Resin Dissolving Agent

Abstract

To provide a resin dissolution agent having excellent dissolution removal performance to resins while not being regulated by various laws such as Fire Defense Law and having suppressed influence on human bodes and environmental load.SOLUTION: A resin dissolution agent includes 70-99 mass% of a hydrochlorofluoroolefin (A) and 1-30 mass% of at least one selected from an alkylbenzenesulfonic acid (B1) and a fluoroalkylcarboxylic acid (B2), where the hydrochlorofluoroolefin (A) has a boiling point of 50°C or over and a kauri-butanol value of 40 or over.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin dissolving agent, and more particularly to a dissolving agent for dissolving and removing resins such as silicone. [Background technology]

[0002] Conventionally, resins such as silicone are used in various industrial fields such as chemical industry, mechanical industry, and electrical industry. Such resins may need to be dissolved and removed during or after the manufacturing process. For example, electronic components may be covered with resin for the purpose of protection or insulation. However, there are cases where the resin needs to be removed for the purpose of repair, part replacement, defect analysis, structural analysis, and the like. Furthermore, there are also cases where the purpose is cleaning equipment, jigs, piping, and the like for applying and applying resin. In order to dissolve and remove such resins, for example, dissolving and removing liquids as described in Patent Document 1 and Patent Document 2 are used.

[0003] Incidentally, the dissolving and removing liquids described in Patent Documents 1 and 2 use, as their main components, chlorine-based solvents and aromatic hydrocarbons such as toluene and benzene, taking into consideration the solubility of resins. Such dissolving and removing liquids containing organic solvents as their main components may be subject to various laws and regulations, such as the Fire Service Act and the Industrial Safety and Health Act, and further have problems such as being difficult to handle, having a large impact on the human body, and putting a large burden on the environment. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 4-216880 [Patent Document 2] Japanese Patent Application Publication No. 4-318075 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin dissolving agent that is not subject to various laws and regulations such as the Fire Service Act, has little effect on the human body and has little burden on the environment, and has excellent dissolving and removing performance for resins. [Means for solving the problem]

[0006] As a result of intensive research into solving the above problems, the present inventors have found a solution comprising the following configuration, and have completed the present invention. (1) A resin dissolving agent comprising 70 to 99 mass% of a hydrochlorofluoroolefin (A) and 1 to 30 mass% of at least one of an alkylbenzenesulfonic acid (B1) and a fluoroalkylcarboxylic acid (B2), wherein the hydrochlorofluoroolefin (A) has a boiling point of 50°C or higher and a Kauri-butanol value of 40 or higher. (2) The resin dissolving agent according to the above (1), wherein the hydrochlorofluoroolefin (A) is at least one of (E)-chloro-2,3,3-trifluoropropene and (Z)-chloro-2,3,3-trifluoropropene. (3) The resin dissolving agent according to (1) or (2) above, wherein the alkylbenzenesulfonic acid (B1) is an alkylbenzenesulfonic acid having one or two alkyl groups each having 1 to 18 carbon atoms on the benzene ring. (4) The resin dissolving agent according to the above (3), wherein the alkylbenzenesulfonic acid (B1) is at least one of dodecylbenzenesulfonic acid and xylenesulfonic acid. (5) The resin dissolving agent according to any one of the above (1) to (4), wherein the fluoroalkyl carboxylic acid (B2) is trifluoroacetic acid. (6) The resin dissolving agent according to any one of the above (1) to (5), wherein the resin is one selected from the group consisting of a silicone resin, a urethane resin, an epoxy resin, a polyamide resin and a polyimide resin. Effect of the Invention

[0007] According to the present invention, it is possible to provide a resin dissolving agent that is not subject to various laws and regulations such as the Fire Service Act, has little effect on the human body and puts little strain on the environment, and has excellent dissolving and removing performance for resins. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] A resin dissolving agent (hereinafter, may be simply referred to as "dissolving agent") according to one embodiment of the present disclosure contains a specific hydrochlorofluoroolefin (component (A)) and at least one of an alkylbenzenesulfonic acid (component (B1)) and a fluoroalkylcarboxylic acid (component (B2)). In claim 1

[0009] Hydrochlorofluoroolefins are a type of alternative fluorocarbon, and are fluorine-based compounds that have low environmental impacts, such as ozone depletion potential and global warming potential. Furthermore, hydrochlorofluoroolefins do not fall under various laws and regulations, such as the Fire Service Act's hazardous materials regulations, the Industrial Safety and Health Act's Organic Solvent Poisoning Prevention Regulations (Organic Solvent Regulations) and the Specified Chemical Substances Hazard Prevention Regulations (Specified Chemical Regulations), and have little impact on the human body.

[0010] The dissolving agent according to one embodiment includes, among hydrochlorofluoroolefins, a specific hydrochlorofluoroolefin having a boiling point of 50°C or more and a Kauri-butanol value (KB value) of 40 or more. If a hydrochlorofluoroolefin having a boiling point of less than 50°C is used, for example, when the dissolving agent is used in a high-temperature environment such as summer, the hydrochlorofluoroolefin is likely to volatilize, causing problems such as a decrease in the solubility of the resin and an increase in the viscosity of the liquid. Furthermore, when the dissolving agent is stored or transported in a high-temperature environment such as summer, the use of a pressure-resistant container or transportation in a low-temperature environment is required, which causes a problem that handling conditions such as storage conditions and transportation conditions are limited. The upper limit of the boiling point is not limited. For example, it is preferable to use a hydrochlorofluoroolefin having a boiling point of 100°C or less, in that a certain degree of dryness makes it easier to remove the dissolving agent after dissolution.

[0011] The Kauri-butanol value (KB value) is a numerical value that expresses the resin solubility of a solvent, and generally the higher the value, the higher the solubility. Specifically, a solvent is added to 20g of a solution in which 100g of Kauri gum is dissolved in 500g of butanol, and the KB value is the amount (mL) added when the solution becomes turbid (cloudy). Toluene, which is commonly used as a solvent, has a KB value of 100.

[0012] In one embodiment, among hydrochlorofluoroolefins, a hydrochlorofluoroolefin having a KB value of 40 or more is used as the dissolving agent. If a hydrochlorofluoroolefin having a KB value of less than 40 is used, the solubility of the resin is poor. Although there is no upper limit for the KB value, for example, it is preferable to use a hydrochlorofluoroolefin having a KB value of 80 or less in terms of suppressing toxicity to the human body.

[0013] For component (A), a specific hydrochlorofluoroolefin having a boiling point of 50°C or more and a KB value of 40 or more may be used alone or in combination of two or more. Such a specific hydrochlorofluoroolefin has, for example, 3 or more carbon atoms. Furthermore, such component (A) may have a specific gravity of 1.32 or more. As component (A), preferably, (E)-chloro-2,3,3-trifluoropropene, (Z)-chloro-2,3,3-trifluoropropene, etc. may be mentioned.

[0014] Alkylbenzene sulfonate (component (B1)) is a type of surfactant that is used to improve the solubility of resins. Alkylbenzene sulfonate does not fall under various laws and regulations such as the Poisonous and Deleterious Substances Control Law, the Organic Solvent Poisoning Prevention Regulations (Organic Solvent Regulations) of the Industrial Safety and Health Law, and the Specific Chemical Substances Hazard Prevention Regulations (Specific Chemical Substance Regulations), and has little impact on the environment and human body.

[0015] The alkyl group portion of component (B1) may be a linear alkyl group or a branched alkyl group. In order to further improve the solubility of the resin, the alkyl group portion of component (B1) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, and particularly preferably an alkyl group having 8 to 14 carbon atoms in terms of compatibility and solubility with component (A). Furthermore, as component (B1), alkylbenzenesulfonic acid having one or two such alkyl groups per benzene ring is preferred.

[0016] Preferred examples of the component (B1) include dodecylbenzenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid, and paratoluenesulfonic acid.

[0017] Component (B1) may contain trace amounts of sulfuric acid, sulfates, organic sulfonic acids or their salts that are mixed in or generated as impurities or by-products (unavoidable components) during the manufacturing process. Such unavoidable components may be contained within a range that does not affect the resin solubility. The range that does not affect the resin solubility is not particularly limited, and is preferably less than 1 mass%.

[0018] Fluoroalkyl carboxylic acid (component (B2)) is a type of surfactant, and is used to further improve the solubility of resins. The alkyl group portion of component (B2) may be either a linear alkyl group or a branched alkyl group. From the viewpoints of further improving the solubility of resins and of low toxicity, the alkyl group portion of component (B2) is preferably an alkyl group having 1 to 4 carbon atoms.

[0019] Examples of the component (B2) include monofluoroethaneacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, etc. These fluoroalkyl carboxylic acids do not fall under various laws and regulations such as the Poisonous and Deleterious Substances Control Law, the Organic Solvent Poisoning Prevention Regulation (Organic Solvent Regulation) of the Industrial Safety and Health Law, and the Specified Chemical Substance Hazard Prevention Regulation (Specified Chemical Substance Regulation), and have little impact on the environment and the human body.

[0020] The solubilizing agent according to one embodiment contains 70 to 99% by mass of component (A) and 1 to 30% by mass of at least one of components (B1) and (B2) (hereinafter, "at least one of components (B1) and (B2)" may be simply referred to as "component (B)"). When components (A) and (B) are outside this range, the solubility of the resin is poor. Specifically, when the content of component (A) is less than 70% by mass and the content of component (B) is more than 30% by mass, the content of component (A) is small and the solubility of the resin is poor. On the other hand, when the content of component (B) is less than 1% by mass and the content of component (A) is more than 99% by mass, the content of component (B) used to further improve the solubility of the resin is small and the solubility of the resin is poor. The component (A) is preferably contained in a proportion of 75 to 95% by mass, and the component (B) is preferably contained in a proportion of 5 to 25% by mass.

[0021] The dissolving agent according to one embodiment may contain 1,1,1,3,3-pentafluorobutane (component (C)) as necessary within a range that does not impair the effects of the present invention. By containing component (C), the workability is excellent, the surface tension tends to be reduced, and the resin dissolving and removing performance can be further improved. Component (C) is contained in a ratio of preferably 1 to 100 parts by mass, more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). Component (C) does not fall under various laws and regulations such as hazardous materials under the Fire Service Act, organic solvent poisoning prevention regulations (organic solvent regulations) and specific chemical substance hazard prevention regulations (specialized chemical regulations), and has little effect on the human body.

[0022] Furthermore, the dissolving agent according to one embodiment may contain additives that are generally added to dissolving agents. Examples of such additives include antioxidants, surfactants other than component (B), thickeners, ultraviolet absorbers, and rust inhibitors. These additives are added in the required amount within the range that does not impair the effects of the present invention.

[0023] The method for producing the dissolving agent according to one embodiment is not limited. For example, the component (A) and the component (B) may be mixed in a specific ratio, and the component (C) and other additives may be added as necessary.

[0024] The resin to be dissolved and removed by the dissolving agent according to the embodiment is not limited, and examples thereof include silicone resin, urethane resin, epoxy resin, polyamide resin, polyimide resin, etc. The dissolving agent according to the embodiment can particularly suitably dissolve and remove silicone resin.

[0025] The silicone resin is not limited as long as it is a polymeric compound having a siloxane bond, and examples thereof include silicone oil, silicone grease, silicone varnish, silicone sealant, silicone-based liquid gasket, and silicone rubber.

[0026] The urethane resin is not limited as long as it is a polymer compound having a urethane bond, and examples thereof include urethane rubber, urethane adhesives, and urethane paints.

[0027] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, aliphatic type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a hydantoin ring.

[0028] Polyamide resins are polymeric compounds having amide bonds, and examples thereof include nylon resins, urea resins, melamine resins, etc. Polyimide resins are polymeric compounds having imide bonds.

[0029] The method of using the dissolving agent according to an embodiment is not limited. For example, the resin to be dissolved and removed may be brought into contact with the dissolving agent. The contact time between the resin to be dissolved and removed and the dissolving agent may vary depending on the type of resin, the amount of resin, and the temperature, but may be, for example, about 1 to 1000 minutes. Furthermore, in order to make the resin more easily dissolved, the dissolving agent may be made to flow by stirring or shaking.

[0030] The component (A) contained in the dissolving agent according to one embodiment has a boiling point of 50° C. or more. Therefore, even when the dissolving agent is used in a high-temperature environment such as summer, the component (A) is unlikely to volatilize, and the dissolving agent according to one embodiment exhibits excellent dissolving and removing performance for resins. On the other hand, when the dissolving agent is used in a low-temperature environment such as winter, the dissolving agent according to one embodiment can be used after being heated. EXAMPLES

[0031] EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0032] Example 1 A solvent was obtained by mixing 90% by mass of AMOLEA AS-300 (manufactured by AGC Corporation, a mixture of (E)-chloro-2,3,3-trifluoropropene and (Z)-chloro-2,3,3-trifluoropropene, boiling point 54°C, KB value 44, specific gravity 1.34) as component (A) and 10% by mass of Teika Power B-121 (manufactured by Teika Corporation), whose main component is branched dodecylbenzenesulfonic acid (having one alkyl group with 12 carbon atoms), as component (B1). The various physical properties of the solvent obtained are shown in Table 1.

[0033] Comparative Example 1 A solvent was obtained by mixing 90% by mass of cis-1-chloro-3,3,3-trifluoropropene (product name: CELEFIN1233Z, manufactured by Central Glass Co., Ltd.) and 10% by mass of the above Teika Power B-121. Cis-1-chloro-3,3,3-trifluoropropene (specific gravity 1.29) has a boiling point of 39°C and a KB value of 34. Various physical properties of the solvent obtained are shown in Table 1.

[0034] Comparative Example 2 A solvent was obtained by mixing 80% by mass of isoparaffinic hydrocarbon (product name: IP Solvent 1620, manufactured by Idemitsu Kosan Co., Ltd., boiling point 160°C or higher) and 20% by mass of the above Teika Power B-121. The various physical properties of the obtained solvent are shown in Table 1.

[0035] Comparative Example 3 A solvent was obtained by mixing 80% by mass of kerosene (Idemitsu Kosan Co., Ltd., boiling point 140°C or higher), 10% by mass of linear alkylbenzene sulfonic acid (product name: Teika Power L-121, Teika Corporation), and 10% by mass of the Teika Power B-121. The physical properties of the obtained solvent are shown in Table 1.

[0036] Comparative Example 4 Dichloromethane (boiling point 41° C. and KB value 136) was used as the solvent. Various physical properties are shown in Table 1.

[0037] Comparative Example 5 Toluene (boiling point 111° C. and KB value 100) was used as the solvent. Various physical properties are shown in Table 1.

[0038] The solubility of silicone resin was verified by the following procedure using the dissolving agents obtained in Example 1 and Comparative Examples 1 to 5. First, a silicone resin with no oxime (product name: KE-44, manufactured by Shin-Etsu Chemical Co., Ltd.) and a dealcohol type silicone resin (product name: KE4895, manufactured by Shin-Etsu Chemical Co., Ltd.) were prepared as silicone resins, a 6-nylon resin (product name: MC nylon, manufactured by Mitsubishi Chemical Advanced Materials Co., Ltd.) was prepared as polyamide resins, and a one-liquid curing type urethane resin adhesive (product name: KU928C-X, manufactured by Konishi Co., Ltd.) was prepared as urethane resins, and a thick-film curing reaction was carried out to produce resin pieces. Next, each cured resin was cut into a 1 cm x 1 cm square to prepare a resin sample. The resin sample was placed in a glass petri dish and immersed in the dissolving agents obtained in Example 1 and Comparative Examples 1 to 5, and the solubility was visually evaluated at regular intervals. The results are shown in Table 1.

[0039] <Evaluation criteria> A: When almost completely dissolved in less than 60 minutes. B: When almost completely dissolved in 60 minutes or more but less than 180 minutes. C: Some of the material has dissolved, but some remains undissolved even after 180 minutes or more. D: Almost no dissolution occurred even after 1200 minutes or more.

[0040] [Table 1]

[0041] As shown in Table 1, the dissolving agent obtained in Example 1 does not fall under various laws and regulations such as the Fire Service Act, and it is understood that it has little effect on the human body and puts little strain on the environment. Furthermore, since it is not highly volatile, it can be immersed for a long time, and it is understood that it exhibits excellent dissolving and removing performance for various resins.

[0042] On the other hand, it is found that the solvents obtained in Comparative Examples 1 to 5 fall under various laws and regulations such as the Fire Service Act, are highly volatile, and have poor resin dissolving and removal performance. Comparative Example 1 is excellent in solubility of various resins, but for some resins that take a long time to dissolve, it is too volatile to be immersed for a long time, and its solubility is inferior to that of Example 1.

[0043] Example 2 The solubility of silicone resin was verified by using the dissolving agent obtained in Example 1 in the following procedure. First, a dealcoholized silicone resin (product name: KE4895, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silicone resin. This silicone resin was cured into a thick film to produce a resin piece. Next, the resin piece was cut into a 1 cm x 1 cm square to prepare a resin sample. The resin sample was placed in a glass petri dish and immersed in the dissolving agent obtained in Example 1, and the solubility was visually evaluated at regular intervals. The results are shown in Table 2.

[0044] <Evaluation criteria> A: When completely dissolved in the liquid. B: It has almost completely dissolved and no longer retains its original shape. C: Only partially dissolved. D: Not dissolved at all.

[0045] Example 3 A dissolving agent was obtained in the same manner as in Example 1, except that xylene sulfonic acid (manufactured by Teika Corporation, having two alkyl groups each having one carbon atom) was used as component (B1) instead of Teika Power B-121. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0046] Example 4 A dissolving agent was obtained in the same manner as in Example 3, except that 80% by mass of component (A) and 20% by mass of component (B1) were mixed. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0047] Example 5 A dissolving agent was obtained in the same manner as in Example 3, except that 70% by mass of component (A) and 30% by mass of component (B1) were mixed. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0048] Example 6 A dissolving agent was obtained in the same manner as in Example 1, except that 95% by mass of component (A) and 5% by mass of trifluoroacetic acid (manufactured by AGC Corporation) were used as component (B2) instead of Teika Power B-121. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0049] Example 7 A dissolving agent was obtained in the same manner as in Example 6, except that 90% by mass of component (A) and 10% by mass of component (B2) were mixed. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0050] Example 8 A dissolving agent was obtained in the same manner as in Example 6, except that 80% by mass of component (A) and 20% by mass of component (B2) were mixed. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0051] Comparative Example 6 A dissolving agent was obtained in the same manner as in Example 3, except that 50% by mass of component (A) and 50% by mass of component (B1) were mixed. The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0052] Comparative Example 7 A dissolving agent was obtained in the same manner as in Example 6, except that ABZOL 8000 (manufactured by Albemarle Japan Co., Ltd., main component 1-bromopropane, boiling point 71° C., KB value 125) was used instead of component (A). The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0053] Comparative Example 8 A dissolving agent was obtained in the same manner as in Example 6, except that the above IP Solvent 1620 was used instead of component (A). The solubility of the obtained dissolving agent was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0054] [Table 2]

[0055] As shown in Table 2, it is seen that the dissolving agents according to the present invention (Examples 2 to 8) almost completely dissolved the resin material in about 1 hour. Therefore, it is seen that the dissolving agents according to the present invention exhibit excellent dissolving and removing performance. On the other hand, it is seen that the dissolving agents obtained in Comparative Examples 6 to 8 hardly dissolved the resin material even after 4 hours.

Claims

1. 70 to 99% by mass of hydrochlorofluoroolefin (A); 1 to 30% by mass of at least one of an alkylbenzenesulfonic acid (B1) and a fluoroalkylcarboxylic acid (B2); A resin dissolving agent comprising: The hydrochlorofluoroolefin (A) is at least one of (E)-chloro-2,3,3-trifluoropropene and (Z)-chloro-2,3,3-trifluoropropene; Resin dissolving agent.

2. The resin dissolving agent according to claim 1, wherein the alkylbenzenesulfonic acid (B1) is an alkylbenzenesulfonic acid having one or two alkyl groups having 1 to 18 carbon atoms on the benzene ring.

3. The resin dissolving agent according to claim 2, wherein the alkylbenzene sulfonic acid (B1) is at least one of dodecylbenzene sulfonic acid and xylene sulfonic acid.

4. The resin dissolving agent according to any one of claims 1 to 3, wherein the fluoroalkyl carboxylic acid (B2) is trifluoroacetic acid.

5. The resin dissolving agent according to any one of claims 1 to 4, wherein the resin is one selected from the group consisting of a silicone resin, a urethane resin, an epoxy resin, a polyamide resin and a polyimide resin.

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