WO2012105442A1 - 粗化硬化物及び積層体 - Google Patents
粗化硬化物及び積層体 Download PDFInfo
- Publication number
- WO2012105442A1 WO2012105442A1 PCT/JP2012/051787 JP2012051787W WO2012105442A1 WO 2012105442 A1 WO2012105442 A1 WO 2012105442A1 JP 2012051787 W JP2012051787 W JP 2012051787W WO 2012105442 A1 WO2012105442 A1 WO 2012105442A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cured product
- silica
- roughened
- image
- epoxy resin
- Prior art date
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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- C08K3/36—Silica
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
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- Y10T428/24372—Particulate matter
- Y10T428/24421—Silicon containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Definitions
- the present invention uses a roughened cured product obtained by proceeding curing of an epoxy resin material to obtain a precured product and then roughening the surface of the precured product, and the roughened cured product. Relates to the laminated body.
- a resin composition is used in order to form an insulating layer for insulating inner layers or to form an insulating layer located in a surface layer portion.
- Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, a phenoxy resin, and an inorganic filler having an average particle diameter of 0.01 to 2 ⁇ m. Has been. Further, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, and an inorganic filler having an average particle diameter of 0.1 to 10 ⁇ m.
- each layer of a multilayer film having a two-layer laminated structure is formed using two different types of resin compositions described above. It is described that this multilayer film is satisfactorily embedded in a gap or the like provided on the substrate.
- Patent Document 2 discloses a resin composition containing an epoxy resin, a curing agent, at least one of a phenoxy resin and a polyvinyl acetal resin, and a phosphorus-containing benzoxazine compound.
- Patent Document 2 when a cured product obtained by curing a resin composition is roughened, the roughened surface exhibits high adhesion to the plated conductor even though the roughness of the roughened surface is relatively small.
- an insulating layer excellent in flame retardancy can be obtained.
- Patent Literature 1 When the resin composition described in Patent Literature 1 is pre-cured and then roughened, the roughness of the roughened surface may not be sufficiently reduced.
- Patent Document 2 describes that the resin composition has the above-described composition, the roughness is reduced. However, even when the resin composition described in Patent Document 2 is used, the roughness of the roughened surface. May not be small enough.
- the object of the present invention is to reduce the surface roughness of the roughened surface and to increase the adhesive strength between the cured product obtained by curing the roughened cured product and the metal layer. And a laminate using the roughened cured product.
- a roughened cured product obtained by roughening the surface of the precured product
- the epoxy resin material contains an epoxy resin, a curing agent, and silica having an average particle diameter of 0.2 ⁇ m or more and 1.2 ⁇ m or less
- the roughened surface is photographed with a scanning electron microscope
- the maximum length of the exposed portion in the above-mentioned image, which is silica exposed from the roughened surface in a 5 ⁇ m ⁇ 5 ⁇ m area of the roughened surface in the photographed image A roughened cured product having 15 or less silica having a diameter of 0.3 ⁇ m or more is provided.
- the roughened surface of the roughened cured product When the roughened surface of the roughened cured product is photographed with a scanning electron microscope, it appears in the image in an area of 5 ⁇ m ⁇ 5 ⁇ m of the roughened surface in the photographed image. Of the total number of holes and silica appearing in the image, the silica is exposed from the roughened surface, and the maximum length of the exposed portion in the image is 0.3 ⁇ m or more. The ratio of the number of certain silica is preferably 20% or less.
- the image is displayed in a region of 5 ⁇ m ⁇ 5 ⁇ m of the roughened surface in the photographed image.
- the ratio of the number of silicas that are exposed from the roughened surface and that have a maximum length of 0.3 ⁇ m or more in the above image of the exposed portion is 50 % Or less is preferable.
- the content of the silica is 55% by weight or more and 80% by weight or less in 100% by weight of the total solid content contained in the epoxy resin material.
- the arithmetic average roughness Ra of the roughened surface is 0.3 ⁇ m or less, and the ten-point average roughness Rz is 3.0 ⁇ m or less.
- the precured product is subjected to a swelling treatment before the roughening treatment.
- the laminated body which concerns on this invention is equipped with the hardened
- the adhesive strength between the cured product and the metal layer is preferably 3.9 N / cm 2 or more.
- the roughened cured product according to the present invention is obtained by proceeding the curing of the epoxy resin material to obtain a precured product, and then roughening the surface of the precured product.
- An image taken when a roughened surface was photographed with a scanning electron microscope, including an epoxy resin, a curing agent, and silica having an average particle diameter of 0.2 ⁇ m or more and 1.2 ⁇ m or less.
- the silica exposed from the roughened surface and the maximum length of the exposed portion in the above image is 0.3 ⁇ m or more Since the number of silica is 15 or less, the surface roughness of the roughened surface of the roughened cured product can be reduced.
- the adhesive strength between the cured product and the metal layer can be increased.
- FIG. 1A is a diagram schematically showing an image obtained by photographing the roughened surface of the roughened cured product with a scanning electron microscope in the roughened cured product according to the embodiment of the present invention.
- FIG.1 (b) is a partial notch front sectional drawing which shows a roughening hardened
- FIG. 2A is a diagram schematically showing an image obtained by photographing a roughened surface of the roughened cured product with a scanning electron microscope in the roughened cured product according to another embodiment of the present invention.
- FIG. 2 (b) is a partially cutaway front sectional view schematically showing the roughened cured product.
- FIG. 3 is a partially cutaway front sectional view schematically showing a laminate using the roughened cured product according to one embodiment of the present invention.
- the roughened cured product according to the present invention is a roughened cured product obtained by proceeding the curing of the epoxy resin material to obtain a precured product and then roughening the surface of the precured product.
- the said epoxy resin material contains an epoxy resin, a hardening
- FIG. 1A is a diagram schematically showing an image obtained by photographing a roughened surface of a roughened cured product with a scanning electron microscope in the roughened cured product according to an embodiment of the present invention.
- FIG.1 (b) is a partially notched front sectional drawing which shows typically the roughening hardened
- the roughened cured product 1 shown in FIG. 1 is laminated on the upper surface 6 a of the lamination target member 6.
- the roughened cured product 1 has a first surface 1a and a second surface 1b.
- the first surface 1a is roughened.
- the second surface 1 b is in contact with the upper surface 6 a of the stacking target member 6.
- the epoxy resin material for obtaining the roughened cured product 1 includes an epoxy resin, a curing agent, and silica 2 having an average particle diameter of 0.2 ⁇ m or more and 1.2 ⁇ m or less.
- FIG. 1A the silica 2 indicated by hatching is exposed, and the exposed portion of the silica 2 indicated by hatching is shown.
- silica 2 indicated by dots is not exposed, but is silica that appears in the photographed image.
- FIG. 2A is a diagram schematically showing an image obtained by photographing the roughened surface of the roughened cured product with a scanning electron microscope in the roughened cured product according to another embodiment of the present invention.
- FIG. 2B is a partially cutaway front sectional view schematically showing a roughened cured product according to an embodiment of the present invention.
- the roughened cured product 11 has a first surface 11a and a second surface 11b.
- the first surface 11a is roughened.
- the second surface 11 b is in contact with the upper surface 16 a of the stacking target member 16.
- the epoxy resin material for obtaining the roughened cured product 11 includes an epoxy resin, a curing agent, and silica 12 having an average particle diameter of 0.2 ⁇ m or more and 1.2 ⁇ m or less.
- a plurality of holes 1c and 11c are present on the roughened first surfaces 1a and 11a.
- silica 2 and 12 are not present, or silica 2 and 12 are present, respectively.
- the roughened cured products 1 and 11 when the roughened first surfaces 1a and 11a were photographed with a scanning electron microscope, the roughened first surfaces 1a and 11a in the photographed images were taken.
- silica number A In a region having a size of 5 ⁇ m ⁇ 5 ⁇ m, silica 2 and 12 exposed from the roughened first surfaces 1a and 11a, and the maximum length of the exposed portion in the above image is 0.3 ⁇ m
- the number of silicas 2 and 12 (hereinafter may be referred to as silica number A) is 15 or less.
- the number A of the silica is preferably 12. Below, more preferably 8 or less. In the present invention, the number A of silica is not 0, but may be 1 or more. If the number A of silica is 1 or more but 15 or less, the surface roughness of the roughened cured product is reduced, and the adhesive strength between the cured product and the metal layer is reduced. Can be high.
- the roughened first surfaces 1a and 11a in the photographed images are taken.
- the ratio of the number n of silica 2 and 12 exposed from 1a and 11a and having a maximum length of 0.3 ⁇ m or more in the above image of the exposed portion hereinafter referred to as the number of silicas).
- the ratio B may be 20% or less.
- the ratio B (%) is obtained by the formula: number n / total number Nb ⁇ 100.
- the ratio B of the number of silica is more preferable. Is 15% or less, more preferably 10% or less.
- the ratio B of the number of silica may not be 0%, may exceed 0%, and may exceed 1%. Even if the ratio B of the number of silica exceeds 0% or exceeds 1%, the surface roughness of the roughened cured surface of the roughened cured product is effective as long as it is 20% or less. And the adhesive strength between the cured product and the metal layer can be effectively increased.
- the roughened first surfaces 1a and 11a when the roughened first surfaces 1a and 11a are photographed with a scanning electron microscope, the roughened first surfaces 1a and 11a in the photographed images are taken.
- the ratio of the number n of silica 2 and 12 whose maximum length in the above image of the exposed portion is 0.3 ⁇ m or more (hereinafter sometimes referred to as the ratio C of the number of silica) is 50% or less.
- the ratio C (%) is obtained by the formula: number n / number nc ⁇ 100.
- the ratio C of the number of silica is more preferable. Is 40% or less, more preferably 30% or less.
- the ratio C of the number of silicas may not be 0%, may exceed 0%, and may exceed 1%. Even if the ratio C of the number of silica exceeds 0% or exceeds 1%, the surface roughness of the roughened cured surface of the roughened cured product is effective if it is 50% or less. And the adhesive strength between the cured product and the metal layer can be effectively increased.
- the plating solution is placed on the exposed silica portion by plating for forming a metal layer. For this reason, there exists a tendency for the adhesive strength of hardened
- the insulation fall by the roughening liquid remaining between a silica and a resin component can be prevented.
- the ratio B of the number of silicas or the ratio C of the number of silicas is not more than the above value, fine pores can be formed more effectively on the roughened surface of the roughened cured product. The surface roughness of the treated surface can be effectively reduced.
- the number A of the silica is not more than the above value in the present invention.
- the ratio B of the number of silicas may be equal to or less than the above value, or the ratio C of the number of silicas may be equal to or less than the above value.
- the ratio B of the number of silicas or the ratio C of the number of silicas is as described above. If it is below the value, the surface roughness of the roughened surface of the roughened cured product can be effectively reduced, and the adhesive strength between the cured product and the metal layer can be effectively increased.
- the metal layer is less likely to swell when the metal layer is formed on the surface of the roughened cured product and the roughened cured product is cured. Becomes difficult to peel off from the surface of the cured product. Further, in the reflow process, the metal layer is hardly swollen and the metal layer is difficult to peel off from the surface of the cured product.
- the ratio B of the number of silicas or the ratio C of the number of silicas is equal to or less than the above value, when forming a metal layer on the surface of the roughened cured product and curing the roughened cured product, Swelling of the metal layer is less likely to occur effectively, and the metal layer is more difficult to peel from the surface of the cured product. Further, even in the reflow process, the metal layer is hardly swelled effectively, and the metal layer is more difficult to peel from the surface of the cured product.
- the number A of silica, the ratio B of the number of silicas, or the ratio C of the number of silicas to the above value or less examples thereof include a method using a resin component and silica that are sometimes appropriately dissolved, and a method using a roughening solution capable of appropriately dissolving the resin component and the silica in order to dissolve the resin component and silica.
- the resin component includes the epoxy resin and the curing agent.
- the exposed amount of silica tends to increase. If the resin component is not excessively dissolved, the pores are not easily formed. Moreover, when the said resin component melt
- the total weight of the epoxy resin used is 100% by weight.
- the first method to make the proportion of the epoxy resin having an epoxy equivalent of 150 or more occupy 75% by weight or more
- (2) of the epoxy resin that is liquid at normal temperature (23 ° C.) occupying 100% by weight of the total epoxy resin used examples include a second method in which the ratio is 40% by weight or more, and (3) a third method in which the surface of silica is treated to be hydrophobic. Methods other than these first to third methods may be used.
- the first method functional groups (hydroxy group, ester group, oxazoline ring, etc.) generated after curing are prevented from concentrating locally, an increase in water absorption is suppressed, and the resin component is hardly roughened. , Silica exposure can be suppressed.
- the second method since the fluidity of the uncured product (B-stage state) is high, a certain degree of fluidity can be secured even during curing until the curing proceeds sufficiently. As a result, the epoxy group of the epoxy resin and the curing agent It becomes easy to approach the reactive group. For this reason, it is possible to increase the reaction rate, to suppress a large amount of unreacted groups from remaining, to suppress an increase in the water absorption rate, to prevent excessive roughening, and to suppress silica exposure.
- silica surface-treated with a silane coupling agent such as epoxy silane, vinyl silane, or phenyl silane can be used to make the surface of the silica hydrophobic. Further, in the third method, the penetration of the roughening liquid from the interface between the resin component and silica is suppressed, the resin component is hardly roughened more than necessary, and the silica exposure can be suppressed.
- holes 11c are present on the first surface 11a subjected to the roughening treatment.
- the hole 11c there is no residual silica 12X, or there is residual silica 12X.
- the size of the roughened first surface 11a in the photographed image is 5 ⁇ m ⁇ 5 ⁇ m.
- the residual silica 12X in the hole 11c appearing in the image, and the maximum length (L2 in FIG. 2A) in the image is 0.3 ⁇ m or more, or the image 2 (L2 in FIG. 2A) is less than 0.3 ⁇ m, and the maximum length in the above image (L2 in FIG.
- the number of residual silica 12X that is two-thirds or more of the maximum length (L1 in FIG. 2A) ( ⁇ m) of the hole 11c in the image (hereinafter referred to as the number D of residual silica) Is preferably 15 or less.
- the surface roughness of the roughened surface of the roughened cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased.
- the “number of remaining silicas D” is the number of remaining silicas 12X in the holes 11c appearing in the image and having a maximum length of 0.3 ⁇ m or more in the image, Residual silica 12X in the holes 11c appearing in the image, wherein the maximum length in the image is less than 0.3 ⁇ m and the maximum length ( ⁇ m) in the image is the residual silica 12X This is the total with the number D2 of residual silica 12X that is two-thirds or more of the maximum length ( ⁇ m) in the above image of the hole 11c.
- the number D2 has a maximum length ( ⁇ m) with respect to the maximum length ( ⁇ m) in the image of the hole 11c in which the maximum length in the image is less than 0.3 ⁇ m and the residual silica 12X is present.
- ⁇ m) is the number of residual silica 12X having two-thirds or more.
- the number D of the residual silica is more preferably 12 or less, more preferably 8 or less.
- the number D of residual silicas is not zero, and may be one or more. If the number D of residual silica is 1 or more and 15 or less, the surface roughness of the roughened surface of the roughened cured product is effectively reduced, and the cured product, the metal layer, The adhesive strength can be effectively increased.
- the roughened first surface 11a in the photographed image has a size of 5 ⁇ m ⁇ 5 ⁇ m.
- the total number Ne of the holes 11c without the residual silica 12X appearing in the image and the holes with the residual silica 12X appearing in the image the residual silica 12X in the hole 11c appearing in the image.
- the maximum length in the image (L2 in FIG. 2A) is 0.3 ⁇ m or more, or the maximum length in the image (L2 in FIG. 2A) is less than 0.3 ⁇ m. And the maximum length in the above image (L2 in FIG.
- the ratio E of the number of a certain residual silica hole and is to be described is preferably 20% or less. In this case, the surface roughness of the roughened surface of the roughened cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased.
- the ratio E is obtained by the formula: number n / total number Ne ⁇ 100.
- ratio E of the number of holes with residual silica appears in the image out of the total number Ne of the holes 11c without residual silica 12X and the holes 11c with residual silica 12X appearing in the image.
- the total number Ne of the holes 11c having no residual holes 11c and the holes 11c having the residual silica 12X the residual silica 12X in the holes 11c appearing in the image, and the maximum length in the image is less than 0.3 ⁇ m.
- the ratio E1 (%) is obtained by the formula: number n1 / total number Ne ⁇ 100.
- the ratio E2 (%) is obtained by the formula: number n2 / total number Ne ⁇ 100.
- the ratio of the number of pores having the residual silica. E is more preferably 15% or less, still more preferably 10% or less.
- the ratio E of the number of pores with the residual silica may not be 0%, may exceed 0%, and may exceed 1%. Even if the ratio E of the number of pores having the residual silica exceeds 0% or exceeds 1%, the surface roughness of the roughened surface of the roughened cured product is 20% or less. The thickness can be effectively reduced, and the adhesive strength between the cured product and the metal layer can be effectively increased.
- the roughened first surface 11a in the photographed image has a size of 5 ⁇ m ⁇ 5 ⁇ m.
- the maximum length in the image (FIG. L2) in 2 (a) is 0.3 ⁇ m or more, or the maximum length in the image (L2 in FIG. 2A) is less than 0.3 ⁇ m and the maximum length in the image (L2 in FIG. 2 (a)) ( ⁇ m) is not less than two-thirds of the maximum length (L1 in FIG.
- the ratio n of the number of holes with a certain residual silica (hereinafter referred to as the ratio of the number of holes with a residual silica) May be referred to as F) is preferably at most 50%. In this case, the surface roughness of the roughened surface of the roughened cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased.
- the ratio F is obtained by the formula: number n / total number Nf ⁇ 100.
- the “ratio F of the number of holes having residual silica” is the residual silica 12X in the holes 11c appearing in the image out of the number Nf of the holes 11c having the residual silica 12X appearing in the image.
- the residual silica 12X in the hole 11c appearing in the image, wherein the maximum length in the image is less than 0.3 ⁇ m and the maximum length ( ⁇ m) in the image is the residual silica 12X 11c is the sum of the ratio F2 of the number n2 of holes 11c having the residual silica 12X that is two-thirds or more of the maximum length ( ⁇ m) in the above image.
- the ratio F1 (%) is obtained by the formula: number n1 / total number Nf ⁇ 100.
- the ratio F2 (%) is determined
- the ratio of the number of pores having the residual silica. F is more preferably 40% or less, still more preferably 30% or less.
- the ratio F of the number of pores with the residual silica may not be 0%, may exceed 0%, and may exceed 1%. Even if the ratio F of the number of pores where the residual silica is present exceeds 0% or exceeds 1%, the surface roughness of the roughened surface of the roughened cured product is 50% or less. The thickness can be effectively reduced, and the adhesive strength between the cured product and the metal layer can be effectively increased.
- the roughening liquid enters the periphery of the residual silica, and defects such as defective plating are likely to occur. Further, the plating solution tends to remain around the remaining silica. If the number D of the residual silica, the ratio E of the pores with the residual silica or the ratio F of the number of the holes with the residual silica is equal to or less than the above value, the surface of the roughened cured product is finely ground. Holes can be formed, and the surface roughness of the roughened surface can be effectively reduced. As a result, the adhesive strength between the cured product and the metal layer is also increased. Moreover, the insulation fall by the roughening liquid remaining between a silica and a resin component can be prevented.
- the number D of residual silica is used in the present invention. May be equal to or less than the above value, the ratio E of the pores with the residual silica may be equal to or less than the above value, or the ratio F of the holes with the residual silica may be equal to or less than the above value.
- the silica content in the total solid content of 100% by weight contained in the epoxy resin material is 55% by weight or more, the number D of the residual silicas and the ratio E of the pores with the residual silicas. If the ratio F of pores with the residual silica is equal to or less than the above value, the surface roughness of the roughened cured product is effectively reduced, and the cured product and the metal layer are bonded. The strength can be effectively increased.
- the number D of the residual silica, the ratio E of the holes with the residual silica, or the ratio F of the holes with the residual silica is equal to or less than the above value, a metal layer is formed on the surface of the roughened cured product.
- swelling of the metal layer is less likely to occur effectively, and the metal layer is more difficult to peel from the surface of the cured product.
- the metal layer is hardly swelled effectively, and the metal layer is more difficult to peel from the surface of the cured product. As a result, the adhesive strength between the cured product and the metal layer is effectively increased.
- the resin component and the silica contained in the epoxy resin material are used.
- the resin component includes the epoxy resin and the curing agent.
- the resin component If the resin component is excessively dissolved by the roughening treatment, it is necessary to shorten the roughening time in order to secure a fine rough surface. Therefore, the residual amount of silica increases. . Moreover, when the said resin component melt
- silica surface-treated with a silane coupling agent such as epoxy silane, vinyl silane, or phenyl silane can be used.
- Epoxy resin material [Epoxy resin]
- Epoxy resin material The epoxy resin contained in the epoxy resin material is not particularly limited. A conventionally well-known epoxy resin can be used as this epoxy resin.
- the epoxy resin refers to an organic compound having at least one epoxy group. As for an epoxy resin, only 1 type may be used and 2 or more types may be used together.
- epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenyl novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, and fluorene type epoxy resin. , Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having adamantane skeleton, epoxy resin having tricyclodecane skeleton, and epoxy resin having triazine nucleus in skeleton Etc.
- the epoxy resin is a bisphenol A type epoxy resin.
- Bisphenol F type epoxy resin, biphenyl novolak type epoxy resin, biphenol type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, or dicyclopentadiene type epoxy resin are preferable.
- the epoxy resin is particularly preferably a biphenyl novolac type epoxy resin, a phenol aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin or a dicyclopentadiene type epoxy resin.
- the epoxy equivalent of the epoxy resin is preferably 90 or more, more preferably 100 or more, preferably 1000 or less, more preferably 800 or less.
- the weight average molecular weight of the epoxy resin is preferably 1000 or less.
- the content of silica in the epoxy resin material can be increased. Furthermore, even if there is much content of a silica, the resin composition which is an epoxy resin material with high fluidity
- the curing agent contained in the epoxy resin material is not particularly limited.
- a conventionally known curing agent can be used as the curing agent.
- curing agent only 1 type may be used and 2 or more types may be used together.
- cyanate ester resin cyanate ester curing agent
- phenol compound phenol curing agent
- amine compound amine curing agent
- thiol compound thiol curing agent
- imidazole compound phosphine compound
- acid anhydride Examples include active ester compounds and dicyandiamide.
- curing agent is cyanate ester resin or a phenol compound.
- the curing agent is preferably a cyanate ester resin, and is preferably a phenol compound.
- the curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy resin.
- the curing agent is a cyanate ester resin, phenol. It is preferably a compound or an active ester compound. Furthermore, from the viewpoint of imparting better insulation reliability with a curing agent, the curing agent is more preferably a cyanate ester resin.
- the cyanate ester resin is not particularly limited.
- a conventionally known cyanate ester resin can be used as the cyanate ester resin.
- As for the said cyanate ester resin only 1 type may be used and 2 or more types may be used together.
- Examples of the cyanate ester resin include novolak type cyanate resin and bisphenol type cyanate resin.
- Examples of the bisphenol type cyanate resin include bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethylbisphenol F type cyanate resin.
- cyanate ester resins include phenol novolac type cyanate resins (“PT-30” and “PT-60” manufactured by Lonza Japan), and prepolymers obtained by triazation of bisphenol A dicyanate into trimers. (Lonza Japan “BA230”, “BA200” and “BA3000”).
- the use of the above phenolic compound can further increase the adhesive strength between the cured product and the metal layer. Moreover, by using the phenol compound, for example, the adhesion between the cured product and copper can be further enhanced by blackening or Cz treatment of the surface of copper provided on the surface of the cured product.
- the phenol compound is not particularly limited.
- a conventionally well-known phenol compound can be used as this phenol compound.
- As for the said phenol compound only 1 type may be used and 2 or more types may be used together.
- phenol compound examples include novolak type phenol, biphenol type phenol, naphthalene type phenol, dicyclopentadiene type phenol, aralkyl type phenol, and dicyclopentadiene type phenol.
- phenol compounds include novolak type phenol (“TD-2091” manufactured by DIC), biphenyl novolac type phenol (“MEH-7851” manufactured by Meiwa Kasei Co., Ltd.) and aralkyl type phenol compound (“MEH manufactured by Meiwa Kasei Co., Ltd.). -7800 ").
- the phenol compound is a biphenyl novolac type phenol, Or it is preferable that it is an aralkyl type phenol compound.
- the active ester compound is not particularly limited. Commercially available products of the above active ester compounds include “HPC-8000” manufactured by DIC.
- the curing agent preferably contains a curing agent having an equivalent weight of 250 or less.
- the equivalent of the curing agent indicates a cyanate ester group equivalent
- the curing agent is a phenol compound
- it indicates a phenolic hydroxyl group equivalent
- the curing agent is an active ester compound. Is the active ester group equivalent.
- the weight average molecular weight of the curing agent is preferably 1000 or less.
- the content of silica in the epoxy resin material can be increased, and a resin composition that is an epoxy resin material having high fluidity can be obtained even if the content of silica is large.
- total content of the epoxy resin and the curing agent in 100% by weight of the total solid content excluding the silica contained in the epoxy resin material is: Preferably it is 75 weight% or more, More preferably, it is 80 weight% or more, 100 weight% or less, Preferably it is 99 weight% or less, More preferably, it is 97 weight% or less.
- the total content of the epoxy resin and the curing agent is not less than the above lower limit and not more than the above upper limit, a better cured product can be obtained and the melt viscosity can be adjusted, so that the presence state of silica is changed.
- the B stage film can be prevented from spreading in an unintended region during the curing process. Furthermore, the dimensional change by the heat
- Total solid content B refers to the total of the epoxy resin, the curing agent, and other solid content blended as necessary. The total solid content B does not contain silica. “Solid content” refers to a non-volatile component that does not volatilize during molding or heating.
- the compounding ratio of the epoxy resin and the curing agent is not particularly limited.
- the compounding ratio of the epoxy resin and the curing agent is appropriately determined depending on the kind of the epoxy resin and the curing agent.
- the epoxy resin material contains silica.
- the average particle diameter of silica contained in the epoxy resin material is 0.2 ⁇ m or more and 1.2 ⁇ m or less.
- the average particle diameter of the silica is preferably 1 ⁇ m or less.
- a median diameter (d50) value of 50% is employed as the average particle diameter of the silica.
- the average particle size can be measured using a laser diffraction / scattering particle size distribution measuring apparatus.
- the silica is preferably surface-treated, and more preferably surface-treated with a coupling agent. As a result, the surface roughness of the roughened surface of the roughened cured product is further reduced, the adhesive strength between the cured product and the metal layer is further increased, and the inter-wiring insulation reliability is further improved. And interlayer insulation reliability can be provided.
- the coupling agent examples include silane coupling agents, titanate coupling agents, and aluminum coupling agents.
- the coupling agent used for the surface treatment is preferably epoxy silane, amino silane, vinyl silane, mercapto silane, sulfur silane, (meth) acrylic acid silane, isocyanate silane or ureido silane.
- the content of silica is not particularly limited.
- the content of the silica is preferably 30% by weight or more, more preferably 40% by weight in 100% by weight of the total solid content (hereinafter sometimes abbreviated as total solid content A) contained in the epoxy resin material. More preferably, it is 50% by weight or more, particularly preferably 55% by weight or more, preferably 85% by weight or less, more preferably 80% by weight or less.
- the content of the silica is particularly preferably 55% by weight or more and 80% by weight or less.
- Total solid content A refers to the sum of the epoxy resin, the curing agent, silica, and the solid content blended as necessary.
- Solid content refers to a non-volatile component that does not volatilize during molding or heating.
- the said epoxy resin material may contain the hardening accelerator as needed.
- the curing rate can be further increased.
- the crosslinked structure of the cured product can be made uniform, the number of unreacted functional groups can be reduced, and as a result, the crosslinking density can be increased.
- the curing accelerator is not particularly limited.
- As the curing accelerator a conventionally known curing accelerator can be used.
- As for the said hardening accelerator only 1 type may be used and 2 or more types may be used together.
- Examples of the curing accelerator include imidazole compounds, phosphorus compounds, amine compounds, and organometallic compounds.
- the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate,
- Examples of the phosphorus compound include triphenylphosphine.
- Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4,4-dimethylaminopyridine, and the like.
- Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III).
- the curing accelerator is particularly preferably an imidazole compound.
- the content of the curing accelerator is not particularly limited. From the viewpoint of efficiently curing the epoxy resin material, the content of the curing accelerator in the total solid content B of 100% by weight is preferably 0.01% by weight or more, and preferably 3% by weight or less.
- the total solid content B includes the curing accelerator.
- the epoxy resin material may contain a thermoplastic resin.
- thermoplastic resin By using thermoplastic resin, the followability to the unevenness of the circuit of the epoxy resin material is increased, the surface roughness of the roughened surface of the roughened cured product is further reduced, and the surface subjected to further roughening treatment The roughness can be made more uniform.
- thermoplastic resin examples include phenoxy resin and polyvinyl acetal resin. From the viewpoint of making silica present satisfactorily, further reducing the surface roughness of the roughened surface of the roughened cured product, and further increasing the adhesive strength between the cured product and the metal layer, the above thermoplasticity
- the resin is preferably a phenoxy resin.
- phenoxy resins examples include phenoxy resins having a skeleton such as a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a biphenyl skeleton, a novolac skeleton, and a naphthalene skeleton.
- the phenoxy resin Since the adhesive strength between the cured product and the metal layer can be increased when the surface of the precured product is roughened and then plated to form a metal layer, the phenoxy resin has a biphenyl skeleton. It is preferable to have a biphenol skeleton.
- phenoxy resin examples include, for example, “YP50”, “YP55” and “YP70” manufactured by Toto Kasei Co., Ltd., and “1256B40”, “4250”, “4256H40”, “4275” manufactured by Mitsubishi Chemical Corporation, “YX6954BH30”, “YX8100BH30”, “YL7600DMAcH25”, “YL7213BH30”, and the like.
- the weight average molecular weight of the phenoxy resin is preferably 5000 or more, and preferably 100,000 or less.
- the content of the thermoplastic resin is not particularly limited.
- the content of the thermoplastic resin in the total solid content B of 100% by weight is preferably 0.1% by weight or more, more preferably 0% 0.5% by weight or more, more preferably 1% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, and particularly preferably 15% by weight or less.
- the content of the thermoplastic resin is not less than the above lower limit and not more than the above upper limit, the dimensional change due to heat of the cured product is further reduced.
- corrugation of the circuit board of an epoxy resin material becomes it favorable that content of the said thermoplastic resin is below the said upper limit.
- the total solid content B includes the thermoplastic resin.
- epoxy resin materials include coupling agents, colorants, antioxidants, UV degradation inhibitors, antifoaming agents, and thickeners.
- a thixotropic agent and other resins other than those mentioned above may be added.
- Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents.
- Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane, and epoxy silane.
- the content of the coupling agent is not particularly limited.
- the content of the coupling agent is preferably 0.01% by weight or more and 5% by weight or less.
- the total solid content B includes the coupling agent.
- Examples of the other resin include polyphenylene ether resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, polyimide resin, benzoxazine resin, benzoxazole resin, bismaleimide resin, and acrylate resin.
- the epoxy resin material may contain a solvent.
- the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, Examples thereof include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone and naphtha which is a mixture.
- the said solvent only 1 type may be used and 2 or more types may be used together.
- a resin composition containing a solvent can be used as a varnish.
- the viscosity of the varnish can be adjusted by adjusting the solvent content according to the application.
- the content of the solvent is preferably 10 parts by weight or more and preferably 1000 parts by weight or less with respect to 100 parts by weight of the total solid content A.
- the epoxy resin material may be a resin composition or a B-stage film in which the resin composition is formed into a film.
- a B-stage film can be obtained by forming the resin composition into a film.
- an extrusion molding method is used in which the resin composition is melt-kneaded using an extruder, extruded, and then formed into a film using a T-die or a circular die.
- examples thereof include a casting molding method in which the resin composition is dissolved or dispersed in a solvent such as an organic solvent and then cast into a film, and other conventionally known film molding methods.
- the extrusion molding method or the casting molding method is preferable because the thickness can be reduced.
- the film includes a sheet.
- a B-stage film can be obtained by forming the resin composition into a film and drying by heating, for example, at 90 to 200 ° C. for 10 to 180 minutes so that curing by heat does not proceed excessively.
- the film-like resin composition that can be obtained by the drying process as described above is referred to as a B-stage film.
- the B-stage film is a semi-cured product in a semi-cured state.
- the semi-cured product is not completely cured and curing can proceed further.
- the said resin composition is used suitably in order to form a laminated film provided with a base material and the B stage film laminated
- a B-stage film of a laminated film is formed from the resin composition.
- Examples of the base material of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, polyimide resin film, metal foil such as copper foil and aluminum foil, and the like. Can be mentioned.
- the surface of the base material may be subjected to a release treatment as necessary.
- the thickness of the layer formed of the epoxy resin material is preferably equal to or greater than the thickness of the conductor layer that forms the circuit.
- the thickness of the layer formed of the epoxy resin material is preferably 5 ⁇ m or more, and preferably 200 ⁇ m or less.
- the epoxy resin material is a B-stage film, and after the B-stage film is laminated on the lamination target member, the B-stage film is cured to obtain a precured product.
- the method of laminating by laminating the B stage film may be a known method, and is not particularly limited.
- the B-stage film is laminated on a circuit board, preferably the laminated film is laminated from the B-stage film side, and pressurized using a pressure laminator. At this time, it may be heated or not heated.
- a parallel plate press type heat press the lamination target member and the B stage film or laminated film are heated and pressurized.
- the pre-cured product may be formed by pre-curing the B-stage film by heating and pressing. The heating temperature and the pressurizing pressure can be appropriately changed and are not particularly limited.
- the roll temperature is set to 20 to 200 ° C. under the conditions of a roll diameter of 60 mm and a roll peripheral speed of 0.1 to 10 m / min.
- the B-stage film is laminated on the circuit board, or the laminated film is laminated on the lamination target member from the B-stage film side.
- the B stage film can be precured by heat treatment to obtain a precured product.
- the base material of the laminated film may be removed before forming the precured product, or may be removed after forming the precured product. After laminating under such conditions, by performing a roughening treatment, fine irregularities can be formed on the surface of the roughened cured product.
- the surface smoothness of the precured product may be increased by performing a parallel plate heating press after roll lamination.
- a laminate of a circuit board and a B stage film or a laminated film may be heated and pressurized with a stainless steel plate having a thickness of 1 mm using a parallel plate heating press.
- a commercially available apparatus can be used as a pressurizing laminator such as a hot pressurizing roll laminator and a press machine such as a parallel plate heating press.
- Lamination with a roll laminator is preferably performed in a vacuum state.
- the material of the roll of the roll laminator can be appropriately selected from a rubber roll having a soft surface and a metal roll having a hard surface.
- the material of the flat plate of the parallel plate heating press is a hard metal.
- a release function is provided between a roll laminator roll and the above-described lamination target member, B-stage film or laminated film, or between a flat plate of a parallel plate heating press and the above-mentioned lamination target member, B-stage film or laminated film.
- a roll laminator roll and the above-described lamination target member, B-stage film or laminated film, or between a flat plate of a parallel plate heating press and the above-mentioned lamination target member, B-stage film or laminated film.
- an aluminum foil, a copper foil, a polyester resin film, a fluororesin film, or the like may be used.
- a flexible material such as a rubber sheet may be used.
- the pre-cured product is formed by laminating the laminated film on the circuit board from the B-stage film side, pressurizing it using a roll laminator, and then heating and heating using a parallel plate press type hot press machine. It is preferable to be a step of forming a precured product by pressing. In addition, the step of forming the precured product is performed by laminating the laminated film on the lamination target member from the B stage film side, pressurizing it using a roll laminator, and then using a parallel plate press type hot press machine. This is a process of heating and pressurizing to form a pre-cured product.
- the roughened cured product according to the present invention is obtained by roughening the first surface of the precured product.
- the rough-cured product is preferably subjected to a swelling treatment before the roughening treatment.
- the pre-cured product is preferably subjected to a swelling treatment after the pre-curing and before the roughening treatment.
- the pre-cured product may not necessarily be subjected to the swelling treatment.
- the laminated body which concerns on this invention is equipped with the hardened
- the adhesive strength between the cured product and the metal layer is preferably 3.9 N / cm 2 or more.
- the metal layer is preferably a copper layer, and more preferably a copper plating layer.
- the said epoxy resin material is used suitably in order to form an insulating layer in a printed wiring board.
- the printed wiring board can be obtained, for example, by heat-pressing the B stage film using a B stage film formed of the resin composition.
- a metal foil can be laminated on one side or both sides of the B-stage film.
- the method for laminating the B-stage film and the metal foil is not particularly limited, and a known method can be used.
- the B-stage film can be laminated on the metal foil using an apparatus such as a parallel plate press or a roll laminator while applying pressure while heating or without heating.
- the said epoxy resin material is used suitably in order to obtain a copper clad laminated board.
- An example of the copper-clad laminate is a copper-clad laminate comprising a copper foil and a B stage film laminated on one surface of the copper foil.
- the B-stage film of this copper-clad laminate is formed from the above epoxy resin material. By pre-curing the B-stage film, a copper-clad laminate having a pre-cured product can be obtained.
- the thickness of the copper foil of the copper-clad laminate is not particularly limited.
- the thickness of the copper foil is preferably in the range of 1 to 50 ⁇ m.
- the said copper foil has a fine unevenness
- the method for forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a formation method by treatment using a known chemical solution.
- the precured product is preferably used for obtaining a multilayer substrate.
- the multilayer substrate there is a multilayer substrate including a circuit board and a cured product layer laminated on the surface of the circuit board.
- the cured product layer of the multilayer substrate is formed by roughening the preliminary cured product and then curing the roughened cured product. It is preferable that the said hardened
- the surface of the cured product layer opposite to the surface on which the circuit substrate is laminated is roughened.
- the roughening method can be any conventionally known roughening method and is not particularly limited.
- the surface of the cured product layer may be swelled before the roughening treatment.
- the said multilayer substrate is further equipped with the copper plating layer laminated
- a circuit board, a cured product layer laminated on the surface of the circuit board, and a surface of the cured product layer opposite to the surface on which the circuit board is laminated are provided.
- substrate provided with the laminated copper foil is mentioned. Using the copper-clad laminate provided with the cured product layer and the copper foil, the copper stage and a B stage film laminated on one surface of the copper foil, the B stage film is precured, roughened, and It is preferably formed by a curing treatment. Furthermore, it is preferable that the copper foil is etched and is a copper circuit.
- the multilayer board includes a multilayer board including a circuit board and a plurality of cured product layers laminated on the surface of the circuit board. At least one of the plurality of cured product layers is formed of the preliminary-cured product. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the cured product layer formed by curing the epoxy resin material.
- FIG. 3 schematically shows a partially cutaway front sectional view of a multilayer substrate using a roughened cured product according to an embodiment of the present invention.
- a plurality of cured product layers 23 to 26 are laminated on the upper surface 22 a of the circuit substrate 22.
- the cured product layers 23 to 26 are insulating layers.
- a metal layer 27 is formed in a part of the upper surface 22 a of the circuit board 22.
- the cured product layers 23 to 25 other than the cured product layer 26 located on the outer surface opposite to the circuit board 22 side include a metal layer in a partial region of the upper surface. 27 is formed.
- the metal layer 27 is a circuit.
- Metal layers 27 are disposed between the circuit board 22 and the cured product layer 23 and between the laminated cured product layers 23 to 26, respectively.
- the lower metal layer 27 and the upper metal layer 27 are connected to each other by at least one of via hole connection and through hole connection (not shown).
- the cured product layers 23 to 26 are formed of the roughened cured product.
- FIG. 3 for convenience of illustration, silica and holes from which silica has been removed in the cured product layers 23 to 26 are not shown.
- fine holes are formed on the surfaces of the cured product layers 23 to 26.
- the metal layer 27 reaches inside the fine holes.
- the width direction dimension (L) of the metal layer 27 and the width direction dimension (S) of the portion where the metal layer 27 is not formed can be reduced.
- good insulation reliability is imparted between an upper metal layer and a lower metal layer that are not connected by via-hole connection and through-hole connection (not shown).
- swelling treatment and roughening treatment As a method for the swelling treatment, for example, a method of treating a precured product with an aqueous solution or an organic solvent dispersion solution of a compound mainly composed of ethylene glycol or the like is used.
- the swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like.
- the swelling liquid preferably contains sodium hydroxide.
- the swelling treatment is carried out by treating the precured material with a 40 wt% ethylene glycol aqueous solution at a treatment temperature of 30 to 85 ° C. for 1 to 30 minutes.
- the swelling treatment temperature is preferably in the range of 50 to 85 ° C. When the temperature of the swelling treatment is too low, it takes a long time for the swelling treatment, and the roughened adhesive strength between the cured product and the metal layer tends to be low.
- a chemical oxidant such as a manganese compound, a chromium compound, or a persulfate compound is used.
- chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added.
- the roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like.
- the roughening solution preferably contains sodium hydroxide.
- Examples of the manganese compound include potassium permanganate and sodium permanganate.
- Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate.
- Examples of the persulfate compound include sodium persulfate, potassium persulfate, and ammonium persulfate.
- the method for the roughening treatment is not particularly limited.
- As the roughening treatment method for example, 30 to 90 g / L permanganic acid or permanganate solution and 30 to 90 g / L sodium hydroxide solution are used, and the treatment temperature is 30 to 85 ° C. and 1 to 30 minutes.
- a method of treating a precured product once or twice under conditions is preferable.
- the temperature of the roughening treatment is preferably in the range of 50 to 85 ° C.
- the arithmetic average roughness Ra of the roughened surface of the roughened cured product is preferably 50 nm or more, more preferably 350 nm or less, and still more preferably 300 nm or less.
- the ten-point average roughness of the roughened surface of the roughened cured product is preferably 500 nm or more, preferably 3.5 ⁇ m or less, more preferably 3 ⁇ m or less.
- a through-hole may be formed in the said precured material or the said hardened
- a via or a through hole is formed as a through hole.
- the via can be formed by irradiation with a laser such as a CO 2 laser.
- the diameter of the via is not particularly limited, but is about 60 to 80 ⁇ m. Due to the formation of the through hole, a smear that is a resin residue derived from the resin component contained in the cured product layer is often formed at the bottom of the via.
- the surface of the precured product is preferably desmeared.
- the desmear process may also serve as a roughening process.
- the desmear process is sometimes called a roughening process.
- a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound is used in the same manner as the roughening treatment.
- chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added.
- the desmear treatment liquid used for the desmear treatment generally contains an alkali.
- the desmear treatment liquid preferably contains sodium hydroxide.
- the above desmear treatment method is not particularly limited.
- As the desmear treatment method for example, using a 30 to 90 g / L permanganate or permanganate solution and a 30 to 90 g / L sodium hydroxide solution, a treatment temperature of 30 to 85 ° C. and a condition of 1 to 30 minutes A method of treating a precured product or a cured product once or twice is preferable.
- the temperature of the desmear treatment is preferably in the range of 50 to 85 ° C.
- Epoxy resin Bisphenol A type epoxy resin ("jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185) Biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC-3000-H”, epoxy equivalent 275) Triazine skeleton-containing epoxy resin (“TEPIC-SP” manufactured by Nissan Chemical Industries, epoxy equivalent 100)
- Cyanate ester type curing agent solution (“BA230S75” manufactured by Lonza Japan Co., Ltd., cyanate ester group equivalent 235, solid content 75% by weight including methyl ethyl ketone)
- Biphenyl type phenol curing agent (“MEH7851-H” manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 223)
- Imidazole compound (1-cyanoethyl-2-phenylimidazole, “2PZ-CN” manufactured by Shikoku Kasei Kogyo Co., Ltd.
- Vinylsilane-treated silica-containing slurry (“SO-C2” manufactured by Admatechs, fused silica having an average particle size of 0.5 ⁇ m, “KBM-1003” 2.0 manufactured by Shin-Etsu Chemical Co., Ltd., in which 100 parts by weight of silica is a vinylsilane coupling agent 70% by weight solids containing cyclohexanone as solvent, surface-treated with parts by weight)
- Imidazole silane-treated silica-containing slurry (“SO-C2” manufactured by Admatechs, fused silica having an average particle size of 0.5 ⁇ m, and “IM-1000” manufactured by Nikko Metal Co., Ltd. in which 100 parts by weight of silica is an imidazole silane coupling agent. (Including N, N-dimethylformamide solvent, surface-treated with 0 part by weight, solid content 50% by weight)
- Example 1 Production of laminated film 85.7 parts by weight of the above-mentioned vinylsilane-treated silica-containing slurry (60 parts by weight in solids), 18 parts by weight of the cyanate ester type curing agent solution (13.5 parts by weight in solids), 13 parts by weight of the bisphenol A type epoxy resin, 13 parts by weight of the biphenyl type epoxy resin, and 0.5 parts by weight of the imidazole compound are mixed and stirred at room temperature until a uniform liquid is obtained. Obtained.
- a release-treated transparent polyethylene terephthalate (PET) film (“PET5011 550” manufactured by Lintec Corporation, thickness 50 ⁇ m) was prepared.
- the obtained resin composition varnish was coated on the release-treated surface of this PET film using an applicator so that the thickness after drying was 25 ⁇ m.
- it was dried in a gear oven at 100 ° C. for 2 minutes to prepare a laminated film of an uncured resin sheet (B stage film) having a length of 200 mm ⁇ width of 200 mm ⁇ thickness of 25 ⁇ m and a PET film.
- Examples 2 to 4 and Comparative Examples 1 to 3 A laminated film and a roughened cured product B were produced in the same manner as in Example 1 except that the type and amount (parts by weight) of the materials used were changed as shown in Table 1 below.
- the number A of silica exposed from the roughened surface and having a maximum length of 0.3 ⁇ m or more in the above image of the exposed portion was counted.
- the ratio B of the number of silicas having a thickness of 0.3 ⁇ m or more was determined.
- the silica exposed from the roughened surface, and the maximum length of the exposed part in the image is 0.3 ⁇ m or more.
- the number ratio C was determined.
- the residual silica in the pores appearing in the image the number D1 of the residual silica having a maximum length of 0.3 ⁇ m or more in the image, and the residual silica in the pores appearing in the image,
- the maximum length in the image is less than 0.3 ⁇ m and the maximum length in the image ( ⁇ m) is 3 minutes of the maximum length ( ⁇ m) in the image of the hole with the residual silica.
- the number D2 of residual silica that was 2 or more was counted. These number D1 and number D2 were added together to determine the number D of the residual silica.
- the residual silica in the holes appearing in the image has a maximum length of 0 in the image.
- E1 having a residual silica that is 3 ⁇ m or more and a hole having no residual silica and a hole having residual silica appearing in the image A residual silica having a maximum length in the above image of less than 0.3 ⁇ m and a maximum length in the above image ( ⁇ m) of the pores with residual silica in the above image ( ⁇ m)
- the ratio E2 of the number of holes with residual silica that is two-thirds or more was determined. The ratio E1 and the ratio E2 were totaled to determine the ratio E of pores with the residual silica.
- the maximum length in the image is 0.3 ⁇ m or more.
- the number F1 of the number of certain holes and the number of holes with the residual silica appearing in the image the residual silica in the holes appearing in the image, and the maximum length in the image is 0.
- the ratio of the number of holes with residual silica that is less than 3 ⁇ m and whose maximum length ( ⁇ m) in the image is 2/3 or more of the maximum length ( ⁇ m) in the image with residual silica F2 was determined. These ratios F1 and F2 were totaled to determine the ratio F of pores with the residual silica.
- the roughened surface of the resulting roughened cured product B was treated with a 55 ° C. alkaline cleaner (Cleaner Securigant 902, manufactured by Atotech Japan) for 5 minutes, and degreased and washed. After washing, the roughened cured product was treated with a 23 ° C. pre-dip solution (Pre-dip Neogant B, manufactured by Atotech Japan) for 2 minutes. Thereafter, the roughened cured product was treated with an activator solution (activator Neogant 834, manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes to attach a palladium catalyst. Next, the roughened cured product was treated with a reducing solution at 30 ° C. (Reducer Neogant WA, manufactured by Atotech Japan) for 5 minutes.
- a reducing solution at 30 ° C. (Reducer Neogant WA, manufactured by Atotech Japan) for 5 minutes.
- the roughened cured product was placed in a chemical copper solution (Kappa Solution Print Gantt MSK, manufactured by Atotech Japan), and electroless plating was performed for 10 minutes until the plating thickness reached about 0.5 ⁇ m.
- a chemical copper solution Kappa Solution Print Gantt MSK, manufactured by Atotech Japan
- electroless plating was performed for 10 minutes until the plating thickness reached about 0.5 ⁇ m.
- annealing was performed for 30 minutes at a temperature of 120 ° C. to obtain a cured product C subjected to the roughening treatment and the electroless plating treatment.
- all the processes from the alkali cleaner treatment to electroless plating were performed with a treatment liquid of 1 L on a beaker scale and while the cured product B was swung.
- the obtained cured product C was subjected to electrolytic plating at a current density of 1 A / dm 2 for 45 minutes until the plating thickness reached about 20 ⁇ m. After the electrolytic plating, heating was performed at 180 ° C. in a gear oven for 1 hour to obtain a laminate D of a copper substrate and a secondary cured product.
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Abstract
Description
特許文献2には、樹脂組成物が上記組成を有することにより粗度が小さくなることが記載されているものの、特許文献2に記載の樹脂組成物を用いた場合でも、粗化面の粗度が十分に小さくならないことがある。
本発明に係る粗化硬化物の別の特定の局面では、上記粗化処理される前に、上記予備硬化物は膨潤処理されている。
上記エポキシ樹脂材料は、エポキシ樹脂と、硬化剤と、平均粒子径が0.2μm以上、1.2μm以下であるシリカとを含む。
以下、先ず、上記エポキシ樹脂材料に含まれている各成分の詳細を説明する。
[エポキシ樹脂]
上記エポキシ樹脂材料に含まれているエポキシ樹脂は特に限定されない。該エポキシ樹脂として、従来公知のエポキシ樹脂を使用可能である。該エポキシ樹脂は、少なくとも1個のエポキシ基を有する有機化合物をいう。エポキシ樹脂は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記エポキシ樹脂材料に含まれている硬化剤は特に限定されない。該硬化剤として、従来公知の硬化剤を使用可能である。硬化剤は1種のみが用いられてもよく、2種以上が併用されてもよい。
上記硬化剤としては、シアネートエステル樹脂(シアネートエステル硬化剤)、フェノール化合物(フェノール硬化剤)、アミン化合物(アミン硬化剤)、チオール化合物(チオール硬化剤)、イミダゾール化合物、ホスフィン化合物、酸無水物、活性エステル化合物及びジシアンジアミド等が挙げられる。なかでも、熱による寸法変化がより一層小さい硬化物を得る観点からは、上記硬化剤は、シアネートエステル樹脂又はフェノール化合物であることが好ましい。上記硬化剤は、シアネートエステル樹脂であることが好ましく、フェノール化合物であることも好ましい。上記硬化剤は、上記エポキシ樹脂のエポキシ基と反応可能な官能基を有することが好ましい。
上記活性エステル化合物は特に限定されない。上記活性エステル化合物の市販品としては、DIC社製「HPC-8000」等が挙げられる。
上記エポキシ樹脂材料はシリカを含む。
上記エポキシ樹脂材料に含まれているシリカの平均粒子径は、0.2μm以上、1.2μm以下である。上記シリカの平均粒子径は好ましくは1μm以下である。上記シリカの平均粒子径として、50%となるメディアン径(d50)の値が採用される。上記平均粒子径は、レーザー回折散乱方式の粒度分布測定装置を用いて測定できる。
上記エポキシ樹脂材料は、必要に応じて硬化促進剤を含んでいてもよい。硬化促進剤の使用により、硬化速度をより一層速くすることができる。エポキシ樹脂材料を速やかに硬化させることで、硬化物の架橋構造を均一にすることができると共に、未反応の官能基数を減らすことができ、結果的に架橋密度を高くすることができる。該硬化促進剤は特に限定されない。該硬化促進剤として、従来公知の硬化促進剤を使用可能である。上記硬化促進剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記イミダゾール化合物としては、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1,2-ジメチルイミダゾール、1-シアノエチル-2-メチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾリウムトリメリテイト、1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-ウンデシルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-エチル-4’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加物、2-フェニルイミダゾールイソシアヌル酸付加物、2-メチルイミダゾールイソシアヌル酸付加物、2-フェニル-4,5-ジヒドロキシメチルイミダゾール及び2-フェニル-4-メチル-5-ジヒドロキシメチルイミダゾール等が挙げられる。
上記アミン化合物としては、ジエチルアミン、トリエチルアミン、ジエチレンテトラミン、トリエチレンテトラミン及び4,4-ジメチルアミノピリジン等が挙げられる。
上記有機金属化合物としては、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸スズ、オクチル酸コバルト、ビスアセチルアセトナートコバルト(II)及びトリスアセチルアセトナートコバルト(III)等が挙げられる。
上記硬化促進剤の含有量は特に限定されない。エポキシ樹脂材料を効率的に硬化させる観点からは、上記全固形分B100重量%中、上記硬化促進剤の含有量は好ましくは0.01重量%以上、好ましくは3重量%以下である。なお、上記全固形分Bには、上記硬化促進剤が含まれる。
上記フェノキシ樹脂の重量平均分子量は、好ましくは5000以上、好ましくは100000以下である。
上記エポキシ樹脂材料は、樹脂組成物であってもよく、該樹脂組成物がフィルム状に成形されたBステージフィルムであってもよい。上記樹脂組成物をフィルム状に成形することにより、Bステージフィルムを得ることができる。
上述のような乾燥工程により得ることができるフィルム状の樹脂組成物をBステージフィルムと称する。
上記樹脂組成物は、基材と、該基材の一方の表面に積層されたBステージフィルムとを備える積層フィルムを形成するために好適に用いられる。積層フィルムのBステージフィルムが、上記樹脂組成物により形成される。
回路基板とBステージフィルム又は積層フィルムとの密着性を高める目的で、ゴムシートなどの柔軟性を有する材料を用いてもよい。
上記エポキシ樹脂材料は、プリント配線板において絶縁層を形成するために好適に用いられる。
上記プリント配線板は、例えば、上記樹脂組成物により形成されたBステージフィルムを用いて、該Bステージフィルムを加熱加圧成形することにより得られる。
上記エポキシ樹脂材料は、銅張り積層板を得るために好適に用いられる。上記銅張り積層板の一例として、銅箔と、該銅箔の一方の表面に積層されたBステージフィルムとを備える銅張り積層板が挙げられる。この銅張り積層板のBステージフィルムが、上記エポキシ樹脂材料により形成される。該Bステージフィルムを予備硬化させることにより、予備硬化物を有する銅張り積層板を得ることができる。
また、上記多層基板の他の例として、回路基板と、該回路基板の表面上に積層された硬化物層と、該硬化物層の上記回路基板が積層された表面とは反対側の表面に積層された銅箔とを備える多層基板が挙げられる。上記硬化物層及び上記銅箔が、銅箔と該銅箔の一方の表面に積層されたBステージフィルムとを備える銅張り積層板を用いて、上記Bステージフィルムを予備硬化、粗化処理及び硬化処理することにより形成されていることが好ましい。さらに、上記銅箔はエッチング処理されており、銅回路であることが好ましい。
上記膨潤処理の方法としては、例えば、エチレングリコールなどを主成分とする化合物の水溶液又は有機溶媒分散溶液などにより、予備硬化物を処理する方法が用いられる。膨潤処理に用いる膨潤液は、一般にpH調整剤などとして、アルカリを含む。膨潤液は、水酸化ナトリウムを含むことが好ましい。具体的には、例えば、上記膨潤処理は、40重量%エチレングリコール水溶液等を用いて、処理温度30~85℃で1~30分間、予備硬化物を処理することにより行なわれる。上記膨潤処理の温度は50~85℃の範囲内であることが好ましい。上記膨潤処理の温度が低すぎると、膨潤処理に長時間を要し、更に硬化物と金属層との粗化接着強度が低くなる傾向がある。
また、上記予備硬化物又は上記硬化物に、貫通孔が形成されることがある。上記多層基板などでは、貫通孔として、ビア又はスルーホール等が形成される。例えば、ビアは、CO2レーザー等のレーザーの照射により形成できる。ビアの直径は特に限定されないが、60~80μm程度である。上記貫通孔の形成により、ビア内の底部には、硬化物層に含まれている樹脂成分に由来する樹脂の残渣であるスミアが形成されることが多い。
実施例及び比較例では、以下に示す材料を用いた。
ビスフェノールA型エポキシ樹脂(三菱化学社製「jER828」、エポキシ当量185)
ビフェニル型エポキシ樹脂(日本化薬社製「NC-3000-H」、エポキシ当量275)
トリアジン骨格含有エポキシ樹脂(日産化学工業社製「TEPIC-SP」、エポキシ当量100)
シアネートエステル型硬化剤溶液(ロンザジャパン社製「BA230S75」、シアネートエステル基当量235、溶剤であるメチルエチルケトンを含む、固形分75重量%)
ビフェニル型フェノール硬化剤(明和化成社製「MEH7851-H」、フェノール性水酸基当量223)
イミダゾール化合物(1-シアノエチル-2-フェニルイミダゾール、四国化成工業社製「2PZ-CN」)
ビニルシラン処理シリカ含有スラリー(アドマテックス社製「SO-C2」、平均粒子径0.5μmの溶融シリカ、シリカ100重量部がビニルシランカップリング剤である信越化学工業社製「KBM-1003」2.0重量部で表面処理されている、溶剤であるシクロヘキサノンを含む、固形分70重量%)
(1)積層フィルムの作製
上記ビニルシラン処理シリカ含有スラリー85.7重量部(固形分で60重量部)と、上記シアネートエステル型硬化剤溶液18重量部(固形分で13.5重量部)と、上記ビスフェノールA型エポキシ樹脂13重量部と、上記ビフェニル型エポキシ樹脂13重量部と、上記イミダゾール化合物0.5重量部とを混合し、均一な液となるまで常温で攪拌し、樹脂組成物ワニスを得た。
MEC社製「CZ-8101」により表面処理された銅基板を用意した。得られた積層フィルムを、樹脂シートの未硬化物が銅基板側となるようにセットした。積層フィルムと銅基板とを、100℃に加熱した平行平板プレス機を用いて、減圧下で0.5MPaで1分間加圧及び加熱し、樹脂シートの一次硬化物(予備硬化物)を含む積層体を得た。その後、PETフィルムを剥がし、150℃ギアオーブン内で1時間加熱し、銅基板と一次硬化物との積層体Aを得た。
上記積層体Aにおける一次硬化物を、下記の(a)膨潤処理をした後、下記の(b)粗化処理をした。
60℃の膨潤液(スウェリングディップセキュリガントP、アトテックジャパン社製)に、上記積層体Aを入れて20分間揺動させた。その後、純水で洗浄した。
80℃の粗化液(コンセントレートコンパクトCP、アトテックジャパン社製)に、膨潤処理された上記積層体Aを入れて、25分間揺動させ、銅基板上に粗化処理された粗化硬化物を得た。得られた粗化硬化物を、23℃の洗浄液(リダクションセキュリガントP、アトテックジャパン社製)により2分間洗浄した後、純水でさらに洗浄した。その後、120℃のギアオーブン中で2時間乾燥し、粗化処理された粗化硬化物Bを得た。
使用した材料の種類及び配合量(重量部)を下記の表1に示すように変更したこと以外は実施例1と同様にして、積層フィルム及び粗化硬化物Bを作製した。
(1)画像観察1
スパッタ装置(日本電子データム社製「JFC-1600」)を用いて、得られた粗化硬化物Bの粗化処理された表面に、下記シリカの個数A、下記シリカの個数の割合B、及び下記シリカの個数の割合Cを測定するために、金スパッタリングを施した。次に、走査型電子顕微鏡(日本電子データム社製「JSM-5610LV」)により、粗化硬化物の金スパッタリングされた表面を二次電子像(倍率5000倍)で撮影し、撮影された画像を得た。得られた画像における粗化処理された表面の5μm×5μmの大きさの領域について評価を実施した。
スパッタ装置(日本電子データム社製「JFC-1600」)を用いて、得られた粗化硬化物Bの粗化処理された表面に、下記残存シリカの個数D、下記残存シリカがある孔の割合E、及び下記残存シリカの割合Fを測定するために、金スパッタリングを施した。次に、走査型電子顕微鏡(日本電子データム社製「JSM-5610LV」)により、粗化硬化物の金スパッタリングされた表面を二次電子像(倍率5000倍)で撮影し、撮影された画像を得た。得られた画像における粗化処理された表面の5μm×5μmの大きさの領域について評価を実施した。
JIS B0601-1994に準拠して、非接触3次元表面形状測定装置(「WYKO NT1100」、Veeco社製)を用いて、粗化硬化物の粗化処理された表面の算術平均粗さRa及び十点平均粗さRzを測定した。測定領域は、94μm×123μmの大きさとした。
上記(b)粗化処理の後、さらに下記の(c)銅めっき処理をした。
(c)銅めっき処理:
次に、得られた粗化硬化物Bに、無電解銅めっき及び電解銅めっき処理を以下の手順で行った。
上記積層体Dにおける銅めっき層の表面に10mm幅に切り欠きを入れた。その後、引張試験機(商品名「オートグラフ」、島津製作所社製)を用いて、クロスヘッド速度5mm/分の条件で、銅めっき層と硬化物との接着強度(ピール強度)を測定した。
結果を下記の表1に示す。また、下記の表1において、「全固形分A」は、上記エポキシ樹脂材料に含まれている全固形分を示す。
1a…第1の表面
1b…第2の表面
1c…孔
2…シリカ
6…積層対象部材
6a…上面
11…粗化硬化物
11a…第1の表面
11b…第2の表面
11c…孔
12…シリカ
12X…残存シリカ
16…積層対象部材
16a…上面
21…多層基板
22…回路基板
22a…上面
23~26…硬化物層
27…金属層
Claims (8)
- エポキシ樹脂材料の硬化を進行させて予備硬化物を得た後、該予備硬化物の表面を粗化処理することにより得られた粗化硬化物であって、
前記エポキシ樹脂材料が、エポキシ樹脂と、硬化剤と、平均粒子径が0.2μm以上、1.2μm以下であるシリカとを含み、
粗化処理された表面を走査型電子顕微鏡により撮影したときに、撮影された画像における粗化処理された表面の5μm×5μmの大きさの領域において、粗化処理された表面から露出しているシリカであって、かつ露出部分の前記画像での最大長さが0.3μm以上であるシリカが15個以下である、粗化硬化物。 - 粗化処理された表面を走査型電子顕微鏡により撮影したときに、撮影された画像における粗化処理された表面の5μm×5μmの大きさの領域において、前記画像に現れている孔と前記画像に現れているシリカとの合計個数のうち、粗化処理された表面から露出しているシリカであって、かつ露出部分の前記画像での最大長さが0.3μm以上であるシリカの個数の割合が20%以下である、請求項1に記載の粗化硬化物。
- 粗化処理された表面を走査型電子顕微鏡により撮影したときに、撮影された画像における粗化処理された表面の5μm×5μmの大きさの領域において、前記画像に現れているシリカの個数のうち、粗化処理された表面から露出しているシリカであって、かつ露出部分の前記画像での最大長さが0.3μm以上であるシリカの個数の割合が50%以下である、請求項1又は2に記載の粗化硬化物。
- 前記エポキシ樹脂材料に含まれている全固形分100重量%中、前記シリカの含有量が55重量%以上、80重量%以下である、請求項1~3のいずれか1項に記載の粗化硬化物。
- 粗化処理された表面の算術平均粗さRaが0.3μm以下であり、かつ十点平均粗さRzが3.0μm以下である、請求項1~4のいずれか1項に記載の粗化硬化物。
- 前記粗化処理される前に、前記予備硬化物が膨潤処理されている、請求項1~5のいずれか1項に記載の粗化硬化物。
- 請求項1~6のいずれか1項に記載の粗化硬化物を硬化させた硬化物と、該硬化物の粗化処理された表面に積層された金属層とを備える、積層体。
- 前記硬化物と前記金属層との接着強度が3.9N/cm2以上である、請求項7に記載の積層体。
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JP2015168714A (ja) * | 2014-03-05 | 2015-09-28 | 三菱瓦斯化学株式会社 | 樹脂構造体、並びにそれを用いたプリプレグ、樹脂シート、金属箔張積層板、及びプリント配線板 |
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