Stripping agent for stripping protective coating agent for cutting process
阅读说明：本技术 用于剥离切割工艺用保护性涂层剂的剥离剂 (Stripping agent for stripping protective coating agent for cutting process ) 是由 全成浩 赵峻辉 于 2019-01-18 设计创作，主要内容包括：本发明涉及一种用于剥离切割工艺用保护性涂层剂的剥离剂,具体地说,一种用于剥离切割工艺用保护性涂层剂的剥离剂,其可以去除在进行晶圆制备工艺时为保护晶圆的表面被涂布的保护性涂层剂而不损伤晶圆的表面。(The present invention relates to a stripping agent for stripping a protective coating agent for a dicing process, and more particularly, to a stripping agent for stripping a protective coating agent for a dicing process, which can remove a protective coating agent coated to protect a surface of a wafer without damaging the surface of the wafer when a wafer preparation process is performed.)
1. A stripping agent for stripping a protective coating agent for a cutting process,
the stripping agent is used for stripping the protective coating agent coated on the wafer.
2. The stripping agent for stripping protective coating agent for cutting process according to claim 1,
the stripping agent comprises a hydrophilic solvent compound, an ether compound, a hydroxide compound and a surfactant.
3. The stripping agent for stripping protective coating agent for cutting process according to claim 2,
the stripping agent comprises the hydrophilic solvent compound, the ether compound and the hydroxide compound in a weight ratio of 1: 1.3-1.96: 0.53-0.8.
4. The stripping agent for stripping protective coating agent for cutting process according to claim 1,
the protective coating agent is a protective coating agent for a cutting process.
5. The stripping agent for stripping protective coating agent for cutting process according to claim 2,
the stripping agent comprises a hydrophilic solvent compound, an ether compound, a hydroxide compound and a surfactant,
the hydrophilic solvent compound includes at least one of di (C1-C5) alkyl sulfoxide, di (C1-C5) alkyl amide, and N- (C1-C5) alkyl-2-pyrrolidone,
the ether compound comprises more than one of diethylene glycol mono (C1-C5) alkyl ether, ethylene glycol mono (C1-C5) alkyl ether and diethylene glycol di (C1-C5) alkyl ether,
the hydroxide compound comprises more than one of tetra (C1-C5) alkyl ammonium hydroxide, metal hydroxide and choline hydroxide.
6. The stripping agent for stripping protective coating agent for cutting process according to claim 4, wherein,
the protective coating agent for a cutting process includes a compound represented by the following chemical formula 10:
[ chemical formula 10]
In the chemical formula 10, R13And R14Each independently is C1-C10 alkylene, R15Is C1-C10 alkyl, R24And R25Each independently is R0Is composed of
7. The stripping agent for stripping protective coating agent for cutting process according to claim 4, wherein,
the protective coating agent further includes one or more of a polar organic solvent, a surface conditioning additive, a fluidity modifier, and an adhesion promoter.
8. The stripping agent for stripping protective coating agent for cutting process according to claim 4, wherein,
the protective coating agent further includes a polar organic solvent, a coating agent for surface conditioning, a fluidity adjuster, and an adhesion promoter.
9. The peeling agent for peeling protective coating agent for cutting process as claimed in claim 5, wherein R in the compound represented by the chemical formula 1024And R25Is composed of
10. The stripping agent for stripping protective coating agent for cutting process according to claim 5, wherein,
r in the compound represented by the chemical formula 1024Is composed of
Technical Field
The present invention relates to a stripping agent for stripping a protective coating agent for a dicing process, and more particularly, to a stripping agent for stripping a protective coating agent for a dicing process, which can remove a protective coating agent coated for protecting a surface of a wafer in a wafer preparation process without damaging the surface of the wafer.
Background
In a semiconductor wafer processing process, a dicing process, i.e., a sawing process, is a process between a wafer preparation process and a packaging process and separates a wafer into individual chip units.
Among them, in the process of separating the chips of the semiconductor wafer from each other by the blade, the chips falling on the surfaces of the chips cause defects. In order to solve the above problems, a method has been used in which nozzles are provided on both sides of a blade in a horizontal direction with respect to a wafer, and a large amount of water is sprayed at high pressure to immediately remove debris falling on the surface of a chip. The method is useful when the semiconductor chip size is large, the processing time is short, and the yield of chips is small, however, when the size of the semiconductor chip is gradually reduced, the processing time is increased, and the yield of chips is increased, the chips cannot be immediately removed.
In this regard, in order to overcome the problems, korean patent application No. 10-2009 0066314 discloses a detergent composition prepared using polyethylene oxide/polypropylene oxide (PEO-PPO), polyethylene glycol (PEG), and other additives, the polyethylene oxide/polypropylene oxide being a nonionic surfactant.
However, when the sawing process is performed using the composition, chips of a certain size can be removed, but minute chips cannot be completely removed. As a result, defects such as scratches and gouges caused by the remaining minute chips remain unsolved.
Therefore, a protective coating agent for a dicing process is required which forms a coating layer on a wafer surface and completely prevents defects such as scratches, gouges, stains, whitening, or corrosion, which occur in a machining process such as a cutting process.
On the other hand, for the protective coating agent for the semiconductor dicing process, it is necessary to rearrange the respective chips and remove the coating agent from the surfaces of the respective chips after the dicing process is completed. Since the substance forming the protective coating agent for a wafer is a polymer resin such as a substance forming a photoresist, a stripping agent for stripping the photoresist can be suitably used.
Among the above-mentioned release agents, the release agent disclosed in U.S. Pat. No. 4,617,251 is well known. That is, the U.S. patent publication discloses a positive type photoresist stripping composition comprising a specific amine compound (e.g., (2- (2-aminoethoxy) ethanol) and a specific polar solvent (e.g., tetrahydrofurfuryl alcohol, isophorone, γ -butyrolactone, N-dimethylacetamide, and mixtures thereof).
Korean patent laid-open publication No. 2001-0018377 proposes a photoresist stripper comprising an amine compound, a glycol-based solvent, and perfluoroalkyl ethylene oxide.
Korean patent laid-open publication No. 2000-0016878 proposes a stripping solution consisting of an alkoxy N-hydroxyalkylalkanamide, a polar substance having a dipole moment of 3 or more, a damage preventing agent, and an alkanolamine.
However, the stripping agents suggested in the prior art are used under high temperature process conditions, and thus are disadvantageous in terms of environmental aspects and disposal costs, and also have a limitation in terms of washing residues. Moreover, the process conditions at high temperatures imply a risk of corrosion, and preservatives are used. When azole additives are used for corrosion prevention, biodegradability may be reduced, and as a result, additional waste liquid treatment may be required.
Therefore, there is a need for a stripping agent which can easily remove a protective coating agent remaining on the surface of a wafer at room temperature and which does not cause damage such as corrosion.
Disclosure of Invention
Technical problem
The present invention has been made in view of the above circumstances, and an object thereof is to provide a stripping agent for stripping a protective coating agent for a dicing process, which can easily remove a coating layer formed on a wafer surface in a semiconductor manufacturing process without damaging the wafer surface.
Technical scheme
In order to solve the technical problems, the stripping agent for stripping the protective coating agent for the cutting process, the protective coating agent for stripping the coating on the surface of the wafer,
for example, the release agent may include a hydrophilic solvent-based compound, an ether-based compound, a hydroxide-based compound, and a surfactant.
For example, the stripping agent comprises a hydrophilic solvent compound, an ether compound and a hydroxide compound in a weight ratio of 1:1.3 to 1.96:0.53 to 0.8.
For example, the release agent may include a hydrophilic solvent-based compound, an ether-based compound, a hydroxide-based compound, and a surfactant.
As an example, the hydrophilic solvent-based compound may include one or more of di (C1-C5) alkyl sulfoxide (di (C1-C5) alkyl sulfoxide), di (C1-C5) alkylamide (di (C1-C5) alkyl amide), and N- (C1-C5) alkyl-2-pyrrolidone (N-alkyl-2-pyrrolidone), the ether compound may include one or more of Diethylene glycol mono (C1-C5) alkyl ether (Diethylene glycol mono (C1-C5) alkyl ether), ethylene glycol mono (C1-C5) alkyl ether (ethylene glycol mono (C1-C5) alkyl ether) and Diethylene glycol di (C1-C5) alkyl ether (Diethylene glycol di (C1-C5) alkyl ether), the hydroxide compound may include at least one of tetra (C1-C5) alkylammonium hydroxide (tetra (C1-C5) alkylammonium hydroxide), metal hydroxide (methahydroxide), and choline hydroxide (choline hydroxide).
As a preferred embodiment of the present invention, the surfactant may have an average HLB (Hydrophile-Lipophile Balance) value of 10 to 15.
In a preferred embodiment of the present invention, the hydrophilic solvent compound, the ether compound, and the hydroxide compound may be present in a weight ratio of 1:1.3 to 1.96:0.53 to 0.8.
As a preferred embodiment of the present invention, the stripping agent may have a pH of 8 to 14.
As a preferred embodiment of the present invention, the protective coating agent for a cutting process may include a compound represented by the following chemical formula 10.
[ chemical formula 10]
In the chemical formula 10, R13And R14Each independently is C1-C10 alkylene, R15Is C1-C10 alkyl, R24And R25Each independently is
As an embodiment, the protective coating agent further includes one of a polar organic solvent, a surface conditioning additive, a fluidity modifier, and an adhesion promoter.
As an embodiment, the protective coating agent further includes one of a polar organic solvent, a surface conditioning additive, a fluidity modifier, and an adhesion promoter.
As a preferred embodiment of the present invention, R in the compound represented by the chemical formula 1024And R25Can be
As a preferred embodiment of the present invention, in the compound represented by the chemical formula 10, R24Can be
R25Can be
In another aspect, the wafer processing process of the present invention may include: a first step of coating the surface of a wafer with a protective coating agent for a dicing process; a second step of disposing the wafer on a pulling device; a third step of dicing the wafer; a fourth step of selecting only good products from the cut parts subjected to the cutting process and arranging the good products; a fifth step of peeling the protective coating agent for a dicing process from the selected good product by using the peeling agent for peeling the protective coating agent for a dicing process; and a sixth step of inspecting a good product after the protective coating agent for dicing process is peeled off.
As a preferred embodiment of the present invention, the first process may be performed at 0 to 50 ℃ for 1 to 60 seconds, and the fifth process may be performed at a temperature of 10 to 50 ℃ for 1 to 10 minutes.
On the other hand, in the case of representing the compound of the present invention, the symbol indicates a chemical bond site, and the compound represented by the above chemical formula 10 is described as an example in the case of constituting R1Is/are as follows
Effects of the invention
With the stripping agent for stripping a protective coating agent for a dicing process of the present invention, the protective coating agent formed on the surface of a wafer is stripped with the stripping agent of the present invention excluding an organic solvent (e.g., alcohol), whereby the protective coating agent formed on the surface of the wafer in a wafer processing process of a semiconductor manufacturing process can be easily removed without damaging the wafer.
Further, the release agent for releasing the protective coating agent for a dicing process of the present invention is hydrophilic and easily mixed with water, and thus not only does not cause problems such as rotten materials during the release process, but also can be washed with water without using an organic solvent such as alcohol.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily implement the embodiments of the present invention. The invention can be implemented in various different ways and is not limited to the embodiments described in the present invention. In the drawings, portions that are not related to the description are omitted for clarity of description, and the same reference numerals are used for the same or similar components throughout the specification.
The stripping agent for stripping the protective coating agent for the cutting process of the present invention is a stripping agent for stripping the protective coating agent used in the cutting process.
The stripping agent for stripping the protective coating agent for the cutting process comprises a hydrophilic solvent compound, an ether compound, a hydroxide compound and a surfactant.
First, the hydrophilic solvent-based compound of the present invention may include one or more of Di (C1 to C5) alkyl sulfoxide (Di (C1 to C5) alkyl sulfoxide), Di (C1 to C5) alkyl amide (Di (C1 to C5) alkyl amide), and N- (C1 to C5) alkyl-2-pyrrolidone (N-alkyl-2-pyrrolidone), preferably may include Di (C1 to C5) alkyl sulfoxide (Di (C1 to C5) alkyl sulfoxide), and more preferably may include Dimethyl sulfoxide (Dimethyl sulfoxide).
Further, the ether compound of the present invention may include one or more of Diethylene glycol mono (C1 to C5) alkyl ether (Diethylene glycol mono (C1 to C5) alkyl ether), ethylene glycol mono (C1 to C5) alkyl ether (ethylene glycol mono (C1 to C5) alkyl ether), and Diethylene glycol di (C1 to C5) alkyl ether (Diethylene glycol di (C1 to C5) alkyl ether), and preferably may include Diethylene glycol mono (C1 to C5) alkyl ether (Diethylene glycol mono (C1 to C5) alkyl ether), and more preferably may include Diethylene glycol monomethyl ether (Diethylene glycol monomethyl ether).
The ether compound of the present invention may be used in an amount of 1.3 to 1.96 parts by weight, preferably 1.47 to 1.80 parts by weight, and more preferably 1.55 to 1.72 parts by weight, based on 1 part by weight of the hydrophilic solvent compound. When the amount of the ether compound is less than 1.3 parts by weight based on 1 part by weight of the hydrophilic solvent compound, the protective coating agent peeled off by the peeling agent of the present invention may be precipitated; when the weight ratio of the ether compound to 1 part by weight of the hydrophilic solvent compound exceeds 1.96 parts by weight, the water solubility may decrease and the release agent may not be removed by water.
The hydroxide-based compound of the present invention may include at least one of tetra (C1 to C5) alkylammonium hydroxide (tetra (C1 to C5) alkylammonium hydroxide), metal hydroxide (metal hydroxide) and choline hydroxide (choline hydroxide), preferably tetra (C1 to C5) alkylammonium hydroxide (tetra (C1 to C5) alkylammonium hydroxide), and more preferably tetramethylammonium hydroxide (tetramethylammonium hydroxide).
The hydroxide-based compound of the present invention may be contained in an amount of 0.53 to 0.8 parts by weight, preferably 0.6 to 0.74 parts by weight, and more preferably 0.63 to 0.7 parts by weight, based on 1 part by weight of the hydrophilic solvent-based compound. When the amount of the hydroxide compound is less than 0.53 parts by weight based on 1 part by weight of the hydrophilic solvent compound, the releasability is reduced; when the amount of the hydroxide compound to 1 part by weight of the hydrophilic solvent compound exceeds 0.8 part by weight, the hydroxide compound may be too basic to corrode.
Finally, the surfactant of the present invention may have an average HLB (Hydrophile-Lipophile Balance) value of 10 to 15, preferably 11 to 14, and more preferably 12 to 13. When the average HLB value is less than 10, there is a problem of deterioration in detergency performance, and when the average HLB value exceeds 15, there is a problem of deterioration in water solubility and non-emulsification of the surfactant.
The surfactant of the present invention may include one or more of a nonionic surfactant and an anionic surfactant, preferably as a nonionic surfactant, may include one or more of alkyl polyglucoside, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene alkyl octyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyethylene glycol fatty acid ester and polyoxyethylene sorbitan fatty acid ester (polyoxyyethylene sorbent fatty acid ester) as an anionic surfactant, may include alkyl ether sulfate, alkyl benzene sulfonate, alkyl sulfosuccinate (alkyl sulfosuccinate), alkyl ether phosphate, alkyl benzene phosphate, and one or more of these salts, and more preferably may include alkyl polyglucoside as a nonionic surfactant and alkyl ether phosphate as an anionic surfactant.
The surfactant of the present invention may be contained in an amount of 0.02 to 0.04 parts by weight, preferably 0.03 to 0.037 parts by weight, based on 1 part by weight of the hydrophilic solvent-based compound. When the amount of the surfactant is less than 0.02 parts by weight based on 1 part by weight of the hydrophilic solvent-based compound, there is a problem that the cleaning performance and the permeability are reduced, and when the weight ratio of the surfactant exceeds 0.04 parts by weight, a large amount of foam is generated.
The stripping agent for stripping the protective coating agent for the cutting process can have an effective alkalinity of 20-35, preferably an effective alkalinity of 22-33, more preferably an effective alkalinity of 25-30, and when the effective alkalinity is less than 20, the stripping performance is reduced when the protective coating agent is stripped by the stripping agent; when the effective basicity exceeds 35, corrosion may occur.
In addition, the stripping agent for stripping the protective coating agent for the cutting process can have a pH of 8-14, preferably a pH of 9-13, more preferably a pH of 10-12, and when the pH is less than 8, the stripping time is increased; when the pH exceeds 14, the stripping agent becomes a strongly alkaline solution, and thus, a problem occurs in treating wastewater.
Further, the protective coating agent for a dicing process peeled by the peeling agent for peeling the protective coating agent for a dicing process of the present invention may include a compound represented by the following chemical formula 10.
[ chemical formula 10]
In the chemical formula 10, R13And R14Each independently may be a C1 to C10 alkylene group, preferably a C1 to C5 alkylene group, R15The alkyl group may be a C1 to C10 alkyl group, and more preferably a C1 to C5 alkyl group.
And, in the chemical formula 10, R24And R25Each independently may be
Also, in the chemical formula 10, R0Can be that
Also, in the chemical formula 10, R1Can be that OrPreferably may be
Also, in the chemical formula 10, R2、R3、R4、R5、R6、R7And R8Each independently may be a C1 to C15 alkylene group, and preferably may beThe alkylene group is a C1-C10 alkylene group, and n, m and l may be each independently an integer of 1-50, preferably an integer of 1-20.
In the chemical formula 10, R16May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group, R20May be a C1-C10 alkylene group,OrIt may preferably be a C1-C10 alkylene group, more preferably a C1-C5 alkylene group, R27、R28、R29、R30And R31Each independently may be a C1 to C10 alkylene group, preferably a C1 to C5 alkylene group, R21、R22And R23Each independently may be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
In the chemical formula 10, A+Can be that
In the compound represented by chemical formula 10, preferably, R24And R25Can be that
In the compound represented by chemical formula 10, preferably, R24Can be that
R25Can be that
The protective coating agent for dicing process to be peeled by the peeling agent for peeling the protective coating agent for dicing process of the present invention may include one or more of a polar organic solvent, an additive for surface conditioning, a fluidity modifier and an adhesion promoter, and preferably may include a polar organic solvent, an additive for surface conditioning, a fluidity modifier and an adhesion promoter. Also, the protective coating agent for a cutting process may further include water.
First, the polar organic solvent may include one or more of an alcohol solvent, a ketone solvent, and a glycol ether solvent, preferably one or more of an alcohol solvent and a ketone solvent, and more preferably a C1 to C10 alcohol solvent, for dissolving the compound represented by chemical formula 10.
The polar organic solvent may be contained in an amount of 8 to 500 parts by weight, preferably 8 to 36 parts by weight, more preferably 9 to 33 parts by weight, and still more preferably 9.5 to 31.5 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 10. When the weight part of the polar organic solvent is less than 8 parts by weight, there is a problem in that the compound represented by chemical formula 10 is precipitated, and when the weight part of the polar organic solvent exceeds 500 parts by weight, there is a problem in that the coating state is poor when the protective coating agent of the present invention is used for coating.
Secondly, the surface conditioning additive exerts the following effects: the protective coating agent of the present invention imparts surface slip characteristics after coating. The surface conditioning additive may include a silicon-based surface conditioning additive, and preferably includes one or more of MODAREZ K-SE 305, MODAREZ K-SL 106, MODAREZ K-SL 107, BYK-331, BYK-333, BYK-348 and BYK-3455 of PROTEX International.
The surface conditioning additive may be contained in an amount of 0.08 to 100 parts by weight, preferably 0.08 to 0.6 part by weight, more preferably 0.09 to 0.55 part by weight, and still more preferably 0.095 to 0.525 part by weight, based on 100 parts by weight of the compound represented by chemical formula 10. When the amount of the surface conditioning additive is less than 0.08 parts by weight, the slip characteristics are insufficient and impurities are adhered; when the amount of the surface conditioning additive exceeds 100 parts by weight, the adhesive force may decrease.
Secondly, a fluidity modifier is used to adjust the viscosity of the protective coating agent in the present invention. The fluidity additive may comprise one or more of PROX A300, PROX AM162S, SYNTHRO THIX 608, BYK-405, BYK-420 and BYK-7420ES available from PROTEX International.
The fluidity modifier may be included in an amount of 0.4 to 200 parts by weight, preferably 0.4 to 0.6 part by weight, more preferably 0.45 to 0.55 part by weight, and still more preferably 0.475 to 0.525 part by weight, based on 100 parts by weight of the compound represented by chemical formula 10. When the fluidity modifier is less than 0.4 part by weight, the coating thickness becomes thin when the protective coating agent of the present invention is used for coating because of low viscosity, and when the fluidity modifier is more than 200 parts by weight, the coating lacks uniformity because of high viscosity.
The adhesion promoter may be one or more of BYK-4509 and BYK-4500 available from BYK corporation, for improving the adhesion of the protective coating agent of the present invention.
The adhesion promoter may be contained in an amount of 0.32 to 250 parts by weight, preferably 0.32 to 1.2 parts by weight, more preferably 0.36 to 1.1 parts by weight, and still more preferably 0.38 to 1.05 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 10. When the adhesion promoter is less than 0.32 part by weight, the adhesion force may be reduced; when the adhesion promoter is contained in an amount of more than 250 parts by weight, the slip characteristics may be deteriorated.
Finally, water may be included in an amount of 24 to 48 parts by weight, preferably 27 to 44 parts by weight, and more preferably 28.5 to 42 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 10. When the amount of water is less than 24 parts by weight, the thickness of the coating layer becomes thick when the wafer is coated with the protective coating agent, which causes problems in peeling; when the amount of water exceeds 48 parts by weight, poor curing may occur.
On the other hand, the protective coating agent for dicing process peeled by the peeling agent for peeling protective coating agent for dicing process of the present invention can be produced according to the following production method.
The method for preparing the protective coating agent for the cutting process of the present invention includes first to third steps.
First, as a first step, a compound represented by the following chemical formula 7, a compound represented by the following chemical formula 8, a compound represented by the following chemical formula 9, and a solvent may be mixed to perform mixing and polymerization reactions to prepare a first polymer.
[ chemical formula 7]
In the chemical formula 7, R1Can be that
Also, in the chemical formula 7, R2、R3、R4、R5、R6、R7And R8Each independently may be a C1-C15 alkylene group, and preferably may be a C1-C10 alkylene group.
In the chemical formula 1, n, m, and l may each independently be an integer of 1 to 50, and preferably may be an integer of 1 to 20.
[ chemical formula 8]
O＝C＝N-R0-N＝C＝O
In the chemical formula 8, R0Can be thatOr isPreferably may be
Also, in the chemical formula 8, R9、R10、R11And R32Each independently may be hydrogen or a C1-C10 alkyl group, preferably may be a C1-C5 alkyl group.
And, in the chemical formula 8, R12May be a C1-C10 alkylene group, and may preferably be a C1-C5 alkylene group.
[ chemical formula 9]
In the chemical formula 9, R13And R14Each independently may be a C1-C10 alkylene group, and preferably may be a C1-C5 alkylene group.
Also, in the chemical formula 9, R15May be a C1-C10 alkyl group, preferably may be a C1-C5 alkyl group.
The solvent used in the first step may include one or more of N-methyl-2-pyrrolidone NMP (N-methyl-2-pyrrolidone), N-dimethylformamide DMF (N, N-dimethylformamide), N-dimethylacetamide DMA (N, N-dimethylacetamide), and methyl ethyl ketone mek (methyl ethyl ketone), and preferably may include N-methyl-2-pyrrolidone NMP (N-methyl pyrrolidone).
In the first step, the compound represented by chemical formula 8 may be contained in an amount of 101 to 153 parts by weight, preferably 114 to 140 parts by weight, and more preferably 120 to 134 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the compound represented by chemical formula 8 accounts for less than 101 parts by weight, the adhesion after curing may be weakened; when the compound represented by chemical formula 8 is contained in an amount of more than 153 parts by weight, the visibility of the surface of the wafer after coating may be reduced.
In the first step, the compound represented by chemical formula 9 may be contained in an amount of 11 to 18 parts by weight, preferably 13 to 17 parts by weight, and more preferably 14 to 16 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the compound represented by chemical formula 9 accounts for less than 11 parts by weight, dispersibility to water may be reduced; when the amount of the compound represented by chemical formula 9 is more than 18 parts by weight, water resistance may be weakened after curing.
In the first step, the solvent may be used in an amount of 40 to 61 parts by weight, preferably 45 to 56 parts by weight, and more preferably 39 to 45 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the solvent is less than 40 parts by weight, the coating may lack uniformity due to excessively high viscosity, and when the solvent is more than 61 parts by weight, the coating may be deteriorated due to excessively low viscosity.
Also, in the first step, the first polymer may be prepared by mixing and/or polymerizing at a temperature of 80 to 150 ℃, preferably 80 to 140 ℃, at 150 to 250rpm (preferably 170 to 230rpm) for 1 hour to 3 hours (preferably 1.5 hours to 2.5 hours).
At this time, the first polymer to be prepared may be a compound represented by the following chemical formula 5.
[ chemical formula 5]
In the chemical formula 5, R13And R14Each independently may be a C1-C10 alkylene group, and preferably may be a C1-C5 alkylene group.
In the chemical formula 5, R15May be a C1-C10 alkyl group, preferably may be a C1-C5 alkyl group.
In the chemical formula 5, R26Can be thatR0Can be thatOr
Also, in the chemical formula 5, R1Can be that OrPreferably may beR2、R3、R4、R5、R6、R7And R8Each independently may be a C1-C15 alkylene group, preferably may be a C1-C10 alkylene group; n, m and l may each independently be an integer of 1 to 50, and preferably may be an integer of 1 to 20.
Next, in the second step of the method for preparing a protective coating agent for a cutting process of the present invention, a second polymer or a third polymer may be prepared by mixing and reacting the first polymer prepared in the first step with one or more of the compound represented by the following chemical formula 6 and the compound represented by the following chemical formula 4.
[ chemical formula 6]
In the chemical formula 6, R20May be a C1-C10 alkylene group,OrIt may preferably be a C1 to C10 alkylene group, and more preferably a C1 to C5 alkylene group. Also, R27、R28、R29、R30And R31Each independently may be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkylene group.
Also, in the chemical formula 6, R21、R22And R23Each independently may be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
[ chemical formula 4]
R16-OH
In the chemical formula 4, R16May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
To describe the method for preparing the second polymer through the second step in the method for preparing the protective coating agent for a cutting process of the present invention, the second polymer may be prepared by mixing the prepared first polymer with the compound represented by the chemical formula 4 to react, and the prepared second polymer may be the compound represented by the following chemical formula 1-1.
[ chemical formula 1-1]
In the chemical formula 1-1, R13And R14Each independently may be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkylene group.
Also, in the chemical formula 1-1, R15May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
In the chemical formula 1-1, R24And R25Can be that
Also, in the chemical formula 1-1, R0Can be thatOrPreferably may beR9、R10、R11And R32Each independently may be hydrogen or C1-C10 alkyl, preferably C1-C5 alkyl, R12May be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkylene group.
In the chemical formula 1-1, R1Can be that OrPreferably may be
In the chemical formula 1-1, R2、R3、R4、R5、R6、R7And R8Each independently may be a C1-C15 alkylene group, preferably a C1-C10 alkylene group, and n, m, and l each independently may be an integer of 1 to 50, preferably an integer of 1 to 20.
Also, in the chemical formula 1-1, R16May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group, R20May be a C1-C10 alkylene group,Or
In addition, in the second step of preparing the second polymer, the compound represented by chemical formula 4 may be contained in an amount of 29 to 45 parts by weight, preferably 33 to 41 parts by weight, and more preferably 34 to 39 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the compound represented by chemical formula 4 is less than 29 parts by weight, it may be sticky after hardening; when the weight part of the compound represented by chemical formula 4 exceeds 45 parts by weight, the thickness of the coating layer becomes thin after curing.
In the second step, the second polymer may be prepared by mixing and/or reacting at a temperature of 70 to 110 ℃ (preferably, at a temperature of 80 to 100 ℃) at 150 to 250rpm (preferably, 170 to 230rpm) for 10 to 40 minutes (preferably, 20 to 30 minutes).
In addition, a method for preparing the third polymer by the method for preparing the protective coating agent for a cutting process of the present invention, which may include the 2 nd-1 st step and the 2 nd-2 nd step, is specifically described.
In the 2 nd-1 st step of the method for preparing a protective coating agent for a cutting process of the present invention, the prepared first polymer may be mixed with the compound represented by said chemical formula 6 to react and prepare a third intermediate polymer, and the prepared third intermediate polymer may be a compound represented by the following chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, R13And R14Each independently may be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkylene group.
Also, in the chemical formula 3, R15May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
Also, in the chemical formula 3, R26Can be that
R25Can be that
In the chemical formula 3, R0Can be that
Also, in the chemical formula 3, R1Can be that
In the chemical formula 3, R2、R3、R4、R5、R6、R7And R8Each independently may be a C1-C15 alkylene group, preferably a C1-C10 alkylene group, and n, m, and l each independently may be an integer of 1 to 50, preferably an integer of 1 to 20.
Also, in the chemical formula 3, R20May be a C1-C10 alkylene group,OrIt may preferably be a C1-C10 alkylene group, more preferably a C1-C5 alkylene group, R27、R28、R29、R30And R31Each independently is a C1 to C10 alkylene group, which may preferably be a C1 to C10 alkylene group, R21、R22And R23Each independently may be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
In addition, in the case of preparing the third intermediate polymer in the 2 nd-1 st step, the compound represented by the chemical formula 6 may be contained in an amount of 33 to 51 parts by weight, preferably 37 to 47 parts by weight, and more preferably 39 to 45 parts by weight, based on 100 parts by weight of the compound represented by the chemical formula 7. When the content of the compound represented by chemical formula 6 is less than 33 parts by weight, uniformity of the coating surface after curing may be poor, and when the content of the compound represented by chemical formula 6 exceeds 51 parts by weight, precipitates may be generated after preparation.
In the second step, the third intermediate polymer may be prepared by mixing and/or reacting at a temperature of 80 to 150 ℃ (preferably, at a temperature of 80 to 140 ℃), at a speed of 150 to 250rpm (preferably, at a speed of 170 to 230rpm) for 60 to 120 minutes (preferably, 75 to 105 minutes).
In the 2 nd to 2 nd steps of the method for preparing a protective coating agent for a cutting process of the present invention, the third intermediate polymer prepared in the 2 nd to 1 nd step may be mixed with the compound represented by the chemical formula 4 and reacted to prepare a third polymer, and the prepared third polymer may be the compound represented by the following chemical formula 1 to 2.
[ chemical formulas 1-2]
In the chemical formula 1-2, R13And R14Each independently may be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkylene group.
Also, in the chemical formula 1-2, R15May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
In the chemical formula 1-2, R24Can be that
R25Can be that
Also, in the chemical formula 1-2, R0Can be thatOrPreferably may beR9、R10、R11And R32Each independently hydrogen or C1-C10 alkyl, preferably C1 ℃C5 alkyl, R12May be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkylene group.
In the chemical formula 1-2, R1Can be that
Also, in the chemical formula 1-2, R2、R3、R4、R5、R6、R7And R8Each independently may be a C1-C15 alkylene group, preferably a C1-C10 alkylene group, and n, m and l each independently may be an integer of 1 to 50, preferably 1 to 20.
Also, in the chemical formula 1-2, R16May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group, R20May be a C1-C10 alkylene group,
In addition, in the case of preparing the third polymer in the 2 nd to 2 nd steps, the compound represented by chemical formula 4 may be contained in an amount of 29 to 45 parts by weight, preferably 33 to 41 parts by weight, and more preferably 34 to 39 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the content of the compound represented by chemical formula 4 is less than 29 parts by weight, a sticky feeling may be left after curing, and when the content of the compound represented by chemical formula 4 exceeds 45 parts by weight, the thickness of the coating layer after curing may be thinned.
In addition, in the case of preparing the third polymer in the 2 nd-2 nd step, the third polymer may be prepared by mixing and/or reacting at a temperature of 70 to 110 ℃ (preferably, at a temperature of 80 to 110 ℃), at 150 to 250rpm (preferably, at 170 to 230rpm) for 10 to 40 minutes (preferably, 20 to 30 minutes).
Finally, in the third step of the preparation method of the protective coating agent for a cutting process, the prepared second polymer or third polymer and the compound represented by the following chemical formula 2 may be mixed with water and reacted to prepare the compound represented by the following chemical formula 10.
[ chemical formula 2]
In the chemical formula 2, R17、R18And R19Each independently may be hydrogen, aryl or C1-C10 alkyl, preferably C1-C5 alkyl.
[ chemical formula 10]
In the chemical formula 10, R13And R14Each independently may be a C1 to C10 alkylene group, preferably a C1 to C5 alkylene group, R15May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
Also, in the chemical formula 10, R24And R25Each independently may be
Also, in the chemical formula 10, R0Can be that
Also, in the chemical formula 10, R1Can be that OrPreferably may be
Also, in the chemical formula 10, R2、R3、R4、R5、R6、R7And R8Each independently may be a C1-C15 alkylene group, preferably a C1-C10 alkylene group, and n, m, and l each independently may be an integer of 1 to 50, preferably an integer of 1 to 20.
Also, in the chemical formula 10, R16May be a C1-C10 alkyl group, preferably a C1-C5 alkyl group, R20May be a C1-C10 alkylene group,It may preferably be a C1-C10 alkylene group, more preferably a C1-C5 alkylene group, R27、R28、R29、R30And R31Each independently may be a C1 to C10 alkylene group, preferably a C1 to C10 alkylene group, R21、R22And R23Each independently may be a C1 to C10 alkylene group, and preferably may be a C1 to C5 alkyl group.
Also, in the chemical formula 10, A+Can be thatR17、R18And R19Each independently may be hydrogen, aryl or C1-C10 alkyl, preferably C1-C5 alkyl.
Further concretely explaining the third step of the method for preparing the protective coating agent for a cutting process, in the compound represented by the following chemical formula 10, R, prepared by mixing the second polymer prepared in the second step with the compound represented by the chemical formula 2 and water to react them, R24And R25Can be that
In the compound represented by the following chemical formula 10 prepared by mixing the third polymer prepared by the second step with the compound represented by the chemical formula 2 and water to react, R24Can be that
R25Can be that
In addition, in the case of preparing the compound represented by chemical formula 10 in the third step, the compound represented by chemical formula 2 may be contained in an amount of 8 to 13 parts by weight, preferably 9 to 12 parts by weight, and more preferably 9.5 to 11 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the content of the compound represented by chemical formula 2 is less than 8 parts by weight, there is difficulty in water dispersion; when the content of the compound represented by chemical formula 2 exceeds 11 parts by weight, the compound represented by chemical formula 2 may remain after removing the coating layer.
In the third step of preparing the compound represented by chemical formula 10, water may be present in an amount of 533 to 800 parts by weight, preferably 600 to 733 parts by weight, and more preferably 632 to 700 parts by weight, based on 100 parts by weight of the compound represented by chemical formula 7. When the water content is less than 533 parts by weight, the stickiness is too strong; when the content of water exceeds 800 parts by weight, the content of the compound represented by chemical formula 1 is greatly reduced and the thickness of the coating layer becomes thin.
Also, in the fourth step, a mixture may be prepared by mixing the compound represented by the chemical formula 2 with water at a temperature of 10 to 50 ℃ (preferably at a temperature of 15 to 30 ℃), at 400 to 700rpm (preferably at 500 to 600rpm), for 10 to 120 minutes (preferably 10 to 60 minutes). The prepared mixture is mixed with the second polymer or the third polymer at a temperature of 10 to 50 c, preferably at a temperature of 15 to 30 c, at 400 to 700rpm, preferably at 500 to 600rpm, for 1 to 5 hours, preferably 1 to 2 hours, to react to prepare the compound represented by the chemical formula 10.
On the other hand, in the method for preparing the protective coating agent for a cutting process of the present invention, a polar organic solvent, a surface-regulating additive, a fluidity modifier, an adhesion promoter, and water may be mixed with the prepared compound represented by chemical formula 10.
In addition, as an example, the stripping agent for stripping the protective coating agent for the dicing process of the present invention can be used for the following wafer processing process.
The wafer processing process may include: a first step of coating the surface of a wafer with the protective coating agent for dicing of the present invention; a second step of disposing the wafer on a pulling device; a third step of dicing the wafer; a fourth step of sorting only good products from the parts cut in the cutting process and arranging the good products; a fifth step of peeling the protective coating agent for dicing process of the present invention with the peeling agent for peeling the protective coating agent for dicing process of the present invention from the selected good products; and a sixth step of inspecting a good product after the protective coating agent for dicing process is peeled off.
The first step may be performed at a temperature of 0 to 50 ℃ for 1 to 60 seconds, and preferably at a temperature of 15 to 35 ℃ for 20 to 50 seconds.
The fifth step may be performed at a temperature of 10 to 50 ℃ for 1 to 10 minutes, and preferably at a temperature of 20 to 40 ℃ for 1 to 5 minutes.
The fifth step may include a method of removing the protective coating agent by immersing the wafer coated with the protective coating agent in a container filled with a release agent.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, and that various changes and modifications may be made by those skilled in the art without departing from the scope of the invention. For example, various components specifically explained in the embodiments of the present invention may be implemented in a modified manner. Such variations and modifications are to be considered as included within the scope of the invention as defined by the appended claims.
< example >
Preparation example 1 preparation of protective coating agent for cutting Process
(1) After a compound represented by the following chemical formula 7-1, a compound represented by the following chemical formula 8-1, a compound represented by the following chemical formula 9-1, and N-methylpyrrolidone NMP (N-methlpyrrolidone) were charged into a reactor, the reactor was heated to adjust the internal temperature of the reactor to 100 ℃. Then, polymerization was carried out with mixing at 200rpm for two hours to prepare a first polymer.
At this time, 126.7 parts by weight of the compound represented by the following chemical formula 8-1, 14.8 parts by weight of the compound represented by the following chemical formula 9-1, and 50.5 parts by weight of N-methylpyrrolidone NMP (N-methlpyrrolidone) were used with respect to 100 parts by weight of the compound represented by the following chemical formula 7-1.
[ chemical formula 7-1]
In the chemical formula 7-1, R1Is composed of
[ chemical formula 8-1]
O＝C＝N-R0-N＝C＝O
In the chemical formula 8-1, R0Is composed of
[ chemical formula 9-1]
In the chemical formula 9-1, R13And R14-Is methylene, R15Is ethyl.
(2) A compound represented by the following chemical formula 6-1 was charged into the prepared first polymer and mixed at a temperature of 90 ℃ for 90 minutes at 200rpm to react, thereby preparing a third intermediate polymer.
At this time, 42 parts by weight of the compound represented by the following chemical formula 6-1 was used with respect to 100 parts by weight of the compound represented by the chemical formula 7-1.
[ chemical formula 6-1]
In the chemical formula 6-1, R20is-CH2CH2CH2-，R21、R22And R23Is methyl.
(3) A third polymer was prepared by charging a compound represented by the following chemical formula 4-1 into the prepared third intermediate polymer at a temperature of 90 c and mixing and reacting at 200rpm for 25 minutes.
At this time, 36.8 parts by weight of the compound represented by the following chemical formula 4-1 was used for 100 parts by weight of the compound represented by the chemical formula 7-1.
[ chemical formula 4-1]
R16-OH
In the chemical formula 4-1, R16Is ethyl.
(4) A compound represented by the following chemical formula 2-1 was mixed with water at a temperature of 25 c at 550rpm for 1 hour to prepare a mixture. The mixture was charged into the prepared third polymer, and mixed at 550rpm for 1 hour at a temperature of 25 ℃ to react, thereby preparing a compound represented by the following chemical formula 10-1.
At this time, 10.1 parts by weight of the compound represented by the following chemical formula 2-1 and 666.3 parts by weight of water were used with respect to 100 parts by weight of the compound represented by the chemical formula 7-1.
[ chemical formula 2-1]
In the chemical formula 2-1, R17、R18And R19Is ethyl.
[ chemical formula 10-1]
In the chemical formula 10-1, R13And R14Is methylene, R15Is ethyl, R24Is composed of
R25Is composed of
R0Is composed of
Preparation example 2
The final compound was prepared according to the same method as preparation example 1, however, the compound represented by the following chemical formula 8-2 was used instead of the compound represented by the chemical formula 8-1, thereby preparing the compound represented by the following chemical formula 10-2 instead of the compound represented by the chemical formula 10-1.
[ chemical formula 8-2]
O＝C＝N-R0-N＝C＝O
In the chemical formula 8-2, R0Is composed ofR32Is methyl.
[ chemical formula 10-2]
In the chemical formula 10-1, R13And R14Is methylene, R15Is an ethyl group, and the content of the ethyl group,
R24is composed of
R25Is composed of
R0Is composed of
Preparation example 3
The final compound was prepared according to the same method as in preparation example 1, however, the compound represented by the following chemical formula 8-3 was used instead of the compound represented by the chemical formula 8-1, thereby preparing the compound represented by the following chemical formula 10-3 instead of the compound represented by the chemical formula 10-1.
[ chemical formula 8-3]
O＝C＝N-R0-N＝C＝O
In the chemical formula (8-3), R0Is composed of
[ chemical formula 10-3]
In the chemical formula (10-3), R13And R14Is methylene, R15Is ethyl, R24Is composed of
R25Is composed of
R0Is composed ofR1Is composed ofR2Is composed of
–CH2CH2CH2CH2CH2CH2CH2-，R3is-CH2CH2CH2CH2CH2CH2CH2CH2-, n is 7, R16Is ethyl, R20is-CH2CH2CH2-，R21、R22And R23Is methyl, A+Is composed ofR17、R18And R19Is ethyl.
Preparation example 1
With respect to 100 parts by weight of the compound represented by chemical formula 10-1 prepared in preparation example 1, 30 parts by weight of tetrahydrofurfuryl alcohol as a polar organic solvent, 0.5 part by weight of an additive for surface conditioning (BYK 331, manufactured by BYK), 0.5 part by weight of a fluidity additive (pro AM162S, manufactured by PROTEX international), 1 part by weight of an adhesion promoter (BYK 4500, manufactured by BYK) and 40 parts by weight of water were mixed at 25 ℃ and 500rpm for 60 minutes to prepare a protective coating agent for a dicing process.
Preparation example 2
With respect to 100 parts by weight of the compound represented by chemical formula 10-2 prepared in preparation example 2, 30 parts by weight of tetrahydrofurfuryl alcohol as a polar organic solvent, 0.5 part by weight of an additive for surface conditioning (BYK-331, manufactured by BYK), 0.5 part by weight of a fluidity modifier (PROTEX AM162S, manufactured by PROTEX International), 1 part by weight of an adhesion promoter (BYK-4500, manufactured by BYK) and 40 parts by weight of water were mixed at 25 ℃ and 500rpm for 60 minutes to prepare a protective coating agent for a dicing process.
Preparation example 3
A protective coating agent for a dicing process was prepared by mixing 30 parts by weight of tetrahydrofurfuryl alcohol as a polar organic solvent, 0.5 parts by weight of an additive for surface conditioning (BYK-331, manufactured by BYK-331), 0.5 parts by weight of a fluidity modifier (PROX AM162S, manufactured by PROTEX International Co., Ltd.), 1 part by weight of an adhesion promoter (BYK-4500, manufactured by BYK-4500 Co., Ltd.) and 40 parts by weight of water at 25 ℃ for 60 minutes at 500rpm, based on 100 parts by weight of the compound represented by chemical formula 10-3 prepared in preparation example 3.
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