CN1651510A - Thermo setting resin composition and its setting coating film - Google Patents
Thermo setting resin composition and its setting coating film Download PDFInfo
- Publication number
- CN1651510A CN1651510A CNA2005100052863A CN200510005286A CN1651510A CN 1651510 A CN1651510 A CN 1651510A CN A2005100052863 A CNA2005100052863 A CN A2005100052863A CN 200510005286 A CN200510005286 A CN 200510005286A CN 1651510 A CN1651510 A CN 1651510A
- Authority
- CN
- China
- Prior art keywords
- thermosetting resin
- compositions
- aforementioned
- record
- coating film
- 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
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 239000011342 resin composition Substances 0.000 title abstract 4
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 48
- -1 hydrogen compound Chemical class 0.000 claims abstract description 42
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 36
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 229910000679 solder Inorganic materials 0.000 abstract description 30
- 239000000126 substance Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000009975 flexible effect Effects 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000010292 electrical insulation Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 26
- 239000002253 acid Substances 0.000 description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 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 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 125000000524 functional group Chemical group 0.000 description 18
- 239000003973 paint Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- 229930185605 Bisphenol Natural products 0.000 description 13
- 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 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 11
- 239000000976 ink Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- 230000006978 adaptation Effects 0.000 description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 238000009998 heat setting Methods 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OSQBFLZKVLCVGI-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalene-1-carbonyl 1,2,3,4-tetrahydronaphthalene-1-carboxylate Chemical compound C1CCC2=CC=CC=C2C1C(=O)OC(=O)C1C2=CC=CC=C2CCC1 OSQBFLZKVLCVGI-UHFFFAOYSA-N 0.000 description 5
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical compound NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010019 resist printing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 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
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical group C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- MGTVNFGFEXMEBM-UHFFFAOYSA-N 4-ethenyltriazine Chemical compound C=CC1=CC=NN=N1 MGTVNFGFEXMEBM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- ILSLNOWZSKKNJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hept-4-ene Chemical compound C1=CCCC2OC21 ILSLNOWZSKKNJQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- QTVOHSMXDSCJTR-UHFFFAOYSA-N CC(C(C)=C1)=CC=C1Cl[PH2]=O Chemical compound CC(C(C)=C1)=CC=C1Cl[PH2]=O QTVOHSMXDSCJTR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical class OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/84—Accessories, not otherwise provided for, for absorbent pads
- A61F13/8405—Additives, e.g. for odour, disinfectant or pH control
- A61F2013/8408—Additives, e.g. for odour, disinfectant or pH control with odour control
- A61F2013/8414—Additives, e.g. for odour, disinfectant or pH control with odour control with anti-microbic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
- A61L2300/104—Silver, e.g. silver sulfadiazine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/30—Compounds of undetermined constitution extracted from natural sources, e.g. Aloe Vera
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/62—Encapsulated active agents, e.g. emulsified droplets
- A61L2300/622—Microcapsules
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/62—Encapsulated active agents, e.g. emulsified droplets
- A61L2300/624—Nanocapsules
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Hematology (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a thermosetting resin composition which reduces hydrolyzing properties useful as a solder resist used in manufacturing printed-wiring boards and a marking ink, excels in heat resistance, chemical resistance, adhesion, electrical insulation properties and the like, is halogen-free, and has stabilized flame retardance, furthermore a thermosetting resin composition which excels in folding resistance suitably used in a semiconductor carrier tape and a solder resist for flexible printed-wiring boards and reduces warpage after curing, and its cured coating film. The thermosetting resin composition comprises (A) a carboxyl group-containing unsaturated polyester resin having one or more carboxyl groups and an ethylenically unsaturated group in one molecule, (B) a resin having two or more epoxy groups in one molecule, (C) an amine based active hydrogen compound, and (D) a phosphoric acid amide compound represented by formula (I).
Description
Technical field
The present invention relates to be used for not halogen-containing, the compositions of thermosetting resin of the manufacturing of printed-wiring board (PWB) with flame retardant resistance.In more detail, relate to and be used for the solder resist that uses at printed-wiring board (PWB) and the compositions of thermosetting resin of marking ink, this resin combination is water-disintegrable low, at solder heat resistance, chemical resistance, adaptation, aspects such as electrical insulating property are good, and it is not halogen-containing, has stable flame retardant resistance, further, also relate to and be suitable for that (belt engages automatically: Tape Automated Bonding) at TAB, CSP (chip size packages: Chip Size Package), Chipon Film) (tape carrier encapsulation: semi-conductor carrier band that uses TapeCarrier Package) and COF (cover brilliant film: the compositions of thermosetting resin and the cured coating film thereof of the solder resist of flexible printed-wiring board (PWB) such as to TCP, this resin combination folding resistance is good, and the distortion after the curing is less.
Background technology
The solder resist that is used for the manufacturing of printed-wiring board (PWB) not only is used to protect irrelevant circuit when welding sequence; plating resist agent during sometimes also as electroplating processes; and then also have the effect of the protective membrane of the circuit after the welding, the insulating reliability after chemical resistance the when thermotolerance in the time of therefore must having welding, electroplating processes and the welding concurrently.In addition, for the semi-conductor carrier band that in TAB (Tape Automated Bonding), CSP (Chip Size Package), TCP (Tape Carrier Package), uses and the solder resist of COF flexible printed-wiring board (PWB)s such as (Chip onFilm), the also necessary folding resistance of cured coating film is good, and the distortion after the curing is less.
In addition, for printed-wiring board (PWB) that outside battery-driven machinery, uses etc., also must have flame retardant resistance.Further, nearest for the method for this fire-retardantization, because contained halogen compounds may be to cause there are two English etc. that in burning ashes therefore requirement does not contain halogen and gives its flame retardant resistance in resin and organic materials.
As this solder resist and marking ink, for example proposed, the composition (with reference to patent documentation 1) that forms by liquid-state epoxy resin, body pigment, tinting pigment, solvent and imdazole derivatives, the composition (with reference to patent documentation 2) that is formed by the multipolymer and the Resins, epoxy of acrylic or methacrylic acid and vinylbenzene etc., still anti-plating etc. is insufficient.In addition, when using it for semi-conductor carrier band and flexibility printed circuit board, it is insufficient to have a folding resistance, the problem that the distortion after the curing is bigger.
Further, have as the general method that makes this fire-retardantization of compositions of thermosetting resin, halid methods such as adding brominated epoxy resin, adding phosphoric acid ester are as the method for fire retardant and the method for adding red phosphorus etc.But, in view of advocating not halogen-containing present situation, so avoid adopting halid methods such as adding brominated epoxy resin.In addition, in the electroplating processes of method when printed-wiring board (PWB) is made of adding phosphoric acid ester etc., the phosphoric acid ester hydrolysis, has the problem that coating characteristics such as making electrical insulating property and electrocorrosion reduces, and then the method that adds red phosphorus has because red phosphorus is painted etc. and causes bad order, and the problem that is subjected to the restriction of fire service law etc. when storage solder resist composition.
The solder resist of using as flexibility printed circuit board, following type is arranged, after with mould the Kapton that is called mulch film being carried out molding with the pattern correspondence, the type of pasting with tackiness agent, form the ultraviolet hardening that has flexible and film, the solder resist printing ink or the liquid polyimide ink of heat curing-type, the type by the silk screen printing coating and forming has the type of the liquid photoresistance solder paste China ink that flexible films.
Yet, for tectum, though can not halogen-containing and fire-retardant change since with the tracing ability existing problems of Copper Foil, have the problem that can not form patterns of high precision.On the other hand, for ultraviolet hardening solder resist printing ink and liquid photoresistance solder paste China ink, the adaptation between itself and the polyimide base material is poor, has the sufficient flexible problem that can not get.In addition because the cure shrinkage of solder resist printing ink and solidify after cooling shrink greatlyyer, can produce distortion and become problem.Further, though proposed to use the composition (with reference to patent documentation 3) of solubility aromatic polyimide as liquid polyimide ink, it has costing an arm and a leg, produce bleeding when printing, can not get the problem of sufficient operability.
Patent documentation 1 spy opens clear 50-6408 communique (claims)
Patent documentation 2 spies open flat 4-239070 communique (claims)
Patent documentation 3 special fair 5-75032 communiques (claims)
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention aims to provide a kind of solder resist that uses at printed-wiring board (PWB) and compositions of thermosetting resin of marking ink of being used for, this resin combination is water-disintegrable low, good at aspects such as solder heat resistance, chemical resistance, adaptation, electrical insulating properties, and not halogen-containing, have a stable flame retardant resistance, further, also relate to the compositions of thermosetting resin that is suitable for semi-conductor carrier band and flexibility printed circuit board usefulness solder resist, this resin combination folding resistance is good, and the distortion after the curing is less.
In addition, another purpose of the present invention provides a kind of by the above-mentioned compositions of thermosetting resin of heating, makes its curing and the cured coating film that obtains, this films water-disintegrable low, good at aspects such as solder heat resistance, chemical resistance, adaptation, electrical insulating properties, and not halogen-containing, have stable flame retardant resistance.
Solve the method for this problem
Present inventors have carried out conscientious research to achieve these goals, found that, contain have in (A) a part 1 above carboxyl and vinyl unsaturated group contain the carboxyl unsaturated polyester resin,
(B) have in a part 2 above epoxy group(ing) resin,
(C) the amine active dydrogen compounds,
(D) the phosphoamide compound shown in the following general formula (I)
(in the formula, R
1, R
2Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.) compositions of thermosetting resin water-disintegrable low, at solder heat resistance, chemical resistance, adaptation, aspects such as electrical insulating property are good, and it is not halogen-containing, has stable flame retardant resistance, further, also found in the reactant of specific linear multi-group epoxy compound (a) and unsaturated monocarboxylic acid (b), make itself and saturated and/or unsaturated multi-anhydride (c) reaction obtain resin, the composition of this resin is used as the above-mentioned carboxyl unsaturated polyester resin (A) that contains, it is good to obtain folding resistance, the cured coating film that distortion after the curing is less has been finished the present invention thus.
Promptly, present inventors find, utilization contain the addition reaction between the epoxy group(ing) in the resin (B) that has 2 above epoxy group(ing) in carboxyl in the carboxyl unsaturated polyester resin (A) and a part and contain vinyl unsaturated group in the carboxyl unsaturated polyester resin (A) and the active hydrogen in the amine active dydrogen compounds (C) between Michael reaction, form crosslinked form, can make water-disintegrable low, at solder heat resistance, chemical resistance, adaptation, the resin combination that aspects such as electrical insulating property are good, and then, make it water-disintegrable low by adding the phosphoamide compound shown in the above-mentioned general formula (I), can under not halogen-containing situation, give stable flame retardant resistance.Have again, by will be in the reactant of specific linear multi-group epoxy compound (a) and unsaturated monocarboxylic acid (b), make resin that the reaction of itself and saturated and/or unsaturated multi-anhydride (c) obtains as the above-mentioned carboxyl unsaturated polyester resin (A) that contains, can obtain good, the less cured coating film of distortion after solidifying of folding resistance, finish the present invention thus.
The invention effect
The compositions of thermosetting resin of the application of the invention, can provide the material that do not produce destruction environment such as two English, not halogen-containing, have a stable flame retardant resistance, and it is water-disintegrable low, good printed-wiring board (PWB) can be made the printed-wiring board (PWB) of high reliability at an easy rate with solder resist and marking ink at aspects such as solder heat resistance, chemical resistance, adaptation, electrical insulating properties.And then, the unsaturated polyester resin (A) that contains specific carboxyl by use, can provide at an easy rate have folding resistance good, solidify the flexibility printed circuit board of the high reliability of the less cured coating film of back distortion, this cured coating film is suitable in the flexible printed-wiring board (PWB)s such as the semi-conductor carrier band that uses in TAB, CSP, TCP and COF.
Embodiment
As first mode of the present invention, a kind of compositions of thermosetting resin is provided, it is characterized in that: contain have in (A) a part 1 above carboxyl and vinyl unsaturated group contain the carboxyl unsaturated polyester resin,
(B) have in a part 2 above epoxy group(ing) resin,
(C) the amine active dydrogen compounds,
(D) the phosphoamide compound shown in the following general formula (I).
(in the formula, R
1, R
2Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.)
As optimal way of the present invention, a kind of compositions of thermosetting resin also is provided, it is characterized in that: the aforementioned carboxyl unsaturated polyester resin (A) that contains is, in the reactant by at least a kind multi-group epoxy compound (a) in being selected from the epoxy compounds shown in following general formula (II), following general formula (III) and the following logical formula V and unsaturated monocarboxylic acid (b), make itself and saturated and/or unsaturated multi-anhydride (c) reaction and the resin that obtains.
(in the formula, R
3, R
4Expression hydrogen atom or methyl, R
5Expression hydrogen atom or glycidyl, n represents 1～50 value.)
(in the formula, M is expressed as follows and states the base shown in the general formula (IV), R
6The residue of expression aliphatics or aromatic series polyfunctional group carboxylic acid, m represents 1～50 value.)
(in the formula, R
7, R
8Expression divalent cyclohexane ring and/or phenyl ring, R
9, R
10Expression hydrogen atom or methyl, R
11Expression hydrogen atom or glycidyl, k represents 0～25 value.)
(in the formula, X represents different divalent aromatic nucleus mutually with Y, and G represents glycidyl and/or hydrogen atom, and p represents 1～20 integer.)
Further, as alternate manner, also provide cured coating film by heating above-mentioned compositions of thermosetting resin and its curing being obtained.
Below each moiety of compositions of thermosetting resin of the present invention is elaborated.
At first, contain carboxyl unsaturated polyester resin (A) as what have 1 above carboxyl and vinyl unsaturated group in a part that uses among the present invention, as long as in molecule, have carboxyl and vinyl unsaturated group, then there is no particular limitation, the preferred especially following resin of enumerating (in oligopolymer and the polymkeric substance any all can) that uses.
Can enumerate, (1) uses glycidyl methacrylate and acrylate chloride in the multipolymer of the compound with unsaturated carboxylic acid and unsaturated double-bond, make the vinyl unsaturated group become side chain and obtain contain the carboxyl unsaturated polyester resin,
(2) in the multipolymer of the compound that in a part, has epoxy group(ing) and a unsaturated double-bond and compound with unsaturated double-bond, make the reaction of itself and unsaturated monocarboxylic acid, the secondary hydroxyl of generation react with saturated or unsaturated multi-anhydride and obtain contain the carboxyl unsaturated polyester resin,
(3) in the multipolymer of the compound with unsaturated double-bond of the acid anhydrides with unsaturated double-bond and other, make that it obtains with the compound reaction that has hydroxyl and unsaturated double-bond in a part contain the carboxyl unsaturated polyester resin,
(4) make the reaction of multi-group epoxy compound and unsaturated monocarboxylic acid, the hydroxyl of generation and saturated or unsaturated multi-anhydride react and obtain contain the carboxyl unsaturated polyester resin,
(5) saturated or unsaturated multi-anhydride is reacted in containing the polymkeric substance of hydroxyl after, in a part of carboxylic acid that generates, make its with a part in have epoxy group(ing) and a unsaturated double-bond compound react and the unsaturated polyester resin that contains hydroxyl and carboxyl that obtains,
(6) multi-group epoxy compound, unsaturated monocarboxylic acid and in a part, have 1 alcohols hydroxyl at least and with the alcohols hydroxyl of epoxy reaction beyond the reaction product of compound of 1 reactive group in, itself and saturated or unsaturated multi-anhydride are reacted and obtain contain the carboxyl unsaturated polyester resin and
(7) unsaturated monocarboxylic acid is had in the polyfunctional group oxetane compound of 2 trimethylene oxide rings at least in a part and react, primary hydroxyl in the modification oxetane resin that obtains and the reaction of saturated or unsaturated multi-anhydride and obtain contain carboxyl unsaturated polyester resin etc.
Wherein, good by the adaptation that contains the carboxyl unsaturated polyester resin of multi-group epoxy compound's deutero-(4), therefore preferred.
Further, as the multi-group epoxy compound who in the manufacturing that contains the carboxyl unsaturated polyester resin of aforementioned (4), uses, by using the following linear multi-group epoxy compound who enumerates, compositions of thermosetting resin and cured coating film that folding resistance is good, distortion is less can be provided in the flexible printed-wiring board (PWB)s such as being suitable for the semi-conductor carrier band that uses and COF in TAB, CSP, TCP.
Promptly, aforementioned contain carboxyl unsaturated polyester resin (A) be by, in being selected from the epoxy compounds shown in following general formula (II), following general formula (III) and the following logical formula V in the reactant of at least a kind multi-group epoxy compound (a) and unsaturated monocarboxylic acid (b), make itself and saturated and/or unsaturated multi-anhydride (c) reaction and the resin that obtains.
(in the formula, R
3, R
4Expression hydrogen atom or methyl, R
5Expression hydrogen atom or glycidyl, n represents 1～50 value.)
(in the formula, M is expressed as follows and states the base shown in the general formula (IV), R
6The residue of expression aliphatics or aromatic series polyfunctional group carboxylic acid, m represents 1～50 value.)
(in the formula, R
7, R
8Expression divalent cyclohexane ring and/or phenyl ring, R
9, R
10Expression hydrogen atom or methyl, R
11Expression hydrogen atom or glycidyl, k represents 0～25 value.)
(in the formula, X represents different divalent aromatic nucleus mutually with Y, and G represents glycidyl and/or hydrogen atom, and p represents 1～20 integer.)
Multi-group epoxy compound (a) shown in the aforementioned formula (II) is a kind of with the R in the general formula (II)
5The value that all is hydrogen atom, n is 1～50 Bisphenol F type or bisphenol A-type 2 functional group's epoxy compoundss in non-proton property polar solvents such as methyl-sulphoxide etc. after the dissolving, the resin of the bis-phenol skeleton of polyfunctional groupization by itself and epoxyhalopropane described later and alkali metal hydroxide are reacted.
During the value less than 1 of n, film-forming properties when touch dry, dry film and anti-fragility reduce, and be therefore not preferred in the general formula (II).On the other hand, when n surpassed 50, viscosity rose, and printing reduces, and solid component concentration reduces, and is difficult to obtain enough thickness, and is therefore also not preferred.
As aforementioned epoxyhalopropane, for example can use epoxy chloropropane, epoxy bromopropane, epoxy iodopropane, β-Jia Jihuanyanglvbingwan, Beta-methyl epoxy bromopropane, Beta-methyl epoxy iodopropane etc.In addition, the addition amount of epoxyhalopropane is preferably on average more than 50%, more preferably more than 80%.When the addition quantity not sufficient 50% of epoxyhalopropane, the cross-linking density by Michael addition reduces, and coating characteristics such as water tolerance reduce, and are therefore not preferred.
In addition,, can use caustic soda, Ke Xingjia, lithium hydroxide, calcium hydroxide etc., preferred especially caustic soda as alkali metal hydroxide.With respect to the epoxidised alcohols hydroxyl of desire 1mol in the linear epoxy compounds of aforementioned terminal epoxy groups, the consumption of this alkali metal hydroxide is preferably 0.5～2mol.
The temperature of the addition reaction of above-mentioned epoxyhalopropane is preferably 20～100 ℃.If the temperature deficiency of addition reaction then reacts slack-off for 20 ℃, the reaction needed long period, on the other hand,, temperature of reaction then causes more side reaction if surpassing 100 ℃, therefore not preferred.
Multi-group epoxy compound (a) shown in the aforementioned formula (III) be by, with bisphenol A-type and/or Bisphenol F type 2 functional group's epoxy compoundss with (d) have the compound of at least 2 carboxyls as raw material in a part, use known as described later esterifying catalyst, make its alternately polymerization and obtain the linear epoxy compounds of terminal epoxy groups, with the multi-group epoxy compound (a) shown in linear epoxy compounds of this terminal epoxy groups and the aforementioned formula (II) similarly, be dissolved in the non-proton property polar solvent such as methyl-sulphoxide, with epoxyhalopropane and alkali metal hydroxide reaction and polyfunctional groupization.
During the value less than 1 of the m of general formula (III), film-forming properties when touch dry, dry film and anti-fragility reduce, and be therefore not preferred.On the other hand, when m surpassed 50, viscosity rose, and printing reduces, and solid component concentration reduces, and is difficult to obtain enough thickness, and is therefore also not preferred.In addition, the addition amount of epoxyhalopropane is preferably on average more than 50%, more preferably more than 80%.When the addition quantity not sufficient 50% of epoxyhalopropane, the cross-linking density by Michael addition reduces, and coating characteristics such as water tolerance reduce, and are therefore not preferred.
As the above-mentioned compound (d) that in a part, has at least 2 carboxyls, for example can enumerate, 1, the 4-cyclohexyl dicarboxylic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, the hexahydro-m-phthalic acid, hexahydroterephthalic acid, phthalic acid, m-phthalic acid, terephthalic acid, succsinic acid, hexanodioic acid, muconic acid, suberic acid, sebacic acid, the adduct of 2-hydroxy-2-methyl succsinic acid and Tetra hydro Phthalic anhydride etc., from giving the angle of flexibility, preferred especially 1, the 4-cyclohexyl dicarboxylic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, the hexahydro-m-phthalic acid, hexahydroterephthalic acid, hexanodioic acid, muconic acid, suberic acid, the dicarboxylic acid compound of aliphatics such as sebacic acid or ester ring type.It can individually or make up more than 2 kinds and use.
In addition, as aforementioned esterifying catalyst, can enumerate the phosphine class that can make epoxy group(ing) and carboxyl quantitative reaction, alkali metal compound, amine etc.Specifically can enumerate the phosphine classes such as salt of trialkyls such as tributylphosphine, triphenylphosphine or triaryl phosphine or itself and oxide compound; Alkali-metal oxyhydroxide such as sodium, lithium, potassium, halogenide, alkoxide, acid amides etc.; Trolamine, N, aliphatics such as N-lupetazin, triethylamine, three n-propyl amine, vulkacit H, pyridine, tetramethylammonium bromide or aromatic primary, second month in a season, uncle, quaternary ammonium etc., it can individually or make up more than 2 kinds and use.
With respect to the epoxy group(ing) 1mol (1 equivalent) with bisphenol A-type and/or Bisphenol F type 2 functional group's epoxy compoundss, these catalyst consumption are preferably the ratio of 0.1～25mol%, more preferably the ratio of 0.5～20mol%, the further ratio of preferred 1～15mol%.Reason is, when catalyst consumption is less than 0.1mol%, needs the certain reaction time, and is therefore uneconomical, on the other hand, when surpassing 25%, is difficult to control because reaction is too fast on the contrary, so not preferred.
Multi-group epoxy compound (a) shown in the aforementioned formula (V) be by, to have two functional group's phenolic compound of 2 phenols hydroxyls as raw material in the aromatic epoxy compound (hereinafter referred to as two functional group's epoxy compoundss) that has 2 glycidyls in a part and a part, use known as described later catalyst for etherification, in solvent or in the presence of solvent-free, make its alternately polymerization and obtain the linear epoxy compounds of terminal epoxy groups, with the multi-group epoxy compound (a) shown in linear epoxy compounds of this terminal epoxy groups and the aforementioned formula (II) similarly, be dissolved in the non-proton property polar solvent such as methyl-sulphoxide, with epoxyhalopropane and alkali metal hydroxide reaction and polyfunctional groupization.
As aforementioned two functional group's epoxy compoundss, can use two functional group's aromatic epoxy compounds of at least a kind of xenol type diglycidylether shown in following formula (VI)～(IX), di-cresylol type diglycidylether, bisphenol type diglycidylether, naphthalene type diglycidylether etc. with aromatic nucleus.By with this two functional group's epoxy compoundss as with the alternating copolymer of two functional group's phenolic compound in a kind of monomer component, can obtain the good epoxy compounds in aspect such as intensity, thermotolerance, electrical insulating property at cured product.
(in the formula, R
12, R
13, R
14, R
15Can be identical or different, expression hydrogen atom or carbonatoms are 1～4 alkyl, R
16, R
17, R
18, R
19Can be identical or different, expression hydrogen atom, carbonatoms are 1～4 alkyl or halogen atom, R
20, R
21Can be identical or different, expression hydrogen atom, methyl or monochloromethyl.)
As aforementioned xenol type, di-cresylol type, bisphenol type, naphthalene type diglycidylether, for example can use, by the product that diphenol compound, di-cresylol compound, bisphenol cpd or dihydroxy naphthlene and epichlorohydrin reaction are made.In addition, also can use commercially available epoxy compounds, for example as xenol type diglycidylether, can enumerate the trade(brand)name " エ ピ コ-ト YL-6056 " of ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) manufacturing etc., as di-cresylol type diglycidylether, can enumerate the trade(brand)name " エ ピ コ-ト YX-4000 " of ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) manufacturing etc., as the bisphenol type diglycidylether, can enumerate the trade(brand)name " ア ラ Le ダ イ ト #260 " that rising sun チ バ (strain) makes, bisphenol type epoxy compounds such as " ア ラ Le ダ イ ト #6071 ", or the trade(brand)name Bisphenol F type epoxy compoundss such as " エ ピ Network ロ Application 830S " of big Japanese イ Application キ chemical industry (strain) manufacturing, or the trade(brand)name bisphenol S type epoxy compoundss such as " エ ピ Network ロ Application EXA1514 " of big Japanese イ Application キ chemical industry (strain) manufacturing, as naphthalene type diglycidylether, can enumerate the trade(brand)name " エ ピ Network ロ Application HP-4032 (D) " of big Japanese イ Application キ chemical industry (strain) manufacturing etc., it can individually or make up more than 2 kinds and use.
As two functional group's phenolic compound of the raw material of the multi-group epoxy compound (a) shown in the aforementioned formula (V), it has feature in configuration aspects, in order to improve thermotolerance, can use the material that contains aromatic nucleus, has symmetrical structure or rigid structure.As this compound, for example can enumerate 1,4-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, 2,7-dihydroxy naphthlene, 2, dihydroxy naphthlene derivatives such as 8-dihydroxy naphthlene, 2,2 '-biphenol derivatives such as di-cresylol, xenol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, alkyl replace bisphenol derivatives such as bis-phenol, hydroquinone derivatives such as quinhydrones, toluhydroquinone, Trimethylhydroquinone etc., it can individually or make up more than 2 kinds and use.
As the catalyst for etherification of the reaction that is used for two functional group's aromatic epoxy compounds and two functional group's phenolic compound, the preferred phosphine class that can make glycidyl and phenolic hydroxyl group quantitative reaction, alkali metal compound, the amine etc. of using either alone or in combination.Catalyzer in addition is because its gelation with the alcohols hydroxyl reaction that generates in the reaction of glycidyl and phenolic hydroxyl group is therefore not preferred.As the phosphine class, can enumerate salt of trialkyls such as tributylphosphine, triphenylphosphine or triaryl phosphine or itself and oxide compound etc.As alkali metal compound, can enumerate alkali-metal oxyhydroxide such as sodium, lithium, potassium, halogenide, alkoxide, acid amides etc., it can individually or make up more than 2 kinds and use.As amine, can enumerate aliphatics or aromatic primary, second month in a season, uncle, quaternary ammonium etc., it can individually or make up more than 2 kinds and use.As the concrete example of amine, can enumerate trolamine, N, N-lupetazin, triethylamine, three n-propyl amine, vulkacit H, pyridine, tetramethylammonium bromide etc.
With respect to add-on is two functional group's aromatic epoxy compounds and two functional group's phenolic compound of 100 weight parts, and these catalyzer are at 0.001～1 weight part, preferably use in the scope of 0.01～1 weight part.Reason is, when catalyst consumption is less than 0.001 weight part, needs the certain reaction time, and is therefore uneconomical, on the other hand, when surpassing 1 weight part, is difficult to control because reaction is too fast on the contrary, so not preferred.In the presence of this catalyzer, the reaction of two functional group's aromatic epoxy resin compounds and two functional group's phenolic compound preferably in inert gas flow or in the air, in the presence of aforementioned catalyzer, makes its reaction in about 130～180 ℃ temperature range.
As with the aforementioned unsaturated monocarboxylic acid (b) of above this linear multi-group epoxy compound (a) reaction, except vinylformic acid, methacrylic acid, TRANSCINNAMIC ACID, Ba Dousuan, Sorbic Acid, the alpha-cyano TRANSCINNAMIC ACID, beyond β-styrene acrylic etc., can also enumerate (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) Propylene glycol monoacrylate, dipentaerythritol five (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid phenyl glycidyl ester, (methyl) vinylformic acid caprolactone affixture etc. contains the unsaturated dicarboxylic acid anhydride affixture etc. of the acrylate of hydroxyl.In unsaturated monocarboxylic acid (b), particularly preferably be vinylformic acid and methacrylic acid.These unsaturated monocarboxylic acids can individually or make up more than 2 kinds and use.In addition, at this moment said " (methyl) acrylate " is the term of the general name of expression acrylate and methacrylic ester, and other similar phraseology also is same.
With respect to per 1.0 equivalents of aforementioned multi-group epoxy compound's (a) epoxy group(ing), the addition amount of these unsaturated monocarboxylic acids (b) is 0.8～1.3 equivalent, is preferably 0.95～1.05 equivalent.When addition quantity not sufficient 0.8 equivalent of unsaturated monocarboxylic acid (b), unreacted epoxy groups and the carboxyl reaction that comes from the saturated and/or unsaturated multi-anhydride (c) of addition after this, storage stability is reduced, become the reason that causes gelation, therefore not preferred.On the other hand, when the addition amount surpassed 1.3 equivalents, the foul smell that is caused by unsaturated monocarboxylic acid smartened, and perhaps excessive unsaturated monocarboxylic acid aerifies when thermofixation, and corrosion Copper Foil etc. are therefore not preferred.
In addition, as aforementioned saturated and/or unsaturated multi-anhydride (c), can enumerate methyltetrahydro Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, carbic anhydride, 3, ester ring type dibasic acid anhydrides such as 6-nadic anhydride, methyl nadic anhydride, tetrabromophthalic anhydride; Succinyl oxide, maleic anhydride, itaconic anhydride, octenyl succinic acid anhydride, five dodecenyl succinic anhydride, Tetra hydro Phthalic anhydride, 1,2, aliphatics or aromatic acid or tricarboxylic anhydrides such as 4-benzenetricarboxylic anhydride, perhaps aliphatics or aromatic tetracarboxylic acid's dianhydrides such as biphenyl tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, fourth tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, pyromellitic acid acid anhydride, benzophenone tetracarboxylic dianhydride, it can individually or make up more than 2 kinds and use.Wherein preferred especially ester ring type dibasic acid anhydride.
The consumption of wishing these saturated and/or unsaturated multi-anhydrides (c) can make the acid value that contains carboxyl unsaturated polyester resin (A) that obtains at 30～200mgKOH/g, preferably in the scope at 50～120mgKOH/g.When containing the acid value deficiency 30KOH/g of carboxyl unsaturated polyester resin (A), reduce by cross-linking reaction density with the oxyethane ring, coating characteristics such as solder heat resistance reduce, and are therefore not preferred.On the other hand, when surpassing 200KOH/g, rise by cross-linking reaction density with the oxyethane ring, hardening, flexibility reduces, and is therefore not preferred.
As the resin (B) that has 2 above epoxy group(ing) in aforementioned a part, can be individually or use the glycidyl ethers such as phenol aldehyde type, xenol type, di-cresylol type, triphenol methane type of bisphenol A-type, hydrogenation bisphenol A-type, Bisphenol F type, bisphenol S type, phenol phenol aldehyde type, cresols phenol aldehyde type, dihydroxyphenyl propane in combination; Glycidyl ester classes such as o-phthalic acid diglycidyl ester; Glycidyl amines such as isocyanic acid three-glycidyl ester and four glycidyl group m-xylene diamine; 3,4-epoxy cyclohexene carboxylate-3 ', alicyclic epoxy resin classes such as 4 '-oxirane ring hexenyl methyl esters; Known Resins, epoxy commonly used such as epoxidized polybutadiene.As particularly preferred resin wherein, can be set forth in the organic solvent etc. to the isocyanic acid three-glycidyl ester of insoluble (as constitutional isomer, α body and β body being arranged, preferred especially β body), give the bigger epoxidized polybutadiene of flexible effect etc.With respect to aforementioned carboxyl 1 equivalent that contains carboxyl unsaturated polyester resin (A), from characteristic aspects such as the anti-plating of cured coating film, solder heat resistances, preferably the additional proportion of these Resins, epoxy is 0.6～2.0 equivalent.
Then, as aforementioned amine active dydrogen compounds (C), be a kind of when thermofixation, the vinyl unsaturated group that contains carboxyl unsaturated polyester resin (A) is carried out the compound of Michael addition, can use the material of the potentiality amine curing agent that generally is used for Resins, epoxy.Specifically can enumerate Dyhard RU 100; Guanamines classes such as trimeric cyanamide, vinyl triazine, acetylguanamine, benzoguanamine; Organic acid hydrazides classes such as hexanodioic acid hydrazides, m-phthalic acid hydrazides etc.Wherein, Dyhard RU 100, trimeric cyanamide also have the Copper Foil rust-proof effect, and be therefore preferred especially.It can individually or make up more than 2 kinds and use.
With respect to aforementioned vinyl unsaturated group 1 equivalent that contains carboxyl unsaturated polyester resin (A), it is 1 equivalent that the add-on of these amine active dydrogen compounds (C) preferably makes the active hydrogen of amine active dydrogen compounds (C), resin (B) reaction that has 2 above epoxy group(ing) in these amine active dydrogen compounds and aforementioned 1 molecule, form chela and thing with Copper Foil, in composition, add 0.1～10 weight %, preferably add 0.2～5 weight %.
As the feature place of not halogen-containing, compositions of thermosetting resin with flame retardant resistance of the present invention, the phosphoamide (D) shown in following general formula (I)
(in the formula, R
1, R
2Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.)
Can pass through two phenenyl phosphinyl chlorine, two phenenyl phosphinyl bromine, two-3, two phenenyl phosphinyl halogenide class that 1～2 hydrogen atom of phenyl such as 5-xylyl phosphinyl chlorine or its aromatic nucleus is replaced by the alkyl of carbonatoms 1～4 and piperazine dissolved add basic catalyst such as triethylamine and synthesize in non-aqueous organic solvents such as ethylene dichloride.For example by the R of general formula two phenenyl phosphinyl chlorine and piperazine derivatives, above-mentioned (I)
1And R
2Be the N of hydrogen atom, N '-two (two phenoxy group phosphinyls) piperazine contains the 11 weight % phosphorus atom of having an appointment, and 5 weight % nitrogen-atoms, fusing point are about 186.7 ℃.As the commercially available prod, there are four countries to change into the SP-703 that society makes.
Phosphoamide compound (D) shown in the above-mentioned general formula (I) that so obtains is compared with phosphoric acid ester, it is water-disintegrable extremely low, can hydrolysis in the chemical treatment of the alkali of the electroplating processes when making printed-wiring board (PWB) etc. or acid and heat treated thereafter yet, can keep stable flame retardant resistance and electrical insulating property.
And because the fusing point height does not have stripping, these phenomenons of pollution Copper Foil yet when thermofixation.Further,, when burning, form phosphorus nitrence ring etc., compare, also have and give the flame retardant resistance effect high feature with phosphoric acid ester owing in molecule, contain nitrogen-atoms.
As the add-on of the phosphoamide (D) shown in the above-mentioned general formula (I), be 5～50 weight % in the compositions of thermosetting resin of the present invention, preferred 10～40 weight %, more preferably 20～40 weight %.When the add-on less than 5 weight % of phosphoamide, the containing ratio of phosphorus atom reduces, even and other flame retardant resistance be used in combination, also can not get sufficient flame retardant resistance, so not preferred.On the other hand, when the add-on of phosphoamide surpassed 50 weight %, coating strength reduced, and is therefore not preferred.
In addition, in compositions of thermosetting resin of the present invention, as required, to improve characteristics such as adaptation, hardness, thermotolerance is purpose, can add known mineral fillers commonly used such as barium sulfate, talcum, silicon-dioxide, clay, aluminium hydroxide, its add-on is advisable to account for 60 weight % in composition below, the ratio of preferred 5～40 weight %.If the add-on of mineral filler surpasses aforementioned proportion, the elasticity of cured coating film and folding resistance reduce, so not preferred.Further, as required, can add known tinting pigment commonly used (for example titanium oxide, carbon, phthalocyanine blue, phthalocyanine green, diazonium Huang etc.), thermal polymerization inhibitor, thickening material, defoamer, dye leveller, silane coupling agent etc.
In addition, in order further to improve flame retardant resistance, can also add water-disintegrable low P contained compounds such as phosphorus nitrence compound.
Compositions of thermosetting resin with above this composition is coated on the printed-wiring board (PWB) and tape carrier encapsulation (Tape CarrierPackage) that has formed circuit by silk screen print method, heating makes its thermofixation under 120～180 ℃ temperature for example, forms good cured coating films in aspect such as the adaptation of base material, anti-plating, solder heat resistance, electrical insulating properties.
[embodiment]
Enumerate embodiment below and comparative example is specifically described the present invention, the present invention is not limited to following embodiment certainly.In addition, following " part " and " % " is to be benchmark with weight not having under the situation about specifying all.
＜contain the synthesis example 1 of carboxyl unsaturated polyester resin (A) 〉
In the flask that thermometer, agitator, dropping funnel and reflux exchanger are housed, measure 210 parts of cresols phenol aldehyde type epoxy resins (エ ピ Network ロ Application N-680, big Japanese イ Application キ chemical industry society makes, epoxy equivalent (weight)=210) and 109.7 parts of Trivalin SF acetic ester, heating for dissolving.Then, add 0.1 part quinhydrones as the triphenylphosphine of polymerization retarder and 2.0 parts as catalysts.With this mixture heating up to 95～105 ℃, slowly drip 72 parts of vinylformic acid, reacted about 16 hours, reach below the 3.0mgKOH/g until acid value.This reaction product is cooled to 80～90 ℃, adds 76.1 parts of tetrahydronaphthalic anhydrides, reacted about 6 hours, until by infrared absorptiometric analysis, the absorption peak of acid anhydrides (1780cm-1) disappears.In this reaction solution, add aromatic series kind solvent イ プ ゾ-Le #150 that 109.7 parts of bright dipping petroleum chemistry societies make, after the dilution, take out.The nonvolatile component that contains carboxyl unsaturated polyester resin (A) paint that obtains thus is 62%, and the acid value of solid state component is 78mgKOH/g.Below this reaction solution is called the A-1 paint.
＜contain the synthesis example 2 of carboxyl unsaturated polyester resin (A) 〉
In the flask that whipping appts, cooling tube and thermometer are housed, 380 parts of bisphenol f type epoxy resin (epoxy equivalent (weight)=950 of packing into, 85 ℃ of softening temperatures, mean polymerisation degree n=6.2) and 925 parts of epoxy chloropropane, after it is dissolved, under agitation in 100 minutes, add 60.9 parts of (1.5mol) purity 98.5% sodium hydroxide in 70 ℃ in 462.5 parts of methyl-sulphoxides.Further reacted 3 hours after the interpolation at 70 ℃.Reaction adds 250 parts of water and washes after finishing.After the oily water separation, under reduced pressure more than half methyl-sulphoxide and excessive unreacted epoxy chloropropane are reclaimed in distillation from oil reservoir, to contain the remaining by-product salt and the reaction product of methyl-sulphoxide dissolves in 750 parts of methyl iso-butyl ketone (MIBK), further add 10 part of 30% aqueous sodium hydroxide solution, reacted 1 hour down at 70 ℃.After reaction finishes, carry out 2 washings with 200 parts of water.After the oily water separation, reclaim methyl iso-butyl ketone (MIBK), obtain epoxy equivalent (weight)=310, the Resins, epoxy that softening temperature is 69 ℃ (a) from the oil reservoir distillation.Multi-group epoxy compound (a) shown in the aforementioned formula that obtains (II) is if calculate from epoxy equivalent (weight), in 6.2 alcohols hydroxyls of aforementioned initial substance bisphenol f type epoxy resin about 5 by epoxidation.310 parts of these multi-group epoxy compounds (a) and 313.2 parts of Trivalin SF acetic ester are put into the four-hole boiling flask that stirrer and reflux exchanger are housed, 90 ℃ of heated and stirred, dissolving.The solution that obtains is disposable to be cooled to 60 ℃, adds 72 parts of vinylformic acid, 0.5 part of toluhydroquinone, 2 parts of triphenylphosphines, is heated to 100 ℃, reacts about 60 hours, obtains the reactant that acid value is 0.2mgKOH/g.It is added 140 parts of tetrahydronaphthalic anhydrides, be heated to 90 ℃, reaction reaches 100mgKOH/g until the solid state component acid value, obtains containing 62.5% solution that contains carboxyl unsaturated polyester resin light-cured resin (A).Below this reaction solution is called the A-2 paint.
＜contain the synthesis example 3 of carboxyl unsaturated polyester resin (A) 〉
In the flask that gas duct, whipping appts, cooling tube and thermometer are housed, add 172 part 1, the hydrogenation bisphenol A diglycidyl ether of 4-cyclohexane dicarboxylic acid and 880 parts of epoxy equivalent (weight)=176 (" YX8000 " that ジ ヤ パ Application エ Port キ シ レ ジ Application society makes), under nitrogen atmosphere, under 100 ℃, stir.Add 0.65 part of triphenylphosphine then, the temperature in the flask is risen to 150 ℃, make temperature remain on about 90 minutes of 150 ℃ of reactions, obtain the normal linear epoxy compounds of epoxy equivalent (weight) 438g/.
Temperature in the flask is cooled to below 70 ℃, adds 780 parts of epoxy chloropropane, 635 parts of methyl-sulphoxides, under agitation be warming up to 70 ℃ and keep this temperature.Substep adds after 150 parts of purity 96% sodium hydroxide in 90 minutes then, further reacts 3 hours.After reaction finishes, the excessive epoxy chloropropane of distillation and more than half methyl-sulphoxide under 120 ℃, the decompression of 50mmHg, the reaction product that will contain by-product salt and methyl-sulphoxide is dissolved in methyl iso-butyl ketone (MIBK), washing.Methyl iso-butyl ketone (MIBK) is reclaimed in distillation from oil reservoir then, obtains the multi-group epoxy compound (a) shown in the aforementioned formula (III) of epoxy equivalent (weight)=247.
Then 494 parts of above-mentioned multi-group epoxy compounds (a) are put into the flask that whipping appts, cooling tube and thermometer are housed, add 563.5 parts of Trivalin SF acetic ester, heating for dissolving, add 0.46 part of toluhydroquinone, 1.38 parts of triphenylphosphines, be heated to 95～105 ℃, slowly 0 part of vinylformic acid of Dropwise 35 reacted 20 hours.This reaction product is cooled to 80～90 ℃, adds 300 parts of tetrahydronaphthalic anhydrides, reacted 8 hours.Carry out the acid value of reaction solution, the mensuration of total acid value by potentiometric titration, follow the trail of the markup percentage that obtains, reactivity is reached more than 95% as reaction end.
The nonvolatile component that contains carboxyl unsaturated polyester resin (A) paint that obtains thus is 6 7%, and the acid value of solid state component is 89.2mgKOH/g.Below this is contained carboxyl unsaturated polyester resin (A) paint and be called the A-3 paint.
＜contain the synthesis example 4 of carboxyl unsaturated polyester resin (A) 〉
In the flask that gas duct, whipping appts, cooling tube and thermometer are housed, pack 203 part 1 into, (the chemical society of big Japanese イ Application キ makes the エ ピ Network ロ Application-840 of 5-dihydroxy naphthlene and 1097 parts of bisphenol A type epoxy resins, epoxy equivalent (weight) 180), under nitrogen atmosphere, under agitation in 120 ℃ of dissolvings down.Add 0.65 part of triphenylphosphine then, the temperature in the flask is risen to 150 ℃, make temperature remain on about 90 minutes of 150 ℃ of reactions, obtain epoxy equivalent (weight) and be 2 functional group's epoxy compoundss of 365.
Temperature in the flask is cooled to below 70 ℃, adds 2058 parts of epoxy chloropropane, 1690 parts of methyl-sulphoxides, under agitation be warming up to 70 ℃ and keep this temperature.Substep adds 122 parts of purity 96% sodium hydroxide in 90 minutes then.After the interpolation, further reacted 3 hours.After reaction finishes, the excessive epoxy chloropropane of distillation and more than half methyl-sulphoxide under 120 ℃, the reduced pressure of 50mmHg, the reaction product that will contain by-product salt and methyl-sulphoxide is dissolved in methyl iso-butyl ketone (MIBK), washing.Methyl iso-butyl ketone (MIBK) is reclaimed in distillation from oil reservoir then, obtains the multi-group epoxy compound (a) shown in the aforementioned formula (V) of epoxy equivalent (weight)=275.The multi-group epoxy compound who obtains (a) is if calculate from epoxy equivalent (weight), in 1.71 alcohols hydroxyls of aforementioned 2 functional group's epoxy compoundss about 0.82 by epoxidation.Therefore, the epoxidation rate of alcohols hydroxyl is 48%.Then 347 parts of multi-group epoxy compounds (a) are put into the flask that whipping appts, cooling tube and thermometer are housed, add 401 parts of Trivalin SF acetic ester, heating for dissolving, add 0.46 part of toluhydroquinone, 1.38 parts of triphenylphosphines, be heated to 95～105 ℃, slowly drip 91 parts of vinylformic acid, reacted 16 hours.This reaction product is cooled to 80～90 ℃, adds 163 parts of tetrahydronaphthalic anhydrides, reacted 8 hours.Carry out the acid value of reaction solution, the mensuration of total acid value by potentiometric titration, follow the trail of the markup percentage that obtains, reactivity is reached more than 95% as reaction end.The nonvolatile component that contains carboxyl unsaturated polyester resin (A) paint that obtains thus is 60%, and the acid value of solid state component is 100mgKOH/g.Below this reaction soln is called the A-4 paint.
＜embodiment 1～4 and comparative example 1～2 〉
Use the paint that obtains in the aforementioned synthesis example, the mixing element with shown in 3 mixing tables 1 of roll-type mixing roll obtains compositions of thermosetting resin.The evaluation result of each compositions of thermosetting resin is as shown in table 2.
[table 1]
| Embodiment | Comparative example | ||||||
| ??1 | ??2 | ??3 | ??4 | ??1 | ??2 | ??3 | |
| The A-1 paint | ??161.3 | ??- | ??- | ??- | ??161.3 | ??161.3 | ??161.3 |
| The A-2 paint | - | 160.0 | - | - | - | - | - | |
| The A-3 paint | - | - | 149.3 | - | - | - | - | |
| The A-4 paint | - | - | - | 166.7 | - | - | - | |
| Dyhard RU 100 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| Trimeric cyanamide | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | |
| ?KS-66 *1 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | |
| Phthalocyanine blue | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| Yellow organic pigment *2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| ?SP-703 *3 | 200.0 | 200.0 | 200.0 | 200.0 | - | - | - | |
| ?TPP *4 | - | - | - | - | - | 232.0 | - | |
| ?YDB400PB85 *5 | - | - | - | - | - | - | 130.0 | |
| ?PnB *6 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | |
| ?N-680CA75 *7 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | - | |
| ?834CA90 *8 | 38.0 | 38.0 | 38.0 | 38.0 | 38.0 | 38.0 | - | |
| ?PB3600 *9 | 12.0 | 12.0 | 12.0 | 12.0 | 12.0 | 12.0 | - | |
| ?M6200 *10 | 35.0 | 35.0 | 35.0 | 35.0 | 35.0 | 35.0 | - | |
| Remarks | *1: the silicone defoamer that chemistry society of SHIN-ETSU HANTOTAI makes *2: Network ロ モ Off Le エ ロ-AGR that チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes *3: four countries change into the phosphoamide based flame retardant shown in the general formula (I) that society makes *4: triphenylphosphate (general phosphoric acid ester fire retardant) *5: the tetrabromo-bisphenol type Resins, epoxy that Dongdu is changed into manufacturing is dissolved in the paint (nonvolatile component 85%) of propylene glycol monobutyl ether *6: the propylene glycol monobutyl ether *7: the paint (nonvolatile component 75%) that the cresols phenol aldehyde type epoxy resin of the chemical society of big Japanese イ Application キ manufacturing is dissolved in the Trivalin SF acetic ester *8: the paint (nonvolatile component 90%) that the bisphenol A type epoxy resin of ジ ヤ パ Application エ Port キ シ レ ジ Application society manufacturing is dissolved in the Trivalin SF acetic ester *9: the epoxidized polybutadiene that ダ イ セ Le chemical industry society makes *10: the multi-functional acrylate that the synthetic society in East Asia makes | |||||||
[table 2]
| Embodiment | Comparative example | ||||||
| ??1 | ??2 | ??3 | ??4 | ??1 | ??2 | ??3 | |
| (1) flame retardant resistance | ??○ | ??○ | ??○ | ??○ | ??× | ??○ | ??○ |
| (2) solder heat resistance | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| (3) acid resistance | ??○ | ??○ | ??○ | ??○ | ??○ | ??△ | ??○ |
| (4) alkali resistance | ??○ | ??○ | ??○ | ??○ | ??○ | ??× | ??○ |
| (5) folding resistance | ??- | ??○ | ??○ | ??△ | ??- | ??- | ??- |
| (6) distortion | ??- | ??○ | ??△ | ??△ | ??- | ??- | ??- |
| Having or not of halogen atom | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have |
In addition, the method for the performance test in the above-mentioned table 2 is as follows.
Performance evaluation
(1) flame retardant resistance
Change in Hitachi on the flame retardant resistance substrate RO-67G (0.2mmt material) of halogen of manufacturing, apply by silk screen printing comprehensively, making on each face is 20 μ m, with the heated air circulation type drying oven 150 ℃, 30 minutes, carry out thermofixation.According to the experiment of UL94 incendivity, this experiment slice is carried out the mensuration of combustion time.
Zero: be equivalent to UL V-0
(5 experiment slices burn total combustion time 2 times the time respectively below 50 seconds):
Be equivalent to UL V-1
(be 50～250 seconds total combustion time that 5 experiment slices burn respectively 2 times the time)
*: there is not self quench
(5 experiment slices burn total combustion time 2 times the time respectively more than 250 seconds)
(2) solder heat resistance
On the printed-wiring board (PWB) that has formed circuit, above-mentioned each compositions of thermosetting resin of pattern printing, making cured coating film was about 20 μ m, 150 ℃, thermofixation 30 minutes.Coating rosin based solder flux on the cured coating film that obtains, dipping is 10 seconds in 260 ℃ solder bath, according to the state of following benchmark evaluation cured coating film.
Zero: on cured coating film, do not expand, peel off, variable color
△: a little expansion is arranged on cured coating film, peel off, variable color
*: on cured coating film, exist expand, peel off, variable color
(3) acid resistance
To in the aqueous sulfuric acid of 50 ℃ 10vol%, flood 30 minutes according to the substrate that obtains with above-mentioned same method, after the washing, peel off experiment, resist peeled off variable color evaluation by the glassine paper adhesive tape.
Zero: do not find fully to change
△: extremely small variation occurs
*: on filming, produce and peel off
(4) alkali resistance
With above-mentioned acid resistance similarly, the substrate that obtains was flooded 30 minutes in the aqueous sodium hydroxide solution of 50 ℃ 10wt%, after the washing, peel off experiment by the glassine paper adhesive tape, resist peeled off variable color evaluation.
Zero: do not find fully to change
△: extremely small variation occurs
*: on filming, produce and peel off
(5) folding resistance
Be printed on each kapton material (high strength polyimide material) (thick 50 μ m) by silk screen printing each compositions of thermosetting resin comprehensively, solidify 30 minutes (dry film thickness 20 μ m) down at 150 ℃ with the foregoing description 2～4.
The cured film that obtains is folded 180 ° laterally, according to following benchmark evaluation.
Zero: do not have crackle on the cured film
△: a small amount of crackle is arranged on the cured film
*: crackle is arranged on the cured film
(6) distortion
Be printed on each kapton material (150 * 110mm, thick 25 μ m) by silk screen printing each compositions of thermosetting resin comprehensively, solidify 30 minutes (dry film thickness 20 μ m) down at 150 ℃ with the foregoing description 2～4.After the cooling, the distortion of the cured coating film that obtains according to following benchmark evaluation.
Zero: not distortion fully
△: a little distortion occurs
*: distortion appears
From the result shown in the table 2 as can be seen, not halogen-containing from the cured coating film that compositions of thermosetting resin of the present invention makes, has the same flame retardant resistance of cured article with the halogen-containing Resins, epoxy of use of comparative example 3, good characteristic with chemical resistance aspects such as acid resistance, alkali resistances.On the other side, the comparative example 1 that does not add the phosphoamide compound shown in the general formula (I) does not have flame retardant resistance.On the other hand, though the comparative example 2 that has added as the triphenylphosphate of general phosphoric acid ester fire retardant demonstrates flame retardant resistance, acid resistance, alkali resistance are relatively poor.
Claims (17)
1, a kind of compositions of thermosetting resin is characterized in that: contain have in (A) a part 1 above carboxyl and vinyl unsaturated group contain the carboxyl unsaturated polyester resin,
(B) have in a part 2 above epoxy group(ing) resin,
(C) the amine active dydrogen compounds,
(D) the phosphoamide compound shown in the following general formula (I).
(in the formula, R
1, R
2Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.)
2, the compositions of thermosetting resin of putting down in writing according to claim 1, it is characterized in that: aforementioned contain carboxyl unsaturated polyester resin (A) be by, in at least a kind of multi-group epoxy compound (a) in being selected from the epoxy compounds that following general formula (II), following general formula (III) and following logical formula V represent and the reactant of unsaturated monocarboxylic acid (b), itself and saturated and/or unsaturated multi-anhydride (c) reaction are obtained.
(in the formula, R
3, R
4Expression hydrogen atom or methyl, R
5Expression hydrogen atom or glycidyl, n represents 1～50 value.)
(in the formula, M is expressed as follows and states the base shown in the general formula (IV), R
6The residue of expression aliphatics or aromatic series polyfunctional group carboxylic acid, m represents 1～50 value.)
(in the formula, R
7, R
8Expression divalent cyclohexane ring and/or phenyl ring, R
9, R
10Expression hydrogen atom or methyl, R
11Expression hydrogen atom or glycidyl, k represents 0～25 value.)
(in the formula, X represents different divalent aromatic nucleus mutually with Y, and G represents glycidyl and/or hydrogen atom, and p represents 1～20 integer.)
3, according to the compositions of thermosetting resin of claim 1 or 2 records, it is characterized in that: the resin (B) that has 2 above epoxy group(ing) in aforementioned a part is for containing the resin of epoxidized polybutadiene.
4, according to the compositions of thermosetting resin of each record in the claim 1 to 2, it is characterized in that: aforementioned amine active dydrogen compounds (C) is trimeric cyanamide and/or Dyhard RU 100.
5, according to the compositions of thermosetting resin of claim 3 record, it is characterized in that: aforementioned amine active dydrogen compounds (C) is trimeric cyanamide and/or Dyhard RU 100.
6, according to the compositions of thermosetting resin of each record in the claim 1 to 2, it is characterized in that: the content of aforementioned phosphoamide compound (D) in composition is 5～50 weight %.
7, according to the compositions of thermosetting resin of claim 3 record, it is characterized in that: the content of aforementioned phosphoamide compound (D) in composition is 5～50 weight %.
8, according to the compositions of thermosetting resin of claim 4 record, it is characterized in that: the content of aforementioned phosphoamide compound (D) in composition is 5～50 weight %.
9, according to the compositions of thermosetting resin of claim 5 record, it is characterized in that: the content of aforementioned phosphoamide compound (D) in composition is 5～50 weight %.
10, by compositions of thermosetting resin that heats each record in the aforementioned claim 1 to 2 and the cured coating film that its curing is obtained.
11, by compositions of thermosetting resin that heats aforementioned claim 3 record and the cured coating film that its curing is obtained.
12, by compositions of thermosetting resin that heats aforementioned claim 4 record and the cured coating film that its curing is obtained.
13, by compositions of thermosetting resin that heats aforementioned claim 5 record and the cured coating film that its curing is obtained.
14, by compositions of thermosetting resin that heats aforementioned claim 6 record and the cured coating film that its curing is obtained.
15, by compositions of thermosetting resin that heats aforementioned claim 7 record and the cured coating film that its curing is obtained.
16, by compositions of thermosetting resin that heats aforementioned claim 8 record and the cured coating film that its curing is obtained.
17, by compositions of thermosetting resin that heats aforementioned claim 9 record and the cured coating film that its curing is obtained.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004029859A JP2005232195A (en) | 2004-02-05 | 2004-02-05 | Thermosetting resin composition and its cured coating film |
| JP2004029859 | 2004-02-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1651510A true CN1651510A (en) | 2005-08-10 |
| CN100457809C CN100457809C (en) | 2009-02-04 |
Family
ID=34879191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100052863A Expired - Fee Related CN100457809C (en) | 2004-02-05 | 2005-02-04 | Thermo setting resin composition and its setting coating film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2005232195A (en) |
| KR (1) | KR20060041704A (en) |
| CN (1) | CN100457809C (en) |
| TW (1) | TW200536886A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927944B (en) * | 2005-09-06 | 2010-05-12 | 太阳油墨制造株式会社 | Resin composition, cured composition and printed circuit board using same |
| CN104808436A (en) * | 2014-01-27 | 2015-07-29 | 太阳油墨（苏州）有限公司 | Alkali-developable photosensitive resin composition, dry film, cured product and printed circuit board |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298613A (en) * | 2004-04-09 | 2005-10-27 | Taiyo Ink Mfg Ltd | Thermosetting resin composition and its cured film |
| CN101218540B (en) | 2005-07-14 | 2011-04-13 | 三井化学株式会社 | Positive photosensitive resin composition and process for pattern formation |
| WO2007061037A1 (en) * | 2005-11-25 | 2007-05-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic component and electronic component device |
| JP4513881B2 (en) * | 2008-03-07 | 2010-07-28 | 株式会社デンソー | Car navigation system |
| JP2010077322A (en) * | 2008-09-26 | 2010-04-08 | Fujifilm Corp | Composition for forming plated layer, production method for metal pattern material and metal pattern material obtained thereby, and production method for surface metal film material and surface metal film material obtained thereby |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6021629B2 (en) * | 1977-06-09 | 1985-05-28 | ソニー株式会社 | adhesive composition |
| US6090891A (en) * | 1997-05-30 | 2000-07-18 | Ciba Specialty Chemicals Corp. | Carboxyl-containing polymer(s) with (2-oxo-1,3-dioxolan-4-yl)methyl groups-containing compound(s) |
-
2004
- 2004-02-05 JP JP2004029859A patent/JP2005232195A/en not_active Withdrawn
-
2005
- 2005-02-01 TW TW094103086A patent/TW200536886A/en unknown
- 2005-02-04 CN CNB2005100052863A patent/CN100457809C/en not_active Expired - Fee Related
- 2005-02-04 KR KR1020050010410A patent/KR20060041704A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927944B (en) * | 2005-09-06 | 2010-05-12 | 太阳油墨制造株式会社 | Resin composition, cured composition and printed circuit board using same |
| CN104808436A (en) * | 2014-01-27 | 2015-07-29 | 太阳油墨（苏州）有限公司 | Alkali-developable photosensitive resin composition, dry film, cured product and printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005232195A (en) | 2005-09-02 |
| CN100457809C (en) | 2009-02-04 |
| KR20060041704A (en) | 2006-05-12 |
| TW200536886A (en) | 2005-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1240772C (en) | Phasphorus-containing epoxy resin composition, flame-retarded sheet resin composite metal forming, semi-solidified sheet, veneer shect, multiply sheet using the phasphorus-containing epoxy resin | |
| CN1651510A (en) | Thermo setting resin composition and its setting coating film | |
| KR101562964B1 (en) | Photosensitive resin composition with good reliability and method for preparing the same | |
| CN1333791A (en) | Polyoxazolidone adhesive resin compoistion prepared from polyepoxides and polyisocyanates | |
| CN1092674C (en) | Epoxy propenoic acid resin and its use | |
| CN1423678A (en) | Flame retardant phosphorus element-containing epoxy resin compositions | |
| CN1942502A (en) | Epoxy resin composition | |
| CN1910519A (en) | Photosensitive resin composition and cured product thereof | |
| JP2007197518A (en) | Epoxy resin compound, thermosetting resin composition, and photosensitive composition | |
| CN101077956A (en) | Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate | |
| JP2770252B2 (en) | Epoxy resin composition, epoxy resin composition for sealing material, epoxy resin composition for laminate, and epoxy resin composition for solder resist | |
| CN101045839A (en) | Liquid photosensitive ink and applied in printing circuit board | |
| CN1296405C (en) | Polycarboxylic acid resin, polycarboxylic acid resin composition, and cured article obtained therefrom | |
| CN1289600C (en) | Thermosetting epoxy resin composition and its formed body and multilayered printed circuit board | |
| CN1239615C (en) | Curable resin composition | |
| CN1626577A (en) | Resin composition, prepreg and laminate using the composition | |
| CN1268664C (en) | Resin composition, composition for solder resist, and cured article obtained therefrom | |
| CN1639223A (en) | Phosphorus-containing epoxy resin, phosphorus-containing epoxy resin composition, process for producing the same, and sealing material and laminate board | |
| CN1370810A (en) | Adhesive composition and adhesive sheet for semiconductor device | |
| JP5142180B2 (en) | Epoxy resin composition and cured product thereof | |
| KR100516161B1 (en) | Silane adduct, manufacturing thereof and method for coupling organic die attach adherevise and inorganic materials using the same | |
| JP4906020B2 (en) | Phosphorus-containing phenol resin and epoxy resin composition using the phenol resin | |
| CN1680470A (en) | Curable resin comosition and coating film thereof | |
| JP2002220435A (en) | Phosphorus-containing epoxy resin composition, prepreg, resin-coated metal foil, adhesive sheet, laminated board and multilayer board, phosphorus-containing epoxy resin varnish for coating, phosphorus-containing epoxy resin sealing material, phosphorus-containing epoxy resin casting material and phosphorus-containing epoxy resin varnish for immersion | |
| JP2001181373A (en) | Phosphorus-containing epoxy resin composition, pre-preg thereby, resin-coated metal foil, adhesive sheet, laminated board and multilayer board, applying resin varnish and multilayer board thereby |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Ink Manufacturing Co., Ltd. Contract record no.: 2010990000679 Denomination of invention: Thermo setting resin composition and its setting coating film Granted publication date: 20090204 License type: Common License Open date: 20050810 Record date: 20100830 |
|
| C56 | Change in the name or address of the patentee |
Owner name: TAIYO HOLDINGS CO., LTD. Free format text: FORMER NAME: TAIYO INK MANUFACTURING CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan, Japan Patentee after: Taiyo Holding Co., Ltd. Address before: Tokyo, Japan, Japan Patentee before: Taiyo Ink Manufacturing Co., Ltd. |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Ink Manufacturing Co., Ltd. Contract record no.: 2010990000679 Date of cancellation: 20110302 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Thermo setting resin composition and its setting coating film Granted publication date: 20090204 License type: Common License Open date: 20050810 Record date: 20110302 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090204 Termination date: 20200204 |