Compositions containing N-substituted piperazines for electronics manufacturing applications

Abstract

A composition comprising at least the following components a), b), and c), wherein a) at least one N-substituted piperazine selected from the following: structure (1) described herein, structure (2) described herein, or a mixture thereof; b) at least one glycol ether selected from the following: structure (3) described herein, structure (4) described herein, or a mixture thereof; and c) water.

Description

[Technical Field]

[0001] Organic amines are widely used in stripping and cleaning formulations for electronic equipment processing. For example, such amines are used in photoresist stripping formulations for preparing RGB (red, green, blue) dyes in displays, and in photoresist stripping formulations for lithography, such as those used in semiconductor manufacturing. Organic amines can provide excellent dissolution for many polar polymers, monomers, and compounds. In the industry, MIPA (monoisopropanolamine) or AEEA (aminoethylethanolamine) are typical amines in photoresist stripping formulations; however, these formulations can cause serious metal corrosion, and their stripping performance is not good at lower doses of the amine. The dose of organic amines in typical electronic equipment processing formulations is typically over 10% by weight to improve the dissolution of polar polymers, monomers, and compounds. More generally, the target dose of organic amines is around 20% by weight. However, such high concentrations of organic amines not only increase the cost of the formulation but also increase the cost of disposing of the waste. A photoresist stripping agent composition containing a low dose of amine is needed that provides good stripping ability and low metal corrosion.

[0002] U.S. Patent No. 7,888,301 discloses aqueous compositions and processes for removing photoresists, bottom anti-reflective coating (BARC) materials, and / or gap-filling materials from substrates having such materials(s) thereon. The aqueous compositions comprise a fluoride source, at least one organic amine, at least one organic solvent (e.g., a diol, glycol, or glycol ether, as described in the said patent), water, and optionally a chelating agent and / or surfactant. See abstract. The compositions are disclosed to achieve highly efficient removal of such materials(s) in the manufacture of integrated circuits without adversely affecting metal species on the substrate, such as copper, and without damaging SiOC-based dielectric materials used in semiconductor architectures. See abstract. Preferred organic amines include, but are not limited to, hydroxyethylpiperazine (HEP), hydroxypropylpiperazine (HPP), aminoethylpiperazine (AEP), aminopropylpiperazine (APP), hydroxy-ethylmorpholine (HEM), hydroxypropylmorpholine (HPM), aminoethylmorpholine (AEM), aminopropylmorpholine (APM), triethanolamine (TEA), pentamethyldiethylenetriamine (PMDETA), dimethylaminoethoxyethanol (DMAEE), aminoethoxyethanol (AEE), ethyleneurea (EU), trimethylaminoethylethanolamine (TMAEEA), trimethylaminopropylethanolamine (TMAPEA), N-(2-cyanoethyl)ethylenediamine (CEEDA), and N-(2-cyanopropyl)ethylenediamine (CPEDA). Particularly preferred organic amines include ethyleneurea, hydroxyethylmorpholine, and N-(2-cyanoethyl)ethylenediamine. Please refer to column 4, line 56 to column 5, line 3. Also, please refer to column 5, lines 4 to 17.

[0003] Korean Patent No. 102057158(B1) (machine translation) discloses a photoresist stripping agent composition comprising N,N-dimethylpropionamide that can replace solvents such as NMP which are harmful to the human body. See abstract. The composition may contain, for example, cyclic amines from 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-(2-hydroxyethyl)methylpiperazine, and N-(3-aminopropyl). See the [Modes for Carrying Out the Invention] section. The composition may also contain protonate solvents such as glycols or glycol ethers, as described in the respective patent documents. See the [Modes for Carrying Out the Invention] section.

[0004] Korean Patent Application Publication No. 20180120397(A) (machine translation) discloses a photoresist stripping solution composition comprising cyclodextrin or a derivative thereof. See abstract. The composition may contain one organic basic compound selected from the group consisting of monomethylamine, dimethylamine, triethylamine, diisopropylethylamine, monoethanolamine, monoisopropanol, diethanolamine, triethanolamine, 2-(2-aminoethoxy)(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-2-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenyl-(2-methylpiperazine-1-yl), piperazine, tetramethylguanidine, 1,8-diazabicycloundec-7-ene, and 1,5-diazabicyclo(4,3,0). See the section on [Modes for Carrying Out the Invention]. The compositions may each contain a polar solvent such as an amide or glycol ether, as described herein. See the section on [Modes for Carrying Out the Invention].

[0005] Korean Patent No. 101221560(B1) (machine translation) discloses a photoresist stripping agent composition comprising (a) 0.1 to 10% by weight of hydrogen peroxide or a hydrogen peroxide derivative, (b) 5 to 50% by weight of an organic solvent, (c) 0.5 to 30% by weight of an organic amine, (d) 5 to 60% by weight of water, (e) 0.0001 to 20% by weight of an ammonium salt, (f) 0.4 to 10% by weight of a corrosion inhibitor, and (g) 0.5 to 30% by weight of a stabilizer of hydrogen peroxide or a hydrogen peroxide derivative. See abstract. The organic amine compounds are monoethanolamine, isopropanolamine, aminoethoxyethanol, n-methylethanolamine, dimethylethanolamine, diethylethanolamine, 2-aminoethylaminoethanol, aminoethylpiperazine, aminopropylpiperazine, hydroxyethylpiperazine, 1-amino-4-methylpiperazine, 2-methylpiperazine, 1-methylpiperazine, 1-benzylpiperazine, 2-phenylpiperazine, and 1-aminoethylpiperazine. See the section on [Modes for Carrying Out the Invention]. The organic solvent (b) is water-soluble and may be dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), or dimethylimidazolidinone (DMI). See the section on [Modes for Carrying Out the Invention].

[0006] Chinese Patent No. 104781732(B) (machine translation) discloses a photoresist stripping composition and method that provides photoresist stripping and corrosion prevention effects (see abstract). The stripping agent composition contains N,N-dimethylpropionamide, a solketal, and an organic amine. This composition is disclosed as a substitute for glycol ether compounds. See abstract. The organic amine includes one or more compounds selected from the group consisting of monoethanolamine (MEA), ethylenediamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, 1-amino-2-propanol, diethanolamine, iminodipropionateamine, 2-methylaminoethanol, methyldiethanolamine, triethylaminoethanol, 1-(2-hydroxyethyl)piperazine (HEP), 1-(2-aminoethyl)piperazine, 1-(2-hydroxyethyl)methylpiperazine, N-(3-aminopropyl)morpholine, 2-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, and 1-phenylpiperazine (see claim 2).

[0007] Chinese Patent Application Publication No. 104216242(A) (machine translation) discloses a stripping composition for use in color photoresists and organic insulating films (see abstract). The stripping composition comprises a quaternary ammonium compound, a polar solvent, an alkylamine, an amine compound of Formula 1 as described in the said patent document, or an amine compound of Formula 2 as described in the said patent document, an inorganic alkali or a salt thereof, and water. See abstract. The amine of Formula 2 is selected from at least one of the following: That is, piperazine, N-methylpiperazine, NEP, N-vinylpiperazine, N-vinylmethylpiperazine, N-vinylethylpiperazine, N-vinyl-N'-methylpiperazine, N-acryloylpiperazines, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N-(2-amino-ethyl)piperazine, N,N'-dimethylpiperazine, morpholine, N-methylmorpholine, N-ethylmorpholine, N N-phenylmorpholine, N-polyvinylmorpholinone, N-vinylmethylmorpholine, N-vinylethylmorpholine, N-acryloylmorpholine, N-cocoamorpholine, N-(2-amino-ethyl)morpholine, N-(2-cyanoethyl)morpholine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxypropyl)morpholine, N-acetylmorpholine, and N-formylmorpholine (see claim 6). The polar solvent may be a sulfur-containing molecule (see the section on embodiments).

[0008] Taiwan Patent Application Publication No. 201732461(A) (machine translation) discloses a photoresist stripping agent composition. Such a composition is disclosed to be able to remove photoresists and avoid corrosion of metal patterns and / or damage to organic / inorganic films. See abstract. The photoresist stripping agent composition comprises, based on the total weight of the stripping agent composition, 15% to 80% by weight of an aprotic polar solvent having N,N-dimethyl-propanamide, 25 to 80% by weight of a protic polar solvent, and 1 to 15% by weight of an amine compound. See abstract. The amine compounds are one or more selected from monoethanolamine, diethanolamine, triethanolamine, glycolamine, diglycolamine, monoisopropanolamine, 2-(2-aminoethoxy)-ethanol, amineethylethanol, 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, pyrazine, 1-(2-hydroxyethyl)methylpiperazine, 1-methylpiperazine, 2-methylpiperazine, and 1-amino-4-methylpiperazine. See the [Claims] section and the [Modes for Carrying Out the Invention] section. The protic polar solvent may be a glycol or a glycol ether, as described herein (see, for example, the Claims section).

[0009] Korean Patent Application Publication No. 20130007402(A) (machine translation) discloses a cleaning solution composition comprising, based on the total weight of the composition, 0.05 to 10% by weight of a cyclic amine, 0.1 to 20% by weight of a water-soluble glycol ether compound, and 79 to 99.5% by weight of water. See Abstract and Claim 1. Examples of cyclic amine compounds represented by Formula 1, as described in the said patent document, include N-methylmorpholine, N-ethylmorpholine, N-formylmorpholine, N-(2-hydroxylethyl)morpholine, N-(3-hydroxylpropyl)morpholine, N-(2-hydroxylethyl)-N'-methylpiperazine, N-(2-hydroxylethyl)-N'-ethylpiperazine, N,N'-bis(2-hydroxyethyl)piperazine, and the like. These compounds may be used alone or in combination of two or more. See the section [Modes for Carrying Out the Invention]. Specific examples of water-soluble glycol ether compounds include ethylene glycol monobutyl ether (BG), ethylene glycol monopropyl ether, diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (BDG), dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG), propylene glycol monomethyl ether (MFG), propylene glycol monopropyl ether, etc., which may be used alone or in combination of two or more. See the section on [Modes for Carrying Out the Invention].

[0010] PCT International Publication No. 02 / 084401(A2) discloses a photoresist suitable for short-wavelength imaging. The resist comprises a fluorine-containing polymer, a photoactive component, and a solvent component (see abstract). The photoresist may also contain basic additives. Examples of basic additives include DBU (1,8-diazobicyclo[5.4.0]undeca-7-ene), DBN (1,5-diaza-bicyclo[4.3.0]non-5-ene, N,N-bis-(2-hydroxyethyl)piperazine, N,N-bis-(2-hydroxyethyl)-2,5-diazobicyclo[2.2.1]heptane, N-triisopropanolamine, dibutylamine, and its branched isomers, such as diisobutylamine and ditertbutylamine, tributylamine, and its branched isomers, such as diterbutylamine and tritertbutylamine. Optionally substituted piperidines and other optionally piperazine compounds are also disclosed as suitable, particularly hydroxy-substituted or (C1-C 12 )-Alcohol-substituted piperidines and piperazines, such as N-ethanolpiperidine and N-diethanolpiperazine (see pages 26-27), are disclosed.

[0011] However, as mentioned above, there is still a need for an electron stripping agent composition containing a low dose of amine that provides good stripping ability and low metal corrosion. This need has been met by the following invention. [Overview of the Initiative]

[0012] A composition comprising at least the following components a), b), and c), a) At least one N-substituted piperazine selected from the following structures 1 and 2, or a mixture thereof,

[0013] [ka] Structure (1), in the formula, R1 and R2 are each independently C1-C6 alkylenes.

[0014] [Chemical formula] Structure (2), wherein R3 is C1-C6 alkylene and R4 is C1-C6 alkyl, b) at least one glycol ether selected from the following structures 3 and 4 or a mixture thereof, and

[0015] [Chemical formula] Structure (3), wherein n≥1, R1 is hydrogen or alkyl, R2 is hydrogen or alkyl, X is hydrogen, alkyl or aryl when n>1, and X is alkyl or aryl when n = 1,

[0016] [Chemical formula] Structure (4), wherein n≥1, R1 is hydrogen or alkyl, R2 is hydrogen or alkyl, X is hydrogen, alkyl or aryl when n>1, and X is alkyl or aryl when n = 1,

[0017] c) water, and a composition containing the same. [Brief Description of the Drawings]

[0018] [Figure 1] A plot of the boiling point of 1,4-bis(2-hydroxyethyl)piperazine according to "mmHg". The formula of the profile is y = 26.385ln(x) + 118.53 (R2 = 0.9616). [Modes for Carrying Out the Invention]

[0019] Novel photoresist stripping compositions have been discovered that provide excellent photoresist dissolution and stripping efficiency without significant metal corrosion. These compositions may also contain relatively low doses of organic amines. As described above, compositions comprising at least the following components a, b, and c are provided, each as described herein.

[0020] The above compositions may include combinations of two or more embodiments as described herein. Component a may include combinations of two or more embodiments as described herein. Component b may include combinations of two or more embodiments as described herein. Each structure, namely structure 1, structure 2, structure 3, and structure 4, may independently include combinations of two or more embodiments as described herein. Note that, as used herein, for structure 1, R1=R1 and R2=R2; for structure 2, R3=R3 and R4=R4; for structure 3, R1=R1 and R2=R2; and for structure 4, R1=R1 and R2=R2, and structure 1 refers to structure (1), and the same applies to structures 2, 3, and 4.

[0021] In each embodiment or combination of two or more embodiments of component a described herein, structure 1 or structure 2 independently has a boiling point (at 760 mmHg) of ≥250°C, or ≥251°C, or ≥252°C, or ≥253°C, or ≥254°C, or ≥255°C. In each embodiment or combination of two or more embodiments of component a described herein, structure 1 or structure 2 independently has a boiling point (at 760 mmHg) of ≤350°C, or ≤345°C, or ≤340°C, or ≤335°C, or ≤330°C, or ≤325°C, or ≤320°C, or ≤315°C, or ≤310°C, or ≤308°C, or ≤307°C, or ≤306°C, or ≤305°C, or ≤304°C, or ≤303°C, or ≤302°C.

[0022] In each embodiment described herein, or in combination of two or more embodiments, the boiling point (760 mmHg) of structure 1 or structure 2 of component a relative to the boiling point (760 mmHg) of structure 3 or structure 4 of component b is independently ≥0.70, or ≥0.72, or ≥0.75, or ≥0.78, or ≥0.80, or ≥0.82, or ≥0.85, or ≥0.88, or ≥0.90, or ≥0.92, or ≥0.94, or ≥0.96, or ≥0.98, or ≥1.0, or ≥1.1. In each embodiment described herein, or in combination of two or more embodiments, the boiling point (760 mmHg) of structure 1 or structure 2 of component a relative to the boiling point (760 mmHg) of structure 3 or structure 4 of component b is independently ≤ 1.9, or ≤ 1.8, or ≤ 1.7, or ≤ 1.6, or ≤ 1.5, or ≤ 1.4, or ≤ 1.3, respectively.

[0023] In each embodiment described herein, or in combination of two or more embodiments, for component a, structure 1 is R1=R2.

[0024] Each embodiment, or combination of two or more embodiments, described herein, Component a is selected from the following structures 1a), 2a), or 3aa): 1a)

[0025] [ka] In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and further between n = m. 2a)

[0026] [ka] In the formula, n is an integer between 0 and 5, further between 0 and 4, further between 0 and 3, further between 0 and 2, further between 0 and 1, and further between 0 and m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, further between 3, or 3aa) is a mixture of structure 1a) and structure 2a).

[0027] In each embodiment described herein, or in combination of two or more embodiments, component a is selected from structure 1a) as shown above, and further n=m, further n=m=2 or 3, further n=m=2.

[0028] In each embodiment described herein, or in combination of two or more embodiments, component a is selected from structure 2a) as shown above, and further n=0 or 1, further n=0, and further m=2 or 3, further m=3.

[0029] In each embodiment described herein, or in combination of two or more embodiments, component a is selected from structure 3aa) as shown above.

[0030] In each embodiment described herein, or in combination of two or more embodiments, with respect to component b, in structures 3 and 4, each n is independently 1 to 10, further 1 to 8, further 1 to 6, further 1 to 4, further 2 to 4, further 2 to 3, and further 2.

[0031] In each embodiment or combination of two or more embodiments described herein, with respect to component b, in Structure 3 and Structure 4, each X is independently alkyl, further C1-C6 alkyl, further C1-C5 alkyl, further C2-C5 alkyl, further C2-C4 alkyl, further C3-C4 alkyl, and further C4 alkyl.

[0032] In each embodiment described herein, or in combination of two or more embodiments, with respect to component b, in structures 3 and 4, each R1 and R2 independently satisfies the following relationship: R1 = R2, and further, R1 = R2 = H.

[0033] In each embodiment or combination of two or more embodiments described herein, component b is selected from the following structures (3a):

[0034] [ka] Structure (3a), wherein the formula, if n≧1 and n>1, X' is hydrogen or alkyl, and if n=1, X' is alkyl. In further embodiments, X' is alkyl.

[0035] In each embodiment or combination of two or more embodiments described herein, component b is selected from the following structures (4a):

[0036] [ka] Structure (4a), wherein the formula, if n≧1 and n>1, X' is hydrogen or alkyl, and if n=1, X' is alkyl. In further embodiments, X' is alkyl.

[0037] In each embodiment or combination of two or more embodiments described herein, the weight ratio of component a to component b is ≥0.40, or ≥0.45, or ≥0.50, or ≥0.55, or ≥0.60, or ≥0.65. In each embodiment or combination of two or more embodiments described herein, the weight ratio of component a to component b is ≤1.00, or ≤0.95, or ≤0.90, or ≤0.85, or ≤0.80, or ≤0.75, or ≤0.70.

[0038] In each embodiment or combination of two or more embodiments described herein, the weight ratio of component c to component a is ≥2.0, or ≥2.5, or ≥3.0, or ≥4.0, or ≥4.5, or ≥5.0, or ≥5.2, or ≥5.4, or ≥5.6. In each embodiment or combination of two or more embodiments described herein, the weight ratio of component c to component a is ≤8.0, or ≤7.5, or ≤7.0, or ≤6.8, or ≤6.6, or ≤6.4, or ≤6.2, or ≤6.0, or ≤5.9, or ≤5.8.

[0039] Each embodiment, or combination of two or more embodiments, described herein, The weight ratio of component c to component b is ≥1.0, or ≥1.5, or ≥2.0, or ≥2.5, or ≥3.0, or ≥3.2, or ≥3.4, or ≥3.6, or ≥3.7, or ≥3.8. In each embodiment described herein, or in combination of two or more embodiments, the weight ratio of component c to component b is ≤5.0, or ≤4.8, or ≤4.6, or ≤4.4, or ≥4.2, or ≤4.1, or ≤4.0.

[0040] In each embodiment or combination of two or more embodiments described herein, the sum of component a and component b is present in an amount of ≥15% by weight, or 18% by weight, or ≥20% by weight, or 22% by weight, or ≥24% by weight, or ≥25% by weight, or ≥26% by weight, or ≥27% by weight, or ≥28% by weight, or ≥30% by weight, or ≥31% by weight, or ≥32% by weight, based on the weight of the composition. In each embodiment or combination of two or more embodiments described herein, the sum of component a and component b is present in an amount of ≤50% by weight, or ≤48% by weight, or ≤45% by weight, or ≤42% by weight, or ≤40% by weight, or ≤38% by weight, or ≤36% by weight, or ≤34% by weight, based on the weight of the composition.

[0041] In each embodiment or combination of two or more embodiments described herein, the sum of component a, component b, and component c is present in an amount of ≥90% by weight, or 92% by weight, or ≥94% by weight, or ≥96% by weight, based on the weight of the composition. In each embodiment or combination of two or more embodiments described herein, the sum of component a, component b, and component c is present in an amount of ≤100% by weight, or ≤99% by weight, or ≤98% by weight, based on the weight of the composition.

[0042] In each embodiment or combination of two or more embodiments described herein, the composition has a "photoresist removal time" of ≤50 seconds, or ≤49 seconds, or ≤48 seconds, or ≤47 seconds, or ≤46 seconds, or ≤45 seconds (see the [Examples] section, without aging of the composition). In each embodiment or combination of two or more embodiments described herein, the composition has a "Cu ion concentration" of ≤1.2 ppm, or ≤1.1 ppm, or ≤1.0 ppm, or ≤0.90 ppm, or ≤0.80 ppm, or ≤0.60 ppm, or ≤0.40 ppm, or ≤0.30 ppm, or ≤0.20 ppm (see the [Examples] section (corrosion test), 30 minutes at 54°C, without aging of the composition).

[0043] In each embodiment described herein, or in combination of two or more embodiments, the composition is a photoresist stripping composition.

[0044] Also provided are processes for forming compositions of any one embodiment or combination of two or more embodiments described herein, each comprising mixing at least component a and component b.

[0045] Also provided is a process for removing a photoresist, the process comprising applying a composition of any one embodiment or combination of two or more embodiments described herein to the surface of the photoresist. In each embodiment or combination of two or more embodiments described herein, the photoresist is applied to a metal surface.

[0046] Component a: N-substituted piperazine Component a is described herein. The synthesis of N-substituted piperazines is well known in the art, and various etheramines are commercially available. For example, N-substituted piperazines can be produced by reacting oxides with piperazine. Furthermore, as an example, 1,4-bis(2-hydroxyethyl)piperazine can be synthesized by reacting EO (ethylene oxide) with piperazine in a target ratio of 2:1. This N-substituted piperazine can be recovered using conventional techniques. Note that the term N-substituted piperazine as used herein refers to N-substituted and N,N'-substituted piperazines on the piperazine ring.

[0047] Component a may be in the form of a liquid composition to be added to an aqueous composition. The N-substituted piperazine itself may be in liquid form at room temperature (22°C), and therefore the "stock" composition may be in the form of undiluted N-substituted piperazine (100% by weight). The stock composition may also be prepared with N-substituted piperazine in one or more suitable solvents, for example, in an amount ranging from about 30% (by weight) to about 99% (by weight) of N-substituted piperazine. The solvent may be water. The N-substituted piperazine may also be in the form of a solid composition, such as a powder or granules, which can be added to the aqueous composition.

[0048] Component b: Glycol ether Component b is described herein. In one embodiment, component b is selected from ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

[0049] Other additives The compositions described herein may optionally contain one or more additional additives. Examples of additives include, but are not limited to, corrosion inhibitors, antioxidants, surfactants, polar aprotic solvents, and combinations thereof. The polar aprotic solvent may be selected from N-methyl-2-pyrrolidone, N-alkyl-2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylalkylamide, and γ-butyrolactone. The additive may be present in an amount of ≥0.01% by weight, or ≥0.02% by weight, or ≥0.05% by weight, or ≥0.10% by weight, or ≥0.20% by weight, or ≥0.40% by weight, or ≥0.60% by weight, or ≥0.80% by weight, and / or ≤20% by weight, or ≤10% by weight, or ≤5.0% by weight, or ≤3.0% by weight, or ≤2.0% by weight, or ≤1.0% by weight, based on the weight of the composition.

[0050] definition Unless otherwise stated, implied by the context, or customary in the art, parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0051] As used herein, the term “composition” includes a mixture of the materials comprising the composition, and reaction and decomposition products formed from the materials of the composition. Any reaction or decomposition products are typically present in trace or residual amounts.

[0052] As used herein, the term “polymer” refers to a polymer compound prepared by polymerizing multiple monomers, whether of the same or different types. Thus, the general term polymer includes the term homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer, as defined herein below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers in very small amounts (in “ppm (parts per million)”).

[0053] As used herein, the term “interpolymer” refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from three or more different types of monomers.

[0054] As used herein, the term “water” refers to H2O or an H2O sample. Such a water (H2O) sample is substantially pure water and therefore may or may not contain one or more impurities, such as dissolved inorganic ions. Typically, the impurities are present in amounts of ≤1000 ppm, preferably ≤100 ppm, more preferably ≤10 ppm, and more preferably ≤1 ppm, based on the weight of the water sample.

[0055] As used herein, the term “photoresist” refers to a photosensitive (e.g., UV light) material used to form a patterned coating on a surface, such as a metal surface.

[0056] With respect to the process of removing a photoresist with the compositions described herein, the phrase "apply to the surface of the photoresist" means bringing the surface into contact with the composition. This contact may be achieved by wetting the photoresist surface with the composition using a spray, brush, or roller, or by dipping the photoresist in the composition, or by immersing the photoresist in the composition, or by any other means well known in the art.

[0057] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may, unless otherwise stated, include any additional additives, adjuvants, or compounds, whether or not they are polymers. In contrast, the term “consisting essentially of” excludes any other components, processes, or procedures from any subsequent enumeration, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically specified or enumerated.

[0058] As used herein, the term “exfoliation” refers to the removal of photoresist. See, for example, the [Examples] section.

[0059] List of some characteristics of the composition and method A) A composition comprising at least the following components a), b), and c), a) At least one N-substituted piperazine selected from the following structures 1 and 2, or a mixture thereof,

[0060] [ka] Structure (1), in the formula, R1 and R2 are each independently C1-C6 alkylenes.

[0061] [ka] Structure (2), in the formula, R3 is a C1-C6 alkylene and R4 is a C1-C6 alkyl, b) At least one glycol ether selected from Structure 3, Structure 4 below, or a mixture thereof,

[0062] [ka] Structure (3), where n≧1, R1 is hydrogen or alkyl, R2 is hydrogen or alkyl, X is hydrogen, alkyl or aryl when n>1, and X is alkyl or aryl when n=1.

[0063] [ka] Structure (4), where n≧1, R1 is hydrogen or alkyl, R2 is hydrogen or alkyl, X is hydrogen, alkyl or aryl when n>1, and X is alkyl or aryl when n=1. c) A composition containing water.

[0064] B] The composition according to A] above, wherein, with respect to component a, structure 1 or structure 2 each independently has a boiling point (at 760 mmHg) of ≥250°C, ≥251°C, ≥252°C, ≥253°C, ≥254°C, or ≥255°C.

[0065] C) The composition according to A] or B] above, wherein, with respect to component a, structure 1 or structure 2 each independently has a boiling point (at 760 mmHg) of ≤350°C, or ≤345°C, or ≤340°C, or ≤335°C, or ≤330°C, or ≤325°C, or ≤320°C, or ≤315°C, or ≤310°C, or ≤308°C, or ≤307°C, or ≤306°C, or ≤305°C, or ≤304°C, or ≤303°C, or ≤302°C.

[0066] D) The composition according to any one of the above A] to C](A] to C], wherein the ratio of the boiling point (760 mmHg) of structure 1 or structure 2 of component a to the boiling point (760 mmHg) of structure 3 or structure 4 of component b is independently ≥0.70, or ≥0.72, or ≥0.75, or ≥0.78, or ≥0.80, or ≥0.82, or ≥0.85, or ≥0.88, or ≥0.90, or ≥0.92, or ≥0.94, or ≥0.96, or ≥0.98, or ≥1.0, or ≥1.1.

[0067] E) The composition according to any one of A] to D] above, wherein the ratio of the boiling point (760 mmHg) of structure 1 or structure 2 of component a to the boiling point (760 mmHg) of structure 3 or structure 4 of component b is independently ≤1.9, or ≤1.8, or ≤1.7, or ≤1.6, or ≤1.5, or ≤1.4, or ≤1.3, respectively.

[0068] F) The composition according to any one of the above A] to E], wherein, with respect to component a, R1 = R2 in structure 1.

[0069] G) The composition according to any one of A) to F) above, wherein in structure 1, R1 is C1-C5 alkylene, further C1-C4 alkylene, further C1-C3 alkylene, further C1-C2 alkylene, and further C2 alkylene.

[0070] H] The composition according to any one of A] to G] above, wherein in structure 1, R2 is C1-C5 alkylene, further C1-C4 alkylene, further C1-C3 alkylene, further C1-C2 alkylene, and further C2 alkylene.

[0071] I) The composition according to any one of A] to H] above, wherein, with respect to component a, in structure 2, R3 is C1-C5 alkylene, further C1-C4 alkylene, further C1-C3 alkylene, further C2-C3 alkylene, and further C3 alkylene.

[0072] J) The composition according to any one of A] to I] above, wherein in structure 2, R4 is a C1-C5 alkyl, further a C1-C4 alkyl, further a C1-C3 alkyl, further a C1-C2 alkyl, and further a C1 alkyl.

[0073] Component a of K is selected from the following structures 1a), 2a), or 3aa): 1a)

[0074] [ka] In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and further between n = m. 2a)

[0075] [ka] In the formula, n is an integer between 0 and 5, further between 0 and 4, further between 0 and 3, further between 0 and 2, further between 0 and 1, and further between 0, and m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 3, or 3aa) A composition according to any one of A] to J] above, which is a mixture of structure 1a) and structure 2a).

[0076] The composition according to K) above, wherein component a is selected from structure 1a) as shown above, and further n=m, further n=m=2 or 3, and further n=m=2.

[0077] M] The composition according to K) above, wherein component a is selected from structure 2a) as shown above, and further n=0 or 1, further n=0, and further m=2 or 3, further m=3.

[0078] N] The composition according to K) above, wherein component a is selected from structure 3aa) as shown above.

[0079] O] Component a is selected from Structure 1, and is a composition according to any one of A] to L] above.

[0080] P] Component a is selected from Structure 2, and is a composition according to any one of A] to K] or M] above.

[0081] Q] The composition according to any one of the above A] to K] or N], wherein component a is selected from a mixture of structure 1 and structure 2.

[0082] R) The composition according to Q) above, wherein structure 1 is selected from structure 1a) as shown above, and further n=m, further n=m=2 or 3, and further n=m=2.

[0083] S) The composition according to Q] or R] above, wherein structure 2 is selected from structure 2a) as shown above, and further n=0 or 1, further n=0, and further m=2 or 3, further m=3.

[0084] T] The composition according to any one of the above A] to S], wherein, with respect to component a, structure 1 or structure 2 each independently has a molecular weight of ≥130, ≥135, ≥140, ≥145, ≥150, or ≥155 g / mol.

[0085] U) The composition according to any one of the above A] to T], wherein, with respect to component a, structure 1 or structure 2 independently has a molecular weight of ≤400, or ≤350, or ≤300, or ≤280, or ≤260, or ≤240, or ≤220, or ≤210, or ≤205, or ≤200, or ≤195, or ≤190, or ≤185, or ≤180, or ≤175 g / mol.

[0086] V) The composition according to any one of A) to U) above, wherein in structure 3 and structure 4, each n is independently 1 to 10, further 1 to 8, further 1 to 6, further 1 to 4, further 2 to 4, further 2 to 3, and further 2.

[0087] The composition according to any one of A] to V] above, wherein, with respect to component b, in structures 3 and 4, each X is independently alkyl, and further C1-C6 alkyl, further C1-C5 alkyl, further C2-C5 alkyl, further C2-C4 alkyl, further C3-C4 alkyl, and further C4 alkyl.

[0088] X] With respect to component b, in structures 3 and 4, each R1 and R2 independently satisfy the following relationship: R1=R2, and furthermore, R1=R2=H, the composition according to any one of the above A] to W].

[0089] Y] Component b is, A composition according to any one of the above A] to V] or X], selected from structure 3, and further wherein X is hydrogen, alkyl, or C5-C8 aryl when n>1, and X is alkyl or C5-C8 aryl when n=1, and further wherein X is hydrogen, alkyl, or alkyl when n>1, and X is alkyl when n=1.

[0090] Component b of [Z] is selected from the following structures (3a):

[0091] [ka] The composition according to Y above, structure (3a), wherein when n≧1 and n>1, X' is hydrogen or alkyl, and when n=1, X' is alkyl.

[0092] A2]X' is alkyl, the composition according to Y] or Z] above.

[0093] [B2] Component b is selected from the following structures (3b):

[0094] [ka] A composition according to structural formula (3b) or any one of the above items Y] to A2].

[0095] C2] The composition according to any one of A] to V] or X] above, wherein component b is selected from structure 4, and further, when n>1, X is hydrogen, alkyl, or C5-C8 aryl, and when n=1, X is alkyl or C5-C8 aryl, and further, when n>1, X is hydrogen, alkyl, and when n=1, X is alkyl.

[0096] [D2] Component b is selected from the following structures (4a):

[0097] [ka] The composition according to C2] above, wherein structure (4a), in which n≧1 and X' is hydrogen or alkyl when n>1, and X' is alkyl when n=1.

[0098] The composition according to C2] or D2] above, wherein E2]X' is alkyl.

[0099] [F2] Component b is selected from the following structures (4b):

[0100] [ka] Structure (4b), a composition according to any one of the above items C2] to D].

[0101] G2] The composition according to any one of A] to X] above, wherein component b is selected from a mixture of structures 3 and 4.

[0102] The composition according to G2] above, wherein component b is selected from a mixture of structures (3a) and (4a) as described above, and each X' is independently alkyl.

[0103] I2] The composition according to G2] or H2] above, wherein component b is selected from a mixture of structure (3b) and structure (4b) as described above.

[0104] J2] The composition according to any one of the above A] to I2], wherein, with respect to component b, structure 3 and structure 4 each independently have a molecular weight of ≥130, ≥135, ≥140, ≥145, ≥150, ≥155, or ≥160 g / mol.

[0105] K2] With respect to component b, structure 3 and structure 4 each independently have a molecular weight of ≤350, or ≤300, or ≤250, or ≤200, or ≤195, or ≤190, or ≤185, or ≤180, or ≤175, or ≤170, or ≤165 g / mol, according to any one of the above A] to J2].

[0106] The composition according to any one of the above A] to K2], wherein the ratio of the molecular weight of structure 1 or structure 2 of component a to the molecular weight of structure 3 or structure 4 of component b is independently ≥0.80, or ≥0.85, or ≥0.90, or ≥0.95, respectively.

[0107] The composition according to any one of the above A] to L2], wherein the ratio of the molecular weight of structure 1 or structure 2 of component a to the molecular weight of structure 3 or structure 4 of component b is independently ≤2.00, or ≤1.80, or ≤1.60, or ≤1.55, or ≤1.50, or ≤1.45, or ≤1.40, or ≤1.35, or ≤1.30, or ≤1.25, or ≤1.20, or ≤1.15, or ≤1.10.

[0108] The composition according to any one of the above A] to M2], wherein the weight ratio of component a to component b is ≥0.40, or ≥0.45, or ≥0.50, or ≥0.55, or ≥0.60, or ≥0.65.

[0109] The composition according to any one of the above A] to N2], wherein the weight ratio of component a to component b is ≤1.00, or ≤0.95, or ≤0.90, or ≤0.85, or ≤0.80, or ≤0.75, or ≤0.70.

[0110] P2] The composition according to any one of A] to O2] above, wherein component a is present in an amount of ≥1.0% by weight, or ≥2.0% by weight, or ≥3.0% by weight, or ≥4.0% by weight, or ≥5.0% by weight, based on the weight of the composition.

[0111] Q2] The composition according to any one of the above A] to P2], wherein component a is present in an amount of ≤30% by weight, or ≤25% by weight, or ≤20% by weight, or ≤18% by weight, or ≤16% by weight, or ≤14% by weight, or ≤12% by weight, based on the weight of the composition.

[0112] R2] The composition according to any one of A] to Q2] above, wherein component a is present in an amount of ≥6.0% by weight, or ≥8.0% by weight, or ≥10% by weight, or ≥11% by weight, or ≥12% by weight, based on the weight of the composition.

[0113] S2] The composition according to any one of A] to R2] above, wherein component a is present in an amount of ≤30% by weight, or ≤28% by weight, or ≤26% by weight, or ≤24% by weight, or ≤22% by weight, or ≤20% by weight, based on the weight of the composition.

[0114] T2] The composition according to any one of A] to S2] above, wherein component b is present in an amount of ≥10% by weight, or ≥11% by weight, or ≥12% by weight, or ≥13% by weight, or ≥14% by weight, or ≥15% by weight, or ≥16% by weight, based on the weight of the composition.

[0115] U2] The composition according to any one of A] to T2] above, wherein component b is present in an amount of ≤40% by weight, or ≤35% by weight, or ≤30% by weight, or ≤25% by weight, or ≤22% by weight, or ≤21% by weight, or ≤20% by weight, or ≤19% by weight, or ≤18% by weight, based on the weight of the composition.

[0116] V2] The composition according to any one of A] to U2] above, wherein component c is present in an amount of ≥50% by weight, or ≥55% by weight, or ≥60% by weight, or ≥62% by weight, or ≥64% by weight, or ≥66% by weight, or ≥68% by weight, based on the weight of the composition.

[0117] W2] The composition according to any one of A] to V2] above, wherein component c is present in an amount of ≤80% by weight, or ≤78% by weight, or ≤76% by weight, or ≤74% by weight, or ≤72% by weight, or ≤70% by weight, based on the weight of the composition.

[0118] X2] The composition according to any one of the above A] to W2], wherein the weight ratio of component c to component a is ≥2.0, or ≥2.5, or ≥3.0, or ≥4.0, or ≥4.5, or ≥5.0, or ≥5.2, or ≥5.4, or ≥5.6.

[0119] Y2] The composition according to any one of the above A] to X2], wherein the weight ratio of component c to component a is ≤8.0, or ≤7.5, or ≤7.0, or ≤6.8, or ≤6.6, or ≤6.4, or ≤6.2, or ≤6.0, or ≤5.9, or ≤5.8.

[0120] Z2] The composition according to any one of the above A] to Y2], wherein the weight ratio of component c to component b is ≥1.0, or ≥1.5, or ≥2.0, or ≥2.5, or ≥3.0, or ≥3.2, or ≥3.4, or ≥3.6, or ≥3.7, or ≥3.8.

[0121] A3] The composition according to any one of the above A] to Z2], wherein the weight ratio of component c to component b is ≤5.0, or ≤4.8, or ≤4.6, or ≤4.4, or ≥4.2, or ≤4.1, or ≤4.0.

[0122] B3] The composition according to any one of A] to A3] above, wherein the sum of component a and component b is present in an amount of ≥15% by weight, or 18% by weight, or ≥20% by weight, or 22% by weight, or ≥24% by weight, or ≥25% by weight, or ≥26% by weight, or ≥27% by weight, or ≥28% by weight, or ≥30% by weight, or ≥31% by weight, or ≥32% by weight, based on the weight of the composition.

[0123] C3) The composition according to any one of A] to B3] above, wherein the sum of component a and component b is present in an amount of ≤50% by weight, or ≤48% by weight, or ≤45% by weight, or ≤42% by weight, or ≤40% by weight, or ≤38% by weight, or ≤36% by weight, or ≤34% by weight, based on the weight of the composition.

[0124] D3] The composition according to any one of A] to C3] above, wherein the sum of component a, component b, and component c is present in an amount of ≥90% by weight, or 92% by weight, or ≥94% by weight, or ≥96% by weight, based on the weight of the composition.

[0125] E3] The composition according to any one of the above A] to D3], wherein the sum of component a, component b, and component c is present in an amount of ≤100% by weight, or ≤99% by weight, or ≤98% by weight, based on the weight of the composition.

[0126] F3] Weight % of component c ≥ The weight % of component b is greater than or equal to the weight % of component a, and each weight % is based on the weight of the composition, as described in any one of the above A] to E3].

[0127] G3] The composition according to any one of the above A] to F3], where the weight % of component c > the weight % of component b > the weight % of component a, and each weight % is based on the weight of the composition.

[0128] H3] The composition comprises, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of surfactant, and further comprises, the composition is free of surfactant, as described in any one of the above A] to G3].

[0129] I3] The composition according to any one of A] to H3] above, wherein the composition contains ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of cyclodextrin or its derivative (e.g., (2-hydroxypropyl)-beta-cyclodextrin, alpha-cyclodextrin-6-sodium phosphorylate, or beta-cyclodextrin monophosphate sodium salt) based on the weight of the composition, and the composition further does not contain cyclodextrin or its derivative.

[0130] J3] The composition comprises ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of ethylamine based on the weight of the composition, and further comprises the composition without ethylamine, as described in any one of A] to I3] above.

[0131] K3] The composition comprises, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of alkylamine, and further, the composition does not contain alkylamine, as described in any one of the above A] to J3].

[0132] L3] The composition comprises, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of an alkanolamine (e.g., monoethanolamine), and further, the composition does not contain an alkanolamine, as described in any one of the above A] to K3].

[0133] M3] The composition comprises, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of a fluoride compound (e.g., ammonium fluoride, ammonium difluoride, hydrogen fluoride, tetraalkylammonium difluoride, alkylphosphonium difluoride, or triethylamine trihydrofluoride), and further, the composition does not contain a fluoride compound, as described in any one of A] to L3] above.

[0134] N3] The composition is based on the weight of the composition, ≤ A composition according to any one of the above A] to M3], comprising 1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of an amide (e.g., N,N-dimethylpropanamide or N-methylformamide), and further comprising a composition that does not contain an amide.

[0135] The composition according to any one of the above A] to N3], comprising, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of a quaternary ammonium compound (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, or tetrabutylammonium hydroxide), and further comprising, the composition not comprising a quaternary ammonium compound.

[0136] P3] The composition is one of the compositions described in any one of A] to O3] above, having a "photoresist removal time" of ≤50 seconds, or ≤49 seconds, or ≤48 seconds, or ≤47 seconds, or ≤46 seconds, or ≤45 seconds (see the [Examples] section, without maturation of the composition).

[0137] Q3] The composition according to any one of A] to P3] above, having a “photoresist removal time” of ≥ 5.0 seconds, or ≥ 10 seconds, or ≥ 15 seconds (see the [Examples] section, without maturation of the composition).

[0138] R3] The composition is one of the compositions described in any one of A] to Q3] above, having a Cu ion concentration of ≤1.2 ppm, or ≤1.1 ppm, or ≤1.0 ppm, or ≤0.90 ppm, or ≤0.80 ppm, or ≤0.60 ppm, or ≤0.40 ppm, or ≤0.30 ppm, or ≤0.20 ppm (see the [Examples] section, 30 minutes at 54°C, without aging of the composition).

[0139] S3] The composition is one of the compositions described in any one of A] to R3] above, having a Cu ion concentration of ≥0 ppm or ≥0.1 ppm (see the [Examples] section, 30 minutes at 54°C without aging of the composition).

[0140] The composition according to any one of A] to S3], wherein the composition is a photoresist stripping composition.

[0141] A process for forming a composition according to any one of items A4]A]~T3], comprising mixing at least component a and component b.

[0142] B4] The process according to A4 above, wherein the process includes mixing at least component a, component b, and component c.

[0143] C4] The mixing is carried out at a temperature of ≥18°C, or ≥19°C, or ≥20°C and / or ≤27°C, or ≤26°C, or ≤25°C, or ≤24°C, or ≤23°C, as described in A4] or B4].

[0144] D4] Mixing is carried out in the ambient atmosphere, as described in any one of the items A4] to C4].

[0145] E4] A process for removing photoresist, wherein the process is A process comprising applying one of the compositions described in any one of the above items A] to T3] to the surface of a photoresist.

[0146] F4] The photoresist is coated onto a metal surface using the process described in E4 above.

[0147] G4] The metal on the metal surface is selected from steel, stainless steel, brass, chromium, titanium, molybdenum, aluminum, aluminum alloy, copper, copper alloy, silver, or gold, as described in F4 above.

[0148] The process according to any one of the above E4] to G4], wherein when the composition is applied to the surface of a photoresist, the temperature of the composition is ≥18°C, or ≥19°C, or ≥20°C, or ≥22°C and / or ≤30°C, or ≤29°C, or ≤28°C, or ≤27°C, or ≤26°C, or ≤25°C, or ≤24°C. [Examples]

[0149] The reagents are shown in Table 1, and the boiling point of N,N'-di(2-hydroxyethyl)piperazine is shown in Table 1b. The compositions are shown in Tables 2a to 2d below. For each composition, the components (amine and / or glycol ether and / or water) were mixed together at room temperature and ambient atmosphere. A homogeneous, clear solution was obtained, which was stable at room temperature.

[0150] [Table 1] * For predicted boiling point, please refer to SciFinder CAS registry number 80744-48-5(2023). Note the reported average predicted boiling point (492.1±40.0℃).

[0151] [Table 2] * Please refer to Figure 1. ** Average = [(Prediction + Extrapolation) / 2]

[0152] [Table 3] * Note: The boiling point (glycol) is the boiling point of glycol ether in the table above and the table below.

[0153] [Table 4]

[0154] [Table 5]

[0155] [Table 6]

[0156] Photoresist stripping: SFP-1400 photoresist solution (2 mL, Merck) was dropped onto the surface of a glass substrate measuring "100 mm × 100 mm × 1 mm" (Corning indium tin oxide coated soda-lime glass). The substrate was spin-coated with the photoresist solution by spinning it at a rotation speed of 500 rpm for 10 seconds in ambient atmosphere (model LabSpin 6 / 8, SSUS MicroTech). The rotation speed was then accelerated to 1000 rpm and maintained for 30 seconds to obtain a spin-coated substrate with a "1 μm thick" photoresist film (Unicorn, model Filmetrics F50, measured by laser thickness gauge). The spin-coated substrate was heated at 130°C (set temperature) (hot plate in nitrogen atmosphere) for 10 minutes to completely evaporate the solvent, causing the photoresist film to curve and forming a baked substrate.

[0157] In the following stripping process, each composition (30g, see Tables 2a to 2d) was prepared in a container with a side length (circumference of the cube) exceeding 100mm (the container volume was 1L). The baked substrate was placed in the container at 22°C and immediately shaken by hand twice back and forth for 1 second. The time it took for the photoresist to be completely removed from the substrate during the shaking process was recorded. The shorter the time required to strip (remove) the photoresist, the better the performance of the composition. Three stripping tests were performed for each composition, and the time range was reported. The results are shown in Tables 3 and 4 below.

[0158] For each composition in Table 4, the composition was exposed to air at 54 o Please note that the material was aged at °C for 6 hours. Subsequently, the photoresist stripping process described above was carried out as shown.

[0159] Metal corrosion: High-purity copper foil with a calender thickness of 1 mm (manufactured by Alfa Aesar, 99.999% purity copper foil) was cut into squares, each weighing 0.90 ± 0.01 g. A passivation layer of copper oxide (CuO or Cu2O) formed on the surface of the copper foil (during storage). Therefore, the cut copper pieces were immersed in a 5% HCl aqueous solution for 5 minutes to completely remove the passivation layer and ensure 99.999% purity (provided by the supplier). The acid-polished copper pieces were rinsed with 20 mL of DI water (deionized water) and dried under a nitrogen gas stream. For each composition, a clean copper piece was placed in a 10 mL glass bottle containing 5 g of the composition. The bottles were stored at 54°C for 30 minutes (corrosion test). After this time, the copper pieces were removed from the bottle, and the remaining composition was examined by ICP-OES (Inductively Coupled Plasma Atomic Emission Spectrometry) using a Perkin Elmer Optima 5300 DV model spectrometer. This spectroscopic measurement was used to determine the amount of copper ions remaining in the composition. A lower concentration of copper ions in the composition indicates better storage stability for the copper foil. For each composition, one test sample was analyzed, and the ICP-OES measurement was repeated three times, with the average concentration value reported. The results are shown in Tables 4, 5a, and 5b below.

[0160] Note that for each composition in Table 4, the composition was aged in air at 54°C for 6 hours before being added to the "10 ml glass bottle". Then, the composition was added to the bottle and a corrosion test was performed as described above.

[0161] [Table 7] * Photoresist removal time. ** Boiling point ratio (amine / glycol) = 0.610.

[0162] [Table 8] * Photoresist removal time. ** Each ppm is based on the total weight of the solution at the end of the corrosion test.

[0163] [Table 9] * Each ppm is based on the total weight of the solution at the end of the corrosion test.

[0164] [Table 10] * Each ppm is based on the total weight of the solution at the end of the corrosion test. ** Not detected

[0165] As shown in Table 3, the photoresist stripping performance of each of Compositions IE1, IE2, and IE3 was superior to that of Compositions CE2, CE3, CE4, CE9, CE10, CE11, CE12, CE16, CE17, and CE20. The photoresist stripping performance of each of Compositions IE1, IE2, and IE3 was equivalent to or better than that of CE1. As shown in Table 4, the photoresist stripping performance of each of Compositions IE5 and IE6 was superior to that of Compositions CE18 and CE19. Note that compositions containing an amine having a boiling point ≧ 250 °C but having a boiling point (amine) / boiling point (glycol) ratio outside the described range of 0.70 to 1.9 had longer photoresist removal times. Compositions IE1, IE2, and IE3 had very low or no detectable metal leaching in the liquid phase during the corrosion process compared to CE1, CE3, CE5 - CE14, and CE20 (see Tables 5a and 5b).

Claims

1. A composition comprising at least the following components a), b), and c), a) At least one N-substituted piperazine selected from the following structures 1 and 2, or a mixture thereof, 【Chemistry 1】 Structure (1), in the formula, R1 and R2 are each independently C1-C6 alkylenes. 【Chemistry 2】 Structure (2), in the formula, R3 is a C1-C6 alkylene and R4 is a C1-C6 alkyl, b) At least one glycol ether selected from the following structures 3 and 4, or a mixture thereof, 【Transformation 3】 Structure (3), where n ≥ 1, R1 is hydrogen or alkyl, R2 is hydrogen or alkyl, and X is hydrogen, alkyl or aryl when n > 1, and alkyl or aryl when n = 1. 【Chemistry 4】 Structure (4), in the formula, n ≥ 1, R1 is hydrogen or alkyl, R2 is hydrogen or alkyl, and X is hydrogen, alkyl or aryl when n > 1, and when n = 1, X is alkyl or aryl. c) A composition containing water.

2. The composition according to claim 1, wherein, with respect to component a, structure 1 or structure 2 each independently has a boiling point of ≥250°C (at 760 mmHg).

3. The composition according to claim 1 or 2, wherein the ratio of the boiling point (760 mmHg) of structure 1 or structure 2 of component a to the boiling point (760 mmHg) of structure 3 or structure 4 of component b is independently ≥ 0.

70.

4. The composition according to any one of claims 1 to 3, wherein the ratio of the boiling point (760 mmHg) of structure 1 or structure 2 of component a to the boiling point (760 mmHg) of structure 3 or structure 4 of component b is independently ≤ 1.

9.

5. The composition according to any one of claims 1 to 4, wherein, with respect to component a, R1 = R2 in structure 1.

6. Component a is Structure 1a), Structure 2a), or Structure 3aa), respectively, as shown below, 1a) 【Transformation 5】 Thus, in the formula, n is an integer from 1 to 6 and m is an integer from 1 to 6, 1a) 2a) 【Transformation 6】 2a) where n is an integer from 0 to 5 and m is an integer from 1 to 6, or A composition according to any one of claims 1 to 5, comprising 3aa), which is a mixture of structure 1a) and structure 2a), selected from the above.

7. The composition according to claim 6, wherein component a is selected from structure 1a).

8. The composition according to claim 6, wherein component a is selected from structure 2a).

9. The composition according to claim 6, wherein component a is selected from structure 3aa).

10. The composition according to any one of claims 1 to 9, wherein, with respect to structure 3 or structure 4 of component b, each n is independently 1 to 10.

11. The composition according to any one of claims 1 to 10, wherein each X in structure 3 or structure 4 of component b is independently alkyl.

12. Component b is as follows: 【Transformation 7】 A composition according to any one of claims 1 to 11, selected from structure (3a), wherein in the formula, n ≥ 1 and if n > 1, X' is hydrogen or alkyl, and if n = 1, X' is alkyl.

13. Component b is as follows: 【Transformation 8】 A composition according to any one of claims 1 to 11, selected from structure (4a), wherein in the formula, n ≥ 1 and if n > 1, X' is hydrogen or alkyl, and if n = 1, X' is alkyl.

14. The composition according to any one of claims 1 to 13, wherein the sum of component a, component b, and component c is present in an amount of 90% to 100% by weight, based on the weight of the composition.

15. The composition according to any one of claims 1 to 14, wherein the composition has a "photoresist removal time" of ≤ 50 seconds (see the [Examples] section, without maturation of the composition).

16. The composition contains ≤1.2 ppm of Cu ions after 30 minutes at 54°C. The composition according to any one of claims 1 to 15, having a concentration (see the [Examples] section, without aging of the composition).

17. The composition according to any one of claims 1 to 16, wherein the composition is a photoresist stripping composition.

18. A process for forming the composition according to any one of claims 1 to 17, wherein the process comprises mixing at least component a and component b.

19. A process for removing a photoresist, the process comprising applying a composition according to any one of claims 1 to 17 to the surface of the photoresist.

20. The process according to claim 19, wherein the photoresist is coated onto a metal surface.

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