WO2007095014A1

WO2007095014A1 - Detergent composition containing fluorine-containing compound and method of use thereof

Info

Publication number: WO2007095014A1
Application number: PCT/US2007/003173
Authority: WO
Inventors: Nobuaki Ando
Original assignee: 3M Innovative Properties Company
Priority date: 2006-02-13
Filing date: 2007-02-05
Publication date: 2007-08-23
Also published as: KR20080098030A; CN101379179A; EP1991649A1; JP2007211203A

Abstract

To provide a detergent composition and resist remover composition which does not deteriorate a substrate to be treated and is cheap, and also has no flammability and has excellent detergency and resist removability. A detergent composition, which does not exhibit a flash point, comprising (a) 70% by weight or more of ethyl lactate, and (b) 30% by weight or less of a fluorine-containing compound having a halogen content of 60% by weight or more, each amount being based on the total weight of the detergent composition.

Description

DETERGENT COMPOSITION CONTAINING FLUORINE-CONTAINING COMPOUND AND METHOD OF USE THEREOF

TECHNICAL FIELD The present invention relates to a detergent composition and a resist remover composition containing ethyl lactate and a fluorine-containing compound, and their use.

BACKGROUND

Heretofore, a solvent has been used as a detergent for greases, waxes, or processed oils used in case of processing precision mechanical components and optical instruments, a detergent for a flux used in case of soldering electronic and electric components, a detergent used in case of cleaning a dyestuff in the production process of an optical recording medium, or a resist remover used in case of removing a resist in the production process of a semiconductor device. As the solvent, for example, a hydroxycarboxylate ester such as ethyl lactate or butyl lactate, an alcohol such as diacetone alcohol, or an ether such as dibutyl ether may be used.

For example, Japanese Unexamined Patent Publication (Kokai) No. 2004-185777 describes a method for producing an optical information recording medium, which comprises the recording layer forming step of forming a recording layer on a substrate, and, after forming the recording layer, the cleaning step of discharging a solvent to the outer peripheral portion of the substrate thereby to remove the recording layer at the outer peripheral portion, wherein an alcohol such as diacetone alcohol or an ether such as dibutyl ether is used as the solvent.

Japanese Patent No. 3,382,028 describes a method for forming a patterned resist film on a substrate in the production process of a semiconductor device, wherein ethyl lactate is used as a resist remover.

The above-described solvent has flammability and there is a restriction in the amount of the solvent to be used or stored. To solve such a problem, there has been made a trial of making the solvent for detergent or resist remover incombustible. For example, Japanese Unexamined Patent Publication (Kokai) No. 2001-172685 discloses a nonflammable detergent composition comprising (a) a nonchlorine-based fluorine compound and (b) at least one compound selected from the group consisting of glycol ether acetates and hydroxycarboxylate esters. In the documents, examples of the hydroxycarboxylate ester include lactate ester, maleate ester, tartrate ester and citrate ester, and examples of the lactate ester include methyl lactate, ethyl lactate, butyl lactate and pentyl lactate. It is described that the nonchlorine-based fluorine compound is obtained by substituting a portion of hydrogen atoms of hydrocarbons and ethers with fluorine atoms, and does not contain a chlorine atom. The hydroxycarboxylate ester used in the present invention is only butyl lactate, and also only a detergent composition containing 60% by weight or more of a nonchlorine fluorine-based compound and 40% by weight or less of butyl lactate is described. Butyl lactate has high detergency, but exhibits high attacking properties to a plastic substrate such as polycarbonate and therefore a substrate to be cleaned may be deteriorated. Since the fluorine-based compound is an expensive compound, the cost increases when it is contained as a main component of the detergent composition.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a detergent composition and a resist remover composition which do not deteriorate a substrate to be treated and are cheap, and also have no flammability and have excellent detergency and resist removability. According to an aspect, the present invention provides (1) a detergent composition, which does not exhibit a flash point, comprising (a) 70% by weight or more of ethyl lactate, and (b) 30% by weight or less of a fluorine-containing compound having a halogen content of 60% by weight or more, each amount being based on the total weight of the detergent composition. . According to another aspect, the present invention provides (2) a resist remover composition, which does not exhibit a flash point, comprising (a) 70% by weight or more of ethyl lactate, and (b) 30% by weight or less of a fluorine-containing compound having a halogen content of 60% by weight or more, each amount being based on the total weight of the resist remover composition. The detergent composition and the resist remover composition of the present invention contain ethyl lactate and have no attacking properties to a plastic substrate such as polycarbonate, and also cart exhibit excellent detergency and removability. Since these compositions do not exhibit flammability even if the content of the fluorine-containing compound is small such as 30% by weight or less (particularly, about 6% by weight), the compositions can be produced at a low cost.

The present invention will now be described by way of preferred aspects. The composition of the present invention contains ethyl lactate (a) as a main component. Since ethyl lactate does not damage a plastic substrate such as polycarbonate, there is less restriction in the substrate to be treated as compared with the case of using butyl lactate which has conventionally been used. On the other hand, ethyl lactate has a Kauri butanol value (KB value) of 216 and high solubility of a contaminant or a resist, and also contributes directly to the cleaning effect and the resist removing effect. However, ethyl lactate is a substance which has a flash point of 53.5⁰C and which itself also has flammability. The composition of the present invention does not exhibit flammability when a small amount of a fluorine-containing compound is added to ethyl lactate. Ethyl lactate is contained in the composition in the amount of 70% or more based on the total weight of the composition. Because of a large amount of ethyl lactate, excellent detergency and resist removability of the composition can be maintained. For the purpose of spin cleaning, it is desired to use a solvent having comparatively high boiling point so as to suppress volatilization. Since ethyl lactate has a boiling point of 154°C, the composition of the present invention is preferably used for spin cleaning. The Kauri butanol value (KB value) is used to evaluate the quality of a petroleum-based solvent. It is indicated by the amount (ml) at 25°C of a solvent required to produce a white turbidity in a solution when the solvent is added to 20 g of the solution. When the KB value is 60 or more, toluene for guaranteed reagent is used for standardization wherein the value of toluene is 105. On the other hand, when the value is less than 60, a mixed solution containing 75% of heptane and 25% of toluene is used wherein the value of the mixed solution is 40.

Regarding the fluorine-containing compound (b) contained in the composition of the present invention, the halogen content in the compound is 60% by weight or more. Such a halogen content imparts sufficient incombustibility even when the amount of the fluorine-containing compound added to composition is small. The fluorine-containing compound may be hydrofluorocarbon (HFC) or hydrofluoroether (HFE). The fluorine- containing compound preferably has a boiling point of 40 to 140⁰C. When the boiling point is too high, the drying rate of the composition decreases and the drying time increases too much. On the other hand, when the boiling point is too low, the composition is vaporized before the substrate is sufficiently wetted and it becomes difficult to perform an operation such as cleaning. Particularly, in case of a detergent composition for spin cleaning, when the boiling point of the fluorine-containing compound is too low, sufficient spin coating cannot be conducted, which is undesirable. The fluorine-containing compound, which satisfies the above conditions, is hydrofluorocarbon (HFC) having 4 to 6 carbon atoms, or hydrofluoroether (HFE) having 4 to 8 carbon atoms. The fluorine- containing compound may contain other halogens such as chlorine. Since such a halogen contributes to incombustibility of the composition, the content is added to the above- described halogen content. However, since chlorine-containing hydrochlorofluorocarbon (HCFC) is known as a substance which promotes ozone layer depletion, a chlorine-free fluorine-containing compound is preferable. In the fluorine-containing compound, a ratio of the number of halogen atoms to the number of hydrogen atoms in the molecule is preferably 1 or more. More specific examples thereof include 1,1,1,2,2,3,4,5,5,5- , decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (halogen content (weight basis) in the molecule: 70.6%) (trade name: Novec 7300, manufactured by Sumitomo 3M Co., Ltd.), mixture of nonafluorobutyl methyl ether and nonafluoroisobutyl methyl ether (halogen content (weight basis) in the molecule: 68.4%) (trade name: Novec HFE-7100, manufactured by Sumitomo 3M Co., Ltd.), mixture of nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether (halogen content (weight basis) in the molecule: 64.8%) (trade name: Novec HFE-7200, manufactured by Sumitomo 3M Co., Ltd.), 1,1,1 ,2,2,3,4,5,5,5-decafluoropentane (halogen content (weight basis) in the molecule: 75.4%) (trade name: Vertrel XF(HFC-4310mee), manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.), l,l,2,2-tetrafluoro-l-(2,2,2-trifluoroethoxy)ethane (halogen content (weight basis) in the molecule: 66.5%) (trade name: AE-3000 (HFE-347pcf)₃ manufactured by Asahi Glass Co., Ltd.), mixture of 1 , 1 ,1 ,2,2-pentafluorodiehloropropane and l,l,2,2,3-pentafluoro-l,3-dichloropropane (halogen content (weight basis) in the molecule: 81.8%) (trade name: AK-225 (HCFC-225), manufactured by Asahi Glass Co., Ltd.) and 1,1,1,3,3-pentafluorobutane (halogen content (weight basis) in the molecule: 64.2%) (trade name: Solkane 365mfc (HFC-365mfc)₃ manufactured by Solvay Co.). The amount of the fluorine-containing compound which is required to impart incombustibility to the composition, that is, the amount required to obtain the composition having no flammability is 30% by weight or less based on the total weight of the composition. In case of a specific fluorine-containing compound, it is sufficient that the amount is from 5 or 6% by weight. When the amount of the fluorine-containing compound is less than 5% by weight, the resulting composition has flammability, and therefore it is not preferable. On the other hand, when the amount of the fluorine- containing compound is more than 30% by weight, the cost of the composition increases and also detergency and resist removability are too deteriorated. Depending on the kind of the fluorine-based compound, it is separated from ethyl lactate without forming a uniform mixture.

A preferable detergent and resist remover composition of the present invention is a composition consisting essentially of 70 to 94% by weight of ethyl lactate and 6 to 30% by weight of 1,1,1, 2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, and particularly a composition consisting of 94% by weight of ethyl lactate and 6% by weight of 1 , 1 , 1 ,2,2,3,4,5, 5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane. These compositions have no flash point and have particularly high detergency. Furthermore, l,l,l,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane is environmentally friendly because it has a low global warming potential (GWP) as low as 200 and has no ozone depletion potential. The global warming potential (GWP) is well known as described in Japanese Patent No. 3,099,964 and the ozone depletion potential is a relative numerical value assumed that the ozone depletion potential of the specified chlorofluorocarbon CFC-I l is 1.

The composition of the present invention may contain other components, in addition to the above components (a) and (b). For example, the composition may contain antioxidants such as phenol-based antioxidants and amine-based antioxidants so as to prevent oxidative deterioration of the composition. The composition of the present invention may further contain additives such as surfactants, stabilizers and antifoamers.

As described above, the detergent composition of the present invention is effective as a detergent composition used in the production process of an optical information recording medium. The composition of the present invention is, for example, used as follows. In a Recordable optical information recording medium known widely as a compact disk (CD-R) or a digital versatile disk (DVD-R), a recording layer containing a dyestuff is formed as a recording region. This recording layer is formed by spin-coating a dyestuff-containing solution onto the surface of a substrate, followed by drying. A spin coater used in spin coating, because of its characteristics, can start coating from a certain definite position in the inner peripheral side, but can not easily control the coating range in the outer peripheral side. Therefore, after forming the recording layer on the entire surface of the substrate, the dyestuff of the outer peripheral edge portion is removed by spin- coating a cleaning solution onto the outer peripheral edge portion (cleaning step). In the cleaning step, the outer peripheral edge portion (edge portion) of the recording layer is cleaned and then this substrate and a cover substrate are bonded at the outer peripheral portion of the substrates, thus making it possible to form an optical recording medium. Deterioration with time of the recording layer can be prevented by cleaning the peripheral edge portion (edge portion) of the recording layer. The present invention provides, in an aspect, a method of using a detergent composition, which comprises the steps of coating a solution for forming a recording layer containing a dyestuff for optical information. recording medium onto a plastic substrate or a metal film formed on the substrate, and drying the solution to form a recording layer on the entire surface of the substrate, then spin-coating the detergent composition of the present invention so as to clean the outer peripheral portion of the substrate, to remove the recording layer in the outer peripheral . portion, and drying the detergent composition. In this method, the optical information recording medium includes a compact disk (for example, CD-R, etc.), a digital versatile disk (for example, DVD-R, etc.) or a next-generation optical recording medium. As the dyestuff for optical information recording medium, which forms the recording layer, for example, a nickel_^containing azo dyestuff is used. As the substrate, a plastic such as polycarbonate is used. In case of the conventional CD-R or DVD-R, a solution for forming a recording layer is coated onto a plastic substrate to form a recording layer and then a metal film such as aluminum film is formed thereon as a reflection film. On the other hand, in case of the next-generation optical recording medium, a metal film made of aluminum is formed on a substrate and a solution for forming a recording layer is formed on the metal film. The detergent composition of the present invention is particularly suited for the above-described method of use because it does not damage the plastic substrate such as polycarbonate and the metal film and can satisfactorily remove the nickel-containing azo dyestuff.

The present invention provides, in another aspect, a method of using a detergent composition, which comprises the step of removing a contaminant adhered onto an electronic circuit board, using the detergent composition of the present invention. The contaminant can be removed by a suitable method of dipping the electronic circuit board in the detergent composition of the present invention or shower cleaning of the electronic circuit board.

The present invention provides, in another aspect, a method of using the resist remover composition of the present invention in the formation of a patterned resist film. Specifically, the method is characterized by comprising the steps of applying a film of a resist material onto the surface of a substrate, patternwise irradiating the film with radiation, removing a resist film by the resist remover composition of the present invention in pattern corresponding to pattern irradiation to form a patterned resist film. In case the resist material is in the form of a liquid, the film made of the resist material is applied by coating the liquid, followed by drying. In case the resist material is in the form a film, the film of the resist material is applied by attaching onto the substrate. Then, the resist film is patternwise irradiated with radiation such as light, electron beam or X-ray, : corresponding to a resist pattern to be formed, to form a substrate having a pattem- irradiated resist film. Then, the resist film is patternwise removed by dipping the substrate having a pattern-irradiated resist film into the resist remover composition of the present invention, or spin-coating a resist remover composition onto the resist film to form a patterned resist film.

EXAMPLES

The present invention will now be described in more detail by way of examples. Abbreviations used in the examples are as follows.

Novec 7300: 1,1,1 ^^S^S^S-decafluoro-S-methoxy-^trifluoromethyO-pentane (trade name: Novec 7300, manufactured by Sumitomo 3M Co., Ltd.) Novec HFE-7100: mixture of nonafluorobutyl methyl ether and nonafluoroisobutyl methyl ether (trade name: Novec HFE-7100, manufactured by Sumitomo 3M Co., Ltd.) Novec HFE-7200: mixture of nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether (trade name: Novec HFE-7200. manufactured by Sumitomo 3M Co., Ltd.)

Vertrel XF: 1,1,1,2,2,3,4,5,5,5-decafluoropentane (trade name: Vertrel XF, manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) AE-3000: l,l,2,2-tetrafluoro-l-(2,2,2-trifluoroethoxy)ethane (trade name: AE-

3000, manufactured by Asahi Glass Co., Ltd.)

AK-225 : mixture of 1 , 1 , 1 ,2,2-pentafluorodichloropropane and 1 , 1 ,2,2,3- pentafluoro-l,3-dichloropropane (trade name: AK-225, manufactured by Asahi Glass Co., Ltd.) Solkane 365mfc: 1,1,1,3,3-pentafluorobutane (trade name: Solkane 365mfc, manufactured by Solvay Co.)

Ethyl lactate: (manufactured by Musashino Chemical Laboratory, Ltd.)

PDS-2072: Nickel-containing azo-based dyestuff for optical information recording medium, PDS-2072 (manufactured by Mitsubishi Kagaku Media Co., Ltd.)

Examples 1 to 10 and Comparative Examples A to G: Flammability

According to the mixing ratio shown in Table 1, the following incombustible fluorine-based compounds and ethyl lactate were mixed at room temperature (25°C) to obtain a mixture. A flash point of each mixture was measured by an Automatic Pensky- Martens Closed Cup Flash Point Tester according to a Pensky-Martens Closed Cup standard test method (ISO 2719: 1988). The results are shown in Table 1 below.

Table 1 : Measurement of flash point

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Example 11 : Method for controlling flash point of composition

A method for controlling a flash point so as to allow the composition to exhibit no flash point will be described. In this example, a mixture of ethyl lactate and l,l,l,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (trade name: Novec 7300, manufactured by Sumitomo 3M Co., Ltd.) was used. In Table 2 below, a specific gravity at each composition is shown.

Table 2: Specific gravity of composition

As is apparent from the results shown in Table 1 , when the content of Novec 7300 ■ is 6% by weight or more, the resulting composition does not exhibit a flash point. Therefore, it is apparent that a composition, which does not exhibit a flash point, can be obtained by controlling the specific gravity to 1.056 or more at a temperature of 25°C. It is apparent that a composition, which does not exhibit a flash point, can be obtained by controlling the specific gravity to 1.042 or more at a temperature of 40⁰C.

Examples 12 to 18 and Comparative Examples H to K

A solution prepared by dissolving a nickel-containing azo dyestuff for an optical information recording medium, PDS-2072 (manufactured by Mitsubishi Kagaku Media

Co., Ltd.) in 2,2,3,3-tetrafluoro-l-propanol (manufactured by Daikin Industries, Ltd.) in a concentration of 0.5% by weight was coated onto a polycarbonate substrate in the form of a circular disk having a diameter of 100 mm using a spin coater at 1000 rpm and then dried. After the polycarbonate substrate coated with a dyestuff was mounted to the spin coater again, a small amount of the detergent composition shown in Table 3 was added dropwise under the spinning condition of 1000 rpm and then the cleaning effect and attacking properties to the polycarbonate were evaluated. With respect to the cleaning effect, the case where the dyestuff is removed and the composition turned to a colorless and transparent, the composition was rated "OK" and the case where the dyestuff is not removed and the composition did not turn to a colorless and transparent, the composition was rated "NG"; Damage to the polycarbonate substrate was not observed using any detergent composition, and "none" was described in the table.

Table 3: Evaluation of detergency

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Examples 19 to 23 and Comparative Examples L to P

Detergency to various contaminants was examined. First, a glass plate and a polycarbonate were used as a substrate, and a flux, a wax and a dyestuff for optical information recording medium were used as a contaminant. Using the detergent and the rinsing agent shown in Table 4 below, cleaning processes 1 to 3 were conducted. The cleaning effect was visually confirmed. The case where the contaminant was completely removed was rated "OK", whereas, the case where the contaminant was not completely removed was rated "NG".

Table 4: Removablity of various contaminants

Table 4 (continued)

O\

Note:

Mixture A: Novec 7300: ethyl lactate = 10:90 (% by weight)

NS-200: hydrocarbon detergent (available from Japan Energy Corporation)

RT: room temperature (25⁰C)

U/S: ultrasonic wave

Claims

1. A detergent composition, which does not exhibit a flash point, comprising (a) 70% by weight or more of ethyl lactate, and (b) 30% by weight or less of a fluorine- containing compound having a halogen content of 60% by weight or more, each amount being based on the total weight of the detergent composition.

2. The detergent composition according to claim 1, comprising 70 to 94% by weight of ethyl lactate and 6 to 30% by weight of l,l,l,2,2,3,4,5,5,5-decafluoro-3- methoxy-4-(trifluoromethyl)pentane.

3. A resist remover composition, which does not exhibit a flash point, comprising (a) 70% by weight or more of ethyl lactate^ and (b) 30% by weight or less of a fluorine-containing compound having a halogen content of 60% by weight or more, each amount being based on the total weight of the resist remover composition.

4. The resist remover composition according to claim 3, comprising 70 to 94% by weight of ethyl lactate and 6 to 30% by weight of l,l,l,2,2,3,4,5,5,5-decafluoro-3- methoxy-4-(trifluoromethyl)pentane.

5. A method of using a detergent composition in the production of an optical information recording medium, which comprises coating a solution for forming a recording layer containing a dyestuff for optical information recording medium, onto a . plastic substrate or a metal film formed on the substrate, and drying the solution to form a. recording layer on the entire surface of the substrate, then spin-coating the detergent composition according to claim 1 or 2 so as to clean the outer peripheral portion of the substrate, to remove the recording layer in the outer peripheral portion, and drying the detergent composition.

6. A method of using a detergent composition, which comprises the step of removing a contaminant adhered onto on an electronic circuit board, by the detergent composition according to claim 1 or 2.

7. A method of using a resist remover, which comprises the steps of applying a film of a resist material onto the surface of a substrate, patternwise irradiating the film with radiation, removing a resist film by the resist remover composition according to claim 3 or 4 in a pattern corresponding to pattern irradiation to form a patterned resist film.