WO2012081615A1 - ポリアミド酸粒子の製造方法、ポリイミド粒子の製造方法、ポリイミド粒子及び電子部品用接合材 - Google Patents
ポリアミド酸粒子の製造方法、ポリイミド粒子の製造方法、ポリイミド粒子及び電子部品用接合材 Download PDFInfo
- Publication number
- WO2012081615A1 WO2012081615A1 PCT/JP2011/078899 JP2011078899W WO2012081615A1 WO 2012081615 A1 WO2012081615 A1 WO 2012081615A1 JP 2011078899 W JP2011078899 W JP 2011078899W WO 2012081615 A1 WO2012081615 A1 WO 2012081615A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- polyimide
- polyamic acid
- polyimide particles
- solution
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 501
- 239000004642 Polyimide Substances 0.000 title claims abstract description 266
- 229920001721 polyimide Polymers 0.000 title claims abstract description 266
- 239000000463 material Substances 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 99
- 239000002253 acid Substances 0.000 title abstract description 6
- 239000004952 Polyamide Substances 0.000 title abstract 5
- 229920002647 polyamide Polymers 0.000 title abstract 5
- -1 diamine compound Chemical class 0.000 claims abstract description 135
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- 229920005575 poly(amic acid) Polymers 0.000 claims description 129
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000013585 weight reducing agent Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 abstract description 59
- 230000009477 glass transition Effects 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 96
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 40
- 238000003756 stirring Methods 0.000 description 27
- 229920000647 polyepoxide Polymers 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- 150000004985 diamines Chemical class 0.000 description 24
- 239000003822 epoxy resin Substances 0.000 description 24
- 239000004065 semiconductor Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 150000008065 acid anhydrides Chemical class 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- 125000003700 epoxy group Chemical group 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000011256 inorganic filler Substances 0.000 description 17
- 229910003475 inorganic filler Inorganic materials 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 15
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 10
- 239000012756 surface treatment agent Substances 0.000 description 10
- 150000004984 aromatic diamines Chemical class 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 6
- UMGYJGHIMRFYSP-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC(N)=CC=C2O1 UMGYJGHIMRFYSP-UHFFFAOYSA-N 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000005462 imide group Chemical group 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- HKNMCRMFQXTDFE-UHFFFAOYSA-N 2-(2-aminophenyl)-1,3-benzoxazol-4-amine Chemical class NC1=CC=CC=C1C1=NC2=C(N)C=CC=C2O1 HKNMCRMFQXTDFE-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BDWOQDZGSYLSCZ-UHFFFAOYSA-N [1,3]oxazolo[4,5-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1OC=N2 BDWOQDZGSYLSCZ-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- IKSUMZCUHPMCQV-UHFFFAOYSA-N 2-(3-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound NC1=CC=CC(C=2OC3=CC=C(N)C=C3N=2)=C1 IKSUMZCUHPMCQV-UHFFFAOYSA-N 0.000 description 2
- VSMRWFMFAFOGGD-UHFFFAOYSA-N 2-(3-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound NC1=CC=CC(C=2OC3=CC(N)=CC=C3N=2)=C1 VSMRWFMFAFOGGD-UHFFFAOYSA-N 0.000 description 2
- IBKFNGCWUPNUHY-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2O1 IBKFNGCWUPNUHY-UHFFFAOYSA-N 0.000 description 2
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PMJNNCUVWHTTMV-UHFFFAOYSA-N [1,3]oxazolo[5,4-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1N=CO2 PMJNNCUVWHTTMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RXCOGDYOZQGGMK-UHFFFAOYSA-N (3,4-diaminophenyl)-phenylmethanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=CC=C1 RXCOGDYOZQGGMK-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- HQDYNFWTFJFEPR-UHFFFAOYSA-N 1,2,3,3a-tetrahydropyrene Chemical compound C1=C2CCCC(C=C3)C2=C2C3=CC=CC2=C1 HQDYNFWTFJFEPR-UHFFFAOYSA-N 0.000 description 1
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- ODANWMOQWMHGCY-UHFFFAOYSA-N 1,4-diaminobutan-2-one Chemical compound NCCC(=O)CN ODANWMOQWMHGCY-UHFFFAOYSA-N 0.000 description 1
- DDAPSNKEOHDLKB-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)naphthalen-2-amine Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=C(N)C=CC2=C1 DDAPSNKEOHDLKB-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 description 1
- YENVMPPRTXICRT-UHFFFAOYSA-N 2-(2,6-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C1=C(C(O)=O)C=CC=C1C(O)=O YENVMPPRTXICRT-UHFFFAOYSA-N 0.000 description 1
- DIXHWJYQQGNWTI-UHFFFAOYSA-N 2-[4-(5-amino-1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazol-5-amine Chemical compound NC1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=C(C=C4N=3)N)=NC2=C1 DIXHWJYQQGNWTI-UHFFFAOYSA-N 0.000 description 1
- SFZGLHDSSSDCHH-UHFFFAOYSA-N 2-[4-(6-amino-1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazol-6-amine Chemical compound C1=C(N)C=C2OC(C3=CC=C(C=C3)C3=NC4=CC=C(C=C4O3)N)=NC2=C1 SFZGLHDSSSDCHH-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- FUJGQJMITCJTFA-UHFFFAOYSA-N 3-[3-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=C(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)C=CC=2)=C1C(O)=O FUJGQJMITCJTFA-UHFFFAOYSA-N 0.000 description 1
- KHDSXXRHWXXXBY-UHFFFAOYSA-N 3-[4-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)=CC=2)=C1C(O)=O KHDSXXRHWXXXBY-UHFFFAOYSA-N 0.000 description 1
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical group C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 1
- 229960004012 amifampridine Drugs 0.000 description 1
- MRSWDOKCESOYBI-UHFFFAOYSA-N anthracene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C=C(C(C(=O)O)=C3)C(O)=O)C3=CC2=C1 MRSWDOKCESOYBI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- RBMTXFLUVLIQGN-UHFFFAOYSA-N dodecane-1,10-diamine Chemical compound CCC(N)CCCCCCCCCN RBMTXFLUVLIQGN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 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
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/27—Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
- H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
- H01L2224/13001—Core members of the bump connector
- H01L2224/13099—Material
- H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
- H01L2224/14—Structure, shape, material or disposition of the bump connectors prior to the connecting process of a plurality of bump connectors
- H01L2224/141—Disposition
- H01L2224/1412—Layout
- H01L2224/1413—Square or rectangular array
- H01L2224/14134—Square or rectangular array covering only portions of the surface to be connected
- H01L2224/14135—Covering only the peripheral area of the surface to be connected, i.e. peripheral arrangements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/16227—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation the bump connector connecting to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/27—Manufacturing methods
- H01L2224/273—Manufacturing methods by local deposition of the material of the layer connector
- H01L2224/2731—Manufacturing methods by local deposition of the material of the layer connector in liquid form
- H01L2224/2732—Screen printing, i.e. using a stencil
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/27—Manufacturing methods
- H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
- H01L2224/2741—Manufacturing methods by blanket deposition of the material of the layer connector in liquid form
- H01L2224/27416—Spin coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/27—Manufacturing methods
- H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
- H01L2224/2743—Manufacturing methods by blanket deposition of the material of the layer connector in solid form
- H01L2224/27436—Lamination of a preform, e.g. foil, sheet or layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29199—Material of the matrix
- H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29299—Base material
- H01L2224/29386—Base material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2224/29387—Ceramics, e.g. crystalline carbides, nitrides or oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29299—Base material
- H01L2224/29386—Base material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2224/29388—Glasses, e.g. amorphous oxides, nitrides or fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29299—Base material
- H01L2224/2939—Base material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29399—Coating material
- H01L2224/2949—Coating material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/8119—Arrangement of the bump connectors prior to mounting
- H01L2224/81191—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed only on the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/812—Applying energy for connecting
- H01L2224/81201—Compression bonding
- H01L2224/81203—Thermocompression bonding, e.g. diffusion bonding, pressure joining, thermocompression welding or solid-state welding
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/8138—Bonding interfaces outside the semiconductor or solid-state body
- H01L2224/81399—Material
- H01L2224/814—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/81438—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/81447—Copper [Cu] as principal constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/818—Bonding techniques
- H01L2224/81801—Soldering or alloying
- H01L2224/81815—Reflow soldering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/832—Applying energy for connecting
- H01L2224/83201—Compression bonding
- H01L2224/83203—Thermocompression bonding, e.g. diffusion bonding, pressure joining, thermocompression welding or solid-state welding
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/838—Bonding techniques
- H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
- H01L2224/92—Specific sequence of method steps
- H01L2224/921—Connecting a surface with connectors of different types
- H01L2224/9211—Parallel connecting processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
- H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
- H01L24/14—Structure, shape, material or disposition of the bump connectors prior to the connecting process of a plurality of bump connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
- H01L24/92—Specific sequence of method steps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01012—Magnesium [Mg]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01029—Copper [Cu]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/35—Mechanical effects
- H01L2924/351—Thermal stress
Definitions
- the present invention relates to a method for producing polyamic acid particles used as a raw material for polyimide particles having a small average particle diameter and high heat resistance. Moreover, this invention relates to the polyimide particle obtained by the manufacturing method of the polyimide particle using the manufacturing method of this polyamic acid particle, and the manufacturing method of this polyimide particle. In addition, the present invention relates to a bonding material for electronic parts, which has a low linear expansion coefficient and elastic modulus in a temperature region below the glass transition temperature after curing and can obtain a highly reliable bonded body.
- an adhesive mainly composed of liquid epoxy or the like, a die attach film, or the like is used.
- Such an adhesive is required to have a property of generating as little stress as possible on the bonded semiconductor chips after bonding.
- stress is generated in the semiconductor chip, for example, the substrate and the semiconductor chip, or the semiconductor chips are peeled off, which may cause a conduction failure of the semiconductor device.
- the linear expansion coefficient of the cured adhesive has been reduced by highly filling the adhesive with an inorganic filler.
- the inorganic filler is highly filled, the linear expansion coefficient of the cured adhesive can be decreased, but at the same time, the elastic modulus is increased, and it becomes difficult to sufficiently suppress the peeling of the semiconductor chip.
- Patent Document 1 includes an adhesive composition, conductive particles, and a plurality of insulating particles including one or both of polyamic acid particles and polyimide particles, and has excellent connection reliability and connection appearance. Circuit connection materials are described.
- a method for producing polyimide particles having a small particle size for example, in Patent Document 2, in a method of synthesizing polyimide from tetracarboxylic anhydride and a diamine compound, (a) a first solution containing tetracarboxylic anhydride and a diamine A first step of preparing a second solution containing a compound, (b) a second step of mixing the first solution and the second solution, and precipitating polyamic acid fine particles from the mixed solution; and (c) obtained.
- a method for producing polyimide fine particles is described that includes a third step of obtaining polyimide fine particles by imidizing polyamic acid fine particles.
- polyimide particles instead of the inorganic filler, the polyimide particles are decomposed at high temperatures during the manufacture of the semiconductor device, or the polyimide particles cause gas generation and voids are generated in the adhesive. A new problem has arisen. Accordingly, polyimide particles are also required to have high heat resistance, but polyimide particles having a sufficiently small particle diameter and high heat resistance have not been obtained by conventional methods.
- JP 2008-150573 A Japanese Patent No. 3478977
- the present invention includes a step of preparing a solution in which a diamine compound is dissolved, and a step of adding polytetracarboxylic anhydride in a non-solution state to the solution in which the diamine compound is dissolved while applying a physical impact to precipitate polyamic acid particles.
- a method for producing polyamic acid particles is a method for producing polyamic acid particles.
- the present invention also includes a curable compound, a curing agent, and polyimide particles, and the polyimide particles have an average particle size of 0.03 to 3 ⁇ m and a CV value of the particle size of 10 to 50%. It is a bonding material for an electronic component.
- the present invention is described in detail below.
- the present inventor adds a non-solution state tetracarboxylic anhydride to the solution in which the diamine compound is dissolved while preparing a solution in which the diamine compound is dissolved, and physical impact, thereby precipitating polyamic acid particles. It has been found that according to the method for producing polyamic acid particles having a process, polyamic acid particles used as a raw material for polyimide particles having a small average particle diameter and high heat resistance can be produced. In addition, the present inventor blends polyimide particles obtained by imidizing polyamic acid particles obtained by using such a method for producing polyamic acid particles into a bonding material for electronic parts, so that the glass transition after curing.
- the present inventor has not only a small average particle diameter of polyimide particles but a large surface area in the bonding material for electronic parts, We found that the value was also important. That is, if the polyimide particles are sufficiently filled to such an extent that the linear expansion coefficient and elastic modulus in the temperature range below the glass transition temperature after curing can be sufficiently reduced only by the small average particle diameter of the polyimide particles, the electronic component As a result, the fluidity of the bonding material for use decreases, and the applicability, film forming property and the like deteriorate.
- the present inventors set the average particle size of the polyimide particles to 0.03 to 3 ⁇ m, and further the CV value of the particle size to 10 to 50%. As a result, the linear expansion coefficient and elastic modulus in the temperature range below the glass transition temperature are lowered after curing, and a highly reliable bonded body can be obtained.
- the present inventors have found that the present invention can be accomplished and have completed the present invention.
- the manufacturing method of the polyamic acid particle of this invention the manufacturing method of the polyimide particle using the manufacturing method of this polyamic acid particle, and the polyimide particle obtained by the manufacturing method of this polyimide particle are demonstrated.
- the method for producing polyamic acid particles of the present invention first has a step of preparing a solution in which a diamine compound is dissolved.
- the said diamine compound is not specifically limited, For example, aromatic diamine, aliphatic diamine, alicyclic diamine etc. are mentioned. Especially, since the polyamic acid produced
- aromatic diamine examples include 1,4-phenylenediamine (PPD), 1,3-phenylenediamine, 1,2-phenylenediamine, 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO), 4,4′-diaminodiphenyl ether (DPE), 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane (DDM), 4,4′-bis (4-aminophenoxy) biphenyl (BAPB), 1,4 '-Bis (4-aminophenoxy) benzene (TPE-Q), 1,3'-bis (4-aminophenoxy) benzene (TPE-R), 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl Sulfone, 3,3'-diaminodiphenylsulfone, 4,4'-methylene-bis (2-chlor
- Examples of the aliphatic diamine include 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,10-diaminododecane, 1,4-diamino-2-butanone, and the like.
- Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4,4′-diaminodicyclohexylmethane, and the like.
- the solvent for dissolving the diamine compound preferably has a boiling point of less than 150 ° C.
- the boiling point is less than 150 ° C.
- the solvent contained in the polyamic acid particles can be easily removed without removing the solvent after the production of the polyamic acid particles without performing a high-temperature and long-time treatment.
- generation of voids due to residual solvent is greatly reduced. be able to.
- Examples of the solvent for dissolving the diamine compound include acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, toluene, xylene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N, N— Examples include dimethylacetamide, N-methyl-2-pyrrolidone, 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetanilide, methanol, ethanol, isopropanol and the like.
- a solvent for dissolving these diamine compounds may be used alone, or two or more of them may be used in combination in order to adjust the solubility of the diamine compound and the solubility of the polyamic acid generated in the steps described later. Also good.
- a preferable minimum is 0.001 mol / L and a preferable upper limit is 0.20 mol / L.
- the content of the diamine compound is less than 0.001 mol / L, the reaction between the diamine compound and tetracarboxylic anhydride does not sufficiently proceed or does not proceed efficiently in the steps described later. There is.
- the content of the diamine compound is more than 0.20 mol / L, the polyamic acid particles may not be deposited well in the form of particles when the polyamic acid particles are precipitated in the step described below.
- the content of the diamine compound in the solution in which the diamine compound is dissolved has a more preferable lower limit of 0.01 mol / L and a more preferable upper limit of 0.10 mol / L.
- the method for producing polyamic acid particles of the present invention is a step of adding polytetracarboxylic anhydride in a non-solution state to a solution in which the diamine compound is dissolved while applying physical impact to precipitate the polyamic acid particles (this specification) It is also referred to as a step of precipitating polyamic acid particles.
- the diamine compound and the tetracarboxylic anhydride react to form a polyamic acid having an amide bond and a carboxyl group, and precipitate as particles.
- a solvent that dissolves the diamine compound but does not dissolve the produced polyamic acid is a solvent for dissolving the diamine compound.
- the solvent which dissolves the diamine compound described above is a solvent having such properties.
- the diamine compound dissolves but the produced polyamic acid does not dissolve.
- the properties such as surface polarity and molecular weight are completely different from those of the diamine compound. It means that different polyamic acids are formed and become insoluble in the solvent in which the diamine compound is dissolved.
- adding tetracarboxylic anhydride in a non-solution state means adding tetracarboxylic anhydride as it is without dissolving it in a solvent.
- adding the tetracarboxylic anhydride as it is without dissolving it in the solvent moisture in the atmosphere that comes into contact with the solvent during the operation of dissolving in the solvent as compared with the case of adding the solution in which the tetracarboxylic anhydride is dissolved, and Inactivation of the tetracarboxylic anhydride due to moisture in the solvent can be suppressed. Therefore, polyamic acid particles having a high degree of polymerization can be precipitated.
- polyimide particles that are hardly decomposed even at high temperatures and have high heat resistance. It is also possible to reduce the content of residual monomers (unreacted diamine compound and tetracarboxylic anhydride) and low molecular weight products.
- the tetracarboxylic anhydride used in the method for producing polyamic acid particles of the present invention is often solid at room temperature in a non-solution state.
- the non-solution-state tetracarboxylic anhydride is added to the solution in which the diamine compound is dissolved.
- the physical impact to be applied is not particularly limited, and examples thereof include stirring, shaking, ultrasonic irradiation, treatment with a homogenizer, and the like. Among them, the average solution was obtained by adding the non-solution-state tetracarboxylic anhydride to the solution in which the diamine compound was dissolved while irradiating ultrasonic waves or vigorously stirring the solution in which the diamine compound was dissolved. Polyamic acid particles having a smaller particle diameter can be precipitated.
- the tetracarboxylic anhydride is not particularly limited, and examples thereof include aromatic tetracarboxylic anhydride, aliphatic tetracarboxylic anhydride, alicyclic tetracarboxylic anhydride, heterocyclic tetracarboxylic anhydride, and the like. . Of these, aromatic tetracarboxylic acid anhydrides are preferred because the polyamic acid produced has a rigid structure. These tetracarboxylic anhydrides may be used alone or in combination of two or more.
- the aromatic tetracarboxylic acid anhydride is not particularly limited.
- Examples of the aliphatic tetracarboxylic anhydride include butane-1,2,3,4-tetracarboxylic dianhydride.
- Examples of the alicyclic tetracarboxylic acid anhydride include cyclobutane-1,2,3,4-tetracarboxylic dianhydride.
- Examples of the heterocyclic tetracarboxylic acid anhydride include thiophene-2,3,4,5-tetracarboxylic acid anhydride and pyridine 2,3,5,6-tetracarboxylic acid anhydride.
- the addition amount of the tetracarboxylic anhydride is not particularly limited, the preferable lower limit is 0.5 mol and the preferable upper limit is 1.5 mol with respect to 1 mol of the diamine compound.
- the addition amount of the tetracarboxylic anhydride is less than 0.5 mol, the content of unreacted tetracarboxylic anhydride or a residue derived from tetracarboxylic anhydride may increase.
- the amount of the tetracarboxylic anhydride added exceeds 1.5 mol, the content of the unreacted diamine compound or residue derived from the diamine compound, which is contained as a volatile component in the polyamic acid particles, may increase.
- a more preferable lower limit is 0.8 mol and a more preferable upper limit is 1.2 mol with respect to 1 mol of the diamine compound.
- the method of irradiating ultrasonic waves to the solution in which the diamine compound is dissolved is not particularly limited.
- the method of performing ultrasonic irradiation by placing a container containing the solution in which the diamine compound is dissolved in a bathtub of an ultrasonic device A method of performing ultrasonic irradiation by bringing an ultrasonic vibrator into contact with a container containing a solution in which the diamine compound is dissolved, and a method of performing ultrasonic irradiation by immersing the ultrasonic vibrator in a solution in which the diamine compound is dissolved Etc.
- the vibration generated by the ultrasonic vibrator is directly transmitted to the reaction component without loss, it is preferable to immerse the ultrasonic vibrator in the solution in which the diamine compound is dissolved.
- the ultrasonic irradiation conditions are not particularly limited, and examples include conditions of 0 to 130 ° C., 20 to 100 kHz, and 20 to 2000 W.
- Examples of the ultrasonic device include conventionally known ultrasonic devices such as an ultrasonic oscillator, an ultrasonic homogenizer, and a desktop ultrasonic cleaner.
- ultrasonic irradiation and other stirring methods may be used in combination.
- the stirring method is not particularly limited, and examples thereof include a stirring method using a magnetic stirrer, a propeller stirring rod, a homogenizer, a shaker, and the like.
- a basic catalyst may be used in order to rapidly advance the reaction between the diamine compound and the tetracarboxylic anhydride.
- the basic catalyst is not particularly limited, and a conventionally known basic catalyst is used, and examples thereof include pyridine, tertiary amine, diazabicycloundecene (DBU), diazabicyclononene (DBN) and the like. These basic catalysts may be used alone or in combination of two or more.
- the polyamic acid particles can be surface-treated.
- the method for surface-treating the polyamic acid particles is not particularly limited, and examples thereof include a method in which a surface treatment agent is dissolved in advance in a solution in which the diamine compound is dissolved in the step of precipitating the polyamic acid particles. .
- the surface treatment agent is not particularly limited.
- polyvinyl pyrrolidone polyvinyl alcohol, diethylene glycol dibenzoate, polytetramethylene oxide, celluloses such as carboxymethyl cellulose or hydroxypropyl methyl erulose, various starches, silane coupling agents, titanates. System coupling agents and the like. With these surface treatment agents, polyamic acid particles can be stably precipitated.
- the amount of the surface treatment agent added is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the weight of the polyamic acid particles to be precipitated.
- the addition amount is less than 0.01% by weight, the effect of the surface treatment agent may be hardly exhibited. Even if it exceeds 10% by weight, no further effect may be obtained.
- polyamic acid particles having a small average particle size and a high degree of polymerization can be produced, and such polyamic acid particles are decomposed even at high temperatures by imidization treatment. It is difficult to produce polyimide particles with high heat resistance.
- content of the residual monomer contained in a polyamic acid particle and a low molecular-weight product can also be reduced.
- Polyimide particles can be produced by imidizing the polyamic acid particles obtained by the method for producing polyamic acid particles of the present invention. Such a method for producing polyimide particles is also one aspect of the present invention. By performing the imidization treatment, the amide bond and the carboxyl group of the polyamic acid particles react to form an imide bond, and polyimide particles are obtained.
- the imidization method is not particularly limited, and a conventionally known method is used. For example, a method in which the polyamic acid particles are heated to cyclize and imidize, and a method in which the polyamic acid particles are chemically cyclized to imidize. Can be mentioned.
- the polyamic acid particles are preferably stored in a dry state until imidization treatment. In this specification, the dry state means a solid, and the dry state may not be positively maintained by a desiccant or the like.
- the method for imidization by heat ring closure is not particularly limited.
- a method in which the polyamic acid particles are dispersed in an organic solvent and heated at a temperature of about 130 to 250 ° C. for about 1 to 10 hours with stirring. Can be mentioned.
- a method for removing water generated as a by-product out of the system for example, a method of flowing a dry inert gas and removing the generated water out of the system as water vapor together with the dry inert gas, For example, a method of removing out of the system by refluxing using an organic solvent azeotroped with water can be used.
- the amount of the polyamic acid particles dispersed in the organic solvent is not particularly limited and can be adjusted as appropriate.
- the preferred lower limit is 1 g / L
- the preferred upper limit is 50 g / L.
- a more preferable lower limit is 5 g / L, and a more preferable upper limit is 10 g / L.
- a method for imidizing by chemical ring closure is not particularly limited.
- the polyamic acid particles are dispersed in a mixed organic solvent of pyridine and acetic anhydride and stirred at a temperature of about 15 to 115 ° C. for 24 hours.
- a method of heating to a certain extent is mentioned.
- the obtained polyimide particles and the organic solvent can be separated and recovered by a conventionally known method such as filtration, centrifuge, decantation, vacuum drying, etc. Accordingly, the obtained polyimide particles may be washed using an organic solvent such as acetone, ethyl acetate, methyl ethyl ketone (MEK), ether, alcohol or the like.
- an organic solvent such as acetone, ethyl acetate, methyl ethyl ketone (MEK), ether, alcohol or the like.
- the polyimide particles can be surface treated.
- the method for surface-treating the polyimide particles include a method of performing a step of surface-treating the obtained polyimide particles.
- the surface treatment method is not particularly limited, and examples thereof include a surface treatment method using a silane coupling agent.
- the method of performing the surface treatment using the silane coupling agent is not particularly limited.
- a method of reacting a functional group present on the surface of the coating layer with a silane coupling agent may be mentioned.
- the method for forming the coating layer is not particularly limited, and examples thereof include a method for physically adsorbing polyvinyl alcohol.
- Examples of the surface treatment method include a method in which polyimide particles and a surface treatment agent are physically contacted.
- the polyimide particles may be mixed with a solution in which the surface treatment agent is dissolved and stirred for a sufficient time.
- the surface treatment agent is not particularly limited, for example, polyvinyl pyrrolidone, polyvinyl alcohol, diethylene glycol dibenzoate, polytetramethylene oxide, cellulose such as carboxymethyl cellulose or hydroxypropyl methyl erulose, various starches, silane coupling agent, Examples include titanate coupling agents.
- the amount of the surface treatment agent added is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the weight of the polyimide particles to be treated.
- the addition amount is less than 0.01% by weight, the effect of the surface treatment agent may be hardly exhibited. Even if it exceeds 10% by weight, no further effect may be obtained.
- a compound having a functional functional group is added to a solution in which the diamine compound is dissolved, without performing the step of surface-treating the polyimide particles as described above.
- the surface-treated polyimide particles can also be obtained by using a compound having a functional functional group in a part of the diamine compound and / or the carboxylic anhydride.
- polyimide particles having an amino group on the surface can be obtained by adding a trivalent amine such as 2,4,6-triaminopyrimidine to a solution in which the diamine compound is dissolved.
- the surface of the polyimide particle can be secondarily modified by reacting the amino group with a functional compound having, for example, a glycidyl group, a carboxyl group, or an alkyl group.
- polyimide particles having a small average particle diameter and a high degree of polymerization are produced. be able to. Since the polyimide particles obtained by the method for producing polyimide particles of the present invention have a high degree of polymerization, they are difficult to decompose even at high temperatures and have high heat resistance. Moreover, according to the manufacturing method of the polyimide particle of this invention, content of the residual monomer contained in a polyimide particle and a low molecular-weight product can also be reduced.
- the polyimide particles obtained by the method for producing polyimide particles of the present invention have high heat resistance and a low content of residual monomers and low molecular weight products, so that the weight reduction rate when heated at high temperatures is small.
- Polyimide particles obtained by the method for producing polyimide particles of the present invention and having a weight reduction ratio of 5% or less when heated from 30 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min are also included. This is one of the present inventions.
- the polyimide particles of the present invention have a weight reduction ratio of 5% or less when heated from 30 ° C. to 300 ° C. at a temperature rising rate of 10 ° C./min.
- the weight reduction ratio is 5% or less
- the polyimide particles of the present invention are blended in the bonding material for electronic parts, the polyimide particles are decomposed even at high temperatures, or the polyimide particles cause gas generation. Generation of voids in the bonding material for electronic parts can be suppressed, and a highly reliable bonded body can be obtained.
- the differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA) is not particularly limited, and examples thereof include EXSTAR6000 (manufactured by SII Nanotechnology).
- the polyimide particle of the present invention has a preferable lower limit of the average particle diameter of 0.03 ⁇ m and a preferable upper limit of 3 ⁇ m.
- the average particle diameter is less than 0.03 ⁇ m, when polyimide particles are blended in the electronic component bonding material, the effect of reducing the linear expansion coefficient of the cured product of the electronic component bonding material may not be sufficiently obtained.
- the blending amount is increased, the fluidity of the bonding material for electronic parts is lowered, and the coating property, film forming property, etc. may be significantly lowered.
- the average particle diameter exceeds 3 ⁇ m, when polyimide particles are blended in the bonding material for electronic components, the polyimide particles become foreign matter in the bonding material for electronic components, or the polyimide particles bite during bonding of the semiconductor chip. Or the bonding material for electronic components may not be thinned.
- the upper limit with the more preferable average particle diameter of the polyimide particle of this invention is 1 micrometer.
- the polyimide particle of the present invention has a preferred lower limit of the particle diameter CV value of 12% and a preferred upper limit of 50%.
- the particle size CV value is less than 12%, when polyimide particles are blended in the electronic component bonding material, the polyimide particles should be highly filled in the electronic component bonding material unless combined with other polyimide particles. However, if the blending amount is increased, the fluidity of the bonding material for electronic parts may be lowered, and the coating property, film forming property, etc. may be significantly lowered.
- the CV value of the particle diameter exceeds 50%, abnormally large particles or abnormally small particles may be included.
- the upper limit with more preferable CV value of the particle diameter of the polyimide particle of this invention is 40%.
- the average particle diameter of the polyimide particles means that 50 or more polyimide particles are arbitrarily selected from SEM photographs obtained by observing the polyimide particles with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the CV value of the particle diameter of the polyimide particles means a value calculated by the following formula from the average particle diameter m of the polyimide particles and the standard deviation ⁇ .
- CV value (%) ⁇ / m ⁇ 100
- the use of the polyimide particles of the present invention is not particularly limited, and examples thereof include uses such as fillers for plastic molded products that require heat resistance and strength, fillers for bonding materials for electronic parts, and the like. Especially, it is preferable that the polyimide particle of this invention is used as a filler of the bonding
- the polyimide particles of the present invention are blended into the bonding material for electronic parts, the high temperature elastic modulus can be increased without increasing the elastic modulus of the cured product of the bonding material for electronic parts in the range from low temperature to normal temperature. The linear expansion coefficient can be sufficiently lowered.
- the polyimide particles of the present invention are particularly preferably used as a filler for a bonding material for flip chip mounting.
- an electrode bonding step is performed at a temperature of about 200 to 300 ° C.
- the polyimide particles of the present invention are blended in the flip chip mounting bonding material, the polyimide particles are decomposed even at high temperatures, or the polyimide particles cause gas generation and voids are generated in the flip chip mounting bonding material. This can be suppressed.
- the bonding material for electronic parts of the present invention contains a curable compound.
- the said curable compound is not specifically limited, For example, the compound hardened
- Specific examples of the curable compound include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, acrylic resin, polyester resin, polyamide resin, polybenzimidazole resin, diallyl phthalate resin, xylene resin, alkyl -Thermosetting compounds such as benzene resin, epoxy acrylate resin, silicon resin, urethane resin.
- an epoxy resin is preferable.
- the epoxy resin is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type, novolac type epoxy resins such as phenol novolak type and cresol novolak type, and trisphenolmethane.
- bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type
- novolac type epoxy resins such as phenol novolak type and cresol novolak type
- trisphenolmethane Trisphenolmethane.
- Aromatic epoxy resins such as triglycidyl ether, naphthalene type epoxy resins, fluorene type epoxy resins, dicyclopentadiene type epoxy resins, modified products thereof, hydrogenated products and the like can be mentioned. These epoxy resins may be used independently and 2 or more types may be used together.
- the curable compound may further contain a polymer compound having a functional group capable of reacting with the epoxy resin.
- the obtained bonding material for electronic parts has toughness and excellent impact resistance.
- the high molecular compound which has a functional group which can react with the said epoxy resin is not specifically limited,
- the high molecular compound etc. which have an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group etc. are mentioned.
- a polymer compound having an epoxy group is preferable.
- the epoxy resin and the polymer compound having the epoxy group are used as the curable compound, the cured product of the obtained bonding material for electronic components has excellent mechanical strength, heat resistance and It has both moisture resistance and excellent toughness derived from the above polymer compound having an epoxy group, and can exhibit high adhesion reliability and high conduction reliability.
- the polymer compound having an epoxy group is not particularly limited as long as it is a polymer compound having an epoxy group at the terminal and / or side chain (pendant position).
- an epoxy group-containing acrylic resin is preferable because it contains a large amount of epoxy groups and the cured product of the obtained bonding material for electronic parts can have excellent mechanical strength, heat resistance, and the like.
- These polymer compounds having an epoxy group may be used alone or in combination of two or more.
- the preferred lower limit of the weight average molecular weight is 10,000.
- the weight average molecular weight is less than 10,000, even if a sheet-like bonding material for electronic parts is used, the film-forming property becomes insufficient and the shape may not be maintained.
- the preferable lower limit of the epoxy equivalent is 200, and the preferable upper limit is 1000.
- the epoxy equivalent is less than 200, the cured product of the obtained bonding material for electronic parts may be hard and brittle.
- the epoxy equivalent exceeds 1000 the mechanical strength or heat resistance of the cured product of the obtained bonding material for electronic parts may be insufficient.
- content of the high molecular compound which has a functional group which can react with the said epoxy resin is not specifically limited, The preferable minimum with respect to 100 weight part of said epoxy resins is 1 weight part, and a preferable upper limit is 500 weight part.
- content of the polymer compound having a functional group capable of reacting with the epoxy resin is less than 1 part by weight, the obtained bonding material for electronic parts lacks toughness when heat distortion occurs, resulting in adhesion reliability. May be inferior.
- content of the high molecular compound which has a functional group which can react with the said epoxy resin exceeds 500 weight part, the heat resistance of the hardened
- the bonding material for electronic parts of the present invention contains a curing agent.
- curing agent is not specifically limited, For example, an amine type hardening
- the acid anhydride curing agent is not particularly limited, but a bifunctional acid anhydride curing agent is preferable.
- the bifunctional acid anhydride curing agent is not particularly limited.
- examples include phthalic acid and maleic anhydride.
- trifunctional or higher functional acid anhydride curing agent particles may be used as the acid anhydride curing agent.
- the trifunctional or higher functional acid anhydride curing agent particles are not particularly limited.
- particles composed of trifunctional acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid.
- examples thereof include particles composed of tetrafunctional or higher functional acid anhydrides such as acid anhydrides and polyazeline acid anhydrides.
- the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is not particularly limited, but a preferable lower limit is 0.1 ⁇ m and a preferable upper limit is 20 ⁇ m.
- a preferable lower limit is 0.1 ⁇ m and a preferable upper limit is 20 ⁇ m.
- the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is less than 0.1 ⁇ m, aggregation of the curing agent particles may occur, and the resulting bonding material for electronic parts may be thickened. If the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles exceeds 20 ⁇ m, the curing agent particles cannot be sufficiently diffused during curing, resulting in poor curing.
- curing agent is not specifically limited, The preferable minimum with respect to 100 weight part of said curable compounds is 5 weight part, and a preferable upper limit is 150 weight part. If the content of the curing agent is less than 5 parts by weight, the obtained bonding material for electronic parts may not be sufficiently cured. When content of the said hardening
- the content of the curing agent is more preferably 10 parts by weight and more preferably 140 parts by weight with respect to 100 parts by weight of the curable compound.
- the said trifunctional or more acid anhydride Value obtained by dividing content (weight) of product curing agent particle by content (weight) of bifunctional acid anhydride curing agent [ (content of trifunctional or higher acid anhydride curing agent particles) / (bifunctional
- the preferred lower limit of the content of the acid anhydride curing agent)] is 0.1, and the preferred upper limit is 10.
- the value is less than 0.1, the effect of adding the trifunctional or higher functional acid anhydride curing agent particles may not be sufficiently obtained.
- the above value exceeds 10 the cured product of the obtained bonding material for electronic parts becomes brittle, and sufficient adhesion reliability may not be obtained.
- the bonding material for electronic parts of the present invention preferably contains a curing accelerator.
- the said hardening accelerator is not specifically limited, For example, an imidazole series hardening accelerator, a tertiary amine type hardening accelerator, etc. are mentioned. Of these, an imidazole curing accelerator is preferred because it is easy to control the reaction system for adjusting the curing speed and the physical properties of the cured product. These hardening accelerators may be used independently and 2 or more types may be used together.
- the imidazole curing accelerator is not particularly limited.
- 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group or an imidazole curing accelerator with basicity protected with isocyanuric acid (trade name “ 2MA-OK ", manufactured by Shikoku Kasei Kogyo Co., Ltd.).
- 2MA-OK an imidazole curing accelerator with basicity protected with isocyanuric acid
- content of the said hardening accelerator is not specifically limited,
- the preferable minimum with respect to 100 weight part of said curable compounds is 1 weight part, and a preferable upper limit is 20 weight part.
- the content of the curing accelerator is less than 1 part by weight, the obtained bonding material for electronic parts may not be sufficiently cured.
- content of the said hardening accelerator exceeds 20 weight part, the adhesive reliability of the bonding
- the bonding material for electronic parts of the present invention contains polyimide particles.
- the coefficient of linear expansion in the temperature region below the glass transition temperature after curing of the bonding material for electronic parts can be reduced without adding an inorganic filler or the like.
- the inorganic filler has the effect of increasing the elastic modulus at the same time as decreasing the linear expansion coefficient, whereas the polyimide particles can decrease the linear expansion coefficient while suppressing an increase in the elastic modulus.
- the polyimide particles have an average particle size of 0.03 to 3 ⁇ m and a CV value of the particle size of 10 to 50%. It can be said that the polyimide particles having such an average particle size and a CV value of the particle size are polyimide particles having a sufficiently small average particle size and an appropriate particle size distribution. Due to the fact that the average particle size of the polyimide particles is sufficiently small and the surface area of the polyimide particles in the bonding material for electronic parts of the present invention is large, the bonding material for electronic parts of the present invention has a glass transition temperature or lower after curing. The linear expansion coefficient and the elastic modulus in the temperature range are sufficiently low, and a highly reliable joined body can be obtained.
- the polyimide particles have an appropriate particle size distribution, in the bonding material for electronic parts of the present invention, the polyimide particles having a small particle size enter the gaps between the polyimide particles having a large particle size. A high filling can be achieved, and a decrease in fluidity can be suppressed as compared with the case where the CV value of the particle diameter is out of the above range.
- the average particle diameter is less than 0.03 ⁇ m, if the polyimide particles are sufficiently filled to such an extent that the effect of reducing the linear expansion coefficient in the temperature region below the glass transition temperature after curing is sufficiently obtained, a bonding material for electronic parts The fluidity of the film is lowered, and the coating property, film forming property, etc. are significantly lowered.
- the average particle diameter exceeds 3 ⁇ m, the effect of lowering the coefficient of linear expansion in the temperature region below the glass transition temperature after curing cannot be obtained sufficiently, or when a miniaturized and thinned semiconductor chip is bonded.
- the polyimide particles become foreign matters, the polyimide particles are bitten when the semiconductor chip is bonded, or the bonding material for electronic components cannot be thinned.
- the minimum with the preferable average particle diameter of the said polyimide particle is 0.05 micrometer, and a preferable upper limit is 1 micrometer.
- the CV value of the particle diameter is less than 10%, it may be difficult to highly fill the polyimide particles while suppressing a decrease in fluidity of the bonding material for electronic components, If an attempt is made to use a sheet-like bonding material for electronic parts, the surface becomes rough and it becomes difficult to form a good sheet.
- the CV value of the particle diameter exceeds 50%, abnormally large particles or abnormally small particles are included, so that, for example, the fluidity of the bonding material for electronic parts is reduced, and the coating property and film forming property are reduced. Etc. decreases.
- the preferable lower limit of the CV value of the particle diameter of the polyimide particles is 15%, and the preferable upper limit is 40%.
- the polyimide compound contained in the polyimide particles is not particularly limited, but a polyimide compound having an aromatic ring in the main skeleton is preferable.
- the polyimide compound has a more rigid and less fluctuating molecular structure, and further lowers the linear expansion coefficient in the temperature range below the glass transition temperature after curing of the bonding material for electronic parts. Can do.
- the polyimide compound having an aromatic ring in the main skeleton is not particularly limited, but a polyimide compound having a benzoxazole structure in the main skeleton is preferable.
- the polyimide compound having an aromatic ring in the main skeleton include, for example, a polyimide compound having an aromatic ring in the main skeleton such as phenyl, biphenyl, and naphthalene. Specifically, for example, poly (N, N′— p-phenylene-biphenyltetracarboxylimide) and the like.
- the method for producing the polyimide particles is not particularly limited. After preparing polyamic acid particles by reacting tetracarboxylic anhydride and a diamine compound, the resulting polyamic acid particles are imidized to obtain polyimide particles. The method is preferred. As a method for producing the polyamic acid particles, for example, in addition to the above-described method for producing the polyamic acid particles of the present invention, a solution in which tetracarboxylic anhydride is dissolved and a solution in which a diamine compound is dissolved are prepared. A method of precipitating polyamic acid particles by mixing a solution includes a method of precipitating polyamic acid particles by dropping a mixed solution obtained by mixing two solutions into a poor solvent of polyamic acid.
- the stirring method is not particularly limited, and examples thereof include a stirring method using a magnetic stirrer, a propeller stirring rod, a homogenizer, a shaker, and the like.
- a method for producing the polyimide particles for example, a diamine compound that forms an imide structure that is soluble in a reaction solvent, a diamine compound that forms an imide structure that is insoluble in a reaction solvent, and a functional group such as an amino group.
- a polyamic acid varnish is prepared by reacting the diamine mixture with tetracarboxylic anhydride in a reaction solvent using a diamine mixture comprising a diamine compound that forms an imide structure having a group.
- a method of precipitating polyimide particles from the reaction solvent by heating is also included. According to this method, the polyimide particle which has a desired average particle diameter can be obtained by adjusting the compounding ratio of the diamine compound in a diamine mixture.
- the manufacturing method of the polyamic acid particle of this invention mentioned above and the manufacturing method of a polyimide particle are preferable. Moreover, heat resistance can be improved more by heat-processing the obtained polyimide particle
- the tetracarboxylic anhydride is not particularly limited.
- the aromatic tetracarboxylic anhydride, the aliphatic tetracarboxylic anhydride, and the fat used in the above-described method for producing the polyamic acid particles and the method for producing the polyimide particles of the present invention examples thereof include cyclic tetracarboxylic acid anhydrides and heterocyclic tetracarboxylic acid anhydrides.
- the said diamine compound is not specifically limited, For example, the aromatic diamine, aliphatic diamine, alicyclic diamine etc. which are used for the manufacturing method of the polyamic acid particle of this invention mentioned above, and the manufacturing method of a polyimide particle are mentioned.
- the said polyimide particle contains the polyimide compound which has a benzoxazole structure in the said main frame
- the aromatic diamine having the benzoxazole structure is not particularly limited.
- amino (aminophenyl) benzoxazole isomers are preferable from the viewpoint of ease of synthesis, and 5-amino-2- (p-aminophenyl) benzoxazole is preferable. Is more preferable.
- the amino (aminophenyl) benzoxazole isomers are isomers determined according to the coordination position of the two amino groups of amino (aminophenyl) benzoxazole.
- 5-amino -2- (p-aminophenyl) benzoxazole 6-amino-2- (p-aminophenyl) benzoxazole, 5-amino-2- (m-aminophenyl) benzoxazole, 6-amino-2- (m -Aminophenyl) benzoxazole and the like.
- aromatic diamines having a benzoxazole structure may be used alone or in combination of two or more.
- the said polyimide particle is surface-treated by the method similar to the polyimide particle of this invention mentioned above, for example.
- the polyimide particles can be highly filled while further suppressing a decrease in fluidity of the bonding material for electronic parts.
- the polyimide particles preferably have a weight reduction ratio of 5% or less when heated from 30 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min.
- the weight loss ratio is 5% or less, so that the resulting bonding material for electronic parts prevents the polyimide particles from decomposing even at high temperatures and the generation of voids due to the polyimide particles causing gas generation. Therefore, a highly reliable bonded body can be obtained.
- content of the said polyimide particle is not specifically limited, The preferable minimum with respect to 100 weight part of said curable compounds is 5 weight part, and a preferable upper limit is 900 weight part. If the content of the polyimide particles is less than 5 parts by weight, the effect of lowering the linear expansion coefficient in the temperature region below the glass transition temperature after curing may not be sufficiently obtained. When content of the said polyimide particle exceeds 900 weight part, the fluidity
- the content of the polyimide particles is more preferably 30 parts by weight, more preferably 700 parts by weight, more preferably 50 parts by weight, and even more preferably 500 parts by weight with respect to 100 parts by weight of the curable compound. is there.
- the bonding material for electronic parts of the present invention is within a range that does not hinder the effects of the present invention, that is, within a range that further reduces the linear expansion coefficient at a temperature lower than the glass transition temperature after curing and does not increase the elastic modulus.
- an inorganic filler may be contained.
- the inorganic filler is not particularly limited, and examples thereof include silica such as fumed silica and colloidal silica, glass fiber, and alumina fine particles.
- the preferred lower limit of the average particle diameter is 0.1 nm, and the preferred upper limit is 30 ⁇ m.
- the average particle diameter of the particulate inorganic filler is less than 0.1 nm, the fluidity of the bonding material for electronic parts may be lowered, and the coating property, film forming property, and the like may be lowered.
- the average particle diameter of the particulate inorganic filler exceeds 30 ⁇ m, the inorganic filler may be bitten when a miniaturized and thin semiconductor chip is joined.
- content of the said inorganic filler is not specifically limited,
- hardenable compound is 5 weight part, and a preferable upper limit is 100 weight part. If the content of the inorganic filler is less than 5 parts by weight, the effect of adding the inorganic filler may be hardly obtained. If the content of the inorganic filler exceeds 100 parts by weight, the coefficient of linear expansion in the temperature region below the glass transition temperature after curing of the bonding material for electronic parts may decrease, but the elastic modulus may increase at the same time.
- the content of the inorganic filler is more preferably 50 parts by weight with respect to 100 parts by weight of the curable compound.
- the bonding material for electronic parts of the present invention may contain a diluent within a range that does not impair the effects of the present invention.
- the said diluent is not specifically limited,
- cured material at the time of heat-hardening of the joining material for electronic components is preferable.
- a reactive diluent having two or more functional groups in one molecule is more preferable in order not to deteriorate the adhesion reliability of the obtained bonding material for electronic parts.
- Examples of the reactive diluent having two or more functional groups in one molecule include aliphatic epoxy, ethylene oxide modified epoxy, propylene oxide modified epoxy, cyclohexane epoxy, dicyclopentadiene epoxy, phenol epoxy and the like. Can be mentioned.
- the content of the diluent is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the curable compound is 1 part by weight, and a preferable upper limit is 50 parts by weight. If the content of the diluent is less than 1 part by weight, the effect of adding the diluent may be hardly obtained. When the content of the diluent exceeds 50 parts by weight, the bonding reliability of the obtained electronic component bonding material may be inferior, or the viscosity characteristics described later may not be obtained.
- the content of the diluent is more preferably 5 parts by weight and more preferably 20 parts by weight based on 100 parts by weight of the curable compound.
- the bonding material for electronic parts of the present invention may contain a solvent, if necessary.
- the solvent is not particularly limited, and examples thereof include aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols, esters, ethers, ketones, glycol ethers (cellosolves), and fats. Examples thereof include cyclic hydrocarbons and aliphatic hydrocarbons.
- the bonding material for electronic parts of the present invention may contain an inorganic ion exchanger as necessary.
- examples of commercially available products include IXE series (manufactured by Toagosei Co., Ltd.).
- content of the said inorganic ion exchanger is not specifically limited, A preferable minimum is 1 weight% and a preferable upper limit is 10 weight%.
- the bonding material for electronic parts of the present invention may contain additives such as an anti-bleeding agent and an adhesion-imparting agent such as an imidazole silane coupling agent, if necessary.
- the preferable lower limit of viscosity at 0.5 rpm is 20 Pa ⁇ s
- the preferable upper limit is 1000 Pa ⁇ s.
- the viscosity is less than 20 Pa ⁇ s, the electronic component bonding material may lack shape retention. If the viscosity exceeds 1000 Pa ⁇ s, the bonding material for electronic parts is deteriorated in applicability, film-forming property, and the like, and for example, it may lack in ejection stability when applied with an air dispenser.
- the preferable lower limit of the linear expansion coefficient in the temperature region below the glass transition temperature after curing is 10 ppm, and the preferable upper limit is 60 ppm.
- the linear expansion coefficient is less than 10 ppm, the linear expansion coefficient of the bonding material for electronic components is lower than that of solder or the substrate, so that stress is concentrated on the bonding portion due to the thermal expansion of the solder or the substrate or the like. May peel off.
- the linear expansion coefficient exceeds 60 ppm, when strain due to heat occurs, stress on the bonded semiconductor chip increases, and cracks in conductive portions such as solder may easily occur.
- a more preferable lower limit of the linear expansion coefficient is 15 ppm, and a more preferable upper limit is 55 ppm.
- the preferable lower limit of the linear expansion coefficient in the temperature range equal to or higher than the glass transition temperature after curing is 50 ppm, and the preferable upper limit is 140 ppm.
- a more preferable lower limit of the linear expansion coefficient is 60 ppm, and a more preferable upper limit is 130 ppm.
- the linear expansion coefficient after curing of the bonding material for electronic parts is a cured product having a thickness of 500 ⁇ m obtained by curing the bonding material for electronic parts at 110 ° C. for 40 minutes and further at 170 ° C. for 30 minutes. Then, using a thermal stress strain measuring device (“EXTEAR TMA / SS 6100”, manufactured by SII Nano Technology), the temperature was raised to 300 ° C. with a load of 2 N, a heating rate of 5 ° C./min, and a sample length of 1 cm. This value is obtained from the slope of the SS curve obtained at this time.
- EXTEAR TMA / SS 6100 manufactured by SII Nano Technology
- the preferable lower limit of the elastic modulus at 25 to 170 ° C. after curing is 10 MPa and the preferable upper limit is 7000 MPa.
- the elastic modulus is less than 10 MPa, the cured product of the electronic component bonding material may not have sufficient heat resistance.
- the elastic modulus exceeds 7000 MPa when strain due to heat occurs, stress on the bonded semiconductor chip increases, and cracks in conductive portions such as solder may easily occur.
- the more preferable lower limit of the elastic modulus is 50 MPa, the more preferable upper limit is 6000 MPa, and the still more preferable upper limit is 5000 MPa.
- the elastic modulus of the cured product of the bonding material for electronic parts is a cured product having a thickness of 500 ⁇ m obtained by curing the bonding material for electronic components at 110 ° C. for 40 minutes and further at 170 ° C. for 30 minutes.
- a viscoelasticity measuring device model “DVA-200”, manufactured by IT Measurement & Control Co., Ltd.
- the form of the bonding material for electronic parts of the present invention is not particularly limited, and may be a paste or a sheet.
- the method for producing the bonding material for electronic parts of the present invention is not particularly limited.
- the bonding material for electronic components of the present invention is in a paste form
- the curable compound, the curing agent, the polyimide particles, and the like are added as necessary as a method for producing the bonding material for electronic components of the present invention.
- Examples include a method of blending a predetermined amount of other additives and the like and mixing them by a conventionally known method.
- a paste-like bonding material for electronic components is formed into a sheet using an extrusion molding method.
- the manufacturing method of the polyamic acid particle used as a raw material of a polyimide particle with a small average particle diameter and high heat resistance can be provided.
- the polyimide particle obtained by the manufacturing method of the polyimide particle using the manufacturing method of this polyamic acid particle and the manufacturing method of this polyimide particle can be provided.
- Example 1 A diamine solution was obtained by adding 0.216 g of 1,4-phenylenediamine (PPD) to 80 g of acetone and stirring. Next, the obtained diamine solution was irradiated with ultrasonic waves of 20 kHz and 600 W at 25 ° C. using an ultrasonic device (UH-600S, manufactured by SMT), and while stirring, 4,4 ′ in a non-solution state. -0.588 g of biphthalic anhydride (BPDA) was quickly added to the diamine solution. Ultrasonic irradiation was performed for 30 minutes, the reaction was advanced, and polyamic acid was produced. At this time, the produced polyamic acid was precipitated in the reaction solution, and polyamic acid particles (a) were obtained.
- PPD 1,4-phenylenediamine
- UH-600S ultrasonic device
- BPDA biphthalic anhydride
- the obtained polyamic acid particles (a) were isolated and then dispersed in 146 g of decane and heated at 160 ° C. for 360 minutes for imidization to obtain polyimide particles (a).
- vibrator of the ultrasonic device was immersed in the diamine solution, and ultrasonic irradiation was performed.
- Example 2 Instead of 0.216 g of 1,4-phenylenediamine (PPD), 0.451 g of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO) is used, and 4,4′-biphthalic anhydride in a non-solution state
- DAMBO 5-amino-2- (p-aminophenyl) benzoxazole
- PMDA pyromellitic anhydride
- BPDA polyamic acid particles
- polyimide particles b
- Example 3 Example 1 except that an ultrasonic device (US-4R, manufactured by ASONE) was used instead of the ultrasonic device (UH-600S, manufactured by SMT), and 40 kHz, 160 W ultrasonic waves were applied. Thus, polyamic acid particles (c) and polyimide particles (c) were obtained. In addition, when irradiating an ultrasonic wave, the beaker which put the diamine solution was put into the water tank of the ultrasonic device, and ultrasonic irradiation was performed.
- an ultrasonic device US-4R, manufactured by ASONE
- UH-600S ultrasonic device
- Example 4 Surface-treated polyamic acid particles (d) and polyimide in the same manner as in Example 1 except that 0.0063 g of Pitscol K-30 (Daiichi Kogyo Seiyaku Co., Ltd., polyvinylpyrrolidone) was added and dissolved in the diamine solution. Particles (d) were obtained.
- Example 5 In the same manner as in Example 1, polyamic acid particles (a) and polyimide particles (a) were obtained. 1 g of the obtained polyimide particles (a) was added to an ethanol solution obtained by dissolving 0.03 g of Pitzcol K-30 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyvinylpyrrolidone) in 100 g of ethanol, and the mixture was sufficiently stirred and mixed. The polyimide particles were filtered and then dried to obtain surface-treated polyimide particles (e).
- Pitzcol K-30 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyvinylpyrrolidone
- a tetracarboxylic anhydride solution was obtained by adding 0.588 g of 4,4′-biphthalic anhydride (BPDA) to 48 g of DMF and stirring. Further, 0.216 g of 1,4-phenylenediamine (PPD) was added to 40 g of acetone and stirred to obtain a diamine solution. The obtained tetracarboxylic anhydride solution and diamine solution were mixed at 25 ° C. and stirred for 30 minutes, whereby BPDA and PPD were reacted to produce polyamic acid. At this time, the produced polyamic acid was dissolved in the reaction solution.
- BPDA 4,4′-biphthalic anhydride
- PPD 1,4-phenylenediamine
- the obtained reaction solution was irradiated with ultrasonic waves of 20 kHz and 600 W at 25 ° C. using an ultrasonic device (UH-600S, manufactured by SMT), and a dropper was put into a container containing 316 g of acetone while stirring. Was added dropwise.
- the polyamic acid particle (f) precipitated rapidly in acetone by dripping the reaction solution.
- the obtained polyamic acid particles (f) were isolated, they were dispersed in 146 g of decane and heated at 160 ° C. for 360 minutes for imidization to obtain polyimide particles (f).
- oscillator of the ultrasonic device was immersed in acetone, and ultrasonic irradiation was performed.
- the produced polyamic acid was precipitated in the reaction solution, and polyamic acid particles (g) were obtained.
- the obtained polyamic acid particles (g) were isolated, they were dispersed in 146 g of decane and heated at 160 ° C. for 360 minutes for imidization to obtain polyimide particles (g).
- vibrator of the ultrasonic device was immersed in the solution, and the ultrasonic irradiation was performed.
- the produced polyamic acid was dissolved in the reaction solution.
- the obtained reaction solution was irradiated with 20 kHz ultrasonic waves at 25 ° C. while setting the output of the ultrasonic apparatus to 5 using an ultrasonic apparatus (UH-600S, manufactured by SMT) while stirring.
- UH-600S ultrasonic apparatus
- 316 g of acetone was dropped into the container using a dropper.
- the polyamic acid particle (h) precipitated rapidly in acetone by dripping the reaction solution.
- the obtained polyamic acid particles (h) were isolated, they were dispersed in 146 g of decane and heated at 160 ° C. for 360 minutes for imidization treatment to obtain polyimide particles.
- the polyimide particles were heat-treated in an oven at 400 ° C. for 30 minutes to obtain polyimide particles (h) (average particle size 0.08 ⁇ m, particle size CV value 21%, weight reduction rate 1.6%).
- the polyimide particles (j) (average particle diameter 0.5 ⁇ m, particles) are the same as the polyimide particles (h) except that the output of the ultrasonic device is set to 2 and the intensity of the ultrasonic waves applied to the reaction solution is weakened. CV value of diameter 30%, weight reduction rate 1.7%).
- polyimide particles (k) were obtained in the same manner as polyimide particles (h) except that 42 kHz ultrasonic waves were irradiated at 25 ° C. (Average particle size 1 ⁇ m, particle size CV value 32%, weight reduction rate 2.0%).
- polyimide particles (l) (Production of polyimide particles (l))
- the polyimide particles (l) (average particles) were obtained in the same manner as the polyimide particles (h) except that no ultrasonic waves were applied and stirring was performed using a homogenizer (manufactured by KINEMATICA, Polytron PT3100) instead of the ultrasonic device. Diameter 3.0 ⁇ m, particle diameter CV value 45%, weight reduction ratio 2.0%).
- a polyimide particle (m) (average particle size of 5 ⁇ m, particle size of the particle size) was the same as that of the polyimide particle (h) except that the ultrasonic wave was not used and stirring was performed using a magnetic stirrer instead of the ultrasonic device. CV value 30%, weight reduction rate 2.5%).
- the polyimide particles (n) are the same as the polyimide particles (h) except that the amount of acetone received is changed to 200 g. 0.5 ⁇ m in diameter, CV value of particle size 58%, weight reduction rate 2.5%).
- a tetracarboxylic anhydride solution was obtained by adding 0.4362 g of pyromellitic anhydride (PMDA) to 40 g of acetone and stirring. Further, 0.216 g of 1,4-phenylenediamine (PPD) was added to 40 g of acetone and stirred to obtain a diamine solution.
- the obtained tetracarboxylic anhydride solution and diamine solution were irradiated with 20 kHz ultrasonic waves at 25 ° C. using an ultrasonic device (UH-600S, manufactured by SMT) with the output of the ultrasonic device set to 5. By mixing with stirring, PMDA and PPD were reacted to precipitate polyamic acid particles.
- polyimide particles (o) (average particle size of 0.5 ⁇ m, particle size of CV value 7%, weight reduction rate 2.7%).
- Polyamic acid particles (h) were obtained in the same manner as in the method for producing polyimide particles (h). 1 g of the obtained polyimide particles (h) was added to an ethanol solution obtained by dissolving 0.03 g of Pitzcol K-30 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyvinylpyrrolidone) in 100 g of ethanol, and the mixture was sufficiently stirred and mixed. The polyimide particles were filtered and then dried to obtain surface-treated polyimide particles (q) (average particle size 0.08 ⁇ m, particle size CV value 21%, weight reduction rate 1.6%).
- Ultrasonic irradiation was performed for 30 minutes, the reaction was advanced, and polyamic acid was produced. At this time, the produced polyamic acid was precipitated in the reaction solution, and polyamic acid particles (r) were obtained. After the obtained polyamic acid particles (r) were isolated, they were dispersed in 146 g of decane and heated at 160 ° C. for 360 minutes for imidization treatment, whereby polyimide particles (r) (average particle size 0.3 ⁇ m, CV value of particle size 35%, weight reduction ratio 4.7%).
- UH-600S ultrasonic vibrators were immersed in the solution and irradiated with ultrasonic waves.
- polyimide particles (s) instead of 0.216 g of 1,4-phenylenediamine (PPD), 0.451 g of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO) is used, and 4,4′-biphthalic anhydride in a non-solution state
- DAMBO 5-amino-2- (p-aminophenyl) benzoxazole
- PMDA pyromellitic anhydride
- BPDA 0.05 g of pyridine
- polyimide particles (t) The polyimide particles (r) were heat-treated in an oven at 400 ° C. for 30 minutes to obtain polyimide particles (t) (average particle size 0.26 ⁇ m, particle size CV value 35%, weight reduction rate 1.2%).
- polyimide particles (v) (average particle size 0) were used in the same manner as the polyimide particles (s) except that pyridine was not used as a reaction catalyst and the ultrasonic wave irradiation time for generating polyimide acid was changed to 60 minutes. 0.7 ⁇ m, particle diameter CV value 45%, weight reduction ratio 4.0%).
- Polyamic acid particles (r) were obtained in the same manner as in the method for producing polyimide particles (r). 1 g of polyimide particles (r) was added to an ethanol solution obtained by dissolving 0.03 g of Pitzcol K-30 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyvinylpyrrolidone) in 100 g of ethanol, and the mixture was sufficiently stirred and mixed. The polyimide particles were filtered and then dried to obtain surface-treated polyimide particles (x) (average particle size 0.3 ⁇ m, particle size CV value 35%, weight reduction rate 4.7%).
- the average particle size of the polyimide particles obtained above was determined by observing the polyimide particles with a scanning electron microscope (SEM), and arbitrarily selecting 50 or more polyimide particles from the obtained SEM photograph. It calculated
- the weight reduction ratio (X) of the polyimide particles obtained above was determined by using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA) (EXSTAR6000, manufactured by SII Nano Technology) at 10 ° C / It heated from 30 degreeC to 300 degreeC with the temperature increase rate of a minute, and calculated
- X ⁇ (AB) / A ⁇ ⁇ 100 (%)
- Bisphenol A type epoxy resin (trade name “YL-980”, manufactured by Japan Epoxy Resin Co., Ltd.)
- Bisphenol A type epoxy resin (trade name “1004AF”, manufactured by Japan Epoxy Resin Co., Ltd.)
- Glycidyl group-containing acrylic resin (trade name “G-2050M”, manufactured by NOF Corporation)
- Polyimide particles (4-1. Polyimide particles having an average particle size of 0.03 to 3 ⁇ m and a CV value of 10 to 50%) Polyimide particles (h) to (l) and (p) to (x) obtained above (4-2. Other polyimide particles) Polyimide particles (m) to (o) obtained above Polyimide particles (trade name “UIP-S”, average particle size 10 ⁇ m, particle size CV value 15%, weight reduction rate 1.0%, manufactured by Ube Industries)
- Silica particles Silica particles (trade name “Sylfil NHM-5N”, average particle size 0.07 ⁇ m, particle size CV value 12%, manufactured by Tokuyama Corporation) Silica particles (trade name “SE2050SPJ”, average particle size 0.5 ⁇ m, CV value 10% of particle size, manufactured by Admatechs) Silica particles (trade name “SE4050SPE”, average particle size 1 ⁇ m, CV value 10% of particle size, manufactured by Admatechs)
- Silane coupling agent (trade name “KBM-573”, manufactured by Shin-Etsu Chemical Co., Ltd.)
- Solvent Metal ethyl ketone (MEK)
- a glass chip (10 mm ⁇ 10 mm, thickness 100 ⁇ m) was bonded onto the applied electronic component bonding material, and this was placed in an oven at 80 ° C. for 1 hour.
- the case where the bonding material for electronic parts has spread to 90% or more of the area under the glass chip, the case where it has spread to less than 90% and 70% or more of the area under the glass chip, and the area under the glass chip.
- the case where it had spread only to less than 70% was evaluated as x.
- Examples 13 and 14 since a sheet-like bonding material for electronic parts was produced, this evaluation was not performed.
- Comparative Examples 3 and 4 the average particle diameter of the added polyimide particles was too large, resulting in poor wetting and spreading.
- the manufacturing method of the polyamic acid particle used as a raw material of a polyimide particle with a small average particle diameter and high heat resistance can be provided.
- the polyimide particle obtained by the manufacturing method of the polyimide particle using the manufacturing method of this polyamic acid particle and the manufacturing method of this polyimide particle can be provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Die Bonding (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Wire Bonding (AREA)
Abstract
Description
粒子径の小さいポリイミド粒子を製造する方法として、例えば、特許文献2には、無水テトラカルボン酸とジアミン化合物からポリイミドを合成する方法において、(a)無水テトラカルボン酸を含む第一溶液と、ジアミン化合物を含む第二溶液とをそれぞれ調製する第一工程、(b)第一溶液と第二溶液とを混合し、混合溶液からポリアミド酸微粒子を析出させる第二工程、及び(c)得られたポリアミド酸微粒子をイミド化することによってポリイミド微粒子を得る第三工程を含むポリイミド微粒子の製造方法が記載されている。
以下、本発明を詳述する。
また、本発明者は、このようなポリアミド酸粒子の製造方法を用いて得られたポリアミド酸粒子をイミド化処理したポリイミド粒子を、電子部品用接合材に配合することで、硬化後にはガラス転移温度以下の温度領域における線膨張率及び弾性率が低くなり、信頼性の高い接合体を得ることができることを見出した。更に、本発明者は、このように信頼性の高い接合体を得るためには、ポリイミド粒子の平均粒子径が小さく電子部品用接合材中での表面積が大きいことに加えて、粒子径のCV値も重要であることを見出した。即ち、単にポリイミド粒子の平均粒子径が小さいだけでは、硬化後のガラス転移温度以下の温度領域における線膨張率及び弾性率を充分に低下させることができる程度にポリイミド粒子を高充填すると、電子部品用接合材の流動性が低下し、塗布性、製膜性等が低下してしまう。
本発明者は、ポリイミド粒子を含有する電子部品用接合材において、ポリイミド粒子の平均粒子径を0.03~3μmとし、更に、粒子径のCV値を10~50%とすることにより、流動性の低下を抑制しながらポリイミド粒子を高充填することができ、その結果、硬化後にはガラス転移温度以下の温度領域における線膨張率及び弾性率が低くなり、信頼性の高い接合体を得ることができることを見出し、本発明を完成させるに至った。
上記ジアミン化合物は特に限定されず、例えば、芳香族ジアミン、脂肪族ジアミン、脂環族ジアミン等が挙げられる。なかでも、後述する工程において生成するポリアミド酸が剛直な構造を有することから、芳香族ジアミンが好ましい。これらのジアミン化合物は単独で用いてもよいし、二種類以上を併用してもよい。
上記脂環族ジアミンとして、例えば、1,4-ジアミノシクロヘキサン、1,2-ジアミノシクロヘキサン、ビス(4-アミノシクロヘキシル)メタン、4,4’-ジアミノジシクロヘキシルメタン等が挙げられる。
上記ジアミン化合物が溶解した溶液における上記ジアミン化合物の含有量は、より好ましい下限が0.01モル/L、より好ましい上限が0.10モル/Lである。
この工程では、上記ジアミン化合物と上記無水テトラカルボン酸とが反応して、アミド結合とカルボキシル基とを有するポリアミド酸が生成し、粒子として析出する。
本明細書中、ジアミン化合物は溶解するが生成するポリアミド酸は溶解しないとは、ジアミン化合物と無水テトラカルボン酸との反応が進行するに従い、例えば表面極性、分子量等の性質がジアミン化合物とは全く異なるポリアミド酸が生成し、ジアミン化合物を溶解していた溶媒に不溶になることを意味する。
なお、本発明のポリアミド酸粒子の製造方法において用いられる無水テトラカルボン酸は、非溶液状態では、常温で固体であることが多い。
なかでも、上記ジアミン化合物が溶解した溶液に対して超音波を照射したり激しく攪拌したりしながら、上記非溶液状態の無水テトラカルボン酸を上記ジアミン化合物が溶解した溶液に添加することにより、平均粒子径のより小さいポリアミド酸粒子を析出させることができる。特に、上記ジアミン化合物が溶解した溶液に対して超音波を照射することにより、液中に非常に微細な振動を生じさせ、非溶液状態であっても上記無水テトラカルボン酸を高分散させることができ、平均粒子径のより小さいポリアミド酸粒子を析出させることができる。また、超音波を照射することにより、上記無水テトラカルボン酸と溶媒中の水分との反応を抑制しながら上記ジアミン化合物と上記無水テトラカルボン酸との反応を促進させることができるため、ポリアミド酸粒子の重合度を高める効果、及び、残存モノマー及び低分子量の生成物の含有量を低減する効果を、更に高めることができる。
上記脂環族テトラカルボン酸無水物として、例えば、シクロブタン-1,2,3,4-テトラカルボン酸二無水物等が挙げられる。
上記複素環族テトラカルボン酸無水物として、例えば、チオフェン-2,3,4,5-テトラカルボン酸無水物、ピリジン2,3,5,6-テトラカルボン酸無水物等が挙げられる。
上記無水テトラカルボン酸の添加量は、上記ジアミン化合物1モルに対してより好ましい下限が0.8モル、より好ましい上限が1.2モルである。
上記攪拌方法は特に限定されず、例えば、マグネチックスターラー、プロペラ攪拌棒、ホモジナイザー、振とう機等を用いた攪拌方法等が挙げられる。
上記塩基性触媒は特に限定されず、従来公知の塩基性触媒が用いられ、例えば、ピリジン、3級アミン、ジアザビシクロウンデセン(DBU)、ジアザビシクロノネン(DBN)等が挙げられる。これらの塩基性触媒は単独で用いてもよいし、二種類以上を併用してもよい。
上記イミド化処理することで、上記ポリアミド酸粒子のアミド結合とカルボキシル基とが反応してイミド結合が形成し、ポリイミド粒子が得られる。上記イミド化処理する方法は特に限定されず、従来公知の方法が用いられ、例えば、上記ポリアミド酸粒子を加熱閉環してイミド化する方法、上記ポリアミド酸粒子を化学閉環してイミド化する方法が挙げられる。
なお、上記ポリアミド酸粒子は、イミド化処理されるまで乾燥状態で保管されることが好ましい。本明細書中、乾燥状態とは、固体であることを意味し、乾燥剤等により積極的に乾燥状態が維持されていなくてもよい。
上記加熱閉環してイミド化する方法では、副生成物として発生する水を系外に効率的に除去することが好ましい。上記副生成物として発生する水を系外に除去する方法として、例えば、乾燥した不活性ガスをフローさせて、この乾燥した不活性ガスと共に、発生した水を水蒸気として系外に除去する方法、水と共沸する有機溶媒を用いて還流等により系外に除去する方法等が挙げられる。
得られたポリイミド粒子を表面処理することにより、電子部品用接合材にポリイミド粒子を配合する場合に、ポリイミド粒子の分散性を向上させたり、増粘を抑えて流動性及び濡れ性を確保しながら、電子部品用接合材中にポリイミド粒子を高充填したりすることができ、電子部品用接合材にポリイミド粒子を添加する効果を更に高めることができる。
上記シランカップリング剤を用いて表面処理する方法は特に限定されず、例えば、ポリイミド粒子の表面に存在する官能基とシランカップリング剤とを反応させる方法、ポリイミド粒子の表面にコーティング層を形成した後、コーティング層の表面に存在する官能基とシランカップリング剤とを反応させる方法等が挙げられる。
上記コーティング層を形成する方法は特に限定されず、例えば、ポリビニルアルコールを物理吸着させる方法等が挙げられる。
例えば、上記ジアミン化合物を溶解した溶液に2,4,6-トリアミノピリミジン等の3価アミンを添加することで、表面にアミノ基を有するポリイミド粒子を得ることができる。更に、このアミノ基に、例えば、グリシジル基、カルボキシル基、アルキル基等を有する機能性化合物を反応させることで、ポリイミド粒子の表面を2次修飾することができる。
本発明のポリイミド粒子の製造方法により得られるポリイミド粒子であって、10℃/分の昇温速度で30℃から300℃まで加熱された場合の重量減少割合が5%以下であるポリイミド粒子もまた、本発明の1つである。
X={(A-B)/A}×100 (%)
示差熱熱重量同時測定装置(TG/DTA)は特に限定されず、例えば、EXSTAR6000(エスアイアイ・ナノテクノロジー社製)等が挙げられる。
本発明のポリイミド粒子の平均粒子径のより好ましい上限は1μmである。
本発明のポリイミド粒子の粒子径のCV値のより好ましい上限は40%である。
CV値(%)=σ/m×100
更に、本発明のポリイミド粒子は、フリップチップ実装用接合材のフィラーとして用いられることが特に好ましい。フリップチップ実装においては、200~300℃程度の温度で電極接合工程が行われる。フリップチップ実装用接合材に本発明のポリイミド粒子を配合すると、高温下でもポリイミド粒子が分解したり、ポリイミド粒子がガス発生の原因となってフリップチップ実装用接合材中にボイドが発生したりすることを抑制することができる。
上記硬化性化合物は特に限定されず、例えば、付加重合、重縮合、重付加、付加縮合、開環重合等の反応により硬化する化合物が挙げられる。上記硬化性化合物として、具体的には、例えば、ユリア樹脂、メラミン樹脂、フェノール樹脂、レゾルシノール樹脂、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリベンズイミダゾール樹脂、ジアリルフタレート樹脂、キシレン樹脂、アルキル-ベンゼン樹脂、エポキシアクリレート樹脂、珪素樹脂、ウレタン樹脂等の熱硬化性化合物が挙げられる。なかでも、得られる接合体が信頼性及び接合強度に優れることから、エポキシ樹脂が好ましい。
上記エポキシ樹脂と反応可能な官能基を有する高分子化合物を含有することで、得られる電子部品用接合材は靭性をもち、優れた耐衝撃性を有することができる。
上記硬化性化合物として上記エポキシ樹脂と、上記エポキシ基を有する高分子化合物とを用いる場合、得られる電子部品用接合材の硬化物は、上記エポキシ樹脂に由来する優れた機械的強度、耐熱性及び耐湿性と、上記エポキシ基を有する高分子化合物に由来する優れた靭性とを兼備し、高い接着信頼性及び高い導通信頼性を発現することができる。
上記硬化剤は特に限定されず、例えば、アミン系硬化剤、酸無水物硬化剤、フェノール系硬化剤等が挙げられる。なかでも、酸無水物硬化剤が好ましい。
上記硬化剤の含有量は、上記硬化性化合物100重量部に対するより好ましい下限が10重量部、より好ましい上限が140重量部である。
上記値のより好ましい下限は0.2、より好ましい上限は8である。
上記硬化促進剤は特に限定されず、例えば、イミダゾール系硬化促進剤、3級アミン系硬化促進剤等が挙げられる。なかでも、硬化速度、硬化物の物性等の調整をするための反応系の制御をしやすいことから、イミダゾール系硬化促進剤が好ましい。これらの硬化促進剤は、単独で用いられてもよく、二種以上が併用されてもよい。
上記ポリイミド粒子を添加することによって、無機充填材等を添加しなくても、電子部品用接合材の硬化後のガラス転移温度以下の温度領域における線膨張率を低下させることができる。更に、無機充填材は線膨張率を低下させると同時に弾性率を上昇させる効果を有するのに対し、上記ポリイミド粒子は、弾性率の上昇を抑制しながら線膨張率を低下させることができる。
上記ポリイミド粒子の平均粒子径が充分に小さく、本発明の電子部品用接合材中での上記ポリイミド粒子の表面積が大きいことにより、本発明の電子部品用接合材は、硬化後にはガラス転移温度以下の温度領域における線膨張率及び弾性率が充分に低くなり、信頼性の高い接合体を得ることができる。また、上記ポリイミド粒子が適度な粒子径分布を有することにより、本発明の電子部品用接合材においては、粒子径の大きいポリイミド粒子の隙間に粒子径の小さいポリイミド粒子が入り込むため、上記ポリイミド粒子を高充填することができ、かつ、粒子径のCV値が上記範囲を外れる場合と比べて流動性の低下も抑制される。
上記ポリイミド粒子の平均粒子径の好ましい下限は0.05μm、好ましい上限は1μmである。
上記ポリイミド粒子の粒子径のCV値の好ましい下限は15%、好ましい上限は40%である。
上記ポリイミド化合物は、主骨格に芳香環を有することで、より剛直で揺らぎの少ない分子構造となり、電子部品用接合材の硬化後のガラス転移温度以下の温度領域における線膨張率を更に低下させることができる。
また、上記主骨格に芳香環を有するポリイミド化合物として、例えば、フェニル、ビフェニル、ナフタレン等の芳香環を主骨格に有するポリイミド化合物も挙げられ、具体的には、例えば、ポリ(N,N’-p-フェニレン-ビフェニルテトラカルボキシルイミド)等が挙げられる。
上記ポリアミド酸粒子を作製する方法として、例えば、上述した本発明のポリアミド酸粒子の製造方法に加えて、無水テトラカルボン酸が溶解した溶液とジアミン化合物が溶解した溶液とをそれぞれ調製し、2つの溶液を混合してポリアミド酸粒子を析出させる方法、2つの溶液を混合した混合溶液をポリアミド酸の貧溶媒に滴下してポリアミド酸粒子を析出させる方法等が挙げられる。
これらの方法においては、ポリアミド酸粒子を析出させる際に、無水テトラカルボン酸が溶解した溶液、ジアミン化合物が溶解した溶液又はポリアミド酸の貧溶媒に対して超音波を照射したり激しく攪拌したりすることにより、平均粒子径のより小さいポリアミド酸粒子を析出させることができる。上記攪拌方法は特に限定されず、例えば、マグネチックスターラー、プロペラ攪拌棒、ホモジナイザー、振とう機等を用いた攪拌方法等が挙げられる。
この方法によれば、ジアミン混合物中のジアミン化合物の配合比を調整することにより、所望の平均粒子径を有するポリイミド粒子を得ることができる。
なお、上述した本発明のポリアミド酸粒子の製造方法及びポリイミド粒子の製造方法以外の方法であっても、得られたポリイミド粒子を300℃程度の高温で熱処理することで、耐熱性の高いポリイミド粒子を得ることができる。
上記ベンゾオキサゾール構造を有する芳香族ジアミンは特に限定されず、例えば、5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、6-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、5-アミノ-2-(m-アミノフェニル)ベンゾオキサゾール、6-アミノ-2-(m-アミノフェニル)ベンゾオキサゾール、2,2’-p-フェニレンビス(5-アミノベンゾオキサゾール)、2,2’-p-フェニレンビス(6-アミノベンゾオキサゾール)、1-(5-アミノベンゾオキサゾロ)-4-(6-アミノベンゾオキサゾロ)ベンゼン、2,6-(4,4’-ジアミノジフェニル)ベンゾ[1,2-d:5,4-d’]ビスオキサゾール、2,6-(4,4’-ジアミノジフェニル)ベンゾ[1,2-d:4,5-d’]ビスオキサゾール、2,6-(3,4’-ジアミノジフェニル)ベンゾ[1,2-d:5,4-d’]ビスオキサゾール、2,6-(3,4’-ジアミノジフェニル)ベンゾ[1,2-d:4,5-d’]ビスオキサゾール、2,6-(3,3’-ジアミノジフェニル)ベンゾ[1,2-d:5,4-d’]ビスオキサゾール、2,6-(3,3’-ジアミノジフェニル)ベンゾ[1,2-d:4,5-d’]ビスオキサゾール等が挙げられる。
なお、上記アミノ(アミノフェニル)ベンゾオキサゾールの各異性体とは、アミノ(アミノフェニル)ベンゾオキサゾールが有する2つアミノ基の配位位置に応じて定められる各異性体であり、例えば、5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、6-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、5-アミノ-2-(m-アミノフェニル)ベンゾオキサゾール、6-アミノ-2-(m-アミノフェニル)ベンゾオキサゾール等が挙げられる。
これらのベンゾオキサゾール構造を有する芳香族ジアミンは単独で用いられてもよく、二種以上が併用されてもよい。
上記ポリイミド粒子に表面処理を施すことにより、電子部品用接合材の流動性の低下を更に抑制しながらポリイミド粒子を高充填することができる。
上記ポリイミド粒子の含有量は、上記硬化性化合物100重量部に対するより好ましい下限が30重量部、より好ましい上限が700重量部であり、更に好ましい下限が50重量部、更に好ましい上限が500重量部である。
上記無機充填材は特に限定されず、例えば、ヒュームドシリカ、コロイダルシリカ等のシリカ、ガラス繊維、アルミナ微粒子等が挙げられる。
上記無機充填材の含有量は、上記硬化性化合物100重量部に対するより好ましい上限が50重量部である。
上記希釈剤は特に限定されないが、電子部品用接合材の加熱硬化時に硬化物に取り込まれる反応性希釈剤が好ましい。なかでも、得られる電子部品用接合材の接着信頼性を悪化させないために、1分子中に2以上の官能基を有する反応性希釈剤がより好ましい。
上記1分子中に2以上の官能基を有する反応性希釈剤として、例えば、脂肪族型エポキシ、エチレンオキサイド変性エポキシ、プロピレンオキサイド変性エポキシ、シクロヘキサン型エポキシ、ジシクロペンタジエン型エポキシ、フェノール型エポキシ等が挙げられる。
上記希釈剤の含有量は、上記硬化性化合物100重量部に対するより好ましい下限が5重量部、より好ましい上限が20重量部である。
上記溶媒は特に限定されず、例えば、芳香族炭化水素類、塩化芳香族炭化水素類、塩化脂肪族炭化水素類、アルコール類、エステル類、エーテル類、ケトン類、グリコールエーテル(セロソルブ)類、脂環式炭化水素類、脂肪族炭化水素類等が挙げられる。
上記無機イオン交換体の含有量は特に限定されないが、好ましい下限が1重量%、好ましい上限が10重量%である。
上記線膨張率のより好ましい下限は15ppm、より好ましい上限は55ppmである。
上記弾性率のより好ましい下限は50MPa、より好ましい上限は6000MPa、更に好ましい上限は5000MPaである。
また、本発明の電子部品用接合材がシート状である場合、本発明の電子部品用接合材を製造する方法として、例えば、ペースト状の電子部品用接合材を押出成型法を用いてシート状に成形する方法、ペースト状の電子部品用接合材を含有する溶液を、溶剤キャスト法、ウェーハに直接塗工するスピンコート法、スクリーン印刷する方法等を用いてシート状に成形する方法が挙げられる。
1,4-フェニレンジアミン(PPD)0.216gをアセトン80gに添加して攪拌することにより、ジアミン溶液を得た。次いで、得られたジアミン溶液に対して超音波装置(UH-600S、SMT社製)を用いて25℃で20kHz、600Wの超音波を照射し、攪拌しながら、非溶液状態の4,4’-ビフタル酸無水物(BPDA)0.588gをジアミン溶液に速やかに添加した。30分間超音波照射し、反応を進行させポリアミド酸を生成させた。このとき、生成したポリアミド酸は反応溶液中で析出し、ポリアミド酸粒子(a)が得られた。得られたポリアミド酸粒子(a)を単離した後、デカン146g中に分散させ、160℃で360分間加熱してイミド化処理することにより、ポリイミド粒子(a)を得た。
なお、超音波を照射する際には、ジアミン溶液に超音波装置の超音波振動子を浸漬させて超音波照射を行った。
1,4-フェニレンジアミン(PPD)0.216gの代わりに5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール(DAMBO)0.451gを用い、非溶液状態の4,4’-ビフタル酸無水物(BPDA)0.588gの代わりに非溶液状態のピロメリット酸無水物(PMDA)0.436gを用いたこと以外は実施例1と同様にして、ポリアミド酸粒子(b)及びポリイミド粒子(b)を得た。
超音波装置(UH-600S、SMT社製)の代わりに超音波装置(US-4R、アズワン社製)を用い、かつ、40kHz、160Wの超音波を照射したこと以外は実施例1と同様にして、ポリアミド酸粒子(c)及びポリイミド粒子(c)を得た。
なお、超音波を照射する際には、ジアミン溶液を入れたビーカーを超音波装置の水槽に入れて超音波照射を行った。
ジアミン溶液に、ピッツコールK-30(第一工業製薬社製、ポリビニルピロリドン)を0.0063g添加溶解したこと以外は実施例1と同様にして、表面処理されたポリアミド酸粒子(d)及びポリイミド粒子(d)を得た。
実施例1と同様にして、ポリアミド酸粒子(a)及びポリイミド粒子(a)を得た。0.03gのピッツコールK-30(第一工業製薬社製、ポリビニルピロリドン)を100gのエタノールに溶解したエタノール溶液に、得られたポリイミド粒子(a)1gを添加して、充分攪拌混合した。ポリイミド粒子をろ過した後、乾燥して、表面処理されたポリイミド粒子(e)を得た。
4,4’-ビフタル酸無水物(BPDA)0.588gをDMF48gに添加して攪拌することにより、無水テトラカルボン酸溶液を得た。また、1,4-フェニレンジアミン(PPD)0.216gをアセトン40gに添加して攪拌することにより、ジアミン溶液を得た。
得られた無水テトラカルボン酸溶液とジアミン溶液とを25℃で混合し、30分間攪拌することにより、BPDAとPPDとを反応させてポリアミド酸を生成させた。このとき、生成したポリアミド酸は反応溶液中に溶解していた。次いで、得られた反応溶液を、超音波装置(UH-600S、SMT社製)を用いて25℃で20kHz、600Wの超音波を照射し、攪拌しながら、アセトン316gを入れた容器にスポイトを用いて滴下した。このようにして反応溶液を滴下することにより、アセトン中で速やかにポリアミド酸粒子(f)が析出した。得られたポリアミド酸粒子(f)を単離した後、デカン146g中に分散させ、160℃で360分間加熱してイミド化処理することにより、ポリイミド粒子(f)を得た。
なお、超音波を照射する際には、アセトンに超音波装置の超音波振動子を浸漬させて超音波照射を行った。
ピロメリット酸無水物(PMDA)0.436gをアセトン40gに添加して攪拌することにより、無水テトラカルボン酸溶液を得た。また、4,4’-ジアミノジフェニルエーテル(DPE)0.401gをアセトン40gに添加して攪拌することにより、ジアミン溶液を得た。
得られた無水テトラカルボン酸溶液とジアミン溶液とを超音波装置(UH-600S、SMT社製)を用いて25℃、20kHz、600Wで混合し、30分間攪拌することにより、PMDAとDPEとを反応させてポリアミド酸を生成させた。このとき、生成したポリアミド酸が反応溶液中で析出し、ポリアミド酸粒子(g)が得られた。得られたポリアミド酸粒子(g)を単離した後、デカン146g中に分散させ、160℃で360分間加熱してイミド化処理することにより、ポリイミド粒子(g)を得た。
なお、超音波を照射する際には、溶液に超音波装置の超音波振動子を浸漬させて超音波照射を行った。
実施例及び比較例で得られたポリアミド酸粒子及びポリイミド粒子について、以下の評価を行った。結果を表1に示した。
ポリアミド酸粒子又はポリイミド粒子を走査型電子顕微鏡(SEM)で観察した。得られたSEM写真から任意に50個以上の粒子を選択し、この任意の50個以上の粒子の粒子径から数平均値を算出することにより、平均粒子径(nm)を求めた。
示差熱熱重量同時測定装置(TG/DTA)(EXSTAR6000、エスアイアイ・ナノテクノロジー社製)を用いて、ポリイミド粒子を10℃/分の昇温速度で30℃から300℃まで加熱した。ポリイミド粒子の初期重量A、及び、300℃まで加熱した後の重量Bから、下記式により、10℃/分の昇温速度で30℃から300℃まで加熱した場合の重量減少割合Xを算出した。
X={(A-B)/A}×100 (%)
下記(I)及び(II)に従ってポリイミド粒子を作製した後、下記(III)に従って電子部品用接合材を作製した。なお、下記(I)は、無水テトラカルボン酸を溶液状態で添加してポリアミド酸粒子及びポリイミド粒子を作製した場合であり、下記(II)は、無水テトラカルボン酸を非溶液状態で添加してポリアミド酸粒子及びポリイミド粒子を作製した場合である。
(ポリイミド粒子(h)の製造)
4,4’-ビフタル酸無水物(BPDA)0.588gをDMF48gに添加して攪拌することにより、無水テトラカルボン酸溶液を得た。また、1,4-フェニレンジアミン(PPD)0.216gをアセトン40gに添加して攪拌することにより、ジアミン溶液を得た。
得られた無水テトラカルボン酸溶液とジアミン溶液とを25℃で混合し、30分間攪拌することにより、BPDAとPPDとを反応させてポリアミド酸を生成させた。このとき、生成したポリアミド酸は反応溶液中に溶解していた。次いで、得られた反応溶液を、超音波装置(UH-600S、SMT社製)を用いて、超音波装置の出力を5に設定して25℃で20kHzの超音波を照射し、攪拌しながら、アセトン316gを入れた容器にスポイトを用いて滴下した。このようにして反応溶液を滴下することにより、アセトン中で速やかにポリアミド酸粒子(h)が析出した。得られたポリアミド酸粒子(h)を単離した後、デカン146g中に分散させ、160℃で360分間加熱してイミド化処理することにより、ポリイミド粒子とした。次いで、このポリイミド粒子を400℃のオーブンで30分間熱処理し、ポリイミド粒子(h)(平均粒子径0.08μm、粒子径のCV値21%、重量減少割合1.6%)を得た。
4,4’-ビフタル酸無水物(BPDA)0.588gの代わりにピロメリット酸無水物(PMDA)0.4362gを用い、1,4-フェニレンジアミン(PPD)0.216gの代わりに5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール(DAMBO)0.4505gを用い、また、反応触媒としてピリジン0.05gを用いたこと以外はポリイミド粒子(h)と同様にして、ポリイミド粒子(i)(平均粒子径0.1μm、粒子径のCV値18%、重量減少割合1.2%)を得た。
超音波装置の出力を2に設定して反応溶液に照射する超音波の強度を弱くしたこと以外はポリイミド粒子(h)と同様にして、ポリイミド粒子(j)(平均粒子径0.5μm、粒子径のCV値30%、重量減少割合1.7%)を得た。
超音波装置として卓上型洗浄機(B-2510J-MT、ブランソン社製)を用いて、25℃で42kHzの超音波を照射したこと以外はポリイミド粒子(h)と同様にして、ポリイミド粒子(k)(平均粒子径1μm、粒子径のCV値32%、重量減少割合2.0%)を得た。
超音波を照射せず、超音波装置の代わりにホモジナイザー(KINEMATICA社製、ポリトロンPT3100)を用いて攪拌を行ったこと以外はポリイミド粒子(h)と同様にして、ポリイミド粒子(l)(平均粒子径3.0μm、粒子径のCV値45%、重量減少割合2.0%)を得た。
超音波を照射せず、超音波装置の代わりにマグネチックスターラーを用いて攪拌を行ったこと以外はポリイミド粒子(h)と同様にして、ポリイミド粒子(m)(平均粒子径5μm、粒子径のCV値30%、重量減少割合2.5%)を得た。
反応溶液を超音波を照射し攪拌しながらアセトン中に滴下する際、滴下を受けるアセトンの量を200gに変更したこと以外はポリイミド粒子(h)と同様にして、ポリイミド粒子(n)(平均粒子径0.5μm、粒子径のCV値58%、重量減少割合2.5%)を得た。
ピロメリット酸無水物(PMDA)0.4362gをアセトン40gに添加して攪拌することにより、無水テトラカルボン酸溶液を得た。また、1,4-フェニレンジアミン(PPD)0.216gをアセトン40gに添加して攪拌することにより、ジアミン溶液を得た。
得られた無水テトラカルボン酸溶液とジアミン溶液とを超音波装置(UH-600S、SMT社製)を用いて、超音波装置の出力を5に設定して25℃で20kHzの超音波を照射し、攪拌しながら混合することにより、PMDAとPPDとを反応させてポリアミド酸粒子を析出させた。得られたポリアミド酸粒子を単離した後、デカン146g中に分散させ、160℃で360分間加熱してイミド化処理することにより、ポリイミド粒子(o)(平均粒子径0.5μm、粒子径のCV値7%、重量減少割合2.7%)を得た。
反応溶液を超音波を照射し攪拌しながらアセトン中に滴下する際、ピッツコールK-30(第一工業製薬社製、ポリビニルピロリドン)を0.025g溶解させたアセトン316gを用いた以外はポリイミド粒子(h)と同様にして、表面処理されたポリイミド粒子(p)(平均粒子径0.08μm、粒子径のCV値21%、重量減少割合1.6%)を得た。
ポリイミド粒子(h)の製造方法と同様にして、ポリアミド酸粒子(h)を得た。0.03gのピッツコールK-30(第一工業製薬社製、ポリビニルピロリドン)を100gのエタノールに溶解したエタノール溶液に、得られたポリイミド粒子(h)1gを添加して、充分攪拌混合した。ポリイミド粒子をろ過した後、乾燥して、表面処理されたポリイミド粒子(q)(平均粒子径0.08μm、粒子径のCV値21%、重量減少割合1.6%)を得た。
(ポリイミド粒子(r)の製造)
1,4-フェニレンジアミン(PPD)0.216gをアセトン80gに添加して攪拌することにより、ジアミン溶液を得た。次いで、得られたジアミン溶液に対して超音波装置(UH-600S、SMT社製)を用いて25℃で20kHz、600Wの超音波を照射し、攪拌しながら、非溶液状態の4,4’-ビフタル酸無水物(BPDA)0.588gをジアミン溶液に速やかに添加した。30分間超音波照射し、反応を進行させポリアミド酸を生成させた。このとき、生成したポリアミド酸は反応溶液中で析出し、ポリアミド酸粒子(r)が得られた。得られたポリアミド酸粒子(r)を単離した後、デカン146g中に分散させ、160℃で360分間加熱してイミド化処理することにより、ポリイミド粒子(r)(平均粒子径0.3μm、粒子径のCV値35%、重量減少割合4.7%)を得た。
なお、超音波を照射する際には、UH-600Sの超音波振動子を溶液に浸漬させて超音波照射を行った。
1,4-フェニレンジアミン(PPD)0.216gの代わりに5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール(DAMBO)0.451gを用い、非溶液状態の4,4’-ビフタル酸無水物(BPDA)0.588gの代わりに非溶液状態のピロメリット酸無水物(PMDA)0.436gを用い、また、反応触媒としてピリジン0.05gを用いたこと以外はポリイミド粒子(r)と同様にして、ポリイミド粒子(s)(平均粒子径0.75μm、粒子径のCV値35%、重量減少割合2.5%)を得た。
ポリイミド粒子(r)を400℃のオーブンで30分間熱処理し、ポリイミド粒子(t)(平均粒子径0.26μm、粒子径のCV値35%、重量減少割合1.2%)を得た。
ジアミン溶液に対して超音波を照射し攪拌しながら非溶液状態のBPDA0.588gのうちまず約0.05gを投入して確実に反応させ、ポリアミド酸の析出を確認した後、再度約0.05gのBPDAを投入した。この作業を繰り返し、BPDA0.588gを分割投入したこと以外はポリアミド酸粒子(r)と同様にして、ポリアミド酸粒子(u)(平均粒子径0.25μm、粒子径のCV値12%、重量減少割合4.7%)を得た。
反応触媒としてのピリジンを使用せず、ポリイミド酸を生成させる際の超音波照射時間を60分間に変更したこと以外はポリイミド粒子(s)と同様にして、ポリイミド粒子(v)(平均粒子径0.7μm、粒子径のCV値45%、重量減少割合4.0%)を得た。
ジアミン溶液に、ピッツコールK-30(第一工業製薬社製、ポリビニルピロリドン)を0.0063g添加溶解したこと以外はポリイミド粒子(r)と同様にして、表面処理されたポリイミド粒子(w)(平均粒子径0.3μm、粒子径のCV値35%、重量減少割合4.7%)を得た。
ポリイミド粒子(r)の製造方法と同様にして、ポリアミド酸粒子(r)を得た。0.03gのピッツコールK-30(第一工業製薬社製、ポリビニルピロリドン)を100gのエタノールに溶解したエタノール溶液に、ポリイミド粒子(r)1gを添加して、充分攪拌混合した。ポリイミド粒子をろ過した後、乾燥して、表面処理されたポリイミド粒子(x)(平均粒子径0.3μm、粒子径のCV値35%、重量減少割合4.7%)を得た。
CV値(%)=σ/m×100
X={(A-B)/A}×100 (%)
表2~4の組成に従って、下記に示す各材料をホモディスパーを用いて攪拌混合して、電子部品用接合材を作製した。実施例6~12、15~21、比較例3~4及び6~9ではペースト状の電子部品用接合材を作製し、実施例13~14及び比較例5ではシート状の電子部品用接合材を作製した。なお、比較列5ではシート状の電子部品用接合材を作製しようとしたが、表面荒れが多く良好にシート状に成形することができなかった。一方、実施例14ではポリイミド粒子が適度な粒子径分布を有するために良好なシート状の電子部品用接合材を得ることができた。
ビスフェノールA型エポキシ樹脂(商品名「YL-980」、ジャパンエポキシレジン社製)
ビスフェノールA型エポキシ樹脂(商品名「1004AF」、ジャパンエポキシレジン社製)
グリシジル基含有アクリル樹脂(商品名「G-2050M」、日油社製)
トリアルキルテトラヒドロ無水フタル酸(商品名「YH306」、JER社製)
2,4-ジアミノ-6-[2’メチルイミダゾリン-(1’)]-エチルs-トリアジンイソシアヌル酸付加物(商品名「2MA-OK」、四国化成工業社製)
(4-1.平均粒子径0.03~3μmかつCV値10~50%のポリイミド粒子)
上記で得られたポリイミド粒子(h)~(l)及び(p)~(x)
(4-2.その他のポリイミド粒子)
上記で得られたポリイミド粒子(m)~(o)
ポリイミド粒子(商品名「UIP-S」、平均粒子径10μm、粒子径のCV値15%、重量減少割合1.0%、宇部興産社製)
シリカ粒子(商品名「シルフィル NHM-5N」、平均粒子径0.07μm、粒子径のCV値12%、トクヤマ社製)
シリカ粒子(商品名「SE2050SPJ」、平均粒子径0.5μm、粒子径のCV値10%、アドマテックス社製)
シリカ粒子(商品名「SE4050SPE」、平均粒子径1μm、粒子径のCV値10%、アドマテックス社製)
シランカップリング剤(商品名「KBM-573」、信越化学工業社製)
溶剤(メチルエチルケトン(MEK))
実施例及び比較例で得られた電子部品用接合材について、以下の評価を行った。評価結果を表2~4に示した。
(1)線膨張率の測定
得られた電子部品用接合材について、110℃40分、更に、170℃30分で硬化させた厚さ500μmの硬化物を作製し、熱応力歪測定装置(型式「EXTEAR TMA/SS 6100」、エスアイアイ・ナノテクノロジー社製)を用い、荷重2N、昇温速度5℃/分、サンプル長1cmで300℃まで昇温し、このとき得られたSSカーブの傾きから線膨張率を求めた。
得られた半電子部品用接合材について、110℃40分、更に、170℃30分で硬化させた厚さ500μmの硬化物を作製し、粘弾性測定機(型式「DVA-200」、アイティー計測制御社製)を用い、昇温速度5℃/分、引っ張り、つかみ幅24mm、10Hzで300℃まで昇温し、25℃、170℃にて測定して得られる値を弾性率とした。
得られた電子部品用接合材について、エアーディスペンサー(SHOT MASTER300、武蔵エンジニアリング社製)を用いて流動性を評価した。このとき、使用した部品は、精密ノズル(武蔵エンジニアリング社製、内径0.3mm)、10mLシリンジ(武蔵エンジニアリング社製)であった。吐出条件を吐出圧0.4MPa、ガラス基板とニードルとのギャップ200μmとし、吐出量5mg狙いで電子部品用接合材をガラス基板上に塗布した。次いで、塗布した電子部品用接合材の上にガラスチップ(10mm×10mm、厚み100μm)をボンディングし、これを80℃1時間オーブンに入れた。
電子部品用接合材がガラスチップ下の領域の90%以上にまで広がっていた場合を○、ガラスチップ下の領域の90%未満70%以上にまで広がっていた場合を△、ガラスチップ下の領域の70%未満までしか広がっていなかった場合を×と評価した。
なお、実施例13及び14ではシート状の電子部品用接合材を作製したため、本評価は行わなかった。比較例3及び4では添加したポリイミド粒子の平均粒子径が大きすぎたためか、濡れ広がりが悪い結果となった。
ハンダボールがペリフェラル状に配置されている半導体チップ(10mm×10mm×30μm厚)と、半導体チップを介して電気的に接続されたときに半導体チップ内のメタル配線とデイジーチェーンとなるように銅が配線された20mm×20mm×1.0mm厚の基板(ガラス/エポキシ系FR-4)とを用い、得られた電子部品用接合材を用いてフリップチップ実装(250℃、10秒、5N)した。得られたサンプルに対し、-55℃~125℃(各10分間ずつ)、1000サイクルの冷熱サイクル試験を行った後、半導体チップ-電子部品用接合材-基板の剥がれの評価を行った。なお、8つのサンプルについて評価を行い、剥がれが見られたサンプルの個数を評価した。
Claims (8)
- ジアミン化合物が溶解した溶液を調製する工程と、
物理的衝撃を加えながら、非溶液状態の無水テトラカルボン酸を前記ジアミン化合物が溶解した溶液に添加し、ポリアミド酸粒子を析出させる工程とを有する
ことを特徴とするポリアミド酸粒子の製造方法。 - ポリアミド酸粒子を析出させる工程において、ジアミン化合物が溶解した溶液に対して超音波を照射しながら、非溶液状態の無水テトラカルボン酸を前記ジアミン化合物が溶解した溶液に添加することを特徴とする請求項1記載のポリアミド酸粒子の製造方法。
- ジアミン化合物が溶解した溶液に対して超音波を照射する際に、前記ジアミン化合物が溶解した溶液に超音波振動子を浸漬させることを特徴とする請求項2記載のポリアミド酸粒子の製造方法。
- ポリアミド酸粒子を表面処理することを特徴とする請求項1、2又は3記載のポリアミド酸粒子の製造方法。
- 請求項1、2、3又は4記載のポリアミド酸粒子の製造方法により得られたポリアミド酸粒子をイミド化処理することを特徴とするポリイミド粒子の製造方法。
- ポリイミド粒子を表面処理することを特徴とする請求項5記載のポリイミド粒子の製造方法。
- 請求項5又は6記載のポリイミド粒子の製造方法により得られるポリイミド粒子であって、10℃/分の昇温速度で30℃から300℃まで加熱した場合の重量減少割合が5%以下であることを特徴とするポリイミド粒子。
- 硬化性化合物と、硬化剤と、ポリイミド粒子とを含有し、
前記ポリイミド粒子は、平均粒子径が0.03~3μmであり、粒子径のCV値が10~50%である
ことを特徴とする電子部品用接合材。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/993,808 US9228118B2 (en) | 2010-12-17 | 2011-12-14 | Production method for polyamide acid particles, production method for polyimide particles, polyimide particles and bonding material for electronic component |
KR1020137018507A KR101848114B1 (ko) | 2010-12-17 | 2011-12-14 | 폴리아미드산 입자의 제조 방법, 폴리이미드 입자의 제조 방법, 폴리이미드 입자 및 전자 부품용 접합재 |
JP2012504943A JP5016738B2 (ja) | 2010-12-17 | 2011-12-14 | ポリアミド酸粒子の製造方法、ポリイミド粒子の製造方法、ポリイミド粒子及び電子部品用接合材 |
CN201180060875.5A CN103261277B (zh) | 2010-12-17 | 2011-12-14 | 聚酰胺酸粒子的制造方法、聚酰亚胺粒子的制造方法、聚酰亚胺粒子及电子部件用接合材料 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-282020 | 2010-12-17 | ||
JP2010282020 | 2010-12-17 | ||
JP2011046613 | 2011-03-03 | ||
JP2011-046613 | 2011-03-03 | ||
JP2011064744 | 2011-03-23 | ||
JP2011-064744 | 2011-03-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012081615A1 true WO2012081615A1 (ja) | 2012-06-21 |
Family
ID=46244712
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/078899 WO2012081615A1 (ja) | 2010-12-17 | 2011-12-14 | ポリアミド酸粒子の製造方法、ポリイミド粒子の製造方法、ポリイミド粒子及び電子部品用接合材 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9228118B2 (ja) |
JP (2) | JP5016738B2 (ja) |
KR (1) | KR101848114B1 (ja) |
CN (1) | CN103261277B (ja) |
TW (1) | TWI526472B (ja) |
WO (1) | WO2012081615A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014192665A1 (en) * | 2013-05-27 | 2014-12-04 | Ricoh Company, Ltd. | Method for producing polyimide precursor and method for producing polyimide |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9641163B2 (en) | 2014-05-28 | 2017-05-02 | Cree, Inc. | Bandwidth limiting methods for GaN power transistors |
US9515011B2 (en) * | 2014-05-28 | 2016-12-06 | Cree, Inc. | Over-mold plastic packaged wide band-gap power transistors and MMICS |
US9472480B2 (en) | 2014-05-28 | 2016-10-18 | Cree, Inc. | Over-mold packaging for wide band-gap semiconductor devices |
CN107108888B (zh) * | 2015-01-05 | 2021-06-08 | 沙特基础工业全球技术有限公司 | 反应性易碎聚酰亚胺及制备方法 |
EP3494165A1 (en) * | 2016-08-03 | 2019-06-12 | SABIC Global Technologies B.V. | Method for the manufacture of a poly(imide) prepolymer powder and varnish, poly(imide) prepolymer powder and varnish prepared thereby, and poly(imide) prepared therefrom |
US10767051B2 (en) * | 2016-09-29 | 2020-09-08 | Sekisui Chemical Co., Ltd. | Cured body and multilayered substrate |
CN117069939B (zh) * | 2023-10-17 | 2024-04-09 | 宁德时代新能源科技股份有限公司 | 一种聚酰亚胺微球及其制备方法、负极极片、电池和用电装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03263463A (ja) * | 1990-03-13 | 1991-11-22 | Sekiyu Sangyo Kasseika Center | 樹脂組成物及びその製造方法 |
JP2004292682A (ja) * | 2003-03-27 | 2004-10-21 | Osaka Prefecture | ポリイミド微粒子及びその製造方法 |
JP2006182845A (ja) * | 2004-12-27 | 2006-07-13 | Osaka Prefecture | ポリアミド酸微粒子及びポリイミド微粒子の製造方法 |
JP2007217487A (ja) * | 2006-02-15 | 2007-08-30 | Arakawa Chem Ind Co Ltd | ポリアミド酸微粒子等の製造方法 |
JP2008222958A (ja) * | 2007-03-15 | 2008-09-25 | Sumitomo Bakelite Co Ltd | 金属皮膜を有するポリイミド微粒子の製造方法 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4098800A (en) * | 1977-04-18 | 1978-07-04 | General Electric Company | Process for preparing polyetheramide-acids |
DE3124401A1 (de) * | 1981-06-22 | 1983-01-27 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von pulverfoermigem polyimid und seine verwendung |
JP3478977B2 (ja) | 1997-08-29 | 2003-12-15 | 大阪府 | ポリアミド酸微粒子及びポリイミド微粒子ならびにそれらの製造方法 |
DE69919092T2 (de) | 1998-08-28 | 2005-07-21 | Osaka Prefectural Government | Mikrofeine Partikel von Polyamidsäure und Polyimid und Verfahren zu deren Herstellung |
JP4025943B2 (ja) * | 1999-02-26 | 2007-12-26 | 大阪府 | 機能性ポリアミド酸微粒子及び機能性ポリイミド微粒子ならびにこれらの製造方法 |
EP1182229B1 (en) * | 2000-08-21 | 2008-04-16 | Osaka Prefectural Government | Processes for the production of functional polyamic acid microfine particles |
US6451955B1 (en) * | 2000-09-28 | 2002-09-17 | Sumitomo Bakelite Company Limited | Method of making a polyimide in a low-boiling solvent |
JP4465143B2 (ja) | 2002-03-04 | 2010-05-19 | 独立行政法人科学技術振興機構 | 粒径および粒度分布が制御されたポリイミド微粒子の製造方法 |
JP5259041B2 (ja) * | 2004-08-10 | 2013-08-07 | 株式会社シミズ | 樹脂組成物および水性電着塗料 |
JP2006143890A (ja) | 2004-11-19 | 2006-06-08 | Sony Chem Corp | ポリイミド微粒子の製造方法 |
JP4661282B2 (ja) * | 2005-03-14 | 2011-03-30 | 住友ベークライト株式会社 | ポリアミド酸微粒子及びポリイミド微粒子の製造方法 |
KR20080049774A (ko) * | 2005-09-02 | 2008-06-04 | 고난 가쿠엔 | 금속 초미립자 함유 폴리아미드산 |
US20080269457A1 (en) * | 2006-04-11 | 2008-10-30 | Sony Chemical & Information Device Corporation | Process For Producing Polyimide Fine Particle |
JP4650456B2 (ja) | 2006-08-25 | 2011-03-16 | 日立化成工業株式会社 | 回路接続材料、これを用いた回路部材の接続構造及びその製造方法 |
CN100506886C (zh) | 2007-06-18 | 2009-07-01 | 南京工业大学 | 一种聚酰亚胺微球的制备方法 |
TWI454375B (zh) | 2008-03-06 | 2014-10-01 | Nippon Steel & Sumikin Chem Co | Laminates for flexible substrates and thermally conductive polyimide films |
JP5283080B2 (ja) | 2009-02-17 | 2013-09-04 | 独立行政法人産業技術総合研究所 | ポリイミド微粒子分散液、ポリイミド微粒子及びそれらの製造方法 |
JP2010239106A (ja) | 2009-03-13 | 2010-10-21 | Sekisui Chem Co Ltd | 半導体チップ接合用接着剤 |
JP5806332B2 (ja) * | 2010-12-22 | 2015-11-10 | サイテク・テクノロジー・コーポレーシヨン | プレプレグ及び構造部品用途における使用のための不溶性及び部分的可溶性又は膨潤性強化粒子を含有するエポキシ樹脂系 |
-
2011
- 2011-12-14 US US13/993,808 patent/US9228118B2/en not_active Expired - Fee Related
- 2011-12-14 JP JP2012504943A patent/JP5016738B2/ja active Active
- 2011-12-14 KR KR1020137018507A patent/KR101848114B1/ko active IP Right Grant
- 2011-12-14 WO PCT/JP2011/078899 patent/WO2012081615A1/ja active Application Filing
- 2011-12-14 CN CN201180060875.5A patent/CN103261277B/zh not_active Expired - Fee Related
- 2011-12-15 TW TW100146426A patent/TWI526472B/zh not_active IP Right Cessation
-
2012
- 2012-06-04 JP JP2012127322A patent/JP2012212895A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03263463A (ja) * | 1990-03-13 | 1991-11-22 | Sekiyu Sangyo Kasseika Center | 樹脂組成物及びその製造方法 |
JP2004292682A (ja) * | 2003-03-27 | 2004-10-21 | Osaka Prefecture | ポリイミド微粒子及びその製造方法 |
JP2006182845A (ja) * | 2004-12-27 | 2006-07-13 | Osaka Prefecture | ポリアミド酸微粒子及びポリイミド微粒子の製造方法 |
JP2007217487A (ja) * | 2006-02-15 | 2007-08-30 | Arakawa Chem Ind Co Ltd | ポリアミド酸微粒子等の製造方法 |
JP2008222958A (ja) * | 2007-03-15 | 2008-09-25 | Sumitomo Bakelite Co Ltd | 金属皮膜を有するポリイミド微粒子の製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014192665A1 (en) * | 2013-05-27 | 2014-12-04 | Ricoh Company, Ltd. | Method for producing polyimide precursor and method for producing polyimide |
Also Published As
Publication number | Publication date |
---|---|
TW201226447A (en) | 2012-07-01 |
JP2012212895A (ja) | 2012-11-01 |
KR101848114B1 (ko) | 2018-04-11 |
CN103261277A (zh) | 2013-08-21 |
JPWO2012081615A1 (ja) | 2014-05-22 |
TWI526472B (zh) | 2016-03-21 |
KR20130126674A (ko) | 2013-11-20 |
US9228118B2 (en) | 2016-01-05 |
CN103261277B (zh) | 2015-12-02 |
US20130289156A1 (en) | 2013-10-31 |
JP5016738B2 (ja) | 2012-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5016738B2 (ja) | ポリアミド酸粒子の製造方法、ポリイミド粒子の製造方法、ポリイミド粒子及び電子部品用接合材 | |
TWI640593B (zh) | 接著劑、接著劑膜、半導體裝置及其製造方法 | |
TWI586747B (zh) | 樹脂組成物、樹脂組成物薄片、半導體裝置及其製造方法 | |
TW201120174A (en) | Adhesive composition, adhesive sheet, circuit board and semiconductor device using same and method for producing same | |
JP2008094870A (ja) | 半導体用接着組成物、それを用いた半導体装置および半導体装置の製造方法 | |
JP2007051215A (ja) | 接着剤組成物及び接着フィルム | |
JP5484706B2 (ja) | Cof半導体封止用フィルム状接着剤及びその接着剤を用いた半導体装置の製造方法並びに半導体装置 | |
KR100941315B1 (ko) | 열경화성 접착제 조성물 및 이를 이용한 접착 필름 | |
JP2017141317A (ja) | 仮貼り樹脂組成物、樹脂層、永久接着剤、仮貼り接着剤、ウエハ加工体およびこれらを用いた半導体装置の製造方法 | |
WO2013179943A1 (ja) | バンプ電極付き半導体装置製造用接着剤シートおよび半導体装置の製造方法 | |
JP2008094993A (ja) | 半導体用接着組成物、それを用いた半導体装置および半導体装置の製造方法。 | |
JP4771071B2 (ja) | スクリーン印刷用樹脂組成物 | |
JP5866209B2 (ja) | 半導体用接着剤 | |
JP2010239106A (ja) | 半導体チップ接合用接着剤 | |
JP2019131704A (ja) | 仮保護膜用樹脂組成物、およびこれを用いた半導体電子部品の製造方法 | |
JP5792598B2 (ja) | ポリアミド酸粒子の製造方法、ポリイミド粒子の製造方法、ポリイミド粒子及び電子部品用接合材 | |
JP6716939B2 (ja) | 接着剤、それからなる接着フィルム、それらの硬化物を含む半導体装置およびその製造方法 | |
JP2005175338A (ja) | 半導体用接着フィルムおよび半導体装置 | |
JP2005120270A (ja) | 接着剤組成物及び接着フイルム | |
JP2005116590A (ja) | 半導体用接着フィルムおよび半導体装置 | |
JP2012231090A (ja) | 電子部品用接合材 | |
TWI287030B (en) | Resin composition, heat-resistant resin paste and semiconductor device using these and method of preparing the same | |
TW202300557A (zh) | 聚合物及其應用 | |
JP2014067789A (ja) | 未硬化接着剤層付配線基板および半導体装置の製造方法 | |
JP2011046809A (ja) | 半導体チップ接合用接着剤 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2012504943 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11848100 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13993808 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20137018507 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11848100 Country of ref document: EP Kind code of ref document: A1 |