JPWO2007148574A1 - Resist stripper - Google Patents

Abstract

An object of the present invention is to provide a resist stripper that is excellent in peelability, safe from flammability, and excellent in corrosion resistance that does not corrode conductors. The resist stripper includes a compound represented by the formula (1). In the formula (1), R3 is an alkyl group having 1 to 18 carbon atoms, and R1 and R2 may each independently have a hydrogen atom or an ether bond having 1 to 6 carbon atoms. Good hydrocarbon group.

Description

  The present invention relates to a resist remover. In particular, the resist remover of the present invention is excellent in releasability, safe from flammability, and excellent in anticorrosive properties that do not corrode the conductor.

  Integrated circuits such as IC and LSI, display devices such as LCD and EL elements, printed circuit boards, and the like are manufactured using photolithography technology. In this photolithography process, unnecessary resist (photosensitive agent) is removed using a resist stripper.

(Conventional example)
In the resist stripping process, various resist stripping agents have been used so far. However, in recent years, the ability to cope with the miniaturization and short-time processing of liquid crystal display panels and semiconductor elements is low, and further performance is desired. At present, a resist stripping agent containing an amine compound having excellent stripping properties has become the mainstay.
This amine release agent can be classified into a solvent type and an aqueous type. For example, dimethyl sulfoxide (about 30% by weight) + monoethanolamine (about 70% by weight), monoethanolamine + N-methylpyrrolidone, or the like is used as a solvent-based release agent. On the other hand, water (about 20-30% by weight) + diethylene glycol monobutyl ether (about 20-30% by weight) + monoethanolamine (about 30-40% by weight), alkylbenzenesulfonic acid + functional water (ozone water) ), Acid (sulfuric acid + hydrogen peroxide) + functional water (ozone water), etc. are used.

  In recent years, the use of aqueous release agents capable of rinsing with water has been increasing. This is because the aqueous release agent is excellent in releasability and is not flammable and is not a dangerous substance. By the way, monoethanolamine is added to the aqueous release agent. For this reason, the water-based release agent has a drawback that corrosion to a conductor such as wiring occurs. Therefore, in practice, it is necessary to adjust the content of monoethanolamine in consideration of peeling performance and corrosivity. Various resist stripping agents have been developed for the purpose of resist stripping performance and prevention of damage (corrosion) to the conductor.

For example, Patent Document 1 discloses a photoresist stripper containing a product obtained by reacting alkanolamine and formaldehyde. This product is produced by reacting alkanolamine and formaldehyde with formaldehyde / alkanolamine (molar ratio) at a ratio of 0.8 or less.
Patent Document 2 discloses a photoresist stripping composition comprising an alkanolamine compound, a sulfone compound or sulfoxide compound, and a hydroxy compound.
Further, Patent Document 3 discloses a resist remover having a stable pH and containing at least a hydroxycarboxylic acid and water. In this resist stripper, the hydroxycarboxylic acid contained after the production is such that the ratio of the condensate of two or more molecules and the hydroxycarboxylic acid monomer (that is, the condensate / monomer) is 1/9 or less. It has been adjusted.
Patent Document 4 discloses a release agent for removing a resist for using an alloy of copper and silver in a wiring process. This resist stripper contains piperazines.
Furthermore, Patent Document 5 discloses a resist remover containing tetraethylenepentamine and ether alcohol.
JP 2004-219486 A Japanese Patent Laid-Open No. 05-281753 JP 2005-049438 A Japanese Patent Laid-Open No. 2004-205673 JP 2004-205675 A

  The techniques described in the above patent documents have been developed for the purpose of improving resist stripping performance and preventing corrosion of conductors (such as wiring made of copper (Cu) or aluminum (Al)). However, these techniques still have a problem that they cannot satisfy both purposes completely.

  The present invention has been made in view of the above problems, and aims to provide a resist remover that is excellent in releasability, safe from flammability, and excellent in corrosion resistance that does not corrode a conductor. .

  In addition, this inventor earnestly examined in view of said situation. As a result, a specific novel alkoxyamide compound having high amphiphilic properties was used as a resist stripper. This resist stripper was excellent in anticorrosion properties and also in stripping performance. The present invention has been completed in this way.

ここで、式（１）において、Ｒ_３は炭素数１〜１８のアルキル基である。Ｒ_１及びＲ_２は、それぞれ独立に水素原子又は炭素数１〜６のエーテル結合を有してもよい炭化水素基である。Ｒ_１とＲ_２は、互いに同一であっても異なっていてもよく、さらに、互いに結合して環構造を形成してもよい。
このように、アルコキシアミド系のレジスト剥離剤は、高い剥離性能を有するとともに、銅やアルミに対して防食性に非常に優れている。また、このレジスト剥離剤は、水溶性を有しているので、ＩＰＡ（イソプロピルアルコール）リンスが不要であり、生産性を向上させることができる。In order to achieve the above object, the resist stripper of the present invention contains a compound represented by the formula (1).

Here, in the formula (1), _{R 3} is an alkyl group having 1 to 18 carbon atoms. R ₁ and R ₂ are each independently a hydrogen atom or a hydrocarbon group that may have an ether bond having 1 to 6 carbon atoms. R ₁ and R ₂ may be the same or different from each other, and may be bonded to each other to form a ring structure.
As described above, the alkoxyamide-based resist stripper has high stripping performance and is extremely excellent in corrosion resistance with respect to copper and aluminum. Moreover, since this resist remover has water solubility, IPA (isopropyl alcohol) rinsing is unnecessary, and productivity can be improved.

Preferably, about 20 to 100% by weight of the compound represented by the formula (1) and about 0 to 80% by weight of water are included.
Thus, the resist remover can also be used as a water-mixed resist remover. In addition, the resist stripping agent can be handled as a non-hazardous material by eliminating the flammability by using a water mixture. Moreover, the resist stripper has high stripping performance even at a high water dilution rate, and the amount of the resist stripper used can be reduced. Furthermore, even when the resist stripper is not a water mixture, the alkoxyamide compound itself has a high flash point and is a third petroleum, so safety can be improved.

Preferably, R ₁ and R ₂ have 1 to 4 carbon atoms.
If it does in this way, the resist stripping agent can suppress that the solubility to water falls, and water rinse becomes possible.

Preferably, the carbon number of R ₁ and R ₂ is 1, and the carbon number of R ₃ is 1-8.
If it does in this way, the resist stripping agent can suppress that the solubility to water falls, without reducing the peelability of a resist.

Preferably, R ₁ and R ₂ have 2 carbon atoms, and R ₃ has 1 to 6 carbon atoms.
Even if it does in this way, the resist remover can suppress that the solubility to water falls, without reducing the peelability of a resist.

In addition, preferably, an anticorrosive agent, a chelating agent, a peeling accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent and / or an antioxidant are added.
Thus, for example, when a surfactant is added, the permeability to fine gaps is improved, and the peelability of the resist can be improved. Further, by adding an antioxidant, the resist stripper can suppress performance deterioration due to oxidation.

FIG. 1 shows Table-1 showing the release agent type (the composition of the release liquid), the release performance, and the anticorrosion performance for Examples 1 to 15. FIG. 2 shows Table-2 showing the release agent species (composition of the release liquid), release performance, and anticorrosion performance for Comparative Examples 1-6.

上記式（１）において、Ｒ_３は炭素数１〜１８のアルキル基である。Ｒ_１及びＲ_２は、それぞれ水素原子、又は、炭素数１〜６のエーテル結合を有してもよい一価の炭化水素基である。[One Embodiment of Resist Stripper]
The resist remover of the present invention is used in the production of liquid crystal display panels, semiconductor elements and the like. That is, in the photolithography process, unnecessary resist (photosensitive agent) is dissolved and removed.
The resist stripper of this embodiment is configured to include an alkoxyamide compound represented by the formula (1).

In the above formula (1), R ₃ is an alkyl group having 1 to 18 carbon atoms. R ₁ and R ₂ are each a hydrogen atom or a monovalent hydrocarbon group that may have an ether bond having 1 to 6 carbon atoms.

Here, examples of the alkyl group for R ₃ include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, and various octyl groups. This alkyl group preferably has 1 to 8 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.
The hydrocarbon group for R ₁ and R ₂ may be linear or branched, but is preferably a saturated hydrocarbon group. Examples thereof include a methyl group, an ethyl group, various propyl groups, various butyl groups, a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group, and the methyl group is the most common. R ₁ and R ₂ may be the same or different from each other, and may be bonded to each other to form a ring structure. This ring structure may be a heterocyclic structure having nitrogen as a heteroatom, or may be a heterocyclic structure having a nitrogen atom and an oxygen atom as heteroatoms. Examples of the group having a heterocyclic structure include a 1-pyrrolidinyl group, a piperidino group, and a morpholino group.

  Examples of the alkoxyamide compounds include 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-diethylpropionamide, 3-ethoxy- N, N-diethylpropionamide and the like can be mentioned.

Here, preferably, the number of carbon atoms of _{R 1} and _{R 2,} may When 1-4, more preferably, the carbon number _{of R 1} and _{R 2,} or equal to 1-2. If it does in this way, it can control that the solubility to water falls, and water rinse becomes possible.

Preferably, when R ₁ and R ₂ have 1 carbon, R ₃ may have 1 to 8 carbon atoms, and more preferably, R ₃ may have 1 to 6 carbon atoms. In this way, the solubility in water can be increased without reducing the resist peelability (including the ability to dissolve the resist). When the carbon number of R ₁ and R ₂ is 1, the reason why the carbon number of R ₃ is preferably 1 to 8 is that the larger the carbon number of R ₃ , the lower the solubility in water, and the water dilution rate is This is because water rinsing becomes difficult as well as decreasing.

Preferably, when R ₁ and R ₂ have 2 carbon atoms, R ₃ may have 1 to 6 carbon atoms, and more preferably R ₃ may have 1 to 3 carbon atoms. If it does in this way, the solubility to water can be increased, without reducing the peelability of a resist. When the carbon number of R ₁ and R ₂ is 2, the reason why the carbon number of R ₃ is preferably 1 to 6 is that the larger the carbon number of R ₃ , the lower the solubility in water, and the water dilution rate is This is because water rinsing becomes difficult as well as decreasing.

  The alkoxyamide compound represented by the above formula (1) is usually mixed with water and used as a water mixed resist remover. This resist stripper can be handled as a non-hazardous material because it is not flammable by using a water mixture. Further, this resist stripper has a high stripping performance even at a high water dilution rate, and the amount of the resist stripper used can be reduced. Furthermore, even if it is not a water mixture, it can be used as a resist stripper. Further, since the flash point of the alkoxyamide compound itself is high and it is a third petroleum, safety can be improved.

  Here, preferably, the resist stripper contains about 20 to 100% by weight of the compound represented by the formula (1) and about 0 to 80% by weight of water. More preferably, it contains about 25 to 100% by weight of the compound represented by the formula (1) and about 0 to 75% by weight of water, and more preferably about 40 to 100% by weight of the formula ( The compound represented by 1) and 0 to 60% by weight of water are preferably contained. If it does in this way, the peeling performance of a resist stripper can be exhibited favorably.

  For example, when an N, N-dimethyl compound is used as the compound represented by the formula (1), the amount of water added may be about 5 to 80% by weight, and preferably about 20 to 60% by weight. Good. That is, when the compound represented by the formula (1) is less than about 40% by weight, or exceeds about 80% by weight, depending on the compound represented by the formula (1), the peeling performance on the resist is lowered. Because there is a worry to do. In addition, when an N, N-diethyl compound is used as the compound represented by the formula (1), the amount of water added may be about 0 to 80% by weight, and preferably about 0 to 40% by weight. Good. If it does in this way, the malfunction that the peeling performance with respect to a resist falls can be prevented.

  In addition, the resist stripper of this embodiment is preferably added with an anticorrosive, a chelating agent, a stripping accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent, and / or an antioxidant. Thus, for example, when a surfactant is added, the permeability to fine gaps is improved, and the peelability of the resist can be improved. Moreover, the performance deterioration by oxidation can be suppressed by adding antioxidant as needed. The anticorrosive agent, chelating agent, peeling accelerator, reducing agent, oxidizing agent, surfactant, and antioxidant can be used alone or in combination of two or more.

  Examples of the anticorrosive or chelating agent include aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds and anhydrides, triazole compounds, saccharides, and oxime compounds. Each of the above anticorrosives or chelating agents can be used alone or in combination of two or more.

  As aromatic hydroxy compounds, phenol, cresol, xylenol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol , P-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxy Examples thereof include benzoic acid, 3,5-dihydroxybenzoic acid, gallic acid and the like.

  As acetylene alcohol, 2-butyne-1,4-diol, 3,5-dimethyl-1-hexyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyne-3- All, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-ol, 2,5-dimethyl-3-hexyne-2 , 5-diol and the like.

  As carboxyl group-containing organic compounds and their anhydrides, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2 , 3-benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid, citric acid, acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, salicylic acid, tartaric acid, acrylic acid, γ-linolenic acid, etc. .

Examples of the triazole compound include benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole, aminotriazole and the like. .
Examples of the saccharide include sorbitol, xylitol, palatinit, arabitol, mannitol, sucrose, starch and the like.
Examples of oxime compounds include dimethylglyoxime and diphenylglyoxime.
The anticorrosive agent or chelating agent may be used either alone or as a mixture thereof.

Examples of the release accelerator include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, or alkylbenzenesulfonic acid such as methyl, propyl, heptyl, octyl, decyl, dodecyl, and the like.
The above peeling accelerator may be used either alone or as a mixture thereof.

Examples of the reducing agent include hyposulfite, sulfate-based reducing agents, amine-based reducing agents, and other reducing agents.
Examples of the hyposulfite and sulfate-based reducing agent include sodium thiosulfate, sodium dithionite, sodium pyrosulfite, and sodium metabisulfite.
Examples of amine-based reducing agents include hydroxylamine, monoethanolamine, tryptophan, histidine, methionine, and phenylalanine.
Examples of other reducing agents include ascorbic acid, butynediols, unsaturated ketones, uric acid, tetraamisole, hydrazines, and derivatives thereof, such as carbazates, oximes, hydroquinone, pyrogallol, Gallic acid, 2,4,5-trihydroxybutyrophenone, tocopherol, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, butylated hydroxytoluene (BHT), butylated hydroxyanisos (BHA), 2,6-di-tert-butyl-4-hydroxymethylphenol, thiols, salicylaldehyde, 4-hydroxybenzaldehyde and glycolaldehyde dialkylacetals and mixtures thereof Etc.
The reducing agent may be used either alone or as a mixture thereof.

As oxidizing agents, ozone, hydrogen peroxide, hypochlorous acid or hypochlorite, chlorous acid or chlorite, perchloric acid or perchlorate, hypobromite or hypobromite, Bromous acid or bromite, perbromide or perbromide, hypoiodous acid or hypoiodite, iodic acid or iodate, periodate or periodate, persulfate or Examples thereof include persulfate, peracetic acid or peracetate, perpropionic acid or perpropionate, perbenzoic acid or perbenzoate, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumene hydroperoxide, and the like.
The oxidizing agent may be used either alone or as a mixture thereof.

Examples of the surfactant include cationic, anionic, nonionic, and fluorine surfactants.
Examples of the cationic surfactant include surfactants such as alkyltrimethylammonium salt, alkylamidoamine, alkyldimethylbenzylammonium salt, polyethylene polyamine cationic resin, cetyltrimethylammonium chloride, and quaternary ammonium salt.
Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbite fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester And the like.
As an anionic surfactant, a group having an anionic property in water and forming a sulfonic acid (hereinafter referred to as a sulfonic acid group) and a group forming a sulfate (hereinafter referred to as a sulfate group). ), A group forming a phosphate ester (hereinafter referred to as a phosphate ester group), a group forming a carboxylic acid (hereinafter referred to as a carboxylic acid group), and the like.

Examples of the compound having a sulfonic acid group include an anionic functional group in a molecular structure such as alkyl diphenyl ether disulfonic acid, alkylene disulfonic acid, naphthalene sulfonic acid formalin condensate, phenol sulfonic acid formalin condensate, and phenyl phenol sulfonic acid formalin condensate. Examples thereof include compounds having two or more compounds, alkylbenzene sulfonic acid, dialkyl succinate sulfonic acid, monoalkyl succinate sulfonic acid, alkylphenoxyethoxyethyl sulfonic acid and the like, or salts thereof.
Compounds having a sulfate ester group include methyl taurines such as alkyl methyl taurine, acyl methyl taurine, and fatty acid methyl taurine, polyoxyalkylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene polycyclic phenyl ether sulfate Examples thereof include compounds such as esters and polyoxyalkylene aryl ether sulfates or salts thereof.
Examples of the compound having a phosphate ester group include compounds such as polyoxyalkylene alkyl ether phosphoric acid and polyoxyalkylene alkyl phenyl ether phosphoric acid, or salts thereof.
Examples of the compound having a carboxylic acid group include sarcosine compounds such as acyl sarcosine and fatty acid sarcosine, fatty acid compounds such as coconut oil, oleic acid, acrylic acid and γ-linolenic acid, and salts thereof.
Furthermore, examples of the compound having two different anionic functional groups in the molecular structure include compounds such as alkylsulfosuccinic acid and polyoxyalkylenealkylsulfosuccinic acid, which are compounds having a sulfonic acid group and a carboxylic acid group, and salts thereof. It is done.

Examples of the fluorine-based surfactant include perfluoroalkyl ethylene oxide adducts, perfluoroalkyl phosphate esters, and perfluoroalkylphenyl glycine.
The above surfactants may be used either alone or as a mixture thereof.

Examples of the buffer include inorganic acid salts and organic acid salts.
For example, organic acids useful in buffer systems include, but are not limited to, formic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, heptanoic acid, lactic acid, oxalic acid, malic acid, malonic acid, succinic acid, fumaric acid, adipine Examples include acids, benzoic acid, phthalic acid, and citric acid.
Conjugated bases useful in the buffer system of the present invention include organic acid salts, ammonia, tetramethylammonium hydroxide, tetraalkylammonium hydroxide, 2- (methylamino) ethanol, monoisopropanolamine, diglycolamine N, N-dimethyl-2- (2-aminoethoxy) ethanol, 1- (2-aminoethyl) piperidine, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- ( 3-aminopropyl) -imidazole, 1,8-diazabicyclo [5.4.0] -7-undecene, N.I. N. N'-trimethylaminoethanolamine, pentamethyldiethylenetriamine, ethylmorpholine, hydroxymorpholine, aminopropylonemorpholine, triethanolamine, methyldiethanolamine and the like. Further, useful conjugate bases are not limited to the above examples.

Further, it is desirable that the salt is at least one salt selected from the group consisting of carboxylate, sulfate, sulfonate, phosphonate, nitrate, hydrochloride and borate. Specific examples include ammonium acetate, ammonium citrate, ammonium oxalate, ammonium sulfosuccinate, ammonium sulfate, ammonium methanesulfonate, ammonium phosphonate, ammonium nitrate, ammonium chloride, ammonium tetraborate, and ammonium acrylate. Paying attention to cations, amine salts or quaternary ammonium salts may be used besides ammonium salts.
Examples of amines include hydroxylamines such as hydroxylamine and diethylhydroxylamine, alkylamines such as ethylamine, propanediamine, dibutylamine and trimethylamine, monoethanolamine, methylethanolamine, methyldiethanolamine, triethanolamine, monoisopropanolamine, Alkanolamines such as diglycolamine, N, N-dimethyl-2- (2-aminoethoxy) ethanol, aromatic amines such as aniline and benzylamine, morpholines such as ethylmorpholine, hydroxymorpholine, aminopropylone morpholine 1- (2-aminoethyl) piperidine, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (3-aminopropyl) Pills) - imidazole, 1,8-diazabicyclo [5.4.0] undec-7-ene, N. N. N'-trimethylaminoethanolamine, pentamethyldiethylenetriamine, etc. are mentioned. The amine is not particularly limited as long as it exhibits basicity.
Examples of the quaternary ammonium ion forming the quaternary ammonium salt include tetramethylammonium ion, tetraethylammonium ion, triethylmethylammonium ion, lauryltrimethylammonium ion, and benzyltrimethylammonium ion.
The above buffering agents may be used either alone or as a mixture thereof.

As the antioxidant, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-α-dimethylamino-p-cresol And monophenolic compounds such as 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-methylene-bis (2,6-di-tert-butylphenol), 2,2′-methylene-bis (4 -Methyl-6-tert-butylphenol), 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), etc. The bisphenol compound can be mentioned. In addition, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (6-tert-butyl-o-cresol), 2,2′-thiobis (4-methyl-6) Thiobisphenol compounds such as (-tert-butylphenol). In addition, tris [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (2-methyl-4-hydroxy-5-tert-butyl-phenol) butane and other tris Mention may be made of phenolic compounds. In addition, phosphite antioxidants such as triphenyl phosphite, trisnonylphenyl phosphite, and tris (mono- and di-nonylphenyl) phosphite can be used. Moreover, sulfur type antioxidants, such as dilauryl dipropionate and distearyl thiodipropionate, can be mentioned.
The above antioxidants may be used either alone or as a mixture thereof. The amount of the antioxidant used is preferably about 0.01 to 1.0% by weight based on the resist stripper.

As described above, the resist stripper according to this embodiment has a high stripping performance by using the alkoxyamide-based compound represented by the formula (1), and is extremely excellent in corrosion resistance against copper, aluminum, and the like. Yes. Also, by using a water-based release agent, it is safe without flammability, and since it has water solubility, water rinsing is possible and no IPA rinsing is required, improving productivity. Can do.
Next, examples and comparative examples of the resist remover will be described with reference to Table-1 in FIG. 1 and Table-2 in FIG.

FIG. 1 shows Table-1 showing the release agent type (the composition of the release liquid), the release performance, and the anticorrosion performance for Examples 1 to 15.
Moreover, FIG. 2 has shown Table-2 showing the peeling agent kind (composition of peeling liquid), peeling performance, and anticorrosion performance with respect to Comparative Examples 1-6.
First, a common resist stripping performance evaluation method (resist substrate, stripping test and corrosion test) for Examples 1 to 15 and Comparative Examples 1 to 6 will be described.

<Resist substrate>
Substrate: Deposition glass (size: about 100 mm × 100 mm) manufactured by Hitachi Metals, Ltd. was used.
Resist: An HPR204 (naphthoquinone diazide / Novolac resin) manufactured by Fuji Film Electronics Materials Co., Ltd. was applied and baked in an oven at a predetermined temperature for about 15 minutes. That is, Examples 1, 2, 3, 5-8, 10-15 and Comparative Examples 1, 3-6 were baked in an oven at about 130 ° C. for about 15 minutes. Examples 4, 9 and Comparative Example 2 were baked in an oven at about 150 ° C. for about 15 minutes.
In addition, when evaluating peelability, the test piece which cut | disconnected the said resist substrate to about 10 mm x 5 mm was used.

<Peel test>
The peeling performance was evaluated by the following two evaluation methods.
Resist stripping ability-1: About 5 ml of stripping agent and one test piece of the resist substrate prepared above are put into a sample bottle of about 30 ml, and the glass substrate in the liquid becomes colorless and transparent while stirring at a predetermined temperature. Time was measured and judged as follows.
○: Time until transparent is less than 40 seconds.
X: Time to become transparent is 40 seconds or more.
In Examples 1, 2, 3, 5-8, 10-15, and Comparative Examples 1, 3-6, the predetermined temperature when stirring is room temperature (for example, 0 to 30 ° C., 20 to 25 ° C.). In Examples 4 and 9, and Comparative Example 2, the predetermined temperature during stirring was set to about 40 ° C.

Resist stripping-2: About 5 ml of stripping agent and one test piece of the resist substrate prepared above are placed in a sample bottle of about 30 ml, stirred for about 60 seconds at a predetermined temperature and stripped, and then the resist substrate is taken out. Immediately after rinsing with acetone, the surface after drying at about 50 ° C. for about 30 minutes was observed and judged as follows.
○: There is no cloudy portion on the glass substrate surface, and the resist is completely washed away.
Δ: There is a slightly cloudy portion on the surface of the glass substrate, and the resist is almost washed away.
×: More than half of the surface of the glass substrate is cloudy, cleaning and peeling are insufficient, and a considerable amount of resist remains.
In Examples 1, 2, 3, 5-8, 10-15, and Comparative Examples 1, 3-6, the predetermined temperature when stirring for about 60 seconds was room temperature (for example, 0 to 30 ° C.). Yes, usually 20 to 25 ° C.). In Examples 4 and 9, and Comparative Example 2, the predetermined temperature when stirring for about 60 seconds was about 40 ° C.

<Corrosion test>
The anticorrosion performance was evaluated by the following two evaluation methods.
Anticorrosion-1: A release agent is put into a sample bottle of about 30 ml, a copper wire having a diameter of about 0.5 mm is rolled and immersed therein, and the degree of coloring after one week is observed. It was judged.
○: No discoloration at all.
Δ: Slightly discolored to light blue.
X: Clearly discolored to blue.
Anticorrosion-2: A laminated wiring board of Mo (molybdenum) / Al / Mo is prepared, and this test piece (about 10 mm × 5 mm) is put into a sample bottle of about 30 ml, about 5 ml of a release agent is added, and about 40 ° C. For about 5 minutes. After the immersion / corrosion operation, observation was made according to the following procedure, and judgment was made as follows.
As a procedure 1, an IPA rinse was performed, as a procedure 2, an acetone rinse was performed, and as a procedure 3, drying was performed at about 50 ° C. for about 30 minutes, and the corrosion state of Al was observed with a SEM (scanning electron microscope).
○: No change at all.
Δ: Al was eluted slightly and corrosion was observed.
X: Al was eluted and severe corrosion was observed.
In addition, the result with respect to Examples 1-15 and Comparative Examples 1-10 was shown in Table-1 and Table-2.

As a release agent according to Example 1, a resist release agent comprising about 80% by weight of 3-methoxy-N, N-dimethylpropionamide (abbreviated as MDMPA as appropriate) and about 20% by weight of water was prepared. . Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 38 seconds)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 2, a resist release agent comprising about 60% by weight of 3-methoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 39 seconds)
Resist peelability-2: △
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). Further, this resist stripper was excellent in stripping performance and anticorrosion performance in other tests.

As a release agent according to Example 3, a resist release agent comprising about 100% by weight of 3-methoxy-N, N-dimethylpropionamide was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 32 seconds)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 4, a resist release agent comprising about 100% by weight of 3-methoxy-N, N-dimethylpropionamide was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (The time until the substrate became transparent was 35 seconds.)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 5, a resist release agent comprising about 100% by weight of 3-butoxy-N, N-dimethylpropionamide (abbreviated as BDMPA as appropriate) was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (The time until the substrate became transparent was 31 seconds.)
Resist peelability-2: △
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). Further, this resist stripper was excellent in stripping performance and anticorrosion performance in other tests.

As a release agent according to Example 6, a resist release agent comprising about 80% by weight of 3-butoxy-N, N-dimethylpropionamide and about 20% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 24 seconds)
Resist peelability-2: △
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). Further, this resist stripper was excellent in stripping performance and anticorrosion performance in other tests.

As a release agent according to Example 7, a resist release agent comprising about 60% by weight of 3-butoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 29 seconds)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 8, a resist release agent comprising about 40% by weight of 3-butoxy-N, N-dimethylpropionamide and about 60% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 24 seconds)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 9, a resist release agent comprising about 60% by weight of 3-butoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 39 seconds)
Resist peelability-2: △
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). Further, this resist stripper was excellent in stripping performance and anticorrosion performance in other tests.

As a release agent according to Example 10, a resist release agent comprising about 100% by weight of 3-methoxy-N, N-diethylpropionamide (abbreviated as MDEPA as appropriate) was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (The time until the substrate became transparent was 30 seconds.)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 11, a resist release agent comprising about 80% by weight of 3-methoxy-N, N-diethylpropionamide and about 20% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (The time until the substrate became transparent was 18 seconds.)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 12, a resist release agent comprising about 60% by weight of 3-methoxy-N, N-diethylpropionamide and about 40% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 28 seconds)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 13, a resist release agent comprising about 100% by weight of 3-ethoxy-N, N-diethylpropionamide (abbreviated as EDEPA as appropriate) was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 19 seconds)
Resist peelability-2: △
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). Further, this resist stripper was excellent in stripping performance and anticorrosion performance in other tests.

As a release agent according to Example 14, a resist release agent comprising about 80% by weight of 3-ethoxy-N, N-diethylpropionamide and about 20% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 19 seconds)
Resist peelability-2: ○
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper was excellent in stripping performance and anticorrosion performance.

As a release agent according to Example 15, a resist release agent comprising about 60% by weight of 3-ethoxy-N, N-diethylpropionamide and about 40% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are as shown in Table 1.
Resist releasability-1: ○ (the time until the substrate became transparent was 29 seconds)
Resist peelability-2: △
Anticorrosion-1: ○
Anticorrosion-2: ○
Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). Further, this resist stripper was excellent in stripping performance and anticorrosion performance in other tests.

Comparative Example 1

As a stripping agent according to Comparative Example 1, a resist stripping agent comprising about 30% by weight of dimethyl sulfoxide (suitably abbreviated as DMSO) and about 70% by weight of monoethanolamine (suitably abbreviated as MEA). Prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are shown in Table-2.
Resist stripping property-1: x (The time until the substrate became transparent was 45 seconds.)
Resist peelability-2: △
Anticorrosion-1: △
Anticorrosion-2: △
Met. This resist stripping agent required a long time for stripping in resist stripping property-1, and a small amount of resist residue was observed in resist stripping property-2. Further, this resist stripper turned slightly light blue in anticorrosion-1, and further, Al was eluted slightly in anticorrosion-2, and corrosion was observed.

Comparative Example 2

As a stripping agent according to Comparative Example 2, a resist stripping agent comprising about 30% by weight of dimethyl sulfoxide (suitably abbreviated as DMSO) and about 70% by weight of monoethanolamine (suitably abbreviated as MEA). Prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are shown in Table-2.
Resist releasability-1: x (The time until the substrate became transparent was 50 seconds.)
Resist peelability-2: △
Anticorrosion-1: △
Anticorrosion-2: △
Met. This resist stripping agent required a long time for stripping in resist stripping property-1, and a small amount of resist residue was observed in resist stripping property-2. Further, this resist stripper turned slightly light blue in anticorrosion-1, and further, Al was eluted slightly in anticorrosion-2, and corrosion was observed.

Comparative Example 3

As a release agent according to Comparative Example 3, a resist release agent comprising about 34% by weight of diethylene glycol monobutyl ether, about 46% by weight of monoethanolamine, and about 20% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are shown in Table-2.
Resist releasability-1: x (The time until the substrate became transparent was 56 seconds.)
Resist peelability-2: x
Anticorrosion-1: △
Anticorrosion-2: △
Met. This resist stripping agent requires a long time for stripping in resist stripping property-1, and further, in resist stripping property-2, it is cloudy on more than half of the surface of the glass substrate, and cleaning stripping is insufficient. Remained. Further, this resist stripper turned slightly light blue in anticorrosion-1, and further, Al was eluted slightly in anticorrosion-2, and corrosion was observed.

Comparative Example 4

As a release agent according to Comparative Example 4, a resist release agent comprising about 26% by weight of diethylene glycol monobutyl ether, about 34% by weight of monoethanolamine, and about 40% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are shown in Table-2.
Resist releasability-1: ○ (the time until the substrate became transparent was 38 seconds)
Resist peelability-2: △
Anticorrosion-1: ×
Anticorrosion-2: x
Met. Although this resist stripper had excellent strippability in resist strippability-1, a small amount of resist residue was observed in resist strippability-2. In addition, this resist stripper clearly changed to blue in the anticorrosion-1, and further, in the anticorrosion-2, Al was clearly eluted and severe corrosion was observed.

Comparative Example 5

As a release agent according to Comparative Example 5, a resist release agent comprising about 17% by weight of diethylene glycol monobutyl ether, about 23% by weight of monoethanolamine, and about 60% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are shown in Table-2.
Resist releasability-1: ○ (the time until the substrate became transparent was 24 seconds)
Resist peelability-2: ○
Anticorrosion-1: ×
Anticorrosion-2: x
Met. This resist remover was excellent in peelability. In addition, this resist stripper clearly changed to blue in the anticorrosion-1, and further, in the anticorrosion-2, Al was clearly eluted and severe corrosion was observed.

Comparative Example 6

As a release agent according to Comparative Example 6, a resist release agent comprising about 9% by weight of diethylene glycol monobutyl ether, about 11% by weight of monoethanolamine, and about 80% by weight of water was prepared. Subsequently, the peeling test and the corrosion test were performed.
The test results are shown in Table-2.
Resist releasability-1: ○ (the time until the substrate became transparent was 29 seconds)
Resist peelability-2: △
Anticorrosion-1: ×
Anticorrosion-2: x
Met. Although this resist stripper had excellent strippability in resist strippability-1, a small amount of resist residue was observed in resist strippability-2. In addition, this resist stripper clearly changed to blue in the anticorrosion-1, and further, in the anticorrosion-2, Al was clearly eluted and severe corrosion was observed.

From the test results of the above examples, it was confirmed that the anticorrosion performance was excellent in all examples. Moreover, in the peeling performance, although a trace amount of resist residue was recognized in Examples 2, 5, 6, 9, 13, and 15, it was confirmed that the peeling performance was excellent in other examples. .
Moreover, from the test result of each said comparative example, in all the comparative examples, it was not able to satisfy both peeling performance and anticorrosion performance.

The resist stripper of the present invention has been described with reference to the preferred embodiment. However, the resist stripper according to the present invention is not limited to the above-described embodiment, and various modifications can be made within the scope of the present invention. It goes without saying that implementation is possible.
For example, the compound represented by the formula (1) contained in the resist stripper is not limited to one type. For example, the resist stripper containing two or more compounds represented by the formula (1) It may be.
In addition, the use of the present invention is not limited to a resist remover for liquid crystal / semiconductors. For example, a remover for a printed circuit board, a resist developer, a flux cleaner, a resin solvent (for example, a polyimide resin solvent, It is also used as a polyamide resin solvent).

Claims (6)

A resist stripper comprising a compound represented by formula (1).

Here, in Formula (1), R ₃ is an alkyl group having 1 to 18 carbon atoms, and R ₁ and R ₂ may each independently have a hydrogen atom or an ether bond having 1 to 6 carbon atoms. It is a hydrocarbon group, which may be the same or different from each other, and may be bonded to each other to form a ring structure.   The resist stripping agent according to claim 1, comprising 20 to 100% by weight of the compound represented by the formula (1) and 0 to 80% by weight of water. The resist remover according to claim 1 or 2, wherein R ₁ and R ₂ have 1 to 4 carbon atoms. Wherein the 1 number of carbon atoms of R ₁ and R _2, and resist stripper according to claim 1 or 2, characterized in that a 1 to 8 carbon atoms of the R _3. The resist remover according to claim 1 or 2, wherein R ₁ and R ₂ have 2 carbon atoms, and R ₃ has 1 to 6 carbon atoms.   6. An anticorrosive agent, a chelating agent, a peeling accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent and / or an antioxidant are added. Resist stripper.

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