KR20090027191A - Resist stripping agent - Google Patents

Abstract

Disclosed is a resist stripping agent which has excellent stripping properties, which has no flammability and therefore is safe, and which does not cause corrosion of a conductive material and therefore has excellent anti-corrosion properties. The resist stripping agent comprises a compound represented by the formula (1). (1) wherein R3 represents an alkyl group having 1 to 18 carbon atoms, and R1 and R2 independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have an ether bond.

Description

Resist Stripper {RESIST STRIPPING AGENT}

The present invention relates to a resist release agent. In particular, the resist releasing agent of the present invention is excellent in peelability, is safe from flammability, and is excellent in anticorrosive property that does not corrode a conductor.

Integrated circuits such as ICs and LSIs, display devices such as LCDs and EL elements, printed boards and the like are manufactured using photolithography techniques. In this photolithography step, the unnecessary resist (photosensitive agent) is removed using a resist releasing agent.

(Conventional example)

In this resist stripping process, various resist stripping agents have been used so far. However, in recent years, the ability to cope with the miniaturization of the process of a liquid crystal display panel or a semiconductor element or a short time process is insufficient, and better performance is desired. At present, the focus of the resist releasing agent containing the amine compound excellent in peelability is focused.

This amine releasing agent can be classified into a solvent system and an aqueous system. For example, dimethyl sulfoxide (about 30 weight%) + monoethanolamine (about 70 weight%), monoethanolamine + N-methylpyrrolidone, etc. are used as a solvent type release agent. On the other hand, as an aqueous peeling agent, water (about 20-30 weight%) + diethylene glycol monobutyl ether (about 20-30 weight%) + monoethanolamine (about 30-40 weight%), alkylbenzene sulfonic acid + functional water ( Ozone water), acid systems (sulfuric acid + hydrogen peroxide) + functional water (ozone water) and the like are used.

In recent years, the use of the water release agent which can rinse water is expanded. This reason is because an aqueous peeling agent is excellent in peelability, and also it is not flammable and is not a dangerous substance. By the way, the monoethanolamine is added to the aqueous peeling agent. For this reason, the aqueous release agent has the drawback that corrosion to conductors, such as wiring, will occur. Therefore, in reality, it is necessary to adjust the content of monoethanolamine in consideration of peeling performance and corrosiveness. In addition, various resist stripping agents have been developed for the purpose of resist stripping performance and prevention of damage to a conductor.

For example, Patent Document 1 discloses a photoresist stripper containing a product obtained by reacting an alkanolamine with formaldehyde. This product is produced by reacting alkanolamine and formaldehyde in a formaldehyde / alkanolamine (molar ratio) at a ratio of 0.8 or less.

In addition, Patent Document 2 discloses a photoresist stripper composition comprising an alkanolamine compound, a sulfone compound or a sulfoxide compound, and a hydroxy compound.

In addition, Patent Document 3 discloses a resist stabilizer having a stable pH, including at least hydroxycarboxylic acid and water. This resist releasing agent is adjusted so that the ratio (that is, condensate / monomer) of the hydroxycarboxylic acid contained after manufacture may be 2/9 or less of the condensate of 2 or more molecules, and a hydroxycarboxylic acid monomer.

In addition, Patent Document 4 discloses a release agent for stripping a resist for using an alloy of copper and silver in a wiring process. This resist releasing agent contains piperazine.

In addition, Patent Literature 5 discloses a resist stripping agent containing tetraethylenepentamine and ether alcohol.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-219486

Patent Document 2: Japanese Patent Application Laid-Open No. 05-281753

Patent Document 3: Japanese Patent Application Laid-Open No. 2005-049438

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-205674

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-205675

(Initiation of invention)

(Tasks to be solved by the invention)

The technique described in each of the above patent documents has been developed for the purpose of improving resist peeling performance and an anti-corrosive method of a conductor (such as a wiring made of copper (Cu), aluminum (Al), etc.). However, these techniques have a problem that they cannot fully satisfy both purposes.

This invention is made | formed in view of the said subject, Comprising: It aims at providing the resist peeling agent which is excellent in peelability, is not flammable, is safe, and is excellent in anticorrosive property which does not corrode a conductor.

In addition, the present inventors earnestly examined in view of the said situation. As a result, a specific novel alkoxyamide compound having high amphipathic properties was used as a resist stripping agent. This resist releasing agent was excellent in anticorrosiveness, and also excellent in peeling performance. This invention is completed in this way.

(Means to solve the task)

In order to achieve the said objective, the resist stripper of this invention contains the compound represented by following formula (1).

[Formula 1]

Here, in General formula (1), R <_3> is a C1-C18 alkyl group. R ₁ and R ₂ are each independently a hydrocarbon group which may have a hydrogen atom or an ether bond having 1 to 6 carbon atoms. R ₁ and R ₂ may be the same as or different from each other, and may also be bonded to each other to form a ring structure.

As described above, the alkoxyamide-based resist stripping agent has high peeling performance and is excellent in corrosion resistance to copper and aluminum. Moreover, since this resist releasing agent has water solubility, IPA (isopropyl alcohol) rinse is unnecessary, and productivity can be improved.

Further, preferably, about 20 to 100% by weight of the compound represented by Formula 1 and about 0 to 80% by weight of water may be included.

Thus, the resist stripping agent can also be used as a resist stripping agent of water mixing system. In addition, the resist releasing agent can be treated as a non-hazardous product by eliminating flammability by using a water mixture. Moreover, even if it is a high water dilution rate, the resist peeling agent has high peeling performance, and the usage-amount of a resist peeling agent can be reduced. In addition, even if it is not made into a water mixture, a resist releasing agent has a high flash point of the alkoxy amide type compound itself, and can improve stability because it is a third petroleum.

Moreover, Preferably, the carbon number of said R <_1> and R <_2> may be 1-4.

In this way, the resist releasing agent can suppress that the solubility to water falls, and water rinsing becomes possible.

Preferably, the carbon number of the R ₁ and R ₂ is 1, and the carbon number of the R ₃ is 1-8.

By doing in this way, a resist releasing agent can suppress that the solubility to water falls, without reducing the peelability of a resist.

Moreover, Preferably, it is good for carbon number of said R <_1> and R <_2> to be 2, and the carbon number of said R <_3> to 1-6.

Even if it does in this way, a resist peeling agent 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 buffer, and / or an antioxidant may be added.

Thus, for example, when surfactant is added, permeability to a fine gap improves and the peelability of a resist can be improved. In addition, by adding the antioxidant, the resist releasing agent can suppress performance deterioration due to oxidation.

BRIEF DESCRIPTION OF THE DRAWINGS Table 1 which shows the peeling agent type (composition of the peeling liquid), peeling performance, and anticorrosive performance about Examples 1-15 is shown.

FIG. 2 has shown Table 2 which shows the peeling agent type (composition of the peeling liquid), peeling performance, and anticorrosive performance with respect to Comparative Examples 1-6.

(The best form to carry out invention)

[One Embodiment of Resist Release Agent]

The resist releasing agent of this invention is used at the time of manufacture of a liquid crystal display panel, a semiconductor element, etc. That is, in the photolithography step, the unnecessary resist (photosensitive agent) is dissolved and removed.

The resist releasing agent of this embodiment is made to contain the alkoxy amide type compound represented by following formula (1).

[Formula 1]

In Formula 1, R ₃ is an alkyl group having 1 to 18 carbon atoms. R ₁ and R ₂ each represent a hydrogen atom or a monovalent hydrocarbon group which may have an ether bond having 1 to 6 carbon atoms.

Here, as an alkyl group of R <_3> , a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, etc. are mentioned. It is preferable that this alkyl group is C1-C8, and it is especially preferable that it is C1-C6.

In addition, as a hydrocarbon group of R <_1> and R <_2> , either linear or branched form may be sufficient, but a saturated hydrocarbon group is preferable. As the example, a methyl group, an ethyl group, various propyl groups, various butyl groups, methoxymethyl group, methoxyethyl group, ethoxyethyl group, etc. are mentioned, A methyl group is the most common. R ₁ and R ₂ may be the same as or different from each other and may be bonded to each other to form a ring structure. The ring structure may be a heterocyclic structure having nitrogen as a hetero atom, or may be a heterocyclic structure having a nitrogen atom and an oxygen atom as a hetero atom. As group which has this heterocyclic structure, a 1-pyrrolidinyl group, a piperidino group, a morpholino group, etc. are mentioned, for example.

As the alkoxyamide-based compound, for example, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-diethylpropion Amide, 3-ethoxy-N, N-diethylpropionamide, and the like.

Here, Preferably, the carbon number of R <_1> and R <_2> may be 1-4, More preferably, the carbon number of R <_1> and R <_2> may be 1-2. By doing in this way, it becomes possible to suppress that the solubility to water falls and it becomes possible to rinse water.

Preferably, when the carbon number of R ₁ and R ₂ is 1, the carbon number of R ₃ may be 1-8, and more preferably, the carbon number of R ₃ may be 1-6. In this way, the solubility in water can be increased without lowering the peelability (including the ability to dissolve the resist) of the resist. When the carbon number of R ₁ and R ₂ is 1, the reason for setting the carbon number of R ₃ to 1 to 8 is that as the carbon number of R ₃ increases, solubility in water decreases, and the water dilution rate decreases, This is because rinsing becomes difficult.

Preferably, when the carbon number of R ₁ and R ₂ is _2, the carbon number of R ₃ may be 1 to 6, and more preferably, the carbon number of R ₃ may be 1 to 3. In this manner, the solubility in water can be increased without lowering the peelability of the resist. When the carbon number of R ₁ and R ₂ is 2, the reason for setting the carbon number of R ₃ to 1 to 6 is that as the carbon number of R ₃ increases, solubility in water decreases, and the water dilution rate decreases. This is because water rinse becomes difficult.

The alkoxyamide compound represented by the formula (1) is usually mixed with water and used as a resist stripping agent of a water mixture system. This resist releasing agent can be treated as a non-hazardous substance because it is not flammable by using a water mixture. Moreover, this resist releasing agent has high peeling performance even at a high water dilution rate, and the usage-amount of a resist releasing agent can be reduced. Moreover, even when it is not made into a water mixture, it can be used as a resist peeling agent. Moreover, since the flash point of the alkoxyamide type compound itself is high and it is 3rd petroleum, safety can be improved.

Here, preferably, the resist release agent 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, about 25 to 100% by weight of the compound represented by the formula (1), about 0 to 75% by weight of water may be included, and more preferably, about 40 to 100% by weight of the compound represented by the formula (1) , 0 to 60% by weight of water may be included. By doing in this way, the peeling performance of a resist releasing agent can be exhibited favorably.

For example, when the N, N-dimethyl body is used as the compound represented by the formula (1), the amount of water added may be about 5 to 80% by weight, preferably about 20 to 60% by weight. That is, when the compound represented by the formula (1) is less than about 40% by weight or exceeds about 80% by weight, the peeling performance of the resist may decrease depending on the compound represented by the formula (1). In addition, when using N, N-diethyl body as a compound represented by General formula (1), the addition amount of water may be about 0 to 80 weight%, Preferably it is about 0 to 40 weight%. By doing in this way, the problem that peeling performance with respect to a resist falls can be prevented.

In addition, the resist release agent of this embodiment, Preferably, an anticorrosive agent, a chelating agent, a peeling accelerator, a reducing agent, an oxidizing agent, surfactant, a buffer, and / or antioxidant may be added. Thus, for example, when surfactant is added, permeability to a microgap improves and the peelability of a resist can be improved. In addition, if necessary, by adding an antioxidant, performance degradation due to oxidation can be suppressed. The said anticorrosive, a chelating agent, a peeling promoter, a reducing agent, an oxidizing agent, surfactant, and antioxidant can be used individually, and can also be used in combination of 2 or more type.

As an anticorrosive agent or a chelating agent, an aromatic hydroxy compound, acetylene alcohol, a carboxyl group-containing organic compound, its anhydride, a triazole compound, a saccharide, an oxime type compound, etc. are mentioned. Each said anticorrosive or chelating agent can be used individually, and can also be used in combination of 2 or more type.

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-dihydrate Roxian acid, 2,5-dihydroxy benzoic acid, 3,4-dihydroxy benzoic acid, 3,5-dihydroxy benzoic 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-pentin-3- Ol, 3,6-dimethyl-4-octin-3,6-diol, 2,4,7,9-tetramethyl-5-decine-4,7-ol, 2,5-dimethyl-3-hexyn-2 And 5-diol.

As the carboxyl group-containing organic compound and its anhydride, 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, and the like.

Examples of the triazole compound include benzotriazole, o-tritriazole, m-tritriazole, p-tritriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole and dihydroxypropylbenzo. Triazole, aminotriazole, and the like.

Examples of the saccharide include sorbitol, xylitol, paratinit, arabitol, mannitol, sucrose, starch and the like.

Moreover, dimethylglyoxime, diphenylglyoxime, etc. are mentioned as an oxime type compound.

The said anticorrosive or chelating agent may be used individually or in mixtures thereof.

Examples of the release accelerator include benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, or alkyl benzene sulfonic acids such as methyl, propyl, heptyl, octyl, decyl, and dodecyl.

The peeling accelerator may be used either alone or in a mixture thereof.

Examples of the reducing agent include sulfurous acid, sulfate-based reducing agents, amine-based reducing agents, or other reducing agents.

Examples of the hyposulfite and sulfate-based reducing agents include sodium thiosulfate, sodium adithionate, sodium pyrosulfite, sodium metabisulfite, and the like.

Examples of the amine-based reducing agent include hydroxylamine, monoethanolamine, tryptophan, histidine, methionine, and phenylalanine.

As other reducing agents, ascorbic acid, butynediols, unsaturated ketones, uric acid, tetraamisol, hydrazines, and derivatives thereof, carbazates, oximes, hydroquinones, pyrogallols, moles, 2,4, 5-trihydroxybutyllophenone, tocopherol, 6-hydroxy-2,5,7,8-detramethylchroman-2-carboxylic acid, butylated hydroxytoluene (BHT), no butylated hydroxy Sol (BHA), 2,6-di- tert-butyl-4-hydroxymethylphenol, thiols, salicylaldehyde, 4-hydroxybenzaldehyde and glycol aldehyde dialkyl acetals and mixtures thereof.

The reducing agent may be used either alone or in a mixture thereof.

As the oxidizing agent, ozone, hydrogen peroxide, hypochlorous acid or hypochlorite, chlorite or chlorite, perchloric acid or perchlorate, hypobromic acid or hypobromite, abromic acid or abromate, perbromic acid or perbromite, hypoiodic acid or hypoamic acid Iodide, iodide or iodide, periodic or periodate, persulfate or persulfate, peracetic acid or peracetic acid, perpropionic acid or perpropionate, perbenzoic acid or perbenzoate, tert-butyl hydride Loperoxide, ethylbenzene hydroperoxide, cumene hydroperoxide, etc. are mentioned.

The oxidizing agent may be used either alone or in a mixture thereof.

As surfactant, surfactant, such as a cation type, anion type, nonionic type, or fluorine type, is mentioned.

Examples of the cationic surfactant include surfactants such as alkyltrimethylammonium salts, alkylamideamines, alkyldimethylbenzylammonium salts, polyethylenepolyamine-based cationic resins, cetyltrimethylammonium chlorides and quaternary ammonium salts.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene glycol fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, sorbitan fatty acid esters, and polyoxy. Surfactants, such as an alkylene sorbitan fatty acid ester type, are mentioned.

As an anionic surfactant, as a group which shows anionicity in water, the group which forms a sulfonic acid (henceforth a sulfonic acid group), the group which forms a sulfate ester (henceforth a sulfate ester group), and a phosphate ester is formed. And groups (hereinafter, referred to as phosphate ester groups) and groups (hereinafter, referred to as carboxylic acid groups) to form carboxylic acids.

As the compound having a sulfonic acid group, a compound having two or more anionic functional groups in molecular structures such as alkyldiphenyl ether disulfonic acid, alkylene disulfonic acid, naphthalene sulfonic acid formalin condensate, phenol sulfonic acid formalin condensate, and phenylphenol sulfonic acid formalin condensate And compounds such as alkylbenzene sulfonic acid, dialkyl succinate sulfonic acid, monoalkyl succinate sulfonic acid and alkyl phenoxy ethoxy ethyl sulfonic acid or salts thereof.

As the compound having a sulfate ester group, methyl taurine such as alkyl methyl taurine, acyl methyl taurine, fatty acid methyl taurine, polyoxyalkylene alkylphenyl ether sulfate ester, polyoxyalkylene alkyl ether sulfate ester, polyoxyalkylene polycyclic phenyl ether Compounds, such as a sulfate ester and polyoxyalkylene aryl ether sulfate ester, or its salt, etc. are mentioned.

As a compound which has a phosphate ester group, compounds, such as polyoxyalkylene alkyl ether phosphoric acid and polyoxyalkylene alkylphenyl ether phosphoric acid, or its salt, etc. are mentioned.

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 palm oil, olein oil, acrylic acid and γ-linolenic acid, and salts thereof.

Moreover, as a compound which has two other anionic functional groups in a molecular structure, compounds, such as alkyl sulfosuccinic acid and polyoxyalkylene alkyl sulfosuccinic acid which are compounds which have a sulfonic acid group and a carboxylic acid group, or its salt, etc. are mentioned.

Examples of the fluorine-based surfactants include perfluoroalkyl ethylene oxide adducts, perfluoroalkyl phosphate esters, and perfluoroalkylphenylglycines.

The surfactant may be used either alone or in 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, adipic acid, benzoic acid Phthalic acid, citric acid, and the like.

Also useful as conjugated bases in the buffer system of the present invention are salts of organic acids, 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, NNN'-trimethylaminoethanolamine, pentamethyldiethylenetriamine, ethylmorpholine, hydroxy Morpholine, aminopropylone morpholine, triethanolamine, methyldiethanolamine and the like. In addition, useful conjugated bases are not limited to the above examples.

Moreover, it is preferable that they are 1 or more types of salts chosen from the group which consists of carboxylate, sulfate, sulfonate, phosphonate, nitrate, hydrochloride, and borate. Specifically, ammonium acetate, ammonium citrate, ammonium oxalate, ammonium sulfosuccinate, ammonium sulfate, ammonium methane sulfonate, ammonium phosphonate, ammonium nitrate, ammonium chloride, ammonium tetraborate, ammonium acrylate, etc. are mentioned. In view of the cation, in addition to the ammonium salt, an amine salt or a quaternary ammonium salt may be used.

Examples of the amine include hydroxylamines such as hydroxylamine and diethylhydroxylamine, alkylamines such as ethylamine, propanediamine, dibutylamine, and trimethylamine, monoethanolamine, methylethanolamine, methyldiethanolamine, and triethanolamine. , Alkanolamines such as monoisopropanolamine, diglycolamine, N, N-dimethyl-2- (2-aminoethoxy) ethanol, aromatic amines such as aniline and benzylamine, ethylmorpholine, hydroxymorpholine and amino Morpholines such as propylron morpholine, 1- (2-aminoethyl) piperidine, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (3-amino Propyl) -imidazole, 1,8-diazabicyclo [5.4.0] undec-7-ene, NNN'-trimethylaminoethanolamine, pentamethyldiethylenetriamine, etc. are mentioned. In addition, the said amine should just be basic, and it does not specifically limit.

As quaternary ammonium ion which forms a quaternary ammonium salt, tetramethylammonium ion, tetraethylammonium ion, triethylmethylammonium ion, lauryl trimethylammonium ion, benzyl trimethylammonium ion, etc. are mentioned.

The buffer may be used either alone or in 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 the like The monophenol type compound can be mentioned. 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 and bisphenol compounds such as -tert-butylphenol). Further, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (6-tert-butyl-o-cresol), 2,2'-thiobis (4 Thiobisphenol type compounds, such as -methyl-6-tert- butylphenol), are mentioned. In addition, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (2-methyl-4-hydroxy-5-tert-butyl-phenol Trisphenol type compounds, such as butane, are mentioned. Moreover, phosphite type antioxidants, such as a triphenyl phosphite, a trisnonyl phenyl phosphite, and a tris (mono and di-nonylphenyl) phosphite, are mentioned. Moreover, sulfur type antioxidants, such as a dilauryl dipropionate and a distearyl thiodipropionate, are mentioned.

The antioxidant may be used either alone or in a mixture thereof. In addition, as for the usage-amount of antioxidant, addition of about 0.01-1.0 weight% is preferable with respect to a resist stripping agent.

Thus, by using the alkoxy amide type compound represented by General formula (1), the resist stripping agent which concerns on this embodiment has high peeling performance, and is very excellent in corrosion resistance with respect to copper, aluminum, etc .. Moreover, since it is safe, and has water solubility, since it is a water-based peeling agent, since water rinsing is possible and IPA rinsing is unnecessary, productivity can be improved.

Next, the Example and the comparative example of the said resist stripping agent are demonstrated with reference to Table 1 of FIG. 1, and Table 2 of FIG.

(Example 1)

BRIEF DESCRIPTION OF THE DRAWINGS Table 1 which shows the peeling agent type (composition of the peeling liquid), peeling performance, and anticorrosive performance about Examples 1-15 is shown.

2 has shown Table 2 which showed the peeling agent type (composition of the peeling liquid), peeling performance, and anticorrosive performance with respect to Comparative Examples 1-6.

First, the common resist peeling performance evaluation method (resist substrate, peeling test, and corrosion test) for Examples 1 to 15 and Comparative Examples 1 to 6 will be described.

<Resist Substrate>

Substrate: The film-forming glass (size about 100 mm x 100 mm) by the Hitachi KINJUKU Corporation was used.

Resist: HPR204 (naphthoquinone diazide / novolak resin) manufactured by Fujifilm Electronics Materials Co., Ltd. was applied and baked in an oven at a predetermined temperature for about 15 minutes. That is, Example 1, 2, 3, 5-8, 10-15, and Comparative Examples 1, 3-6 used the thing baked in oven at about 130 degreeC for about 15 minutes. In addition, Example 4, 9 and the comparative example 2 used what baked in oven at about 150 degreeC 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>

Peeling performance was evaluated by the following two evaluation methods.

Resist peelability-1: In about 30 ml of sample bottles, about 5 ml of a peeling agent and one test piece of the produced said resist substrate were put, and the time until the glass substrate in a liquid becomes colorless and transparent was stirred at predetermined temperature, It judged as follows.

(Circle): Time to become transparent is less than 40sec.

X: The time until it becomes transparent is 40 sec or more.

In addition, in Example 1, 2, 3, 5-8, 10-15, and Comparative Examples 1, 3-6, the said predetermined temperature at the time of stirring is room temperature (for example, 0-30 degreeC, Usually, it was set to 20-25 degreeC). In addition, Example 4, 9 and the comparative example 2 made the said predetermined temperature at the time of stirring about 40 degreeC.

Resist stripping property-2: About 5 ml of releasing agent and one test piece of the produced said resist substrate were put into a sample bottle of about 30 ml, stirred at a predetermined temperature for about 60 sec, and peeled off, and after taking out a resist substrate, the acetone was immediately taken out. After rinsing, the surface after drying for about 30 minutes was observed at about 50 degreeC, and it judged as follows.

(Circle): There is no opaque part in the glass substrate surface at all, and the resist is wash | cleaning and peeling completely.

(Triangle | delta): There exists a part which is slightly opaque on the glass substrate surface, and the resist is wash | cleaned and peeled off substantially.

X: There exists an opaque part in more than half of the surface of a glass substrate, insufficient cleaning peeling, and the resist remain | survives considerably.

In addition, in Examples 1, 2, 3, 5-8, 10-15, and Comparative Examples 1, 3-6, the said predetermined temperature at the time of stirring for about 60 sec is room temperature (for example, 0-30). It is C, and is usually 20-25 degreeC). In addition, in Example 4, 9 and the comparative example 2, the said predetermined temperature at the time of stirring for about 60 sec was made into about 40 degreeC.

Corrosion Test

Anticorrosive performance was evaluated by the following two evaluation methods.

Anticorrosive-1: A peeling agent was put in about 30 ml of sample bottles, and about 100 mm of copper wire of about 0.5 mm in diameter was agglomerated and immersed, and the coloring degree after 1 week was observed, and it judged as follows.

(Circle): No discoloration at all.

(Triangle | delta): It changes into very light blue.

X: Discoloration to blue reliably.

Anticorrosive-2: A laminated wiring board of Mo (molybdenum) / Al / Mo was produced, and this test piece (about 10 mm x 5 mm) was placed in a sample bottle of about 30 ml, about 5 ml of a release agent was added, and the solution was about 40 ° C. Soak for 5 minutes. After immersion and corrosion operation, it observed in the following procedure, and judged as follows.

As step 1, IPA rinse was performed, as step 2, acetone rinse was performed, and as step 3, it was dried at about 50 degreeC for about 30 minutes, and the corrosion state of Al was observed with SEM (scanning electron microscope).

○: no change at all.

(Triangle | delta): Al eluted very little and corrosion was observed.

X: Al eluted reliably and severe corrosion was observed.

Moreover, the result about 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 consisting of about 80% by weight of 3-methoxy-N, N-dimethylpropionamide (abbreviated as MDMPA) and about 20% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist stripping property-1 (circle) (The time until a board | substrate became transparent was 38 second.)

Resist stripping property-2:

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 2)

As a release agent according to Example 2, a resist release agent consisting of about 60% by weight of 3-methoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 39 second.)

Resist Peelability-2: △

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. In this resist stripper-2, the resist stripping agent has a slightly opaque portion on the surface of the glass substrate, and the resist is almost washed off (a trace amount of resist residue is found). In addition, this resist releasing agent was excellent in peeling performance and anticorrosive performance in another test.

(Example 3)

As a release agent according to Example 3, a resist release agent composed of about 100% by weight of 3-methoxy-N, N-dimethylpropionamide was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until the board became transparent was 32 seconds.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 4)

As a release agent according to Example 4, a resist release agent composed of about 100% by weight of 3-methoxy-N, N-dimethylpropionamide was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 35 second.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 5)

As a release agent according to Example 5, a resist release agent consisting of about 100% by weight of 3-butoxy-N, N-dimethylpropionamide (suitably abbreviated as BDMPA) was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 31 second.)

Resist Peelability-2: △

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. In this resist stripper-2, the resist stripping agent has a slightly opaque portion on the surface of the glass substrate, and the resist is almost washed off (a trace amount of resist residue is found). In addition, this resist releasing agent was excellent in peeling performance and anticorrosive performance in another test.

(Example 6)

As a release agent according to Example 6, a resist release agent consisting of about 80% by weight of 3-butoxy-N, N-dimethylpropionamide and about 20% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until the board became transparent was 24 seconds.)

Resist Peelability-2: △

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. In this resist stripper-2, the resist stripping agent has a slightly opaque portion on the surface of the glass substrate, and the resist is almost washed off (a trace amount of resist residue is found). In addition, this resist releasing agent was excellent in peeling performance and anticorrosive performance in another test.

(Example 7)

As a release agent according to Example 7, a resist release agent consisting of about 60% by weight of 3-butoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 29 second.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 8)

As a release agent according to Example 8, a resist release agent consisting of about 40% by weight of 3-butoxy-N, N-dimethylpropionamide and about 60% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until the board became transparent was 24 seconds.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 9)

As a release agent according to Example 9, a resist release agent consisting of about 60% by weight of 3-butoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 39 second.)

Resist Peelability-2: △

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. In this resist stripper-2, the resist stripping agent has a slightly opaque portion on the surface of the glass substrate, and the resist is almost washed off (a trace amount of resist residue is found). In addition, this resist releasing agent was excellent in peeling performance and anticorrosive performance in another test.

(Example 10)

As a release agent according to Example 10, a resist release agent composed of about 100% by weight of 3-methoxy-N, N-diethylpropionamide (suitably abbreviated as MDEPA) was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 30 second.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 11)

As a release agent according to Example 11, a resist release agent consisting of about 80% by weight of 3-methoxy-N, N-diethylpropionamide and about 20% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until the board became transparent was 18 seconds.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 12)

As a release agent according to Example 12, a resist release agent consisting of about 60% by weight of 3-methoxy-N, N-diethylpropionamide and about 40% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate becomes transparent was 28 second.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 13)

As a release agent according to Example 13, a resist release agent consisting of about 100% by weight of 3-ethoxy-N, N-diethylpropionamide (suitably abbreviated as EDEPA) was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate becomes transparent was 19 second.)

Resist Peelability-2: △

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. In this resist stripper-2, the resist stripping agent has a slightly opaque portion on the surface of the glass substrate, and the resist is almost washed off (a trace amount of resist residue is found). In addition, this resist releasing agent was excellent in peeling performance and anticorrosive performance in another test.

(Example 14)

As a release agent according to Example 14, a resist release agent consisting of about 80% by weight of 3-ethoxy-N, N-diethylpropion amide and about 20% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate becomes transparent was 19 second.)

Resist Peelability-2: ○

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. This resist releasing agent was excellent in peeling performance and anticorrosive performance.

(Example 15)

As a release agent according to Example 15, a resist release agent consisting of about 60% by weight of 3-ethoxy-N, N-diethylpropionamide and about 40% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

Test results, as shown in Table 1,

Resist peelability -1: (The time until a board | substrate became transparent was 29 second.)

Resist Peelability-2: △

Anticorrosive-1: ○

Anticorrosive-2: ○

It was. In this resist stripper-2, the resist stripping agent has a slightly opaque portion on the surface of the glass substrate, and the resist is almost washed off (a trace amount of resist residue is found). In addition, this resist releasing agent was excellent in peeling performance and anticorrosive performance in another test.

(Comparative Example 1)

As a releasing agent according to Comparative Example 1, a resist releasing agent consisting of about 30% by weight of dimethyl sulfoxide (suitably abbreviated as DMSO) and about 70% by weight of monoethanolamine (as appropriately abbreviated as MEA) was prepared. Then, the said peeling test and the corrosion test were done.

The test results are shown in Table 2,

Resist peelability -1: x (time until board became transparent was 45 second.)

Resist Peelability-2: △

Anticorrosive-1: △

Anticorrosion-2: △

It was. This resist releasing agent required a long time for peeling in resist peelability-1, and a trace amount of resist residue was found in resist peelability-2. In addition, in this anticorrosive-1, this resist releasing agent discolored very light blue, and in anticorrosive-2, Al eluted very little and corrosion was observed.

(Comparative Example 2)

As a releasing agent according to Comparative Example 2, a resist releasing agent consisting of about 30% by weight of dimethyl sulfoxide (as appropriately abbreviated as DMSO) and about 70% by weight of monoethanolamine (as appropriately abbreviated as MEA) was prepared. Subsequently, the peeling test and the corrosion test were performed.

The test results are shown in Table 2,

Resist peelability -1: x (time until board became transparent was 50 second.)

Resist Peelability-2: △

Anticorrosive-1: △

Anticorrosion-2: △

It was. This resist releasing agent required a long time for peeling in resist peelability-1, and a trace amount of resist residue was found in resist peelability-2. In addition, in this anticorrosive-1, this resist releasing agent discolored very light blue, and in anticorrosive-2, Al eluted very little and corrosion was observed.

(Comparative Example 3)

As a release agent according to Comparative Example 3, a resist release agent composed of about 34% by weight of diethylene glycol monobutyl ether, about 46% by weight of monoethanolamine, and about 20% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

The test results are shown in Table 2,

Resist Peeling Properties-1: × (The time until the substrate became transparent was 56 seconds.)

Resist Peelability-2: ×

Anticorrosive-1: △

Anticorrosion-2: △

It was. This resist releasing agent requires a long time for peeling in resist peelability-1, and in resist peelability-2, there is an opaque portion on at least half of the glass substrate surface, and the cleaning peeling is insufficient. There was considerable resist remaining. In addition, in this anticorrosive-1, this resist releasing agent discolored very light blue, and in anticorrosive-2, Al eluted very little and corrosion was observed.

(Comparative Example 4)

As a release agent according to Comparative Example 4, a resist release agent consisting of about 26% by weight of diethylene glycol monobutyl ether, about 34% by weight of monoethanolamine, and about 40% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

The test results are shown in Table 2,

Resist peelability -1: (The time until a board | substrate became transparent was 38 second.)

Resist Peelability-2: △

Anticorrosive-1: ×

Anticorrosive-2: ×

It was. Although this resist releasing agent was excellent in peelability in resist peelability-1, a trace amount of resist residue was found in resist peelability-2. In addition, this resist releasing agent discolored blue reliably in anticorrosive-1, and Al reliably eluted in anticorrosive-2, and severe corrosion was observed.

(Comparative Example 5)

As a release agent according to Comparative Example 5, a resist release agent consisting of about 17% by weight of diethylene glycol monobutyl ether, about 23% by weight of monoethanolamine, and about 60% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

The test results are shown in Table 2,

Resist peelability -1: (The time until the board became transparent was 24 seconds.)

Resist Peelability-2: ○

Anticorrosive-1: ×

Anticorrosive-2: ×

It was. This resist releasing agent was excellent in peelability. In addition, this resist releasing agent discolored blue reliably in anticorrosive-1, and Al reliably eluted in anticorrosive-2, and severe corrosion was observed.

(Comparative Example 6)

As a release agent according to Comparative Example 6, a resist release agent composed of about 9% by weight of diethylene glycol monobutyl ether, about 11% by weight of monoethanolamine, and about 80% by weight of water was prepared. Then, the said peeling test and the corrosion test were done.

The test results are shown in Table 2,

Resist peelability -1: (The time until a board | substrate became transparent was 29 second.)

Resist Peelability-2: △

Anticorrosive-1: ×

Anticorrosive-2: ×

It was. Although this resist releasing agent was excellent in peelability in resist peelability-1, a trace amount of resist residue was found in resist peelability-2. In addition, this resist releasing agent discolored blue reliably in anticorrosive-1, and Al reliably eluted in anticorrosive-2, and severe corrosion was observed.

From the test results of the above examples, it was confirmed that the anticorrosive performance was excellent in all the examples. In addition, in Example 2, 5, 6, 9, 13, 15, although a trace amount of the resist residue was found in peeling performance, it was confirmed that peeling performance is also excellent in another Example.

In addition, from the test result of each said comparative example, in all the comparative examples, both peeling performance and anticorrosive performance could not be satisfied.

As mentioned above, although the preferred embodiment was demonstrated and demonstrated about the resist stripper of this invention, it is not limited only to embodiment mentioned above, and the resist stripper which concerns on this invention can be variously changed in the scope of the present invention. Needless to say.

For example, the compound represented by Formula (1) contained in a resist stripping agent is not limited to one type, For example, the resist stripping agent containing two or more compounds represented by Formula (1) may be sufficient.

In addition, the use of this invention is not limited to the resist stripping agent for liquid crystals and semiconductors, For example, the stripping agent for printed boards, a resist developing solution, a flux cleaning agent, a resin solvent (for example, a solvent for polyimide resins, a polyamide) Solvent for resins).

Claims (6)

A resist releasing agent comprising a compound represented by the formula (1). [Formula 1]

In the general formula (1), R ₃ is an alkyl group having 1 to 18 carbon atoms, R ₁ and R ₂ are each independently a hydrocarbon group which may have a hydrogen atom or an ether bond having 1 to 6 carbon atoms, and may be the same as or different from each other. You may combine with each other and form a ring structure. The method of claim 1, A resist stripper comprising about 20 to 100% by weight of the compound represented by Formula 1 and about 0 to 80% by weight of water. The method according to claim 1 or 2, The carbon number of said R <_1> and R <_2> was 1-4, The resist releasing agent characterized by the above-mentioned. The method according to claim 1 or 2, The carbon number of said R <_1> and R <_2> was 1, and the carbon number of said R <_3> was 1-8, The resist stripper characterized by the above-mentioned. The method according to claim 1 or 2, The carbon number of said R <_1> and R <_2> was 2, and the carbon number of said R <_3> was 1-6, The resist peeling agent characterized by the above-mentioned. The method according to any one of claims 1 to 5, A resist release agent characterized by the addition of an anticorrosive agent, a chelating agent, a peeling accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffer, and / or an antioxidant.

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