配線板。
- 請求項11に記載のプリント配線板に半導体素子を搭載してなる半導体パッケージ。
- 下記工程を有する、プリプレグの製造方法。
(1)ガラス繊維束を開繊して複数のガラス繊維フィラメントを形成する、開繊工程。
(2)熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に、前記開繊工程で形成した複数のガラス繊維フィラメントを一方向に略平行に延在して配置し、プリプレグを形成する工程。 - 下記工程を有する、積層板の製造方法。
(1)ガラス繊維束を開繊して複数のガラス繊維フィラメントを形成する、開繊工程。
(2)熱硬化性樹脂組成物を表面に塗布したキャリア材の当該表面上に、前記開繊工程で形成した複数のガラス繊維フィラメントを一方向に略平行に延在して配置し、プリプレグを形成する工程。
(3)前記工程(2)によって形成されたプリプレグ2枚以上を準備し、少なくとも1対のプリプレグにおいて、一方のプリプレグ中の複数のガラス繊維フィラメントの延在方向と、他方のプリプレグ中の複数のガラス繊維フィラメントの延在方向とが異なるように積層し、加熱加圧する工程。 - 一方のプリプレグ中の複数のガラス繊維フィラメントの延在方向と、他方のプリプレグ中の複数のガラス繊維フィラメントの延在方向とが略直交する、請求項14に記載の積層板の製造方法。
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2017
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2018
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CN111448044A (zh) | 2020-07-24 |
CN111448043A (zh) | 2020-07-24 |
US20200404783A1 (en) | 2020-12-24 |
CN111448044B (zh) | 2022-07-08 |
JP7210847B2 (ja) | 2023-01-24 |
CN111432995A (zh) | 2020-07-17 |
WO2019112065A1 (ja) | 2019-06-13 |
JPWO2019112067A1 (ja) | 2020-12-10 |
TW201932283A (zh) | 2019-08-16 |
KR20200092979A (ko) | 2020-08-04 |
TW202327858A (zh) | 2023-07-16 |
JPWO2019112065A1 (ja) | 2020-12-03 |
WO2019111416A1 (ja) | 2019-06-13 |
JPWO2019112066A1 (ja) | 2020-12-10 |
WO2019112067A1 (ja) | 2019-06-13 |
TWI798309B (zh) | 2023-04-11 |
JPWO2019111416A1 (ja) | 2020-12-10 |
TW201925291A (zh) | 2019-07-01 |
TW201930423A (zh) | 2019-08-01 |
CN111448043B (zh) | 2022-05-13 |
TWI805658B (zh) | 2023-06-21 |
CN111432995B (zh) | 2022-11-29 |
TWI797210B (zh) | 2023-04-01 |
KR102649654B1 (ko) | 2024-03-19 |
JP7276142B2 (ja) | 2023-05-18 |
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