CN115837790A - Photosensitive dry film laminated body, preparation method and circuit board - Google Patents
Photosensitive dry film laminated body, preparation method and circuit board Download PDFInfo
- Publication number
- CN115837790A CN115837790A CN202211540703.4A CN202211540703A CN115837790A CN 115837790 A CN115837790 A CN 115837790A CN 202211540703 A CN202211540703 A CN 202211540703A CN 115837790 A CN115837790 A CN 115837790A
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- Prior art keywords
- photosensitive
- photosensitive layer
- layer
- dry film
- resin composition
- Prior art date
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011342 resin composition Substances 0.000 claims description 46
- 239000000945 filler Substances 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 229920002799 BoPET Polymers 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052737 gold Inorganic materials 0.000 abstract description 16
- 239000010931 gold Substances 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 185
- 229910000679 solder Inorganic materials 0.000 description 22
- 239000000126 substance Substances 0.000 description 22
- 239000003822 epoxy resin Substances 0.000 description 17
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- 150000001875 compounds Chemical class 0.000 description 14
- 238000011161 development Methods 0.000 description 13
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 230000036211 photosensitivity Effects 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
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- 239000000463 material Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
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- 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 5
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- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 5
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 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 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
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- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
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- 239000002390 adhesive tape Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
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- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- OEDAJYOQELMMFC-UHFFFAOYSA-N octadecanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCCCCCCCCCC(O)=O OEDAJYOQELMMFC-UHFFFAOYSA-N 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- CWRBWLKXTXSMEH-UHFFFAOYSA-N 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C CWRBWLKXTXSMEH-UHFFFAOYSA-N 0.000 description 1
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- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- WTOUYJXPUNLWSZ-UHFFFAOYSA-N 2,4-diethyl-1,3-thiazole 1-oxide Chemical compound C(C)C=1S(C=C(N1)CC)=O WTOUYJXPUNLWSZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IQYWSAQGMJBBCZ-UHFFFAOYSA-N 2-(1-ethoxy-1-propoxyethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound C(C)OC(C(CO)(CO)CO)(C)OCCC IQYWSAQGMJBBCZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
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- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention discloses a photosensitive dry film laminated body, which comprises a substrate layer and a photosensitive layer, wherein the photosensitive layer comprises a first photosensitive layer and a second photosensitive layer, the first photosensitive layer and the second photosensitive layer are positioned on the same side of the substrate layer, and the second photosensitive layer is far away from the substrate layer; the energy required by a sample prepared from the first photosensitive layer and the second photosensitive layer when the exposure grid number of the stouffer 21-order exposure ruler is 7 orders is recorded as A and B; wherein, A-B is more than or equal to 50mJ and less than or equal to 700mJ, A is more than or equal to 50mJ and less than or equal to 900mJ, and B is more than or equal to 50mJ and less than or equal to 200mJ. The invention also discloses a preparation method of the laminated body and a circuit board. The photosensitive dry film laminate has good gold resistance, storage stability and resolution, is simple in process and is suitable for industrial popularization.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a photosensitive dry film laminated body, a preparation method and a circuit board.
Background
When an electronic device is mounted on a printed circuit board for electronic equipment, in order to prevent solder from falling on other areas, a solder resist is commonly used to form a solder resist layer on the circuit board to cover the circuit board, and the solder resist layer can also play a role in protecting the circuit board in an environment with high temperature, humidity, pollutants or corrosive gases. At present, the mainstream solder resist is solder resist ink; when in use, the ink is coated on the circuit board and is cured to form a film. In addition, a dry film solder resist is proposed; and coating the solder resist on the substrate to form a photosensitive dry film, and directly attaching the photosensitive dry film to the circuit board in the circuit board manufacturing process for use. The latter can omit the process of curing film forming, and the formed solder mask is smoother.
In the structure of the circuit board, the electroless nickel-gold plating layer has the functions of welding, conduction, heat dissipation, flat plating layer and the like, and accords with the trend that the circuit design of electronic equipment is more and more complex, so that the electroless nickel-gold plating process is widely applied to the manufacture of the circuit board. However, after the electroless nickel gold plating, the solder mask on the circuit board is very easy to whiten and even peel off, so that short circuit and electrochemical corrosion open circuit are caused between conductors due to moisture, chemicals and the like, tin is adhered during production and assembly, and the insulation and protection effects are lost. The improvement of the resistance to chemical gold of the solder mask layer is a powerful measure for eliminating the solder mask stripping phenomenon of the circuit.
Many efforts have been made to improve the resistance of solder resists to gold. Patent CN103145988B uses polyimide oligomer with a specific structure as a host resin to prepare liquid photosensitive solder resist ink, which has excellent resistance to chemical gold; however, the preparation of the resin is difficult, the use steps of the liquid photosensitive solder resist ink are complicated and inconvenient, and the surface of the formed solder resist layer is not smooth enough. Patent CN1088526C adds nano-grade intercalated clay, and because it can be dispersed to nano-grade, the membrane of ink can be firmer, thus increasing its gold resistance, but its cost is high.
In summary, it is an urgent need to solve the problem of providing a photosensitive dry film with excellent chemical resistance and other properties meeting the requirements.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive dry film laminate having excellent gold plating resistance.
In order to achieve the purpose, the technical method adopted by the invention is as follows:
a photosensitive dry film laminate comprising a substrate layer and a photosensitive layer, the photosensitive layer comprising a first photosensitive layer and a second photosensitive layer, the first and second photosensitive layers being located on the same side of the substrate layer and the second photosensitive layer being disposed away from the substrate layer; the first photosensitive layer and the second photosensitive layer satisfy: arranging a 30cm multiplied by 20cm multiplied by 10um first photosensitive layer on a 30cm multiplied by 20cm multiplied by 15um PET film to form a laminated body 1, bonding the laminated body 1 and a 30cm multiplied by 20cm copper-clad plate in the direction that the first photosensitive layer is close to the copper surface of the copper-clad plate at 70 ℃ under 4 kg pressure to form a sample 1, and recording the energy required by the sample 1 when the number of exposure grids of a stouffer 21-order exposure ruler (Stouffer company in America) is 7 orders; arranging a second photosensitive layer of 30cm multiplied by 20cm multiplied by 10um on another PET film of 30cm multiplied by 20cm multiplied by 15um to form a laminated body 2, and bonding the laminated body 2 and the copper-clad plate of 30cm multiplied by 20cm in the direction that the second photosensitive layer is close to the copper surface of the copper-clad plate at 70 ℃ under 4 kg pressure to form a sample 2, wherein the required energy of the sample 2 when the exposure lattice number of the stouffer 21-order exposure ruler is 7 orders is recorded as B; wherein, A-B is more than or equal to 50mJ and less than or equal to 700mJ, A is more than or equal to 50mJ and less than or equal to 900mJ, and B is more than or equal to 50mJ and less than or equal to 200mJ.
Further, the first photosensitive layer and the second photosensitive layer are formed by respectively curing a first photosensitive resin composition and a second photosensitive resin composition, the first photosensitive resin composition comprises (A1) a main body resin, (B1) an initiator, (C1) a curing agent and (D1) a filler, the second photosensitive resin composition comprises (A2) a main body resin, (B2) an initiator, (C2) a curing agent and (D2) a filler, and the mass ratio of the (D2) filler to the (D1) filler is 0-0.7.
Further, the first photosensitive resin composition and the second photosensitive resin composition respectively comprise (E1) a reactive monomer and (E2) a reactive monomer, wherein the equivalent weight of double bonds in the (E1) reactive monomer is 100-600 g/mol, and the equivalent weight of double bonds in the (E2) reactive monomer is 100-600 g/mol.
Further, the equivalent weight of the double bond in the (E1) reactive monomer is taken as M, and the equivalent weight of the double bond in the (E2) reactive monomer is taken as N, wherein (M-N)/(M + N) is not less than-0.1 and not more than 0.1.
Further, the first photosensitive resin composition comprises, in parts by mass, 100 parts by mass of (A1) a host resin, 0 to 5 parts by mass of (B1) an initiator, 5 to 20 parts by mass of (C1) a curing agent, 5 to 20 parts by mass of (D1) a filler, and 10 to 50 parts by mass of (E1) a reactive monomer, and the second photosensitive resin composition comprises 100 parts by mass of (A2) a host resin, 0 to 5 parts by mass of (B2) an initiator, 5 to 20 parts by mass of (C2) a curing agent, 0 to 5 parts by mass of (D2) a filler, and 10 to 50 parts by mass of (E2) a reactive monomer.
Further, the first photosensitive layer has an L value of 92 to 99, an a value of-2 to 2, a value of-2 to 5, the second photosensitive layer has an L value of 70 to 100, an a value of-2.5 to-0.5, and a b value of-6.0 to-2.5.
Further, the CTE value of the first photosensitive layer is 50-70 ppm/deg.C and the CTE value of the second photosensitive layer is 80-120 ppm/deg.C.
Another object of the present invention is to provide a method for preparing the photosensitive dry film laminate, comprising the steps of:
(1) Providing a substrate layer, coating a first photosensitive resin composition on one side of the substrate layer, and then carrying out drying treatment to form a first photosensitive layer;
(2) Coating a second photosensitive resin composition on one side of the first photosensitive layer, which is far away from the substrate layer, and then carrying out drying treatment to form a second photosensitive layer; obtaining the photosensitive dry film laminate.
Further, the temperature of the drying treatment of the first photosensitive resin composition is 65-85 ℃, and the time is 1-10 min; preferably, the solvent content of the first photosensitive layer after drying treatment is 2 to 5wt%; further, the temperature of the second photosensitive resin composition is 80-100 ℃ and the time is 10-20 min; preferably, the solvent content of the second photosensitive layer after drying treatment is 0.1wt% to 0.3wt%.
Another object of the present invention is to provide a wiring board comprising an insulating base film layer, a metal foil layer and a photosensitive layer obtained after peeling off a base material layer from the above photosensitive dry film laminate or a photosensitive layer obtained after peeling off a base material layer from the photosensitive dry film laminate prepared according to the above preparation method.
The technical scheme of the invention has the following beneficial effects:
the invention provides a photosensitive dry film laminated body, a preparation method and a circuit board, which are different from a single-layer photosensitive layer in the prior art, wherein the photosensitive layer comprises a multi-layer structure, photosensitive sub-layers with exposure energy difference within a certain range and certain difference in photosensitivity are selected for superposition, the storage stability is ensured, the sealing effect of the photosensitive layer and the circuit board is improved, and the gold resistance is improved by reducing the possibility of infiltration of a nickel-gold chemical liquid.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in further detail with reference to specific examples.
Unless defined otherwise, technical or scientific terms used in the present disclosure shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
As analyzed by the background technology, after chemically depositing nickel gold, a solder mask on a circuit board is very easy to whiten and even peel off, so that short circuit and electrochemical corrosion open circuit are caused between conductors due to moisture, chemicals and the like, tin is adhered during production and assembly, and insulation and protection effects are lost; the improvement of the chemical resistance is to improve the chemical stability of the solder mask layer and prevent the solder mask layer from participating in chemical reaction, and to improve the adhesion between the solder mask layer and the circuit board and prevent the chemical solution of the chemical gold from permeating. In addition, the solder resist layer is required to have a certain storage stability during transportation and storage. The prior art cannot meet the basic requirements of an industrialization process on simple process and low cost and simultaneously consider storage stability and chemical resistance, and the invention provides a photosensitive dry film laminated body, a preparation method and a circuit board containing the photosensitive dry film laminated body to solve the problem.
In an exemplary embodiment of the present application, there is provided a photosensitive dry film laminate comprising a substrate layer and a photosensitive layer, the photosensitive layer comprising a first photosensitive layer and a second photosensitive layer, the first and second photosensitive layers being located on the same side of the substrate layer and the second photosensitive layer being disposed away from the substrate layer; the first photosensitive layer and the second photosensitive layer satisfy: arranging a first photosensitive layer of 30cm multiplied by 20cm multiplied by 10um on a PET film of 30cm multiplied by 20cm multiplied by 15um to form a laminated body 1, and bonding the laminated body 1 and a copper-clad plate of 30cm multiplied by 20cm in the direction that the first photosensitive layer is close to the copper surface of the copper-clad plate at 70 ℃ under 4 kg pressure to form a sample 1, wherein the required energy of the sample 1 when the exposure lattice number of a stouffer 21-order exposure ruler is 7 orders is recorded as A; arranging a second photosensitive layer of 30cm multiplied by 20cm multiplied by 10um on another PET film of 30cm multiplied by 20cm multiplied by 15um to form a laminated body 2, and bonding the laminated body 2 and the copper-clad plate of 30cm multiplied by 20cm in the direction that the second photosensitive layer is close to the copper surface of the copper-clad plate at 70 ℃ under 4 kg pressure to form a sample 2, wherein the required energy of the sample 2 when the exposure lattice number of the stouffer 21-order exposure ruler is 7 orders is recorded as B; wherein, A-B is more than or equal to 50mJ and less than or equal to 700mJ, A is more than or equal to 50mJ and less than or equal to 900mJ, and B is more than or equal to 50mJ and less than or equal to 200mJ.
Further, the photosensitive dry film laminate may further include a protective layer on a side of the photosensitive layer away from the base material layer.
In the use process of the photosensitive dry film laminated body, the protective layer is required to be stripped firstly, then one side of the exposed photosensitive layer is attached to the circuit board by means of a hot pressing roller or a vacuum laminating machine, then the photosensitive layer is exposed from one side of the substrate layer, the substrate layer is removed, and the rest part is immersed in alkali liquor for development; or removing the substrate layer and then carrying out exposure and development treatment. The photosensitive layer is formed by superposing two photosensitive sublayers with different photosensitivities, the photosensitive layer is limited to have better photosensitivity, namely the photosensitive sublayer (a second photosensitive layer) with the energy of 50-200 mJ required by the sample 2 when the exposure grid number of the stouffer 21-order exposure ruler is 7 orders is positioned on one side far away from the substrate layer, the photosensitive sublayer (the second photosensitive layer) with the better photosensitivity is far away from an energy source and the photosensitive sublayer with the slightly worse photosensitivity is closer to the energy source when exposure is carried out, the disadvantage that the total amount of received energy of the photosensitive sublayer farther away from the energy source is less is remedied to a certain degree, the reaction degree of photo-initiated crosslinking reaction is higher and the reaction is more sufficient, the whole photosensitive layer and a circuit board have better bonding effect, the infiltration of chemical-resistant gold liquid medicine can be reduced and even avoided, and the chemical-resistant gold is improved. Meanwhile, the photosensitivity of the photosensitive sublayer (first photosensitive layer) close to one side of the substrate layer is slightly poor, and the energy required by the sample 1 when the exposure grid number of the stouffer 21-order exposure ruler is 7 orders is 50-900 mJ, so that the possibility that the sample is subjected to crosslinking reaction in advance under the influence of light or heat in the storage process and even fails is reduced, and the influence on the resolution in the use process is prevented. Therefore, the photosensitive dry film laminate has better smoothness and uniformity than solder resist ink, and can give consideration to chemical resistance, storage stability and better resolution.
In addition, the difference of the energy required for the samples 1 and 2 in the exposure of the stouffer 21-stage exposure ruler with the number of exposure grids of 7 stages is limited to be in the range of 50-700 mJ, namely, the difference of the photosensitivity of the samples is limited to be within a certain limit, and the following situations can be prevented, such as (1) under the same energy source and the same exposure time, the second photosensitive layer is fully exposed, the first photosensitive layer is not fully subjected to crosslinking reaction, at the moment, the exposure is stopped, the surface hardness of the upper layer is insufficient, and the pattern part is also subjected to reaction with the developing solution and removed during development; (2) The exposure time is the same under the same energy source, in order to ensure that the first photosensitive layer is fully exposed, the time required by the full exposure of the whole photosensitive layer is too long, and the production efficiency is influenced; or the second photosensitive layer is too crosslinked, and the non-pattern portion is difficult to remove, resulting in poor resolution.
Further, the difference between the energies required for the samples 1 and 2 to have the exposure lattice number of 7 orders in the stouffer21 order exposure ruler is between 100 and 650mJ, more preferably between 150 and 600mJ, between 200 and 550mJ, and between 250 and 500 mJ.
Further, the energy A required for the sample 1 to have an exposure rule number of 7 orders in the stouffer21 order exposure rule is 200 to 850mJ, more preferably 250 to 800mJ, 300 to 750mJ, 350 to 700 mJ. The energy B required for the sample 2 to be exposed in the stouffer21 exposure scale with 7 orders is 50-180 mJ, more preferably 55-170 mJ, 60-160 mJ, 65-150 mJ and 25-140 mJ.
Further, the photosensitive layer includes, but is not limited to, a first photosensitive layer and a second photosensitive layer. The photosensitive layer of the present invention may include two or more photosensitive sublayers, and the photosensitivity of the photosensitive sublayer that is closer to the base material layer gradually deteriorates in the thickness direction of the photosensitive layer. Furthermore, the energy required by the samples made of all the photosensitive sublayers when the exposure grid number of the stouffer 21-step exposure ruler is 7 steps is between 50 and 800 mJ.
Furthermore, the difference of the required energy of the sample made of the adjacent photosensitive sublayers in the exposure grid number of 7 orders of the stouffer 21-order exposure ruler is between 50 and 500 mJ.
Further, the thickness of the substrate layer is 15-40 microns, and the thickness of the photosensitive layer is 25-60 microns.
Further, the thickness of the first photosensitive layer is 10 to 45 micrometers, and the thickness of the second photosensitive layer is 5 to 10 micrometers.
Further, the thickness of the protective layer is 15-40 microns.
Further, the substrate layer and the protective layer are respectively selected from one or more of a PET film, a PP film, a PE film and release paper.
Further, the first photosensitive layer and the second photosensitive layer are formed by respectively curing a first photosensitive resin composition and a second photosensitive resin composition, wherein the first photosensitive resin composition comprises (A1) a main body resin, (B1) an initiator, (C1) a curing agent and (D1) a filler, the second photosensitive resin composition comprises (A2) a main body resin, (B2) an initiator, (C2) a curing agent and (D2) a filler, and the mass ratio of the (D2) filler to the (D1) filler is 0-0.7.
The filler can change the propagation direction of incident light, and if the content of the filler in the second photosensitive layer is too much, the total amount of light received by the second photosensitive layer is influenced, and the crosslinking degree of the second photosensitive layer is further influenced; by limiting the filler content of the second photosensitive layer to 70% or less of that of the first photosensitive layer, the photoreaction degree of the second photosensitive layer can be ensured while satisfying the overall physical strength and appearance requirements of the photosensitive layer.
Further, the mass ratio of the filler (D2) to the filler (D1) is 0.3 to 0.6.
Further, the filler comprises a colored filler, in particular, the filler is selected from organic or inorganic fillers, including but not limited to: red fillers such as monoazo-based, disazo-based, azo lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, quinacridone-based, etc.; blue fillers such as phthalocyanine-based, anthraquinone-based, etc.; yellow fillers such as monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindoline-based, anthraquinone-based, and the like; black fillers such as carbon black, graphite, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, bismuth sulfide, and the like; white fillers such as rutile or anatase titanium oxide, barium sulfate, and the like; orange, green, violet fillers and the like may also be added as necessary.
Further, in order to improve the intensity of the photosensitive layer, a system filler such as one or more of silica, talcum powder, barium sulfate, calcium carbonate and zinc oxide can be added.
Further, the host resin is an alkali-soluble resin, particularly a carboxyl group-containing resin. And may be selected from alkali-soluble resins conventionally used in the art, including acrylic resins and/or alkali-soluble polyimide resins. The acrylic resins include the following:
(1) A carboxylic acid-containing photosensitive resin obtained by adding an ethylenically unsaturated group to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond other than the unsaturated carboxylic acid as a side chain, via a compound having an epoxy group and an unsaturated double bond or (meth) acryloyl chloride;
(2) A photosensitive carboxylic acid-containing copolymer resin obtained by reacting a copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond other than the compound with an unsaturated carboxylic acid, and reacting the generated secondary hydroxyl group with a polybasic acid anhydride;
(3) A carboxylic acid-containing photosensitive resin obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond and a compound having an unsaturated double bond other than the acid anhydride with a compound having a hydroxyl group and an unsaturated double bond;
(4) A carboxylic acid-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride;
(5) A hydroxyl group-and carboxylic acid-containing photosensitive resin obtained by reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride and then reacting the resulting carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule;
(6) A carboxylic acid-containing photosensitive resin obtained by reacting a reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and a compound having at least 1 alcoholic hydroxyl group in one molecule and 1 reactive group other than the alcoholic hydroxyl group which reacts with an epoxy group, with a saturated or unsaturated polybasic acid anhydride;
(7) A carboxylic acid-containing photosensitive resin obtained by reacting a polyfunctional oxetane compound having at least two oxetane rings in one molecule with an unsaturated monocarboxylic acid and reacting a primary hydroxyl group in the resulting modified oxetane resin with a saturated or unsaturated polybasic acid anhydride;
(8) A carboxylic acid-containing photosensitive resin is obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid, then reacting the resultant with a polybasic acid anhydride to obtain a carboxylic acid-containing resin, and then reacting the carboxylic acid-containing resin with a compound having 1 oxirane ring and 1 or more ethylenically unsaturated groups in the molecule.
Further, the acid value of the host resin is 10 to 120mgKOH/g. When the acid value is less than 10mgKOH/g, the development difficulty is large, and a pattern with good appearance is difficult to obtain under the conventional development condition; when the acid value exceeds 120mgKOH/g, pattern peeling is likely to occur during development, resulting in development defects. Preferably, the acid value is from 50 to 100mgKOH/g.
Further, the weight average molecular weight of the host resin is 2000 to 80000. When the weight average molecular weight is more than 80000, the resolution of the photosensitive layer after exposure development becomes poor; when the weight average molecular weight is less than 2000, the development operation window may become narrow, and the adhesion of the developed pattern to the substrate may be reduced. In order to further control the fluidity of the photosensitive layer and to improve the adhesion of the pattern obtained after development as much as possible, the weight average molecular weight is preferably 5000 to 35000.
The molar ratio of the (B1) initiator to the (B2) initiator is 0.3-2. The content of the initiator is an important factor influencing the photosensitivity of the photosensitive layer, and under the same other conditions, the higher the content of the initiator, the faster the photoreaction rate, and the higher the curing reaction degree in the same time. The content of the initiator in the second photosensitive layer is greater than or equal to that in the first photosensitive layer, so that the second photosensitive layer has better photosensitivity than or the same photosensitivity as the first photosensitive layer.
Further, the initiator is selected from conventional photopolymerization initiators and photosensitizers such as ferrocene series, acetophenone series, oxime ester series, phosphine oxide series, anthrone series, benzoin ether, benzophenone series, anthraquinone series, thioxanthone series compounds, hexaarylbisimidazoles compounds, acridines series compounds, and the like, including but not limited to 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (acetoxyiminomethyl) thioxanthen-9-one, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetoxime), 1-hydroxycyclohexylphenylmethanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxy) -phenyl ] -3-hydroxy-2-methyl-1-propanone-1-one, 2,4, 6-trimethylbenzoyl-diphenylphosphineoxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphineoxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-methyl-1- (4-methylthiophenyl) -2-morphinyl-1-propanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, diethyl 2, 4-ethanedioate, 2, 4-diethyl thiazolone, 2-isopropyl thioxanthone, 2-ethyl anthraquinone, 2, 4-diethyl thioxanthone and benzophenone.
Further, the curing agent is selected from one or more of epoxy resin, isocyanate or isocyanurates compounds or triazine compounds; the epoxy resin is selected from bisphenol epoxy resin, biphenyl epoxy resin, novolac epoxy resin, epoxy resin containing naphthalene ring and alicyclic epoxy resin; the bisphenol type epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; the novolac epoxy resin is selected from phenol novolac epoxy resin and novolac epoxy resin.
Further, the epoxy equivalent of the epoxy resin is 50 to 350g/eq, more preferably 50 to 300g/eq, and still more preferably 100 to 200g/eq. When the epoxy equivalent of the epoxy resin is in a specific range, stress due to heat generated during use can be reduced from the viewpoint of densification by crosslinking, and the possibility of thermal cracking can be reduced.
The softening point of the epoxy resin is 40 to 200 ℃, more preferably 50 to 100 ℃, and the softening point is a value measured according to the method described in JIS K7234. The epoxy resin is limited within the range, so that the heat resistance and crack resistance of the photosensitive layer are further improved, the compatibility and the mixing performance of the inorganic filler in a photosensitive resin composition system are improved, and the bonding strength of the photosensitive layer and a circuit board is improved.
Further, the first photosensitive resin composition and the second photosensitive resin composition respectively comprise (E1) a reactive monomer and (E2) a reactive monomer, wherein the equivalent weight of double bonds in the (E1) reactive monomer is 100-600 g/mol, and the equivalent weight of double bonds in the (E2) reactive monomer is 100-600 g/mol. More preferably, the equivalent weight of the double bond in the (E1) reactive monomer is 200 to 500g/mol and 300 to 400g/mol, and the equivalent weight of the double bond in the (E2) reactive monomer is 200 to 500g/mol and 300 to 400g/mol. The main groups participating in photopolymerization in the reactive monomer are double bonds, and the higher the double bond content per unit mass is, the higher the photoreaction efficiency is, and the higher the crosslinking curing reaction degree is in the same exposure time. However, too high a double bond content will affect the storage stability of the photosensitive dry film product. Further, from the viewpoint of resistance to gold plating, the equivalent weight of the double bond in the (E1) reactive monomer is designated as M, and the equivalent weight of the double bond in the (E2) reactive monomer is designated as N, and-0.1. Ltoreq. (M-N)/(M + N). Ltoreq.0.1. Research shows that the double bond equivalent of the reactive monomer in the first photosensitive resin composition and the second photosensitive resin composition is limited within the proportion range, so that the second photosensitive layer can be better cured, and further, the second photosensitive layer is fully closely adhered to a circuit board, and the infiltration of a gold chemical solution is reduced. Further preferably 0. Ltoreq. M-N)/(M + N. Ltoreq.0.1.
Further, the reactive monomer may be selected from conventional photopolymerizable monomers, including, but not limited to, any one or more of monofunctional (meth) acrylates, difunctional (meth) acrylates, trifunctional (meth) acrylates, or multifunctional (meth) acrylates, specifically, such as (ethoxy) phenol (meth) acrylate, stearic acid acrylate, ethoxy (propoxy) nonylphenol (meth) acrylate, ethoxy (propoxy) tetrahydrofurfuryl (meth) acrylate, 1, 6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, dioxane glycol diacrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, polyethylene glycol (400) diacrylate, polypropylene glycol (600) diacrylate, ethoxy (propoxy) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, dipentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.
Further, the (E2) reactive monomer is preferably a bifunctional (meth) acrylate, a trifunctional (meth) acrylate, or a multifunctional (meth) acrylate.
Further, the first photosensitive resin composition comprises, in parts by mass, 100 parts by mass of (A1) a host resin, 0 to 5 parts by mass of (B1) an initiator, 5 to 20 parts by mass of (C1) a curing agent, 5 to 20 parts by mass of (D1) a filler, and 10 to 50 parts by mass of (E1) a reactive monomer, and the second photosensitive resin composition comprises 100 parts by mass of (A2) a host resin, 0 to 5 parts by mass of (B2) an initiator, 5 to 20 parts by mass of (C2) a curing agent, 0 to 5 parts by mass of (D2) a filler, and 10 to 50 parts by mass of (E2) a reactive monomer.
Further, the first photosensitive layer has an L value of 92 to 99, an a value of-2 to 2, a value of-2 to 5, the second photosensitive layer has an L value of 70 to 100, an a value of-2.5 to-0.5, and a b value of-6.0 to-2.5. The color value ranges of the first photosensitive layer and the second photosensitive layer are set, so that the required color of the whole photosensitive layer can be ensured, the whole heterogeneity caused by the different colors of the two photosensitive layers is avoided, the light reflectivity of the photosensitive layer can be ensured, and the light utilization rate of the light-emitting device is improved.
Further, the CTE value of the first photosensitive layer is 50-70 ppm/DEG C, and the CTE value of the second photosensitive layer is 80-120 ppm/DEG C. The CTE values of the first photosensitive layer and the second photosensitive layer are limited within a certain limit and have small difference, and the delamination or the peeling of a circuit board caused by heating and dimensional change in the using process is prevented.
In another exemplary embodiment of the present application, there is provided a method of preparing the photosensitive dry film laminate, including the steps of:
(1) Providing a substrate layer, coating a first photosensitive resin composition on one side of the substrate layer, and then carrying out drying treatment to form a first photosensitive layer;
(2) Coating a second photosensitive resin composition on one side of the first photosensitive layer, which is far away from the substrate layer, and then carrying out drying treatment to form a second photosensitive layer; obtaining the photosensitive dry film laminate.
Further, the temperature of the drying treatment of the first photosensitive resin composition is 65-85 ℃, and the time is 1-10 min; preferably, the solvent content of the first photosensitive layer after drying treatment is 2wt% to 5wt%; preferably, the temperature of the drying treatment of the second photosensitive resin composition is 80 to 100 ℃ and the time is 10 to 20min; preferably, the solvent content of the second photosensitive layer after drying treatment is 0.1wt% to 0.3wt%. The second photosensitive layer is dried, and the first photosensitive layer is dried again, namely the first photosensitive layer is dried twice, so that the solvent content range of the first photosensitive layer after the first drying is controlled to be large, and the film can be formed, and the solvent content can still be kept within a certain limit after the second drying.
Further, the above production method further comprises a step (3) of laminating a protective film on the second photosensitive layer to obtain the photosensitive dry film laminate.
In another exemplary embodiment of the present application, there is provided a wiring board including an insulating base film layer, a metal foil layer, and a photosensitive layer of the above photosensitive dry film laminate after peeling off the base layer or a photosensitive layer of the photosensitive dry film laminate prepared according to the above preparation method after peeling off the base layer.
Further, the photosensitive resin composition further includes other additives (F). The additive (F) is one or more of a color developing agent, a plasticizer, a defoaming agent, a polymerization inhibitor and an antioxidant.
Further, the color developing agent is selected from any one or more of amyl bromide, ethylene dibromide, benzyl bromide, methylene bromide, tribromomethyl phenyl sulfone, trichloroacetamide, amyl iodide and Liu chloroethane.
Further, the plasticizer is selected from phthalic acid compounds or sulfonamide compounds; preferably, the plasticizer is selected from any one or more of diethyl phthalate, diphenyl phthalate and p-toluenesulfonamide.
Further, the defoaming agent is selected from one or more of non-silicon defoaming agent, polyether defoaming agent, organic silicon defoaming agent and polyether modified organic silicon defoaming agent.
Further, the polymerization inhibitor is selected from any one or more of p-methoxyphenol, hydroquinone, pyrogallol, tert-butyl catechol and N-nitrosophenylhydroxylamine aluminum salt.
Further, the antioxidant is selected from any one or more of amine antioxidants, phenol antioxidants, thioester auxiliary antioxidants, phosphite auxiliary antioxidants and thioether auxiliary antioxidants.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
1. Disposed photosensitive resin composition
The first photosensitive resin composition and the second photosensitive resin composition were arranged as shown in Table 1.
Table 1: photosensitive resin composition proportioning table (according to parts by mass)
Description of the drawings:
a-1: acid-modified epoxy acrylate resin (Nippon Kagaku ZFR-1401H, bisphenol F type, solid content 60%, acid value 98 mgKOH/g);
a-2: acrylate resin (celluloid CYCLOMER P (ACA) Z250, solid content 45%, acid value 70 mgKOH/g); b-1:2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1, 1' -diimidazole (Changzhou strong electron);
b-2: 9-phenylacridine (Shanghai ladder loving chemical);
c-1: cresol novolac type epoxy resin (DIC EPICLON-660, epoxy equivalent 202-212 g/eq);
c-2: bisphenol A epoxy resin (Japanese epoxy resin jER828, epoxy equivalent 184-194 g/eq);
d-1: chloride rutile titanium oxide (dupont R931);
d-2: sulfuric acid rutile titanium oxide (made by Sakai chemical R-7E);
d-3: barium sulfate (Sakai chemical BARIECE B-30);
e-1: acrylic acid stearate (Osaka organic chemistry, double bond equivalent of 325 g/mol);
e-2: ethoxynonylphenol acrylate (Kedi chemical LM158, double bond equivalent 450 g/mol);
e-3: poly (propylene glycol) diacrylate (Michael, double bond equivalent 527 g/mol);
e-4: propoxylated trimethylolpropane tri (propyl) acrylate (sartomer, double bond equivalent 213 g/mol); g: dipropylene glycol methyl ether (dow chemical).
2. Preparation of photosensitive Dry film laminate
Uniformly coating the first photosensitive resin composition glue solution on a substrate layer PET (thickness of 15 μm) on a production line, and drying through a channel at the temperature of 80 ℃ to form a first photosensitive layer; and then coating a second photosensitive resin composition glue solution on one side of the first photosensitive layer, which is far away from the substrate layer, and drying through a channel with the temperature of 90 ℃ to form a second photosensitive layer. A PE film (20 μm) as a protective layer was attached to the photosensitive layer on the side away from the base material layer to form a photosensitive dry film laminate.
Table 2: examples and comparative examples
The sample preparation methods (including film application, exposure, and development), sample evaluation methods, and evaluation results of the examples and comparative examples are described below.
[ FILM-APPLICATION ]
And polishing the copper surface of the copper-clad plate by a grinder, washing with water, and wiping to obtain a bright and fresh copper surface. The press roll temperature of the laminator is set to be 110 ℃, the conveying speed is 1.5m/min, and the hot lamination is carried out under the standard pressure.
[ Exposure ] to light
Exposure was carried out using an exposure machine of type M-522 from Saint technology and photosensitivity test was carried out using a stouffer 21-stage exposure ruler.
[ DEVELOPING ]
Gradually increasing the line width/line distance of the film selected by developing from 10 mu m to 100 mu m; the developing solution was 1% by weight of sodium carbonate aqueous solution, the developing temperature was 30 deg.C, the developing pressure was 1.8bar, the developing speed was 1.5m/min, and the developing machine model was Yunsu science XY-430. The minimum time required for the photosensitive layer of the unexposed portion to be completely dissolved is taken as the minimum development time.
[ CTE value evaluation ]
Respectively coating the first photosensitive layer glue solution and the second photosensitive layer glue solution on the substrate layer, drying the substrate layer and the second photosensitive layer glue solution in a hot air circulating drying furnace at 80 ℃ for 10 minutes, cutting the substrate layer into 3mm multiplied by 10mm sample strips, and stripping the substrate layer; the test specimens were measured for dimensional change with temperature and the CTE values were obtained under Hitachi TMA7100 thermomechanical Analyzer at a temperature rise rate of 10 ℃/min from room temperature.
[ evaluation of color value ]
The substrate layer was coated with the first photosensitive layer paste and the second photosensitive layer paste, respectively, and dried in a hot air circulation type drying oven at 80 ℃ for 10 minutes using a CM-2600d spectrocolorimeter from konica minolta, CIEL a b.
[ evaluation of solvent content ]
The photosensitive dry film laminate was prepared by the above coating and drying methods, and the total mass before and after the first drying treatment and before and after the second drying treatment were measured, respectively, and the difference at each time, i.e., the mass of the reduced solvent, was calculated, and the solvent content = (mass of the initially added solvent-mass of the reduced solvent) × 100%/(mass of the photosensitive layer gum solution-mass of the reduced solvent).
[ evaluation of analytical Properties ]
And laminating the photosensitive layer on the copper-clad plate by using a heating press roller. Here, the analysis was evaluated by the minimum value of the line width which was able to completely remove the unexposed portion and remained without distortion or chipping of the line by exposing the pattern to light through a mask having a wiring pattern with a width of 1 (10 to 100 μm) of the exposed portion and the unexposed portion, developing the pattern 1.5 times the developing removal time, and observing the pattern through a magnifying glass, and the smaller the value, the better the analysis.
[ evaluation of resistance to chemical attack ]
Taking a photosensitive dry film laminated body and a copper-clad plate with the sizes of 10cm multiplied by 10cm respectively, enabling a second photosensitive layer of the laminated body to face to the copper surface of the copper-clad plate, attaching the laminated body to the copper-clad plate at 70 ℃ under the pressure of 4 kg, carrying out exposure development and thermosetting, and removing a base material layer to form a test sample; immersing a test sample in a gold dissolving solution at the temperature of 85 ℃ for 30s, scribing and forming 10 multiplied by 10 square grids with the size of 1 multiplied by 1mm on the surface of a first photosensitive layer of the test sample by using a hundred-grid knife, exposing copper surfaces in all grid gaps, and removing scraps in a grid area by using a brush; pasting a No. 3M 600 adhesive tape with the grid area and pressing to remove air bubbles between the adhesive tape and the grid area; the tape was pulled substantially perpendicular to the test specimen and the number n of squares where flaking occurred was recorded.
[ evaluation of Overflow Rate ]
Several pieces of approximately 10cm by 10cm square PET film were cut for use, and the photosensitive dry film laminate to be tested was cut into a square of 2.54cm by 2.54cm (1 inch by 1 inch). The PE film (protective layer) of the cut photosensitive dry film laminate was peeled off, the exposed surface of the photosensitive layer was tightly attached to the central portion of the inner side of the cut PET film (four sides to be photosensitive were kept parallel to four sides of PET), and another PET film was covered on the base material layer of the photosensitive dry film laminate. And (3) setting the laminating temperature to be 40 ℃ and the pressure to be 10MPa by using a flat vulcanizing instrument, and after the temperature is stabilized for 1 hour, placing the sample into the middle position of the laminated board for laminating for 5 minutes. Observing the overflowing width of the sample on each side under a 2D optical image measuring instrument, and measuring the overflowing width of each side and the actual width of the sample. The overflow width of each side was divided by the actual width of the side before lamination of the photosensitive dry film laminate to calculate the average of each side, and the average of 3 samples was taken as the overflow rate of the sample (the reading was observed within 1 hour after pressing). A smaller bleed rate value indicates that bleed is less likely.
[ evaluation of storage stability ]
And (3) respectively placing the photosensitive dry film laminated body in a constant-temperature constant-humidity aging box at room temperature (5-25 ℃) and 50 ℃, controlling the relative humidity of the two to be between 40% and 70%, and observing the side edge glue overflow condition of the photosensitive dry film laminated body after a period of time.
Storage at room temperature:
1: standing for 6 months without glue running;
2: slight gummosis appeared after 6 months of standing;
3: slight gummosis appeared after 3 months of standing;
4: severe gummosis appeared after 3 months of standing;
storage at 50 ℃:
1: standing for 1 month without glue running;
2: slight gummosis appears after the mixture is placed for 1 month;
3: slight gummosis appeared after 2 weeks of standing;
4: severe gummosis occurred after 2 weeks of standing;
[ evaluation results ]
The evaluation results of the examples and comparative examples are shown in table 3. All data were measured with an exposure grid number of 7.
Table 3: evaluation results of examples and comparative examples are shown in the table
As shown in Table 3, the storage stability and the resistance to chemical attack of examples 1 to 10 were better than those of comparative examples 1 to 5, and the resolution was excellent and the phenomenon of flash was significantly suppressed. The invention adopts double-layer or multi-layer photosensitive sublayers to superpose to form the photosensitive layer, limits the curing difference between the layers, can improve the adhesion between the photosensitive layer and the circuit board so as to improve the gold resistance, and has better storage stability and better resolution. Specifically, the formulations of the second photosensitive layer are the same and the formulations of the first photosensitive layer are different in examples 7-9, and the gold resistance is slightly poor because the filler content of the first photosensitive layer is more in example 8, which affects the light energy receiving of the second photosensitive layer. The formulations of the first photosensitive layer and the second photosensitive layer in examples 3-6 are the same, and the storage stability and resolution are poor because the initiator content in the second photosensitive layer is too low and the monomer addition amount is large in example 5.
In conclusion, the photosensitive dry film laminated body adopting the scheme of the invention is favorable for improving the gold resistance and has good industrial applicability.
The above-described preferred embodiments of the present invention are not intended to limit the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the claims of the present invention.
Claims (10)
1. A photosensitive dry film laminate comprising a substrate layer and a photosensitive layer, the photosensitive layer comprising a first photosensitive layer and a second photosensitive layer, the first photosensitive layer and the second photosensitive layer being located on the same side of the substrate layer and the second photosensitive layer being disposed away from the substrate layer; the first photosensitive layer and the second photosensitive layer satisfy: arranging a first photosensitive layer of 30cm multiplied by 20cm multiplied by 10um on a PET film of 30cm multiplied by 20cm multiplied by 15um to form a laminated body 1, and bonding the laminated body 1 and a copper-clad plate of 30cm multiplied by 20cm in the direction that the first photosensitive layer is close to the copper surface of the copper-clad plate at 70 ℃ under 4 kg pressure to form a sample 1, wherein the required energy of the sample 1 when the exposure lattice number of a stouffer 21-order exposure ruler is 7 orders is recorded as A; arranging a second photosensitive layer of 30cm multiplied by 20cm multiplied by 10um on another PET film of 30cm multiplied by 20cm multiplied by 15um to form a laminated body 2, and bonding the laminated body 2 and the copper-clad plate of 30cm multiplied by 20cm in the direction that the second photosensitive layer is close to the copper surface of the copper-clad plate at 70 ℃ under 4 kg pressure to form a sample 2, wherein the required energy of the sample 2 when the exposure lattice number of the stouffer 21-order exposure ruler is 7 orders is recorded as B; wherein, A-B is more than or equal to 50mJ and less than or equal to 700mJ, A is more than or equal to 50mJ and less than or equal to 900mJ, and B is more than or equal to 50mJ and less than or equal to 200mJ.
2. The photosensitive dry film laminate according to claim 1, wherein the first photosensitive layer and the second photosensitive layer are formed by curing a first photosensitive resin composition and a second photosensitive resin composition, respectively, the first photosensitive resin composition comprises (A1) a host resin, (B1) an initiator, (C1) a curing agent, and (D1) a filler, the second photosensitive resin composition comprises (A2) a host resin, (B2) an initiator, (C2) a curing agent, and (D2) a filler, and the mass ratio of the (D2) filler to the (D1) filler is 0 to 0.7.
3. The photosensitive dry film laminate of claim 2, wherein the first photosensitive resin composition and the second photosensitive resin composition further comprise (E1) a reactive monomer and (E2) a reactive monomer, respectively, wherein the equivalent weight of the double bond in the (E1) reactive monomer is 100 to 600g/mol, and the equivalent weight of the double bond in the (E2) reactive monomer is 100 to 600g/mol.
4. A photosensitive dry film laminate according to claim 3, wherein the equivalent weight of the double bond in the (E1) reactive monomer is denoted as M, and the equivalent weight of the double bond in the (E2) reactive monomer is denoted as N, -0.1 ≦ (M-N)/(M + N) ≦ 0.1.
5. A photosensitive dry film laminate according to any one of claims 2 to 4, wherein the first photosensitive resin composition comprises 100 parts by mass of (A1) a host resin, 0 to 5 parts by mass of (B1) an initiator, 5 to 20 parts by mass of (C1) a curing agent, 5 to 20 parts by mass of (D1) a filler, and 10 to 50 parts by mass of (E1) a reactive monomer, and the second photosensitive resin composition comprises 100 parts by mass of (A2) a host resin, 0 to 5 parts by mass of (B2) an initiator, 5 to 20 parts by mass of (C2) a curing agent, 0 to 5 parts by mass of (D2) a filler, and 10 to 50 parts by mass of (E2) a reactive monomer.
6. The photosensitive dry film laminate as claimed in claim 1, wherein the first photosensitive layer has an L value of 92 to 99, an a value of-2 to 2, a value of-2 to 5, the second photosensitive layer has an L value of 70 to 100, an a value of-2.5 to-0.5, and a b value of-6.0 to-2.5.
7. The photosensitive dry film laminate of claim 1, wherein the CTE value of the first photosensitive layer is 50 to 70ppm/° c and the CTE value of the second photosensitive layer is 80 to 120ppm/° c.
8. The method of preparing a photosensitive dry film laminate according to any one of claims 1 to 7, comprising the steps of:
(1) Providing a substrate layer, coating a first photosensitive resin composition on one side of the substrate layer, and then carrying out drying treatment,
forming a first photosensitive layer;
(2) Coating a second photosensitive resin composition on one side of the first photosensitive layer, which is far away from the substrate layer, and then carrying out drying treatment to form a second photosensitive layer; obtaining the photosensitive dry film laminate.
9. The method of claim 8, wherein the first photosensitive resin composition is dried at a temperature of 65 to 85 ℃ for 1 to 10min; the solvent content of the first photosensitive layer after drying treatment is 2 to 5 weight percent; the temperature of the second photosensitive resin composition is 80-100 ℃, and the time is 10-20 min; the solvent content of the second photosensitive layer after drying treatment is 0.1wt% -0.3 wt%.
10. A wiring board comprising an insulating base film layer, a metal foil layer and the photosensitive layer described in any one of claims 1 to 7 or the photosensitive layer obtained after peeling off the base layer from the photosensitive dry film laminate obtained by the production method described in any one of claims 8 to 9.
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