JP2007211203A - Detergent composition containing fluorine-containing compound and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition, which does not cause deterioration of the substrate to be treated with the detergent composition, is inexpensive, has no inflammability, and is capable of achieving excellent washing and resist removal. <P>SOLUTION: The detergent composition includes (a) 70% by mass or more of an ethyl lactate and (b) 30% by mass or less of a fluorine-containing compound, in which compound the halogen content is 60% by mass or more, based on the total mass of the detergent composition and shows no flash point. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cleaning agent composition containing ethyl lactate and a fluorine-containing compound, a resist remover composition, and a method for using the same.

  Conventionally, cleaning agents for processing oils used when processing greases, waxes, precision machine parts and optical instrument parts, cleaning agents for fluxes used when soldering electronic and electrical parts, optical recording A solvent is used as a cleaning agent used for dye cleaning performed in the manufacturing process of a medium or a resist removing agent used for resist removal performed in the manufacturing process of a semiconductor device. As such a solvent, for example, a hydroxycarboxylic acid ester such as ethyl lactate or butyl lactate, an alcohol such as diacetone alcohol, or an ether such as dibutyl ether is used.

  For example, Patent Document 1 discloses a recording layer forming step of forming a recording layer on a substrate, and a cleaning step of removing the recording layer at the outer peripheral portion by discharging a solvent to the outer peripheral portion of the substrate after the recording layer is formed. In the method for producing an optical information recording medium including the above, the use of an alcohol such as diacetone alcohol or an ether such as dibutyl ether as the solvent is described.

  Patent Document 2 uses ethyl lactate as a resist remover in a method for forming a patterned resist film on a substrate in a semiconductor device manufacturing process.

  The above solvents are flammable and are limited in their use or storage. In order to solve such a problem, an attempt has been made to incombust a solvent for a cleaning agent or a resist removing agent. For example, Patent Document 3 discloses a non-flammable cleaning containing (a) a non-chlorine fluorine compound and (b) one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters. An agent composition is disclosed. In the literature, hydroxycarboxylic acid esters widely include lactic acid esters, malic acid esters, tartaric acid esters, citric acid esters and the like, and examples of lactic acid esters include methyl lactate, ethyl lactate, butyl lactate and pentyl lactate. Has been. On the other hand, as non-chlorine fluorine compounds, it is widely described that some of hydrogen atoms of hydrocarbons and ethers are substituted with fluorine atoms and do not contain chlorine atoms. The hydroxycarboxylic acid ester used in the examples is only butyl lactate, and a cleaning composition containing 60% by mass or more of a non-chlorine fluorine-based compound and 40% by mass or less of butyl lactate is exemplified. There is only.

  However, although butyl lactate has a high detergency, it is highly aggressive against plastic substrates such as polycarbonate, and the substrate to be cleaned may deteriorate. Moreover, since a fluorine-type compound is an expensive compound, when it contains as a main component of a cleaning composition, cost will increase.

JP 2004-185777 A Japanese Patent No. 3382028 JP 2001-172585 A

  Therefore, the present invention provides a cleaning composition and a resist removing composition that do not deteriorate the substrate to be treated, are inexpensive, have no flammability, and have excellent cleaning power and resist removal capability. Objective.

  According to one aspect of the present invention, (1) based on the total mass of the cleaning composition, (a) 70% by mass or more of ethyl lactate, and (b) the halogen content in the compound is 60% by mass. Provided is a cleaning composition containing the above fluorine-containing compound in an amount of 30% by mass or less and exhibiting no flash point.

  According to another aspect of the present invention, (2) based on the total mass of the resist remover composition, (a) 70% by mass or more of ethyl lactate, and (b) the halogen content in the compound is 60% by mass. Provided is a resist remover composition containing a fluorine-containing compound that is not less than 30% in an amount of not more than 30% by mass and exhibiting no flash point.

  The detergent composition and resist remover composition of the present invention contain ethyl lactate, have no aggressiveness against plastic substrates such as polycarbonate, and can exhibit excellent detergency and removal ability. Even if the amount of the fluorine-containing compound is a small amount of 30% by mass or less (particularly about 6% by mass), it does not exhibit flammability, so that the composition can be produced at low cost.

Below, this invention is demonstrated based on the suitable aspect.
The composition of the present invention contains ethyl lactate (a) as a main component. Since ethyl lactate does not cause damage to plastic substrates such as polycarbonate, there are fewer restrictions on the substrate to be treated than when butyl lactate that has been generally used is used. On the other hand, ethyl lactate has a Kauributanol value (KB value) of 276, has high solubility in contaminants and resists, and contributes directly to the cleaning effect and resist removal effect. However, ethyl lactate has a flash point of 53.5 ° C. and is a flammable substance by itself. The composition of the present invention does not exhibit flammability by adding a small amount of a fluorine-containing compound to ethyl lactate. Ethyl lactate is contained in the composition in an amount of 70% by mass or more based on the total mass of the composition. With such a large amount of ethyl lactate, the cleaning power and resist removal capability of the composition can be maintained at a sufficiently high level. For the purpose of spin cleaning, it is desirable to use a solvent having a relatively high boiling point so as to suppress the volatilization rate. However, since ethyl lactate has a boiling point of 154 ° C., the composition of the present invention is spin-cleaned. It is suitably used for applications. The Kauributanol value (KB value) is used for evaluating the quality of petroleum solvents. When the solvent is dropped into 20 g of the kauributanol solution, it is shown as the number of ml of the solvent required at 25 ° C. until the solution becomes a certain cloudy state. When the KB value is 60 or more, reagent grade special grade toluene is used for standardization, and the value is set to 105. In the case of less than 60, a mixed solution of 75% heptane and 25% toluene is used for standardization, and the value is set to 40.

  The fluorine-containing compound (b) contained in the composition of the present invention has a halogen content in the compound of 60% by mass or more. Such a halogen-containing component imparts sufficient nonflammability to the composition by adding a small amount of the fluorine-containing compound to the composition. The fluorine-containing compound can be, for example, a hydrofluorocarbon (HFC) or a hydrofluoroether (HFE). The fluorine-containing compound preferably has a boiling point of 40 to 140 ° C. If the boiling point is too high, the drying rate of the composition will be slow, and the drying time will be too long. On the other hand, if the boiling point is too low, the composition evaporates before the substrate is sufficiently wetted, and operations such as washing become difficult. In particular, a cleaning composition for spin cleaning is not suitable if the boiling point of the fluorine-containing compound is too low, because it is not sufficiently spin-coated. The fluorine-containing compound that satisfies such conditions is, for example, a hydrofluorocarbon (HFC) having 4 to 6 carbon atoms or a hydrofluoroether (HFE) having 4 to 8 carbon atoms. Further, the fluorine-containing compound may contain other halogens such as chlorine. Since such halogen also contributes to the nonflammability of the composition, it is counted as the halogen content described above. However, since hydrochlorofluorocarbon (HCFC) containing chlorine is known as a substance that promotes ozone layer destruction, a fluorine-containing compound that does not contain chlorine is desirable. The fluorine-containing compound preferably has a ratio of the number of halogen atoms to the number of hydrogen atoms in the molecule of 1 or more. More specifically, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) -pentane (halogen content in the molecule ( (Mass basis): 70.6%) (trade name: Novec 7300, manufactured by Sumitomo 3M Limited), a mixture of nonafluorobutyl methyl ether and nonafluoroisobutyl methyl ether (halogen content in the molecule (mass basis): 68. 4%) (trade name: Novec HFE-7100, manufactured by Sumitomo 3M Limited), a mixture of nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether (halogen content in the molecule (mass basis): 64.8%) (Product name: Novec HFE-7200, manufactured by Sumitomo 3M Limited), 1,1,1,2,2,3,4,5,5,5-decuff Luopentane (halogen content in the molecule (mass basis): 75.4%) (trade name: Vertrel XF (HFC-4310mee), manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), 1,1,2,2-tetrafluoro -1- (2,2,2-trifluoroethoxy) ethane (halogen content in the molecule (mass basis): 66.5%) (trade name: AE-3000 (HFE-347pcf), manufactured by Asahi Glass Co., Ltd. ), 1,1,1,2,2-pentafluorodichloropropane and 1,1,2,2,3-pentafluoro-1,3-dichloropropane mixture (halogen content in the molecule (mass basis): 81.8%) (trade name: AK-225 (HCFC-225), manufactured by Asahi Glass Co., Ltd.), 1,1,1,3,3-pentafluorobutane (halogen content in the molecule (mass basis) : 64.2%) (trade name: Solkane 365mfc (HFC-365mfc), manufactured by Solvay), and the like.

  In order to make the composition nonflammable, that is, in order to prevent the composition from exhibiting flammability, the amount of the fluorine-containing compound required is 30% by mass or less based on the total mass of the composition. In the case of a specific fluorine-containing compound, 5 or 6% by mass is sufficient. When the amount of the fluorine-containing compound is less than 5% by mass, it generally has flammability and is not preferable. On the other hand, when the amount of the fluorine-containing compound exceeds 30% by mass, the cost of the composition increases, and the cleaning power and resist removal capability are too low. Further, depending on the type of the fluorine-based compound, it cannot be formed into a uniform mixture with ethyl lactate and is separated.

  A preferred cleaning agent and resist remover composition of the present invention comprises 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- A composition consisting essentially of decafluoro-3-methoxy-4- (trifluoromethyl) pentane, in particular 94% by weight of ethyl lactate and 6% by weight of 1,1,1,2,2, It is a composition comprising 3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane. These compositions do not have a flash point and are particularly high in detergency. Furthermore, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane has a low global warming potential (GWP) of 200. In addition, it has no ozone depletion coefficient, so it is environmentally friendly. The global warming potential (GWP) is well known as described in Japanese Patent No. 3099964, and the ozone destruction coefficient is 1 when the ozone destruction coefficient of CFC-11, which is a specific CFC, is 1. Is the relative value of.

  The composition of the present invention may contain other components in addition to the components (a) and (b). For example, in order to prevent oxidative deterioration of the composition, an antioxidant such as a phenol-based antioxidant and an amine-based antioxidant may be included. The composition of the present invention may further contain additives such as surfactants, stabilizers and antifoaming agents.

  As described above, the cleaning composition of the present invention is effective as a cleaning composition used in the production process of an optical information recording medium. The composition of the present invention is used, for example, as follows. A write-once type optical information recording medium widely known as a compact disc (CD-R) or a digital multipurpose disc (DVD-R) has a recording layer containing a dye as a recording region. This recording layer is formed by spin-coating the dye-containing solution on the substrate surface and drying. A spin coater used for spin coating can start application from a position limited to some extent on the inner periphery side of the substrate due to its characteristics, but it is difficult to control the application range on the outer periphery side. For this reason, the recording layer is once formed on the entire surface of the substrate, and the outer peripheral edge portion is removed by spin-coating and removing the cleaning liquid (cleaning step). In the cleaning step, the outer peripheral edge portion (edge portion) of the recording layer is cleaned, and then the base material and the cover base material are bonded at the outer peripheral edge portion of the base material to form an optical recording medium. Can do. In addition, it is possible to prevent deterioration of the recording layer over time by cleaning the outer peripheral edge (edge portion) of the recording layer. In one embodiment of the present invention, a recording layer forming solution containing a dye for an optical information recording medium is applied onto a plastic substrate or a metal film formed on the substrate, and dried. After the recording layer is formed on the entire surface of the substrate, the cleaning composition of the present invention is spin-coated to remove the recording layer at the outer periphery, and the cleaning composition is dried in order to clean the outer periphery of the substrate. The method of using the cleaning composition of the present invention in the production of an optical information recording medium is provided. In this method, the optical information recording medium includes a compact disc (such as a CD-R), a digital multipurpose disc (such as a DVD-R), or a next-generation optical recording medium. Further, for example, a nickel-containing azo dye is used as the dye for the optical information recording medium forming the recording layer. In addition, a plastic such as polycarbonate is used as the substrate. In the case of a conventional CD-R or DVD-R, a recording layer forming solution is applied on a plastic substrate to form a recording layer, and a metal film such as aluminum is formed thereon as a reflective film. On the other hand, in the case of a next-generation optical recording medium, a metal film such as aluminum is formed on a substrate, and a recording layer forming solution is applied on the metal film. The cleaning composition of the present invention is particularly suitable for the above-mentioned method of use because it can remove nickel-containing pigments satisfactorily without damaging plastic substrates such as polycarbonate and metal films.

  In another aspect, the present invention provides a method for using a cleaning composition, wherein the contaminant on an electronic circuit board to which contaminants such as flux are attached is removed by the cleaning composition of the present invention. Contaminants can be removed by an appropriate method such as immersing the electronic circuit board in the cleaning composition of the present invention or shower cleaning.

  In another aspect, the present invention provides a method of using the resist remover composition of the present invention in the formation of a patterned resist film. Specifically, a resist material film is applied to the surface of the substrate, energy rays are pattern-irradiated, and then the resist film is removed in a pattern corresponding to pattern irradiation by the resist remover composition of the present invention. Then, a patterned resist film is formed. When the resist material is a liquid, the resist material film is applied by applying the liquid and drying. Moreover, the film | membrane of a resist material is applicable by affixing on a base material, if a resist material is a film form. Next, in response to the resist pattern to be formed, energy beams such as light, electron beams, and X-rays are pattern-irradiated on the resist film to form a substrate having the resist film subjected to pattern irradiation. Next, the substrate having the resist film irradiated with the pattern is immersed in the resist remover composition of the present invention, or the resist remover composition is spin-coated on the resist film to remove the resist film in a pattern. Then, a patterned resist film is formed.

In the following, the present invention will be described in more detail using examples.
Abbreviations used in the examples are as follows.
Novec7300: 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) -pentane (trade name: Novec7300, manufactured by Sumitomo 3M Limited) )
Novec HFE-7100: Mixture of nonafluorobutyl methyl ether and nonafluoroisobutyl methyl ether (trade name: Novec HFE-7100, manufactured by Sumitomo 3M Limited)
Novec HFE-7200: Mixture of nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether (trade name: Novec HFE-7200, manufactured by Sumitomo 3M Limited)
Vertrel XF: 1,1,1,2,2,3,4,5,5,5-decafluoropentane (trade name: Vertrel XF, manufactured by Mitsui Dupont Chemical Co., Ltd.)
AE-3000: 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (trade name: AE-3000, manufactured by Asahi Glass Co., Ltd.)
AK-225: A mixture of 1,1,1,2,2-pentafluorodichloropropane and 1,1,2,2,3-pentafluoro-1,3-dichloropropane (trade name: AK-225, Asahi Glass ( Made by Co., Ltd.)
Solkane 365mfc: 1,1,1,3,3-pentafluorobutane (trade name: Solkane 365mfc, manufactured by Solvay)
Ethyl lactate: (Musashino Chemical Laboratory Co., Ltd.)
PDS-2072: Nickel-containing azo dye PDS-2072 (manufactured by Mitsubishi Chemical Media Corporation) for optical information recording media

Examples 1 to 10 and Comparative Examples A to G: Flammability The following incombustible fluorine-based compounds and ethyl lactate were mixed at room temperature (25 ° C.) according to the blending ratio in Table 1 to obtain a mixture. These were subjected to flash point measurement using a Penscourt Lents closed automatic flash point measuring machine in accordance with the Penske Lutense closed test method (ISO 2719: 1988). The results are shown in Table 1 below.

Example 11: Flash point management method of a composition A flash point management method for preventing a composition from exhibiting a flash point will be described. In this example, ethyl lactate and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) -pentane (trade name: Novec 7300, A mixture with Sumitomo 3M Co., Ltd.) was used. Table 2 below shows the specific gravity of each composition.

  From Table 1 above, it is known that the composition does not exhibit a flash point when the Novec 7300 is 6% by mass or more. Therefore, it can be seen that by controlling the specific gravity of the composition to 1.056 or more at a temperature of 25 ° C., a composition having no flash point can be obtained. Moreover, it turns out that it can be set as the composition which does not show flash point by controlling the specific gravity of a composition to 1.042 or more at the temperature of 40 degreeC.

Examples 12 to 18 and Comparative Examples H to K
For an optical information recording medium dissolved in a concentration of 0.5 wt% in 2,2,3,3-tetrafluoro-1-propanol (manufactured by Daikin Industries, Ltd.) on a polycarbonate substrate of a circular disk having a diameter of 100 mm The nickel-containing azo dye PDS-2072 (manufactured by Mitsubishi Chemical Media Co., Ltd.) was applied with a spin coater at 1000 rpm and dried. After that, the polycarbonate base material coated with the dye was placed on the spin coater again, and a small amount of the cleaning composition shown in Table 3 below was dropped under the condition of 1000 rpm, and the cleaning effect and attack property to the polycarbonate were visually observed. It was evaluated with. Regarding the cleaning effect, the case where the pigment was removed and became colorless and transparent was indicated as OK, and the case where it was not indicated as NG. Moreover, the damage with respect to a polycarbonate base material was not seen when any detergent composition was used, and was described as "none".

Examples 19 to 23 and Comparative Examples L to P
In the following, detergency against various contaminants was examined. First, a glass plate and polycarbonate were used as a base material, and flux, wax, and an optical information recording medium dye were used as contaminants. Cleaning processes 1 to 3 were performed using the cleaning agents and rinsing agents shown in Table 4 below. The cleaning effect was confirmed visually. The case where the contaminant was completely removed was designated as “OK”, and the case where the contaminant was not completely removed was designated as “NG”.

Claims (7)

  Based on the total mass of the cleaning composition, (a) 70% by mass or more of ethyl lactate and (b) 30% by mass or less of the fluorine-containing compound having a halogen content in the compound of 60% by mass or more A cleaning composition that contains no flash point.   70-94% by weight of ethyl lactate and 6-30% by weight of 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) The cleaning composition according to claim 1, comprising pentane.   Based on the total mass of the resist remover composition, (a) 70% by mass or more of ethyl lactate and (b) 30% by mass or less of a fluorine-containing compound having a halogen content in the compound of 60% by mass or more. A resist remover composition comprising an amount and no flash point.   70-94% by weight of ethyl lactate and 6-30% by weight of 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) The resist remover composition according to claim 3, comprising pentane.   After a recording layer forming solution containing a dye for optical information recording media is applied on a plastic substrate or a metal film formed on the substrate and dried to form a recording layer on the entire surface of the substrate In order to clean the outer peripheral portion of the substrate, the cleaning composition according to claim 1 or 2 is spin-coated, the recording layer in the outer peripheral portion is removed, and the cleaning composition is dried. A method of using a cleaning composition in the production of an information recording medium.   A method for using a cleaning composition, wherein the contaminant on the electronic circuit board to which the contamination is attached is removed by the cleaning composition according to claim 1.   Applying a resist material film to the surface of the substrate, pattern irradiating energy rays, then removing the resist film in a pattern corresponding to pattern irradiation by the resist remover composition according to claim 3 or 4, A method of using a resist remover for forming a patterned resist film.