CN104349599B - The manufacturing method of component-mounted substrate - Google Patents
The manufacturing method of component-mounted substrate Download PDFInfo
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- CN104349599B CN104349599B CN201410381036.9A CN201410381036A CN104349599B CN 104349599 B CN104349599 B CN 104349599B CN 201410381036 A CN201410381036 A CN 201410381036A CN 104349599 B CN104349599 B CN 104349599B
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- resin
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- 238000001723 curing Methods 0.000 claims abstract description 179
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- VLWUKSRKUMIQAX-UHFFFAOYSA-N diethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[SiH](OCC)CCCOCC1CO1 VLWUKSRKUMIQAX-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical class CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- JIVYAYWWEQOVRW-UHFFFAOYSA-N octadecanoic acid;tin Chemical compound [Sn].CCCCCCCCCCCCCCCCCC(O)=O JIVYAYWWEQOVRW-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 150000003505 terpenes Chemical group 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
-
- 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
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3494—Heating methods for reflowing of solder
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides the manufacturing method of component-mounted substrate, after the further slimming that can cope with component-mounted substrate, the high temperature installed even across the component for using reflow step, it is also difficult to generate the warpage of substrate；And the present invention provides hot curing resin composition, suitably forms the insulating layer of slim component-mounted substrate.The manufacturing method of component-mounted substrate, which is characterized in that include：The hot curing resin composition layer formed on internal substrate is heating and curing and forms the thermal cure step of solidified material layer and utilizes Reflow Soldering in the reflow step of the substrate upper mounting component with solidified material layer, the shrinking percentage (S1) in x y direction of the hot curing resin composition layer after thermal cure step is 0.35% or less, the shrinking percentage (S2) in x y direction of the solidified material layer after reflow step be 0.4% hereinafter, and S1 and S2 meet the relationship of S1≤0.08 S2；And hot curing resin composition, be used to form insulating layer, which is characterized in that with the shrinking percentage in the directions x y after the solidfied material of the hot curing resin composition being heated according to the thermal reflow profile figure of IPC/JEDEC J STD 020C（S2）For 0.4% hereinafter, the solidfied material of the hot curing resin composition is the shrinking percentage in the directions x y after heat cure（S1）The solidfied material of heat cure is carried out under the conditions of below for 0.35%, and S1 and S2 meet the relationship of S1≤0.08 S2.
Description
Technical field
Insulating layer formation the present invention relates to the manufacturing method of component-mounted substrate and for component-mounted substrate is useful
Hot curing resin composition.
Background technology
Manufacturing technology as multilayer printed board, it is known that be utilized on core substrate and replace lapped insulation layer and conductor layer
Stacking (ビ Le De ア ッ プ) mode manufacturing method.In the manufacturing method that stack manner is utilized, usually, insulating layer
Resin combination is set to be solidified to form.It is known as the resin combination, is used composition epoxy resin (patent document 1).
In recent years, when manufacturing multilayer printed board, in order to prevent caused by insulating layer and the thermal expansion difference of conductor layer
Crackle, circuit modifications have the tendency that the inorganic filling materials (patent document such as high cooperation silicon dioxide granule in resin combination
2)。
Existing technical literature
Patent document
Patent document 1：Japanese Laid-Open 2007-254709 bulletins
Patent document 2：Japanese Laid-Open 2010-202865 bulletins.
Invention content
During the further slimming of desired multilayer printed board, core substrate, insulating layer thickness have gradually
Thinning tendency.But due to the slimming of core substrate, insulating layer, insulating layer is caused to be susceptible to contraction caused by heat
It influences.The inventors of the present invention are found that following problems：Component be installed on substrate is manufactured using Reflow Soldering (reflow) step
When component-mounted substrate, the warpage of substrate is caused to be easy to bright due to the contraction of insulating layer under high temperature especially for slim substrate
It is clear.
Therefore, the subject of the invention is to provide the manufacturing methods of component-mounted substrate, wherein even if in order to cope with component peace
The further slimming of substrate is filled, and after the high temperature of the installation of the component by being generated by reflow step, it is also difficult to generate substrate
Warpage.And then the subject of the invention is to provide hot curing resin compositions, suitably form slim component-mounted substrate
Insulating layer.
The inventors of the present invention have carried out making great efforts research in view of the above subject, as a result, it has been found that for the insulation in component-mounted substrate
The hot curing resin composition that layer uses in being formed, is conceived to the hot curing resin composition layer formed on internal substrate
Thermal cure step after shrinking percentage and pass through heat cure formed solidified material layer (insulating layer) reflow step after contraction
The difference of rate and these shrinking percentages, when the difference of these each shrinking percentages and these shrinking percentages is certain value or less, even if being slim
Substrate can also inhibit the warpage of the substrate after reflow step, so as to complete the present invention.I.e. the present invention is containing below interior
Hold.
[1] manufacturing method of component-mounted substrate, which is characterized in that including：The heat cure that will be formed on internal substrate
Property resin composition layer be heating and curing and form the thermal cure step of solidified material layer and have at this using Reflow Soldering (reflow)
The reflow step of the substrate upper mounting component of solidified material layer, hot curing resin composition layer is after thermal cure step in x-y
The shrinking percentage (S1) in direction is 0.35% hereinafter, solidified material layer is 0.4% in the shrinking percentage (S2) in the directions x-y after reflow step
Hereinafter, and S1 and S2 meet the relationship of S2-S1≤0.08；
[2] according to the method described in [1], wherein hot curing resin composition contains epoxy resin, curing agent and inorganic
Packing material；
[3] according to the method described in [2], wherein contain silica as inorganic filling material；
[4] according to the method described in [2], wherein contain the silica doped with titanium as inorganic filling material；
[5] method according to any one of [2]~[4], wherein non-volatile in being thermally cured property resin combination
Property at 100 mass % is divided into when, the content of the inorganic filling material in hot curing resin composition is 40 mass % or more；
[6] method according to any one of [1]~[5], wherein the heating temperature in thermal cure step is 120 DEG C
~240 DEG C；
[7] according to the method described in any one of [1]~[6], wherein the peak temperature in reflow step is 210 DEG C~
330℃；
[8] method according to any one of [1]~[7], wherein hot curing resin composition layer utilizes prepreg
It is formed, the prepreg is impregnated into fiber base material by being thermally cured property resin combination and is formed；
[9] method according to any one of [1]~[8], wherein hot curing resin composition layer is in internal layer base
Laminate bond film on plate and the layer formed, the adhering film is to be formed with the thick composition of heat-curing resin on a carrier film
The film of layer；
[10] method according to any one of [1]~[8], wherein hot curing resin composition layer is in internal layer
Laminating strips have the prepreg of carrier and the layer that is formed on substrate, and the prepreg with carrier is formed on a carrier film will be hot
Prepreg made of hardening resin composition is impregnated into fiber base material；
[11] method according to any one of [1]~[10], wherein the thickness of solidified material layer is 3~200 μm；
[12] method according to any one of [1]~[11], wherein component is semiconductor chip, insertion piece or nothing
Source element；
[13] according to the method described in [12], wherein component is semiconductor chip；
[14] hot curing resin composition is used to form insulating layer, which is characterized in that with according to IPC/JEDEC J-
The thermal reflow profile figure of STD-020C the solidfied material of the hot curing resin composition is heated after the directions x-y
Shrinking percentage (S2) is 0.4% hereinafter, the solidfied material of the hot curing resin composition is the directions x-y after heat cure
Shrinking percentage (S1) has carried out the solidfied material of heat cure under the conditions of being 0.35% below, and S1 and S2 meet the pass of S2-S1≤0.08
System；
[15] according to the hot curing resin composition described in [14], wherein the peak temperature of Reflow Soldering is 260 DEG C；
[16] according to the hot curing resin composition described in [15], wherein hot curing resin composition contains epoxy
Resin, curing agent and inorganic filling material；
[17] according to the hot curing resin composition described in [16], wherein contain titanium dioxide as inorganic filling material
Silicon；
[18] according to the hot curing resin composition described in [16], wherein as inorganic filling material contain doped with
The silica of titanium；
[19] hot curing resin composition according to any one of [16]~[18], wherein being thermally cured property tree
When involatile constituent in oil/fat composition is set as 100 mass %, inorganic filling material in hot curing resin composition contains
Amount is 40 mass % or more；
[20] prepreg, by making the hot curing resin composition described in any one of [15]~[19] be impregnated into fibre
It is formed in Wiki material；
[21] multilayer printed circuit board, wherein the heat-curing resin described in any one of [15]~[19] is utilized to combine
The solidfied material of object and form insulating layer；
[22] component-mounted substrate, wherein utilize the hot curing resin composition described in any one of [15]~[19]
Solidfied material and form insulating layer；
[23] according to the component-mounted substrate described in [22], wherein component is semiconductor chip, insertion piece or passive member
Part；
[24] according to the component-mounted substrate described in [23], wherein component is semiconductor chip.
According to the present invention, it is possible to provide the manufacturing method of component-mounted substrate, this method are walked even across Reflow Soldering is utilized
After the high temperature of rapid component installation, it is also difficult to generate the warpage of substrate.And then according to the present invention, it is possible to provide heat-curing resin group
Object is closed, the insulating layer for being suitable for slim component-mounted substrate is formed.The present invention can be easy to generate particularly suitable for manufacture
The slim component-mounted substrate of the warpage of substrate.
Description of the drawings
Fig. 1 is the figure of the title between A, B, C, D each point shown when calculating S1 and S2；
Fig. 2 is the figure for illustrating the thermal reflow profile figure described in IPC/JEDEC J-STD-020C.
Specific implementation mode
The present invention is explained in detail following with suitable embodiment of the invention.
The embodiment of the present invention is the manufacturing method of component-mounted substrate, which is characterized in that includes：It will be in internal layer base
The hot curing resin composition layer formed on plate is heating and curing and forms the thermal cure step of solidified material layer and utilize back
Fluid welding is in the reflow step of the substrate upper mounting component with solidified material layer, and hot curing resin composition layer is through heat cure
After step the shrinking percentage (S1) in the directions x-y be 0.35% hereinafter, solidified material layer after reflow step in the contraction in the directions x-y
Rate (S2) be 0.4% hereinafter, and S1 and S2 meet the relationship of S2-S1≤0.08.
＜ thermal cure steps ＞
The manufacturing method of the present invention contains thermal cure step, in thermal cure step, the heat that will be formed on internal substrate
Cured resin composition layer is heating and curing and forms solidified material layer.
The temperature of heat cure can be different according to the composition of specifically used hot curing resin composition, but from when solidification
Between shortening and substrate heat resistance balance from the point of view of, generally 120 DEG C~240 DEG C, preferably 140 DEG C~210 DEG C,
More preferably 150 DEG C~200 DEG C.
" internal substrate " in the present invention is to manufacture object when manufacturing the printed base plates such as the built-in substrate of component as centre
Substrate refers to enterprising in internal substrate and forms insulating layer and/or conductor layer, constitutes the substrate of the internal layer of printed base plate.Internal layer
The one or both sides of substrate can have the circuit layout for having carried out pattern processing.It, can be with as the substrate for internal substrate
Enumerate such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrates, thermohardening type polyphenylene oxide
Substrate, centreless (coreless) substrate etc..
When having circuit layout on the one or both sides of substrate, the thickness of the circuit layout is not particularly limited, but from
Layer slimming from the point of view of, preferably 70 μm hereinafter, more preferably 30 μm hereinafter, in turn be preferably 20 μm or less.Circuit
The lower limit of the thickness of wiring is not particularly limited, preferably 1 μm or more, more preferably 3 μm or more, and then preferably 5 μm or more.
The line width of circuit layout/spacing ratio (ラ イ Application/ス ペ ー ス ratios) is not particularly limited, but in order to inhibit firming body
The fluctuating on surface, preferably 200/200 μm hereinafter, more preferably 100/100 μm hereinafter, in turn be preferably 40/40 μm hereinafter, into
And more preferably 20/20 μm hereinafter, particularly preferably 8/8 μm.Line width/spacing of circuit layout than lower limit do not limit especially
System, but in order to keep imbedibility of the resin between spacing good, preferably 0.5/0.5 μm or more, more preferably 1/1 μm or more.
The hot curing resin composition used in the hot curing resin composition layer of the present invention is not particularly limited,
As long as its solidfied material as insulating layer, have sufficient hardness and insulating properties.Such as it is preferable to use contain epoxy resin, solid
The hot curing resin composition of agent and inorganic filling material.
(epoxy resin)
Epoxy resin used in the present invention, is not particularly limited, and can enumerate bisphenol A type epoxy resin, Bisphenol F
Type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, novolac type epoxy resin, tert butyl-catechol
Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy, glycidyl amine epoxy tree
Fat, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, has fourth two at Cresol formaldehyde type epoxy resin
The epoxy resin of alkene structure, hetero ring type epoxy resin, contains whorled epoxy resin, hexamethylene diformazan at alicyclic epoxy resin
Alcohol type epoxy resin, trihydroxy methyl type epoxy resin, halogenated epoxy resin, dicyclopentadiene-type epoxy resin etc..These epoxies
Resin can use a kind or two or more is applied in combination.
Wherein, it is improved from heat resistance, from the point of view of insulating reliability raising and the adaptation raising of metal foil, preferably
It is bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type asphalt mixtures modified by epoxy resin
Fat, anthracene type epoxy resin, the epoxy resin with butadiene structure, dicyclopentadiene-type epoxy resin.Specifically, it can enumerate
Such as bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) makes " エ ピ コ ー ト 828EL ", " YL980 "), bisphenol f type epoxy resin
1: 1 melange (Nippon Steel's chemistry (strain) of (Mitsubishi Chemical's (strain) makes " jER806H ", " YL983U "), bisphenol A-type and bisphenol-f type
Make " ZX1059 "), 2 functional epoxy resins of naphthalene type (DIC (strain) make " HP4032 ", " HP4032D ", " HP4032SS ",
" EXA4032SS "), 4 functional epoxy resins of naphthalene type (DIC (strain) make " HP4700 ", " HP4710 "), naphthol type epoxy resin (east
All chemical conversion (strain) systems " ESN-475V "), (ダ イ セ Le chemical industry (strain) makes " PB- for epoxy resin with butadiene structure
3600 "), (Japanese chemical drug (strain) system " NC3000H ", " NC3000L ", " NC3100 ", the Mitsubishi of the epoxy resin with biphenyl structural
Chemical (strain) system " YX4000 ", " YX4000H ", " YX4000HK ", " YL6121 "), (Mitsubishi Chemical's (strain) makes anthracene type epoxy resin
" YX8800 "), naphthylene ether type epoxy (DIC (strain) make " EXA-7310 ", " EXA-7311 ", " EXA-7311L ",
" EXA7311-G3 "), dicyclopentadiene-type epoxy resin (DIC (strain) make " HP-7200H ") etc..
Epoxy resin may be two kinds or more, and preferably comprise the asphalt mixtures modified by epoxy resin with 2 or more epoxy groups in 1 molecule
Fat.Wherein, it is the aromatic system ring of liquid with 2 or more epoxy groups, at a temperature of 20 DEG C further preferably in 1 molecule
Oxygen resin (hereinafter referred to as " liquid-state epoxy resin ") and in 1 molecule have 3 or more epoxy groups, be at a temperature of 20 DEG C
The mode of solid aromatic system epoxy resin (hereinafter referred to as " solid epoxy resin ").It should be noted that heretofore described
Aromatic system epoxy resin refers to the epoxy resin for having aromatic ring structure in its intramolecular.As epoxy resin, by liquid ring
Oxygen resin and solid epoxy resin and used time, from the flexibility with appropriateness when using resin combination in the form of adhering film
Angle or from the solidfied material of resin combination have suitable fracture strength from the point of view of, mixing ratio (liquid epoxy tree
Fat: solid epoxy resin) by quality ratio be preferably 1: 0.1~1: 2 range, more preferably 1: 0.3~1: 1.8 range,
Preferably 1: 0.6~1: 1.5 range in turn.
Liquid-state epoxy resin be preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin,
And naphthalene type epoxy resin, more preferably bisphenol A type epoxy resin and naphthalene type epoxy resin.They can use a kind or by 2 kinds
Combination of the above uses.
Solid epoxy resin is preferably 4 function naphthalene type epoxy resins, Cresol formaldehyde type epoxy resin, bicyclopentadiene type ring
Oxygen resin, triphenol (trisphenol) epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin or naphthylene ether type
Epoxy resin, more preferably 4 function naphthalene type epoxy resins, biphenyl type epoxy resin and naphthylene ether type epoxy.They can
To use a kind or two or more be applied in combination.
It is strong from the machinery for the solidfied material for improving resin combination in the resin combination suitable for the manufacturing method of the present invention
From the point of view of degree, water resistance, when the non-volatile component in resin combination is set as 100 mass %, the content of epoxy resin
Preferably 3~35 mass %, more preferably 5~40 mass %, and then preferably 10~45 mass %.
(curing agent)
Curing agent used in the present invention, is not particularly limited, and can enumerate such as phenol (phenol) system solidification
Agent, naphthols system curing agent, active ester system curing agent, benzoxazine system curing agent, cyanate system curing agent, acid anhydrides system curing agent
Deng wherein preferably phenol system curing agent, naphthols system curing agent, active ester system curing agent.These curing agent can use a kind,
Or two or more is applied in combination.
It as phenol system curing agent, naphthols system curing agent, is not particularly limited, novolak tree of for example having can be enumerated
The phenol system curing agent of fat (ノ ボ ラ ッ Network) structure or the naphthols system curing agent with linear phenol-aldehyde resin structure, preferably line
Type phenolic resin, naphthol novolac resin, naphthols aralkyl-type resin, contains triazine at the linear phenol-aldehyde resin containing triazine skeleton
The naphthol resin of skeleton, biphenyl aralkyl-type phenol resin.As commercially available product, biphenyl aralkyl-type phenol resin can be enumerated
" MEH-7700 ", " MEH-7810 ", " MEH-7851 ", " MEH7851-4H " (bright and chemical conversion (strain) system), " GPH " (Japanese chemical drug
(strain) makes), naphthol novolac resin can enumerate " NHN ", " CBN " (Japanese chemical drug (strain) system), and naphthols aralkyl-type resin can be with
Enumerate " SN170 ", " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN395 ", " SN375 " (Dongdu chemical conversion
(strain) makes), linear phenol-aldehyde resin can enumerate " TD2090 " (DIC (strain) systems), the linear phenol-aldehyde resin containing triazine skeleton
" LA3018 ", " LA7052 ", " LA7054 ", " LA1356 " (DIC (strain) systems) etc..They can use a kind, or by two or more
It is used in combination.
Active ester system curing agent is not particularly limited, it is generally preferable to use phenolic ester class (phenol esters), benzenethiol ester
(thiophenol esters) class, N- hydroxylamines esters, esters of heterocycle hydroxyl compound etc. have 2 or more in 1 molecule
The compound of the high ester group of reactivity.The active ester system curing agent preferably passes through carboxylic acid compound and/or thiocarboxylic acid chemical combination
The condensation reaction of object and hydroxy compounds and/or mercaptan compound and obtain.From the viewpoint of improving heat resistance, particularly preferably
The active ester system curing agent obtained by carboxylic acid compound and hydroxy compounds.More preferably by carboxylic acid compound and oxybenzene compound
And/or the active ester system curing agent that naphthol compound obtains.As carboxylic acid compound, it can be mentioned, for example：Benzoic acid, acetic acid, amber
Amber acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..As phenol chemical combination
Object or naphthol compound, it can be mentioned, for example：Quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, the bisphenol-A that methylates,
Methylate Bisphenol F, the bisphenol S that methylates, phenol, o-cresol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- bis-
Hydroxyl naphthalene, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxy hexichol first
Ketone, phloroglucin, benzenetriol (benzenetriol), the dicyclopentadiene-type bisphenol compounds (hexichol of polycyclopentadithio.henes ene-type
Phenolic compounds), linear phenol-aldehyde resin (phenol novolac) etc..Active ester system curing agent can use one kind or two or more.
As active ester system curing agent, active ester system curing agent disclosed in Japanese Unexamined Patent Publication 2004-277460 bulletins can be used, separately
Commercially available commodity can also be used outside.As commercially available active ester system curing agent, preferably contain dicyclopentadiene-type biphenol
It is condensed the benzoylate etc. of the substance of structure, the acetylate of linear phenol-aldehyde resin, linear phenol-aldehyde resin, wherein being more preferably
The substance of structure is condensed containing dicyclopentadiene-type biphenol.Specifically, it is condensed knot as containing dicyclopentadiene-type biphenol
The substance of structure, can enumerating EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T, (DIC (strain) systems, active group are worked as
About 223), as the acetylate of linear phenol-aldehyde resin, can enumerating DC808, (Mitsubishi Chemical's (strain) system, active group equivalent are about for amount
149), as the benzoylate of linear phenol-aldehyde resin, can enumerating YLH1026, (Mitsubishi Chemical's (strain) system, active group equivalent are about
200), (Mitsubishi Chemical's (strain) system, active group are worked as by YLH1030 (Mitsubishi Chemical's (strain) system, active group equivalent about 201), YLH1048
Amount about 245) etc., wherein HPC-8000-65T from the storage stability of varnish, solidfied material coefficient of thermal expansion from the point of view of be
Preferably.
As the active ester system curing agent for being condensed structure containing dicyclopentadiene-type biphenol, more specifically, can enumerate
The compound of following formula.
[chemical formula 1]
(in formula, R is phenyl, naphthalene, and k indicates 0 or 1, and n is calculated as 0.05~2.5 with being averaged for repetitive unit).
From the point of view of so that dielectric loss tangent is reduced, heat resistance is made to improve, R is preferably naphthalene, and on the other hand, k is excellent
It is selected as 0, in addition n is preferably 0.25~1.5.
Benzoxazine system curing agent is not particularly limited, and as concrete example, can enumerating F-a, P-d, (four countries are melted into (strain)
System), HFB2006M (Showa macromolecule (strain) system) etc..
Cyanate system curing agent is not particularly limited, and can enumerate such as linear phenol-aldehyde resin (ノ ボ ラ ッ Network) type (line style
Phenolic resin type, alkyl novalac-type etc.) it is cyanate system curing agent, dicyclopentadiene-type cyanate system curing agent, double
Phenolic (bisphenol A-type, bisphenol-f type, bisphenol S type etc.) cyanate system curing agent and their part are by the prepolymer of triazine
Deng.The weight average molecular weight of cyanate system curing agent is not particularly limited, preferably 500~4500, more preferably 600~3000.
As the concrete example of cyanate system curing agent, such as bisphenol A dicyanate, polyphenol cyanate (oligomeric (3- methylenes can be enumerated
Base -1,5- phenylenecyanates)), 4,4' methylene bis (2,6- 3,5-dimethylphenyls cyanate), 4,4'- ethylenes phenyl two
It is bis- (4- cyanates) phenyl-propanes of cyanate, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- bis- (4- cyanates phenylmethanes), double
Bis- (4- cyanate phenyl -1- (methyl the ethylidene)) benzene of (4- cyanate -3,5- 3,5-dimethylphenyls) methane, 1,3-, bis- (4- cyanic acid
Ester phenyl) the 2 function cyanate ester resins such as thioether, bis- (4- cyanates phenyl) ethers, by linear phenol-aldehyde resin, cresol formaldehyde resin,
A part of quilt of multifunctional cyanate ester resin, these cyanate ester resins derived from phenolic resin containing bicyclopentadiene structure etc.
The prepolymer etc. of triazine.They can use a kind or two or more is applied in combination.
As commercially available cyanate ester resin, can enumerate：Novalac-type multifunctional cyanate ester tree shown in following formula
Fat (ロ Application ザ ジ ャ パ Application (strain) system, PT30S, cyanate equivalent 124)
[chemical formula 2]
[in formula, n indicates arbitrary number (preferably 0~20) in terms of average value]；
Part or all of bisphenol A dicyanate shown in following formula is formed the prepolymer (ロ of tripolymer by triazine
Application ザ ジ ャ パ Application (strain) system, BA230, cyanate equivalent 232)
[chemical formula 3]
；
Cyanate ester resin (ロ Application ザ ジ ャ パ Application (strain) system, DT- shown in following formula containing bicyclopentadiene structure
4000、DT-7000)
[chemical formula 4]
(in formula, n indicates 0~5 number in terms of average value) etc..
Acid anhydrides system curing agent is not particularly limited, but can enumerate for example phthalic anhydride, tetrabydrophthalic anhydride,
Hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogen
Change methylnadic anhydride, trialkyl tetrabydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2,5- dioxotetrahydros -3-
Furyl (Off ラ ニ Le)) -3- methyl -3- cyclohexene -1,2- dicarboxylic acid anhydrides, trimellitic anhydride, pyromellitic dianhydride, benzophenone
Tetracarboxylic acid dianhydride, bibenzene tetracarboxylic dianhydride, naphthalenetetracarbacidic acidic dianhydride, two O-phthalic acid dianhydride of hydroxyl, 3,3'-4,4'- diphenyl sulphone (DPS)s
Tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b- hexahydros -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-C] furans -1,
3- diketone, ethylene glycol are bis- (dehydration trimellitate)（エチレングリコールビス（アンヒドロトリメリテート））、
Styrene with it is maleic acid copolymerized obtained by the polymer-types such as styrene-maleic acid resin acid anhydrides etc..
In hot curing resin composition, from the mechanical strength or water resistance of the solidfied material for improving resin combination
The ratio between sum of reactive group of angle consideration, the sum of the epoxy group of (A) epoxy resin and (B) curing agent preferably 1: 0.2~
1: 2, more preferably 1: 0.3~1: 1.5, and then preferably 1: 0.4~1: 1.It should be noted that epoxy present in resin combination
The sum of the epoxy group of resin refers to for whole epoxy resin, will be worked as with the solid constituent quality divided by epoxy of each epoxy resin
Value obtained by amount carries out total value, the sum of the reactive group of curing agent refer to for whole curing agent, will be with each curing agent
Value carries out total value obtained by solid constituent quality divided by reactive group equivalent.
In above-mentioned resin combination, examined from the mechanical strength of solidfied material or the angle of water resistance for improving resin combination
Consider, when the non-volatile component in resin combination is set as 100 mass %, the content of curing agent is preferably 3~30 mass %, more excellent
It is selected as 5~25 mass %, and then preferably 10~20 mass %.
(inorganic filling material)
The hot curing resin composition of the present invention preferably comprises inorganic fill from the point of view of coefficient of thermal expansion reduction
Material.As the inorganic filling material used, be not particularly limited, can enumerate for example silica, aluminium oxide, barium sulfate,
Talcum, clay, mica powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium borate, barium titanate,
Strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, barium zirconate, calcium zirconate etc..Wherein it is preferably silica.In addition, excellent
It is selected as amorphous silica, silica is crushed, dissolves silica, crystalline silica, synthetic silica, hollow two
Silica, preparing spherical SiO 2, doped with silica such as the silica of titanium.In addition, as silica, preferably spherical
Silica.As the example of spherical silica, " SOC1 ", " SOC2 " of (strain) ア De マ テ ッ Network ス can be enumerated.
Inorganic filling material can use a kind or two or more is applied in combination.In the present invention, the adjustment of coefficient of thermal expansion can lead to
The type, amount of ingredient contained in adjustment hot curing resin composition are crossed to carry out, particularly, inorganic filling material has significantly
Help the low thermal expansion of thermally curable resin composition, therefore can be by the adjustment of the type, amount of inorganic filling material, suitably
Ground carries out the adjustment of coefficient of thermal expansion.In addition, doped with titanium silica especially have in inorganic filling material it is low
Tendency is thermally expanded, therefore in the present invention, especially can suitably be used to adjust the value of coefficient of thermal expansion.
" doped with silica of titanium " is, for example, by making TiO2-SiO2The glass of glass forms raw material, i.e. TiCl4With
SiCl4It is mixed after each autopneumatolysis, and makes TiO obtained by its heating hydrolysis (flame hydrolysis) in oxyhydrogen flame2-SiO2Glass
Glass particle.Silica doped with titanium is well known, as the example of commercially available product, can enumerate " the AZ of Asahi Glass (strain) system
Filler (AZ Off ィ ラ ー) ".It, will be contained in resin combination when coordinating the silica doped with titanium in inorganic filling material
The amount of inorganic filling material be set as 100 mass %, the use level of the silica doped with titanium preferably in inorganic filling material
For 10 mass % or more, more preferably 20 mass % or more, more preferably 30 mass % or more, more preferably 40 mass % or more, more
Preferably 50 mass % or more, more preferably 60 mass % or more, more preferably 70 mass % or more, more preferably 80 mass % with
On, more preferably 90 mass % or more, particularly preferably 100 mass %.
It should be noted that as inorganic filling material, in order to improve moisture-proof, dispersibility, silane coupling agent (ring is preferably used
Oxosilane system coupling agent, amino silicone methane series coupling agent, hydrosulphonyl silane system coupling agent etc.), titanate esters system coupling agent, silazane chemical combination
The inorganic filling material that the surface conditioning agents such as object are surface-treated.They can use a kind or two or more is applied in combination.
As epoxy silane system coupling agent, such as glycidoxypropyltrime,hoxysilane, the third oxygen of epoxy can be enumerated
Base propyl-triethoxysilicane, glycidoxypropyl diethoxy silane, glycidyl butyl trimethoxy silane,
(3,4- epoxycyclohexyl) ethyl trimethoxy silane etc., as amino silicone methane series coupling agent, can enumerate such as aminopropyl
Methoxy silane, aminopropyltriethoxywerene werene, N- phenyl -3- TSL 8330s, N-2 (amino-ethyl) ammonia
Base propyl trimethoxy silicane etc. can enumerate such as mercaptopropyi trimethoxy silane, mercapto as hydrosulphonyl silane system coupling agent
Base propyl-triethoxysilicane etc..They can use a kind or two or more is applied in combination.It, can be with as commercially available coupling agent
Enumerate such as SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3- glycidoxypropyltrime,hoxysilanes), SHIN-ETSU HANTOTAI's chemical industry
(strain) makes " KBM803 " (3-mercaptopropyi trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) makes " KBE903 " (3- aminopropyls
Triethoxysilane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N- phenyl -3- TSL 8330s) etc..
The average grain diameter of inorganic filling material is not particularly limited, but the upper limit value of the average grain diameter of inorganic filling material,
From the point of view of carrying out fine wiring formation on the insulating layer, preferably 5 μm hereinafter, more preferably 3 μm hereinafter, in turn preferably
For 1 μm hereinafter, be more preferably in turn 0.7 μm hereinafter, be especially more preferably 0.5 μm hereinafter, particularly preferably 0.4 μm hereinafter, outstanding
It is preferably 0.3 μm or less.On the other hand, when composition epoxy resin is formed resin composition Chinese varnish, from preventing varnish
Viscosity increase, from the point of view of operability reduces, the lower limiting value of the average grain diameter of inorganic filling material be preferably 0.01 μm with
On, more preferably 0.03 μm or more, and then preferably 0.05 μm or more, especially and then preferably 0.07 μm or more, particularly preferably
It is 0.1 μm or more.The average grain diameter of above-mentioned inorganic filling material can utilize the laser based on Michaelis (Mie) scattering theory to spread out
Penetrate-scattering method measures.Specifically, using laser diffraction formula particle size distribution device, inorganic fill is made with volume reference
Its median diameter is set as average grain diameter, it is possible thereby to measure by the size distribution of material.Determination sample can it is preferable to use utilizations
Ultrasonic wave makes the substance that inorganic filling material is dispersed in water.As laser diffraction formula particle size distribution device, can use
Horiba Ltd LA-500,750,950 etc..
From the point of view of coefficient of thermal expansion reduction, when the non-volatile component in resin combination is set as 100 mass %,
Content when coordinating inorganic filling material is preferably 40 mass % or more, more preferably 50 mass % or more, and then more preferably 60
Quality %.When the content of inorganic filling material is very few, the coefficient of thermal expansion of solidfied material has the tendency that getting higher.Inorganic filling material
When content is excessive, have the tendency that the tendency that solidfied material becomes fragile or peel strength reduces, therefore the maximum of preferred inorganic filling material
Content is 90 mass % or less, preferably 85 mass % or less.
The present invention resin combination in, and then can coordinate other compositions (such as thermoplastic resin, solidification promote
The additives such as agent, fire retardant).
Thermoplastic resin-
Thermoplastic resin can enumerate such as phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide acyl
Imide resin, polyethersulfone resin and polysulfone resin etc..Thermoplastic resin can be used alone, or be two kinds or more.
The weight average molecular weight of the polystyrene conversion of thermoplastic resin is preferably 8000~70000 range, more preferably
10000~60000 range, so preferably 20000~60000 range.The weight of the polystyrene conversion of thermoplastic resin
Average molecular weight is measured with gel permeation chromatography (GPC) method.Specifically, the weight average molecular weight of the polystyrene conversion of thermoplastic resin
(strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A can be used as measurement device, use Showa electrician (strain) Shodex K- processed
800P/K-804L/K-804L is as pillar, using chloroform etc. as mobile phase, and is measured under 40 DEG C of column temperature, uses
The standard curve of standard polystyren calculates.
Phenoxy resin can be enumerated for example with selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol acetophenone
Skeleton, linear phenol-aldehyde resin skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, enb skeleton, naphthalene skeleton, anthracene bone
The phenoxy resin of the skeleton of one or more of frame, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton.Phenoxy resin
End can be the arbitrary functional group such as phenolic hydroxyl group, epoxy group.Phenoxy resin can be used alone or by two or more simultaneously
With.As the concrete example of phenoxy resin, bisphenol-A bone (is contained in " 1256 " and " 4250 " that can enumerate Mitsubishi Chemical's (strain) system
The phenoxy resin of frame), " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (contain bis-phenol acetyl benzene skeleton
Phenoxy resin), it is other can also enumerate Dongdu chemical conversion (strain) system " FX280 " and " FX293 ", Mitsubishi Chemical's (strain) make
" YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc..
As the concrete example of polyvinyl acetal resin, the electrochemical Block チ ラ ー of electrochemically industrial (strain) system can be enumerated
Le 4000-2,5000-A, 6000-C, 6000-EP, the エ ス レ ッ Network BH series of ponding chemical industry (strain) system, BX series, KS
Series, BL series, BM series etc..
As the specific example of polyimide resin, can enumerate new Japan Chemical (strain) system " リ カ コ ー ト SN20 " and
“リカコートPN20”.As the specific example of polyimide resin, can also enumerate makes 2 functional hydroxyl groups end polybutadienes
Linear polyimides (Japanese Unexamined Patent Publication 2006-37083 bulletins obtained by alkene, diisocyanate cpd and quaternary anhydride reaction
The substance of record), polyimides (Japanese Unexamined Patent Publication 2002-12667 bulletins and Japanese Unexamined Patent Publication containing silicone matrix
Substance described in 2000-319386 bulletins etc.) etc. modified polyimides.
As the concrete example of polyamide-imide resin, " the バ イ ロ マ ッ Network ス of Japan's weaving (strain) system can be enumerated
HR11NN " and " バ イ ロ マ ッ Network ス HR16NN ".As the concrete example of polyamide-imide resin, Hitachi in addition can be enumerated
The polyamidoimide " KS9100 " containing silicone matrix, modified polyamides acyl such as " KS9300 " of chemical conversion industry (strain) system
Imines.
As the concrete example of polyethersulfone resin, can enumerate " PES5003P " etc. of Sumitomo Chemical (strain) system.
As the concrete example of polysulfone resin, the polysulfones of ソ Le ベ イ ア De バ Application ス ト Port リ マ ー ズ (strain) systems can be enumerated
" P1700 ", " P3500 " etc..
When the content of non-volatile component in resin combination is set as 100%, thermoplastic resin in resin combination
Content is preferably 0.1 mass of mass %~20 %.By making the content of thermoplastic resin be the range, the viscosity of resin combination
Become suitable, thickness or the uniform resin combination of volume character can be formed.Non-volatile component in resin combination is set
For 100 mass % when, the content of the thermoplastic resin in resin combination is more preferably 1 mass of mass %~10 %.
Curing accelerator-
Curing accelerator can enumerate for example phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator,
Guanidine system curing accelerator, metal system curing accelerator etc., preferably amine system curing accelerator, imidazoles system curing accelerator, metal
It is curing accelerator.
As phosphorus system curing accelerator, such as triphenylphosphine, Peng Suan phosphonium compounds, tetraphenylphosphoniphenolate tetraphenyl boron can be enumerated
Hydrochlorate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyls) triphenyl phosphonium rhodanate, tetraphenyl
Phosphonium rhodanate, Ding base triphenyl phosphonium rhodanates etc., preferably triphenylphosphine, 4-butyl-phosphonium caprate.
Amine system curing accelerator can enumerate trialkylamine, 4-dimethylaminopyridine, benzyl such as triethylamine, tri-n-butylamine
Base dimethyl amine, 2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diazabicyclos [5.4.0]-hendecene etc., preferably
4-dimethylaminopyridine, 1,8- diazabicyclos [5.4.0]-hendecene.
As imidazoles system curing accelerator, such as 2-methylimidazole, 2- undecyl imidazoles, 2- heptadecyls can be enumerated
Imidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl
Imidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazoles, 1- cyano ethyl -2- methyl
Imidazoles, 1- cyano ethyl -2- undecyl imidazoles, 1- cyano ethyls -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl
Imidazoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acids salt, 1- cyano ethyl -2- phenylimidazole trimellitic acids salt,
2,4- diamino -6- [2'- methylimidazolyls-are (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- undecyl imidazoles
Base-is (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- ethyl -4'- methylimidazolyls-are (1')]-ethyl-s-triazine, 2,
4- diamino -6- [2'- methylimidazolyls-are (1')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acids
Addition product, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles, 2,3- dihydro -1H- pyrroles
Cough up simultaneously [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazoles chloride, 2-methylimidazole quinoline, 2- phenyl
The adduct of the imidazolium compounds such as imidazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyls
Base -2- phenylimidazoles.
As guanidine system curing accelerator, such as dicyandiamide, 1- methylguanidines, 1- ethyl guanidines, 1- cyclohexyl guanidine, 1- can be enumerated
Guanidines, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, pentamethyl guanidine, tri- nitrogen of 1,5,7-
Miscellaneous bicyclic [4.4.0] decyl- 5- alkene, 7- methyl-1s, tri- azabicyclos of 5,7- [4.4.0] decyl- 5- alkene, 1- methyl biguanides, 1- ethyls
Biguanides, 1- normal-butyls biguanides, 1- n-octadecane bases biguanides, 1,1- dimethylbiguanides, 1,1- diethyl biguanides, 1- cyclohexyl are double
Guanidine, 1- allyls biguanides, 1- phenyl biguanides, 1- (o-tolyl) biguanides etc., preferably dicyandiamide, 1,5,7- tri- azabicyclos
[4.4.0] decyl- 5- alkene.
Metal system curing accelerator is not particularly limited, and can enumerate the metal such as cobalt, copper, zinc, iron, nickel, manganese, tin
, metal-organic complex or organic metal salt.As the concrete example of metal-organic complex, acetylacetone cobalt can be enumerated
(II), organic copper complex, the zinc acetylacetonate such as organic cobalt complex such as acetylacetone cobalt (III), acetylacetone copper (II)
(II) the organic nickels complexing such as Organic-iron complexes, nickel acetylacetonate (II) such as organozinc complexes, ferric acetyl acetonade (III) such as
Organic manganese complexs such as object, manganese acetylacetonate (II) etc..As organic metal salt, such as zinc octoate, tin octoate, ring can be enumerated
Alkanoic acid zinc, cobalt naphthenate, stearic acid tin, zinc stearate etc..They can use a kind or two or more is applied in combination.
In the resin combination of the present invention, as metal system curing accelerator, it is preferable to use organic cobalt complex, especially
It is preferable to use acetylacetone cobalt (III).It is solid for metal system when non-volatile component in resin combination is set as 100 mass %
Change the content of accelerating agent, the content of the metal based on metal system curing catalysts is preferably the range of 25ppm~500ppm, more excellent
It is selected as the range of 30ppm~200ppm.
Curing accelerator can be used alone, two or more can also be applied in combination.It will be non-in resin combination
When volatile ingredient is set as 100 mass %, the content of the curing accelerator in resin combination is preferably the 0.01 mass % of mass %~1,
The more preferably 0.02 mass % of mass %~0.5, and then more preferably 0.03 mass of mass %~0.1 %.
Fire retardant-
Fire retardant can enumerate the phosphorus compound, nitrogen compound, organosilicon that for example organic phosphorus flame retardant, organic system are nitrogenous
Flame retardant, metal hydroxides etc., preferably 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrenes -10-
Oxide (such as three light (strain) system " HCA-HQ ").Fire retardant can be used alone a kind, or be two kinds or more.Resin combination
The content of fire retardant in layer is not particularly limited, when the non-volatile component in resin combination is set as 100 mass %, preferably
For the 0.5 mass % of mass %~10, the more preferably 1 mass % of mass %~5, and then preferably 1.5 mass of mass %~3 %.
＜ reflow steps ＞
The manufacturing method of the present invention includes reflow step, in reflow step, using Reflow Soldering with by above-mentioned
The substrate upper mounting component of the solidified material layer of thermal cure step manufacture.
It as the component of installation, is not particularly limited, can enumerate such as semiconductor, insertion piece, passive element, this hair
Bright manufacturing method can be particularly suitable for the installation of semiconductor.
Heating temperature in reflow step can be according to the type etc. of the component of the type or installation of the slicken solder used
Condition and it is different, generally 210 DEG C~330 DEG C, preferably 220 DEG C~300 DEG C, more preferably 230 DEG C~280 DEG C.The present invention
Manufacturing method be more particularly suitable when using unleaded slicken solder as slicken solder.
The manufacturing method of the present invention contains above-mentioned thermal cure step and above-mentioned reflow step.
The manufacturing method of component-mounted substrate of the present invention is characterized in that, the heat cure of hot curing resin composition layer
The shrinking percentage (S1) in the directions x-y after step compared with the hot curing resin composition layer before thermal cure step, be 0.35% with
Under, preferably 0.3% or less, more preferably 0.2% hereinafter, the directions x-y of solidified material layer after reflow step shrinking percentage
(S2) compared with the hot curing resin composition layer before thermal cure step, it is 0.4% or less, is preferably 0.3% or less, more preferably
For 0.2% hereinafter, and S1 and S2 meet the relationship of S2-S1≤0.08, preferably S2-S1≤0.05, more preferable S2-S1≤0.04.
The measurement of above-mentioned S1 and S2 carries out as follows.
The measurement ＞ of ＜ S1
The measurement of (1-1) initial length
4 jiaos in the rectangular resins of 200mm from hot curing resin composition layer (40 μm of thickness) count 20mm's or so
Part forms 4 through holes (by hole to be set as A, B, C, D clockwise using punching.), it is measured with non-contact type Image analyzer
Length L (L between the center in each hole formedAB、LBC、LCD、LDA、LAC、LBD) (referring to Fig.1).
The heat cure of (1-2) hot curing resin composition layer
The hot curing resin composition layer heating that length measurment is finished, carries out heat cure.
The measurement of (1-3) heat cure shrinking percentage
After heat cure, for thermoplastic resin composition's layer after solidification, non-contact type Image analyzer is used in the same manner as L
Measure the length L'(L' after the solidification between the center in each hole formed in (1-1)AB、L'BC、L'CD、L'DA、L'AC、L'BD),
Calculate s1AB=(LAB-L'AB)/LAB
Similarly, for LBCAnd L'BC、LCDAnd L'CD、LDAAnd L'DA、LACAnd L'AC、LBDAnd L'BDCalculate s1BC、s1CD、
s1DA、s1AC、s1DA,
Heat cure shrinking percentage is calculated with following formula,
Heat cure shrinking percentage [the shrinking percentage in the directions x-y：S1](%)
={ (s1AB+ s1BC+ s1CD+ s1DA+ s1AC+ s1DA)/6}×100。
The measurement ＞ of ＜ S2
(1-4) reflow step
The base material for the step of (1-3) will be completed carries out Reflow Soldering.
The measurement of (1-5) Reflow Soldering shrinking percentage
After reflow step, with (1-3) completely in the same manner as, with non-contact type Image analyzer in a manner of identical with L
Measure the length L " (L " after the Reflow Soldering between the center in each hole formed in (1-1)AB、L"BC、L"CD、L"DA、L"AC、L"BD),
Calculate s2AB=(LAB-L"AB)/LAB
Similarly, for LBCWith L "BC、LCDWith L "CD、LDAWith L "DA、LACWith L "AC、LBDWith L "BDCalculate s2BC、s2CD、
s2DA、s2AC、s2DA,
Reflow Soldering shrinking percentage is calculated with following formula,
Reflow Soldering shrinking percentage [the shrinking percentage in the directions x-y：S2](%)
={ (s2AB+ s2BC+ s2CD+ s2DA+ s2AC+ s2DA)/6}×100。
Above-mentioned parameter passes through heat being recorded it is preferable to use front, containing epoxy resin, curing agent and inorganic filling material
Hardening resin composition and can meet.According to such hot curing resin composition, can obtain suitable for insulating layer
Solidfied material, the insulating layer are that the contraction of insulating layer is suppressed, warpage is repressed, is difficult to generate the insulation of the deformation of substrate
Layer.The solidfied material of the hot curing resin composition is suitable for the manufacture of component-mounted substrate (especially semiconductor mounting substrate),
It is particularly suitable to form the insulating layer of substrate.The thickness of one solidified material layer (insulating layer) is usually 3~200 μm or so, in multilayer
When change, the thickness of insulating layer entirety can also be thicker than this, usually 10~300 μm or so.
＜ hot curing resin compositions ＞
The embodiment of the present invention is to provide the hot curing resin composition for being used to form insulating layer.
For above-mentioned hot curing resin composition, with according to the thermal reflow profile of IPC/JEDEC J-STD-020C
Figure the solidfied material of the hot curing resin composition is heated after the directions x-y shrinking percentage (S2) for 0.4% hereinafter, institute
The solidfied material for stating the hot curing resin composition is that the shrinking percentage (S1) in the directions x-y after heat cure is 0.35% below
Under the conditions of carried out the solidfied material of heat cure, and S1 and S2 meet the relationship of S2-S1≤0.08.
Heat cure has been carried out under the conditions of as long as being 0.35% below by the shrinking percentage (S1) in the directions x-y after heat cure
The hot curing resin composition solidfied material, to be added according to the thermal reflow profile figure of IPC/JEDEC J-STD-020C
The shrinking percentage (S2) in the directions x-y after heat be 0.4% hereinafter, and S1 and S2 meet the relationship of S2-S1≤0.08, then the thermoplasticity
After the high temperature that resin combination is installed even across the component for using reflow step, it is also difficult to generate the warpage of substrate, fit
Together in the insulating layer for forming slim component-mounted substrate.
The suitable example for the raw material that can be used in thermoplastic resin composition is as described above.
For the assay method of S1 and S2, as described above.
The thermal reflow profile figure described in IPC/JEDEC J-STD-020C is referred in Fig. 2 and table 1~3.For
It time, can be any condition of the range described in table, for example, if being Sn-Pb eutectic solders, then can enumerate ts=
90 seconds, tLCondition as=105 seconds, tp=20 seconds can then enumerate ts=120 seconds, t if it is no Pb slicken soldersL=105
Condition as second, tp=30 seconds.In addition component mentioned here in the present invention, is equivalent to and carries out component peace using Reflow Soldering
Substrate before dress.As component thickness, if it is Sn-Pb eutectic solders, then preferably smaller than 2.5mm, if it is no Pb soft solderings
Material, then preferably smaller than 2.5mm, most preferably less than 2.5mm~1.6mm, and then most preferably less than 1.6mm.
Table 1
。
Reflow Soldering peak temperature when 2 SnPb eutectics of table
。
Reflow Soldering peak temperature when table 3 is without Pb
。
Above-mentioned hot curing resin composition can be suitable as being used to form the tree of the insulating layer of multilayer printed circuit board
Oil/fat composition (resin compositions for insulating layer on internal substrate) uses.By using above-mentioned hot curing resin composition
The insulating layer for forming multilayer printed circuit board, can inhibit the contraction of insulating layer, can realize the exhausted of the deformation for being difficult to generate substrate
Edge layer, the problem of warpage of substrate can be significantly improved.It, can in the manufacture for the multilayer printed circuit board that stack manner is utilized
To be suitable as being used to form the resin combination (the stacking resin compositions for insulating layer of multilayer printed circuit board) of insulating layer
It uses, being suitable as being used to form the resin combination of insulating layer in turn, (multilayer that conductor layer is formed using plating is printed
The stacking resin compositions for insulating layer of brush wiring board) it uses, the insulating layer is to utilize plating to form conductor layer on it
Layer.In addition, above-mentioned hot curing resin composition also may be used in the case where multilayer printed circuit board is component built-in circuit plate
With it is preferable to use.I.e. resin combination of the invention can be suitable as the resin of the component for embedding component built-in circuit plate
Composition (component resin composition for sealing) uses.For the core substrate used in the manufacture of component built-in circuit plate, tool
It is useful for the cavity of inside components, and the requirement of the miniaturization due to component built-in circuit plate itself, and has cavity density change
High tendency, due to core substrate rigidity insufficient warpage the problem of have the tendency that becoming even more serious, but by using upper
Hot curing resin composition is stated as component resin composition for sealing, even if using the high and thin core substrate of cavity density
When, the problem of can also significantly alleviating warpage.
＜ prepregs ＞
Above-mentioned hot curing resin composition can be impregnated into sheet-like fiber base material and become prepreg.Prepreg is to make
Substance made of above-mentioned hot curing resin composition is impregnated into sheet-like fiber base material.
The sheet-like fiber base material used in prepreg is not particularly limited, and can use glass cloth, aromatic polyamides nonwoven
Cloth, liquid crystal polymer non-woven fabrics etc. are used as the common substance of prepreg base material.It is being used to form the exhausted of multilayer printed circuit board
When edge layer, can be suitble to using thickness be 50 μm of slim sheet-like fiber base materials below, in particular it is preferred to thickness be 10 μm~
40 μm of sheet-like fiber base material, the sheet-like fiber base material that more preferable thickness is 10 μm~30 μm, and then preferred thickness are 10~20 μ
The sheet-like fiber base material of m.As the concrete example of the glass cloth base material as sheet-like fiber base material, rising sun シ ュ エ ー ベ can be enumerated
" ス タ イ Le 1027MS " (75/25mm of warp count, 75/25mm of weft count, cloth weight 20g/m of Le (strain) system2、
19 μm of thickness), rising sun シ ュ エ ー ベ Le (strain) system " ス タ イ Le 1037MS " (70/25mm of warp count, weft count 73
Root/25mm, cloth weight 24g/m2, 28 μm of thickness), (strain) You swamp makes made " 1078 " (54/25mm of warp count, latitude
54/25mm of yarn density, cloth weight 48g/m2, 43 μm of thickness), (strain) You swamp makes made " 1037NS " (warp count 72
Root/25mm, 69/25mm of weft count, cloth weight 23g/m2, 21 μm of thickness), (strain) You swamp makes made " 1027NS "
(75/25mm of warp count, 75/25mm of weft count, cloth weight 19.5g/m2, 16 μm of thickness), (strain) You swamp make institute
" 1015NS " (95/25mm of warp count, 95/25mm of weft count, cloth weight 17.5g/m of system2, 15 μm of thickness),
(strain) You swamp makes made " 1000NS " (85/25mm of warp count, 85/25mm of weft count, cloth weight 11g/m2、
10 μm of thickness) etc..Additionally as the concrete example of liquid crystal polymer non-woven fabrics, (strain) Network ラ レ, fragrant adoption can be enumerated
" ベ Network Le ス " (6~15g/m of weight per unit area that meltblown is utilized of ester non-woven fabrics2), " ベ Network ト ラ Application " etc..
Prepreg can utilize method well known to hot melt, solvent method etc. to manufacture.
In the embodiment of the present invention, preferably component-mounted substrate, wherein hot curing resin composition layer is
On internal substrate upper layer, pressure zone has the prepreg of carrier and the layer that is formed, and the prepreg with carrier is formed on a carrier film
There is prepreg made of above-mentioned hot curing resin composition is impregnated into fiber base material.
＜ has used the multilayer printed circuit board ＞ of prepreg
Then, an example for using the method for the prepreg manufactured as described above manufacture multilayer printed circuit board is said
It is bright.It is overlapped 1 in circuit board or is overlapped multiple prepregs of the invention as needed and is pressed from both sides with metallic plate via mold release film
It holds, vacuum pressed lamination is carried out under pressurization, heating condition.Pressurization, heating condition are preferably 5~40kgf/cm in pressure2
(49×104~392 × 104N/m2), temperature be 120~200 DEG C in the case of carry out 20~100 minutes.In addition also can with it is bonding
Film similarly, after being laminated prepreg in circuit board using vacuum layer platen press, is heating and curing.Then, with it is above-mentioned
The method of record similarly, after cured prepreg surface roughening, forms conductor layer using plating and can manufacture multilayer
Printed wiring board.
＜ adhering films ＞
Adhering film can be formed using above-mentioned hot curing resin composition.
In one embodiment, the resin combination that adhering film of the invention contains supporter and engaged with the supporter
Nitride layer, resin composition layer include above-mentioned hot curing resin composition.
Adhering film can for example be formed as got off：Above-mentioned heat-curing resin combination has been dissolved in preparation in organic solvent
The resin varnish is coated on supporter by the resin varnish of object using chill coating machine etc., and resin varnish drying is made to carry out shape
At.
Organic solvent can enumerate ketone, second such as acetone, methyl ethyl ketone (hereinafter also referred to " MEK ") and cyclohexanone
It is the acetate esters such as acetoacetic ester, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, molten
Aromatic hydrocarbon, dimethylformamide, the dimethylacetylamides such as the carbitols such as fine agent and butyl carbitol class, toluene and dimethylbenzene
With the acid amides series solvents such as N-Methyl pyrrolidone etc..Organic solvent can be used alone, or be two kinds or more.
The drying of resin varnish can be brushed etc. using heating, hot wind well known to drying means implement.It is clear according to resin
The boiling point of organic solvent in paint and it is different such as clear using the resin of the organic solvent containing 30 mass of mass %~60 %
When paint, by the way that in 50 DEG C~150 DEG C dryings 3 minutes~10 minutes, adhering film can be formed.
As the supporter used in the formation of adhering film, the film being molded of plastic material, metal foil can be enumerated
(copper foil, aluminium foil etc.), processing release paper are suitble to using the film being molded of plastic material.As plastic material, such as poly- pair can be enumerated
Polyethylene terephthalate (hereinafter sometimes referred to simply as " PET "), polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN ") etc. are poly-
The acrylic acid series such as ester, makrolon (hereinafter sometimes referred to simply as " PC "), polymethyl methacrylate (PMMA), cyclic polyolefin,
Tri acetyl cellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferred poly terephthalic acid second
Diester, polyethylene naphthalate, particularly preferably cheap polyethylene terephthalate.In a suitable embodiment party
In formula, supporter is polyethylene terephthalate film.
It can implement delustring processing, sided corona treatment to the face of supporter engaged with resin composition layer.
In addition, as supporter, the carrying with release layer on the face engaged with resin composition layer can be used to take off
The supporter of mold layer.As the releasing agent used in the release layer of the supporter with release layer, can enumerate for example selected from
The releasing agent of one or more of alkyd resin, vistanex, polyurethane resin and organic siliconresin.
In the present invention, the supporter for carrying release layer can use commercially available product.As commercially available product, it can enumerate and for example have
Have using alkyd resin system releasing agent as the PET film of the release layer of principal component, i.e. リ Application テ ッ Network (strain) system " SK-1 ", " AL-5 ",
" AL-7 " etc..
The thickness of supporter is not particularly limited, preferably 5 μm~75 μm, more preferably 10 μm~60 μm.It should be noted that
When supporter is the supporter with release layer, the thickness of the supporter entirety of release layer is preferably carried within the above range.
In the adhering film manufactured as described above using above-mentioned hot curing resin composition, the thickness of resin composition layer
Degree is not particularly limited, and from the point of view of the slimming of multilayer printed circuit board, preferably 100 μm hereinafter, more preferably 80 μ
M hereinafter, in turn be preferably 60 μm hereinafter, in turn be more preferably 50 μm or less.The lower limit of the thickness of resin composition layer is usually
15 μm or more.
In the adhering film manufactured as described above using above-mentioned hot curing resin composition, in resin composition layer
On the face (that is, face with supporter opposite side) not engaged with supporter, can and then the protective film being consistent with supporter be folded
Layer.The thickness of protective film is not particularly limited, for example, 1 μm~40 μm.By the way that protective film is laminated, can prevent dust etc. to
The attachment on the surface of resin composition layer prevents scar.Adhering film can be rolled into a roll to preserve, in multilayered printed circuit
When forming insulating layer in the manufacture of plate, it can be used by removing protective film.
In the embodiment of the present invention, preferably component-mounted substrate, wherein hot curing resin composition layer is logical
It crosses and the adhering film for foring the thick composition layer of heat-curing resin on a carrier film is pressed on internal substrate upper layer and is formed.
＜ has used the multilayer printed circuit board ＞ of adhering film
For use the adhering film that manufactures as described so manufacture multilayer printed circuit board method an example into
Row explanation.
First, adhering film is laminated to the one or both sides of circuit board using vacuum laminator.As in circuit base
The substrate used in plate can enumerate such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resins
Substrate, thermohardening type polyphenylene oxide substrate etc..It should be explained that, wherein circuit board refer to above-mentioned such substrate one side or
The substance for the conductor layer (circuit) for having carried out pattern processing is formed on two sides.In addition, folded for replacing conductor layer with insulating layer
Multilayer printed circuit board made of layer, the outermost one or both sides for being formed as the multilayer printed circuit board have carried out pattern and have added
The substance of the conductor layer (circuit) of work is also contained in circuit board described here.It should be noted that can by Darkening process,
Copper etching etc. implements roughening treatment in advance in conductor layer surface.
In above-mentioned lamination, when adhering film has protective film, after removing the protective film, as needed by adhering film and
Circuit board preheats, and adhering film is crimped on while being pressurizeed and being heated in circuit board.For the viscous of the present invention
Film is connect, it is preferable to use being laminated to the method in circuit board under reduced pressure using vacuum layer platen press.The condition of lamination is without spy
It does not limit, such as crimping temperature (laminating temperature) is preferably made to be preferably 70~140 DEG C, crimping pressure is made to be preferably 1~11kgf/
cm2(9.8×104~107.9 × 104N/m2), it is laminated in the case where air pressure is 20mmHg (26.7hPa) decompression below.Separately
Outside, the method for lamination can be intermittent, can also be the continous way that roller is utilized.Vacuum lamination can use commercially available vacuum
Laminating machine carries out.As commercially available vacuum laminator, such as ニ チ ゴ ー モ ー ト Application (strain) バ キ ュ ー system processed can be enumerated
ア ッ プ リ ケ ー タ ー, (strain) name mechanism make made vacuum pressure type laminating machine, (strain) Hitachi イ Application ダ ス ト リ イ ズ roll-types
Dry type coating machine, Hitachi エ ー ア イ ー シ ー (strain) vacuum laminator processed etc..
In addition, under reduced pressure, the laminating step that is heated and pressurizeed can also be carried out using general vacuum hotpressing machine.
Such as it can be carried out by the way that the metallic plates such as warmed-up SUS plates pressurize from support body layer side.Pressurized conditions are to make vacuum degree
Usually 1 × 10-2MPa or less, preferably 1 × 10-3Under MPa decompressions below.Being heated and pressurizeed also can be within a stage
It carries out, but from the point of view of the exudation of control resin, it is more than the stage to be preferably divided into two for condition to carry out.For example, excellent
Choosing is by the pressurization in the 1st stage temperature is 70~150 DEG C, pressure is 1~15kgf/cm2Range under conditions of carry out, by the 2nd
The pressurization in stage is temperature is 150~200 DEG C, pressure is 1~40kgf/cm2Range under conditions of carry out.Each stage when
Between preferably carry out 30~120 minutes.As commercially available vacuum hotpressing machine, such as MNPC-V-750-5-200 ((strain) can be enumerated
Name mechanism is made made), VH1-1603 (Beichuan essence machine (strain) system) etc..
Hot curing resin composition layer preferably will form the thick composition layer of heat-curing resin on a carrier film
The layer that adhering film is formed in internal substrate upper layer pressure.After adhering film is laminated in circuit board, it is cooled to room temperature attached
It after close, is removed in the case where removing supporter, heat cure is carried out, it is possible thereby to form insulating layer in circuit board.Thermosetting
The condition of change is suitably selected according to type, content of the resin component in resin combination etc., preferably select 150 DEG C~
220 DEG C, 20 minutes~180 minutes, more preferably 160 DEG C~210 DEG C of selection, 30~120 minutes ranges.
After forming the insulating layer, it in the case of not removing supporter before curing, is removed herein.Then, according to need
Trepanning is carried out to the insulating layer being formed in circuit board, form through-hole, open-work.Trepanning for example can by drill bit, laser,
Method well known to plasma etc. or as needed combine these methods carries out, using carbon dioxide gas laser,
The trepanning of the lasers such as YAG laser is most conventional methods.
Then, conductor layer is formed on the insulating layer using dry type plating or wet type plating.Dry type plating can use vapor deposition,
Method well known to sputtering, ion plating etc..It is the case where for wet type plating, molten by carrying out surface of insulating layer successively to be utilized
The swelling treatment of swollen liquid, the roughening treatment that oxidant is utilized and the neutralisation treatment that neutralizer is utilized, form the anchor of convex-concave
(anchor).The swelling treatment of swelling solution is utilized by making insulating layer be impregnated 5~20 minutes at 50~80 DEG C, in swelling solution
Come carry out.As swelling solution, aqueous slkali, surfactant solution etc., preferably aqueous slkali can be enumerated, as the aqueous slkali,
It can enumerate such as sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling solution, such as ア ト テ ッ Network can be enumerated
ス ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス P (the Swelling Dip Securiganth of ジ ャ パ Application (strain) system
P), ス ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス SBU (Swelling Dip Securiganth SBU) etc..It is utilized
The roughening treatment of oxidant by make insulating layer impregnate at 60 DEG C~80 DEG C, in oxidizing agent solution 10 minutes~30 minutes come
It carries out.As oxidant, the alkali that potassium permanganate or sodium permanganate have for example been dissolved in the aqueous solution of sodium hydroxide can be enumerated
Property permanganic acid solution, bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc..In addition, the permanganic acid in alkaline permanganic acid solution
The concentration of salt is preferably 5~10 weight %.As commercially available oxidant, such as ア ト テ ッ Network ジ ャ パ Application (strain) system can be enumerated
The alkalinity Gao Meng such as U Application セ Application ト レ ー ト U Application パ Network ト CP, De ー ジ Application グ ソ リ ュ ー シ ョ Application セ キ ュ リ ガ Application ス P
Acid solution.The neutralisation treatment that neutralizer is utilized is carried out by impregnating 3~10 minutes at 30~50 DEG C, in neutralizer.Make
For neutralizer, preferably acid aqueous solution the リ ダ Network of ア ト テ ッ Network ジ ャ パ Application (strain) system can be enumerated as commercially available product
ションソリューシン・セキュリガントP。
Then, electroless coating and plating compositions are formed into conductor layer.Alternatively, it is also possible to formed with conductor layer be opposite pattern
Resist pattern, merely with electroless coating formed conductor layer.As the method that pattern later is formed, such as ability can be used
Subtract each other (subtractive) method, semi-additive process etc. well known to field technique personnel.
By using multilayer printed circuit board, it can manufacture and be mounted with the components such as semiconductor chip, insertion piece, passive element
Substrate, the multilayer printed circuit board manufactured using above-mentioned hot curing resin composition.
An example of the manufacturing method of semiconductor mounting substrate is shown.
＜ semiconductor mounting substrates ＞
By the conducting position installation half for stating the multilayer printed circuit board of hot curing resin composition manufacture in use
Conductor chip can manufacture semiconductor mounting substrate." conducting position " refers to " electric signal in conduction multilayer printed circuit board
Position ", position can be any one of surface or the position of landfill.In addition, as long as semiconductor chip is using semiconductor as material
The circuit element of material, is not particularly limited.
As long as the installation method of semiconductor chip when manufacturing above-mentioned semiconductor mounting substrate makes semiconductor chip effectively
It functions, is not particularly limited, specifically, wire bonding installation method, flip-chip installation method, profit can be enumerated
With the installation method of bumpless build up layer (バ Le プ な ビ Le De ア ッ プ Layer, BBUL), utilize anisotropic conductive film
(ACF) installation method utilizes the installation method etc. of non-conductive film (NCF).
Embodiment
Hereinafter, the present invention is further illustrated based on embodiment and comparative example, but the present invention is not limited to embodiments below.
It should be noted that " part " in following record refers to " mass parts ".
It is illustrated firstly, for the assay method of the evaluation of physical property in this specification, evaluation method.
[measurement of shrinking percentage]
The preparation of the polyimide film of (1-1) with resin
Using intermittent vacuum pressurization laminating machine, (2 stage of (strain) ニ チ go ー モ ー ト Application systems stacks laminating machine
CVP700), by the resin sheet (200mm square) made in following making examples so that resin composition layer and polyimide film
(mode that the center of the even surface of the emerging production (strain) ユ ー ピ レ ッ Network ス 25S, 25 μ m-thicks, 240mm square) in space portion connects,
It is laminated on single side,.Lamination is by making air pressure for after 13hPa or less by carrying out decompression in 30 seconds, in 100 DEG C, pressure 0.74MPa
Under the conditions of crimp 30 seconds to implement.
The measurement of (1-2) initial length
For the polyimide film with resin of gained, from the supporter of resin sheet, from the rectangular resins of 200mm
4 jiaos of parts for counting 20mm or so, using punching formed 4 through holes (diameter about 6mm) (by hole be set as clockwise A, B, C,
D.), after the supporter of resin sheet is removed, with non-contact type Image analyzer ((strain) ミ Star ト ヨ systems, Quick Vision types
Formula：QVH1X606-PRO III_BHU2G) measure formed each hole center between length L (LAB、LBC、LCD、LDA、LAC、LBD)
(referring to Fig.1).
The heat cure of (1-3) resin composition layer
The polyimides film surface for surveying the long polyimide film with resin finished is arranged in 255mm × 255mm rulers
In very little glass cloth base material epoxy resin double-sided copper-clad laminated board (0.7mm is thick, Matsushita Electrician (strain) makes " R5715ES "), by four
While it is fixed with Kapton Tape (width 10mm), it is heated 90 minutes at 150 DEG C, resin composition layer is subjected to heat cure, is obtained
To solidified material layer.Similarly, 90 minutes are heated at 190 DEG C, is heated 90 minutes at 200 DEG C, and solidified material layer is respectively obtained.
The measurement of (1-4) heat cure shrinking percentage
After heat cure, Kapton Tape is removed, the polyimide film with solidified material layer is removed from laminated plate, in turn
Solidified material layer is removed from polyimide film, is measured in (1-2) with non-contact type Image analyzer in a manner of same as L
The length L'(L' after solidification between the center in each hole formedAB、L'BC、L'CD、L'DA、L'AC、L'BD),
Calculate s1AB=(LAB-L'AB)/LAB；
Similarly, for LBCAnd L'BC、LCDAnd L'CD、LDAAnd L'DA、LACAnd L'AC、LBDAnd L'BDCalculate s1BC、s1CD、
s1DA、s1AC、s1DA,
Heat cure shrinking percentage is calculated with following formula,
Heat cure shrinking percentage [the shrinking percentage in the directions x-y：S1](%)
={ (s1AB+ s1BC+ s1CD+ s1DA+ s1AC+ s1DA)/6}×100。
(1-5) reflow step
Reflow soldering apparatus (Japanese ア Application ト system (strain) system of the base material for the step of (1-3) will be completed in 260 DEG C of peak temperature
" HAS-6116 ", temperature profile are according to IPC/JEDEC J-STD-020C) in by primary.
The measurement of (1-6) Reflow Soldering shrinking percentage
After reflow step, with (1-4) completely in the same manner as, with non-contact type Image analyzer in a manner of identical with L
Measure the length L " (L " after the Reflow Soldering between the center in each hole formed in (1-2)AB、L"BC、L"CD、L"DA、L"AC、L"BD),
Calculate s2AB=(LAB-L"AB)/LAB；
Similarly, for LBCWith L "BC、LCDWith L "CD、LDAWith L "DA、LACWith L "AC、LBDWith L "BDCalculate s2BC、s2CD、
s2DA、s2AC、s2DA,
Reflow Soldering shrinking percentage is calculated with following formula,
Reflow Soldering shrinking percentage [the shrinking percentage in the directions x-y：S2](%)
={ (s2AB+ s2BC+ s2CD+ s2DA+ s2AC+ s2DA)/6}×100。
[preparation of Reflow Soldering behavior evaluation substrate]
The preparation of (2-1) internal substrate
As internal substrate, preparing glass cloth base material epoxy resin laminate plate, [copper foil etches the ア Application Network ラ ッ De after coming
Plate, 0.06mm are thick, Sumitomo ベ ー Network ラ イ ト (strain) make " LaXY-4785TH-B "].
The lamination of (2-2) resin sheet
Using intermittent vacuum pressurization laminating machine, (2 stage of (strain) ニ チ go ー モ ー ト Application systems stacks laminating machine
CVP700), in a manner of so that resin composition layer is connected with internal substrate, the resin sheet made in following making examples is laminated to
Internal substrate it is two-sided.It is laminated implementation of such as getting off：Decompression 30 seconds, after making air pressure be 13hPa or less, in 100 DEG C, pressure
It is set to crimp under conditions of 0.74MPa 30 seconds.Then, hot pressing in 60 seconds is carried out in the condition of 100 DEG C, pressure 0.5MPa.
The heat cure of (2-3) resin composition layer
After removing the supporter of resin sheet from the substrate for be laminated resin sheet, heated 90 minutes at 150 DEG C, by resin
Composition layer carries out heat cure, obtains solidified material layer.Similarly, 90 minutes are heated at 190 DEG C, are heated 90 minutes at 200 DEG C, point
Solidified material layer is not obtained.
(2-4) Reflow Soldering behavior evaluation
A piece (Ge pieces) of 45mm square is cut into afterwards (n=5), in 260 DEG C of reflow soldering apparatus (Japanese ア Application ト of peak temperature
System (strain) makes " HAS-6116 ") in pass through primary (condition is also according to IPC/JEDEC J-STD-020C).Then, it uses
Shadow Moire devices (Akrometrix TherMoire AXP), with according to IPC/JEDEC J-STD-020C (peak temperatures
260 DEG C) temperature profile from substrate lower part heat, measure the buckling behavior of the 10mm square part of substrate center.
Even if the difference of the maximum height of the displacement data of gained and minimum height is had 1 sample in whole temperature ranges
Product be 40 μm or more of situation be denoted as ×, the case where whole samples are both less than 40 μm, is denoted as zero.
The resin sheet 1,2,3 and 4 used in embodiment and comparative example is according to following sequentially builts.
＜ makes example 1 (making of resin sheet 1) ＞
Make bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) makes " 828EL ", epoxide equivalent about 185) 12 while stirring
Part, 3 parts of naphthalene type epoxy resin (DIC (strain) makes " P4032SS ", epoxide equivalent about 144), biphenyl type epoxy resin (Mitsubishi Chemical
(strain) makes " YX4000HK ", epoxide equivalent about 185) 6 parts, biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", ring
(Mitsubishi Chemical's (strain) makes the MEK/ rings of " YX6954BH30 ", 30 mass % of solid constituent for about 288) 25 parts of oxygen equivalent, phenoxy resin
The solution of hexanone=1/1) 20 parts dissolve by heating in 15 parts of solvent naphtha.After being cooled to room temperature, mixing thereto contains triazine
(DIC (strain) systems " LA-7054 ", hydroxyl equivalent 125, the MEK of solid constituent 60% are molten for the linear phenol-aldehyde resin system curing agent of skeleton
Liquid) 20 parts, (Nippon Steel's chemistry (strain) system " SN485 ", hydroxyl equivalent 215, the MEK of solid constituent 60% are molten for naphthols system curing agent
Liquid) 10 parts, it is 0.4 part of the curing accelerator MEK solution of 5 mass % of solid constituent (4-dimethylaminopyridine (DMAP)), fire-retardant
(three light (strain) are made " HCA-HQ ", 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, are put down for agent
Equal 2 μm of grain size) 3 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain) makes " KBM573 ") carried out surface treatment
(0.25 μm of average grain diameter, (strain) ア De マ テ ッ Network ス systems " SOC1 ", the carbon amounts of per unit surface area are preparing spherical SiO 2
0.36mg/m2) 40 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain) makes " KBM573 ") carried out surface treatment
(0.2 μm of average grain diameter, Asahi Glass (strain) system " AZ fillers ", the carbon amounts of per unit surface area are 0.38mg/ to spherical glass filler
m2) 10 parts, it is uniformly dispersed with high speed rotation mixer, prepares resin varnish 1.
Then, in the de- of the PET film (リ Application テ ッ Network (strain) makes " AL5 ", 38 μm of thickness) with alkyd resin system release layer
Mold layer side is equably coated with resin varnish 1, so that the thickness of the resin composition layer after dry is 40 μm, it is (flat at 80~120 DEG C
Equal 100 DEG C) it is 5 minutes dry, make resin sheet 1.
＜ makes example 2 (making of resin sheet 2) ＞
Make bisphenol-type epoxy resin (Nippon Steel's chemistry (strain) system " ZX1059 ", bisphenol A-type and Bisphenol F while stirring
(Mitsubishi Chemical's (strain) makes " YX4000HK ", epoxy to about 169) 5 parts of 1: 1 melange, epoxide equivalent, the biphenyl type epoxy resin of type
About 185) 12 parts of equivalent, 9 parts of dicyclopentadiene-type epoxy resin (DIC (strain) makes " HP-7200H ", epoxide equivalent about 275), benzene
16 parts of oxygen resin (Mitsubishi Chemical's (strain) makes MEK/ cyclohexanone=1/1 solution of " YL7553BH30 ", 30 mass % of solid constituent) plus
Heat of solution is in 30 parts of solvent naphtha.After being cooled to room temperature, (DIC (strain) makes mixed active ester system curing agent thereto
The toluene solution of " HPC8000-65T ", active group equivalent about 223, non-volatile point of 65 mass %) 40 parts, curing accelerator (4- bis-
The MEK solution of dimethylaminopyridine, 5 mass % of solid constituent) 3 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain)
System " KBM573 ") preparing spherical SiO 2 (0.5 μm of average grain diameter, (strain) ア De マ テ ッ Network ス systems that are surface-treated
The carbon amounts 0.39mg/m of " SOC2 ", per unit surface area2) 100 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain)
System " KBM573 ") be surface-treated spherical glass filler (0.2 μm of average grain diameter, Asahi Glass (strain) system " AZ fillers ", often
The carbon amounts 0.38mg/m of per surface area2) 40 parts, it is uniformly dispersing with high speed rotation mixer, prepare resin varnish 2.
Then, using resin varnish 2, resin sheet 2 is made with process same as example 1 is made.
＜ makes example 3 (making of resin sheet 3) ＞
Make 6 parts of naphthalene type epoxy resin (DIC (strain) makes " HP4032SS ", epoxide equivalent about 144), biphenyl while stirring
6 parts of type resin (Mitsubishi Chemical's (strain) makes " YX4000HK ", epoxide equivalent about 185), biphenyl type epoxy resin (Japanese chemical drug (strain)
Make " NC3000H ", about 288) 20 parts of epoxide equivalent, phenoxy resin (Mitsubishi Chemical's (strain) system " YL7553BH30 ", solid constituent 30
The MEK solution of quality %) 8 parts dissolve by heating in 15 parts of solvent naphtha.After being cooled to room temperature, bisphenol-A dicyan is mixed thereto
(ロ Application ザ ジ ャ パ Application (strain) makes " BA230S75 ", cyanate equivalent about 232, non-volatile point of 75 mass % to the prepolymer of acid esters
MEK solution) 20 parts, (ロ Application ザ ジ ャ パ Application (strain) makes " PT30S ", cyanic acid to novalac-type multifunctional cyanate ester resin
The MEK solution of ester equivalent about 133, non-volatile point of 85 mass %) 8 parts, (DIC (strain) makes " HPC8000- to active ester system curing agent
65T ", active group equivalent about 223 non-volatile point of 65 mass % toluene solution) 8 parts, curing accelerator (4- dimethylamino pyrroles
Pyridine, 5 mass % of solid constituent MEK solution) 0.4 part, (Tokyo is melted into (strain) system, acetylacetone cobalt (III), consolidates curing accelerator
The MEK solution of 1 mass % of body ingredient) 3 parts, (three light (strain) make " HCA-HQ ", 10- (2,5- dihydroxy phenyls) -10- to fire retardant
Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 2 μm of average grain diameter) 3 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry
(strain) makes " KBM573 ") preparing spherical SiO 2 (0.5 μm of average grain diameter, (strain) ア De マ テ ッ Network ス systems that are surface-treated
The carbon amounts 0.39mg/m of " SOC2 ", per unit surface area2) 50 parts, with amino silicone methane series coupling agent, (SHIN-ETSU HANTOTAI's chemical industry (strain) is made
" KBM573 ") be surface-treated spherical glass filler (0.2 μm of average grain diameter, Asahi Glass (strain) system " AZ fillers ", per single
The carbon amounts 0.38mg/m of bit surface area2) 50 parts, it is uniformly dispersing with high speed rotation mixer, prepare resin varnish 3.
Then, using resin varnish 3, resin sheet 3 is made with process same as example 1 is made.
＜ makes example 4 (making of resin sheet 4) ＞
Make bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) makes " 828EL ", epoxide equivalent about 185) 12 while stirring
Part, 3 parts of naphthalene type epoxy resin (DIC (strain) makes " HP4032SS ", epoxide equivalent about 144), biphenyl type epoxy resin (Mitsubishi Chemical
(strain) makes " YX4000HK ", epoxide equivalent about 185) 6 parts, biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", ring
(Mitsubishi Chemical's (strain) makes the MEK/ rings of " YX6954BH30 ", 30 mass % of solid constituent for about 288) 25 parts of oxygen equivalent, phenoxy resin
The solution of hexanone=1/1) 20 parts dissolve by heating in 10 parts of solvent naphtha.After being cooled to room temperature, mixing thereto contains triazine
(DIC (strain) systems " LA-7054 ", hydroxyl equivalent 125, the MEK of solid constituent 60% are molten for the linear phenol-aldehyde resin system curing agent of skeleton
Liquid) 20 parts, (Nippon Steel's chemistry (strain) system " SN485 ", hydroxyl equivalent 215, the MEK of solid constituent 60% are molten for naphthols system curing agent
Liquid) 10 parts, it is 0.4 part of the curing accelerator MEK solution of 5 mass % of solid constituent (4-dimethylaminopyridine (DMAP)), fire-retardant
(three light (strain) are made " HCA-HQ ", 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, are put down for agent
Equal 2 μm of grain size) 3 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain) makes " KBM573 ") carried out surface treatment
Preparing spherical SiO 2 (0.25 μm of average grain diameter, (strain) ア De マ テ ッ Network ス systems " SOC1 ", the carbon amounts of per unit surface area
0.36mg/m2) 40 parts, it is uniformly dispersing with high speed rotation mixer, prepare resin varnish 4.
Then, using resin varnish 4, resin sheet 4 is made using process same as example 1 is made.
＜ makes example 5 (making of resin sheet 5) ＞
Make 6 parts of naphthalene type epoxy resin (DIC (strain) makes " HP4032SS ", epoxide equivalent about 144), biphenyl while stirring
6 parts of type resin (Mitsubishi Chemical's (strain) makes " YX4000HK ", epoxide equivalent about 185), biphenyl type epoxy resin (Japanese chemical drug (strain)
Make " NC3000H ", about 288) 20 parts of epoxide equivalent, phenoxy resin (Mitsubishi Chemical's (strain) system " YL7553BH30 ", solid constituent 30
The MEK solution of quality %) 16 parts dissolve by heating in 5 parts of solvent naphtha.After being cooled to room temperature, bisphenol-A dicyan is mixed thereto
(ロ Application ザ ジ ャ パ Application (strain) makes " BA230S75 ", cyanate equivalent about 232, non-volatile point of 75 mass % to the prepolymer of acid esters
MEK solution) 20 parts, (ロ Application ザ ジ ャ パ Application (strain) makes " PT30S ", cyanic acid to novalac-type multifunctional cyanate ester resin
The MEK solution of ester equivalent about 133, non-volatile point of 85 mass %) 8 parts, (DIC (strain) makes " HPC8000- to active ester system curing agent
65T ", active group equivalent about 223 non-volatile point of 65 mass % toluene solution) 8 parts, curing accelerator (4- dimethylamino pyrroles
Pyridine, 5 mass % of solid constituent MEK solution) 0.4 part, (Tokyo is melted into (strain) system, acetylacetone cobalt (III), consolidates curing accelerator
The MEK solution of 1 mass % of body ingredient) 3 parts, (three light (strain) make " HCA-HQ ", 10- (2,5- dihydroxy phenyls) -10- to fire retardant
Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 2 μm of average grain diameter) 3 parts, with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry
(strain) makes " KBM573 ") preparing spherical SiO 2 (0.25 μm of average grain diameter, (strain) ア De マ テ ッ Network ス that are surface-treated
Make the carbon amounts 0.36mg/m of " SOC1 ", per unit surface area2) 40 parts, it is uniformly dispersing with high speed rotation mixer, prepare resin
Varnish 5.
Then, using resin varnish 5, resin sheet 5 is made using process same as example 1 is made.
The composition of the resin composition layer of resin sheet 1 to 5 is shown in table 4.
Table 4
。
The result of evaluation is shown in table 5.
Table 5
。
As shown in Table 5, it is 190 DEG C of (test examples in the temperature of thermal cure step even if equally using resin sheet 1
× 90 minute 1) in the case of, can be met present invention provide that composition, in contrast, 150 DEG C (test examples 5) ×
In the case of 90 minutes, cannot be met present invention provide that composition.In addition, even if equally using resin sheet 2, equally exist
In the case that the temperature of thermal cure step is 200 DEG C of (test example 2) × 90 minute, can be met present invention provide that combination
Object, in contrast, in the case of 150 DEG C of (test example 6) × 90 minute, cannot be met present invention provide that composition.
Resin sheet 1 has similar composition with resin sheet 4, but although thermal cure step is the same terms, test example 1AZ is filled out
The defined composition that material can obtain meeting the present invention cannot obtain meeting this hair in contrast, in the case of test example 4
Bright defined composition.
Resin sheet 3 has similar composition with resin sheet 5, although thermal cure step is the same terms, (the experiment of resin sheet 3
Example 3) the defined composition that can obtain meeting the present invention cannot obtain in contrast, the case where for resin sheet 5 (test example 7)
To the defined composition for meeting the present invention.In addition, the case where for resin sheet 5, even if changing the temperature of thermal cure step
It cannot obtain the defined composition (test example 8) for meeting the present invention.
Claims (36)
1. the manufacturing method of component-mounted substrate, which is characterized in that including：
The hot curing resin composition layer formed on internal substrate is heating and curing to and is formed the heat cure step of solidified material layer
Suddenly and
Using Reflow Soldering the substrate upper mounting component with solidified material layer reflow step,
Above-mentioned hot curing resin composition layer is formed by hot curing resin composition, or utilizes being thermally cured property resin group
Prepreg made of object is infiltrated in fiber base material is closed to be formed,
For above-mentioned hot curing resin composition, to be incited somebody to action according to the thermal reflow profile figure of IPC/JEDEC J-STD-020C
The solidfied material of the hot curing resin composition heated after the directions x-y shrinking percentage (S2) be 0.4% hereinafter, it is described should
The solidfied material of hot curing resin composition is that the shrinking percentage (S1) in the directions x-y after heat cure is 0.35% condition below
The lower solidfied material for carrying out heat cure, and S1 and S2 meet the relationship of S2-S1≤0.08.
2. according to the method described in claim 1, wherein, S1 is 0.3% or less.
3. according to the method described in claim 1, wherein, S1 is 0.2% or less.
4. according to the method described in claim 1, wherein, S2 is 0.3% or less.
5. according to the method described in claim 1, wherein, S2 is 0.2% or less.
6. according to the method described in claim 1, wherein, S1 and S2 meet the relationship of S2-S1≤0.05.
7. according to the method described in claim 1, wherein, S1 and S2 meet the relationship of S2-S1≤0.04.
8. according to the method described in claim 1, wherein, hot curing resin composition contains epoxy resin, curing agent and nothing
Machine packing material.
9. according to the method described in claim 8, wherein, containing silica as inorganic filling material.
10. according to the method described in claim 8, wherein, containing the silica doped with titanium as inorganic filling material.
11. according to the method described in claim 8, wherein, the involatile constituent in being thermally cured property resin combination is set as
When 100 mass %, the content of the inorganic filling material in hot curing resin composition is 40 mass % or more.
12. according to the method described in claim 1, wherein, the heating temperature in thermal cure step is 120 DEG C~240 DEG C.
13. according to the method described in claim 1, wherein, the peak temperature in reflow step is 210 DEG C~330 DEG C.
14. according to the method described in claim 1, wherein, hot curing resin composition layer is formed using above-mentioned prepreg.
15. according to the method described in claim 1, wherein, hot curing resin composition layer is in internal substrate upper layer pressure viscosity
The layer for connecing film and being formed, the adhering film are the films for being formed with the thick composition layer of heat-curing resin on a carrier film.
16. according to the method described in claim 1, wherein, hot curing resin composition layer is in internal substrate upper layer pressure zone
The layer for having the prepreg of carrier and being formed, the prepreg with carrier are formed with being thermally cured property resin group on a carrier film
Close prepreg made of object is impregnated into fiber base material.
17. according to the method described in claim 1, wherein, the thickness of solidified material layer is 3~200 μm.
18. according to the method described in claim 1, wherein, component is semiconductor chip, insertion piece or passive element.
19. according to the method for claim 18, wherein component is semiconductor chip.
20. hot curing resin composition is used to form insulating layer, which is characterized in that with according to IPC/JEDEC J-STD-
The thermal reflow profile figure of 020C the solidfied material of the hot curing resin composition is heated after the directions x-y contraction
Rate（S2）For 0.4% hereinafter, the solidfied material of the hot curing resin composition is the contraction in the directions x-y after heat cure
Rate（S1）The solidfied material of heat cure is carried out under the conditions of below for 0.35%, and S1 and S2 meet the relationship of S2-S1≤0.08.
21. hot curing resin composition according to claim 20, wherein S1 is 0.3% or less.
22. hot curing resin composition according to claim 20, wherein S1 is 0.2% or less.
23. hot curing resin composition according to claim 20, wherein S2 is 0.3% or less.
24. hot curing resin composition according to claim 20, wherein S2 is 0.2% or less.
25. hot curing resin composition according to claim 20, wherein S1 and S2 meets the pass of S2-S1≤0.05
System.
26. hot curing resin composition according to claim 20, wherein S1 and S2 meets the pass of S2-S1≤0.04
System.
27. hot curing resin composition according to claim 20, wherein the peak temperature of Reflow Soldering is 260 DEG C.
28. hot curing resin composition according to claim 27, wherein hot curing resin composition contains epoxy
Resin, curing agent and inorganic filling material.
29. hot curing resin composition according to claim 28, wherein contain titanium dioxide as inorganic filling material
Silicon.
30. hot curing resin composition according to claim 28, wherein as inorganic filling material contain doped with
The silica of titanium.
31. hot curing resin composition according to claim 28, wherein non-in being thermally cured property resin combination
When volatile ingredient is set as 100 mass %, the content of the inorganic filling material in hot curing resin composition be 40 mass % with
On.
32. prepreg, by the way that the hot curing resin composition described in any one of claim 27~31 is impregnated into fibre
It is formed in Wiki material.
33. multilayer printed circuit board, wherein utilize the hot curing resin composition described in any one of claim 27~31
Solidfied material and form insulating layer.
34. component-mounted substrate, wherein utilize the hot curing resin composition described in any one of claim 27~31
Solidfied material and form insulating layer.
35. component-mounted substrate according to claim 34, wherein component is semiconductor chip, insertion piece or passive member
Part.
36. component-mounted substrate according to claim 35, wherein component is semiconductor chip.
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| CN109454955B (en) * | 2018-12-19 | 2021-07-06 | 广东生益科技股份有限公司 | Packaging carrier tape base material and preparation method thereof |
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| CN1033065A (en) * | 1987-11-04 | 1989-05-24 | 株式会社日立制作所 | Compositions of thermosetting resin reaches by its prepreg that makes and laminated plate material |
| TW201311453A (en) * | 2011-06-21 | 2013-03-16 | Sumitomo Bakelite Co | Method for manufacturing laminated board |
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| JP4983228B2 (en) | 2005-11-29 | 2012-07-25 | 味の素株式会社 | Resin composition for insulating layer of multilayer printed wiring board |
| JP5256681B2 (en) * | 2007-10-05 | 2013-08-07 | 住友ベークライト株式会社 | Semiconductor device, printed wiring board for semiconductor device, and copper-clad laminate |
| JP2010087013A (en) * | 2008-09-29 | 2010-04-15 | Kyocera Chemical Corp | Method for manufacturing inter-layer insulating sheet, built-up multilayer substrate, and circuit board |
| TWI477549B (en) | 2009-02-06 | 2015-03-21 | Ajinomoto Kk | Resin composition |
| JP5703570B2 (en) * | 2010-03-01 | 2015-04-22 | 住友ベークライト株式会社 | Prepreg, laminated board, multilayer printed wiring board, and semiconductor device |
| WO2012176424A1 (en) * | 2011-06-21 | 2012-12-27 | 住友ベークライト株式会社 | Method for manufacturing laminated plate |
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| CN1033065A (en) * | 1987-11-04 | 1989-05-24 | 株式会社日立制作所 | Compositions of thermosetting resin reaches by its prepreg that makes and laminated plate material |
| TW201311453A (en) * | 2011-06-21 | 2013-03-16 | Sumitomo Bakelite Co | Method for manufacturing laminated board |
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