JP2021157025A - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- JP2021157025A JP2021157025A JP2020056393A JP2020056393A JP2021157025A JP 2021157025 A JP2021157025 A JP 2021157025A JP 2020056393 A JP2020056393 A JP 2020056393A JP 2020056393 A JP2020056393 A JP 2020056393A JP 2021157025 A JP2021157025 A JP 2021157025A
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- JP
- Japan
- Prior art keywords
- meth
- resin composition
- mass
- photosensitive resin
- parts
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 82
- -1 acrylic compound Chemical class 0.000 claims abstract description 60
- 239000003063 flame retardant Substances 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 48
- 239000011574 phosphorus Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 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 claims description 55
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- ROQAKKQKBRVKRR-UHFFFAOYSA-N 1-diphenylphosphorylbut-3-en-2-one Chemical compound C=CC(=O)CP(=O)(c1ccccc1)c1ccccc1 ROQAKKQKBRVKRR-UHFFFAOYSA-N 0.000 claims description 5
- CQCGPNRIAFVNBY-UHFFFAOYSA-N [ethenyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(C=C)C1=CC=CC=C1 CQCGPNRIAFVNBY-UHFFFAOYSA-N 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 2
- 230000036211 photosensitivity Effects 0.000 claims 2
- 150000005088 phosphanthrenes Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 31
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 28
- 239000003822 epoxy resin Substances 0.000 description 21
- 229920000647 polyepoxide Polymers 0.000 description 21
- 239000003086 colorant Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical group C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WMHZPRXLNKKFAR-UHFFFAOYSA-N 1-diphenylphosphoryl-3-methylbut-3-en-2-one Chemical compound C=1C=CC=CC=1P(=O)(CC(=O)C(=C)C)C1=CC=CC=C1 WMHZPRXLNKKFAR-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 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
- 229960002130 benzoin Drugs 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000038 blue colorant Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000040 green colorant Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001060 yellow colorant Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- DTKZDHKPNHOYKJ-UHFFFAOYSA-N (6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl prop-2-enoate Chemical compound C=CC(=O)OCP1(=O)Oc2ccccc2-c2ccccc12 DTKZDHKPNHOYKJ-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- RYMJROMJFXGJCU-UHFFFAOYSA-N 6-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)CCC1CC2OC2CC1 RYMJROMJFXGJCU-UHFFFAOYSA-N 0.000 description 1
- ZZFKPYDOCNLUOD-UHFFFAOYSA-N 6-[3-(oxiran-2-ylmethoxy)propyl]benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)CCCOCC1CO1 ZZFKPYDOCNLUOD-UHFFFAOYSA-N 0.000 description 1
- HDXGUOZQUVDYMC-UHFFFAOYSA-N 6h-benzo[c][2,1]benzoxaphosphinine Chemical group C1=CC=C2OPC3=CC=CC=C3C2=C1 HDXGUOZQUVDYMC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- DHNQMJPIVOCZMQ-UHFFFAOYSA-N C(C=C)(=O)O.[N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical class C(C=C)(=O)O.[N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O DHNQMJPIVOCZMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Natural products CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- AKTGKEBIBGSCLD-UHFFFAOYSA-N [ethyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(CC)C1=CC=CC=C1 AKTGKEBIBGSCLD-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本発明は、リジッド基板やフレキシブル基板を用いたプリント配線板等の基板上に、例えば、インクジェット法を用いて塗工できる、難燃性を備えた感光性樹脂組成物に関するものである。 The present invention relates to a flame-retardant photosensitive resin composition that can be applied, for example, by using an inkjet method on a substrate such as a printed wiring board using a rigid substrate or a flexible substrate.
従来、所望の回路パターンを有する基板（例えば、プリント配線板）に絶縁被覆を形成するにあたり、スクリーン印刷法、スプレー塗工法等を用いて、感光性樹脂組成物を塗布後、予備乾燥し、回路パターンのランド以外を透光性にしたパターンを有するネガフィルムを、塗布した感光性樹脂組成物上に密着させ、その上から紫外線等の活性エネルギー線を照射し、ランドに対応する非露光領域を希アルカリ水溶液で除去して、感光性樹脂組成物の塗膜を現像し、ポストキュアを行っていた。 Conventionally, in forming an insulating coating on a substrate having a desired circuit pattern (for example, a printed wiring board), a photosensitive resin composition is applied by using a screen printing method, a spray coating method, or the like, and then pre-dried to form a circuit. A negative film having a pattern having a translucent pattern other than the land of the pattern is brought into close contact with the coated photosensitive resin composition, and an active energy ray such as ultraviolet rays is irradiated from above to create an unexposed area corresponding to the land. After removing with a dilute alkaline aqueous solution, the coating film of the photosensitive resin composition was developed and post-cured.
しかし、上記絶縁被膜の形成方法は、フォトマスクを用いた現像等、処理工程が多く、作業が繁雑であり、また、塗工デザインの自由度にも制限がある。そこで、近年、インクジェット法を用いて所望の回路パターンを有する基板上に感光性樹脂組成物を所望の塗工デザインにて吐出して塗膜を形成し、該塗膜上にレーザーや紫外線等の活性エネルギー線を露光することで硬化塗膜を形成し、硬化塗膜をさらに熱硬化処理をすることで、所望のパターンを有する絶縁被覆を形成することも行われている。 However, the method for forming the insulating film involves many processing steps such as development using a photomask, and the work is complicated, and the degree of freedom in coating design is also limited. Therefore, in recent years, a photosensitive resin composition is discharged on a substrate having a desired circuit pattern by a desired coating design using an inkjet method to form a coating film, and a laser, ultraviolet rays, or the like is applied onto the coating film. A cured coating film is formed by exposing the active energy rays, and the cured coating film is further heat-cured to form an insulating coating having a desired pattern.
プリント配線板の絶縁被覆の製造に用いる、インクジェット用の硬化性樹脂組成物として、例えば、ビスアリルナジイミド化合物と、所定の化学構造を有するビスマレイミド化合物と、希釈剤と、ラジカル重合開始剤と、を含有し、粘度が２５℃で１５０ｍＰａ・ｓ以下である硬化性樹脂組成物が提案されている（特許文献１）。特許文献１では、耐熱性、耐薬品性、無電解金めっき耐性に優れるインクジェット用硬化性樹脂組成物を得ることを主眼としている。 Examples of the curable resin composition for inkjet used for producing an insulating coating of a printed wiring board include a bisallyl nadiimide compound, a bismaleimide compound having a predetermined chemical structure, a diluent, and a radical polymerization initiator. , And a curable resin composition having a viscosity of 150 mPa · s or less at 25 ° C. has been proposed (Patent Document 1). Patent Document 1 focuses on obtaining a curable resin composition for inkjet, which is excellent in heat resistance, chemical resistance, and electroless gold plating resistance.
一方で、プリント配線板には発熱素子が搭載されることがあるので、絶縁被覆を形成する感光性樹脂組成物の硬化塗膜には、耐熱性等だけではなく、難燃性も要求されることがある。難燃性を有する感光性樹脂組成物を、インクジェット法を用いて安定的に吐出するには、粒子径の細かい難燃剤を感光性樹脂組成物に配合する必要があった。そこで、インクジェット法を用いて感光性樹脂組成物を塗工するために、粉体状の難燃剤を粉砕処理して細粒化したものを感光性樹脂組成物に配合することが行われることがある。 On the other hand, since a heat generating element may be mounted on the printed wiring board, the cured coating film of the photosensitive resin composition forming the insulating coating is required to have not only heat resistance but also flame retardancy. Sometimes. In order to stably eject the flame-retardant photosensitive resin composition by using the inkjet method, it is necessary to add a flame retardant having a fine particle size to the photosensitive resin composition. Therefore, in order to apply the photosensitive resin composition by using the inkjet method, it is possible to add a powdery flame retardant pulverized to be finely divided into the photosensitive resin composition. be.
しかし、粉砕処理した粉体状の難燃剤を用いても、インクジェット法を用いて難燃性を有する感光性樹脂組成物を安定的に吐出する点で、改善の余地があった。また、インクジェット法を用いて難燃性を有する感光性樹脂組成物を安定的に吐出するために、液体状の難燃剤を配合すると、硬化塗膜が所望のパターンから染み出してしまうことがあり、硬化塗膜の耐ブリード性に問題が生じる場合があった。 However, even if a powdered flame retardant that has been pulverized is used, there is room for improvement in that a photosensitive resin composition having flame retardancy is stably discharged by using an inkjet method. Further, if a liquid flame retardant is blended in order to stably discharge the flame-retardant photosensitive resin composition by using the inkjet method, the cured coating film may exude from a desired pattern. In some cases, there may be a problem with the bleed resistance of the cured coating film.
また、絶縁被覆を形成する感光性樹脂組成物の硬化塗膜には、上記の通り、耐熱性も要求されることがある。難燃剤を感光性樹脂組成物に配合しても、耐熱性は得られず、また、耐熱性を付与するために、フィラー等の添加剤を配合すると、インクジェット法を用いて安定的に吐出することができなくなるという問題があった。 Further, as described above, the cured coating film of the photosensitive resin composition forming the insulating coating may be required to have heat resistance. Even if the flame retardant is blended in the photosensitive resin composition, heat resistance cannot be obtained, and if an additive such as a filler is blended in order to impart heat resistance, stable ejection is performed using the inkjet method. There was a problem that it could not be done.
上記事情に鑑み、本発明は、インクジェット法での吐出性に優れ、また、耐ブリード性、耐熱性及び難燃性に優れた硬化物を形成することができる感光性樹脂組成物を提供することを目的とする。 In view of the above circumstances, the present invention provides a photosensitive resin composition capable of forming a cured product having excellent ejection properties by an inkjet method and excellent bleed resistance, heat resistance and flame retardancy. With the goal.
本発明の構成の要旨は、以下の通りである。
［１］（Ａ）ビスアリルナジイミド化合物と、（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物と、（Ｃ）リン系難燃剤と、（Ｄ）光重合開始剤と、を含む感光性樹脂組成物であり、
前記（Ｃ）リン系難燃剤が、２５℃の前記（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、１０質量部以上溶解する溶解度を有する感光性樹脂組成物。
［２］前記（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物が、（メタ）アクリレート化合物である［１］に記載の感光性樹脂組成物。
［３］前記（Ａ）ビスアリルナジイミド化合物が、前記（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、５．０質量部以上５０質量部以下含まれる［１］または［２］に記載の感光性樹脂組成物。
［４］前記（Ａ）ビスアリルナジイミド化合物が、前記（Ｃ）リン系難燃剤１００質量部に対して、２５質量部以上１００質量部以下含まれる［１］乃至［３］のいずれか１つに記載の感光性樹脂組成物。
［５］前記（Ａ）ビスアリルナジイミド化合物が、下記一般式（１）
［６］前記（Ｃ）リン系難燃剤が、（メタ）アクリロイルメチルジフェニルフォスフィンオキサイド、ジフェニル（ビニル）ホスファン＝オキシド及びホスファフェナントレン骨格を有する化合物からなる群から選択された少なくとも１種である［１］乃至［５］のいずれか１つに記載の感光性樹脂組成物。
［７］さらに、重量平均分子量が５００以上の（メタ）アクリル系樹脂を含む［１］乃至［６］のいずれか１つに記載の感光性樹脂組成物。
［８］インクジェット用である［１］乃至［７］のいずれか１つに記載の感光性樹脂組成物。
［９］［１］乃至［８］のいずれか１つに記載の感光性樹脂組成物の硬化物。
［１０］［９］に記載の硬化物を備えたプリント配線板。
The gist of the structure of the present invention is as follows.
[1] (A) bisallyl nadiimide compound, (B) (meth) acrylic compound having a weight average molecular weight of less than 500, (C) phosphorus-based flame retardant, and (D) photopolymerization initiator. It is a photosensitive resin composition containing
A photosensitive resin composition having a solubility of 10 parts by mass or more of the (C) phosphorus-based flame retardant in 100 parts by mass of the (meth) acrylic compound having a weight average molecular weight of less than 500 at 25 ° C. thing.
[2] The photosensitive resin composition according to [1], wherein the (meth) acrylic compound having a weight average molecular weight of less than 500 is the (meth) acrylate compound.
[3] The (A) bisallyl nadiimide compound is contained in an amount of 5.0 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic compound having the (B) weight average molecular weight of less than 500. The photosensitive resin composition according to [1] or [2].
[4] Any one of [1] to [3], wherein the (A) bisallyl nadiimide compound is contained in an amount of 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the phosphorus-based flame retardant (C). The photosensitive resin composition according to 1.
[5] The bisallyl nadiimide compound (A) has the following general formula (1).
[6] The (C) phosphorus-based flame retardant is at least one selected from the group consisting of (meth) acryloylmethyldiphenylphosphine oxide, diphenyl (vinyl) phosphine-oxide, and a compound having a phosphaphenanthrene skeleton. The photosensitive resin composition according to any one of [1] to [5].
[7] The photosensitive resin composition according to any one of [1] to [6], further comprising a (meth) acrylic resin having a weight average molecular weight of 500 or more.
[8] The photosensitive resin composition according to any one of [1] to [7] for inkjet.
[9] The cured product of the photosensitive resin composition according to any one of [1] to [8].
[10] A printed wiring board provided with the cured product according to [9].
上記［１］の態様では、（Ｃ）リン系難燃剤が２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して１０質量部以上溶解する特性を有しているので、（Ｃ）リン系難燃剤は、感光性樹脂組成物の成分である（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物に対して溶解しやすい特性を有している。 In the above aspect [1], the (C) phosphorus-based flame retardant has a property of dissolving 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic compound having a (B) weight average molecular weight of less than 500 at 25 ° C. Therefore, the (C) phosphorus-based flame retardant has the property of being easily dissolved in (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, which is a component of the photosensitive resin composition. There is.
本発明の感光性樹脂組成物の態様によれば、（Ａ）ビスアリルナジイミド化合物と、（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物と、（Ｃ）リン系難燃剤と、（Ｄ）光重合開始剤と、を含む感光性樹脂組成物であり、（Ｃ）リン系難燃剤が、２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して１０質量部以上溶解する溶解度を有することにより、インクジェット法での吐出性に優れ、また、耐ブリード性、耐熱性及び難燃性に優れた硬化物を形成することができる感光性樹脂組成物を得ることができる。 According to the aspect of the photosensitive resin composition of the present invention, (A) a bisallyl nadiimide compound, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, and (C) a phosphorus flame retardant. , (D) A photosensitive resin composition containing a photopolymerization initiator, wherein (C) a phosphorus-based flame retardant is (B) 100 mass of a (meth) acrylic compound having a weight average molecular weight of less than 500 at 25 ° C. By having a solubility of 10 parts by mass or more in parts, it is possible to form a cured product having excellent ejection properties by the inkjet method and excellent bleeding resistance, heat resistance and flame retardancy. A resin composition can be obtained.
本発明の感光性樹脂組成物の態様によれば、（Ａ）ビスアリルナジイミド化合物が、（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して５．０質量部以上５０質量部以下含まれることにより、インクジェット法での吐出性と耐ブリード性を有しつつ、耐熱性と難燃性を確実に向上させることができる。 According to the aspect of the photosensitive resin composition of the present invention, the (A) bisallyl nadiimide compound is 5.0% by mass with respect to 100 parts by mass of the (meth) acrylic compound having a weight average molecular weight of less than 500. By containing 50 parts by mass or more, heat resistance and flame retardancy can be reliably improved while having ejection property and bleeding resistance in the inkjet method.
本発明の感光性樹脂組成物の態様によれば、（Ａ）ビスアリルナジイミド化合物が、（Ｃ）リン系難燃剤１００質量部に対して２５質量部以上１００質量部以下含まれることにより、インクジェット法での吐出性、耐ブリード性、耐熱性及び難燃性を、バランスよく向上させることができる。 According to the aspect of the photosensitive resin composition of the present invention, the (A) bisallyl nadiimide compound is contained in an amount of 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the (C) phosphorus-based flame retardant. It is possible to improve the ejection property, bleeding resistance, heat resistance and flame retardancy in the inkjet method in a well-balanced manner.
本発明の感光性樹脂組成物の態様によれば、（Ｃ）リン系難燃剤が、（メタ）アクリロイルメチルジフェニルフォスフィンオキサイド、ジフェニル（ビニル）ホスファン＝オキシド及びホスファフェナントレン骨格を有する化合物からなる群から選択された少なくとも１種であることにより、耐ブリード性にさらに優れた硬化物を得ることができる。 According to the aspect of the photosensitive resin composition of the present invention, the (C) phosphorus-based flame retardant comprises a compound having a (meth) acryloylmethyldiphenylphosphine oxide, a diphenyl (vinyl) phosphine-oxide and a phosphaphenanthrene skeleton. By using at least one selected from the group, a cured product having further excellent bleed resistance can be obtained.
本発明の感光性樹脂組成物の態様によれば、さらに、重量平均分子量が５００以上の（メタ）アクリル系樹脂を含むことにより、光硬化性をさらに向上させることができる。 According to the aspect of the photosensitive resin composition of the present invention, the photocurability can be further improved by further containing a (meth) acrylic resin having a weight average molecular weight of 500 or more.
次に、本発明の感光性樹脂組成物の詳細について、以下に説明する。本発明の感光性樹脂組成物は、（Ａ）ビスアリルナジイミド化合物と、（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物と、（Ｃ）リン系難燃剤と、（Ｄ）光重合開始剤と、を含む感光性樹脂組成物であり、前記（Ｃ）リン系難燃剤が、２５℃の前記（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、１０質量部以上溶解する溶解度を有する。 Next, the details of the photosensitive resin composition of the present invention will be described below. The photosensitive resin composition of the present invention comprises (A) a bisallyl nadiimide compound, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, (C) a phosphorus-based flame retardant, and (D). A photosensitive resin composition containing a photopolymerization initiator, wherein the (C) phosphorus-based flame retardant is added to 100 parts by mass of the (meth) acrylic compound having a weight average molecular weight of less than 500 at 25 ° C. On the other hand, it has a solubility of 10 parts by mass or more.
＜（Ａ）ビスアリルナジイミド化合物＞
本発明の感光性樹脂組成物では、ビスアリルナジイミド化合物が、後述する所定の（Ｃ）リン系難燃剤と併用されることで、インクジェット法での吐出性に優れ、また、耐ブリード性、耐熱性及び難燃性に優れた硬化物を形成することができる。
<(A) Bisallyl nadiimide compound>
In the photosensitive resin composition of the present invention, when the bisallyl nadiimide compound is used in combination with a predetermined (C) phosphorus-based flame retardant described later, it is excellent in ejection property by an inkjet method and has bleed resistance. A cured product having excellent heat resistance and flame retardancy can be formed.
ビスアリルナジイミド化合物としては、例えば、下記一般式（１）
上記ビスアリルナジイミド化合物としては、例えば、ＢＡＮＩ−Ｍ（Ｒ１がフェニレン基−Ｒ４−フェニレン基であり、Ｒ４がメチレン基）、ＢＡＮＩ−Ｘ（Ｒ１がＲ２−フェニレン基−Ｒ３であり、Ｒ２、Ｒ３が、メチレン基）（いずれも、丸善石油化学株式会社）が挙げられる。これらのビスアリルナジイミド化合物は、単独で使用してもよく、２種以上を併用してもよい。 Examples of the bisallyl nadiimide compound include BANI-M (R 1 is a phenylene group-R 4 -phenylene group and R 4 is a methylene group) and BANI-X (R 1 is an R 2 -phenylene group-R). 3 and R 2 and R 3 are methylene groups) (both are Maruzen Petrochemical Co., Ltd.). These bisallyl nadiimide compounds may be used alone or in combination of two or more.
ビスアリルナジイミド化合物の配合量は、特に限定されないが、その下限値は、後述する（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、耐熱性と難燃性を確実に向上させる点から、５．０質量部が好ましく、１０．０質量部がより好ましく、１２．５質量部が特に好ましい。一方で、ビスアリルナジイミド化合物の配合量の上限値は、（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、インクジェット法での吐出性と耐ブリード性を確実に得る点から、５０質量部が好ましく、３５質量部がより好ましく、２０質量部が特に好ましい。 The blending amount of the bisallyl nadiimide compound is not particularly limited, but the lower limit thereof is heat resistance and flame retardancy with respect to 100 parts by mass of the (meth) acrylic compound having (B) a weight average molecular weight of less than 500, which will be described later. From the viewpoint of surely improving the properties, 5.0 parts by mass is preferable, 10.0 parts by mass is more preferable, and 12.5 parts by mass is particularly preferable. On the other hand, the upper limit of the blending amount of the bisallyl nadiimide compound is (B) 100 parts by mass of the (meth) acrylic compound having a weight average molecular weight of less than 500, and the ejection property and bleed resistance by the inkjet method. From the viewpoint of reliable acquisition, 50 parts by mass is preferable, 35 parts by mass is more preferable, and 20 parts by mass is particularly preferable.
また、（Ｃ）リン系難燃剤に対するビスアリルナジイミド化合物の配合量は、特に限定されないが、その下限値は、（Ｃ）リン系難燃剤リン系難燃剤１００質量部に対して、耐熱性と難燃性を確実に向上させる点から２５質量部が好ましく、３５質量部がより好ましく、４０質量部が特に好ましい。一方で、（Ｃ）リン系難燃剤に対するビスアリルナジイミド化合物の配合量の上限値は、（Ｃ）リン系難燃剤１００質量部に対して、インクジェット法での吐出性と耐ブリード性の低下を確実に防止する点から、１００質量部が好ましく、８０質量部がより好ましく、６０質量部が特に好ましい。 The amount of the bisallyl nadiimide compound to be added to the (C) phosphorus-based flame retardant is not particularly limited, but the lower limit thereof is heat resistance to 100 parts by mass of the (C) phosphorus-based flame retardant phosphorus-based flame retardant. From the viewpoint of surely improving the flame retardancy, 25 parts by mass is preferable, 35 parts by mass is more preferable, and 40 parts by mass is particularly preferable. On the other hand, the upper limit of the blending amount of the bisallyl nadiimide compound with respect to the (C) phosphorus-based flame retardant is a decrease in ejection property and bleed resistance by the inkjet method with respect to 100 parts by mass of the (C) phosphorus-based flame retardant. From the viewpoint of reliably preventing the above, 100 parts by mass is preferable, 80 parts by mass is more preferable, and 60 parts by mass is particularly preferable.
なお、本発明の感光性樹脂組成物では、耐熱性を付与するために、ビスアリルナジイミド化合物以外のイミド化合物を配合する必要はない。 In the photosensitive resin composition of the present invention, it is not necessary to add an imide compound other than the bisallyl nadiimide compound in order to impart heat resistance.
＜（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物＞
重量平均分子量（Ｍｗ）が５００未満の（メタ）アクリル系化合物（以下、「（メタ）アクリル系化合物（Ｂ）」ということがある。）は、重量平均分子量が５００未満の（メタ）アクリル系化合物であれば、化学構造は特に限定されない。（メタ）アクリル系化合物（Ｂ）としては、例えば、単官能の（メタ）アクリレートモノマー、２官能以上の（メタ）アクリレートモノマー等の（メタ）アクリレート化合物を挙げることができる。本発明の感光性樹脂組成物に（メタ）アクリル系化合物（Ｂ）が配合されることで、後述する所定の（Ｃ）リン系難燃剤の所定量が（メタ）アクリル系化合物（Ｂ）に溶解するので、インクジェット法での吐出性に優れた感光性樹脂組成物を得ることができ、また、感光性樹脂組成物の難燃性を向上させることができる。さらに、（メタ）アクリル系化合物（Ｂ）が配合されることで、感光性樹脂組成物の２５℃における粘度が低下するので、非反応性希釈剤（例えば、有機溶剤）を配合しなくても、インクジェット用として使用することが可能となる。
<(B) (Meta) acrylic compound having a weight average molecular weight of less than 500>
A (meth) acrylic compound having a weight average molecular weight (Mw) of less than 500 (hereinafter, may be referred to as “(meth) acrylic compound (B)”) is a (meth) acrylic compound having a weight average molecular weight of less than 500. If it is a compound, its chemical structure is not particularly limited. Examples of the (meth) acrylic compound (B) include (meth) acrylate compounds such as a monofunctional (meth) acrylate monomer and a bifunctional or higher (meth) acrylate monomer. By blending the (meth) acrylic compound (B) with the photosensitive resin composition of the present invention, a predetermined amount of the predetermined (C) phosphorus-based flame retardant described later becomes the (meth) acrylic compound (B). Since it dissolves, it is possible to obtain a photosensitive resin composition having excellent ejection properties by the inkjet method, and it is possible to improve the flame retardancy of the photosensitive resin composition. Further, since the viscosity of the photosensitive resin composition at 25 ° C. is lowered by blending the (meth) acrylic compound (B), it is not necessary to blend a non-reactive diluent (for example, an organic solvent). , Can be used for inkjet.
（メタ）アクリル系化合物（Ｂ）の２５℃における粘度は、特に限定されないが、インクジェット法での吐出性がさらに向上しつつ、より優れた耐ブリード性を得る点から、１．０ｍＰａ・ｓ以上５０ｍＰａ・ｓ以下が好ましく、２．０ｍＰａ・ｓ以上３０ｍＰａ・ｓ以下が特に好ましい。 The viscosity of the (meth) acrylic compound (B) at 25 ° C. is not particularly limited, but is 1.0 mPa · s or more from the viewpoint of obtaining more excellent bleed resistance while further improving the ejection property by the inkjet method. 50 mPa · s or less is preferable, and 2.0 mPa · s or more and 30 mPa · s or less is particularly preferable.
（メタ）アクリル系化合物（Ｂ）としては、例えば、ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェノール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリルレート、イソシアヌル（メタ）アクリレート等の単官能（メタ）アクリレート化合物、１，４‐ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、エチレンオキサイド変性燐酸ジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレート等の２官能（メタ）アクリレート化合物、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の３官能以上の（メタ）アクリレート化合物を挙げることができる。これらは、単独で使用してもよく、２種以上を併用してもよい。 Examples of the (meth) acrylic compound (B) include benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenol (meth) acrylate, phenoxyethyl (meth) acrylate, and diethylene glycol mono (). Monofunctional (meth) acrylate compounds such as meta) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylicate, isocyanul (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Didiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Bifunctional (meth) acrylate compounds such as ethylene oxide-modified di (meth) acrylate, cyclohexyl allylated di (meth) acrylate, and isocyanurate di (meth) acrylate, trimethyl propantri (meth) acrylate, ditrimethylol propanetetra ( Examples thereof include trifunctional or higher functional (meth) acrylate compounds such as meta) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.
（Ｃ）リン系難燃剤
リン系難燃剤が感光性樹脂組成物に配合されることで、感光性樹脂組成物の難燃性向上に寄与する。リン系難燃剤としては、２５℃の（メタ）アクリル系化合物（Ｂ）１００質量部に対して、１０質量部以上溶解する溶解度を有するリン系難燃剤（溶解性リン系難燃剤）が使用される。２５℃の（メタ）アクリル系化合物（Ｂ）１００質量部に対して上記溶解度を有するリン系難燃剤であれば、感光性樹脂組成物に配合される前の状態は、固体状でもよく、液体状でもよい。２５℃の（メタ）アクリル系化合物（Ｂ）１００質量部に対して１０質量部以上溶解するリン系難燃剤は、所定割合以上のリン系難燃剤が（メタ）アクリル系化合物（Ｂ）に溶解することから、インクジェット法での吐出性を損なうことがなく、また、感光性樹脂組成物の難燃性向上に寄与できる。
(C) Phosphorus-based flame retardant By blending the phosphorus-based flame retardant into the photosensitive resin composition, it contributes to the improvement of the flame retardancy of the photosensitive resin composition. As the phosphorus-based flame retardant, a phosphorus-based flame retardant (soluble phosphorus-based flame retardant) having a solubility of 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ° C. is used. NS. As long as it is a phosphorus-based flame retardant having the above solubility with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ° C., the state before being blended in the photosensitive resin composition may be solid or liquid. It may be in the form. A phosphorus-based flame retardant that dissolves 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ° C. has a predetermined ratio or more of the phosphorus-based flame retardant dissolved in the (meth) acrylic compound (B). Therefore, the ejection property of the inkjet method is not impaired, and the flame retardancy of the photosensitive resin composition can be improved.
リン系難燃剤の２５℃の（メタ）アクリル系化合物（Ｂ）１００質量部に対する溶解度は１０質量部以上であれば、特に限定されないが、インクジェット法での吐出性をさらに向上させる点から１５質量部以上が好ましく、２０質量部以上が特に好ましい。一方で、リン系難燃剤の２５℃の（メタ）アクリル系化合物（Ｂ）１００質量部に対する溶解度の上限値は、高ければ高いほど好ましいが、例えば、５０質量部が挙げられる。従って、Ｃ成分のリン系難燃剤は、粉体等の固体の場合には、感光性樹脂組成物中において、一部は溶解し、他の一部は粉体等の固体のまま混合されている場合がある。 The solubility of the phosphorus flame retardant in 100 parts by mass of the (meth) acrylic compound (B) at 25 ° C. is not particularly limited as long as it is 10 parts by mass or more, but 15 mass by mass from the viewpoint of further improving the ejection property by the inkjet method. 20 parts or more is preferable, and 20 parts by mass or more is particularly preferable. On the other hand, the higher the upper limit of the solubility of the phosphorus-based flame retardant with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ° C. is preferably, for example, 50 parts by mass. Therefore, in the case of a solid such as powder, the phosphorus-based flame retardant of the C component is partially dissolved in the photosensitive resin composition and the other part is mixed as a solid such as powder. May be present.
２５℃の（メタ）アクリル系化合物（Ｂ）１００質量部に対して１０質量部以上溶解するリン系難燃剤の具体例としては、（メタ）アクリロイルメチルジフェニルフォスフィンオキサイド、２−（３，４−エポキシシクロヘキシル）エチルジフェニルフォスフィンオキサイド等のフォスフィンオキサイド類、１０−（３−グリシジルオキシプロピル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、１０−［２−（３，４−エポキシシクロヘキシル）エチル］−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、９，１０−ジヒドロ−９−オキサ−１０−ビニル−１０−ホスファフェナントレン−１０−オキシロ、１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、１０−（アクリロイルオキシメチル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド等の（メタ）アクリロイル基を有する１０−オキソ−９−オキサ−１０−ホスファフェナントレン骨格を有する化合物などのホスファフェナントレン骨格を有する化合物、ホスファゼン化合物、フェニルビニルホスフィン酸、ジフェニル（ビニル）ホスファン＝オキシド等を挙げることができる。 Specific examples of the phosphorus-based flame retardant that dissolves 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ° C. include (meth) acryloylmethyldiphenylphosphine oxide, 2- (3,4). -Epoxycyclohexyl) Phosphine oxides such as ethyldiphenylphosphine oxide, 10- (3-glycidyloxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- [2 -(3,4-Epoxycyclohexyl) ethyl] -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-vinyl-10-phospha Phenanthrene-10-oxylo, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (acryloyloxymethyl) -9,10-dihydro Compounds having a phosphaphenanthrene skeleton, such as compounds having a (meth) acryloyl group such as -9-oxa-10-phosphaphenanthrene-10-oxide, and compounds having a 10-oxo-9-oxa-10-phosphaphenanthrene skeleton, Examples thereof include phosphazenic compounds, phenylvinylphosphinic acid, diphenyl (vinyl) phosphane = oxide and the like.
これらは、単独で使用してもよく、２種以上を併用してもよい。これらのうち、耐ブリード性にさらに優れた硬化物を得ることができる点から、（メタ）アクリロイルメチルジフェニルフォスフィンオキサイド、ジフェニル（ビニル）ホスファン＝オキシド及び（メタ）アクリロイル基を有する１０−オキソ−９−オキサ−１０−ホスファフェナントレン骨格を有する化合物が好ましい。 These may be used alone or in combination of two or more. Of these, 10-oxo-having (meth) acryloylmethyldiphenylphosphine oxide, diphenyl (vinyl) phosphine-oxide, and (meth) acryloyl group can be obtained from the viewpoint that a cured product having more excellent bleed resistance can be obtained. Compounds having a 9-oxa-10-phosphaphenanthrene skeleton are preferred.
リン系難燃剤の含有量は、特に限定されないが、その下限値は、感光性樹脂組成物に確実に難燃性を付与する点から、（メタ）アクリル系化合物（Ｂ）１００質量部に対して、５．０質量部が好ましく、１０質量部がより好ましく、２０質量部が特に好ましい。一方で、リン系難燃剤の含有量の上限値は、インクジェット法での吐出性と耐ブリード性の低下を確実に防止する点から、（メタ）アクリル系化合物（Ｂ）１００質量部に対して、６０質量部が好ましく、５０質量部がより好ましく、４０質量部が特に好ましい。 The content of the phosphorus-based flame retardant is not particularly limited, but the lower limit thereof is relative to 100 parts by mass of the (meth) acrylic compound (B) from the viewpoint of surely imparting flame retardancy to the photosensitive resin composition. Therefore, 5.0 parts by mass is preferable, 10 parts by mass is more preferable, and 20 parts by mass is particularly preferable. On the other hand, the upper limit of the content of the phosphorus-based flame retardant is set with respect to 100 parts by mass of the (meth) acrylic compound (B) from the viewpoint of surely preventing deterioration of ejection property and bleed resistance in the inkjet method. , 60 parts by mass is preferable, 50 parts by mass is more preferable, and 40 parts by mass is particularly preferable.
（Ｄ）光重合開始剤
光重合開始剤は、特に限定されず、公知のものを適宜使用することができる。光重合開始剤としては、例えば、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキシド、２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキシド、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２−メチル−４’−（メチルチオ）−２−モルフォリノプロピオフェノン、２−ベンジル−２−ジメチルアミノ−１−(４−モルフォリノフェニル）−ブタノン−１、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、４−（２−ヒドロキシエトキシ）フェニル−２−（ヒドロキシ−２−プロピル）ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４，４′−ビス（ジエチルアミノ）ベンゾフェノン、ジクロルベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリーブチルアントラキノン、２−アミノアントラキノン、２−メチルチオキサントン、２−エチルチオキサントン、２−クロルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、Ｐ−ジメチルアミノ安息香酸エチルエステル等が挙げられる。これらは単独で使用してもよく、２種以上を併用してもよい。
(D) Photopolymerization Initiator The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be appropriately used. Examples of the photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin. Isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-methyl-4'-(methylthio) ) -2-Molphorinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, Benzophenone, p-Phenylbenzophenone, 4,4'-bis (diethylamino) benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary butyl anthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2 -Ethylthioxanthone, 2-chlorthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenonedimethylketal, P-dimethylaminobenzoic acid ethyl ester and the like can be mentioned. These may be used alone or in combination of two or more.
光重合開始剤の含有量は、特に限定されないが、（メタ）アクリル系化合物（Ｂ）１００質量部に対して、３．０質量部以上３０質量部以下が好ましく、５．０質量部以上１５質量部以下が特に好ましい。 The content of the photopolymerization initiator is not particularly limited, but is preferably 3.0 parts by mass or more and 30 parts by mass or less, and 5.0 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic compound (B). More than parts by mass is particularly preferable.
本発明の感光性樹脂組成物では、上記（Ａ）成分〜（Ｄ）成分に加えて、必要に応じて、さらに、重量平均分子量が５００以上の（メタ）アクリル系樹脂を配合してもよい。重量平均分子量が５００以上の（メタ）アクリル系樹脂を配合することで、光硬化性をさらに向上させることができる。 In the photosensitive resin composition of the present invention, in addition to the above components (A) to (D), a (meth) acrylic resin having a weight average molecular weight of 500 or more may be further blended, if necessary. .. By blending a (meth) acrylic resin having a weight average molecular weight of 500 or more, the photocurability can be further improved.
重量平均分子量が５００以上の（メタ）アクリル系樹脂（以下、単に、「（メタ）アクリル系樹脂）」ということがある。）は、重量平均分子量が５００以上の（メタ）アクリル系樹脂であれば、化学構造は特に限定されない。なお、本明細書において「重量平均分子量」とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、常温で測定し、ポリスチレン換算にて算出される重量平均分子量を意味する。 A (meth) acrylic resin having a weight average molecular weight of 500 or more (hereinafter, simply referred to as “(meth) acrylic resin”). ) Is a (meth) acrylic resin having a weight average molecular weight of 500 or more, and the chemical structure is not particularly limited. In the present specification, the "weight average molecular weight" means a weight average molecular weight measured at room temperature using gel permeation chromatography (GPC) and calculated in terms of polystyrene.
（メタ）アクリル系樹脂としては、例えば、（メタ）アクリル酸を含むモノマーの重合体、（メタ）アクリレートを含むモノマーの重合体、（メタ）アクリル酸と（メタ）アクリレートを含むモノマーの重合体、エポキシ樹脂に（メタ）アクリル酸を反応させて得ることができるエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等を挙げることができる。このうち、インクジェット法での吐出性がさらに向上し、また、耐ブリード性にさらに優れた硬化物を得ることができる点から、（メタ）アクリレート化合物が好ましく、エポキシ（メタ）アクリレートが特に好ましい。 Examples of the (meth) acrylic resin include a polymer of a monomer containing (meth) acrylic acid, a polymer of a monomer containing (meth) acrylate, and a polymer of a monomer containing (meth) acrylic acid and (meth) acrylate. , Epoxy (meth) acrylate, urethane (meth) acrylate, etc., which can be obtained by reacting an epoxy resin with (meth) acrylic acid. Of these, a (meth) acrylate compound is preferable, and an epoxy (meth) acrylate is particularly preferable, from the viewpoint that the ejection property of the inkjet method is further improved and a cured product having further excellent bleed resistance can be obtained.
エポキシ（メタ）アクリレートは、１分子中にエポキシ基を１個以上有するエポキシ樹脂のエポキシ基の少なくとも一部に、（メタ）アクリル酸を反応させることで得ることができる。エポキシ樹脂は、特に限定されないが、例えば、ビフェニルアラルキル型エポキシ樹脂、フェニルアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、シリコーン変性エポキシ樹脂等のゴム変性エポキシ樹脂、ε−カプロラクトン変性エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、環状脂肪族多官能エポキシ樹脂、グリシジルエステル型多官能エポキシ樹脂、グリシジルアミン型多官能エポキシ樹脂、複素環式多官能エポキシ樹脂、ビスフェノール変性ノボラック型エポキシ樹脂、多官能変性ノボラック型エポキシ樹脂等を挙げることができる。上記から、（メタ）アクリル系樹脂であるエポキシ（メタ）アクリレートは、遊離のカルボキシル基を有していない。 Epoxy (meth) acrylate can be obtained by reacting (meth) acrylic acid with at least a part of the epoxy groups of an epoxy resin having one or more epoxy groups in one molecule. The epoxy resin is not particularly limited, and is, for example, a rubber-modified epoxy resin such as a biphenyl aralkyl type epoxy resin, a phenyl aralkyl type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a silicone-modified epoxy resin. , Ε-caprolactone modified epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidyl amine Examples thereof include a type polyfunctional epoxy resin, a heterocyclic polyfunctional epoxy resin, a bisphenol-modified novolac type epoxy resin, and a polyfunctional modified novolac type epoxy resin. From the above, the epoxy (meth) acrylate, which is a (meth) acrylic resin, does not have a free carboxyl group.
（メタ）アクリル系樹脂の重量平均分子量は、５００以上であれば、特に限定されないが、インクジェット法における吐出性をより向上させる点から、５５０以上が好ましく、１０００以上が特に好ましい。一方で、（メタ）アクリル系樹脂の重量平均分子量の上限値は、感光性樹脂組成物の粘度の増大を確実に防止してインクジェット法でも優れた吐出性を得る点から５０００が好ましく、４０００が特に好ましい。 The weight average molecular weight of the (meth) acrylic resin is not particularly limited as long as it is 500 or more, but is preferably 550 or more, and particularly preferably 1000 or more, from the viewpoint of further improving the ejection property in the inkjet method. On the other hand, the upper limit of the weight average molecular weight of the (meth) acrylic resin is preferably 5000 from the viewpoint of surely preventing an increase in the viscosity of the photosensitive resin composition and obtaining excellent ejection properties even by the inkjet method, preferably 4000. Especially preferable.
また、本発明の感光性樹脂組成物では、上記（Ａ）成分〜（Ｄ）成分に加えて、必要に応じて、他の成分、例えば、着色剤、各種添加剤、非反応性希釈剤等を配合することができる。 Further, in the photosensitive resin composition of the present invention, in addition to the above-mentioned components (A) to (D), other components such as a colorant, various additives, a non-reactive diluent and the like are required. Can be blended.
着色剤は、顔料、色素等、特に限定されない。また、着色剤は、感光性樹脂組成物の硬化物に付与する所望の色彩に応じて、適宜選択可能であり、白色着色剤、青色着色剤、緑色着色剤、黄色着色剤、紫色着色剤、黒色着色剤等、いずれの色彩も使用可能である。上記着色剤には、例えば、白色着色剤である酸化チタン、黒色着色剤であるカーボンブラック等の無機系着色剤や、緑色着色剤であるフタロシアニングリーン及び青色着色剤であるフタロシアニンブルーやリオノールブルー等のフタロシアニン系、黄色着色剤であるクロモフタルイエロー等のクロモフタル系、アントラキノン系等の有機系着色剤などを挙げることができる。 The colorant is not particularly limited, such as a pigment and a pigment. Further, the colorant can be appropriately selected according to the desired color to be applied to the cured product of the photosensitive resin composition, and is a white colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, Any color such as a black colorant can be used. Examples of the colorant include inorganic colorants such as titanium oxide which is a white colorant and carbon black which is a black colorant, phthalocyanine green which is a green colorant, and phthalocyanine blue and lyonol blue which are blue colorants. Examples thereof include phthalocyanine-based colorants such as phthalocyanine-based, chromophthal-based colorants such as chromophthal-yellow which is a yellow colorant, and organic-based colorants such as anthraquinone-based.
各種添加剤には、例えば、シリコーン系、炭化水素系及びアクリル系等の消泡剤、タルク、硫酸バリウム、アルミナ、水酸化アルミニウム、マイカ、シリカ等の無機フィラー、粉末ウレタン樹脂、（メタ）アクリルポリマー、ビニル系重合物、カルボキシル基含有ポリマー変性物、カルボン酸エステル等の有機フィラー、チキソ剤、酸化防止剤等が挙げられる。 Various additives include, for example, defoaming agents such as silicone-based, hydrocarbon-based and acrylic-based, inorganic fillers such as talc, barium sulfate, alumina, aluminum hydroxide, mica and silica, powdered urethane resin, and (meth) acrylic. Examples thereof include polymers, vinyl-based polymers, modified carboxyl group-containing polymers, organic fillers such as carboxylic acid esters, thixo agents, and antioxidants.
非反応性希釈剤は、必要に応じて、感光性樹脂組成物の、インクジェット法での吐出性、粘度、乾燥性を調節するために配合する。非反応性希釈剤として、例えば、有機溶剤を挙げることができる。有機溶剤には、例えば、メチルエチルケトン、シクロヘキサン等のケトン類、トルエン、キシレン等の芳香族炭化水素類、メタノール、イソプロパノール、シクロヘキサノール等のアルコール類、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類、セロソルブ、ブチルセロソルブ等のセロソルブ類、カルビトール、ブチルカルビトール等のカルビトール類、酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート等のエステル類等を挙げることができる。 The non-reactive diluent is blended, if necessary, to adjust the ejection property, viscosity, and drying property of the photosensitive resin composition by the inkjet method. Examples of the non-reactive diluent include organic solvents. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Examples thereof include esters such as acetate.
本発明の感光性樹脂組成物の製造方法は、特定の方法に限定されず、例えば、上記各成分を所定割合で配合後、室温にて、三本ロール、ボールミル、ビーズミル、サンドミル等の混練手段、またはスーパーミキサー、プラネタリーミキサー等の攪拌手段により混練または混合して製造することができる。また、前記混練または混合の前に、必要に応じて、予備混練または予備混合を行ってもよい。 The method for producing the photosensitive resin composition of the present invention is not limited to a specific method. , Or can be produced by kneading or mixing by a stirring means such as a super mixer or a planetary mixer. In addition, pre-kneading or pre-mixing may be performed before the kneading or mixing, if necessary.
次に、本発明の感光性樹脂組成物の使用方法例について説明する。本発明の感光性樹脂組成物は、例えば、インクジェット印刷法を用いて、基板（例えば、所定の回路パターンを有するプリント配線板）に絶縁被覆（例えば、ソルダーレジスト膜）を形成するために使用することができる。まず、本発明の感光性樹脂組成物をインクジェット法（例えば、ジェットディスペンサーを用いたインクジェット法）によりプリント配線板上に所望のパターンにて塗工する。塗工後、ＬＤＩ（Ｌａｓｅｒ Ｄｉｒｅｃｔ Ｉｍａｇｉｎｇ）を用いたレーザー直描、または紫外線等の活性エネルギー線により、塗工した塗膜を光硬化させる。なお、紫外線等の活性エネルギー線にて光硬化処理を行う場合には、照射光量は、例えば、１００〜２０００ｍＪ／ｃｍ２の範囲である。塗膜の光硬化処理後、１３０〜１７０℃の熱風循環式の乾燥機等で、２０〜８０分間、ポストキュア（熱硬化処理）を行うことにより、所望のパターンを有する硬化物として、ソルダーレジスト膜をプリント配線板に形成することができる。このように、本発明の感光性樹脂組成物では、塗工方法として、インクジェット印刷法を用いることができることから、フォトマスクを用いた現像工程が不要なので、絶縁被覆の形成工程が簡易であり、また、塗工デザインの自由度にも優れている。 Next, an example of how to use the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention is used, for example, to form an insulating coating (for example, a solder resist film) on a substrate (for example, a printed wiring board having a predetermined circuit pattern) by using an inkjet printing method. be able to. First, the photosensitive resin composition of the present invention is coated on a printed wiring board in a desired pattern by an inkjet method (for example, an inkjet method using a jet dispenser). After coating, the coated coating film is photocured by laser direct drawing using LDI (Laser Direct Imaging) or by active energy rays such as ultraviolet rays. When the photocuring treatment is performed with active energy rays such as ultraviolet rays, the amount of irradiation light is, for example, in the range of 100 to 2000 mJ / cm 2. After the photocuring treatment of the coating film, post-cure (thermosetting treatment) is performed for 20 to 80 minutes in a hot air circulation type dryer or the like at 130 to 170 ° C. to obtain a solder resist as a cured product having a desired pattern. A film can be formed on the printed wiring board. As described above, in the photosensitive resin composition of the present invention, since the inkjet printing method can be used as the coating method, the developing step using a photomask is unnecessary, so that the insulating coating forming step is simple. It also has excellent flexibility in coating design.
次に、本発明の実施例を説明するが、本発明はその趣旨を超えない限り、これらの例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
実施例１〜１２、比較例１〜３
下記表１、２に示す各成分を下記表１、２に示す配合割合にて配合し、ビーズミルを用いて室温にて混合分散させて、実施例１〜１２、比較例１〜３にて使用する感光性樹脂組成物を調製した。下記表１、２に示す各成分の配合量は、特に断りのない限り質量部を示す。なお、下記表１、２中の配合量の空欄部は、配合なしを意味する。
Examples 1-12, Comparative Examples 1-3
Each component shown in Tables 1 and 2 below was blended in the blending ratio shown in Tables 1 and 2 below, mixed and dispersed at room temperature using a bead mill, and used in Examples 1 to 12 and Comparative Examples 1 to 3. A photosensitive resin composition was prepared. Unless otherwise specified, the blending amount of each component shown in Tables 1 and 2 below is shown in parts by mass. In addition, the blank part of the blending amount in Tables 1 and 2 below means that there is no blending.
なお、表１、２中の各成分についての詳細は、以下の通りである。
（Ａ）ビスアリルナジイミド化合物
・ＢＡＮＩ−Ｍ：丸善石油化学株式会社
・ＢＡＮＩ−Ｘ：丸善石油化学株式会社
The details of each component in Tables 1 and 2 are as follows.
(A) Bisallyl nadiimide compound ・ BANI-M: Maruzen Petrochemical Co., Ltd. ・ BANI-X: Maruzen Petrochemical Co., Ltd.
（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物
・ピスコート♯１６０：大阪有機化学株式会社
・ライトエステル１．４ＢＧ：共栄社化学株式会社
・アロニックスＭ−２２０：東亞合成株式会社
・ＩＢＸＡ：大阪有機化学株式会社
・ピスコート♯１５０：大阪有機化学株式会社
・４ＨＢＡ：大阪有機化学株式会社
・Ｍ−３１３：東亞合成株式会社
(B) (Meta) acrylic compound with a weight average molecular weight of less than 500, Piscort # 160: Osaka Organic Chemical Co., Ltd., Light Ester 1.4BG: Kyoeisha Chemical Co., Ltd., Aronix M-220: Toa Synthetic Co., Ltd., IBXA: Osaka Organic Chemistry Co., Ltd. ・ Piscort # 150: Osaka Organic Chemistry Co., Ltd. ・ 4HBA: Osaka Organic Chemistry Co., Ltd. ・ M-313: Toa Synthetic Co., Ltd.
（Ｃ）リン系難燃剤（溶解性リン系難燃剤）
・ＭＣ−４：２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００ｇに対する溶解度１５ｇ、粉体、片山化学工業株式会社
・ＦＲＭ−１０００：下記式の（メタ）アクリロイル基を有する１０−オキソ−９−オキサ−１０−ホスファフェナントレン骨格を有する化合物（１０−（アクリロイルオキシメチル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド）であり、２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００ｇに対する溶解度（難相溶性となる量）約１００ｇ、高粘度液体、日本化薬株式会社
-MC-4: Solubility 15 g in 100 g of (meth) acrylic compound having (B) weight average molecular weight of less than 500 at 25 ° C, powder, Katayama Chemical Industry Co., Ltd.-FRM-1000: (meth) acryloyl group of the following formula It is a compound having a 10-oxo-9-oxa-10-phosphaphenanthrene skeleton (10- (acryloyloxymethyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). , (B) solubility in 100 g of (meth) acrylic compound having a weight average molecular weight of less than 500 at 25 ° C. (amount of in-phase solubility) of about 100 g, high-viscosity liquid, Nippon Kayaku Co., Ltd.
（Ｄ）光重合開始剤
・ＩＲＧＡＣＵＲＥ９０７：ＢＡＳＦジャパン株式会社
・ＬＵＣＩＲＩＮ ＴＰＯ：ＢＡＳＦジャパン株式会社
・Ｃｈｅｍｃｕｒｅ ＤＥＴＸ：Ｃｈｅｍｂｒｉｄｇｅ Ｉｎｔｅｒｎａｔｉｏｎａｌ社
(D) Photopolymerization Initiator, IRGACURE907: BASF Japan Ltd., LUCIRIN TPO: BASF Japan Ltd., Chemcure DETX: Chembridge International Inc.
重量平均分子量が５００以上の（メタ）アクリル系樹脂
・ＥＢＥＣＲＹＬ ３９０７：ダイセル・サイテック株式会社
着色剤
・リオノールブルーＦＧ−７３５１：トーヨーカラー株式会社
・クロモフタルイエローＡＧＲ：チバスペシャルティケミカルズ株式会社
添加剤
・ＢＹＫ−３６１Ｎ：ビックケミージャパン株式会社
(Meta) acrylic resin with a weight average molecular weight of 500 or more ・ EBECRYL 3907: Daicel Cytec Co., Ltd. Colorant ・ Lionol Blue FG-7351: Toyo Color Co., Ltd. ・ Chromophthal Yellow AGR: Ciba Specialty Chemicals Co., Ltd. Additive ・BYK-361N: Big Chemie Japan Co., Ltd.
２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して溶解度が１０質量部未満のリン系難燃剤（難溶性リン系難燃剤）
・ＯＰ−９３５：２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００ｇに対する溶解度０〜５ｇ、クラリアント社
A phosphorus-based flame retardant having a solubility of less than 10 parts by mass with respect to 100 parts by mass of a (meth) acrylic compound having a (B) weight average molecular weight of less than 500 at 25 ° C.
OP-935: solubility 0-5 g in 100 g of (meth) acrylic compound having a (B) weight average molecular weight of less than 500 at 25 ° C., Clariant AG
試験体作製工程
基板：銅張積層板（厚さ１．６ｍｍ）
表面処理：バフスクラブ研磨
印刷法：インクジェット印刷（インクジェット装置：「ＭＪＰ２０１３Ｆ１−ＤＵ」、Ｍｉｃｒｏｃｒａｆｔ社）
ＤＲＹ膜厚：２０〜２３μｍ
露光：塗膜上に１０００ｍＪ／ｃｍ２、アイグラフィックス株式会社「ＵＢ０９３−５ＡＭ」
ポストキュア：ＢＯＸ型乾燥炉 １５０℃、６０分
Specimen manufacturing process Substrate: Copper-clad laminate (thickness 1.6 mm)
Surface treatment: Buff scrub polishing Printing method: Inkjet printing (inkjet equipment: "MJP2013F1-DU", Microcraft)
DRY film thickness: 20-23 μm
Exposure: 1000mJ / cm 2 on the coating film, Eye Graphics Co., Ltd. "UB093-5AM"
Post-cure: BOX type drying oven 150 ° C, 60 minutes
評価項目
（１）吐出性
上記インクジェット装置を用いて、以下の基準で評価した。
◎：ノズルへの感光性樹脂組成物の詰まりがなく、吐出し、室温２４時間放置後もノズルへの感光性樹脂組成物の詰まりがなく、吐出した。
〇：ノズルへの感光性樹脂組成物の詰まりがなく、吐出し、室温２４時間放置後、若干感光性樹脂組成物がノズルに詰まる傾向があった。
×：感光性樹脂組成物がノズルに詰まり、吐出しない。
Evaluation items (1) Ejectability Using the above inkjet device, evaluation was performed according to the following criteria.
⊚: The photosensitive resin composition was not clogged in the nozzle and was discharged, and even after being left at room temperature for 24 hours, the nozzle was not clogged with the photosensitive resin composition and was discharged.
◯: The photosensitive resin composition was not clogged in the nozzle, and after being discharged and left at room temperature for 24 hours, the photosensitive resin composition tended to be slightly clogged in the nozzle.
X: The photosensitive resin composition is clogged in the nozzle and does not eject.
（２）耐ブリード性
上記試験体作製工程で作製した試験体を、１５０℃、３ＭＰａ、３００秒にてプレスを行った後の試験体からの染み出しの状況を、目視及び拡大鏡（３０倍）を用いて観察し、下記のように評価した。
◎：プレス後に拡大鏡で判別可能な染み出し無し
○：プレス後に拡大鏡で判別可能な染み出し有り
△：プレス後に目視で判別可能な染み出し有り
×：試験体作製後に染み出し有り
(2) Bleed resistance The state of exudation from the test piece after pressing the test piece prepared in the above test piece preparation step at 150 ° C., 3 MPa, and 300 seconds can be visually observed and magnified (30 times). ) Was observed and evaluated as follows.
⊚: No exudation that can be discerned by a magnifying glass after pressing ○: Exud that can be discriminated by a magnifying glass after pressing
（３）はんだ耐熱性
上記試験体作製工程で作製した試験体を２６０℃のはんだ槽に１０秒間浸漬させた後、塗膜の基板からの剥がれを目視で確認した。
〇：１回浸漬し、剥離がない
×：１回浸漬し、剥離がある
(3) Solder Heat Resistance After immersing the test piece prepared in the above test piece preparation step in a solder bath at 260 ° C. for 10 seconds, peeling of the coating film from the substrate was visually confirmed.
〇: Immersed once, no peeling ×: Immersed once, peeled
（４）難燃性
基板を銅張積層板から厚さ２５μｍのポリイミド基板に変更した以外は、上記試験体作製工程に準じて、両面にＤＲＹ膜厚が２０μｍになるよう塗布して硬化塗膜を形成後、ＵＬ９４ＶＴＭ相当の試験を行った。
◎：Ｎ＝１０を行い、その平均消火時間が４秒未満
〇：Ｎ＝１０を行い、その平均消火時間が４秒以上６秒未満
×：Ｎ＝１０を行い、その平均消火時間が６秒以上
(4) Except for changing the flame-retardant substrate from a copper-clad laminate to a polyimide substrate with a thickness of 25 μm, a cured coating film was applied to both sides so that the DRY film thickness was 20 μm according to the above-mentioned test piece manufacturing process. Was formed, and a test equivalent to UL94VTM was performed.
⊚: N = 10 and the average fire extinguishing time is less than 4 seconds 〇: N = 10 and the average fire extinguishing time is 4 seconds or more and less than 6 seconds ×: N = 10 and the average fire extinguishing time is 6 seconds that's all
評価結果を、下記表１、２に示す。 The evaluation results are shown in Tables 1 and 2 below.
上記表１に示すように、（Ａ）ビスアリルナジイミド化合物と、（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物と、２５℃の（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、１０質量部以上の溶解度を有する（Ｃ）リン系難燃剤と、（Ｄ）光重合開始剤と、を含む感光性樹脂組成物である実施例１〜１２では、インクジェット法での吐出性に優れ、また、耐ブリード性、耐熱性及び難燃性に優れた硬化塗膜を形成することができた。特に、（Ｃ）リン系難燃剤（溶解性リン系難燃剤）として、メタクリロイルメチルジフェニルフォスフィンオキサイド、上記式の（メタ）アクリロイル基を有する１０−オキソ−９−オキサ−１０−ホスファフェナントレン骨格を有する化合物を使用した実施例１〜４、６〜１２では、耐ブリード性がさらに向上した。また、実施例４、６から、上記式の（メタ）アクリロイル基を有する１０−オキソ−９−オキサ−１０−ホスファフェナントレン骨格を有する化合物を使用すると、難燃性がさらに向上した。特に、（Ｃ）リン系難燃剤として、上記式の（メタ）アクリロイル基を有する１０−オキソ−９−オキサ−１０−ホスファフェナントレン骨格を有する化合物のみを使用した実施例４では、吐出性もさらに向上した。また、実施例７から、メタクリロイルメチルジフェニルフォスフィンオキサイドをジフェニル（ビニル）ホスファン＝オキシドと併用しても、耐ブリード性がさらに向上した。 As shown in Table 1 above, (A) a bisallyl nadiimide compound, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, and (B) a weight average molecular weight of less than 500 at 25 ° C. Example 1 is a photosensitive resin composition containing (C) a phosphorus-based flame retardant and (D) a photopolymerization initiator having a solubility of 10 parts by mass or more with respect to 100 parts by mass of a meta) acrylic compound. In Nos. 12 to 12, a cured coating film having excellent ejection properties by the inkjet method and excellent bleed resistance, heat resistance and flame retardancy could be formed. In particular, as the (C) phosphorus-based flame retardant (soluble phosphorus-based flame retardant), methacryloylmethyldiphenylphosphine oxide, a 10-oxo-9-oxa-10-phosphaphenanthrene skeleton having the (meth) acryloyl group of the above formula. In Examples 1 to 4 and 6 to 12 in which the compound having the above was used, the bleed resistance was further improved. Further, from Examples 4 and 6, when a compound having a 10-oxo-9-oxa-10-phosphaphenanthrene skeleton having a (meth) acryloyl group of the above formula was used, the flame retardancy was further improved. In particular, in Example 4 in which only the compound having the 10-oxo-9-oxa-10-phosphaphenanthrene skeleton having the (meth) acryloyl group of the above formula was used as the (C) phosphorus-based flame retardant, the ejection property was also good. Further improved. Further, from Example 7, even when methacryloylmethyldiphenylphosphine oxide was used in combination with diphenyl (vinyl) phosphine oxide, the bleed resistance was further improved.
一方で、（Ａ）ビスアリルナジイミド化合物を配合しなかった比較例１、３では、難燃性が得られず、比較例３では、耐熱性も得られなかった。なお、比較例１では、イソシアヌルアクリレートのシアヌル骨格が耐熱性に寄与したと考えられる。また、溶解性リン系難燃剤に代えて、難溶性リン系難燃剤であるリン酸金属塩を使用した比較例２では、インクジュット装置では吐出ができなかった。従って、比較例２では、耐ブリード性、耐熱性及び難燃性の評価用試験体を得ることができなかった。 On the other hand, in Comparative Examples 1 and 3 in which the (A) bisallyl nadiimide compound was not blended, flame retardancy was not obtained, and in Comparative Example 3, heat resistance was not obtained either. In Comparative Example 1, it is considered that the cyanuric skeleton of isocyanuric acrylate contributed to the heat resistance. Further, in Comparative Example 2 in which a metal phosphate salt which is a sparingly soluble phosphorus flame retardant was used instead of the soluble phosphorus flame retardant, the ink jut device could not discharge. Therefore, in Comparative Example 2, it was not possible to obtain a test body for evaluation of bleed resistance, heat resistance and flame retardancy.
本発明の感光性樹脂組成物は、インクジェット法を用いての吐出性に優れ、また、耐ブリード性、耐熱性及び難燃性に優れた硬化塗膜を形成することができるので、例えば、所望の回路パターンを有するプリント配線板に絶縁被覆を形成する分野で利用価値が高い。
The photosensitive resin composition of the present invention is excellent in ejection property by using an inkjet method, and can form a cured coating film excellent in bleeding resistance, heat resistance and flame retardancy. Therefore, for example, it is desired. It is highly useful in the field of forming an insulating coating on a printed wiring board having the above circuit pattern.
Claims (10)
前記（Ｃ）リン系難燃剤が、２５℃の前記（Ｂ）重量平均分子量が５００未満の（メタ）アクリル系化合物１００質量部に対して、１０質量部以上溶解する溶解度を有する感光性樹脂組成物。 Photosensitivity containing (A) bisallyl nadiimide compound, (B) (meth) acrylic compound having a weight average molecular weight of less than 500, (C) phosphorus-based flame retardant, and (D) photopolymerization initiator. It is a resin composition
A photosensitive resin composition having a solubility of 10 parts by mass or more of the (C) phosphorus-based flame retardant in 100 parts by mass of the (meth) acrylic compound having a weight average molecular weight of less than 500 at 25 ° C. thing.
A printed wiring board comprising the cured product according to claim 9.
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