CN1533516A - Resist removing agent - Google Patents
Resist removing agent Download PDFInfo
- Publication number
- CN1533516A CN1533516A CNA038003554A CN03800355A CN1533516A CN 1533516 A CN1533516 A CN 1533516A CN A038003554 A CNA038003554 A CN A038003554A CN 03800355 A CN03800355 A CN 03800355A CN 1533516 A CN1533516 A CN 1533516A
- Authority
- CN
- China
- Prior art keywords
- corrosion inhibitor
- copper
- ring compound
- inhibitor stripper
- heterogeneous ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims description 72
- 230000007797 corrosion Effects 0.000 claims description 72
- 239000003112 inhibitor Substances 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 40
- LAIQKCIHZIGVGJ-UHFFFAOYSA-N [S].C1=CN=CN=C1 Chemical class [S].C1=CN=CN=C1 LAIQKCIHZIGVGJ-UHFFFAOYSA-N 0.000 claims description 19
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 14
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 11
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 claims description 10
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims description 10
- UQJLPBLXSJWAKG-UHFFFAOYSA-N 6-methyl-1h-pyrimidin-3-ium-2-thione;chloride Chemical compound Cl.CC1=CC=NC(=S)N1 UQJLPBLXSJWAKG-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 46
- 229910052802 copper Inorganic materials 0.000 abstract description 33
- 239000010949 copper Substances 0.000 abstract description 33
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001431 copper ion Inorganic materials 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 210000000981 epithelium Anatomy 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 238000005530 etching Methods 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000005219 brazing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 2
- LVJOFJVCBFMGPW-UHFFFAOYSA-N SC1=C(C(=O)O)C=C(C=C1C(=O)O)C Chemical compound SC1=C(C(=O)O)C=C(C=C1C(=O)O)C LVJOFJVCBFMGPW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical class S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/062—Etching masks consisting of metals or alloys or metallic inorganic compounds
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Detergent Compositions (AREA)
Abstract
The resist removing agent is prepared as an alkali aqueous solution containing at least a heterocyclic compound having the structure expressed by formula (1) in the molecule as an additive. The solution prevents re-crystallization of tin on copper caused by copper ions dissolving in the resist removing agent.
Description
Technical field
The present invention relates to corrosion inhibitor stripper, particularly relate to the resist that in accordance with regulations figure on copper is formed and form zinc-plated epithelium, peel off the corrosion inhibitor stripper that resist is used from copper then as mask.
Background technology
For example, peel off in PWB (Printed WiringBoard) manufacturing process of method, use the aqueous solution of alkali metal hydroxides such as NaOH, potassium hydroxide during the resist after forming scolding tin plating epithelium is peeled off at panel figure secondary brazing tin.Corrosion inhibitor stripper as such alkaline aqueous solution constitutes in order to prevent the dissolving and plumbous the separating out of scolding tin plating epithelium, discloses and has contained 1, the corrosion inhibitor stripper (spy opens flat 6-250401 communique) of 10-phenanthroline etc.In addition, developed water-soluble amine by making it to contain regulation, ammonium hydroxide, benzotriazole etc., thereby the splitting time of resist is shortened, but high density, the height corrosion inhibitor stripper (spy opens the 2001-5201 communique) that forms figure etc. that becomes more meticulous thus.
, be subjected to unleaded up till now influence, advance from of the transformation of scolding tin epithelium to zinc-plated epithelium.Accompany therewith, use panel figure secondary brazing tin to peel off in the resist stripping process of the existing corrosion inhibitor stripper that uses in the method, zinc-plated epithelium stripping to alkali metal hydroxide aqueous solution, and, the tin of stripping is separated out above metallic copper again, and this problem is remarkable day by day.Like this, separate out the tin epithelium above metallic copper again, in the etching work procedure of the copper after peeling off resist, play a role as the etching resist, therefore etching uniformly becomes difficult, becomes the reason that the loop forms bad grade.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind ofly after forming zinc-plated epithelium on the copper, tin separating out again on copper can not taken place, the corrosion inhibitor stripper of peelable resist.
In order to reach such purpose, corrosion inhibitor stripper of the present invention is following formation: be to contain the alkaline aqueous solution that the heterogeneous ring compound of structure shown in the following formula (1) is arranged in molecule at least.
In addition, corrosion inhibitor stripper of the present invention is following formation: aforementioned heterogeneous ring compound is a 2-benzimidazole mercaptan, contains this 2-benzimidazole mercaptan in the scope of 10-50000ppm.
In addition, corrosion inhibitor stripper of the present invention is following formation: aforementioned heterogeneous ring compound is 2-sulfydryl-1-methylimidazole, contains this 2-sulfydryl-1-methylimidazole in the scope of 20-50000ppm.
In addition, corrosion inhibitor stripper of the present invention is following formation: aforementioned heterogeneous ring compound is the 2-thiouracil, contains this 2-thiouracil in the scope of 500-50000ppm.
In addition, corrosion inhibitor stripper of the present invention is following formation: aforementioned heterogeneous ring compound is 2,4-two sulphur pyrimidines, the scope of 200-50000ppm contain this 2,4-two sulphur pyrimidines.
In addition, corrosion inhibitor stripper of the present invention is following formation: aforementioned heterogeneous ring compound is 2-sulfydryl-4-methylpyrimidine hydrochloride, contains this 2-sulfydryl-4-methylpyrimidine hydrochloride in the scope of 2000-50000ppm.
According to the present invention, be the alkaline aqueous solution that contains the heterogeneous ring compound that the regulation structure is arranged at least in molecule by making corrosion inhibitor stripper, thereby heterogeneous ring compound is adsorbed on the copper surface, produces insoluble epithelium.In corrosion inhibitor stripper, dissolve (oxidation) because this epithelium suppresses copper, so can prevent that tin from separating out (Sn again
2+Reduction) time, peel off resist.
Embodiment
The following describes embodiment of the present invention.
Corrosion inhibitor stripper of the present invention is to contain the alkaline aqueous solution that the heterogeneous ring compound of structure shown in the following formula (1) is arranged in molecule at least.
Formula (1)
This corrosion inhibitor stripper of the present invention, heterogeneous ring compound is adsorbed on the copper surface, produces insoluble epithelium, and this epithelium suppresses copper and dissolve (oxidation) in corrosion inhibitor stripper.Therefore, can prevent that tin from separating out (Sn again
2+Reduction) time, peel off resist.
As the heterogeneous ring compound that structure shown in the following formula (1) is arranged in molecule, specifically can enumerate 2 shown in the 2-thiouracil shown in the 2-sulfydryl-1-methylimidazole shown in the 2-benzimidazole mercaptan shown in the following structural formula (A), the following structural formula (B), the following structural formula (C), the following structural formula (D), the 2-sulfydryl shown in 4-two sulphur pyrimidines, the following structural formula (E)-4-methylpyrimidine hydrochloride etc.
Structural formula (A)
Structural formula (B)
Structural formula (C)
Structural formula (D)
The content of heterogeneous ring compound in corrosion inhibitor stripper that structure shown in the following formula (1) is arranged in molecule can wait setting aptly according to kind, the stripping quantity (for example about 30-50ppm) of copper in corrosion inhibitor stripper of the heterogeneous ring compound that uses.For example, as heterogeneous ring compound, contain the occasion of above-mentioned 2-benzimidazole mercaptan, can be the above content of 10ppm, contain the occasion of above-mentioned 2-sulfydryl-1-methylimidazole, can be the above content of 20ppm, the occasion that contains above-mentioned 2-thiouracil, can be the above content of 500ppm, contain above-mentioned 2, the occasion of 4-two sulphur pyrimidines, can be the above content of 200ppm, in addition, contain the occasion of above-mentioned 2-sulfydryl-4-methylpyrimidine hydrochloride, can be the above content of 2000ppm.During the heterogeneous ring compound quantity not sufficient that contained in the corrosion inhibitor stripper, effect of the present invention can not embody fully.On the other hand, for the not restriction especially of upper content limit of the heterogeneous ring compound in the corrosion inhibitor stripper, but content surpasses the occasion of 50000ppm, can not get further effect, and produce drawbacks such as the reduction of resist peeling rate, the variable color of substrate Copper Foil, therefore be preferably the following content of 50000ppm.
The pH of corrosion inhibitor stripper of the present invention can be 11-14, is preferably 12.8-13.4.Water-soluble amines such as alkali metal hydroxides such as dissolved hydrogen sodium oxide molybdena, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine can access desirable pH.
In addition, in corrosion inhibitor stripper of the present invention,, can add defoamer that the non-ionic surfactant of polyethers system constitutes etc. as required as other adjuvant.This content of additive is preferably below the 1g/L.
Use corrosion inhibitor stripper of the present invention to carry out the occasion that resist is peeled off, the temperature of corrosion inhibitor stripper is not particularly limited, but for example be set at 40-50 ℃ scope.Corrosion inhibitor stripper can be any methods such as infusion process, gunite with contacting of resist.
Embodiment is shown below illustrates in greater detail the present invention.
[embodiment 1]
(making of test film)
Go up use dry film photoresist (Hitachi changes into industry (strain) system PHOTEC HN240) at the Copper Foil (the thick 18 μ m of copper, glass epoxide base material) of two sides band resin and form figure.Then, on Copper Foil, form the zinc-plated epithelium of thickness 5 μ m, then cut the size of 5cm * 5cm, make test film.
(modulation of corrosion inhibitor stripper)
As the heterogeneous ring compound that the structure shown in the following formula (1) is arranged in molecule, with the 2-benzimidazole mercaptan shown in the said structure formula (A)-(E), 2-sulfydryl-1-methylimidazole, 2-thiouracil, 2,4-two sulphur pyrimidines, 2-sulfydryl-4-methylpyrimidine hydrochloride add 2000ppm respectively in 3% sodium hydrate aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature), modulate 5 kinds of corrosion inhibitor strippers (sample 1-5).In addition, in these corrosion inhibitor strippers (sample 1-5), add trace copper-ammonia (ア Application シ Application) complex solution, make it to contain copper ion with the concentration shown in the following table 1.
The corrosion inhibitor stripper (duplicate 1) that modulation only is made of 3% sodium hydrate aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature) is arranged again.In addition, as heterogeneous ring compound, with the benzotriazole shown in the following structural formula (I), 2-[4-morpholinodithio mercaptan shown in the following structural formula (II), 2-sulfydryl-5-methyl isophthalic acid shown in the following structural formula (III), 3, the 4-thiadiazoles, shown in the following structural formula (IV) 2,5-dimercapto-1,3, the 4-thiadiazoles, 2-thiazoline-2-mercaptan shown in the following structural formula (V), 2-imidazolidinethione shown in the following structural formula (VI) is respectively to 3% sodium hydrate aqueous solution (liquid measure 200mL, 45 ℃ of liquid temperature) add 2000ppm in, modulate 6 kinds of corrosion inhibitor strippers (duplicate 2-7).
Structural formula (II)
Structural formula (VI)
In addition, by in these corrosion inhibitor strippers (duplicate 1-7), adding trace copper-ammino-complex aqueous solution, make it to contain the copper ion of concentration shown in the following table 1.
(resist is peeled off and the Copper Foil etching)
Test film was flooded 5 minutes in each corrosion inhibitor stripper (sample 1-5, duplicate 1-7), carry out resist and peel off.
Then, press 1.5kg/cm to spray
2The ammonia alkaline etching agent that the jetting fluid temperature is 50 ℃ (copper concentration=138g/L, cl concn=160g/L, ammonia concentration=8.7N, pH=8.4) about 30 seconds, carry out the Copper Foil etch processes of test film.
(evaluation)
Test film after the etch processes that detects by an unaided eye is estimated by following benchmark, the results are shown in table 1.
(metewand)
Zero: can't see remaining copper, Copper Foil is removed equably.
*: removing of Copper Foil is inhomogeneous, can see the remaining copper of the part of separating out based on the displacement of tin.
Table 1
| Corrosion inhibitor stripper | The heterogeneous ring compound that contains | Copper concentration [ppm] | ||||||
| ??0 | ??10 | ??20 | ??50 | ??100 | ??200 | ??300 | ||
| Sample 1 | 2-benzimidazole mercaptan | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Sample 2 | 2-sulfydryl-1-methylimidazole | ??○ | ??○ | ??○ | ??○ | ??○ | ??× | ??× |
| Sample 3 | The 2-thiouracil | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Sample 4 | 2,4-two sulphur pyrimidines | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Sample 5 | 2-sulfydryl-4-methylpyrimidine hydrochloride | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Duplicate 1 | ????- | ??○ | ??× | ??× | ??× | ??× | ??× | ??× |
| Duplicate 2 | Benzotriazole | ??○ | ??× | ??× | ??× | ??× | ??× | ??× |
| Duplicate 3 | 2-[4-morpholinodithio mercaptan | ??○ | ??○ | ??× | ??× | ??× | ??× | ??× |
| Duplicate 4 | 2-sulfydryl-5-methyl isophthalic acid, 3, the 4-thiadiazoles | ??○ | ??○ | ??× | ??× | ??× | ??× | ??× |
| Duplicate 5 | 2,5-dimercapto-1,3,4-thiadiazoles | ??○ | ??○ | ??○ | ??× | ??× | ??× | ??× |
| Duplicate 6 | 2-thiazoline-2-mercaptan | ??○ | ??○ | ??○ | ??× | ??× | ??× | ??× |
| Duplicate 7 | The 2-imidazolidinethione | ??○ | ??○ | ??○ | ??○ | ??× | ??× | ??× |
As shown in table 1, contain the corrosion inhibitor stripper of the present invention (sample 1-5) that the heterogeneous ring compound of structure shown in the following formula (1) is arranged in molecule, the occasion that does not have copper ion in corrosion inhibitor stripper much less, even there is the occasion of copper ion, tin separating out again on copper do not taken place yet, peelable resist.But for sample 2 (containing 2-sulfydryl-1-methylimidazole as heterogeneous ring compound), copper concentration can be seen tin separating out again on copper when 200ppm is above., in the corrosion inhibitor stripper of PWB manufacturing process, the copper concentration of dissolving is approximately about 30-50ppm, so the corrosion inhibitor stripper of decidable sample 2 is fully practical level.
Relative therewith, do not contain the corrosion inhibitor stripper (duplicate 1-7) that the heterogeneous ring compound of structure shown in the following formula (1) is arranged in molecule, only in corrosion inhibitor stripper, do not exist the occasion of copper ion that tin separating out again on copper, peelable resist do not take place., in corrosion inhibitor stripper, there is the occasion of copper ion, can sees tin separating out again on copper, can not be used for practicality.
[embodiment 2]
(making of test film)
Make test film similarly to Example 1.
(modulation of corrosion inhibitor stripper)
As the heterogeneous ring compound that structure shown in the following formula (1) is arranged in molecule, with the 2-benzimidazole mercaptan shown in the said structure formula (A)-(E), 2-sulfydryl-1-methylimidazole, 2-thiouracil, 2,4-two sulphur pyrimidines, 2-sulfydryl-4-methylpyrimidine hydrochloride add in 3% sodium hydrate aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature) respectively, make it to reach the concentration shown in the following table 2 (10-2000ppm is totally 8 concentration scales), modulate 40 kinds of corrosion inhibitor strippers.In addition, by in these corrosion inhibitor strippers, adding trace copper-ammino-complex aqueous solution, make it to contain copper ion 50ppm.
(resist is peeled off and the Copper Foil etching)
The resist that carries out test film is peeled off similarly to Example 1, carries out the etch processes of Copper Foil then.
(evaluation)
Test film by after the benchmark evaluation etch processes similarly to Example 1 the results are shown in table 2.
Table 2
| The heterogeneous ring compound that corrosion inhibitor stripper contains | The concentration of heterogeneous ring compound [ppm] | |||||||
| ????10 | ????20 | ????50 | ????100 | ????200 | ????500 | ????1000 | ????2000 | |
| 2-benzimidazole mercaptan | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ |
| 2-sulfydryl-1-methylimidazole | ????× | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ |
| The 2-thiouracil | ????× | ????× | ????× | ????× | ????× | ????○ | ????○ | ????○ |
| 2,4-two sulphur pyrimidines | ????× | ????× | ????× | ????× | ????○ | ????○ | ????○ | ????○ |
| 2-sulfydryl-4-methylpyrimidine hydrochloride | ????× | ????× | ????× | ????× | ????× | ????× | ????× | ????○ |
As shown in table 2, each corrosion inhibitor stripper of the present invention that contains the heterogeneous ring compound that structure shown in the following formula (1) is arranged in molecule, kind corresponding to the heterogeneous ring compound that contains, the suitable lower limit that has heterogeneous ring compound content, under its content more than content lower limit, tin separating out again on copper do not taken place, peelable resist.
[embodiment 3]
(making of test film)
Make test film similarly to Example 1.
(modulation of corrosion inhibitor stripper)
As the heterogeneous ring compound that structure shown in the following formula (1) is arranged, prepared 2 shown in the said structure formula (D), 4-two sulphur pyrimidines in molecule.In addition, prepared 3% monoethanolamine+0.5% tetramethyl ammonium hydroxide aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature).Add above-mentionedly 2 in this aqueous solution, 4-two sulphur pyrimidine 2000ppm modulate corrosion inhibitor stripper (sample 6).In addition, in this corrosion inhibitor stripper, add trace copper-ammino-complex aqueous solution, make it to contain the copper ion of the concentration shown in the following table 3.
The corrosion inhibitor stripper (duplicate 8) that modulation only is made of 3% monoethanolamine+0.5% tetramethyl ammonium hydroxide aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature) is arranged again.In addition, as heterogeneous ring compound, to in embodiment 1, in 3% monoethanolamine+0.5% tetramethyl ammonium hydroxide aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature), add 2000ppm respectively by the 2-[4-morpholinodithio mercaptan shown in the benzotriazole shown in the structural formula (I), the structural formula (II), modulate 2 kinds of corrosion inhibitor strippers (duplicate 9,10).In addition, in these corrosion inhibitor strippers (duplicate 8-10), add trace copper-ammino Heshui solution, make it to contain the copper ion of the concentration shown in the following table 3.
(resist is peeled off and the Copper Foil etching)
The resist that carries out test film is peeled off similarly to Example 1, then, carries out the etch processes of Copper Foil.
(evaluation)
Test film by after the benchmark evaluation etch processes similarly to Example 1 the results are shown in table 3.
Table 3
| Corrosion inhibitor stripper | The heterogeneous ring compound that contains | Copper concentration [ppm] | ||||||
| ??0 | ??10 | ??20 | ??50 | ??100 | ??200 | ??300 | ||
| Sample 6 | 2,4-two sulphur pyrimidines | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Duplicate 8 | ????- | ??○ | ??× | ??× | ??× | ??× | ??× | ??× |
| Duplicate 9 | Benzotriazole | ??○ | ??× | ??× | ??× | ??× | ??× | ??× |
| Duplicate 10 | 2-[4-morpholinodithio mercaptan | ??○ | ??○ | ??× | ??× | ??× | ??× | ??× |
As shown in table 3, contain 2 of structure shown in the following formula (1) is arranged in molecule, the corrosion inhibitor stripper of the present invention (sample 6) of 4-two sulphur pyrimidines, the occasion that does not have copper ion in corrosion inhibitor stripper much less, even there is the occasion of copper ion, tin separating out again on copper do not taken place yet, peelable resist.
Relative therewith, do not contain the corrosion inhibitor stripper (duplicate 8-10) that the heterogeneous ring compound of structure shown in the following formula (1) is arranged in molecule, only in corrosion inhibitor stripper, do not exist the occasion of copper ion that tin separating out again on copper, peelable resist do not take place., in corrosion inhibitor stripper, there is the occasion of copper ion, can sees tin separating out again on copper, can not be used for practicality.
[embodiment 4]
(making of test film)
Make test film similarly to Example 1.
(modulation of corrosion inhibitor stripper)
As the heterogeneous ring compound that structure shown in the following formula (1) is arranged in molecule, with 2 shown in the said structure formula (D), 4-two sulphur pyrimidines add to respectively in 3% monoethanolamine+0.5% tetramethyl ammonium hydroxide aqueous solution (45 ℃ of liquid measure 200mL, liquid temperature), make it reach the concentration shown in the following table 4 (10-2000ppm is totally 8 grades), modulate 8 kinds of corrosion inhibitor strippers.In addition, by in these corrosion inhibitor strippers, adding trace copper-ammino-complex aqueous solution, make it to contain copper ion 50ppm.
(resist is peeled off and the Copper Foil etching)
The resist that carries out test film is peeled off similarly to Example 1, then, carries out the etch processes of Copper Foil.
(evaluation)
Test film by after the benchmark evaluation etch processes similarly to Example 1 the results are shown in table 4.
Table 4
| The heterogeneous ring compound that corrosion inhibitor stripper contains | 2, the concentration [ppm] of 4-two sulphur pyrimidines | |||||||
| ????10 | ????20 | ????50 | ??100 | ??200 | ??500 | ??1000 | ??2000 | |
| 2,4-two sulphur pyrimidines | ????× | ????× | ????× | ???× | ???○ | ???○ | ???○ | ???○ |
As shown in table 4, containing has 2 of structure shown in the following formula (1) in molecule, the corrosion inhibitor stripper of the present invention of 4-two sulphur pyrimidines, and 2, the content of 4-two sulphur pyrimidines is 200ppm when above, tin separating out again on copper is not taken place, peelable resist.
As with as described in, corrosion inhibitor stripper of the present invention is applicable to after forming zinc-plated epithelium at the resist that forms with the figure of stipulating on the copper as mask, tin separating out again on copper can not taken place, peel off resist from copper, for example, in peeling off PWB (the Printed Wiring Board) manufacturing process etc. of method, panel figure secondary brazing tin can utilize.
Claims (6)
1. a corrosion inhibitor stripper is characterized in that, is to contain the alkaline aqueous solution that the heterogeneous ring compound of structure shown in the following formula (1) is arranged at least in molecule.
Formula (1)
2. the corrosion inhibitor stripper of putting down in writing according to claim 1, aforementioned heterogeneous ring compound is a 2-benzimidazole mercaptan, contains this 2-benzimidazole mercaptan in the scope of 10-50000ppm.
3. the corrosion inhibitor stripper of putting down in writing according to claim 1, aforementioned heterogeneous ring compound is 2-sulfydryl-1-methylimidazole, contains this 2-sulfydryl-1-methylimidazole in the scope of 20-50000ppm.
4. the corrosion inhibitor stripper of putting down in writing according to claim 1, aforementioned heterogeneous ring compound is the 2-thiouracil, contains this 2-thiouracil in the scope of 500-50000ppm.
5. the corrosion inhibitor stripper of putting down in writing according to claim 1, aforementioned heterogeneous ring compound is 2,4-two sulphur pyrimidines, the scope of 200-50000ppm contain this 2,4-two sulphur pyrimidines.
6. the corrosion inhibitor stripper of putting down in writing according to claim 1, aforementioned heterogeneous ring compound is 2-sulfydryl-4-methylpyrimidine hydrochloride, contains this 2-sulfydryl-4-methylpyrimidine hydrochloride in the scope of 2000-50000ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94056/2002 | 2002-03-29 | ||
| JP2002094056A JP3854523B2 (en) | 2002-03-29 | 2002-03-29 | Resist stripper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1533516A true CN1533516A (en) | 2004-09-29 |
| CN1238771C CN1238771C (en) | 2006-01-25 |
Family
ID=28671776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03800355 Expired - Fee Related CN1238771C (en) | 2002-03-29 | 2003-03-27 | Resist removing agent |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3854523B2 (en) |
| CN (1) | CN1238771C (en) |
| WO (1) | WO2003083581A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102213921A (en) * | 2011-05-27 | 2011-10-12 | 惠州市星之光科技有限公司 | Solder-dissolution-preventing stripping liquid for etching PCB (Printed Circuit Board) as well as preparation method and application thereof |
| CN101794087B (en) * | 2009-11-26 | 2013-04-17 | 株式会社Lg化学 | Stripper composition for photoresist and method for using the stripper composition to strip the photoresist |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060154186A1 (en) * | 2005-01-07 | 2006-07-13 | Advanced Technology Materials, Inc. | Composition useful for removal of post-etch photoresist and bottom anti-reflection coatings |
| JP4692497B2 (en) * | 2007-02-28 | 2011-06-01 | ナガセケムテックス株式会社 | Photoresist stripper composition |
| WO2011037300A1 (en) * | 2009-09-25 | 2011-03-31 | 주식회사 엘지화학 | Photoresist stripper composition and photoresist peeling method employing same |
| KR101420571B1 (en) * | 2013-07-05 | 2014-07-16 | 주식회사 동진쎄미켐 | Remover composition for dryfilm resist and removing method using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60108286T2 (en) * | 2000-03-27 | 2005-12-29 | Shipley Co., L.L.C., Marlborough | Removal agent for polymer |
| JP2002062668A (en) * | 2000-08-14 | 2002-02-28 | Mitsubishi Gas Chem Co Inc | Method for removing photoresist |
| JP2002072505A (en) * | 2000-08-29 | 2002-03-12 | Nagase Kasei Kogyo Kk | Photoresist-removing agent composition and method for use thereof |
| JP4692799B2 (en) * | 2001-05-22 | 2011-06-01 | ナガセケムテックス株式会社 | Resist stripping composition |
-
2002
- 2002-03-29 JP JP2002094056A patent/JP3854523B2/en not_active Expired - Fee Related
-
2003
- 2003-03-27 CN CN 03800355 patent/CN1238771C/en not_active Expired - Fee Related
- 2003-03-27 WO PCT/JP2003/003824 patent/WO2003083581A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101794087B (en) * | 2009-11-26 | 2013-04-17 | 株式会社Lg化学 | Stripper composition for photoresist and method for using the stripper composition to strip the photoresist |
| CN102213921A (en) * | 2011-05-27 | 2011-10-12 | 惠州市星之光科技有限公司 | Solder-dissolution-preventing stripping liquid for etching PCB (Printed Circuit Board) as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003295476A (en) | 2003-10-15 |
| CN1238771C (en) | 2006-01-25 |
| WO2003083581A1 (en) | 2003-10-09 |
| JP3854523B2 (en) | 2006-12-06 |
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