CN102163011A - Stripping liquid composition of photoresist - Google Patents
Stripping liquid composition of photoresist Download PDFInfo
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- CN102163011A CN102163011A CN 201110109687 CN201110109687A CN102163011A CN 102163011 A CN102163011 A CN 102163011A CN 201110109687 CN201110109687 CN 201110109687 CN 201110109687 A CN201110109687 A CN 201110109687A CN 102163011 A CN102163011 A CN 102163011A
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Abstract
The invention provides a stripping liquid composition of a photoresist, comprising inorganic alkali, organic alkali, water-soluble organic solvent, anti-corrosion agent and water. The mass proportion rate between the inorganic alkali and the organic alkali is 1: 30 to 30: 1. The stripping liquid of the invention is specifically suitable for stripping a dry film of which the thickness is more than 100 mum; and the thick dry film is totally stripped under the low temperature (45-55 DEG C) and the short time (less than 30 min).
Description
Technical field
The present invention relates to a kind of remover composition of photoresist, the thickness that is specially adapted to base plate for packaging is peeling off of the above photoresist film of 100 μ m, also is applicable to the peeling off of photoresist film of PCB.
Background technology
Base plate for packaging can be chip effects such as electrical connection, protection, support, heat radiation, assembling is provided, and to realize many pinizations, dwindles the encapsulating products volume, improves the purpose of electrical property and thermal diffusivity, super-high density or multi-chip moduleization.The thickness of used photoresist film in the base plate for packaging processing procedure (100u, 120 μ m), relatively the thickness (30 μ m, 40 μ m) of the photoresist film of being used always in PCB, FPC, TFT, LCD increases a lot.For peeling off of thin dry film, propose quaternary ammonium hydroxide, water-soluble amine, water-miscible organic solvent composition among the Chinese patent CN1428659A and peel off photoresist film.Chinese patent CN101692155A has proposed a kind ofly to comprise cyclammonium or/and the photoresist film stripping composition of diamines, gylcol ether, polar solvent.In addition, proposed to contain the photoresist film stripping composition of azanol, solvent, amine among the Chinese patent CN101544932A.For thick dry film greater than 100 μ m, use existing stripping means, be difficult to strip fully totally in lower temperature (45-55 ℃), short period (in the 30min).Though by extending contact time, improve working temperature, the aggressiveness that perhaps increases solution can make to be peeled off effect and improves, and also brings new problem, reduces as production efficiency, and machine utilization increases, and base material corrodes and increases the weight of.
Summary of the invention
The invention provides a kind of remover composition of photoresist, the thickness that is specially adapted to base plate for packaging is peeling off of the above photoresist film of 100 μ m, can't photoresist film be stripped totally and make easily technical matterss such as the base material corrosion increases the weight of fully to overcome the prior art stripping means.
Technical scheme of the present invention is as follows:
A kind of remover composition of photoresist comprises
(1) inorganic base, content are 0.1-35wt%;
(2) organic base, content are 0.01-50wt%;
(3) water-miscible organic solvent, content are 1-60wt%;
(4) anticorrosive, content are 0.05-15wt%;
(5) surplus is a water.
The quality proportioning of above-mentioned inorganic base and organic base generally is defined as: inorganic base: organic base=1: 30～30: 1.
In the preferred NaOH of above-mentioned inorganic base, potassium hydroxide, the lithium hydroxide one or both.In fact, inorganic base generally commonly used all can be applied to the present invention.
The preferred alkanolamine of above-mentioned organic base is or/and at least a in the quaternary amine alkali.In fact, organic base generally commonly used all can be applied to the present invention.
The preferred N-Methyl pyrrolidone of above-mentioned water-miscible organic solvent, N, any mixing of one or more in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), the alkyl alcohol ether.In fact, organic solvent generally commonly used all can be applied to the present invention.
Above-mentioned anticorrosive optimization aromatic hydroxyl compound is or/and at least a in the azole compounds.In fact, organic solvent generally commonly used all can be applied to the present invention.
At least a in the preferred gallic acid of above-mentioned aromatic hydroxy compound, tannic acid, phytic acid, catechol, the p-dihydroxy-benzene; At least a in the preferred triazole of azole compounds, methyl triazole, benzotriazole, benzo tetrazole, the amino tetrazole.
The preferable prescription of remover composition of the present invention is:
(1) inorganic base, content are 0.5-20wt%;
(2) organic base, content are 0.1-30wt%;
(3) water-miscible organic solvent, content are 5-40wt%;
(4) anticorrosive, content are 0.1-10wt%;
(5) surplus is a water.
The better prescription of remover composition of the present invention is:
(1) inorganic base, content are 1-10wt%;
(2) organic base, content are 1-20wt%;
(3) water-miscible organic solvent, content are 10-25wt%;
(4) anticorrosive, content are 0.5-8wt%;
(5) surplus is a water.
The remover composition of photoresist of the present invention is used for the peeling off of photoresist film of base plate for packaging, also is used for the peeling off of photoresist film of PCB, FPC, TFT, LCD.
The present invention has the following advantages:
1, for thickness be more than the 100 μ m photoresist film peel off excellent.
2, implement temperature low (45-55 ℃), time short (＜30min).
3, the water requirement is low, and content range is wide, and service condition is simple, and by optimizing technology, it is minimized to reach cost.
4, the low bubble property of system need not be added defoamer, and therefore, the plate face does not have silicon spot, gel defective.
Embodiment
Photoresist release agent compositions of the present invention is the composition that contains inorganic base, organic base, water-miscible organic solvent, anticorrosive and water.
Inorganic base described in the present invention comprises a kind or 2 kinds in NaOH, potassium hydroxide, the lithium hydroxide.The content of described inorganic base is 0.1wt%-35wt%., and preferred 0.5-20wt% when more preferably 1-10wt%. concentration is less than 0.1wt%, does not have the effect of concerted attack photoresist film; During greater than 35wt%, the base material corrosion is increased the weight of.
Organic base described in the present invention comprises at least a in alkanolamine, the quaternary amine alkali.Concrete example as alkanolamine, can be selected from monoethanolamine, diethanolamine, triethanolamine, 2-(the amino methoxyl of 2-) ethanol, 2-(2-ethoxy) ethanol, N-methylethanolamine, N, N-dimethylethanolamine, N-ehtylethanolamine, N, in N-diethyl ethanolamine, N methyldiethanol amine, N-butylethanolamine, single isopropyl hydramine, diisopropyl hydramine, the triisopropyl hydramine a kind or 2 kinds.As the concrete example of quaternary amine alkali, can be selected from a kind or 2 kinds in tetramethyl ammonium hydroxide, hydroxide trimethyl ethyl ammonium, hydroxide dimethyl diethyl ammonium, tetrabutylammonium, tetrapropylammonium hydroxide, hydroxide methyltributylammoni,m, hydroxide (2-hydroxyethyl) trimethyl ammonium.The content of described organic base is 0.01-50wt%, and preferred 0.1-30wt% when more preferably 1-20wt%. concentration is less than 0.01wt%, does not have the effect of concerted attack photoresist film; During greater than 30wt%, the attack of base material corrosion is increased the weight of.
Water-miscible organic solvent described in the present invention comprises N-Methyl pyrrolidone, N, at least a in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), the alkyl alcohol ether.As the concrete example of alkyl alcohol ether, can be selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, Glycol Monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol one propyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol one propyl ether, the dipropylene glycol monobutyl ether more than a kind or 2 kinds.Described water-miscible organic solvent content is for being 1-60wt%, and preferred 5-40wt% when more preferably 10-25wt%. concentration is less than 1wt%, does not have the effect that improves the dissolving photoresist film; During greater than 60wt%, can not get better improving the effect of dissolving rete.
Anticorrosive described in the present invention comprises at least a in aromatic hydroxy compound and the azole compounds.The aromatic hydroxy compound concrete example has at least a in gallic acid, tannic acid, phytic acid, catechol, the p-dihydroxy-benzene.The azole compounds concrete example has at least a in triazole, methyl triazole, benzotriazole, benzo tetrazole, the amino tetrazole.Described anticorrosive content 0.05-15wt%, preferred 0.1-10wt%, more preferably 0.5-8wt%. concentration can not get the effect that prevents that fully substrate metal is corroded less than 0.05% o'clock; Greater than 15% o'clock, reduce the detachment rate of photoresist rete.
Water is to comprise tap water, ion exchange water, pure water, ultrapure water among the present invention, content be 5-85wt%. content less than 5% o'clock, the composition stripping ability reduces; Content was greater than 85% o'clock, and stripping ability reduces, and corrosion increases the weight of to the copper layer simultaneously.
Photoresist release agent compositions of the present invention, serviceability temperature is not particularly limited, and preferred 45-55 ℃, when being lower than 45 ℃, photoresist rete detachment rate is slow, is uneconomic on the production time; When being higher than 55 ℃, though photoresist rete detachment rate increases, the component volatilization amount increases, and stable unfavorable to system can increase machine utilization simultaneously.
The following embodiment of the invention be used for the present invention is further specified, but the present invention is not limited to following examples.
Plate size as test is 5 * 5cm, and the photoresist bed thickness is 120 a μ m. preparation 500mL stripper, water-bath 55-65 ℃, under the stirring condition, test board is dipped in the stripper liquid 30 minutes.Take out, washing, drying, microscopically is observed and is peeled off effect, degree of oxidation, base material extent of corrosion.
Table 1 photoresist remover composition (wt%)
Should illustrate that each material is as follows shown in the table 1.
NaOH: NaOH
KOH: potassium hydroxide
LiOH: lithium hydroxide
MEA: monoethanolamine
The BEA:N-butylethanolamine
TMAH: tetramethyl ammonium hydroxide
DDAH: hydroxide dimethyl diethyl ammonium
The NMP:N-N-methyl-2-2-pyrrolidone N-
DMF:N, dinethylformamide
DMSO: dimethyl sulfoxide (DMSO)
BTZ: benzotriazole
BTT: benzo tetrazole
The amino tetrazole of ATZ:5-
GC: gallic acid
TC: tannic acid
CC: catechol
Table 2 photoresist remover composition is peeled off effect
| Temperature ℃ | Time min | Peel off effect | Degree of oxidation | The base material corrosion | |
| Embodiment 1 | 60 | ?30 | A | a | d |
| Embodiment 2 | 60 | ?30 | A | a | d |
| Embodiment 3 | 60 | ?30 | A | a | d |
| Embodiment 4 | 60 | ?30 | A | a | d |
| Embodiment 5 | 60 | ?30 | A | a | d |
| Embodiment 6 | 60 | ?30 | A | a | d |
| Embodiment 7 | 60 | ?30 | A | b | e |
| Embodiment 8 | 60 | ?30 | A | b | e |
| Embodiment 9 | 60 | ?30 | A | b | e |
| Embodiment 10 | 60 | ?30 | A | a | d |
| Embodiment 11 | 60 | ?30 | A | a | d |
| Comparative example 1 | 60 | ?30 | B | a | d |
| Comparative example 2 | 60 | ?30 | C | b | f |
| Comparative example 3 | 60 | 30 | B | a | d |
| Comparative example 4 | 60 | 30 | A | c | e |
| Comparative example 5 | 60 | 30 | C | b | f |
The implication of each code name is as follows in the table 2:
Peel off effect
A: peel off B fully: small amount of residual, C: more residual.
Degree of oxidation
A: non-oxidation, b: mild oxidation, C: severe oxidation.
The base material corrosion
D: do not have corrosion, e: mild corrosion, f: seriously corroded.
According to above-mentioned inorganic base, organic base, water-miscible organic solvent, antioxidant, anticorrosive, the physics of the selectable concrete reagent of surfactant, chemical property, can theory know by inference, adopt its other various concrete reagent in above-mentioned optional scope and composition thereof respectively, the remover composition that obtains also can play essentially identical effect.
Claims (10)
1. the remover composition of a photoresist is characterized in that: comprise
(1) inorganic base, content are 0.1-35wt%;
(2) organic base, content are 0.01-50wt%;
(3) water-miscible organic solvent, content are 1-60wt%;
(4) anticorrosive, content are 0.05-15wt%;
(5) surplus is a water.
2. the remover composition of photoresist according to claim 1 is characterized in that, the quality proportioning of described inorganic base and organic base is: inorganic base: organic base=1: 30～30: 1.
3. the remover composition of photoresist according to claim 2, it is characterized in that: described inorganic base comprises one or both in NaOH, potassium hydroxide, the lithium hydroxide.
4. the remover composition of photoresist according to claim 2 is characterized in that: described organic base comprises alkanolamine or/and at least a in the quaternary amine alkali.
5. the remover composition of photoresist according to claim 2, it is characterized in that: described water-miscible organic solvent comprises N-Methyl pyrrolidone, N, the any mixing of in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), the alkyl alcohol ether one or more.
6. the remover composition of photoresist according to claim 2 is characterized in that: described anticorrosive comprises aromatic hydroxy compound or/and at least a in the azole compounds.
7. the remover composition of photoresist according to claim 6 is characterized in that: described aromatic hydroxy compound comprises at least a in gallic acid, tannic acid, phytic acid, catechol, the p-dihydroxy-benzene; Azole compounds comprises at least a in triazole, methyl triazole, benzotriazole, benzo tetrazole, the amino tetrazole.
8. according to the remover composition of the arbitrary described photoresist of claim 1 to 7, it is characterized in that: (1) inorganic base, content are 0.5-20wt%;
(2) organic base, content are 0.1-30wt%;
(3) water-miscible organic solvent, content are 5-40wt%;
(4) anticorrosive, content are 0.1-10wt%;
(5) surplus is a water.
9. the remover composition of photoresist according to claim 8 is characterized in that:
(1) inorganic base, content are 1-10wt%;
(2) organic base, content are 1-20wt%;
(3) water-miscible organic solvent, content are 10-25wt%;
(4) anticorrosive, content are 0.5-8wt%;
(5) surplus is a water.
10. the remover composition of photoresist according to claim 1 is used for the peeling off of photoresist film of base plate for packaging, also is used for the peeling off of photoresist film of PCB, FPC, TFT, LCD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201110109687 CN102163011A (en) | 2011-04-29 | 2011-04-29 | Stripping liquid composition of photoresist |
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|---|---|---|---|
| CN 201110109687 CN102163011A (en) | 2011-04-29 | 2011-04-29 | Stripping liquid composition of photoresist |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102944986A (en) * | 2012-11-13 | 2013-02-27 | 大连三达维芯半导体材料有限公司 | Polyimide stripping liquid for chips and preparation method of polyimide stripping liquid |
| CN102968002A (en) * | 2012-11-13 | 2013-03-13 | 大连三达维芯半导体材料有限公司 | Drying film remover for chip and preparation method of remover |
| CN104195558A (en) * | 2014-08-06 | 2014-12-10 | 东莞市凯昶德电子科技股份有限公司 | Film-stripping liquid |
| CN105116696A (en) * | 2015-10-10 | 2015-12-02 | 蓝思科技（长沙）有限公司 | Photoresist stripper and application thereof |
| CN105388713A (en) * | 2015-12-16 | 2016-03-09 | 无锡吉进环保科技有限公司 | Aluminum film drainage photoresist stripper in thin-film liquid crystal display |
| CN105573070A (en) * | 2015-12-16 | 2016-05-11 | 无锡吉进环保科技有限公司 | Preparation method of aluminum film water-based light-resistant stripping liquid in thin film liquid crystal display |
| CN106227004A (en) * | 2016-09-19 | 2016-12-14 | 江阴江化微电子材料股份有限公司 | A kind of copper or copper alloy wiring water system photoresistance stripper |
| CN107908084A (en) * | 2017-11-21 | 2018-04-13 | 东莞市广华化工有限公司 | A kind of new-type inorganic environmental protection moves back film liquid |
| CN107957661A (en) * | 2016-10-18 | 2018-04-24 | 东友精细化工有限公司 | Anticorrosive additive stripping liquid controlling composition and the stripping means using its resist |
| CN108319118A (en) * | 2018-03-15 | 2018-07-24 | 昆山长优电子材料有限公司 | Organic stripper solution |
| CN108693717A (en) * | 2017-03-29 | 2018-10-23 | 东友精细化工有限公司 | Anticorrosive additive stripping liquid controlling composition |
| CN106227004B (en) * | 2016-09-19 | 2019-07-16 | 江阴江化微电子材料股份有限公司 | A kind of copper or copper alloy wiring water system photoresist stripper |
| CN110874026A (en) * | 2018-08-31 | 2020-03-10 | 易案爱富科技有限公司 | Stripping liquid composition for color filter and method for using same |
| CN111142341A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Environment-friendly high-stability aqueous photoresist stripping liquid for panels and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102944986A (en) * | 2012-11-13 | 2013-02-27 | 大连三达维芯半导体材料有限公司 | Polyimide stripping liquid for chips and preparation method of polyimide stripping liquid |
| CN102968002A (en) * | 2012-11-13 | 2013-03-13 | 大连三达维芯半导体材料有限公司 | Drying film remover for chip and preparation method of remover |
| CN104195558A (en) * | 2014-08-06 | 2014-12-10 | 东莞市凯昶德电子科技股份有限公司 | Film-stripping liquid |
| CN105116696A (en) * | 2015-10-10 | 2015-12-02 | 蓝思科技（长沙）有限公司 | Photoresist stripper and application thereof |
| CN105388713A (en) * | 2015-12-16 | 2016-03-09 | 无锡吉进环保科技有限公司 | Aluminum film drainage photoresist stripper in thin-film liquid crystal display |
| CN105573070A (en) * | 2015-12-16 | 2016-05-11 | 无锡吉进环保科技有限公司 | Preparation method of aluminum film water-based light-resistant stripping liquid in thin film liquid crystal display |
| CN106227004A (en) * | 2016-09-19 | 2016-12-14 | 江阴江化微电子材料股份有限公司 | A kind of copper or copper alloy wiring water system photoresistance stripper |
| CN106227004B (en) * | 2016-09-19 | 2019-07-16 | 江阴江化微电子材料股份有限公司 | A kind of copper or copper alloy wiring water system photoresist stripper |
| CN107957661A (en) * | 2016-10-18 | 2018-04-24 | 东友精细化工有限公司 | Anticorrosive additive stripping liquid controlling composition and the stripping means using its resist |
| CN108693717A (en) * | 2017-03-29 | 2018-10-23 | 东友精细化工有限公司 | Anticorrosive additive stripping liquid controlling composition |
| CN107908084A (en) * | 2017-11-21 | 2018-04-13 | 东莞市广华化工有限公司 | A kind of new-type inorganic environmental protection moves back film liquid |
| CN108319118A (en) * | 2018-03-15 | 2018-07-24 | 昆山长优电子材料有限公司 | Organic stripper solution |
| CN110874026A (en) * | 2018-08-31 | 2020-03-10 | 易案爱富科技有限公司 | Stripping liquid composition for color filter and method for using same |
| CN111142341A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Environment-friendly high-stability aqueous photoresist stripping liquid for panels and preparation method thereof |
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Application publication date: 20110824 |