CN104407500B - A kind of photosensitive resin composition with good side pattern - Google Patents
A kind of photosensitive resin composition with good side pattern Download PDFInfo
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- CN104407500B CN104407500B CN201410763055.8A CN201410763055A CN104407500B CN 104407500 B CN104407500 B CN 104407500B CN 201410763055 A CN201410763055 A CN 201410763055A CN 104407500 B CN104407500 B CN 104407500B
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- resin composition
- photosensitive resin
- acrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims abstract description 8
- PBOSTUDLECTMNL-UHFFFAOYSA-N dodecyl prop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- -1 hydroxy ethyl Chemical group 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 230000003287 optical Effects 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive Effects 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N Benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- RZVHIXYEVGDQDX-UHFFFAOYSA-N Anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- 229960002130 Benzoin Drugs 0.000 claims description 4
- SEGLCEQVOFDUPX-UHFFFAOYSA-N Di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 4
- 240000008975 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- 206010034960 Photophobia Diseases 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000003754 machining Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000005039 chemical industry Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- MTPIZGPBYCHTGQ-UHFFFAOYSA-N 2-[2,2-bis(2-prop-2-enoyloxyethoxymethyl)butoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCC(CC)(COCCOC(=O)C=C)COCCOC(=O)C=C MTPIZGPBYCHTGQ-UHFFFAOYSA-N 0.000 description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000012773 waffles Nutrition 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1R,3aS,4S,5aR,5bR,7R,7aR,11aR,11bR,13aS,13bR)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1H-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical class COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-Ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HDMIWIXLPFMCFC-UHFFFAOYSA-N 2-chloro-2H-thiopyrano[3,2-b]chromen-10-one Chemical class O1C2=CC=CC=C2C(=O)C2=C1C=CC(Cl)S2 HDMIWIXLPFMCFC-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
- DYFBLPLMEXMYND-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylethanone;phenoxybenzene Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1.C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 DYFBLPLMEXMYND-UHFFFAOYSA-N 0.000 description 1
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2H-benzotriazole-5-carboxylic acid Chemical class C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- QCFQUXGEMVWDLK-UHFFFAOYSA-N CCC.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C Chemical compound CCC.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C QCFQUXGEMVWDLK-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N Diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N Diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- VVBLNCFGVYUYGU-UHFFFAOYSA-N Michler's ketone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 235000012544 Viola sororia Nutrition 0.000 description 1
- 241001106476 Violaceae Species 0.000 description 1
- NNJVILVZKWQKPM-UHFFFAOYSA-N Xylocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N butane-1,1,1-triol Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- GUOJYIXWHMJFDM-UHFFFAOYSA-N decan-2-yl prop-2-enoate Chemical compound CCCCCCCCC(C)OC(=O)C=C GUOJYIXWHMJFDM-UHFFFAOYSA-N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N ethylene glycol monomethyl ether Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229960004194 lidocaine Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of photosensitive resin composition, the dry film image formed afterwards through exposure and development has good side pattern and higher resolution ratio.The photopolymerization resin that carries out as key component has having structure formula：(A)u(B)v(C)w(D)x(E)y(F)z, wherein, A is methacrylic acid, and B is acrylic acid, and C is methyl methacrylate, and D is lauryl acrylate, and E is that carbochain number is 38（Methyl）Acrylate, F are phenoxyethyl acrylate；Photosensitve resin composition provided by the invention, it, as resist material against corrosion, there is the characteristics such as good light sensitivity, resolution ratio and side pattern in the fields such as printed circuit board (PCB), lead frame, semiconductor packages, the Precision Machining of metal.
Description
Technical field
It is rear through exposure and development to be formed the present invention relates to a kind of photosensitive resin composition with good side pattern
Dry film image there is good side pattern and higher resolution ratio.
Background technology
Since ultraviolet curable resin polymer comes out, ultraviolet curable resin polymer has turned into hyundai electronicses field, has been particularly
The important materials of art of printed circuit boards.
In recent years, with the Highgrade integration of electronic equipment, to the highly integrated electricity with narrow distribution and thin space figure
The demand on road is continuously increased.In order to prepare thin space figure with higher qualification rate, it is desirable to which dry film avoids producing surface defect, such as
The figures such as zigzag, also imply that dry film must have good side pattern and higher resolution ratio.
Japan Patent JP07333846 proposes a kind of method for improving side pattern, passes through two kinds of different molecular weights and composition
Alkali soluble resins the side pattern of ultraviolet curable resin polymer is adjusted, but there is limitation.Both alkali solubles
Property resin property can not possibly be completely compatible, it will so that the resolution ratio of ultraviolet curable resin polymer declines.European patent
EP0909990 improves light sensitivity by changing the ratio, component and preparation method of (methyl) acrylic compounds alkali soluble resins
The side pattern of resinous polymer, the good image of side pattern can be obtained.But regrettably, the patent not to resolution ratio,
Many major issues such as exposure energy are discussed.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided a kind of ultraviolet curable resin with good side pattern
Composition.
The purpose of the present invention is achieved through the following technical solutions：A kind of ultraviolet curable resin with good side pattern
Composition, comprising：The alkali soluble resins of 50-70% mass fractions, the optical free radical that carries out of 25-45% mass fractions polymerize instead
Monomer, the light trigger of 0.1-10% mass fractions answered；The alkali-soluble resin has below general formula：(A)u(B)v(C)w
(D)x(E)y(F)z；Wherein, A is methacrylic acid, and B is acrylic acid, and C is methyl methacrylate, and D is lauryl acrylate, E
(methyl) acrylate for being 3-8 for carbochain number, F is phenoxyethyl acrylate；U, v, w, x, y, z represent respectively A, B, C,
D, the mass percent of E, F in alkali soluble resins；Wherein, u 10-25%；V is 5-15%；W is 30-50%；X is 5-
15%；Y is 5-18%；Z is 5-15%.
Further, the alkali soluble resins weight average molecular weight is 30000-120000.
Further, the E is n-BMA or n-butyl acrylate.
Further, the total mass fraction of the A and B in alkali soluble resins is less than 27%.
Further, the monomer for carrying out optical free radical polymerisation at least contains di(2-ethylhexyl)phosphate (hydroxy ethyl)
Ester.
Further, the mass fraction of the light trigger is 0.5-5%.
Further, the light trigger is by benzoin ether, benzophenone and its derivative, thioxanthone system class chemical combination
It is one or more according to appointing in thing, anthraquinone and its derivative, thioxanthones series compound, hexa-aryl bi-imidazole series compound
Meaning proportioning mixing composition.
Further, the light trigger at least contains 2,4,5- triarylimidazoles dimers or 2,4,5- triarylimidazoles
The derivative of dimer.
Further, the photosensitive resin composition also includes the additive of 0~1 parts by weight, and the additive is by having
One or more in engine dyeing material, levelling agent and plasticizer combine according to any proportioning.
The beneficial effects of the invention are as follows：Photosensitve resin composition provided by the invention, it is in printed circuit board (PCB), lead frame
In the fields such as frame, semiconductor packages, the Precision Machining of metal, as resist material against corrosion, have good light sensitivity, resolution ratio with
And the characteristic such as side pattern, be advantageous to improve the qualification rate of PCB batch productions, improve production efficiency, reduce production cost.
Embodiment
A kind of photosensitive resin composition, comprising：Alkali soluble resins, the 25-45% mass fractions of 50-70% mass fractions
The monomer for carrying out optical free radical polymerisation, the light trigger of 0.1-10% mass fractions；The alkali soluble resins has
Below general formula：(A)u(B)v(C)w(D)x(E)y(F)z；
Wherein, A is methacrylic acid, and B is acrylic acid, and C is methyl methacrylate, and D is lauryl acrylate, and E is carbon
Chain number is 3-8 (methyl) acrylate, and F is phenoxyethyl acrylate；U, v, w, x, y, z represent respectively A, B,
C, the mass percent of D, E, F in alkali soluble resins；Wherein, u 10-25%；V is 5-15%；W is 30-50%；x
For 5-15%；Y is 5-18%；Z is 5-15%.
It is 30000-120000 in the alkali soluble resins weight average molecular weight that the present invention uses, goes out from the angle for improving developability
Hair, preferably 120000 and its less；From improve masking hole ability, suppress Fusion Edges angle, preferably 30000 and its more than.
More preferably 60000-90000.
In alkali soluble resins, E is (methyl) acrylate that carbochain number is 3-8, and preferably carbochain number is 4-6 (first
Base) acrylate, more preferably n-BMA or n-butyl acrylate, most preferably n-BMA.
In order to improve the developing performance of the reliability of pad pasting and photosensitive resin composition, the A and B are in alkali soluble resins
In total mass fraction be less than 27%.
The monomer for carrying out Raolical polymerizable, its intramolecular is at least containing the second that polymerisation can occur
Alkene unsaturated functional group, the monomer can be polymerize after light energy is absorbed with alkali soluble resins or cross-linking reaction.Relative to
The ratio of whole optical polymerism resin compositions, preferably 25-45% mass ratioes.Described monomer both can be mono-functionalized
Compound can also be polyfunctional compound, and wherein mono-functional compounds are lauryl acrylate, isodecyl acrylate, propylene
Sour tetrahydrofuran methyl esters, Bing olefin(e) acid Er Evil cyclopentadienyl esters etc.；Difunctional is polyethyleneglycol diacrylate, polypropylene glycol dimethyl propylene
Olefin(e) acid ester, Ethoxylated bisphenol A diacrylate acid fat, 1,6 hexanediol diacrylate etc.；Polyfunctional group can be three hydroxyl first
Base propane triacrylate, ethoxylated trimethylolpropane triacrylate, the propylene of propoxylation trihydroxy methyl propane three
Acid esters, glycerol propoxylate triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol six
Acrylate etc..From the angle for improving adhesive force, it at least contains di(2-ethylhexyl)phosphate (hydroxy ethyl) ester.
In the present invention, the ratio of light trigger is 0.1-10% weight ratio, from realize good sensitivity, resolution ratio,
Caking property is set out, more preferably 0.5-5% weight ratio.
Light trigger, can be benzoin ether, benzophenone and its derivative, thioxanthone system class compound, anthraquinone and
One or more in its derivative, thioxanthones series compound, hexa-aryl bi-imidazole series compound are used in mixed way.Specific bag
Include：Benzoin double methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, thioxanthones, CTX, 4- diurils
Ton ketone, ITX, ITX, benzophenone, 4,4 '-bis- (dimethylamino) benzophenone (Michaelis
Ketone), 4,4 '-bis- (lignocaine) benzophenone, isopropyl thioxanthone, 2- chlorothiaxanthenones, 2,4- diethyl thioxanthones,
2- EAQs, 2- tert-butyl groups anthraquinone, N, N- mesitylenic acids ethyl ester, benzoic acid dimethylaminoethyl, N, N- dimethyl second
Hydramine, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-diimidazole, 2,2 '-bis- (the bromo- 5- methoxybenzenes of 2-) -
4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-bis- (2,4 dichloro benzene bases) -4,4 ', 5,5 '-tetraphenyl diimidazole etc..From high score
Resolution and high sensitivity angle are set out, and at least contain hexa-aryl bi-imidazole series compound in light trigger, and particularly preferred 2,2 ',
4- tri- (2- chlorphenyls) -5- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl -1,1 '-diimidazole.
In order to facilitate producing and being easy to observe, other materials can also be added in photosensitive resin composition, it is such as organic
Dyestuff, levelling agent and plasticizer, this is known technology in industry, be will not be described here.
It is known method as the method that photosensitive resin composition is coated in support film.Gather to ultraviolet curable resin
One or more organic solvents arbitrarily than mixing are added in compound and are prepared into optical polymerism resin mixed liquor, these organic solvents
The composition of photosensitive resin layer can be dispersed or dissolved and not with these component chemically reactives.Coating machine is reused in support membrane
On be coated, by drying, thermal-adhering protective layer.So as to form photosensitive dry film.Organic solvent can be acetone, butanone, first
Alcohol, ethanol, ethyl acetate, glycol monoethyl ether, glycol methyl ether acetate etc..For the ease of producing and operating, other additions
Agent also includes tackifier, plasticizer, pigment, light irradiation chromophoric dyestuffs, hot polymerization inhibitor, antioxidant, levelling agent etc..Support membrane is
PET film, thickness 10-30um；Covering protection film is PE films, thickness 10-30um.
Presently preferred embodiments of the present invention and comparative example are illustrated below.But following embodiments are in the present invention
Preferable embodiment be not intended to limit the present invention.
First, following alkali soluble resins polymer is prepared.
Under inert gas shielding, to equipped with mechanical agitator, reflux condensing tube 500mL three-necked bottles in add 150mL
Butanone, by methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/n-BMA/phenoxy group
Ethyl propylene acid esters is added in three-necked bottle according to solution of 15/10/47/10/8/10 weight than being configured to middle 300g.Rise
Temperature is to 80 DEG C.
Separately 1g azodiisobutyronitriles are dissolved in 10mL butanone, are added drop-wise in three-necked bottle.Mixed liquor gathers at 80 DEG C
Close 4 hours.Then, the 10mL butanone solutions dissolved with 0.8g azodiisobutyronitriles, heating stirring 8 hours are added dropwise again.Wait to mix
After conjunction liquid is down to room temperature, binder solution A-1 is obtained.GPC measures its weight average molecular weight (Mw) it is 82000, solid content is
40.8%.
Alkali soluble resins A-2, A3, A4, Comparative Example I -1, I-2, I3, I4 can be carried out according to similar synthetic method synthesis.
Alkali soluble resins A-2：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/acrylic acid is just
Butyl ester/phenoxyethyl acrylate=13/10/47/12/5/13 (weight ratio) (Mw=78000, solid content 40.4%).
Alkali soluble resins A-3：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/acrylic acid is just
Butyl ester/phenoxyethyl acrylate=10/7/50/15/5/13 (weight ratio) (Mw=120000, solid content 40.5%).
Alkali soluble resins A-4：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/metering system
Different monooctyl ester/phenoxyethyl acrylate=10/5/40/15/18/12 (weight the ratio) (M of acidw=31000, solid content is
40.2%).
Comparative example：
I-1：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/ethyl acrylate/phenoxy group second
Base acrylate=15/10/47/10/8/10 (weight ratio) (Mw=86000, solid content 41.1%).
I-2：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/EMA/benzene oxygen
Base ethyl propylene acid esters=13/10/47/12/5/13 (weight ratio) (Mw=81000, solid content 40.7%).
I-3：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/lauryl methacrylate/
Phenoxyethyl acrylate=10/7/50/15/5/13 (weight ratio) (Mw=95000, solid content 40.3%).
I4：Methacrylic acid/acrylic acid/methyl methacrylate/acrylic acid lauryl/ethyl acrylate/phenoxy group second
Base acrylate=10/5/40/15/18/12 (weight ratio) (Mw=38500, solid content 40.0%).
Prepare following monomers that can carry out photopolymerization：
B-1：Di(2-ethylhexyl)phosphate (hydroxy ethyl) ester (Japanese chemical drug PM-2)
B-2：Ethoxylated trimethylolpropane triacrylate (Tianjin proud son of heaven chemical industry EO9-TMPTA)
B-3：Ethoxylated bisphenol a diacrylate (Tianjin proud son of heaven chemical industry EO4-BPADA)
B-4：Trimethylolpropane trimethacrylate (U.S. Sartomer SR351NS)
Prepare following Photoepolymerizationinitiater initiater：
C-1：2,2 ', 4- tri- (2- chlorphenyls) -5- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl -1,1 '-diimidazole
(Changzhou electronic strong material)
C-2：4,4 '-bis- (diethylamino) benzophenone (Changzhou electronic strong material)
C-3：2,4,5- triarylimidazoles dimer (West Asia chemistry)
Additive：
D-1 diamond greens (the uncommon love chemical industry of Shanghai ladder)
D-2 trisbromomethyl phenyl sulfone (the uncommon love chemical industry of Shanghai ladder)
D-3 leuco crystal violets (the uncommon love chemical industry of Shanghai ladder)
D-4 5- carboxyl benzotriazoles (Shanghai lark waffle Technology Co., Ltd.)
D-5 hydroquinones (Shanghai lark waffle Technology Co., Ltd.)
It is prepared by Photosensitve resin composition：
Free radical polymerizable monomer, additive, Photoepolymerizationinitiater initiater are added in alkali soluble resins solution, are completely dissolved
Afterwards, it is stirred at room temperature 4 hours, goes out decontamination with 200 mesh filters, obtain Photosensitve resin composition.
The preparation of photosensitive dry film：
The use of bar coater it was evenly coated on 15 μm of PET films up to thickness it is 30 μm by Photosensitve resin composition
Film, dry, using the μ m thick PE films of rubber rollers thermal-adhering 18, so as to obtain photosensitive dry film.Photosensitve resin composition composition is such as
Shown in table 1.
Table 1
Note：* all photosensitive resin compositions are all tested in coating film forming and after drying, and organic solvent is gone
Remove.
Testing example and comparative example：
The side pattern after resolution ratio and dry film development is evaluated using the photosensitive resin layer of 30 μ m-thicks.
Pad pasting：The electronics CYL-M25 that often shone using Changzhou carries out thermal-adhering under standard pressure, and fitting speed is 1 m/min
Clock, binding temperature are 105 DEG C.
Exposure：It is exposed using the holy scientific and technological M-552 types exposure machine of will, is exposed using the lattice exposure guide rules of stouffer 21
Light energy determines, and exposure lattice number is 6-8 lattice, exposure energy 30-45mJ/cm2。
Development：Film line width/line-spacing progressively increases to 100um from 10um selected by development；Developer solution is 1% sodium carbonate
The aqueous solution, development temperature are 30 DEG C, developer pressure 1.8bar, and developing powder is 1.5 ms/min, and developing machine model is far revived
Scientific and technological XY-430.The resist layer of unexposed portion is completely dissolved the minimum time of needs as minimum developing time.
Sample is observed by SEM, 500 times of enlargement ratio.
【Resolution ratio is evaluated】
After the PE films of manufactured photosensitive dry film resist are removed, carry out stacking on copper coin using Heating roll and do
Film.Here, it is 1 using the width with exposed portion and unexposed portion:The mask of 1 wiring pattern is exposed, with most
The 1.5 of small developing time show movie queen, will normally form value of the minimum mask width as resolution ratio of solidification resist line.
◎：Resolution value is less than or equal to 20 μm；
○：Resolution value is more than 20 μm, less than or equal to 30 μm；
▽:Resolution value is more than 30 μm, less than or equal to 40 μm；△：Resolution value is more than 40 μm.
【Side pattern evaluation】
After the PE films of manufactured photosensitive dry film resist are removed, carry out stacking on copper coin using Heating roll and do
Film.Here, it is 1 using the width with exposed portion and unexposed portion:The mask of 1 wiring pattern is exposed, with most
The 1.5 of small developing time show movie queen, the dry film image of acquisition.
Good side pattern, refer to photosensitive resin composition in the image side formed after overexposure, development
Pattern has the characteristics that：(a) zigzag pattern is not present in side, does not have the defects of pit；(2) side is straight, and perpendicular to
Copper-based bottom, is not expanded in developer solution；(c) higher development latitude
▲ side is straight, perpendicular to copper-based bottom, without obvious expansion and defect.
◆ side is straight, perpendicular to copper-based bottom, slight expansion and defect be present.
, obvious expansion be present in ▼ lateral sections region existing defects.
● side is serrated.
【Evaluation result】
Embodiment and the evaluation result of comparative example are shown in table 2.
Table 2
As shown in Table 2, Photosensitve resin composition provided by the invention, it is in printed circuit board (PCB), lead frame, semiconductor package
Dress, metal the field such as Precision Machining in, as resist material against corrosion, there is good light sensitivity, resolution ratio and side pattern
Etc. characteristic, be advantageous to improve the qualification rate of PCB batch productions, improve production efficiency, reduce production cost.
Claims (7)
1. a kind of photosensitive resin composition with good side pattern, it is characterised in that include：The alkali of 50-70 parts by weight
Soluble resin, the monomer for carrying out optical free radical polymerisation of 25-45 parts by weight, the light trigger of 0.1-10 parts by weight；Institute
Stating alkali-soluble resin has below general formula：(A)u(B)v(C)w(D)x(E)y(F)z；Wherein, A is methacrylic acid, and B is propylene
Acid, C are methyl methacrylate, and D is lauryl acrylate, and F is phenoxyethyl acrylate；U, v, w, x, y, z difference table
Show the mass percent of A, B, C, D, E, F in alkali soluble resins；Wherein, u 10-25%；V is 5-15%；W is 30-50%；X is
5-15%；Y is 5-18%；Z is 5-15%；The alkali soluble resins weight average molecular weight is 30000-120000；The E is methyl-prop
Olefin(e) acid N-butyl or n-butyl acrylate.
2. photosensitive resin composition according to claim 1, it is characterised in that the A and B are in alkali soluble resins
Total mass fraction is less than 27%.
3. photosensitive resin composition according to claim 1, it is characterised in that described to carry out optical free radical polymerization instead
The monomer answered includes di(2-ethylhexyl)phosphate (hydroxy ethyl) ester.
4. photosensitive resin composition according to claim 1, it is characterised in that the mass fraction of the light trigger is
0.5-5%。
5. photosensitive resin composition according to claim 1, it is characterised in that the light trigger by benzoin ether,
Benzophenone and its derivative, thioxanthone system class compound, anthraquinone and its derivative, thioxanthones series compound, six aryl
It is one or more according to any proportioning mixing composition in double imidazoles series compounds.
6. photosensitive resin composition according to claim 5, it is characterised in that the light trigger is 2,4,5- tri- virtues
The derivative of base imidazoles dimer or 2,4,5- triarylimidazoles dimers.
7. photosensitive resin composition according to claim 1, it is characterised in that the photosensitive resin composition also wraps
The additive of 0 ~ 1 parts by weight is included, the additive is by the one or more in organic dyestuff, levelling agent and plasticizer according to any
Proportioning combines.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410763055.8A CN104407500B (en) | 2014-12-12 | A kind of photosensitive resin composition with good side pattern |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410763055.8A CN104407500B (en) | 2014-12-12 | A kind of photosensitive resin composition with good side pattern |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876173A (en) * | 1985-01-23 | 1989-10-24 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition on polyethylene terephthalate film support |
| US4925768A (en) * | 1986-12-11 | 1990-05-15 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition containing a tetrapolymer binder |
| JPH06214382A (en) * | 1993-01-18 | 1994-08-05 | Sekisui Chem Co Ltd | Photosensitive image receptive sheet |
| EP0529643B1 (en) * | 1991-08-30 | 1995-10-18 | Hercules Incorporated | Aqueous-developable dry film photoresist |
| JPH07333846A (en) * | 1994-06-09 | 1995-12-22 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive film using the same |
| US6180323B1 (en) * | 1997-08-27 | 2001-01-30 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions having improved sidewall geometry and development latitude |
| CN1734351A (en) * | 2004-08-09 | 2006-02-15 | 东进世美肯株式会社 | Photosensitive resin composition for isolator |
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876173A (en) * | 1985-01-23 | 1989-10-24 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition on polyethylene terephthalate film support |
| US4925768A (en) * | 1986-12-11 | 1990-05-15 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition containing a tetrapolymer binder |
| EP0529643B1 (en) * | 1991-08-30 | 1995-10-18 | Hercules Incorporated | Aqueous-developable dry film photoresist |
| JPH06214382A (en) * | 1993-01-18 | 1994-08-05 | Sekisui Chem Co Ltd | Photosensitive image receptive sheet |
| JPH07333846A (en) * | 1994-06-09 | 1995-12-22 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive film using the same |
| US6180323B1 (en) * | 1997-08-27 | 2001-01-30 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions having improved sidewall geometry and development latitude |
| CN1734351A (en) * | 2004-08-09 | 2006-02-15 | 东进世美肯株式会社 | Photosensitive resin composition for isolator |
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