Removal method, laminate, formation method and polyimide resin

Abstract

The present invention provides a polyimide resin having good stripping properties, a method for removing a photoresist, a laminate, a method for forming a metal pattern, and a stripping solution. The method for removing a photoresist comprises: forming a release layer on a substrate, the release layer having a first surface and a second surface opposite to each other, wherein the first surface of the release layer contacts the substrate; forming a photoresist layer on the second surface of the release layer; and removing the release layer and the photoresist layer. The release layer is formed by a polyimide resin. The polyimide resin is obtained by polymerization reaction of tetracarboxylic dianhydrides, diamines, and phenolamines. The diamines include hydroxyfluorinated diamines, benzoic acid diamines, and aminotetramethyldisiloxanes.

Description

Technical Field

[0001] The present invention relates to a method for removing photoresist, and in particular to a method for removing photoresist from a laminate comprising a film layer formed of a polyimide resin, a method for forming a metal pattern, and a stripping solution used in the method. Background Art

[0002] Polyimide (PI) is a thermosetting polymer formed by the polymerization reaction of dianhydride and diamine. It has excellent thermal stability, chemical corrosion resistance, mechanical properties and electrical properties. Therefore, it is often used as a molding material, electronic material, optical material, etc., and is widely used in various fields. Polyimide can also be used in the process of forming a metal pattern. However, the film formed by polyimide has the problem of being difficult to dissolve in solvents after a high-temperature process. For example, in the process of forming a metal pattern, a lift-off method is often used to form a metal pattern. When the film formed by polyimide is difficult to dissolve in a stripping solution, the photoresist used to form the metal pattern may not be easily stripped and remains in the device using the film, thereby affecting the performance of the device. Summary of the invention

[0003] In view of this, the present invention provides a polyimide resin having good stripping properties, a method for removing a photoresist, a laminate, a method for forming a metal pattern, and a stripping solution.

[0004] A method for removing a photoresist of the present invention comprises: forming a release layer on a substrate, the release layer having a first surface and a second surface opposite to each other, wherein the first surface of the release layer contacts the substrate; forming a photoresist layer on the second surface of the release layer; and removing the release layer and the photoresist layer. The release layer is formed of a polyimide resin. The polyimide resin is obtained by polymerization of tetracarboxylic dianhydrides, diamines and phenolamines. The diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes.

[0005] According to an embodiment of the present invention, the above-mentioned diamines also include phenylene ether diamines.

[0006] According to an embodiment of the present invention, the stripping liquid used to remove the release layer and the photoresist layer is a mixture of ethylene glycol and diethylene glycol monobutyl ether.

[0007] According to an embodiment of the present invention, the polyimide resin has a structure represented by general formula (1):

[0008] In the general formula (1), p is an integer of 2 to 30, and Z is an alkylene group.

[0009] According to an embodiment of the present invention, the above-mentioned Z is a methylene group (-CH2-).

[0010] According to an embodiment of the present invention, the photoresist layer is a negative photoresist layer.

[0011] A laminate of the present invention comprises a substrate, a release layer and a photoresist layer. The release layer has a first surface and a second surface opposite to each other. The first surface of the release layer contacts the substrate. The photoresist layer has a third surface and a fourth surface opposite to each other. The third surface of the photoresist layer contacts the second surface of the release layer. There is a gap between the edge of the third surface of the photoresist layer and the edge of the second surface of the release layer.

[0012] According to an embodiment of the present invention, the above-mentioned spacing is 1 μm (micrometer) to 35 μm.

[0013] According to an embodiment of the present invention, the cross-section of the photoresist layer along the lamination direction of the substrate, the release layer and the photoresist layer is in an inverted cone shape.

[0014] According to an embodiment of the present invention, the thickness of the release layer is 0.1 μm to 10 μm.

[0015] According to an embodiment of the present invention, the release layer is formed by polyimide resin. The polyimide resin is obtained by polymerization of tetracarboxylic dianhydride, diamine and phenol amine. The diamine includes hydroxy fluorinated diamine, benzoic acid diamine and aminotetramethyldisiloxane.

[0016] According to an embodiment of the present invention, the above-mentioned diamines also include phenylene ether diamines.

[0017] According to an embodiment of the present invention, the release layer is formed by a polyimide resin. The polyimide resin has a structure represented by general formula (2) or a structure represented by general formula (3).

[0018]

[0019]

[0020] In the general formula (2) and the general formula (3), m is an integer of 5 to 150, n is an integer of 5 to 150, and Ar 1 is a tetravalent organic radical, Ar 2 is a divalent organic group, Ar 3 is a divalent aromatic group, R 1 It is a hydroxyl group or a carboxyl group.

[0021] According to an embodiment of the present invention, the above-mentioned Ar 1 for *Indicates the bonding position.

[0022] According to an embodiment of the present invention, the above-mentioned Ar 2 for

[0023] *Indicates the bonding position.

[0024] According to an embodiment of the present invention, the above-mentioned Ar 3 It is phenylene.

[0025] According to an embodiment of the present invention, the weight average molecular weight of the polyimide resin is 5,000-50,000.

[0026] According to an embodiment of the present invention, the photoresist layer is a negative photoresist layer.

[0027] A method for forming a metal pattern of the present invention includes: forming a release layer on a substrate; forming a photoresist layer on the release layer; performing an exposure and development process on the release layer and the photoresist layer to form a composite photoresist on the substrate; forming a metal layer on the composite photoresist and on a portion of the substrate exposed by the composite photoresist; and removing the composite photoresist and a portion of the metal layer on the composite photoresist to form a metal pattern on the substrate. The release layer is formed by a polyimide resin. The polyimide resin is obtained by polymerization reaction of tetracarboxylic dianhydrides, diamines and phenolamines. The diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes.

[0028] According to an embodiment of the present invention, the above-mentioned diamines also include phenylene ether diamines.

[0029] According to an embodiment of the present invention, the stripping solution used to remove the composite photoresist is a mixture of ethylene glycol and diethylene glycol monobutyl ether.

[0030] According to an embodiment of the present invention, the photoresist layer is a negative photoresist layer.

[0031] The polyimide resin of the present invention is obtained by polymerization reaction of tetracarboxylic dianhydride, diamine and phenol amine. The diamine includes hydroxy fluorinated diamine, benzoic acid diamine and aminotetramethyldisiloxane.

[0032] According to an embodiment of the present invention, the above-mentioned diamines also include phenylene ether diamines.

[0033] A polyimide resin of the present invention has a structure represented by general formula (2) or a structure represented by general formula (3),

[0034]

[0035] In the general formula (2) and the general formula (3), m is an integer of 5 to 150, n is an integer of 5 to 150, and Ar 1 is a tetravalent organic group, Ar 2 is a divalent organic group, Ar 3 is a divalent aromatic group, R 1 It is a hydroxyl group or a carboxyl group.

[0036] According to an embodiment of the present invention, the above-mentioned Ar 1 for *Indicates the bonding position.

[0037] According to an embodiment of the present invention, the above-mentioned Ar 2 for

[0038] *Indicates the bonding position.

[0039] According to an embodiment of the present invention, the above-mentioned Ar 3 It is phenylene.

[0040] According to an embodiment of the present invention, the weight average molecular weight of the polyimide resin is 5,000-50,000.

[0041] The stripping solution of the present invention is used in the above-mentioned method for removing photoresist or the above-mentioned method for forming metal pattern. The stripping solution is a mixture of ethylene glycol and diethylene glycol monobutyl ether.

[0042] Based on the above, the method for removing photoresist of the present invention is formed on the release layer by a photoresist layer and in contact with the release layer, wherein the release layer is formed by a polyimide resin, and the polyimide resin is obtained by polymerization reaction of tetracarboxylic dianhydrides, diamines and phenolamines, wherein the diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes. Thereby, the structure including the release layer can have good stripping properties, and the photoresist layer can be well removed. In addition, the composite photoresist can also be well removed in the method for forming a metal pattern. In addition, the stripping solution of the present invention is a mixture of ethylene glycol and diethylene glycol monobutyl ether, which can be applied to the above-mentioned method for removing photoresist or the method for forming a metal pattern, and the photoresist layer or the composite photoresist can be well removed. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The accompanying drawings are included to provide a further understanding of the present invention and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the present invention and together with the description serve to explain the principles of the present invention.

[0044] Figures 1A to 1Cis a schematic diagram of a manufacturing process of a laminate according to an embodiment of the present invention;

[0045] FIG. 2A to FIG. 2B 1 is a partial flow chart of a method for forming a metal pattern according to an embodiment of the present invention.

[0046] Description of Figure Numbers

[0047] 100: Laminated board;

[0048] 110: substrate;

[0049] 120, 120': release layer;

[0050] 120a, 120'a: first surface;

[0051] 120b, 120'b: second surface;

[0052] 120'e, 130'e: edge;

[0053] 130, 130': photoresist layer;

[0054] 130a, 130'a: third surface;

[0055] 130b: fourth surface;

[0056] 140: composite photoresist;

[0057] 150: metal layer;

[0058] 150': Metal pattern;

[0059] L: Spacing. DETAILED DESCRIPTION

[0060] The present invention provides a laminated board, which includes a release layer formed of a polyimide resin and a photoresist layer. In addition, a method for removing the photoresist and a method for forming a metal pattern are also provided. The polyimide resin, the laminated board, the method for removing the photoresist and the method for forming the metal pattern are described in detail below.

[0061] It should be noted that, in this article, the so-called "tetravalent organic group" is a substituent derived from an organic compound, which is a group formed by removing four hydrogen atoms from an atom of the organic compound, thereby forming four chemical bonds with other atoms.

[0062] As used herein, the term "divalent organic group" refers to a substituent derived from an organic compound, which is a group formed by removing two hydrogen atoms from an atom of the organic compound, thereby forming two chemical bonds with other atoms.

[0063] As used herein, the term "divalent aromatic group" refers to a substituent derived from an aromatic monocyclic or polycyclic hydrocarbon ring system, which is formed by removing two hydrogen atoms from a carbon atom on the aromatic monocyclic or polycyclic ring, thereby forming two chemical bonds with other atoms.

[0064] <Polyimide resin>

[0065] A polyimide resin according to this embodiment is obtained by polymerization of tetracarboxylic dianhydrides, diamines and phenolamines. The above monomers will be described in detail below.

[0066] Tetracarboxylic dianhydride

[0067] There is no particular limitation on the tetracarboxylic dianhydride, and an appropriate tetracarboxylic dianhydride compound can be selected according to the needs.

[0068] For example, the tetracarboxylic dianhydride may include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4,4'-diphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxytetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarbonic anhydride, 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride or other suitable tetracarboxylic dianhydride compounds, preferably bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. As the tetracarboxylic dianhydride, one tetracarboxylic dianhydride compound may be used alone, or a plurality of tetracarboxylic dianhydride compounds may be used in combination.

[0069] Diamines

[0070] The diamines include hydroxyfluorinated diamines, benzoic acid diamines, and aminotetramethyldisiloxanes.

[0071] For example, the hydroxy fluorinated diamines may include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-4-hydroxyphenyl)hexafluoropropane or other suitable hydroxy fluorinated diamine compounds, preferably 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The hydroxy fluorinated diamines may be used alone or in combination of multiple hydroxy fluorinated diamine compounds.

[0072] The benzoic acid diamines may include bis(4-amino-3-carboxyphenyl)methane, bis(3-amino-3-carboxyphenyl)methane, bis(4-amino-4-carboxyphenyl)methane or other suitable benzoic acid diamine compounds, preferably bis(4-amino-3-carboxyphenyl)methane. The benzoic acid diamines may be used alone or in combination of multiple benzoic acid diamine compounds.

[0073] The aminotetramethyldisiloxanes may include 1,3-Bis(3-aminopropyl)tetramethyldisiloxane, 1,3-Bis(3-aminopropyl)tetramethyldisiloxane or other suitable aminotetramethyldisiloxane compounds, preferably 1,3-Bis(3-aminopropyl)tetramethyldisiloxane. The aminotetramethyldisiloxanes may be used alone or in combination of multiple aminotetramethyldisiloxane compounds.

[0074] In other embodiments, the diamines may further include phenylene ether diamines. In addition, in other embodiments, the diamines may also include other suitable diamine compounds.

[0075] The phenylene ether diamines may include 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether or other suitable phenylene ether diamine compounds, preferably including 4,4'-diaminodiphenyl ether. The phenylene ether diamines may be used alone or in combination with a plurality of phenylene ether diamine compounds.

[0076] When the diamines in the polyimide resin include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes, the structure of the release layer formed therefrom has good stripping properties, so that the photoresist layer or the composite photoresist can be well removed when removing the photoresist or forming a metal pattern.

[0077] Phenolamines

[0078] In this embodiment, phenolamines are used as the end-capping agent. There is no particular limitation on the phenolamines, and appropriate phenolamine compounds can be selected according to the requirements.

[0079] For example, the phenolamines may include any suitable phenolamine compounds, preferably 3-aminophenol. The phenolamines may be used as a single phenolamine compound or in combination of multiple phenolamine compounds.

[0080] <Preparation of polyimide resin>

[0081] Tetracarboxylic dianhydrides, hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes can be polymerized to form polyamic acid polymers. Then, phenolamines are added and dehydration ring-closure reaction is carried out, so that the amic acid functional groups in the polyamic acid polymer are converted into imide functional groups (i.e., imidization) through dehydration ring-closure reaction, and a polyimide resin having a structure including imide functional groups and a phenol group at the end is obtained.

[0082] The polymerization reaction and the dehydration ring-closing reaction can be carried out in the presence of a solvent. The solvent may include gamma-Butyrolactone (GBL), N-methylpyrrolidone, dimethylacetamide, methylformamide or a combination thereof, preferably including a solvent with low solubility for the polyimide resin, such as gamma-butyrolactone. For example, when a polar solvent containing nitrogen atoms, such as N-methylpyrrolidone, is used, the polyimide resin dissolved in the solvent may produce a whitening phenomenon due to hygroscopicity, resulting in poor stability of the polyimide resin, thereby reducing the toughness and electrical properties of the film formed by the polyimide resin. However, the present invention is not limited to this, and other solvents may be selected as needed. Based on the use amount of GBL as 100% by weight, the use amount of the solvent used in the polymerization reaction may be 15 to 80% by weight, preferably 30 to 75% by weight.

[0083] The polymerization reaction temperature may be 50 to 80° C. and the polymerization time may be 3 to 6 hours.

[0084] The dehydration ring-closing reaction can be carried out using a high-temperature dehydration ring-closing method or a chemical dehydration ring-closing method. The temperature of the high-temperature dehydration ring-closing method can be 250-350°C, and the time can be 3-6 hours. The chemical dehydration ring-closing method can add a dehydrating agent and a catalyst to the reaction solution, and react for 3-6 hours at a temperature of 160-180°C. The dehydrating agent is, for example, an anhydride of acetic anhydride, propionic anhydride, trifluoroacetic anhydride, etc., but the present invention is not limited thereto, and other dehydrating agents can be selected as needed. The catalyst is, for example, a tertiary amine of triethylamine, pyridine, dimethylpyridine, etc., but the present invention is not limited thereto, and other catalysts can be selected as needed.

[0085] For example, a chemical dehydration ring-closing method is used and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride is used as tetracarboxylic dianhydrides, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is used as hydroxyfluorinated diamines, bis(4-amino-3-carboxyphenyl)methane is used as benzoic acid diamines, 1,3-bis(3-aminopropyl)tetramethyldisiloxane is used as aminotetramethyldisiloxanes, and 3-aminophenol is used as phenolamines to react to form a polyimide resin having a structure including an imide functional group and a phenol group at the end. For example, the polyimide resin may have a structure represented by the following general formula (1).

[0086]

[0087] In the general formula (1), p is an integer of 2 to 30, and Z is an alkylene group.

[0088] The alkylene group represented by Z may be derived from the above-mentioned benzoic acid diamines. In one embodiment, Z may be an alkylene group having 1 to 10 carbon atoms. In one embodiment, Z is preferably a methylene group.

[0089] Specifically, the polyimide resin has a structure represented by the following general formula (2) or a structure represented by the following general formula (3). Next, the structures represented by the general formula (2) and the general formula (3) are described in detail.

[0090]

[0091] In the general formula (2), m is an integer of 5 to 150, Ar 1 is a tetravalent organic group, Ar 2 is a divalent organic group, Ar 3 is a divalent aromatic group, R 1 It is a hydroxyl group or a carboxyl group.

[0092] Furthermore, Ar 1 The tetravalent organic group shown may be derived from the above-mentioned tetracarboxylic dianhydride compounds. 1 Preferably *Indicates the bonding position.

[0093] Ar 2 The divalent organic group shown may be derived from the diamines described above. 2 The divalent organic group shown may be derived from the above-mentioned hydroxyfluorinated diamines, benzoic acid diamines, aminotetramethyldisiloxanes or phenylene ether diamines. 2 Preferably

[0094] * indicates the bonding position. In one embodiment, Ar2 More preferably *Indicates the bonding position.

[0095] Ar 3 The divalent aromatic group shown may be derived from the above-mentioned phenolamines. 3 Preferred is phenylene.

[0096] R 1 The hydroxyl group shown may be derived from the above-mentioned phenolamines. 1 The carboxyl group shown may be derived from aminobenzoic acid. 1 A hydroxy group is preferred.

[0097] m is preferably an integer of 5-100, more preferably an integer of 5-50.

[0098]

[0099] In the general formula (3), n is an integer of 5 to 150, Ar 1 ,Ar 2 ,Ar 3 and R 1 The group shown is the same as Ar in the general formula (2) 1 ,Ar 2 ,Ar 3 and R 1 The groups shown are the same and will not be described again here.

[0100] n is preferably an integer of 5-100, more preferably an integer of 5-50.

[0101] The weight average molecular weight of the polyimide resin is 5000 to 50000, preferably 10000 to 40000, and more preferably 25000 to 35000. When the weight average molecular weight of the polyimide resin is 5000 to 50000, the release layer formed by the polyimide resin can have different spacings and thicknesses, thereby obtaining an ideal evaporation or sputtering material shape.

[0102] <Method of Removing Photoresist>

[0103] The method of removing the photoresist includes forming a laminate. Figures 1A to 1C 1 is a schematic diagram of a manufacturing process of a laminate according to an embodiment of the present invention. The laminate 100 includes a substrate 110, a release layer 120' and a photoresist layer 130'.

[0104] Please refer to Figure 1A, providing a substrate 110, and forming a release layer 120 on the substrate 110. The substrate 110 may be a glass substrate, a silicon wafer substrate, or a plastic base material (such as a polyethersulfone (PES) board or a polycarbonate (PC) board), and its type is not particularly limited.

[0105] The release layer 120 has a first surface 120a and a second surface 120b opposite to each other. The first surface 120a of the release layer 120 contacts the substrate 110. The release layer 120 is formed by the above-mentioned polyimide resin. In the present embodiment, the release layer 120 is used to form a laminate with the substrate 110, but the present invention is not limited thereto. In other embodiments, the release layer can also be used alone as a release layer. In the present embodiment, the thickness of the release layer can be about 0.1μm to 10μm, preferably about 1μm to 10μm, but the present invention is not limited thereto. The release layer can be formed by applying a solution formed by the above-mentioned polyimide resin on the substrate to form a coating film, and soft-baking the coating film. For example, after applying a solution formed by the polyimide resin on the substrate to form a coating film, a soft-baking step is performed at a temperature of 160 to 220°C for 2 minutes to form a release layer on the substrate.

[0106] Please refer to Figure 1B , a photoresist layer 130 is formed on the second surface 120b of the release layer 120. The photoresist layer 130 has a third surface 130a and a fourth surface 130b opposite to each other. The third surface 130a of the photoresist layer 130 is in contact with the second surface 120b of the release layer 120. In the present embodiment, the thickness of the photoresist layer may be about 0.5μm to 20μm, but the present invention is not limited thereto. In the present embodiment, the photoresist layer may be a negative photoresist layer. The photoresist layer may be formed by coating a photoresist on a substrate to form a coating film, and soft-baking the coating film. For example, after coating a photoresist on a substrate to form a coating film, a soft-baking step is performed at a temperature of 90 to 130°C for 2 minutes to form a photoresist layer on the release layer.

[0107] The coating method is not particularly limited, but spray coating, roll coating, spin coating or the like may be used, and generally, spin coating is widely used. In addition, a coating film is formed, and then in some cases, the residual solvent may be partially removed under reduced pressure.

[0108] Please refer to Figure 1C, the release layer 120 and the photoresist layer 130 may be subjected to an exposure and development process to form a patterned release layer 120' and a photoresist layer 130' on the substrate 110. The composite photoresist 140 may include a release layer 120' and a photoresist layer 130'. The release layer 120' has a first surface 120'a in contact with the substrate 110 and a second surface 120'b opposite to the first surface 120'a. The photoresist layer 130' has a third surface 130'a in contact with the first surface 120'a. In the present embodiment, an edge 130'e of the third surface 130'a of the photoresist layer 130' may have a spacing L with an edge 120'e of the second surface 120'b of the release layer 120', and the laminate 100 is substantially completed. In the present embodiment, the spacing L may be 1 μm to 35 μm, but the present invention is not limited thereto. In the present embodiment, the cross section of the photoresist layer 130 ′ along the stacking direction of the substrate 110 , the release layer 120 ′ and the photoresist layer 130 ′ may be an inverted cone, but the present invention is not limited thereto.

[0109] Next, the release layer 120' and the photoresist layer 130' are removed. In the present embodiment, the release layer 120' and the photoresist layer 130' can be removed by lift-off, but the present invention is not limited thereto. The lift-off method is to use a stripping liquid to remove the release layer 120' and the photoresist layer 130'. There is no particular limitation on the stripping liquid, and an appropriate stripping liquid can be selected according to the requirements; preferably, it is a mixture of ethylene glycol and diethylene glycol monobutyl ether.

[0110] <Method of Forming Metal Pattern>

[0111] The method for forming the metal pattern includes performing an exposure and development process on the release layer 120 and the photoresist layer 130 to form a composite photoresist 140 (eg, Figure 1B to Figure 1C For example, at 4000 J / m 2 The release layer 120 and the photoresist layer 130 are exposed to light for 0.05 minutes. Then, post-baking is performed at 90-130°C for 120-180 seconds. Next, development is performed with a developer for 13-26 seconds, and hard baking is performed at 220°C for 20 minutes after development to form a composite photoresist 140 on the substrate 110. There is no particular limitation on the developer, and an appropriate developer can be selected according to the needs. For example, the developer can be tetramethyl ammonium hydroxide (TMAH), and its concentration can be 2.38 weight %.

[0112] Next, please refer to Figure 2AA metal layer 150 is formed on the composite photoresist 140 and on the portion of the substrate 110 exposed by the composite photoresist 140. The material of the metal layer 150 can be a single layer or a multi-layer stacked metal material, for example, at least one selected from the group consisting of copper (Cu), molybdenum (Mo), titanium (Ti), aluminum (Al), tungsten (W), silver (Ag), gold (Au) and alloys thereof.

[0113] Please refer to Figure 2B , remove the composite photoresist 140 and a portion of the metal layer on the composite photoresist 140 to form a metal pattern 150' on the substrate. In this embodiment, the method for removing the composite photoresist 140 and a portion of the metal layer on the composite photoresist 140 can be the same as the above-mentioned method for removing the photoresist, which is not further described herein.

[0114] Hereinafter, the present invention will be described in detail with reference to examples. The following examples are provided for describing the present invention, and the scope of the present invention includes the scope described in the following claims and its substitutes and modifications, and is not limited to the scope of the examples.

[0115] Examples of polyimide resin and laminate

[0116] The following describes Examples 1 to 3 and Comparative Examples 1 to 2 of polyimide resins and laminates:

[0117] Example 1

[0118] a. Polyimide resin

[0119] 153.13 g of bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 112.99 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 61.82 g of bis(4-amino-3-carboxyphenyl)methane and 15.33 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to a 1000 ml three-necked round-bottom flask filled with nitrogen, and then 647.20 g of γ-butyrolactone (GBL) was added and stirred at 70°C for 4 hours. Then, 6.73 g of 3-aminophenol was added and stirred at 70°C for another 4 hours. Then, 2.80 g of 1-ethylpiperidine was added and the temperature was raised to 180°C and stirred for 4 hours. After cooling, a viscous polyimide resin solution was obtained.

[0120] b. Laminated board

[0121] The polyimide resin solutions prepared in the examples were coated on the substrate by spin coating (spin coater model Clean Track MK-8, manufactured by Tokyo Electron Limited (TEL), with a rotation speed of 1200 rpm). Then, soft baking was performed at a temperature of 220°C for 2 minutes to form a release layer with a thickness of 2 μm. Then, the negative photoresist (trade name: SCN series photoresist, manufactured by eChem Solutions Corp. (ECSC)) was soft baked on a baking plate at 90°C for 2 minutes by spin coating to form a negative photoresist layer with a thickness of 8 μm. Then, the molten-crystal was heated to 4000 J / m 2 The release layer and the photoresist layer were exposed to light for 0.05 minutes. Then, the post-baking was performed on a baking plate at 100°C for 2.5 minutes. Next, the development was performed for 13 seconds using TMAH with a concentration of 2.38 wt % as a developer, and after the development, the composite photoresist was hard-baked at 220°C for 20 minutes to form a composite photoresist on the substrate, and a laminate was obtained. The prepared laminate was evaluated in the following evaluation methods, and the results are shown in Table 1.

[0122] Examples 2 to 3 and Comparative Examples 1 to 2

[0123] The polyimide resins of Examples 2 to 3 and Comparative Examples 1 to 2 were prepared in the same steps as Example 1, and the difference was that the types of components and the amounts of the polyimide resins were changed (as shown in Table 1 and Table 1 (Continued)). The prepared polyimide resins were made into release films and evaluated in the following evaluation methods, and the results are shown in Table 1 and Table 1 (Continued).

[0124] [Table 1]

[0125]

[0126] [Table 1] (Continued)

[0127]

[0128] <Evaluation method>

[0129] a. Alkali dissolution rate

[0130] The initial film thickness (T1, in μm) of the prepared photoresist film was measured. Next, the photoresist film was immersed in a developer (TMAH with a concentration of 2.38 wt%), and the changes in the photoresist film were observed until the photoresist film completely disappeared. The time required for the photoresist film to disappear from the initial film thickness (T time , in seconds), the alkali dissolution rate is calculated according to the following formula:

[0131]

[0132] b. Spacing

[0133] The prepared laminate was measured by a field emission scanning electron microscope (FESEM) (model: SU8010, manufactured by Hitachi, Ltd.) at a magnification of 1.5k times to measure the distance between the release layer and the photoresist layer due to undercutting.

[0134] <Evaluation Results>

[0135] As shown in Table 1, the laminates formed by Examples 1 to 3 including release layers formed by polyimide resins containing benzoic acid diamines have good alkali dissolution rates and spacings, thereby forming a photoresist layer or composite photoresist with a special pattern, and the photoresist layer or composite photoresist can be well removed. In contrast, the laminate (Comparative Example 1) including a release layer formed by a polyimide resin not containing benzoic acid diamines has poor alkali dissolution rates and spacings.

[0136] In addition, compared with the laminates formed by the release layer formed by the polyimide resin (Examples 1 to 3), the laminate formed by the release layer formed by the phenolic resin (Comparative Example 2) has poor alkali dissolution rate and spacing.

[0137] In addition, compared with the laminate formed by the release layer formed by the polyimide resin not containing phenylene ether diamines (Example 1), the laminate formed by the release layer formed by the polyimide resin containing phenylene ether diamines (Examples 2-3) has a lower alkali dissolution rate and a smaller spacing. It can be seen that when the laminate includes a release layer formed by the polyimide resin containing phenylene ether diamines, the patterning of the photoresist layer or the composite photoresist may not be significant, making the photoresist layer or the composite photoresist less likely to be removed, and thus remaining in the device using the release layer.

[0138] In summary, the method for removing photoresist of the present invention is to form a photoresist layer on a release layer and contact the release layer, wherein the release layer is formed by a polyimide resin, and the polyimide resin is obtained by polymerization of tetracarboxylic dianhydrides, diamines and phenolamines, wherein the diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes, so that the laminate formed by the release layer formed by the polyimide resin has a good alkali dissolution rate and spacing, so that the photoresist layer or the composite photoresist can be well removed when removing the photoresist or forming a metal pattern, and can be applied to the method for removing the photoresist or the method for forming a metal pattern, thereby improving the performance of the device using the release layer. In addition, when the stripping liquid of the present invention is a mixture of ethylene glycol and diethylene glycol monobutyl ether, the photoresist layer or the composite photoresist in the above-mentioned laminate can be well removed, and can be applied to the method for removing the photoresist or the method for forming a metal pattern.

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for removing a photoresist, comprising: forming a release layer on a substrate, wherein the release layer has a first surface and a second surface opposite to each other, wherein the first surface of the release layer contacts the substrate; forming a photoresist layer on the second surface of the release layer; as well as removing the release layer and the photoresist layer, The release layer is formed by a polyimide resin, which is obtained by polymerization of tetracarboxylic dianhydrides, diamines and phenolamines, wherein the tetracarboxylic dianhydrides include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes, and the phenolamines include 3-aminophenol. 2 . The method for removing a photoresist according to claim 1 , wherein the diamines further comprise phenylene ether diamines. 3 . The method for removing photoresist according to claim 1 , wherein the stripping liquid used to remove the release layer and the photoresist layer is a mixture of ethylene glycol and diethylene glycol monobutyl ether.

4. The method for removing a photoresist according to claim 1, wherein the polyimide resin has a structure represented by general formula (1), In the general formula (1), p is an integer of 2 to 30, and Z is an alkylene group. The method for removing a photoresist according to claim 4 , wherein the Z is a methylene group. The method for removing a photoresist according to claim 1 , wherein the photoresist layer is a negative photoresist layer.

7. A laminate comprising: substrate; A release layer having a first surface and a second surface opposite to each other, wherein the first surface of the release layer is in contact with the substrate; as well as The photoresist layer has a third surface and a fourth surface opposite to each other, wherein the third surface of the photoresist layer contacts the second surface of the release layer, wherein there is a distance between the edge of the third surface of the photoresist layer and the edge of the second surface of the release layer, The release layer is formed by a polyimide resin, which is obtained by polymerization of tetracarboxylic dianhydrides, diamines and phenolamines, wherein the tetracarboxylic dianhydrides include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes, and the phenolamines include 3-aminophenol. The laminate according to claim 7 , wherein the pitch is 1 μm to 35 μm. 9 . The laminate according to claim 7 , wherein a cross section of the photoresist layer along a lamination direction of the substrate, the release layer, and the photoresist layer is in an inverted tapered shape. 10 . The laminate according to claim 7 , wherein the release layer has a thickness of 0.1 μm to 10 μm.

11. The laminate according to claim 7, wherein the diamines further comprise phenylene ether diamines.

12. The laminate according to claim 7, wherein the release layer is formed of a polyimide resin having a structure represented by general formula (2) or a structure represented by general formula (3), In the general formula (2) and the general formula (3), m is an integer of 5 to 150, n is an integer of 5 to 150, and Ar 1 is a tetravalent organic group, Ar 2 is a divalent organic group, Ar 3 is a divalent aromatic group, R 1 It is a hydroxyl group or a carboxyl group.

13. The laminate according to claim 12, wherein the Ar 1 for *Indicates the bonding position.

14. The laminate according to claim 12, wherein the Ar 2 for *Indicates the bonding position.

15. The laminate according to claim 12, wherein the Ar 3 It is phenylene. 16 . The laminate according to claim 12 , wherein the weight average molecular weight of the polyimide resin is 5,000 to 50,000.

17. The laminate according to claim 7, wherein the photoresist layer is a negative photoresist layer.

18. A method for forming a metal pattern, comprising: forming a release layer on the substrate; forming a photoresist layer on the release layer; Performing an exposure and development process on the release layer and the photoresist layer to form a composite photoresist on the substrate; forming a metal layer on the composite photoresist and on a portion of the substrate exposed by the composite photoresist; as well as removing the composite photoresist and a portion of the metal layer on the composite photoresist to form a metal pattern on the substrate, The release layer is formed by a polyimide resin, which is obtained by polymerization of tetracarboxylic dianhydrides, diamines and phenolamines, wherein the tetracarboxylic dianhydrides include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes, and the phenolamines include 3-aminophenol. 19 . The method for forming a metal pattern according to claim 18 , wherein the diamines further comprise phenylene ether diamines. 20 . The method for forming a metal pattern according to claim 18 , wherein a stripping solution for removing the composite photoresist is a mixture of ethylene glycol and diethylene glycol monobutyl ether.

21. The method for forming a metal pattern according to claim 18, wherein the photoresist layer is a negative photoresist layer.

22. A polyimide resin obtained by polymerization reaction of tetracarboxylic dianhydrides, diamines and phenolamines, wherein the tetracarboxylic dianhydrides include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the diamines include hydroxyfluorinated diamines, benzoic acid diamines and aminotetramethyldisiloxanes, and the phenolamines include 3-aminophenol.

23. The polyimide resin according to claim 22, wherein the diamines further comprise phenylene ether diamines.

24. A polyimide resin having a structure represented by general formula (2) or a structure represented by general formula (3), In the general formula (2) and the general formula (3), m is an integer of 5 to 150, n is an integer of 5 to 150, Ar 1 for * indicates the bonding position, Ar 3 is phenylene, R 1 is a hydroxyl group or a carboxyl group, Ar 2 It is a divalent organic group derived from diamines, including 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-carboxyphenyl)methane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 4,4'-diaminodiphenyl ether. 25 . The polyimide resin according to claim 24 , wherein the weight average molecular weight of the polyimide resin is 5,000 to 50,000.

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