JPWO2019123943A1 - Hydroxy compounds, compositions, cured products and laminates - Google Patents
Hydroxy compounds, compositions, cured products and laminates Download PDFInfo
- Publication number
- JPWO2019123943A1 JPWO2019123943A1 JP2019560890A JP2019560890A JPWO2019123943A1 JP WO2019123943 A1 JPWO2019123943 A1 JP WO2019123943A1 JP 2019560890 A JP2019560890 A JP 2019560890A JP 2019560890 A JP2019560890 A JP 2019560890A JP WO2019123943 A1 JPWO2019123943 A1 JP WO2019123943A1
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy compound
- resin
- compound
- base material
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002440 hydroxy compounds Chemical class 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- 229940126062 Compound A Drugs 0.000 claims abstract description 32
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- -1 isocyanate compound Chemical class 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 29
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 62
- 239000011347 resin Substances 0.000 description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 46
- 239000003822 epoxy resin Substances 0.000 description 37
- 229920000647 polyepoxide Polymers 0.000 description 37
- 239000000835 fiber Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 35
- 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 33
- 239000000047 product Substances 0.000 description 31
- 238000001723 curing Methods 0.000 description 26
- 238000000465 moulding Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000010419 fine particle Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 4
- 239000008393 encapsulating agent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- QYJOVSLBSPJZHH-UHFFFAOYSA-N 2-[12-(oxiran-2-ylmethoxy)dodecoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCCCCCCOCC1CO1 QYJOVSLBSPJZHH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- YGYPMFPGZQPETF-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C=2C=C(C)C(O)=C(C)C=2)=C1 YGYPMFPGZQPETF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000434 field desorption mass spectrometry Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 2
- ICVYBDCJUNRFED-UHFFFAOYSA-N 2-[14-(oxiran-2-ylmethoxy)tetradecoxymethyl]oxirane Chemical compound C(CCCCCCCOCC1CO1)CCCCCCOCC1CO1 ICVYBDCJUNRFED-UHFFFAOYSA-N 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
本発明は、一般式(1)の構造を有するヒドロキシ化合物Aを提供するものである。・・・(1)(式(1)中、Arはそれぞれ独立して無置換または置換基を有する芳香環を有する構造を表し、R1およびR2はそれぞれ独立して水素原子または炭素数1〜2のアルキル基を表し、R3およびR4はそれぞれ独立して水酸基またはメチル基を表し、nは11〜16の整数であって、mは繰り返し数の平均値で0.5〜10である。(但し、繰り返し単位中に存在する各繰り返し単位はそれぞれ同一であっても異なっていても構わない)。)The present invention provides a hydroxy compound A having the structure of the general formula (1). ... (1) (In the formula (1), Ar represents a structure having an aromatic ring independently unsubstituted or a substituent, and R1 and R2 independently represent a hydrogen atom or 1 to 2 carbon atoms, respectively. R3 and R4 each independently represent a hydroxyl group or a methyl group, n is an integer of 11 to 16, and m is an average value of the number of repetitions of 0.5 to 10 (provided that it is 0.5 to 10). , Each repeating unit existing in the repeating unit may be the same or different).
Description
本発明は、特定の構造を有するヒドロキシ化合物、及び該ヒドロキシ化合物を有する組成物、該組成物を硬化してなる硬化物に関する。また、該硬化物層を有する積層体に関する。 The present invention relates to a hydroxy compound having a specific structure, a composition having the hydroxy compound, and a cured product obtained by curing the composition. It also relates to a laminate having the cured product layer.
CO2削減・燃費向上などから自動車・飛行機の軽量化は益々進み、これに伴いスポット溶接数の低減や繊維強化樹脂と金属の併用などによる軽量化が進められ、これらに用いられる構造材料用接着剤の高性能化が強く求められている。特に、熱膨張差の大きい金属と繊維強化樹脂との加熱接着においては、膨張と収縮に伴う、界面応力による反りや波打ちの発生による接着力の低下が課題となっている。
一方、半導体封止材料や多層プリント基板用絶縁層などに用いられる先端電子材料にも、金属とプラスチックやシリコンチップの積層体が用いられている。このとき、伝送速度等の関係から表面が平滑な金属を用いる必要があるが、アンカー効果の減少から接着力の低下が深刻な問題となっており、特に接着が難しい金属側の接着剤や接着剤用プライマーが求められている。
一方、産業上利用する金属表面は、大気中に存在する有機物や無機物により汚染されていることが多い。これら有機物や無機物は酸化物層の上に堆積し、金属の接着性をさらに低下させる。よって、有機物等によって汚染された状態であっても高い接着性を発揮するプライマーが求められている。The weight of automobiles and airplanes has been further reduced due to CO 2 reduction and fuel efficiency improvement, and along with this, the number of spot welds has been reduced and the weight has been reduced by using fiber reinforced plastic and metal together. Adhesion for structural materials used for these There is a strong demand for higher performance agents. In particular, in the heat adhesion between a metal having a large difference in thermal expansion and a fiber reinforced resin, a decrease in adhesive force due to warpage or waviness due to interfacial stress due to expansion and contraction is a problem.
On the other hand, a laminate of metal and plastic or a silicon chip is also used as an advanced electronic material used for a semiconductor encapsulating material or an insulating layer for a multilayer printed circuit board. At this time, it is necessary to use a metal with a smooth surface due to the transmission speed, etc., but the decrease in adhesive strength has become a serious problem due to the decrease in the anchor effect, and the adhesive and adhesion on the metal side, which are particularly difficult to bond Medicinal primers are required.
On the other hand, metal surfaces used industrially are often contaminated with organic substances and inorganic substances existing in the atmosphere. These organic and inorganic substances are deposited on the oxide layer, further reducing the adhesiveness of the metal. Therefore, there is a demand for a primer that exhibits high adhesiveness even when it is contaminated with an organic substance or the like.
例えば特許文献1では、ビスフェノールA型エポキシ樹脂と、ノボラック型エポキシ樹脂とを併用する金属用プライマー組成物が開示されている。しかし、これらのような通常のエポキシ樹脂を用いたプライマーは、汚染された金属表面に対する接着性という課題は解決していない。 For example, Patent Document 1 discloses a primer composition for a metal in which a bisphenol A type epoxy resin and a novolak type epoxy resin are used in combination. However, primers using ordinary epoxy resins such as these do not solve the problem of adhesiveness to contaminated metal surfaces.
本発明の課題は、金属表面、特に汚染された金属表面であっても高い接着性とプライマー性を発揮する化合物を提供することにある。
また、該化合物を含有する組成物、及び金属用プライマー、及び該組成物層と基材とを有することを特徴とする積層体を提供することにある。An object of the present invention is to provide a compound that exhibits high adhesiveness and primer property even on a metal surface, particularly a contaminated metal surface.
Another object of the present invention is to provide a composition containing the compound, a primer for a metal, and a laminate characterized by having the composition layer and a base material.
本発明者らは、鋭意検討した結果、下記式(1)で表されるヒドロキシ化合物Aを提供することで、前記課題が解決できることを見出した。すなわち本発明は、一般式(1)の構造を有するヒドロキシ化合物Aを提供するものである。 As a result of diligent studies, the present inventors have found that the above problems can be solved by providing the hydroxy compound A represented by the following formula (1). That is, the present invention provides the hydroxy compound A having the structure of the general formula (1).
・・・(1)
... (1)
式(1)中、Arはそれぞれ独立して無置換または置換基を有する芳香環を有する構造を表し、
R1およびR2はそれぞれ独立して水素原子または炭素数1〜2のアルキル基を表し、
R3およびR4はそれぞれ独立して水酸基またはメチル基を表し、
nは11〜16の整数であって、mは繰り返し数の平均値で0.5〜10である
(但し、繰り返し単位中に存在する各繰り返し単位はそれぞれ同一であっても異なっていても構わない)。)In formula (1), Ar represents a structure having an aromatic ring independently of an unsubstituted or substituent.
R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
R3 and R4 independently represent a hydroxyl group or a methyl group, respectively.
n is an integer of 11 to 16, and m is an average value of the number of repetitions, which is 0.5 to 10 (however, each repeating unit existing in the repeating unit may be the same or different. Absent). )
さらに、また、該ヒドロキシ化合物Aを含有する組成物、また、該化合物を含有する組成物、及び金属用プライマー、及び該組成物層と基材とを有することを特徴とする積層体を提供することで、前記課題を解決する。 Further, the present invention provides a composition containing the hydroxy compound A, a composition containing the compound, a primer for a metal, and a laminate characterized by having the composition layer and a base material. By doing so, the above-mentioned problem is solved.
本発明のヒドロキシ化合物Aは、金属表面、特に汚染された金属表面であっても高い接着性とプライマー性を発揮することができる。 The hydroxy compound A of the present invention can exhibit high adhesiveness and primer property even on a metal surface, particularly a contaminated metal surface.
<ヒドロキシ化合物A> 本発明のヒドロキシ化合物Aは、下記式(1)で表される化合物である。 <Hydroxy compound A> The hydroxy compound A of the present invention is a compound represented by the following formula (1).
・・・(1)
... (1)
(式(1)中、Arはそれぞれ独立して無置換または置換基を有する芳香環を有する構造を表し、
R1およびR2はそれぞれ独立して水素原子または炭素数1〜2のアルキル基を表し、
R3およびR4はそれぞれ独立して水酸基またはメチル基を表し、
nは11〜16の整数であって、mは繰り返し数の平均値で0.5〜10である
(但し、繰り返し単位中に存在する各繰り返し単位はそれぞれ同一であっても異なっていても構わない)。(In formula (1), Ar represents a structure having an aromatic ring having an unsubstituted or substituent, respectively.
R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
R 3 and R 4 independently represent a hydroxyl group or a methyl group, respectively.
n is an integer of 11 to 16, and m is an average value of the number of repetitions, which is 0.5 to 10 (however, each repeating unit existing in the repeating unit may be the same or different. Absent).
これらの中でも、前記ヒドロキシ化合物Aの水酸基当量が100〜10000g/eqであるものは接着剤層との反応性や、金属表面への配位性が適当であり、柔軟強靭性と耐熱性とを兼備できる点から好ましいものである。又、前記ヒドロキシ化合物Aの25℃における粘度が100〜20000Pa・sであるものが、作業性が良好で、硬化物の柔軟性と密着性に優れる点から好ましく、特に2,000〜15,000Pa・sであることが好ましい。 Among these, those having a hydroxyl group equivalent of 100 to 10,000 g / eq of the hydroxy compound A are suitable for reactivity with the adhesive layer and coordination to the metal surface, and have flexible toughness and heat resistance. It is preferable because it can be combined. Further, the hydroxy compound A having a viscosity at 25 ° C. of 100 to 20000 Pa · s is preferable from the viewpoint of good workability and excellent flexibility and adhesion of the cured product, and particularly 2,000 to 15,000 Pa · s. -It is preferably s.
前記一般式(1)において、それぞれ独立してArは無置換または置換基を有する芳香環を有する構造を表す。ここでいう芳香環とは、例えばベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。これら芳香環を有する構造であるArとしては、好ましくは下記式(2)で表される構造を表す。 In the general formula (1), Ar independently represents a structure having an aromatic ring having no substituent or a substituent. Examples of the aromatic ring here include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Ar, which is a structure having these aromatic rings, preferably represents a structure represented by the following formula (2).
(式(2)において、芳香環は置換または無置換であってよく、*は結合点を表す。) (In the formula (2), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point.)
上記式(2)において、硬化物の柔軟性、弾性率および接着性のバランスに優れる点から、Arの構造としては以下のものが特に好ましい。 In the above formula (2), the following Ar structure is particularly preferable from the viewpoint of excellent balance of flexibility, elastic modulus and adhesiveness of the cured product.
Arが置換基を有する場合、置換基としては好ましくはアルキル基、ハロゲン原子、水酸基等が挙げられる。好ましくはアルキル基と水酸基であり、水酸基を有する場合は接着剤層との反応性や、金属表面への配位性が優れることから特に好ましい。 When Ar has a substituent, the substituent preferably includes an alkyl group, a halogen atom, a hydroxyl group and the like. It is preferably an alkyl group and a hydroxyl group, and when it has a hydroxyl group, it is particularly preferable because it is excellent in reactivity with the adhesive layer and coordination to the metal surface.
置換基を有するArとしての特に好ましい構造としては、以下の構造が挙げられる。 Particularly preferable structures of Ar having a substituent include the following structures.
前記式1で表されるヒドロキシ化合物Aにおいて、繰り返し単位nとしては、11〜16の整数であり、好ましくは12〜15である。nが11以上であることで、接着力が向上する上、基材の膨張と収縮に伴う、界面応力による反りや波打ちを緩和することが出来る。また、nが16以下であることで、架橋密度の低下を抑制できる。 In the hydroxy compound A represented by the above formula 1, the repeating unit n is an integer of 11 to 16, preferably 12 to 15. When n is 11 or more, the adhesive strength is improved, and warpage and waviness due to interfacial stress due to expansion and contraction of the base material can be alleviated. Further, when n is 16 or less, a decrease in the crosslink density can be suppressed.
<ヒドロキシ化合物Aの製造方法>
本発明のヒドロキシ化合物Aの製造方法としては、特に限定されるものではないが、例えば、脂肪族系ジヒドロキシ化合物のジグリシジルエーテル(a1)と芳香族系ヒドロキシ化合物(a2)とを、モル比(a1)/(a2)が1/1.01〜1/5.0の範囲で反応させて得られる<Method for producing hydroxy compound A>
The method for producing the hydroxy compound A of the present invention is not particularly limited, but for example, the aliphatic dihydroxy compound diglycidyl ether (a1) and the aromatic hydroxy compound (a2) are mixed in a molar ratio (a2). It is obtained by reacting a1) / (a2) in the range of 1 / 1.01 to 1 / 5.0.
ヒドロキシ化合物A中には未反応の芳香族系ヒドロキシ化合物(a2)が含まれるが、本発明ではそのまま用いてもよく、また、芳香族系ヒドロキシ化合物(a2)を取り除いて用いても良い。 Although the hydroxy compound A contains an unreacted aromatic hydroxy compound (a2), it may be used as it is in the present invention, or the aromatic hydroxy compound (a2) may be removed and used.
未反応の前記芳香族系ヒドロキシ化合物(a2)の除去方法としては種々の方法に準じて行うことができる。例えば、極性の違いを利用するカラムクロマトグラフィー分離法、沸点の違いを利用する蒸留分留法、アルカリ水への溶解度の違いを利用するアルカリ水溶抽出法などが挙げられる。なかでも、熱変質を伴わないため、アルカリ水溶抽出法が効率などの点で好ましく、この時目的物を溶解させるために使用する有機溶媒はトルエンやメチルイソブチルケトンなど水と混合しないものなら使用可能であるが、目的物との溶解性の観点からメチルイソブチルケトンが好ましい。得られるヒドロキシ化合物A中の未反応の前記芳香族系ヒドロキシ化合物(a2)の存在率は質量%で0.1〜30であることが硬化物の強靱性と柔軟性とのバランスが良好となる点から好ましい。 As a method for removing the unreacted aromatic hydroxy compound (a2), various methods can be followed. For example, a column chromatography separation method utilizing a difference in polarity, a distillation fractional distillation method utilizing a difference in boiling point, an alkaline water-soluble extraction method utilizing a difference in solubility in alkaline water, and the like can be mentioned. Of these, the alkaline water-soluble extraction method is preferable in terms of efficiency because it does not involve thermal alteration. At this time, the organic solvent used to dissolve the target product can be used as long as it is not mixed with water, such as toluene or methyl isobutyl ketone. However, methyl isobutyl ketone is preferable from the viewpoint of solubility in the target product. When the abundance of the unreacted aromatic hydroxy compound (a2) in the obtained hydroxy compound A is 0.1 to 30 by mass, the balance between the toughness and the flexibility of the cured product is good. It is preferable from the point of view.
前記脂肪族系ジヒドロキシ化合物のジグリシジルエーテル(a1)としては、特に限定されるものではなく、例えば1,11−ウンデカンジオールジグリシジルエーテル、1,12−ドデカンジオールジグリシジルエーテル、1,13−トリデカンジオール、1,14−テトラデカンジオールジグリシジルエーテル、1,15−ペンタデカンジオールジグリシジルエーテル、1,16−ヘキサデカンジオールジグリシジルエーテル、2−メチル−1,11−ウンデカンジオールジグリシジルエーテル、3−メチル−1,11−ウンデカンジオールジグリシジルエーテル、2,6,10−トリメチル−1,11−ウンデカンジオールジグリシジルエーテル等が挙げられる。これらは、ヒドロキシ化合物のグリシジルエーテル化において生成する有機塩素不純物を含有していても良く、下記構造で表される1−クロロメチルー2−グリシジルエーテル(クロルメチル体)等の有機塩素を含有していても良い。これらのジグリシジルエーテルは単独でも、2種類以上を併用しても良い。 The diglycidyl ether (a1) of the aliphatic dihydroxy compound is not particularly limited, and is, for example, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tride. Candiol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl Examples thereof include -1,11-undecanediol diglycidyl ether and 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether. These may contain organic chlorine impurities generated in the glycidyl etherification of the hydroxy compound, or may contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the following structure. good. These diglycidyl ethers may be used alone or in combination of two or more.
これらの中でも、得られる硬化物の柔軟性と耐熱性のバランスに優れる点から炭素数12〜14のアルキレン鎖の両末端にエーテル基を介してグリシジル基が連結した構造である化合物であることが好ましく、1,12−ドデカンジオールジグリシジルエーテル、1,13−トリデカンジオール、1,14−テトラデカンジオールジグリシジルエーテルを用いることが最も好ましい。 Among these, the compound has a structure in which a glycidyl group is linked to both ends of an alkylene chain having 12 to 14 carbon atoms via an ether group from the viewpoint of excellent balance between flexibility and heat resistance of the obtained cured product. Most preferably, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether are used.
前記芳香族系ヒドロキシ化合物(a2)としては、特に限定されるものではなく、例えば、ハイドロキノン、レゾルシン、カテコール等のジヒドロキシベンゼン類、ピロガロール、1,2,4−トリヒドロキシベンゼン、1,3,5−トリヒドロキシベンゼン等のトリヒドロキシベンゼン類、4,4‘,4“−トリヒドロキシトリフェニルメタン等のトリフェニルメタン型フェノール類、1,6−ジヒドロキシナフタレン、2,7−ジヒドロキシナフタレン、1,4−ジヒドロキシナフタレン、1,5−ジヒドロキシナフタレン、2,3−ジヒドロキシナフタレン、及び2,6−ジヒドロキシナフタレン等のジヒドロキシナフタレン類、ジヒドロキシナフタレン類をカップリング反応させた、1,1‘−メチレンビスー(2,7−ナフタレンジオール)、1,1’−ビナフタレン−2,2‘,7,7’−テトラオール、1,1‘−オキシビスー(2,7−ナフタレンジオール)等の4官能フェノール類、ビス(4−ヒドロキシフェニル)メタン、2,2−ビス(4−ヒドロキシフェニル)プロパン、2,2−ビス(3−メチル−4−ヒドロキシフェニル)プロパン、1,1−ビス(4−ヒドロキシフェニル)シクロヘキサン、及び1,1−ビス(4−ヒドロキシフェニル)−1−フェニルエタン、及びビス(4−ヒドロキシフェニル)スルホン等のビスフェノール類、2,2’―ビフェノール、4,4‘−ビフェノール、(1,1’−ビフェニル)−3,4−ジオール、3,3’−ジメチルー(1,1‘−ビフェニル)−4,4’−ジオール、3−メチルー(1,1‘−ビフェニル)−4,4’−ジオール、3,3’、5,5’−テトラメチルビフェニル−2,2’−ジオール、3,3’、5,5’−テトラメチルビフェニル−4,4’−ジオール、5−メチル−(1,1‘−ビフェニル)−3,4’ジオール、3‘−メチル−(1,1‘−ビフェニル)−3,4’ジオール、4’−メチル−(1,1‘−ビフェニル)−3,4’ジオール等のビフェノール類、フェノールとジシクロペンタジエンとの重付加物、及びフェノールとテルペン系化合物との重付加物等の脂環式構造含有フェノール類、ビス(2−ヒドロキシ−1−ナフチル)メタン、及びビス(2−ヒドロキシ−1−ナフチル)プロパン等のナフトール類、フェノールとフェニレンジメチルクロライド又はビフェニレンジメチルクロライドとの縮合反応生成物である所謂ザイロック型フェノール樹脂が挙げられ、単独でも、2種以上を併用して用いても良い。更に、上記の各化合物の芳香核に置換基としてメチル基、t−ブチル基、又はハロゲン原子が置換した構造の2官能性フェノール化合物も挙げられる。尚、前記脂環式構造含有フェノール類や、前記ザイロック型フェノール樹脂は、2官能成分のみならず、3官能性以上の成分も同時に存在し得るが、本発明ではそのまま用いてもよく、又、カラム等の精製工程を経て、2官能成分のみを取り出して用いても良い。 The aromatic hydroxy compound (a2) is not particularly limited, and is, for example, dihydroxybenzenes such as hydroquinone, resorcin, and catechol, pyrogallol, 1,2,4-trihydroxybenzene, 1,3,5. -Trihydroxybenzenes such as trihydroxybenzene, triphenylmethane-type phenols such as 4,4', 4 "-trihydroxytriphenylmethane, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4 1,1'-Methylenebisu (2,1'-methylenebisu) obtained by coupling dihydroxynaphthalenes such as −dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, and dihydroxynaphthalenes. 7-Naphthalenediol), 1,1'-binaphthalene-2,2', 7,7'-tetraol, 1,1'-oxybisu (2,7-naphthalenediol) and other tetrafunctional phenols, bis (4) -Hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and Biphenols such as 1,1-bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) sulfone, 2,2'-biphenol, 4,4'-biphenol, (1,1' -Biphenyl) -3,4-diol, 3,3'-dimethyl- (1,1'-biphenyl) -4,4'-diol, 3-methyl- (1,1'-biphenyl) -4,4'-diol , 3,3', 5,5'-tetramethylbiphenyl-2,2'-diol, 3,3', 5,5'-tetramethylbiphenyl-4,4'-diol, 5-methyl- (1, 1'-biphenyl) -3,4'diol, 3'-methyl- (1,1'-biphenyl) -3,4'diol, 4'-methyl- (1,1'-biphenyl) -3,4' Biphenols such as diols, alicyclic structure-containing phenols such as heavy additions of phenol and dicyclopentadiene, and heavy additions of phenol and terpene compounds, bis (2-hydroxy-1-naphthyl) methane, And naphthols such as bis (2-hydroxy-1-naphthyl) propane, and the condensation reaction product of phenol with phenylenedimethyl chloride or biphenylenedimethyl chloride. A so-called Zyroc-type phenol resin may be mentioned, and may be used alone or in combination of two or more. Further, a bifunctional phenol compound having a structure in which a methyl group, a t-butyl group or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can also be mentioned. In the alicyclic structure-containing phenols and the Zyroc-type phenol resin, not only bifunctional components but also components having trifunctionality or higher may be present at the same time, but they may be used as they are in the present invention. Only the bifunctional component may be taken out and used through a purification step of a column or the like.
これらの中でも、硬化物にした際の柔軟性と強靭性のバランスに優れる点からビスフェノール類が好ましく、特に靱性付与の性能が顕著である点からビス(4−ヒドロキシフェニル)メタン、2,2−ビス(4−ヒドロキシフェニル)プロパンが好ましい。又、硬化物の耐湿性を重視する場合には、脂環式構造を含有するフェノール類を用いることが好ましい。 Among these, bisphenols are preferable from the viewpoint of excellent balance between flexibility and toughness when made into a cured product, and bis (4-hydroxyphenyl) methane, 2,2- because of the remarkable performance of imparting toughness. Bis (4-hydroxyphenyl) propane is preferred. Further, when the moisture resistance of the cured product is important, it is preferable to use phenols containing an alicyclic structure.
前記脂肪族系ジヒドロキシ化合物のジグリシジルエーテル(a1)と前記芳香族系ヒドロキシ化合物(a2)との反応比率は、得られる化合物をエポキシ樹脂の硬化剤として用いるために、(a1)/(a2)が1/1.01〜1/5.0(モル比)の範囲で反応させることを必須とし、得られる硬化物の柔軟性と耐熱性をバランスよく兼備する点から、(a1)/(a2)が1/1.1〜1/3.0(モル比)であることが好ましい。 The reaction ratio of the aliphatic dihydroxy compound diglycidyl ether (a1) to the aromatic hydroxy compound (a2) is (a1) / (a2) in order to use the obtained compound as a curing agent for an epoxy resin. (A1) / (a2) from the viewpoint that it is essential to react in the range of 1 / 1.01 to 1 / 5.0 (molar ratio) and the obtained cured product has a good balance of flexibility and heat resistance. ) Is preferably 1 / 1.1 to 1 / 3.0 (molar ratio).
前記脂肪族系ジヒドロキシ化合物のジグリシジルエーテル(a1)と前記芳香族系ヒドロキシ化合物(a2)との反応は、触媒の存在下で行うことが好ましい。前記触媒としては、種々のものが使用でき、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム等のアルカリ(土類)金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、トリフェニルホスフィン等のリン系化合物、DMP−30、DMAP、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム、ベンジルトリブチルアンモニウム等のクロライド、ブロマイド、ヨーダイド、テトラメチルホスホニウム、テトラエチルホスホニウム、テトラブチルホスホニウム、ベンジルトリブチルホスホニウム等のクロライド、ブロマイド、ヨーダイド等の4級アンモニウム塩、トリエチルアミン、N,N−ジメチルベンジルアミン、1,8−ジアザビシクロ[5.4.0]ウンデセン、1,4−ジアザビシクロ[2.2.2]オクタン等の3級アミン類、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール等のイミダゾール類等が挙げられる。これらは2種以上の触媒を併用しても構わない。なかでも反応が速やかに進行すること、および不純物量の低減効果が高い点から水酸化ナトリウム、水酸化カリウム、トリフェニルホスフィン、DMP−30が好ましい。これら触媒の使用量は特に限定されるものではないが、前記芳香族系ヒドロキシ化合物(a2)のフェノール性水酸基1モルに対し0.0001〜0.01モル用いるのが好ましい。これら触媒の形態も特に限定されず、水溶液の形態で使用してもよいし、固形の形態で使用しても構わない。 The reaction between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) is preferably carried out in the presence of a catalyst. Various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, and alkali metals such as sodium hydroxide and potassium carbonate. Phosphorus compounds such as carbonates and triphenylphosphine, chlorides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium and benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium , Chloride such as benzyltributylphosphonium, quaternary ammonium salt such as bromide and iodide, triethylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene, 1,4-diazabicyclo [2. 2.2] Examples thereof include tertiary amines such as octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. These may be used in combination with two or more kinds of catalysts. Of these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferable because the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 mol with respect to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2). The form of these catalysts is not particularly limited, and may be used in the form of an aqueous solution or in the form of a solid.
また、前記脂肪族系ジヒドロキシ化合物のジグリシジルエーテル(a1)と前記芳香族系ヒドロキシ化合物(a2)との反応は、無溶剤下で、あるいは有機溶剤の存在下で行うことができる。用いうる有機溶剤としては、例えば、メチルセロソルブ、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトン、ジメチルスルホキシド、プロピルアルコール、ブチルアルコールなどが挙げられる。有機溶剤の使用量としては、仕込んだ原料の総質量に対して通常50〜300質量%、好ましくは100〜250質量%である。これらの有機溶剤は単独で、あるいは数種類を混合して用いることが出来る。反応を速やかに行うためには無溶媒が好ましく、一方、最終生成物の不純物を低減できる点からはジメチルスルホキシドの使用が好ましい。 Further, the reaction between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, butyl alcohol and the like. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in admixture of several types. Solvent-free is preferable for rapid reaction, while dimethyl sulfoxide is preferable from the viewpoint of reducing impurities in the final product.
前記反応を行う場合の反応温度としては、通常50〜180℃、反応時間は通常1〜10時間である。最終生成物の不純物を低減できる点からは反応温度は100〜160℃が好ましい。また、得られる化合物の着色が大きい場合は、それを抑制するために、酸化防止剤や還元剤を添加しても良い。酸化防止剤としては特に限定されないが、例えば2,6−ジアルキルフェノール誘導体などのヒンダードフェノール系化合物や2価のイオウ系化合物や3価のリン原子を含む亜リン酸エステル系化合物などを挙げることができる。還元剤としては特に限定されないが、例えば次亜リン酸、亜リン酸、チオ硫酸、亜硫酸、ハイドロサルファイトまたはこれら塩などが挙げられる。 When the reaction is carried out, the reaction temperature is usually 50 to 180 ° C., and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 100 to 160 ° C. from the viewpoint of reducing impurities in the final product. Further, when the color of the obtained compound is large, an antioxidant or a reducing agent may be added in order to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. Can be done. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfite, hydrosulfite, and salts thereof.
前記反応の終了後、反応混合物のpH値が3〜7、好ましくは5〜7になるまで中和あるいは水洗処理を行うこともできる。中和処理や水洗処理は常法にしたがって行えばよい。例えば塩基性触媒を用いた場合は塩酸、第一リン酸水素ナトリウム、p−トルエンスルホン酸、シュウ酸等の酸性物質を中和剤として用いることができる。中和あるいは水洗処理を行った後、必要時には減圧加熱下で溶剤を留去し生成物の濃縮を行い、化合物を得ることが出来る。 After completion of the reaction, neutralization or washing with water can be performed until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. Neutralization treatment and washing treatment may be performed according to a conventional method. For example, when a basic catalyst is used, acidic substances such as hydrochloric acid, monosodium hydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as the neutralizing agent. After neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure heating to concentrate the product, and the compound can be obtained.
前記式(1)で表されるヒドロキシ化合物Aの好ましい構造としては、以下の構造が挙げられる。 Preferred structures of the hydroxy compound A represented by the formula (1) include the following structures.
上記各構造式において、R13は水素原子およびまたはメチル基であり、nは11〜16の整数であり、mは繰り返しの平均値であり、0.5〜10である。In each of the above structural formulas, R 13 is a hydrogen atom and / or a methyl group, n is an integer of 11 to 16, m is an average value of repetition, and is 0.5 to 10.
上記各構造式の中でも、得られる硬化物の物性バランスに優れる点から、前記構造式(A−1)、(A−2)、(A−3)、(A−5)、(A−8)、(A−9)、(A−10)で表されるものを用いることが最も好ましい。 Among the above structural formulas, the structural formulas (A-1), (A-2), (A-3), (A-5), and (A-8) are excellent in terms of excellent physical property balance of the obtained cured product. ), (A-9), and (A-10) are most preferable.
<組成物>
本発明の組成物は、本発明のヒドロキシ化合物Aを含有するものである。<Composition>
The composition of the present invention contains the hydroxy compound A of the present invention.
本発明の組成物としては、ヒドロキシ化合物A以外に、該ヒドロキシ化合物Aと反応する化合物を含有していても良い。該ヒドロキシ化合物Aと反応する化合物としては、エポキシ化合物、及びまたはイソシアネート化合物等が挙げられる。 The composition of the present invention may contain a compound that reacts with the hydroxy compound A in addition to the hydroxy compound A. Examples of the compound that reacts with the hydroxy compound A include an epoxy compound and an isocyanate compound.
併用できるエポキシ化合物としては、なんら制限されるものではなく、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂、レゾルシン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、カテコール型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂等の液状エポキシ樹脂、ブロム化フェノールノボラック型エポキシ樹脂等の臭素化エポキシ樹脂、固形ビスフェノールA型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、フェニレンエーテル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂等が挙げられ、単独でも、2種以上を併用してもよく、目的とする用途や硬化物の物性等に応じて種々選択して用いることが好ましい。 The epoxy compound that can be used in combination is not limited in any way. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin. , Catecol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, liquid epoxy resin such as tetramethylbiphenyl type epoxy resin, brominated epoxy resin such as brominated phenol novolac type epoxy resin, solid bisphenol A type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthic Lene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin , Biphenyl-modified novolak type epoxy resin and the like, and may be used alone or in combination of two or more, and it is preferable to select and use variously depending on the intended use and the physical properties of the cured product.
また、エポキシ化合物の硬化剤としてアミン系化合物、酸無水物系化合物、アミド系化合物、フェノ−ル系化合物を併用しても構わない。 Further, as a curing agent for the epoxy compound, an amine compound, an acid anhydride compound, an amide compound, or a phenol compound may be used in combination.
本発明の組成物中にエポキシ化合物とエポキシ硬化剤を含有する場合の配合量としては、特に制限されるものではないが、得られる硬化物の機械的物性等が良好である点から、エポキシ化合物全量中のエポキシ基の合計1当量に対して、ヒドロキシ化合物Aの水酸基及び硬化剤中の活性基の合計が、0.7〜1.5当量になる量が好ましい When the composition of the present invention contains the epoxy compound and the epoxy curing agent, the blending amount is not particularly limited, but the epoxy compound is excellent in terms of the mechanical properties of the obtained cured product. The total amount of the hydroxyl groups of the hydroxy compound A and the active groups in the curing agent is preferably 0.7 to 1.5 equivalents with respect to the total 1 equivalent of the epoxy groups in the total amount.
イソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂環族ポリイソシアネート、脂肪族ポリイソシアネート等が挙げられる。 Examples of the isocyanate compound include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
芳香族ポリイソシアネートとしては、例えば、フェニレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、ジメチルジフェニルメタンジイソシアネート、トリフェニルメタントリイソシアネート、ナフタレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート等が挙げられる Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate and the like.
脂環族ポリイソシアネートとしては、例えば、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ジメチルジシクロヘキシルメタンジイソシアネート等が挙げられる。 Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.
脂肪族ポリイソシアネートとしては、例えば、メチレンジイソシアネート、エチレンジイソシアネート、プロピレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられる。 Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.
これらイソシアネート化合物は1種もしくは2種以上を使用することができる。これらは単独で用いてもよいし、2種以上混合して用いても構わない。 As these isocyanate compounds, one kind or two or more kinds can be used. These may be used alone or in combination of two or more.
<硬化促進剤>
例えば、本発明の組成物は硬化促進剤を含有しても構わない。前記硬化促進剤としては種々のものが使用できるが、例えば、ウレア化合物、リン系化合物、第3級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。接着剤用途として使用する場合には、作業性、低温硬化性に優れる点から、ウレア化合物、特に3,4−ジクロロフェニル−ジメチルウレア(DCMU)が好ましい。半導体封止材料用途として使用する場合には、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第3級アミンでは1,8−ジアザビシクロ−[5.4.0]−ウンデセンが好ましい。 <Curing accelerator>
For example, the composition of the present invention may contain a curing accelerator. Various types of curing accelerators can be used, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. When used as an adhesive, urea compounds, particularly 3,4-dichlorophenyl-dimethylurea (DCMU), are preferable from the viewpoint of excellent workability and low-temperature curability. When used as a semiconductor encapsulant material, it is excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc., so it is triphenylphosphine for phosphorus compounds and 1,8-diazabicyclo- [for tertiary amines. 5.4.0] -Undesen is preferred.
<フィラー>
本発明の組成物は、更にフィラーを含有してもよい。フィラーとしては、無機フィラーと有機フィラーが挙げられる。無機フィラーとしては、例えば無機微粒子が挙げられる。<Filler>
The composition of the present invention may further contain a filler. Examples of the filler include an inorganic filler and an organic filler. Examples of the inorganic filler include inorganic fine particles.
無機微粒子としては、例えば、耐熱性に優れるものとしては、アルミナ、マグネシア、チタニア、ジルコニア、シリカ(石英、ヒュームドシリカ、沈降性シリカ、無水ケイ酸、溶融シリカ、結晶性シリカ、超微粉無定型シリカ等)等;熱伝導に優れるものとしては、窒化ホウ素、窒化アルミ、酸化アルミナ、酸化チタン、酸化マグネシウム、酸化亜鉛、酸化ケイ素、ダイヤモンド等;導電性に優れるものとしては、金属単体又は合金(例えば、鉄、銅、マグネシウム、アルミニウム、金、銀、白金、亜鉛、マンガン、ステンレスなど)を用いた金属フィラー及び/又は金属被覆フィラー、;バリア性に優れるものとしては、マイカ、クレイ、カオリン、タルク、ゼオライト、ウォラストナイト、スメクタイト等の鉱物等やチタン酸カリウム、硫酸マグネシウム、セピオライト、ゾノライト、ホウ酸アルミニウム、炭酸カルシウム、酸化チタン、硫酸バリウム、酸化亜鉛、水酸化マグネシウム;屈折率が高いものとしては、チタン酸バリウム、酸化ジルコニア、酸化チタン等;光触媒性を示すものとしては、チタン、セリウム、亜鉛、銅、アルミニウム、錫、インジウム、リン、炭素、イオウ、テリウム、ニッケル、鉄、コバルト、銀、モリブデン、ストロンチウム、クロム、バリウム、鉛等の光触媒金属、前記金属の複合物、それらの酸化物等;耐摩耗性に優れるものとしては、シリカ、アルミナ、ジルコニア、酸化マグネシウム等の金属、及びそれらの複合物及び酸化物等;導電性に優れるものとしては、銀、銅などの金属、酸化錫、酸化インジウム等;絶縁性に優れるものとしては、シリカ等;紫外線遮蔽に優れるものとしては、酸化チタン、酸化亜鉛等である。
これらの無機微粒子は、用途によって適時選択すればよく、単独で使用しても、複数種組み合わせて使用してもかまわない。また、上記無機微粒子は、例に挙げた特性以外にも様々な特性を有することから、適時用途に合わせて選択すればよい。Examples of the inorganic fine particles include alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, molten silica, crystalline silica, and ultrafine powder amorphous. (Silica, etc.), etc .; Boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc., as those with excellent thermal conductivity; For example, metal fillers and / or metal-coated fillers using iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc .; Mica, clay, kaolin, etc. have excellent barrier properties. Minerals such as talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; high refractive index Barium titanate, zirconia oxide, titanium oxide, etc .; Titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, etc. Photocatalyst metals such as silver, molybdenum, strontium, chromium, barium, lead, composites of the metals, oxides thereof, etc .; Metals such as silica, alumina, zirconia, magnesium oxide, etc. have excellent wear resistance, and Such composites and oxides; metals such as silver and copper, tin oxide, indium oxide, etc. as having excellent conductivity; silica, etc. as having excellent insulation; as those having excellent ultraviolet shielding, Titanium oxide, zinc oxide, etc.
These inorganic fine particles may be selected in a timely manner depending on the intended use, and may be used alone or in combination of two or more. Further, since the inorganic fine particles have various properties other than the properties mentioned in the examples, they may be selected according to the timely application.
例えば無機微粒子としてシリカを用いる場合、特に限定はなく粉末状のシリカやコロイダルシリカなど公知のシリカ微粒子を使用することができる。市販の粉末状のシリカ微粒子としては、例えば、日本アエロジル(株)製アエロジル50、200、旭硝子(株)製シルデックスH31、H32、H51、H52、H121、H122、日本シリカ工業(株)製E220A、E220、富士シリシア(株)製SYLYSIA470、日本板硝子(株)製SGフレ−ク等を挙げることができる。
また、市販のコロイダルシリカとしては、例えば、日産化学工業(株)製メタノ−ルシリカゾル、IPA−ST、MEK−ST、NBA−ST、XBA−ST、DMAC−ST、ST−UP、ST−OUP、ST−20、ST−40、ST−C、ST−N、ST−O、ST−50、ST−OL等を挙げることができる。For example, when silica is used as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. Commercially available powdered silica fine particles include, for example, Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silysia Chemical Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Chemical Ltd., SG flakes manufactured by Nippon Plate Glass Co., Ltd., and the like.
Examples of commercially available colloidal silica include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, etc. Examples thereof include ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like.
表面修飾をしたシリカ微粒子を用いてもよく、例えば、前記シリカ微粒子を、疎水性基を有する反応性シランカップリング剤で表面処理したものや、(メタ)アクリロイル基を有する化合物で修飾したものがあげられる。(メタ)アクリロイル基を有する化合物で修飾した市販の粉末状のシリカとしては、日本アエロジル(株)製アエロジルRM50、R711等、(メタ)アクリロイル基を有する化合物で修飾した市販のコロイダルシリカとしては、日産化学工業(株)製MIBK−SD等が挙げられる。 Surface-modified silica fine particles may be used. For example, the silica fine particles are surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth) acryloyl group. can give. Commercially available powdered silica modified with a compound having a (meth) acryloyl group includes Aerosil RM50, R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth) acryloyl group. MIBK-SD manufactured by Nissan Chemical Industry Co., Ltd. can be mentioned.
前記シリカ微粒子の形状は特に限定はなく、球状、中空状、多孔質状、棒状、板状、繊維状、または不定形状のものを用いることができる。また一次粒子径は、5〜200nmの範囲が好ましい。5nm未満であると、分散体中の無機微粒子の分散が不十分となり、200nmを超える径では、硬化物の十分な強度が保持できないおそれがある。 The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or indefinite shapes can be used. The primary particle size is preferably in the range of 5 to 200 nm. If it is less than 5 nm, the dispersion of the inorganic fine particles in the dispersion becomes insufficient, and if the diameter exceeds 200 nm, the sufficient strength of the cured product may not be maintained.
酸化チタン微粒子としては、体質顔料のみならず紫外光応答型光触媒が使用でき、例えばアナターゼ型酸化チタン、ルチル型酸化チタン、ブルッカイト型酸化チタンなどが使用できる。更に、酸化チタンの結晶構造中に異種元素をドーピングさせて可視光に応答させるように設計された粒子についても用いることができる。酸化チタンにドーピングさせる元素としては、窒素、硫黄、炭素、フッ素、リン等のアニオン元素や、クロム、鉄、コバルト、マンガン等のカチオン元素が好適に用いられる。また、形態としては、粉末、有機溶媒中もしくは水中に分散させたゾルもしくはスラリーを用いることができる。市販の粉末状の酸化チタン微粒子としては、例えば、日本アエロジル(株)製アエロジルP−25、テイカ(株)製ATM−100等を挙げることができる。また、市販のスラリー状の酸化チタン微粒子としては、例えば、テイカ(株)TKD−701等が挙げられる。 As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used, and for example, anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide and the like can be used. Further, particles designed to be made to respond to visible light by doping a different element into the crystal structure of titanium oxide can also be used. As the element to be doped in titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine and phosphorus, and cationic elements such as chromium, iron, cobalt and manganese are preferably used. Further, as a form, a powder, a sol or a slurry dispersed in an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by TAYCA Corporation, and the like. Examples of commercially available slurry-like titanium oxide fine particles include TAYCA Corporation TKD-701.
<繊維質基質>
本発明の組成物は、更に繊維質基質を含有してもよい。本発明の繊維質基質は、特に限定はないが、繊維強化樹脂に用いられるものが好ましく、無機繊維や有機繊維が挙げられる。<Fibrous substrate>
The composition of the present invention may further contain a fibrous substrate. The fibrous substrate of the present invention is not particularly limited, but those used for fiber reinforced resins are preferable, and inorganic fibers and organic fibers can be mentioned.
無機繊維としては、カーボン繊維、ガラス繊維、ボロン繊維、アルミナ繊維、炭化ケイ素繊維等の無機繊維のほか、炭素繊維、活性炭繊維、黒鉛繊維、ガラス繊維、タングステンカーバイド繊維、シリコンカーバイド繊維(炭化ケイ素繊維)、セラミックス繊維、アルミナ繊維、天然繊維、玄武岩などの鉱物繊維、ボロン繊維、窒化ホウ素繊維、炭化ホウ素繊維、及び金属繊維等を挙げることができる。上記金属繊維としては、例えば、アルミニウム繊維、銅繊維、黄銅繊維、ステンレス繊維、スチール繊維を挙げることができる。 Inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers and other inorganic fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers and silicon carbide fibers (silicon carbide fibers). ), Ceramic fibers, alumina fibers, natural fibers, mineral fibers such as genbuiwa, boron fibers, boron nitride fibers, boron carbide fibers, metal fibers and the like. Examples of the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless fiber, and steel fiber.
有機繊維としては、ポリベンザゾール、アラミド、PBO(ポリパラフェニレンベンズオキサゾール)、ポリフェニレンスルフィド、ポリエステル、アクリル、ポリアミド、ポリオレフィン、ポリビニルアルコール、ポリアリレート等の樹脂材料からなる合成繊維や、セルロース、パルプ、綿、羊毛、絹といった天然繊維、タンパク質、ポリペプチド、アルギン酸等の再生繊維等を挙げる事ができる。 Examples of organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate, cellulose, pulp, and the like. Examples include natural fibers such as cotton, wool and silk, and regenerated fibers such as proteins, polypeptides and arginic acid.
中でも、カーボン繊維とガラス繊維は、産業上利用範囲が広いため、好ましい。これらのうち、一種類のみ用いてもよく、複数種を同時に用いてもよい。 Among them, carbon fiber and glass fiber are preferable because they have a wide range of industrial use. Of these, only one type may be used, or a plurality of types may be used at the same time.
本発明の繊維質基質は、繊維の集合体であってもよく、繊維が連続していても、不連続状でもかまわず、織布状であっても、不織布状であってもかまわない。また、繊維を一方方向に整列した繊維束でもよく、繊維束を並べたシート状であってもよい。また、繊維の集合体に厚みを持たせた立体形状であってもかまわない。 The fibrous substrate of the present invention may be an aggregate of fibers, may be continuous or discontinuous, and may be woven or non-woven. Further, a fiber bundle in which the fibers are arranged in one direction may be used, or a sheet in which the fiber bundles are arranged may be used. Further, the aggregate of fibers may have a three-dimensional shape having a thickness.
<分散媒>
本発明の組成物は、組成物の固形分量や粘度を調整する目的として、分散媒を使用してもよい。分散媒としては、本発明の効果を損ねることのない液状媒体であればよく、各種有機溶剤、液状有機ポリマー等が挙げられる。<Dispersion medium>
In the composition of the present invention, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity of the composition. The dispersion medium may be a liquid medium that does not impair the effects of the present invention, and examples thereof include various organic solvents and liquid organic polymers.
前記有機溶剤としては、例えば、アセトン、メチルエチルケトン(MEK)、メチルイソブチルケトン(MIBK)等のケトン類、テトラヒドロフラン(THF)、ジオキソラン等の環状エーテル類、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類、トルエン、キシレン等の芳香族類、カルビトール、セロソルブ、メタノール、イソプロパノール、ブタノール、プロピレングリコールモノメチルエーテルなどのアルコール類が挙げられ、これらを単独又は併用して使用可能であるが、中でもメチルエチルケトンが塗工時の揮発性や溶媒回収の面から好ましい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolane, and esters such as methyl acetate, ethyl acetate and butyl acetate. , Aromatic substances such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanone and propylene glycol monomethyl ether. These can be used alone or in combination, and among them, methyl ethyl ketone is applied. It is preferable from the viewpoint of volatileness during construction and solvent recovery.
前記液状有機ポリマーとは、硬化反応に直接寄与しない液状有機ポリマーであり、例えば、カルボキシル基含有ポリマー変性物(フローレンG−900、NC−500:共栄社)、アクリルポリマー(フローレンWK−20:共栄社)、特殊変性燐酸エステルのアミン塩(HIPLAAD ED−251:楠本化成)、変性アクリル系ブロック共重合物(DISPERBYK2000;ビックケミー)などが挙げられる。 The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. For example, a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha). , Amine salt of special modified phosphoric acid ester (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymer (DISPERBYK2000; Big Chemie) and the like.
<樹脂>
また、本発明の組成物は、本発明の前述した各種化合物以外の樹脂を有していてもよい。樹脂としては、本発明の効果を損なわない範囲であれば公知慣用の樹脂を配合すればよく、例えば熱硬化性樹脂や熱可塑性樹脂を用いることができる。<Resin>
Further, the composition of the present invention may have a resin other than the various compounds described above of the present invention. As the resin, a known and commonly used resin may be blended as long as the effect of the present invention is not impaired, and for example, a thermosetting resin or a thermoplastic resin can be used.
熱硬化性樹脂とは、加熱または放射線や触媒などの手段によって硬化される際に実質的に不溶かつ不融性に変化し得る特性を持った樹脂である。その具体例としては、エポキシ樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、ベンゾグアナミン樹脂、アルキド樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルテレフタレート樹脂、シリコーン樹脂、ウレタン樹脂、フラン樹脂、ケトン樹脂、キシレン樹脂、熱硬化性ポリイミド樹脂、ベンゾオキサジン樹脂、活性エステル樹脂、アニリン樹脂、シアネートエステル樹脂、スチレン・無水マレイン酸(SMA)樹脂、マレイミド樹脂などが挙げられる。これらの熱硬化性樹脂は1種または2種以上を併用して用いることができる。 A thermosetting resin is a resin having a property of being substantially insoluble and insoluble when cured by means such as heating or radiation or a catalyst. Specific examples thereof include epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, silicone resin, urethane resin, furan resin, ketone resin, and xylene. Examples thereof include resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene / maleic anhydride (SMA) resins, and maleimide resins. These thermosetting resins can be used alone or in combination of two or more.
熱可塑性樹脂とは、加熱により溶融成形可能な樹脂を言う。その具体例としてはポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ゴム変性ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン(ABS)樹脂、アクリロニトリル−スチレン(AS)樹脂、ポリメチルメタクリレート樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリエチレンテレフタレート樹脂、エチレンビニルアルコール樹脂、酢酸セルロース樹脂、アイオノマー樹脂、ポリアクリロニトリル樹脂、ポリアミド樹脂、ポリアセタール樹脂、ポリブチレンテレフタレート樹脂、ポリ乳酸樹脂、ポリフェニレンエーテル樹脂、変性ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリサルホン樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルサルフォン樹脂、ポリアリレート樹脂、熱可塑性ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリケトン樹脂、液晶ポリエステル樹脂、フッ素樹脂、シンジオタクチックポリスチレン樹脂、環状ポリオレフィン樹脂などが挙げられる。これらの熱可塑性樹脂は1種または2種以上を併用して用いることができる。 The thermoplastic resin is a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethylmethacrylate resin, acrylic resin, and polyvinyl chloride resin. Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyether sulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, Shinji Examples thereof include otakutic polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.
<その他の配合物>
本発明の組成物は、その他の配合物を有していてもかまわない。例えば、触媒、重合開始剤、無機顔料、有機顔料、体質顔料、粘土鉱物、ワックス、界面活性剤、安定剤、流動調整剤、カップリング剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、難燃剤、可塑剤等が挙げられる。<Other formulations>
The composition of the present invention may have other formulations. For example, catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, coupling agents, dyes, leveling agents, leology control agents, UV absorbers, etc. Examples thereof include antioxidants, flame retardants, and plasticizers.
<硬化物>
本発明の組成物においては、脂肪族系ジヒドロキシ化合物のジグリシジルエーテルと芳香族系ヒドロキシ化合物との反応物を適用することで、従来になく柔軟で強靱な硬化物を得ることが可能となる。例えば、前記した液状ビスフェノールA型エポキシ樹脂をダイマー酸やセバシン酸のような脂肪族ジカルボン酸を分子鎖延長剤として反応させた高分子量化エポキシ化合物は、柔軟な構造の硬化物を与えるが、エステル基の凝集によりその効果は十分なものではない。<Cured product>
In the composition of the present invention, by applying a reaction product of diglycidyl ether, which is an aliphatic dihydroxy compound, and an aromatic hydroxy compound, it is possible to obtain a cured product which is softer and tougher than ever before. For example, a high-molecular-weight epoxy compound obtained by reacting the above-mentioned liquid bisphenol A type epoxy resin with an aliphatic dicarboxylic acid such as dimer acid or sebacic acid as a molecular chain extender gives a cured product having a flexible structure, but an ester. The effect is not sufficient due to the aggregation of groups.
これに対して本発明では脂肪族系化合物から生じる骨格が、柔軟性を付与する所謂ソフトセグメントとして機能するため、本発明のヒドロキシ化合物Aを硬化させて得られる硬化物は極めて柔軟なものとなる。一方、芳香族系ヒドロキシ化合物から生じる骨格が、本発明のヒドロキシ化合物Aに剛直性を付与する所謂ハードセグメントとして機能するため、柔軟性と靭性とを兼備する硬化物を与えることができる。 On the other hand, in the present invention, the skeleton generated from the aliphatic compound functions as a so-called soft segment that imparts flexibility, so that the cured product obtained by curing the hydroxy compound A of the present invention becomes extremely flexible. .. On the other hand, since the skeleton generated from the aromatic hydroxy compound functions as a so-called hard segment that imparts rigidity to the hydroxy compound A of the present invention, it is possible to provide a cured product having both flexibility and toughness.
特に本発明のヒドロキシ化合物Aの場合は、ハードセグメントとして機能する部分と、ソフトセグメントとして機能する部分とが結合することにより、ヒドロキシ化合物構造に柔軟性を付与すると共に優れた耐湿性を発現させることができる。更に、本発明では芳香核に直接ヒドロキシ基が結合することにより、硬化物の靱性が極めて優れたものとなる。即ち、例えば、低分子量タイプの液状ビスフェノールA型エポキシ樹脂をエチレンオキサイド又はプロピレンオキサイドで変性して得られるヒドロキシ化合物骨格自体が柔軟になるものの、ヒドロキシ基自体の活性に劣り、硬化時に靱性を発現するに充分な架橋が得られないものであったところ、本発明のヒドロキシ化合物Aは、ヒドロキシ基が直接芳香核に結合することによりヒドロキシ基の活性が高くなる為、樹脂自体が柔軟であるにも拘わらず、硬化反応時には適度な架橋を形成して優れた靱性を発現する。更に、前記ハードセグメントが架橋点となるヒドロキシ基に隣接することで架橋点における物理的な強度が高まり靱性が向上するものである。 In particular, in the case of the hydroxy compound A of the present invention, the portion that functions as a hard segment and the portion that functions as a soft segment are bonded to impart flexibility to the hydroxy compound structure and exhibit excellent moisture resistance. Can be done. Further, in the present invention, the toughness of the cured product becomes extremely excellent by directly bonding the hydroxy group to the aromatic nucleus. That is, for example, although the hydroxy compound skeleton itself obtained by modifying a low molecular weight type liquid bisphenol A type epoxy resin with ethylene oxide or propylene oxide becomes flexible, the activity of the hydroxy group itself is inferior and toughness is exhibited at the time of curing. However, in the hydroxy compound A of the present invention, the activity of the hydroxy group is increased by directly binding the hydroxy group to the aromatic nucleus, so that the resin itself is flexible. Nevertheless, during the curing reaction, it forms an appropriate crosslink and exhibits excellent toughness. Further, since the hard segment is adjacent to the hydroxy group serving as the cross-linking point, the physical strength at the cross-linking point is increased and the toughness is improved.
本発明の組成物を硬化させる場合には、常温または加熱による硬化をおこなえばよい。硬化する際には、公知慣用の硬化触媒や、硬化剤としてエポキシ化合物やイソシアネート化合物を用いれば良い。
熱硬化を行う場合、1回の加熱で硬化させてもよいし、多段階の加熱工程を経て硬化させてもかまわない。When the composition of the present invention is cured, it may be cured at room temperature or by heating. When curing, a known and commonly used curing catalyst or an epoxy compound or isocyanate compound may be used as a curing agent.
When thermosetting is performed, it may be cured by one heating, or it may be cured through a multi-step heating step.
硬化触媒を用いる場合には、例えば、塩酸、硫酸、燐酸等の無機酸類;p−トルエンスルホン酸、燐酸モノイソプロピル、酢酸等の有機酸類;水酸化ナトリウム又は水酸化カリウム等の無機塩基類;テトライソプロピルチタネート、テトラブチルチタネート等のチタン酸エステル類;1,8−ジアザビシクロ[5.4.0]ウンデセン−7(DBU)、1,5−ジアザビシクロ[4.3.0]ノネン−5(DBN)、1,4−ジアザビシクロ[2.2.2]オクタン(DABCO)、トリ−n−ブチルアミン、ジメチルベンジルアミン、モノエタノールアミン、イミダゾール、2−エチル−4−メチル−イミダゾール、1−メチルイミダゾール、N,N−ジメチルー4−アミノピリジン(DMAP)等の各種の塩基性窒素原子を含有する化合物類;テトラメチルアンモニウム塩、テトラブチルアンモニウム塩、ジラウリルジメチルアンモニウム塩等の各種の4級アンモニウム塩類であって、対アニオンとして、クロライド、ブロマイド、カルボキシレートもしくはハイドロオキサイドなどを有する4級アンモニウム塩類;ジブチル錫ジアセテート、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、ジブチル錫ジアセチルアセトナート、オクチル酸錫又はステアリン酸錫など錫カルボン酸塩、;過酸化ベンゾイル、クメンハイドロパーオキサイド、ジクミルパーオキサイド、過酸化ラウロイル、ジ−t−ブチルパーオキサイド、t−ブチルハイドロパーオキサイド、メチルエチルケトン過酸化物、t−ブチルパーベンゾエートなどの有機過酸化物等を使用することができる。触媒は単独で使用しても良いし、2種以上併用しても良い。 When a curing catalyst is used, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide or potassium hydroxide; tetra. Titanium esters such as isopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) , 1,4-Diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 2-ethyl-4-methyl-imidazole, 1-methylimidazole, N , N-dimethyl-4-aminopyridine (DMAP) and other compounds containing various basic nitrogen atoms; various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt and dilauryldimethylammonium salt. Quaternary ammonium salts having chloride, bromide, carboxylate, hydroxyoxide, etc. as counter anions; dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate, tin stearate, etc. Tin carboxylate ,; benzoyl peroxide, cumene hydroperoxide, dicamyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate, etc. Organic peroxides and the like can be used. The catalyst may be used alone or in combination of two or more.
<積層体>
本発明の組成物は基材と積層することで積層体とすることができる。
積層体の基材としては、金属やガラス等の無機材料や、プラスチックや木材といった有機材料等、用途によって適時使用すればよく、積層体の形状としても、平板、シート状、あるいは三次元構造を有していても立体状であってもかまわない。全面にまたは一部に曲率を有するもの等目的に応じた任意の形状であってよい。また、基材の硬度、厚み等にも制限はない。<Laminated body>
The composition of the present invention can be laminated with a base material to form a laminated body.
The base material of the laminate may be an inorganic material such as metal or glass, an organic material such as plastic or wood, etc., depending on the application, and the laminate may be shaped like a flat plate, a sheet, or a three-dimensional structure. It does not matter whether it is held or three-dimensional. It may have any shape depending on the purpose, such as one having a curvature on the entire surface or a part thereof. In addition, there are no restrictions on the hardness, thickness, etc. of the base material.
本発明の組成物は、金属及びまたは金属酸化物に対する接着性が特に高い為、金属用のプライマーとして特に良好に使用可能である。金属としては銅、アルミ、金、銀、鉄、プラチナ、クロム、ニッケル、錫、チタン、亜鉛、各種合金、及びこれらを複合した材料が挙げられ、金属酸化物としてはこれら金属の単独酸化物及びまたは複合酸化物が挙げられる。特に鉄、銅、アルミに対しての接着力に優れる為、鉄、銅、アルミ用のプライマーとして良好に使用可能である。 Since the composition of the present invention has particularly high adhesiveness to metals and / or metal oxides, it can be used particularly well as a primer for metals. Examples of the metal include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials thereof, and metal oxides include single oxides of these metals and materials. Alternatively, a composite oxide may be mentioned. In particular, it has excellent adhesive strength to iron, copper, and aluminum, so it can be used satisfactorily as a primer for iron, copper, and aluminum.
本発明の積層体において、組成物層は、基材に対し直接塗工や成形により形成してもよく、すでに成形したものを積層させてもかまわない。直接塗工する場合、塗工方法としては特に限定は無く、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレードコート法、ドクターロール法、ドクターブレード法、カーテンコート法、スリットコート法、スクリーン印刷法、インクジェット法等が挙げられる。直接成形する場合は、インモールド成形、インサート成形、真空成形、押出ラミネート成形、プレス成形等が挙げられる。 In the laminated body of the present invention, the composition layer may be formed by directly coating or molding on the base material, or the already molded one may be laminated. In the case of direct coating, the coating method is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method. In the case of direct molding, in-mold molding, insert molding, vacuum forming, extrusion laminating molding, press molding and the like can be mentioned.
<第2基材および接着剤層>
本発明の積層体は、基材と組成物層に対し、さらに第2基材を形成しても構わない。このとき第2基材の材質には特に限定は無く、前記基材で挙げられた各種材質について利用可能である。好ましくは、基材と第2基材の組合せが、金属または金属酸化物とプラスチックとのいずれかの組合せである場合である。<Second base material and adhesive layer>
In the laminate of the present invention, a second base material may be further formed on the base material and the composition layer. At this time, the material of the second base material is not particularly limited, and various materials listed in the base material can be used. Preferably, the combination of the base material and the second base material is a combination of either a metal or a metal oxide and a plastic.
また、本発明の積層体は、基材と、本発明の組成物層と、接着剤層と、第2基材とがこの順に積層してなる積層体であっても良い。本発明の組成物は、金属または金属酸化物のプライマーとして良好に働くことから、基材が金属または金属酸化物の時に特に良好である。接着剤層を形成する接着剤としては特に限定は無いが、エポキシ樹脂系の接着剤であると接着性が良好であることから好ましい。 Further, the laminate of the present invention may be a laminate in which the base material, the composition layer of the present invention, the adhesive layer, and the second base material are laminated in this order. The composition of the present invention works well as a primer for a metal or metal oxide, and is particularly good when the substrate is a metal or metal oxide. The adhesive for forming the adhesive layer is not particularly limited, but an epoxy resin-based adhesive is preferable because it has good adhesiveness.
<繊維強化樹脂>
本発明の組成物が繊維質基質を有し、該繊維質基質が強化繊維の場合、繊維質基質を含有する組成物は繊維強化樹脂として用いることができる。
組成物に対し繊維質基質を含有させる方法は、本発明の効果を損なわない範囲であればとくに限定はなく、繊維質基質と組成物とを、混練、塗布、含浸、注入、圧着、等の方法で複合化する方法が挙げられ、繊維の形態及び繊維強化樹脂の用途によって適時選択することができる。<Fiber reinforced plastic>
When the composition of the present invention has a fibrous substrate and the fibrous substrate is a reinforcing fiber, the composition containing the fibrous substrate can be used as a fiber-reinforced resin.
The method for incorporating the fibrous substrate into the composition is not particularly limited as long as the effect of the present invention is not impaired, and the fibrous substrate and the composition are kneaded, coated, impregnated, injected, pressure-bonded, etc. Examples thereof include a method of compounding by a method, which can be selected in a timely manner depending on the form of the fiber and the use of the fiber reinforced resin.
本発明の繊維強化樹脂を成形する方法については、特に限定されない。板状の製品を製造するのであれば、押し出し成形法が一般的であるが、平面プレスによっても可能である。この他、押し出し成形法、ブロー成形法、圧縮成形法、真空成形法、射出成形法等を用いることが可能である。またフィルム状の製品を製造するのであれば、溶融押出法の他、溶液キャスト法を用いることができ、溶融成形方法を用いる場合、インフレーションフィルム成形、キャスト成形、押出ラミネーション成形、カレンダー成形、シート成形、繊維成形、ブロー成形、射出成形、回転成形、被覆成形等が挙げられる。また、活性エネルギー線で硬化する樹脂の場合、活性エネルギー線を用いた各種硬化方法を用いて硬化物を製造する事ができる。特に、熱硬化性樹脂をマトリクス樹脂の主成分とする場合には、成形材料をプリプレグ化してプレスやオートクレーブにより加圧加熱する成形法が挙げられ、この他にもRTM(Resin Transfer Molding)成形、VaRTM(Vaccum assist Resin Transfer Molding)成形、積層成形、ハンドレイアップ成形等が挙げられる。 The method for molding the fiber-reinforced resin of the present invention is not particularly limited. If a plate-shaped product is to be manufactured, an extrusion molding method is common, but a flat press can also be used. In addition, an extrusion molding method, a blow molding method, a compression molding method, a vacuum forming method, an injection molding method and the like can be used. In addition to the melt extrusion method, a solution cast method can be used to manufacture film-like products. When the melt molding method is used, inflation film molding, cast molding, extrusion lamination molding, calendar molding, and sheet molding can be used. , Fiber molding, blow molding, injection molding, rotary molding, coating molding and the like. Further, in the case of a resin that is cured by active energy rays, a cured product can be produced by using various curing methods using active energy rays. In particular, when a thermosetting resin is used as the main component of the matrix resin, a molding method in which the molding material is made into a prepreg and pressurized and heated by a press or an autoclave can be mentioned. In addition, RTM (Resin Transfer Molding) molding, Examples thereof include VaRTM (Vaccum assist Resin Transfer Molding) molding, laminated molding, and hand lay-up molding.
<プリプレグ>
本発明の繊維強化樹脂は、未硬化あるいは半硬化のプリプレグと呼ばれる状態を形成することができる。プリプレグの状態で製品を流通させた後、最終硬化をおこなって硬化物を形成してもよい。積層体を形成する場合は、プリプレグを形成した後、その他の層を積層してから最終硬化を行うことで、各層が密着した積層体を形成できるため、好ましい。
この時用いる組成物と繊維質基質の質量割合としては、特に限定されないが、通常、プリプレグ中の樹脂分が20〜60質量%となるように調製することが好ましい。<Prepreg>
The fiber-reinforced resin of the present invention can form a state called an uncured or semi-cured prepreg. After the product is distributed in the state of prepreg, final curing may be performed to form a cured product. When forming a laminate, it is preferable to form a prepreg, then laminate other layers, and then perform final curing to form a laminate in which each layer is in close contact with each other.
The mass ratio of the composition to the fibrous substrate used at this time is not particularly limited, but it is usually preferable to prepare the prepreg so that the resin content is 20 to 60% by mass.
<耐熱材料および電子材料>
本発明の組成物は、その硬化物が、ガラス転移温度が高く、耐熱分解性に優れることから、耐熱部材に好適に使用可能である。また、基材への密着性に優れることから、特に電子部材に好適に使用可能である。特に、半導体封止材、回路基板、ビルドアップフィルム、ビルドアップ基板等や、接着剤やレジスト材料に好適に使用可能である。また、繊維強化樹脂のマトリクス樹脂にも好適に使用可能であり、高耐熱性のプリプレグとして特に適している。こうして得られる耐熱部材や電子部材は、各種用途に好適に使用可能であり、例えば、産業用機械部品、一般機械部品、自動車・鉄道・車両等部品、宇宙・航空関連部品、電子・電気部品、建築材料、容器・包装部材、生活用品、スポーツ・レジャー用品、風力発電用筐体部材等が挙げられるが、これらに限定される物ではない。<Heat-resistant materials and electronic materials>
The composition of the present invention can be suitably used for a heat-resistant member because the cured product has a high glass transition temperature and is excellent in heat-resistant decomposition. Further, since it has excellent adhesion to the base material, it can be particularly preferably used for electronic members. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up boards, etc., adhesives and resist materials. Further, it can be suitably used for a matrix resin of a fiber reinforced resin, and is particularly suitable as a prepreg having high heat resistance. The heat-resistant members and electronic members thus obtained can be suitably used for various purposes, for example, industrial mechanical parts, general mechanical parts, automobile / railway / vehicle parts, space / aviation-related parts, electronic / electrical parts, etc. Building materials, container / packaging materials, daily necessities, sports / leisure products, wind power generation housing materials, etc. are included, but are not limited to these.
以下、代表的な製品について例を挙げて説明する。 Hereinafter, typical products will be described with examples.
1.半導体封止材料
本発明の組成物から半導体封止材料を得る方法としては、前記組成物、及び硬化促進剤、及び無機充填剤等の配合剤とを必要に応じて押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に溶融混合する方法が挙げられる。その際、無機充填剤としては、通常、溶融シリカが用いられるが、パワートランジスタ、パワーIC用高熱伝導半導体封止材として用いる場合は、溶融シリカよりも熱伝導率の高い結晶シリカ,アルミナ,窒化ケイ素などの高充填化、または溶融シリカ、結晶性シリカ、アルミナ、窒化ケイ素などを用いるとよい。その充填率は硬化性樹脂組成物100質量部当たり、無機充填剤を30〜95質量%の範囲で用いることが好ましく、中でも、難燃性や耐湿性や耐ハンダクラック性の向上、線膨張係数の低下を図るためには、70質量部以上がより好ましく、80質量部以上であることがさらに好ましい。1. 1. Semiconductor encapsulation material As a method for obtaining a semiconductor encapsulation material from the composition of the present invention, the composition, a curing accelerator, and a compounding agent such as an inorganic filler are used as necessary in an extruder, a feeder, or the like. Examples thereof include a method of sufficiently melting and mixing until the mixture becomes uniform using a roll or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica High filling of silicon or the like, or molten silica, crystalline silica, alumina, silicon nitride or the like may be used. It is preferable to use an inorganic filler in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition, and among them, improvement of flame retardancy, moisture resistance and solder crack resistance, linear expansion coefficient. In order to reduce the amount of the mixture, 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.
2.半導体装置
本発明の硬化性樹脂組成物から半導体装置を得る半導体パッケージ成形としては、上記半導体封止材料を注型、或いはトランスファー成形機、射出成形機などを用いて成形し、さらに50〜250℃で2〜10時間の間、加熱する方法が挙げられる。2. 2. Semiconductor device For semiconductor package molding to obtain a semiconductor device from the curable resin composition of the present invention, the above semiconductor encapsulant material is cast or molded using a transfer molding machine, injection molding machine, or the like, and further 50 to 250 ° C. There is a method of heating for 2 to 10 hours.
3.プリント回路基板
本発明の組成物からプリント回路基板を得る方法としては、上記プリプレグを、常法により積層し、適宜銅箔を重ねて、1〜10MPaの加圧下に170〜300℃で10分〜3時間、加熱圧着させる方法が挙げられる。3. 3. Printed circuit board As a method for obtaining a printed circuit board from the composition of the present invention, the above prepregs are laminated by a conventional method, copper foils are appropriately laminated, and a pressure of 1 to 10 MPa is applied at 170 to 300 ° C. for 10 minutes. A method of heat-bonding for 3 hours can be mentioned.
4.ビルドアップ基板
本発明の組成物からビルドアップ基板を得る方法は、例えば以下の工程が挙げられる。まず、ゴム、フィラーなどを適宜配合した上記組成物を、回路を形成した回路基板にスプレーコーティング法、カーテンコーティング法等を用いて塗布した後、硬化させる工程(工程1)。その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって凹凸を形成させ、銅などの金属をめっき処理する工程(工程2)。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成する工程(工程3)。なお、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行う。また、本発明のビルドアップ基板は、銅箔上で当該樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、170〜300℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を作製することも可能である。4. Build-up substrate A method for obtaining a build-up substrate from the composition of the present invention includes, for example, the following steps. First, a step (step 1) of applying the above composition, which is appropriately mixed with rubber, filler, etc., to a circuit board on which a circuit is formed by using a spray coating method, a curtain coating method, or the like, and then curing the composition. After that, if necessary, a predetermined through-hole portion or the like is drilled, treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is plated (process). 2). A step (step 3) in which such an operation is sequentially repeated as desired to alternately build up and form a resin insulating layer and a conductor layer having a predetermined circuit pattern. The through-hole portion is drilled after the outermost resin insulating layer is formed. Further, the build-up substrate of the present invention is roughened by heat-pressing a resin-containing copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by omitting the steps of forming a surface and plating.
5.ビルドアップフィルム
本発明の組成物からビルドアップフィルムを得る方法としては、基材である支持フィルム(Y)の表面に、上記組成物を塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶剤を乾燥させて組成物の層(X)を形成させることにより製造することができる。5. Build-up film As a method of obtaining a build-up film from the composition of the present invention, the above composition is applied to the surface of the support film (Y) which is a base material, and an organic solvent is further applied by heating or blowing hot air. It can be produced by drying to form a layer (X) of the composition.
ここで用いる有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等を用いることが好ましく、また、不揮発分30〜60質量%となる割合で使用することが好ましい。 Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the non-volatile content is 30 to 60% by mass. preferable.
形成される層(X)の厚さは、通常、導体層の厚さ以上とする。回路基板が有する導体層の厚さは通常5〜70μmの範囲であるので、樹脂組成物層の厚さは10〜100μmの厚みを有するのが好ましい。なお、本発明における上記組成物の層(X)は、後述する保護フィルムで保護されていてもよい。保護フィルムで保護することにより、樹脂組成物層表面へのゴミ等の付着やキズを防止することができる。 The thickness of the layer (X) formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The layer (X) of the composition in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.
前記した支持フィルム及び保護フィルムは、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート(以下「PET」と略称することがある。)、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミド、更には離型紙や銅箔、アルミニウム箔等の金属箔などを挙げることができる。なお、支持フィルム及び保護フィルムはマッド処理、コロナ処理の他、離型処理を施してあってもよい。支持フィルムの厚さは特に限定されないが、通常10〜150μmであり、好ましくは25〜50μmの範囲で用いられる。また保護フィルムの厚さは1〜40μmとするのが好ましい。 The support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further release. Examples include metal foils such as patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.
上記した支持フィルム(Y)は、回路基板にラミネートした後に、或いは加熱硬化することにより絶縁層を形成した後に、剥離される。ビルドアップフィルムを構成する硬化性樹脂組成物層が加熱硬化した後に支持フィルム(Y)を剥離すれば、硬化工程でのゴミ等の付着を防ぐことができる。硬化後に剥離する場合、通常、支持フィルムには予め離型処理が施される。 The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing step. When peeling off after curing, the support film is usually subjected to a mold release treatment in advance.
上記のようにして得られたビルドアップフィルムを用いて多層プリント回路基板を製造することができる。例えば、層(X)が保護フィルムで保護されている場合はこれらを剥離した後、層(X)を回路基板に直接接するように回路基板の片面又は両面に、例えば真空ラミネート法によりラミネートする。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。また必要により、ラミネートを行う前にビルドアップフィルム及び回路基板を必要により加熱(プレヒート)しておいてもよい。ラミネートの条件は、圧着温度(ラミネート温度)を70〜140℃とすることが好ましく、圧着圧力を1〜11kgf/cm2(9.8×104〜107.9×104N/m2)とすることが好ましく、空気圧を20mmHg(26.7hPa)以下の減圧下でラミネートすることが好ましい。 A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the layer (X) is protected by a protective film, the layer (X) is peeled off and then laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be preheated if necessary before laminating. As for the laminating conditions, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure is preferably 1 to 11 kgf / cm2 (9.8 × 104 to 107.9 × 104 N / m2). , It is preferable to laminate under a reduced air pressure of 20 mmHg (26.7 hPa) or less.
6.導電ペースト
本発明の組成物から導電ペーストを得る方法としては、例えば、導電性粒子を該組成物中に分散させる方法が挙げられる。上記導電ペーストは、用いる導電性粒子の種類によって、回路接続用ペースト樹脂組成物や異方性導電接着剤とすることができる。6. Conductive Paste As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned. The conductive paste can be used as a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.
次に本発明を実施例、比較例により具体的に説明するが、以下において「部」及び「%」は特に断わりのない限り質量基準である。 Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified.
1Hおよび13C−NMR、FD−MSスペクトル、GPCは以下の条件にて測定した。 1 H and 13 C-NMR, FD-MS spectrum, and GPC were measured under the following conditions.
1H−NMR:JEOL RESONANCE製「JNM−ECA600」
磁場強度:600MHz
積算回数:32回
溶媒:DMSO−d6
試料濃度:30質量% 1 1 H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE
Magnetic field strength: 600MHz
Number of integrations: 32 times Solvent: DMSO-d 6
Sample concentration: 30% by mass
13C−NMR:JEOL RESONANCE製「JNM−ECA600」
磁場強度:150MHz
積算回数:320回
溶媒:DMSO−d6
試料濃度:30質量% 13 C-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE
Magnetic field strength: 150MHz
Number of integrations: 320 Solvent: DMSO-d 6
Sample concentration: 30% by mass
FD−MS:日本電子株式会社製「JMS−T100GC AccuTOF」
測定範囲:m/z=50.00〜2000.00
変化率:25.6mA/min
最終電流値:40mA
カソード電圧:−10kVFD-MS: "JMS-T100GC AccuTOF" manufactured by JEOL Ltd.
Measurement range: m / z = 50.00 to 2000.00
Rate of change: 25.6 mA / min
Final current value: 40mA
Cathode voltage: -10kV
GPC:東ソー株式会社製「HLC−8320GPC」
カラム:東ソー株式会社製「TSK−GEL G2000HXL」+「TSK−GEL G3000HXL」+「TSK−GEL G4000HXL」
検出器:RI(示唆屈折率計)
測定条件:40℃
移動相:テトラヒドロフラン
流速:1ml/min
標準:東ソー株式会社製「PStQuick A」「PStQuick B」「PStQuick E」「PStQuick F」GPC: "HLC-8320GPC" manufactured by Tosoh Corporation
Column: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Measurement conditions: 40 ° C
Mobile phase: tetrahydrofuran Flow rate: 1 ml / min
Standard: "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F" manufactured by Tosoh Corporation
水酸基当量および繰り返し単位数の算出方法としては、GPC分子量測定や、FD−MS、NMR等の適切な各種の機器分析結果からの算出が例示できる。 Examples of the method for calculating the hydroxyl group equivalent and the number of repeating units include GPC molecular weight measurement and calculation from appropriate instrumental analysis results such as FD-MS and NMR.
実施例1 C12型(BPA)のヒドロキシ化合物Ph−1
温度計、撹拌機を取り付けたフラスコに1,12−ドデカンジオールのジグリシジルエーテル(四日市合成株式会社製:エポキシ当量210g/eq)210g(0.5モル)とビスフェノールA(水酸基当量114g/eq)228g(1.0モル)を仕込み、140℃まで30分間要して昇温した後、4%水酸化ナトリウム水溶液1gを仕込んだ。その後、30分間要して150℃まで昇温し、さらに150℃で3時間反応させた。その後、中和量のリン酸ソーダを添加し、ヒドロキシ化合物(Ph−1)を430g得た。このヒドロキシ化合物(Ph−1)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=771のピークが得られたことから前記構造式(A−1)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−1)のGPCより算出した水酸基当量は330g/eq、水酸基当量から算出した前記構造式(A−1)中のmの平均値は0.8であった。Example 1 C12 type (BPA) hydroxy compound Ph-1
Diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Chemical Co., Ltd .: epoxy equivalent 210 g / eq) 210 g (0.5 mol) and bisphenol A (hydroxyl equivalent 114 g / eq) in a flask equipped with a thermometer and a stirrer. 228 g (1.0 mol) was charged, the temperature was raised to 140 ° C. for 30 minutes, and then 1 g of a 4% sodium hydroxide aqueous solution was charged. Then, it took 30 minutes to raise the temperature to 150 ° C., and further reacted at 150 ° C. for 3 hours. Then, a neutralized amount of sodium phosphate was added to obtain 430 g of a hydroxy compound (Ph-1). This hydroxy compound (Ph-1) is represented by the structural formula (A-1) because a peak of M + = 771 corresponding to the theoretical structure in which m of the general formula (1) is 1 was obtained in the mass spectrum. It was confirmed that it contained a hydroxy compound having the same structure. The hydroxyl group equivalent of this hydroxy compound (Ph-1) calculated from GPC was 330 g / eq, and the average value of m in the structural formula (A-1) calculated from the hydroxyl group equivalent was 0.8.
実施例2 C12型(ピロガロール)のヒドロキシ化合物Ph−2
実施例1におけるビスフェノールA228g(1.0モル)をピロガロール126g(1.0モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−2を330g得た。このヒドロキシ化合物(Ph−2)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=567のピークが得られたことから前記構造式(A−8)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−2)のGPCより算出した水酸基当量は121g/eq、水酸基当量から算出した前記構造式(A−8)中のmの平均値は0.8であった。Example 2 C12 type (pyrogallol) hydroxy compound Ph-2
The reaction was carried out in the same manner as in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was changed to 126 g (1.0 mol) of pyrogallol, and 330 g of the hydroxy compound Ph-2 was obtained. This hydroxy compound (Ph-2) is represented by the structural formula (A-8) because a peak of M + = 567 corresponding to the theoretical structure in which m of the general formula (1) is 1 was obtained in the mass spectrum. It was confirmed that it contained a hydroxy compound having the same structure. The hydroxyl group equivalent of this hydroxy compound (Ph-2) calculated from GPC was 121 g / eq, and the average value of m in the structural formula (A-8) calculated from the hydroxyl group equivalent was 0.8.
実施例3 C12型(ビフェノール、テトラメチルビフェノール併用)のヒドロキシ化合物Ph−3
実施例1におけるビスフェノールA228g(1.0モル)を、4,4‘−ビフェノール93g(0.5モル)と、3,3’、5,5’−テトラメチルビフェニル−4,4’−ジオール121g(0.5モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−3を415g得た。このヒドロキシ化合物(Ph−3)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=687、744、800のピークが得られたことから前記構造式(A−3)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−1)のGPCより算出した水酸基当量は318g/eq、水酸基当量から算出した前記構造式(A−3)中のmの平均値は0.8であった。Example 3 C12 type (combined use of biphenol and tetramethylbiphenol) hydroxy compound Ph-3
228 g (1.0 mol) of bisphenol A in Example 1, 93 g (0.5 mol) of 4,4'-biphenol and 121 g of 3,3', 5,5'-tetramethylbiphenyl-4,4'-diol The reaction was carried out in the same manner as in Example 1 except that the mixture was changed to (0.5 mol) to obtain 415 g of the hydroxy compound Ph-3. This hydroxy compound (Ph-3) has the structural formula (A-3) because peaks of M + = 687, 744, 800 corresponding to the theoretical structure in which m of the general formula (1) is 1 were obtained in the mass spectrum. ) Was confirmed to contain a hydroxy compound having a structure represented by). The hydroxyl group equivalent of this hydroxy compound (Ph-1) calculated from GPC was 318 g / eq, and the average value of m in the structural formula (A-3) calculated from the hydroxyl group equivalent was 0.8.
実施例4 C12型(テトラメチルビフェノール)のヒドロキシ化合物Ph−4
実施例1におけるビスフェノールA228g(1.0モル)を、3,3’、5,5’−テトラメチルビフェニル−4,4’−ジオール242g(1.0モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−4を458g得た。このヒドロキシ化合物(Ph−4)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=800のピークが得られたことから前記構造式(A−3)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−4)のGPCより算出した水酸基当量は342g/eq、水酸基当量から算出した前記構造式(A−3)中のmの平均値は0.8であった。Example 4 C12 type (tetramethylbiphenol) hydroxy compound Ph-4
Same as Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was changed to 242 g (1.0 mol) of 3,3', 5,5'-tetramethylbiphenyl-4,4'-diol. The reaction was carried out in the same manner to obtain 458 g of the hydroxy compound Ph-4. This hydroxy compound (Ph-4) is represented by the structural formula (A-3) because a peak of M + = 800 corresponding to the theoretical structure in which m of the general formula (1) is 1 was obtained in the mass spectrum. It was confirmed that it contained a hydroxy compound having the same structure. The hydroxyl group equivalent of this hydroxy compound (Ph-4) calculated from GPC was 342 g / eq, and the average value of m in the structural formula (A-3) calculated from the hydroxyl group equivalent was 0.8.
実施例5 C12型(2,7−ジヒドロキシナフタレン)のヒドロキシ化合物Ph−5
実施例1におけるビスフェノールA228g(1.0モル)を、2,7−ジヒドロキシナフタレン160g(1.0モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−5を361g得た。このヒドロキシ化合物(Ph−5)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=635のピークが得られたことから前記構造式(A−5)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−5)のGPCより算出した水酸基当量は271g/eq、水酸基当量から算出した前記構造式(A−5)中のmの平均値は0.8であった。Example 5 C12 type (2,7-dihydroxynaphthalene) hydroxy compound Ph-5
The reaction was carried out in the same manner as in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was changed to 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, and 361 g of the hydroxy compound Ph-5 was obtained. .. This hydroxy compound (Ph-5) is represented by the structural formula (A-5) because a peak of M + = 635 corresponding to the theoretical structure in which m of the general formula (1) is 1 was obtained in the mass spectrum. It was confirmed that it contained a hydroxy compound having the same structure. The hydroxyl group equivalent of this hydroxy compound (Ph-5) calculated from GPC was 271 g / eq, and the average value of m in the structural formula (A-5) calculated from the hydroxyl group equivalent was 0.8.
実施例6 C12型(トリフェニロールメタン)のヒドロキシ化合物Ph−6
実施例1におけるビスフェノールA228g(1.0モル)を、トリフェニロールメタン(群栄化学工業株式会社「TPM−100」)292g(1.0モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−6を498g得た。このヒドロキシ化合物(Ph−6)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=900のピークが得られたことから前記構造式(A−9)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−6)のGPCより算出した水酸基当量は192g/eq、水酸基当量から算出した前記構造式(A−9)中のmの平均値は0.8であった。Example 6 C12 type (triphenylol methane) hydroxy compound Ph-6
The reaction was the same as in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was changed to 292 g (1.0 mol) of triphenylol methane (Gun Ei Chemical Industry Co., Ltd. "TPM-100"). Then, 498 g of the hydroxy compound Ph-6 was obtained. This hydroxy compound (Ph-6) is represented by the structural formula (A-9) because a peak of M + = 900 corresponding to the theoretical structure in which m of the general formula (1) is 1 was obtained in the mass spectrum. It was confirmed that it contained a hydroxy compound having the same structure. The hydroxyl group equivalent of this hydroxy compound (Ph-6) calculated from GPC was 192 g / eq, and the average value of m in the structural formula (A-9) calculated from the hydroxyl group equivalent was 0.8.
実施例7 C12型(ビスーナフタレンジオール)のヒドロキシ化合物Ph−7
実施例1におけるビスフェノールA228g(1.0モル)を、1,1‘−メチレンビスー(2,7−ナフタレンジオール)332g(1.0モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−7を522g得た。このヒドロキシ化合物(Ph−7)はマススペクトルで前記一般式(1)のmが1の理論構造に相当するM+=979のピークが得られたことから前記構造式(A−10)で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物(Ph−7)のGPCより算出した水酸基当量は139g/eq、水酸基当量から算出した前記構造式(A−10)中のmの平均値は0.8であった。Example 7 C12 type (bisunaphthalene diol) hydroxy compound Ph-7
The reaction was carried out in the same manner as in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was changed to 332 g (1.0 mol) of 1,1'-methylenebis- (2,7-naphthalenediol). 522 g of compound Ph-7 was obtained. This hydroxy compound (Ph-7) is represented by the structural formula (A-10) because a peak of M + = 979 corresponding to the theoretical structure in which m of the general formula (1) is 1 was obtained in the mass spectrum. It was confirmed that it contained a hydroxy compound having the same structure. The hydroxyl group equivalent of this hydroxy compound (Ph-7) calculated from GPC was 139 g / eq, and the average value of m in the structural formula (A-10) calculated from the hydroxyl group equivalent was 0.8.
比較例1 C6型(BPA)のヒドロキシ化合物Ph−8
実施例1における1,12−ドデカンジオールのジグリシジルエーテル210g(0.5モル)を1,6−ヘキサンジオールのジグリシジルエーテル(DIC株式会社製:商品名EPICLON 726D、エポキシ当量124g/eq)124g(0.5モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−8を340g得た。このヒドロキシ化合物Ph−8は、マススペクトルにてM+=687のピークが確認された。このヒドロキシ化合物Ph−8のGPCより算出した水酸基当量は262g/eqであった。Comparative Example 1 C6 type (BPA) hydroxy compound Ph-8
210 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol in Example 1 and 124 g of diglycidyl ether of 1,6-hexanediol (manufactured by DIC Co., Ltd .: trade name EPICLON 726D, epoxy equivalent 124 g / eq) The reaction was carried out in the same manner as in Example 1 except that the mixture was changed to (0.5 mol) to obtain 340 g of hydroxy compound Ph-8. The peak of M + = 687 was confirmed in the mass spectrum of this hydroxy compound Ph-8. The hydroxyl group equivalent calculated from the GPC of this hydroxy compound Ph-8 was 262 g / eq.
比較例2 C9型(BPA)のヒドロキシ化合物Ph−9
実施例1における1,12−ドデカンジオールのジグリシジルエーテル210g(0.5モル)を1,9−ノナンジオールのジグリシジルエーテル(坂本薬品工業株式会社製:エポキシ当量156g/eq)156g(0.5モル)に変えた以外は実施例1と同様に反応し、ヒドロキシ化合物Ph−9を350g得た。このヒドロキシ化合物Ph−9は、マススペクトルにてM+=729のピークが確認された。このヒドロキシ化合物Ph−9のGPCより算出した水酸基当量は328g/eqであった。Comparative Example 2 C9 type (BPA) hydroxy compound Ph-9
210 g (0.5 mol) of 1,12-dodecanediol diglycidyl ether in Example 1 and 156 g (0.) of 1,9-nonanediol diglycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd .: epoxy equivalent 156 g / eq). The reaction was carried out in the same manner as in Example 1 except that the mixture was changed to 5 mol) to obtain 350 g of the hydroxy compound Ph-9. The peak of M + = 729 was confirmed in the mass spectrum of this hydroxy compound Ph-9. The hydroxyl group equivalent calculated from the GPC of this hydroxy compound Ph-9 was 328 g / eq.
配合例1 接着剤組成物の作成
エポキシ樹脂としてエピクロン850S(DIC株式会社製、ビスフェノールA型エポキシ樹脂)を100部、硬化剤としてDICY(三菱ケミカル株式会社製、「DICY7」)を5.59部、および硬化促進剤としてDCMU(DIC株式会社製、B−605−IM)0.85部を混合機(株式会社シンキー製「あわとり練太郎ARV−200」)にて均一混合して、接着剤組成物を得た。Formulation Example 1 Preparation of Adhesive Composition 100 parts of Epicron 850S (manufactured by DIC Corporation, bisphenol A type epoxy resin) as an epoxy resin, and 5.59 parts of DICY (manufactured by Mitsubishi Chemical Corporation, "DICY7") as a curing agent. , And 0.85 parts of DCMU (B-605-IM manufactured by DIC Corporation) as a curing accelerator are uniformly mixed with a mixer (“Awatori Rentaro ARV-200” manufactured by Shinky Co., Ltd.) to prepare an adhesive. The composition was obtained.
〔実施例8〜14及び比較例3〜5〕
<プライマー処理>
実施例1〜7および比較例1、2で合成した各ヒドロキシ化合物の3%エタノール溶液を調製した。冷間圧延鋼板(TP技研株式会社製「SPCC−SB」)を脱脂せずに室温で60分間浸積させた後に,室温で5時間乾燥させた。[Examples 8 to 14 and Comparative Examples 3 to 5]
<Primer treatment>
A 3% ethanol solution of each hydroxy compound synthesized in Examples 1 to 7 and Comparative Examples 1 and 2 was prepared. A cold-rolled steel sheet (“SPCC-SB” manufactured by TP Giken Co., Ltd.) was immersed for 60 minutes at room temperature without degreasing, and then dried at room temperature for 5 hours.
<引張せん断試験>
配合例1で得られた接着剤層を、プライマー処理を施した2枚の冷間圧延鋼板(TP技研株式会社製「SPCC−SB」,1.0mm×25mm×100mm)のうち1枚に塗布し、スペーサーとしてガラスビーズ(ポッターズ・バロティーニ株式会社製「J−80」)を添加し、もう1枚のアルミ板を貼り合わせた(接着面積:25mm×12.5mm)。これを170℃で30分加熱硬化を行い、試験片を得た。その試験片を用いて引張りせん断試験を行うことで接着性を評価した。試験はJIS K 6850に従って行い,最大点応力および最大点歪み率を比較した。
また、比較例5としては、プライマーを使用せず接着剤組成物のみで積層体を作成した。<Tension shear test>
The adhesive layer obtained in Formulation Example 1 is applied to one of two primer-treated cold-rolled steel sheets (“SPCC-SB” manufactured by TP Giken Co., Ltd., 1.0 mm × 25 mm × 100 mm). Then, glass beads (“J-80” manufactured by Potters Barotini Co., Ltd.) were added as spacers, and another aluminum plate was bonded (adhesive area: 25 mm × 12.5 mm). This was heat-cured at 170 ° C. for 30 minutes to obtain a test piece. Adhesiveness was evaluated by performing a tensile shear test using the test piece. The test was performed according to JIS K 6850, and the maximum point stress and the maximum point strain rate were compared.
Further, as Comparative Example 5, a laminate was prepared using only the adhesive composition without using a primer.
<T型剥離試験>
配合例1で得られた接着剤層を、プライマー処理を施した2枚の冷間圧延鋼板(TP技研株式会社製「SPCC−SB」、0.5mm×25mm×200mm)のうち1枚に塗布し、スペーサーとしてガラスビーズ(ポッターズ・バロティーニ株式会社製「J−80」)を添加し、もう1枚のアルミ板を貼り合わせた(接着面積:25mm×150mm)。これを170℃で30分加熱硬化を行い、試験片を得た。その試験片を用いてT型剥離試験を行うことで接着性を評価した。試験はJIS K 6854−3に従って行い、平均応力を比較した。
また、比較例5としては、プライマーを使用せず接着剤組成物のみで積層体を作成した。<T-type peeling test>
The adhesive layer obtained in Formulation Example 1 is applied to one of two primer-treated cold-rolled steel sheets (“SPCC-SB” manufactured by TP Giken Co., Ltd., 0.5 mm × 25 mm × 200 mm). Then, glass beads (“J-80” manufactured by Potters Barotini Co., Ltd.) were added as spacers, and another aluminum plate was bonded (adhesive area: 25 mm × 150 mm). This was heat-cured at 170 ° C. for 30 minutes to obtain a test piece. Adhesiveness was evaluated by performing a T-type peeling test using the test piece. The test was performed according to JIS K 6854-3 and the average stress was compared.
Further, as Comparative Example 5, a laminate was prepared using only the adhesive composition without using a primer.
実施例8〜14に示すように、本発明は引張りせん断試験およびT型剥離試験における高い接着力を有する。さらに、引張りせん断試験において高い歪み率を有し、優れた応力緩和性を有する。 As shown in Examples 8-14, the present invention has high adhesive strength in a tensile shear test and a T-type peeling test. Furthermore, it has a high strain rate in a tensile shear test and has excellent stress relaxation properties.
本発明のヒドロキシ化合物Aは、金属表面、特に汚染された金属表面であっても高い接着性とプライマー性を発揮することができる。 The hydroxy compound A of the present invention can exhibit high adhesiveness and primer property even on a metal surface, particularly a contaminated metal surface.
Claims (14)
・・・(1)
(式(1)中、Arはそれぞれ独立して無置換または置換基を有する芳香環を有する構造を表し、
R1およびR2はそれぞれ独立して水素原子または炭素数1〜2のアルキル基を表し、
R3およびR4はそれぞれ独立して水酸基またはメチル基を表し、
nは11〜16の整数であって、mは繰り返し数の平均値で0.5〜10である。
(但し、繰り返し単位中に存在する各繰り返し単位はそれぞれ同一であっても異なっていても構わない)。)The hydroxy compound A having the structure of the general formula (1).
... (1)
(In formula (1), Ar represents a structure having an aromatic ring having an unsubstituted or substituent, respectively.
R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
R 3 and R 4 independently represent a hydroxyl group or a methyl group, respectively.
n is an integer of 11 to 16, and m is an average value of the number of repetitions of 0.5 to 10.
(However, each repeating unit existing in the repeating unit may be the same or different). )
・・・(2)
(式(2)において、芳香環は置換または無置換であってよく、*は結合点を表す。)The hydroxy compound A according to claim 1, wherein in the formula (1), Ar has any structure represented by the following formula (2).
... (2)
(In the formula (2), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point.)
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JP2014227344A (en) * | 2013-05-17 | 2014-12-08 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator |
WO2016017446A1 (en) * | 2014-07-28 | 2016-02-04 | 日東電工株式会社 | Primer composition and composite article |
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TWI783090B (en) | 2022-11-11 |
JP6825723B2 (en) | 2021-02-03 |
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CN111527063A (en) | 2020-08-11 |
KR102627148B1 (en) | 2024-01-23 |
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WO2019123943A1 (en) | 2019-06-27 |
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