JP4830445B2 - Metal container cleaning method and resin molded product cleaning method - Google Patents

Abstract

The invention provides a method for cleaning a metallic vessel, by which a photosensitive composition as a contaminant stuck to the object to be cleaned can be cleaned and easily removed, in which specific equipment such as explosion-proof equipment is not required, the waste cleaning liquid is easily treated and the influence to be exerted on the environment is sufficiently taken into consideration. This method for cleaning the metallic vessel comprises the step of removing the photosensitive composition stuck to the metallic vessel by carrying out ultrasonic cleaning of the metallic vessel while using a semi-aqueous cleaning liquid containing at least diethylene glycol alkyl ether, sodium xylene sulfonate and sodium silicate.

Description

  The present invention relates to a cleaning method for a metal container and a resin molded product, and more particularly, to a cleaning method for a metal container and a resin molded product that can easily remove the attached photosensitive composition.

  Photosensitive compositions including colored resist compositions, protective film compositions, and insulating film compositions that are cured by irradiation with light rays such as ultraviolet rays and radiation include color filters and display panel spacers. It is generally used as a material for manufacturing electronic device parts such as thin film transistor (TFT) type liquid crystal display elements (see, for example, Patent Documents 1 to 3).

  For example, the colored resist composition is a resist composition colored by containing a colorant such as a pigment, and is a photosensitive composition that is cured when irradiated with radiation or the like. The protective film composition or the insulating film composition is a colorless organic composition that is not particularly colored, and is a photosensitive composition that is cured by irradiation with radiation or the like, similar to the colored resist composition. is there. Such a photosensitive composition is generally stored, transported, etc. while being contained in a metal container.

  When the photosensitive composition is taken out from the metal container and used, a part of the removed photosensitive composition may spill out and adhere to the outside of the metal container. The photosensitive composition adhering to the outside of the metal container volatilizes the solvent contained therein to form a film or hardens due to the influence of illumination light, etc., so it adheres firmly to the outside of the metal container as dirt. To do. On the other hand, a resin inner bag is accommodated in the metal container, and the photosensitive composition is often contained in the metal container in a state of being filled in the resin inner bag. In such a case, since there is a resin inner bag, the photosensitive composition is unlikely to adhere to the inside of the metal container. However, depending on usage, the resin inner bag may be damaged, and the photosensitive composition may spill inside the metal container and adhere firmly as dirt like the outside. The photosensitive composition also adheres as dirt to resin accessories used with the metal container, such as resin molded products such as tubes and O-rings.

  Examples of the cleaning method for removing the photosensitive composition attached to the metal container and its accessories include a manual method such as brushing or wiping using a volatile organic solvent. However, in manual cleaning, the cleaning efficiency is not necessarily high, and it is necessary to improve the cleaning efficiency. In addition, although the cleaning efficiency is improved by mechanical cleaning using an organic solvent, there is an inconvenience that a large and special facility such as an explosion-proof facility is indispensable, and it is difficult to treat the waste liquid generated by the cleaning. There's a problem.

  As a cleaning method for efficiently removing the photosensitive composition while eliminating these problems, a cleaning method using a so-called quasi-aqueous cleaning liquid that contains an organic compound that is relatively accustomed to water and has a high polarity as a cleaning component. Can be mentioned. As a related art, a cleaning method using a cleaning liquid composed of a specific amino alcohol and a polar organic solvent (for example, see Patent Document 4), a cleaning liquid containing a glycol ether organic solvent and a cleaning method using the same (for example, a patent) Documents 5 to 7) are disclosed.

However, with the cleaning methods disclosed in these patent documents, the cleaning effect is not always sufficient, and it may be necessary to rely on manual work. For this reason, there is a need to develop an unnecessary cleaning method such as an explosion-proof facility that can obtain a sufficient cleaning effect without relying on manual work.
Japanese Patent Laid-Open No. 10-260309 JP 2001-151829 A JP 2001-354822 A JP 2004-66155 A JP 2003-171692 A JP 2003-171694 A JP 2003-201498 A

  The present invention has been made in view of such problems of the prior art, and the problem is that the photosensitive composition as a contaminant attached to the object to be cleaned is easily removed by cleaning. Provides cleaning methods for metal containers and resin molded products with sufficient consideration for the environment, which does not require special equipment such as explosion-proof equipment and is easy to handle cleaning waste liquid. There is to do.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors can achieve the above-mentioned problems by using a semi-aqueous cleaning liquid containing at least a component such as diethylene glycol alkyl ether as a cleaning liquid under specific conditions. The inventors have found that this is possible and have completed the present invention.

  That is, according to the present invention, the following metal container cleaning method and resin molded product cleaning method are provided.

  [1] A step of removing the photosensitive composition adhering to the metal container by ultrasonic cleaning using a semi-aqueous cleaning solution containing at least diethylene glycol alkyl ether, sodium xylene sulfonate, and sodium silicate. For cleaning metal containers including

  [2] The method for cleaning a metal container according to [1], wherein the diethylene glycol alkyl ether is diethylene glycol monobutyl ether, and the concentration of the diethylene glycol monobutyl ether in the cleaning liquid is 0.05 to 10% by mass.

  [3] The method for cleaning a metal container according to [2], wherein a ratio of the amount of the sodium xylene sulfonate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass.

  [4] The metal container according to [2] or [3], wherein a ratio of the amount of the sodium silicate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass. Cleaning method.

  [5] The method for cleaning a metal container according to any one of [1] to [4], wherein the cleaning liquid has a solid content concentration of 0.1 to 30% by mass.

  [6] The metal according to any one of [1] to [5], wherein the temperature of the cleaning liquid is 40 to 80 ° C., the pH is 10 to 12.5, and ultrasonic cleaning is performed for 0.5 to 60 minutes. How to clean the container.

  [7] The method for cleaning a metal container according to any one of [1] to [6], wherein the photosensitive composition is a colored resist composition, a protective film composition, or an insulating film composition.

[8] A resin comprising a step of removing a photosensitive composition adhering to a resin molded article by washing with a semi-aqueous washing solution containing at least diethylene glycol alkyl ether , sodium xylene sulfonate, and sodium silicate. Cleaning method for molded products.

  [9] The method for cleaning a resin molded product according to [8], wherein the diethylene glycol alkyl ether is diethylene glycol monobutyl ether, and the concentration of the diethylene glycol monobutyl ether in the cleaning liquid is 0.05 to 10% by mass.

  [10] The method for cleaning a resin molded product according to [9], wherein a ratio of the amount of the sodium xylene sulfonate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass.

  [11] The resin molded article according to [9] or [10], wherein a ratio of the amount of the sodium silicate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass. Cleaning method.

  [12] The method for cleaning a resin molded product according to any one of [8] to [11], wherein the cleaning liquid has a solid content concentration of 0.1 to 30% by mass.

  [13] The resin molded product according to any one of [8] to [12], wherein the temperature of the cleaning liquid is 40 to 80 ° C., the pH is 10 to 12.5, and the cleaning is performed for 0.5 to 60 minutes. Cleaning method.

  [14] The method for cleaning a resin molded product according to any one of [8] to [13], wherein ultrasonic cleaning is performed using the cleaning liquid.

  [15] The method for cleaning a resin molded product according to any one of [8] to [14], wherein the photosensitive composition is a colored resist composition, a protective film composition, or an insulating film composition.

  According to the metal container cleaning method of the present invention, it is possible to easily remove the photosensitive composition as a contaminant adhering to the object to be cleaned without requiring special equipment such as explosion-proof equipment. It is. In addition, the metal container cleaning method of the present invention is easy to process the cleaning waste liquid, and is sufficiently considered for the influence on the environment.

In addition, according to the method for cleaning a resin molded product of the present invention, the photosensitive composition as a contaminant adhering to the object to be cleaned can be easily removed by cleaning without requiring special equipment such as explosion-proof equipment. Is possible. In addition, the method for cleaning a resin molded product of the present invention is easy to treat the cleaning waste liquid, and is sufficiently considered for the influence on the environment.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

  One embodiment of the method for cleaning a metal container of the present invention uses a semi-aqueous cleaning liquid containing at least diethylene glycol alkyl ether, sodium xylene sulfonate, and sodium silicate as the photosensitive composition attached to the metal container. And it is a cleaning method including the process of removing by performing ultrasonic cleaning. The details will be described below.

  In the metal container cleaning method of the present embodiment, the shape of the metal container to be cleaned, the type of metal constituting the metal container, and the like are not particularly limited. As an example of a metal container, there can be mentioned a container having a shape such as a so-called Ito can or a drum can. Examples of suitable metals constituting the metal container include stainless steel, aluminum, and carbon steel. As a more specific example of the metal container, a canister can 1 having a shape as shown in FIG. The canister 1 is a metal container capable of accommodating a resin inner bag for filling a photosensitive composition therein, and a container body 4 and an upper portion disposed in the container body 4. Similarly to the protector 3a and the lower protector 3b, the container body 4 is provided with an injection / discharge port portion 2a for injecting / discharging the contents and a sealing plug 2b. The photosensitive composition tends to adhere mainly around the upper surface of the container body 4, the upper protector 3a, or the inlet / outlet port portion 2a and the sealing plug 2b in which screw grooves are formed. According to the method for cleaning a metal container of the present embodiment, even a photosensitive composition attached to a part having a complicated shape such as a screw groove that is difficult to remove by manual work can be effectively cleaned and removed. .

  The cleaning liquid used in the metal container cleaning method of this embodiment is a cleaning liquid containing at least diethylene glycol alkyl ether, sodium xylene sulfonate, and sodium silicate. When ultrasonic cleaning is performed using this cleaning liquid, the photosensitive composition stuck to the surface of the metal container can be effectively removed. In addition, diethylene glycol alkyl ether is a kind of polar organic solvent and is easy to be familiar with water, and for a cleaning liquid (quasi-aqueous cleaning liquid) containing this, it is easy to treat waste water after cleaning. That is, the washed liquid (waste liquid) after washing can be easily discarded by performing oil / water separation and pH adjustment, or by separating the solid content using a filter or the like.

  If the concentration of diethylene glycol alkyl ether in the entire cleaning solution is too high, the solubility of the resist composition in the solvent increases, and recycling tends to be difficult. Further, the alkyl group constituting the diethylene glycol alkyl ether is preferably an n-butyl group from the viewpoint of cleaning effect. That is, the diethylene glycol alkyl ether is preferably diethylene glycol monobutyl ether.

  When the diethylene glycol alkyl ether contained in the cleaning liquid is diethylene glycol monobutyl ether, the concentration of the diethylene glycol monobutyl ether in the cleaning liquid is preferably 0.05 to 10% by mass, and preferably 0.1 to 2% by mass. It is further more preferable and it is especially preferable that it is 0.3-1 mass%. When the concentration of diethylene glycol monobutyl ether in the cleaning liquid is less than 0.05% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, if it exceeds 10% by mass, the solubility of the resist composition in the solvent increases and recycling tends to be difficult.

  The ratio of the amount of sodium xylene sulfonate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is preferably 10 to 150% by mass, more preferably 30 to 100% by mass, and 50 to 50%. It is especially preferable that it is 80 mass%. When the ratio of the amount of sodium xylene sulfonate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is 10% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, if it exceeds 150% by mass, the required cleaning time tends to be longer.

  The ratio of the amount of sodium silicate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is preferably 10 to 150% by mass, more preferably 30 to 100% by mass, and 50 to 80% by mass. It is particularly preferred that When the ratio of the amount of sodium silicate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is 10% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, if it exceeds 150% by mass, the required cleaning time tends to be longer.

  In the method for cleaning a metal container of the present embodiment, it is preferable to use a cleaning liquid having a solid content concentration of 0.1 to 30% by mass, and more preferably to use a cleaning liquid of 0.2 to 20% by mass, It is particularly preferable to use 0.5 to 5% by weight of cleaning liquid. When the solid content concentration of the cleaning liquid is less than 0.1% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, when the solid content concentration of the cleaning liquid is more than 30% by mass, the solubility of the photosensitive composition in the solvent increases, and recycling tends to be difficult. The “solid content of the cleaning liquid” referred to in the present specification refers to components other than moisture among all the components contained in the cleaning liquid. Accordingly, the “solid content” includes not only a solid component at normal temperature but also a liquid component at normal temperature.

  In the method for cleaning a metal container according to the present embodiment, a semi-aqueous cleaning liquid that substantially does not contain a volatile organic solvent is used, so that a large and special facility such as an explosion-proof facility is not required for cleaning. Therefore, the metal container cleaning method of the present embodiment has an advantage that it can be carried out in a simple facility / facility. In the present embodiment, from the viewpoints of cleaning effect, ease of processing of cleaning waste liquid, and the need for explosion-proof equipment, as specific examples of cleaning liquid that can be suitably used, the trade name “Blue Gold J-100”, “Blue Gold J-200” (manufactured by Modern Chemical Co., Ltd.) and the like can be mentioned.

  In the metal container cleaning method of the present embodiment, the temperature of the cleaning liquid is preferably 40 to 80 ° C, more preferably 50 to 70 ° C, and particularly preferably 55 to 65 ° C. If the temperature of the cleaning liquid is less than 40 ° C., the cleaning effect may not be sufficient. Moreover, when the liquid temperature of the cleaning liquid is higher than 80 ° C., the cleaning effect is sufficiently exerted, but the energy cost tends to be disadvantageous.

  In the metal container cleaning method of the present embodiment, the pH of the cleaning liquid is preferably 10 to 12.5, more preferably 11 to 12, and particularly preferably 11.5 to 12. preferable. When the pH of the cleaning liquid is less than 10, there is a tendency that the cleaning is insufficient. On the other hand, if the pH of the cleaning liquid is more than 12.5, the degree of cleaning becomes difficult to change, while equipment for a rinsing process, which is a subsequent process for washing off the cleaning liquid, tends to increase.

  In the metal container cleaning method of this embodiment, ultrasonic cleaning is preferably performed for 0.5 to 60 minutes, more preferably 5 to 40 minutes, and particularly preferably 10 to 30 minutes. If the ultrasonic cleaning time is less than 3 minutes, the cleaning effect may not be sufficient. Further, if the ultrasonic cleaning time is more than 60 minutes, the cleaning effect is sufficiently exerted, but the energy cost tends to be disadvantageous.

  In the cleaning method for a metal container according to this embodiment, the photosensitive composition as a contaminant attached to the metal container is a colored resist composition, a protective film composition, or an insulating film composition. Is preferably employed. Examples of the color resist composition include color filters containing a colorant containing an azo pigment and / or a diketone compound, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. Mention may be made of radiation compositions. More specifically, predetermined pigments (for example, Color Index (CI; issued by The Society of Dyers and Colorists) Pigment Yellow 150, CI Pigment Yellow 155, CI Pigment Green 36, C Pigment Red 254), methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, dipentaerythritol pentaacrylate, 2,2'-bis (2-chlorophenyl) -4,4 ', Examples include a mixture of 5,5′-tetraphenylbiimidazole and 4,4′-bis (diethylamino) benzophenone dissolved in ethylene glycol monoethyl ether acetate.

  Examples of the protective film composition include copolymerization of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, an epoxy group-containing unsaturated compound, and a specific olefinically unsaturated compound, and ethylenically unsaturated. The radiation sensitive resin composition containing the polymeric compound which has a coupling | bonding, a radiation sensitive polymerization initiator, and cyclohexanone can be mentioned. More specifically, 2,2′-azobis (2,4-dimethylvaleronitrile), styrene, methacrylic acid, dicyclopentanyl methacrylate, and glycidyl methacrylate (and propylene glycol monomethyl ether acetate and / or 1,4- Butadiene), KAYARAD DPHA (trade name (manufactured by Nippon Kayaku Co., Ltd.)), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure) 369 (trade name (manufactured by Ciba Specialty Chemicals))) and the like dissolved in cyclohexanone.

  Further, the insulating film composition includes an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, an epoxy group-containing unsaturated compound, a maleimide monomer, and a copolymer of other olefinic unsaturated compounds, 1 , 2-quinonediazide compounds, and radiation sensitive resin compositions. More specifically, 2,2′-azobis (2,4-dimethylvaleronitrile), styrene, methacrylic acid, glycidyl methacrylate, and phenylmaleimide (and p-vinylbenzyl glycidyl ether and / or 1,3-butadiene) ) And a mixture of 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester in diethylene glycol ethyl methyl ether. .

  Next, further details of the metal container cleaning method of the present embodiment will be described with reference to the drawings. FIG. 2 is a cross-sectional view schematically showing an example of a process for cleaning the metal container, and shows a state in which the plurality of metal containers 10 are sequentially cleaned by a flow operation. The metal container 10 to which the photosensitive composition is adhered is cleaned in the presence of a predetermined cleaning liquid in a cleaning process 12 including an ultrasonic transducer 20 that is an ultrasonic wave generation source. Here, prior to the cleaning step 12, it is preferable to provide a preliminary immersion step 11 in which the metallic container 10 is pre-immersed in the cleaning liquid because the attached photosensitive composition can be swollen and a higher cleaning effect can be obtained. .

  The metal container 10 that has finished the cleaning process 12 is a rinsing process 13 in which the cleaning liquid is poured off with water or the like according to the direction of the arrow in FIG. 2, and a drying process in which the metal container 10 is dried by blowing an air flow or the like. 14 may be sequentially advanced. The metal container 10 that has finished the drying process 14 proceeds to the unloading tray 16 through the unloading unit 15.

  Next, an embodiment of the method for cleaning a resin molded product of the present invention will be described. One embodiment of the method for cleaning a resin molded product of the present invention uses a semi-aqueous cleaning solution containing at least diethylene glycol alkyl ether, sodium xylene sulfonate, and sodium silicate as the photosensitive composition attached to the resin molded product. Then, it is a method for cleaning a resin molded product including a step of removing by washing. The details will be described below.

  The shape of the resin molded product to be cleaned in the resin molded product cleaning method of the present embodiment is not particularly limited. For example, from a simple shape such as a cup shape, a ring shape, and a tube shape, complex shapes such as various attachment parts can be exemplified. More specifically, a dip tube 35 composed of a coupling 31 and a tube 32 having a shape as shown in FIG. 3, an O-ring 40, and the like can be given. These molded articles are so-called accessories that are used in the canister can 1 (see FIG. 1). Further, the type of resin constituting the resin molded product to be cleaned is not particularly limited, and examples of suitable resins include fluororesin, polyethylene, and nylon. According to the method for cleaning a resin molded product of this embodiment, even a photosensitive composition attached to a resin molded product having a complicated shape that is difficult to remove by manual work can be effectively cleaned and removed.

  The cleaning liquid used in the method for cleaning a resin molded product of the present embodiment is a cleaning liquid containing at least diethylene glycol alkyl ether, sodium xylene sulfonate, and sodium silicate. When the cleaning liquid is used for cleaning, the photosensitive composition sticking to the surface of the resin molded product can be effectively removed. In addition, diethylene glycol alkyl ether is a kind of polar organic solvent and is easily compatible with water, and a cleaning liquid containing this (quasi-aqueous cleaning liquid) can easily treat waste water after cleaning. That is, the washed liquid (waste liquid) after washing can be easily discarded by performing oil / water separation and pH adjustment, or by separating the solid content using a filter or the like. The alkyl group constituting the diethylene glycol alkyl ether is preferably an n-butyl group from the viewpoint of cleaning effect. That is, the diethylene glycol alkyl ether is preferably diethylene glycol monobutyl ether.

  When the diethylene glycol alkyl ether contained in the cleaning liquid is diethylene glycol monobutyl ether, the concentration of the diethylene glycol monobutyl ether in the cleaning liquid is preferably 0.05 to 10% by mass, and preferably 0.1 to 2% by mass. It is further more preferable and it is especially preferable that it is 0.3-1 mass%. When the concentration of diethylene glycol monobutyl ether in the cleaning liquid is less than 0.05% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, if it exceeds 10% by mass, the solubility of the resist composition in the solvent increases and recycling tends to be difficult.

  The ratio of the amount of sodium xylene sulfonate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is preferably 10 to 150% by mass, more preferably 30 to 100% by mass, and 50 to 50%. It is especially preferable that it is 80 mass%. When the ratio of the amount of sodium xylene sulfonate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is 10% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, if it exceeds 150% by mass, the required cleaning time tends to be longer.

  The ratio of the amount of sodium silicate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is preferably 10 to 150% by mass, more preferably 30 to 100% by mass, and 50 to 80% by mass. It is particularly preferred that When the ratio of the amount of sodium silicate to the amount of diethylene glycol monobutyl ether contained in the cleaning liquid is 10% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, if it exceeds 150% by mass, the required cleaning time tends to be longer.

  In the resin molded product cleaning method of the present embodiment, it is preferable to use a cleaning liquid having a solid content concentration of 0.1 to 30% by mass, and more preferably 0.2 to 20% by mass. It is particularly preferable to use 0.5 to 5% by weight of cleaning liquid. When the solid content concentration of the cleaning liquid is less than 0.1% by mass, the cleaning effect tends to be hardly exhibited. On the other hand, when the solid content concentration of the cleaning liquid is more than 30% by mass, the solubility of the photosensitive composition in the solvent increases, and recycling tends to be difficult.

  The resin molded product cleaning method of the present embodiment uses a semi-aqueous cleaning liquid that does not substantially contain a volatile organic solvent, and therefore does not require large and special equipment such as explosion-proof equipment. Therefore, the method for cleaning a resin molded product according to this embodiment has an advantage that it can be carried out in a simple facility / facility. In the present embodiment, from the viewpoints of cleaning effect, ease of processing of cleaning waste liquid, and the need for explosion-proof equipment, as specific examples of cleaning liquid that can be suitably used, the trade name “Blue Gold J-100”, “Blue Gold J-200” (manufactured by Modern Chemical Co., Ltd.) and the like can be mentioned.

  In the resin molded product cleaning method of the present embodiment, the temperature of the cleaning liquid is preferably 40 to 80 ° C, more preferably 50 to 70 ° C, and particularly preferably 55 to 65 ° C. If the temperature of the cleaning liquid is less than 40 ° C., the cleaning effect may not be sufficient. Moreover, when the liquid temperature of the cleaning liquid is higher than 80 ° C., the cleaning effect is sufficiently exerted, but the energy cost tends to be disadvantageous.

  In the method for cleaning a resin molded product according to this embodiment, the pH of the cleaning liquid is preferably 10 to 12.5, more preferably 11 to 12, and particularly preferably 11.5 to 12. preferable. When the pH of the cleaning liquid is less than 10, there is a tendency that the cleaning is insufficient. On the other hand, if the pH of the cleaning liquid is more than 12.5, the degree of cleaning becomes difficult to change, while equipment for a rinsing process, which is a subsequent process for washing off the cleaning liquid, tends to increase.

  In the method for cleaning a resin molded product according to the present embodiment, the specific mode of the cleaning method performed using the above-described cleaning liquid is not particularly limited. For example, a sufficient cleaning effect can also be obtained by a method in which an object to be cleaned is immersed in a cleaning liquid and cleaned (immersion cleaning). Also suitable is a method in which manual cleaning using a cleaning tool such as a brush or spatula is used in combination with the above-described immersion cleaning, or a method in which a resin molded product (object to be cleaned) is ultrasonically cleaned in a state of being immersed in a cleaning liquid. As an example. Among these, in the method for cleaning a resin molded product according to the present embodiment, ultrasonic cleaning is performed in a state where the resin molded product (object to be cleaned) is immersed in a cleaning liquid. This is more preferable because the composition can be more effectively cleaned and removed. The ultrasonic cleaning is preferably performed for 0.5 to 60 minutes, more preferably 5 to 40 minutes, and particularly preferably 10 to 30 minutes. If the ultrasonic cleaning time is less than 3 minutes, the cleaning effect may not be sufficiently improved. Further, if the ultrasonic cleaning time is more than 60 minutes, the cleaning effect is sufficiently exerted, but the energy cost tends to be disadvantageous.

  In the method for cleaning a resin molded product of the present embodiment, the photosensitive composition as a contaminant attached to the resin molded product is a colored resist composition, a protective film composition, or an insulating film composition. Is preferably employed. Specific examples of the colored resist composition, the protective film composition, and the insulating film composition include the same ones as exemplified in the above-described method for cleaning a metal container.

  Next, further details of the resin molded product cleaning method of the present embodiment will be described. The resin molded product to which the photosensitive composition is adhered is cleaned in a state where the entire resin molded product is immersed in a predetermined cleaning solution. It is not necessary to wash the resin molded products one by one, and a plurality of resin molded products can be washed together. Specifically, a plurality of resin molded products can be cleaned by immersing them in a cleaning solution in a state where they are put together in a net or a basket. As described above, it is preferable to perform ultrasonic cleaning in a state where the resin molded article is immersed in a cleaning liquid because the attached photosensitive composition can be removed and a higher cleaning effect can be obtained.

  After the cleaning is completed, the cleaning liquid may be poured off with water or the like, and then the resin molded product may be dried by blowing an air flow or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

(1) Cleaning metal containers

Example 1
Canister 1 made of stainless steel having a shape as shown in FIG. 1 (H ₁ (total height of can) = 470 mm, H ₂ (effective height of can) = 400 mm, D (can diameter) = 280 mm, capacity = 19 L, mass = 5 kg The diameter of the inlet / outlet part 2 = 50.8 mmφ, the thickness of the container body 4 = 1.0 mm, the thickness of the upper protector 3a = 0.8 mm, the thickness of the lower protector 3b = 1.0 mm), and the can A resist composition was adhered to the inner and outer surface portions. "Blue Gold J-100" (trade name (manufactured by Modern Chemical Co., Ltd.)) diluted with water to 7% by volume (pH = 11.5, liquid temperature = 65 ° C.) is used as a cleaning (agent) liquid, In a state where the canister 1 was immersed in this cleaning (agent) solution, ultrasonic cleaning was performed for 10 minutes while applying an ultrasonic wave of 28 kHz. The resulting wastewater was treated as industrial waste after separating the solids using a filter. The resist composition includes C.I. I. Pigment yellow 83 and C.I. I. 80 parts by mass of a 17/83 (mass ratio) mixture of CI Pigment Green 36 and a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization mass ratio = 25/65/10, weight average molecular weight = 55,000) 50 Parts by weight, 40 parts by weight of dipentaerythritol pentaacrylate, 10 parts by weight of 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 4,4′-bis A mixture prepared by dissolving 10 parts by mass of (diethylamino) benzophenone in 800 parts by mass of ethylene glycol monoethyl ether acetate was used.

  The solid concentration of the cleaning liquid (agent) prepared by diluting “Blue Gold J-100” (trade name (manufactured by Modern Chemical Co., Ltd.) with water to 7% by volume is 1.5% by mass. Further, this cleaning liquid (agent) contains 0.57% by mass of diethylene glycol monobutyl ether, 0.44% by mass of sodium xylene sulfonate, and 0.39% by mass of sodium silicate.

(Example 2, Comparative Examples 1-12)
The canister can 1 was cleaned in the same manner as in Example 1 except that the cleaning (agent) solutions shown in Tables 1 and 2 were used and the cleaning method shown in Tables 1 and 2 was used. In Table 2, “Composition (1)” is 90% by mass of ethylene glycol monobutyl ether, 0.03% by mass of ammonium fluoride, and the balance is water detergent. It is a cleaning agent having the same composition as the cleaning agent disclosed in the examples of the publication. In the description of Table 2, “Composition (2)” refers to a 25% by weight aqueous solution of diethylene glycol monobutyl ether, a 25% by weight aqueous solution of triethylene glycol monomethyl ether, and a 10% by weight aqueous solution of NH ₄ OH, 1: 1: 0. A cleaning agent obtained by mixing at a volume ratio of .4, and having the same composition as the cleaning agent disclosed in the examples of JP-A-2003-171694. Hereinafter, “Composition (1)” and “Composition (2)” in each table are used in the same meaning as described above.

(Example 3, Comparative Examples 13-17)
Instead of the resist composition, the protective film composition was adhered to the canister 1. Thereafter, the canister can 1 was cleaned in the same manner as in Example 1 except that the cleaning (agent) liquid shown in Table 3 was used and the cleaning method shown in Table 3 was used. In addition, what was shown below was used as a composition for protective films.

  [Protective film composition]: A flask equipped with a condenser and a stirrer was charged with 6 parts by mass of 2,2'-azobis (isobutyronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by mass of styrene, 65 parts by mass of glycidyl methacrylate, and 15 parts by mass of N-phenylmaleimide were charged and purged with nitrogen, and then gently stirred. The solution was kept at a temperature of 95 ° C. for 4 hours to obtain a copolymer solution containing the copolymer (solid content concentration: 32.8% by mass). After the obtained copolymer solution (corresponding to 100 parts by mass (solid content) of the copolymer) was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, a cyclic aliphatic epoxy resin (trade name “Epicoat 1032H60”, (Oilized Shell Epoxy Co., Ltd.) 20 parts by mass, γ-glycidoxypropyldiethoxysilane 5 parts by mass, and fluorosurfactant (trade name “Megafac 172”, manufactured by Dainippon Ink & Chemicals, Inc.) 0.02 A part by mass was added as a main ingredient, and further, 20 parts by mass of trimellitic anhydride in terms of solid content was added as a diethylene glycol methyl ethyl ether solution (25% by mass concentration). Then, the composition for protective films was obtained by fully stirring. This protective film composition is the same as the curable composition described in Example 1 of JP-A-2001-158816.

(Example 4, Comparative Examples 18-22)
Instead of the resist composition, the insulating film composition was adhered to the canister 1. Thereafter, the canister 1 was cleaned in the same manner as in Example 1 except that the cleaning (agent) liquid shown in Table 4 was used and the cleaning method shown in Table 4 was used. In addition, what was shown below was used as a composition for insulating films.

  [Insulating film composition]: A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by mass of methacrylic acid, 38 parts by mass of dicyclopentanyl methacrylate, 40 parts by mass of glycidyl methacrylate, and 1.5 parts by mass of α-methylstyrene dimer were charged, and gently stirring was started while replacing with nitrogen. The temperature of the solution was raised to 70 ° C. for 5 hours to obtain a copolymer solution containing the copolymer (solid content concentration: 31.2% by mass). The weight average molecular weight of the copolymer was 18500, and the molecular weight distribution was 1.8. The weight average molecular weight is an average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography) (trade name “HLC-8020”, manufactured by Tosoh Corporation). The obtained copolymer solution (corresponding to 100 parts by weight (solid content) of the copolymer) and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl ] Ethylidene] condensate of bisphenol (1 mol) and 1,2-naphthoquinonediazide-6-sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1- 30 parts by weight of methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester) and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed. After dissolving in propylene glycol monomethyl ether acetate so that the solid content concentration was 30% by mass, the solution was filtered through a Millipore filter having a pore size of 0.5 μm to prepare an insulating film composition solution. In addition, the solution of this composition for insulating films is the same as the solution of the radiation sensitive resin composition described in Example 1 of Unexamined-Japanese-Patent No. 2001-240757.

(Example 5, Comparative Examples 23 to 27)
Instead of the resist composition, the spacer composition was adhered to the canister 1. Thereafter, the canister can 1 was cleaned in the same manner as in Example 1 except that the cleaning (agent) solution shown in Table 5 was used and the cleaning method shown in Table 5 was used. In addition, what was shown below was used as a composition for spacers.

[Composition for spacer]: A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 20 parts by mass of methacrylic acid, 45 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, and 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate were charged, and the atmosphere was replaced with nitrogen. After that, stirring was started gently. The temperature of the solution was raised to 70 ° C. for 5 hours to obtain a copolymer solution containing the copolymer (solid content concentration: 33.2% by mass). The weight average molecular weight of the copolymer was 24,000. The weight average molecular weight is an average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography) (trade name “HLC-8020”, manufactured by Tosoh Corporation). The obtained copolymer solution (corresponding to 100 parts by weight of copolymer (solid content)), 80 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and the following structural formula (1) 25 parts by mass of a photopolymerization initiator was mixed. After dissolving in propylene glycol monomethyl ether acetate so that the solid content concentration was 35% by mass, the solution was filtered through a Millipore filter having a pore diameter of 0.2 μm to prepare a spacer composition solution. In addition, the solution of this composition for spacers is the same as the composition solution described in Example 1 of Unexamined-Japanese-Patent No. 2001-261661.

(Evaluation method of cleaning effect)
The cleaning effect was evaluated in three stages by visual observation according to the following criteria. The evaluation results are shown in Tables 1-5.
○: Remaining residue is not visible (can be cleaned by 99% (area ratio) or more)
Δ: Remaining residue can be visually recognized (approximately 50 to less than 99% (area ratio) can be cleaned)
×: Remaining residue visible (generally less than 50% (area ratio) washable)

(Discussion)
As shown in Tables 1 to 5, in Examples 1 to 5, it was confirmed that an excellent cleaning effect was exhibited as compared with Comparative Examples 1 to 27.

(2) Cleaning resin molded products

(Example 6)
As an object to be cleaned, a coupling, a tube, and an O-ring (all made of a fluororesin) having a shape as shown in FIG. 3 are prepared, and the same resist composition as that used in Example 1 is provided on the surface. Was attached. "Blue Gold J-100" (trade name (manufactured by Modern Chemical Co., Ltd.)) diluted with water to 7% by volume (pH = 11.5, liquid temperature = 65 ° C.) is used as a cleaning (agent) liquid, With the object to be cleaned immersed in this cleaning (agent) solution, ultrasonic cleaning was performed for 20 minutes while applying 28 kHz ultrasonic waves. The resulting wastewater was treated as industrial waste after separating the solids using a filter.

(Examples 7 and 8)
Instead of ultrasonic cleaning, the cleaning target (coupling, tube, and O-ring) was cleaned in the same manner as in Example 6 except that cleaning was performed using a spray nozzle. The cleaning liquid (agent) prepared by diluting “Blue Gold J-200” (trade name (manufactured by Modern Chemical Co.)) to 7% by volume with water used in Example 8 includes diethylene glycol monobutyl ether and xylene. Sodium sulfonate and sodium silicate are included.

(Comparative Examples 28-33)
The object to be cleaned (coupling, tube, and O-ring) was used in the same manner as in Example 6 except that the cleaning (agent) solution shown in Table 6 was used and cleaning was performed by the cleaning method shown in Table 6. Was washed.

(Evaluation method of cleaning effect)
The cleaning effect was evaluated in three stages by visual observation according to the following criteria. The evaluation results are shown in Table 6.
○: Remaining residue is not visible (can be cleaned by 99% (area ratio) or more)
△: Residue can be visually recognized (50 to less than 99% (area ratio) can be washed)
×: Remaining residue visible (less than 50% (area ratio) can be washed)

(Discussion)
As shown in Table 6, in Examples 6-8, it was confirmed that an excellent cleaning effect was exhibited as compared with Comparative Examples 28-33.

  The metal container cleaning method and the resin molded product cleaning method of the present invention efficiently clean a metal container to which a photosensitive composition as a contaminant easily adheres and a resin molded product that is an accessory thereof. It is suitable as a method.

It is sectional drawing which shows typically the canister can which is an example of metal containers. It is sectional drawing which shows typically an example of the process of wash | cleaning metal containers. It is sectional drawing which shows an example of a dip tube typically.

Explanation of symbols

1: canister can, 2a: inlet / outlet part, 2b: sealing stopper, 3a: upper protector, 3b: lower protector, 4: container body, 10: metal container, 11: preliminary immersion process, 12: washing process, 13: Rinsing process, 14: Drying process, 15: Unloading part, 16: Unloading base, 20: Ultrasonic vibrator, 31: Coupling, 32: Tube, 35: Dip tube, 40: O-ring, H ₁ : Overall height of can, H ₂ : Effective height of can, D: Can diameter

Claims (15)

  A metal comprising a step of removing a photosensitive composition attached to a metal container by ultrasonic cleaning using a semi-aqueous cleaning liquid containing at least diethylene glycol alkyl ether, sodium xylene sulfonate, and sodium silicate. How to clean the container. The diethylene glycol alkyl ether is diethylene glycol monobutyl ether;
The method for cleaning a metal container according to claim 1, wherein the concentration of the diethylene glycol monobutyl ether in the cleaning liquid is 0.05 to 10% by mass.   The method for cleaning a metal container according to claim 2, wherein a ratio of the amount of the sodium xylene sulfonate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass.   The method for cleaning a metal container according to claim 2 or 3, wherein a ratio of the amount of the sodium silicate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass.   The metal container cleaning method according to any one of claims 1 to 4, wherein the cleaning liquid has a solid content concentration of 0.1 to 30% by mass.   The washing | cleaning of the metal container as described in any one of Claims 1-5 whose liquid temperature of the said washing | cleaning liquid is 40-80 degreeC, pH is 10-12.5, and ultrasonic cleaning is performed for 0.5 to 60 minutes. Method.   The method for cleaning a metal container according to claim 1, wherein the photosensitive composition is a colored resist composition, a protective film composition, or an insulating film composition. A resin molded article comprising a step of removing a photosensitive composition adhering to a resin molded article by washing with a semi-aqueous washing liquid containing at least diethylene glycol alkyl ether , sodium xylene sulfonate, and sodium silicate . Cleaning method. The diethylene glycol alkyl ether is diethylene glycol monobutyl ether;
The method for cleaning a resin molded article according to claim 8, wherein the concentration of the diethylene glycol monobutyl ether in the cleaning liquid is 0.05 to 10% by mass.   The method for cleaning a resin molded product according to claim 9, wherein a ratio of the amount of the sodium xylene sulfonate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass.   The method for cleaning a resin molded product according to claim 9 or 10, wherein a ratio of the amount of the sodium silicate to the amount of the diethylene glycol monobutyl ether contained in the cleaning liquid is 10 to 150% by mass.   The method for cleaning a resin molded product according to any one of claims 8 to 11, wherein a solid content concentration of the cleaning liquid is 0.1 to 30% by mass.   The washing | cleaning method of the resin molded product as described in any one of Claims 8-12 with which the liquid temperature of the said washing | cleaning liquid is 40-80 degreeC, pH is 10-12.5, and washing | cleaning is performed for 0.5 to 60 minutes.   The method for cleaning a resin molded product according to any one of claims 8 to 13, wherein the cleaning liquid is used for ultrasonic cleaning.   The method for cleaning a resin molded product according to any one of claims 8 to 14, wherein the photosensitive composition is a colored resist composition, a protective film composition, or an insulating film composition.

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