Release agent composition
The release agent composition with amine-based nonionic surfactants and inorganic compounds addresses the inefficiencies of conventional methods by thoroughly removing functional layers and ink films from plastic substrates and PET bottle contents, ensuring high-quality recycling without substrate damage.
Patent Information
- Application Number
- JP2024104238
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-06-27
- Publication Date
- 2026-01-16
Smart Images
Figure 2026005716000001 
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Figure 2026005716000003
Abstract
Description
[Technical Field]
[0001] The present invention relates to a stripper composition, and more particularly to a stripper composition for removing a functional layer from a plastic material having a functional layer thereon, and for removing dirt from used plastic containers. [Background technology]
[0002] Conventionally, waste plastics have been disposed of by landfilling, dumping in the ocean, or incineration, but it is becoming increasingly difficult to secure landfill sites, and ocean dumping poses environmental problems because plastics do not decompose. Incineration can be used to generate heat, but this releases carbon dioxide, which contributes to global warming.
[0003] Therefore, in light of the recent growing environmental issues, there is a need for recycling, such as reuse and regeneration of waste plastics, and research and development for this purpose is being actively conducted. Furthermore, since most plastics are produced using fossil fuels, the development of recycling methods is also required from the perspective of effective resource utilization.
[0004] Polyester films, which are a type of plastic film, are useful as substrate films and are often used as laminate films having various functional layers laminated on one or both sides thereof. The functional layers in such laminate films include various functional layers such as a hard coat layer, a pressure-sensitive adhesive layer, a decorative layer, a light-shielding layer, a polarizing layer, and an ultraviolet-shielding layer, and materials appropriate for the functional layers are laminated on the polyester film.
[0005] Conventionally, such laminated films have rarely been reused after use, but have been discarded, incinerated, or the like. Furthermore, even if attempts were made to re-melt a laminated film with a functional layer laminated thereon as is and recycle it, problems arose, such as the generation of an unpleasant odor during extrusion or a decrease in the melt viscosity of the polymer, leading to breakage during film formation, because the material constituting the functional layer was mixed into the molten polymer. Even if film formation were possible, there were also problems such as unavoidable deterioration in the quality of the resulting film due to discoloration or the inclusion of foreign matter.
[0006] Furthermore, even if the functional layer is physically removed by scraping or the like and the recovered polymer is melt-extruded, there is a problem in that the functional layer remaining in the molten polymer clogs the filter during the filtration process during extrusion, making it impossible to produce a normal film.
[0007] Furthermore, when a substrate film that has suffered damage such as whitening is recycled, there is a problem that the melt viscosity of the polymer decreases during extrusion, causing breakage during film formation. Even if film formation is possible, there is a problem that the resulting film has poor physical properties such as transparency. Furthermore, when a roll-shaped film that has suffered damage such as whitening is recycled, there is a problem that the film's physical properties such as mechanical strength are insufficient, making it impossible to employ a roll-to-roll process.
[0008] Therefore, Patent Publication No. 2022-095599 (Patent Document 1) discloses a functional layer remover for polyester film that can peel off the functional layer and recover the base film, and contains an alkalizing agent such as an alkali metal hydroxide, a compatibilizer such as an alkanolamine compound, and a compound having at least one hydroxyl group such as an alcohol.
[0009] Furthermore, International Publication No. 2022 / 044941 (Patent Document 2) discloses an ink cleaner that contains at least one surfactant selected from amphoteric surfactants or cationic surfactants, and water, as an ink cleaner that can easily peel off ink films printed on plastic substrates.
[0010] These technologies involve forming a laminated film by laminating an easily soluble resin layer and a surface functional layer, in that order, on at least one side of a base film, and then, after use, washing the laminated film with a solvent that can dissolve only the easily soluble resin layer but not the base film, thereby separating and recovering the base film from the laminated film.The separated and recovered film can then be remelted, making it possible to regenerate the resin composition that constituted the base film.
[0011] On the other hand, plastic containers are widely used in large quantities for various liquids such as seasonings, cooking oil, alcoholic beverages, fuel, detergents, etc. This is particularly true for so-called plastic bottles (i.e., bottles made from polyester resin), especially PET (polyethylene terephthalate) bottles.
[0012] Due to recent urban issues such as reducing the burden on the environment and reducing waste, there is a growing demand for the recycling of plastic bottles, which are used in large quantities.Recycling methods include thermal energy recovery through incineration, chemical recycling, which returns the bottles to monomers, raw material recycling, which returns the bottles to raw resin materials through crushing and refining processes, and returnable recycling, which reuses the bottles again.In particular, the raw material recycling method, which returns the bottles to raw resin materials through crushing and refining processes, is used in the case of PET bottles, and the recovered raw resin materials are often reused as fibers, etc.
[0013] However, in some cases, the contents of collected PET bottles have penetrated into the resin that makes up the bottle, and these contents are often not easily removed by rinsing with water. If the attached matter or contents cannot be removed from collected PET bottles even by washing, they will be carried over as residual foreign matter into subsequent processes, causing a problem of reduced quality.
[0014] Therefore, Japanese Patent Laid-Open Publication No. 2003-191241 (Patent Document 3) discloses a method for cleaning crushed used polyethylene terephthalate bottles, which is characterized by cleaning crushed used polyethylene terephthalate bottles with ethylene glycol. This method makes it possible to efficiently remove labels, contents, etc., and recycle them by cleaning with ethylene glycol. [Prior art documents] [Patent documents]
[0015] [Patent Document 1] Japanese Patent Publication No. 2022-095599 [Patent Document 2] International Publication No. 2022 / 044941 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-191241 Summary of the Invention [Problem to be solved by the invention]
[0016] However, conventional functional layer removers and ink cleaners do not necessarily have sufficient removal performance for the various functional layers and ink films formed on plastic substrates, and functional layer removal and ink cleaning can sometimes cause damage to the plastic substrate, such as whitening.
[0017] Furthermore, the method of washing crushed used polyethylene terephthalate bottles with ethylene glycol was not sufficient to remove oils and other contaminants from the contents.
[0018] The present invention has been made in consideration of the problems associated with the above-mentioned conventional techniques, and aims to provide a release agent composition that has excellent removal performance for various functional layers and ink films formed on plastic substrates, is less likely to cause damage such as whitening of the plastic substrate due to functional layer removal or ink washing, and further has excellent removal performance for stains originating from the contents of used polyethylene terephthalate containers. [Means for solving the problem]
[0019] The present inventors have conducted extensive research to achieve the above-mentioned object, and as a result have found that a release agent composition containing a specific amine-based nonionic surfactant and an inorganic basic compound has excellent performance in removing various functional layers (e.g., release layers and adhesive layers made of a cured silicone resin) and ink films formed on plastic substrates, is less likely to damage (e.g., whiten) the plastic substrate, and further has excellent performance in removing stains derived from the contents of used polyethylene terephthalate containers, thereby completing the present invention.
[0020] That is, the present invention provides the following aspects. [1] The following general formula (1):
[0021] [ka]
[0022] [In general formula (1), R 1 represents an alkyl group having 4 to 18 carbon atoms or an alkenyl group having 4 to 18 carbon atoms, and A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n and m represent A 1 represents the average number of repeating units of O, each independently being a number of 0 or more, and n+m being a number of 1 to 50; 1 When there are multiple O groups, they may be the same or different. and an inorganic basic compound (B). [2] The following general formula (2):
[0023] [ka]
[0024] [In general formula (2), R 2 represents an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a hydroxyalkenyl group having 8 to 22 carbon atoms; A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and i represents A 2 represents the average number of repeating units, and is a number between 1 and 100. 2 When there are multiple O's, they may be the same or different. and a compound represented by the following general formula (3):
[0025] [ka]
[0026] [In general formula (3), A 3 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and j and k represent A 3 represents the average number of repeating units of O, each independently being a number of 0 or more, and j+k being a number of 1 to 30; 3 When there are multiple O's, they may be the same or different. A compound represented by The stripping composition according to [1], further comprising at least one nonionic surfactant (C) selected from the group consisting of: [3] The following general formula (4):
[0027] [ka]
[0028] [In general formula (4), R 3represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and A 4 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and p represents A 4 represents the average number of repeating units, and is a number between 0 and 10. 4 When a plurality of O's are present, they may be the same or different, M represents an alkali metal, an alkaline earth metal, ammonium or a basic group, and x represents the valence of M and is an integer of 1 to 3. A compound represented by the following general formula (5):
[0029] [ka]
[0030] [In general formula (5), R 4 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and R 5 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or hydrogen; A 5 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and q and r represent A 5 represents the average number of repeating units of O, each independently being a number of 0 or more, and q+r is a number of 0 to 20; 5 When a plurality of O's are present, they may be the same or different, M represents an alkali metal, an alkaline earth metal, ammonium or a basic group, and y represents the valence of M and is an integer of 1 to 3. and a compound represented by the following general formula (6):
[0031] [ka]
[0032] [In general formula (6), R 6 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, M represents an alkali metal, an alkaline earth metal, ammonium, or a basic group, and z represents the valence of M and is an integer of 1 to 3. A compound represented by The stripping composition according to [1] or [2], further comprising at least one anionic surfactant (D) selected from the group consisting of: [Effects of the Invention]
[0033] According to the present invention, it is possible to sufficiently remove various functional layers (e.g., release layers and adhesive layers made of cured silicone resin) and ink films formed on plastic substrates, and it is also possible to suppress damage such as whitening of the plastic substrate due to functional layer removal and ink cleaning, and further it is possible to sufficiently remove dirt derived from the contents of used polyethylene terephthalate containers. DETAILED DESCRIPTION OF THE INVENTION
[0034] The present invention will be described in detail below based on preferred embodiments thereof.
[0035] The stripping composition of the present invention is a composition represented by the following general formula (1):
[0036] [ka]
[0037] [In general formula (1), R 1 represents an alkyl group having 4 to 18 carbon atoms or an alkenyl group having 4 to 18 carbon atoms, and A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n and m represent A 1 represents the average number of repeating units of O, each independently being a number of 0 or more, and n+m being a number of 1 to 50; 1 When there are multiple O's, they may be the same or different. The composition contains an amine-based nonionic surfactant (A) which is a compound represented by the formula: and an inorganic basic compound (B).
[0038] Furthermore, the release agent composition of the present invention is a compound represented by the following general formula (2):
[0039] [ka]
[0040] [In general formula (2), R 2 represents an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a hydroxyalkenyl group having 8 to 22 carbon atoms; A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and i represents A 2 represents the average number of repeating units, and is a number between 1 and 100. 2 When there are multiple O's, they may be the same or different. and a compound represented by the following general formula (3):
[0041] [ka]
[0042] [In general formula (3), A 3 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and j and k represent A 3 represents the average number of repeating units of O, each independently being a number of 0 or more, and j+k being a number of 1 to 30; 3 When there are multiple O's, they may be the same or different. A compound represented by It is preferable that the composition further contains at least one nonionic surfactant (C) selected from the group consisting of:
[0043] The release agent composition of the present invention also comprises a compound represented by the following general formula (4):
[0044] [ka]
[0045] [In general formula (4), R 3 represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and A 4O represents an alkyleneoxy group having 2 to 4 carbon atoms, and p represents A 4 represents the average number of repeating units, and is a number between 0 and 10. 4 When a plurality of O's are present, they may be the same or different, M represents an alkali metal, an alkaline earth metal, ammonium or a basic group, and x represents the valence of M and is an integer of 1 to 3. A compound represented by the following general formula (5):
[0046] [ka]
[0047] [In general formula (5), R 4 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and R 5 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or hydrogen; A 5 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and q and r represent A 5 represents the average number of repeating units of O, each independently being a number of 0 or more, and q+r is a number of 0 to 20; 5 When a plurality of O's are present, they may be the same or different, M represents an alkali metal, an alkaline earth metal, ammonium or a basic group, and y represents the valence of M and is an integer of 1 to 3. and a compound represented by the following general formula (6):
[0048] [ka]
[0049] [In general formula (6), R 6 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, M represents an alkali metal, an alkaline earth metal, ammonium, or a basic group, and z represents the valence of M and is an integer of 1 to 3. A compound represented by It is also preferable that the composition further contains at least one anionic surfactant (D) selected from the group consisting of:
[0050] <Amine-based nonionic surfactant (A)> The amine-based nonionic surfactant (A) used in the present invention is a compound represented by the general formula (1) and has one alkyl or alkenyl chain and one or two alkylene oxide chains.
[0051] (Compound represented by general formula (1)) In the general formula (1), R 1 represents an alkyl group having 4 to 18 carbon atoms or an alkenyl group having 4 to 18 carbon atoms. Of these, from the viewpoint of improving the removal performance for various functional layers and ink films, and improving the performance of removing stains from the contents of used polyethylene terephthalate containers, an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms is preferred, and an alkyl group having 8 to 14 carbon atoms or an alkenyl group having 8 to 14 carbon atoms is more preferred. Furthermore, the alkyl group and alkenyl group may be linear or branched, but are preferably linear, and are more preferably linear alkyl groups.
[0052] In the general formula (1), A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms. 1 O) n and (A 1 O) m ) may be composed of one type of alkyleneoxy group or may be a mixed chain composed of two or more types of alkyleneoxy groups.
[0053] Also, A 1From the viewpoints of improving the removal performance of various functional layers and ink films, and improving the removal performance of stains from contents in used polyethylene terephthalate containers, O is preferably an ethyleneoxy group (hereinafter abbreviated as "EO") alone or a mixed chain of ethyleneoxy groups and propyleneoxy groups (hereinafter abbreviated as "PO") (hereinafter abbreviated as "EO / PO"), and more preferably an EO / PO mixed chain. The molar ratio of EO to PO in the EO / PO mixed chain is preferably EO / PO=10 / 90 to 90 / 10, and more preferably EO / PO=25 / 75 to 75 / 25.
[0054] In the general formula (1), n and m are each independently selected from the group consisting of A 1 represents the average number of repeating units of O, and each is independently a number equal to or greater than 0. Furthermore, the total number of n and m (n+m) is a number from 1 to 50, and is preferably a number from 2 to 30, more preferably a number from 2 to 20, from the viewpoint of improving the performance of removing various functional layers and ink films, and improving the performance of removing stains from contents in used polyethylene terephthalate containers. 1 When there are multiple O's, they may be the same or different.
[0055] The method for synthesizing the compound represented by the general formula (1) is not particularly limited, and a known synthesis method can be used in which an alkylene oxide having 2 to 4 carbon atoms is added to an alkylamine containing an alkyl group or alkenyl group having a predetermined number of carbon atoms. 1 The target compound can be obtained by adding an alkylamine higher alcohol having the formula (I) and an alkali catalyst, dehydrating the mixture under reduced pressure while heating to 100°C, and then introducing an equivalent amount of alkylene oxide to be added, and heating to 120 to 150°C to carry out an addition reaction.
[0056] <Inorganic basic compound (B)> Examples of the inorganic basic compound (B) used in the present invention include ammonia; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal phosphates such as trisodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, tripotassium phosphate, potassium pyrophosphate, and potassium tripolyphosphate; and alkali metal silicates such as sodium orthosilicate, sodium metasilicate, and potassium silicate. These inorganic basic compounds may be used alone or in combination. Among these inorganic basic compounds, alkali metal hydroxides are preferred, with sodium hydroxide and potassium hydroxide being more preferred from the viewpoint of availability. The combined use of potassium hydroxide and sodium hydroxide is particularly preferred from the viewpoints of improving the removal performance of various functional layers and ink films, improving the removal performance of stains from the contents of used polyethylene terephthalate containers, and ease of handling.
[0057] In the present invention, commercially available inorganic basic compounds such as caustic soda (sodium hydroxide, manufactured by Tokuyama Corporation), caustic potash (potassium hydroxide, manufactured by Toagosei Co., Ltd.), sodium metasilicate (nonahydrate) (sodium metasilicate, manufactured by Nippon Chemical Industry Co., Ltd.), and potassium diphosphate (potassium pyrophosphate, manufactured by Yoneyama Pharmaceutical Co., Ltd.) can be appropriately used as such inorganic basic compounds.
[0058] <Nonionic surfactant (C)> The nonionic surfactant (C) used in the present invention is at least one selected from the group consisting of compounds represented by the general formula (2) and compounds represented by the general formula (3).
[0059] (Compound represented by general formula (2)) The compound represented by the general formula (2) is a compound in which an alkyl group or an alkyleneoxy group having a hydroxyl group at its terminal is bonded to an alkyl group or an alkenyl group which may have a hydroxyl group, and functions as a nonionic surfactant.
[0060] In the general formula (2), R 2 represents an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a hydroxyalkenyl group having 8 to 22 carbon atoms. Of these, from the viewpoints of improving the removability of various functional layers and ink films, and improving the performance of removing stains from the contents of used polyethylene terephthalate containers, an alkyl group having 8 to 18 carbon atoms, a hydroxyalkyl group having 8 to 18 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, or a hydroxyalkenyl group having 8 to 18 carbon atoms is preferred, and an alkyl group having 8 to 16 carbon atoms, a hydroxyalkyl group having 8 to 16 carbon atoms, an alkenyl group having 8 to 16 carbon atoms, or a hydroxyalkenyl group having 8 to 16 carbon atoms is more preferred. Furthermore, the alkyl group, hydroxyalkyl group, alkenyl group, and hydroxyalkenyl group may be linear or branched, but are preferably linear, and a linear alkyl group is more preferred.
[0061] In the general formula (2), A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms. 2 O) i may be composed of one type of alkyleneoxy group or a mixed chain composed of two or more types of alkyleneoxy groups.
[0062] Also, A 2 From the viewpoint of antifoaming properties, EO is preferably EO alone or an EO / PO mixed chain, more preferably an EO / PO mixed chain. The molar ratio of EO to PO in the EO / PO mixed chain is preferably EO / PO=10 / 90 to 90 / 10, more preferably EO / PO=25 / 75 to 75 / 25.
[0063] In the general formula (2), i is A 2 represents the average number of repeating units of O, and is a number from 1 to 100. From the viewpoint of improving the removal performance for various functional layers and ink films, and the removal of stains from the contents of used polyethylene terephthalate containers, it is preferably a number from 4 to 50, and more preferably a number from 4 to 20. 2 When there are multiple O's, they may be the same or different.
[0064] The method for synthesizing the compound represented by the general formula (2) is not particularly limited, and a known synthesis method can be used in which an alkylene oxide having 2 to 4 carbon atoms is added to a higher alcohol containing an alkyl or alkenyl group having a predetermined number of carbon atoms. 2 The target compound can be obtained by adding a higher alcohol having the formula (I) and an alkali catalyst, dehydrating the mixture under reduced pressure while heating to 100°C, and then introducing an alkylene oxide in an amount equivalent to the amount to be added, and heating to 120 to 150°C to carry out an addition reaction.
[0065] (Compound represented by general formula (3)) The compound represented by the general formula (3) is a compound in which an alkyl group or alkyleneoxy group having a hydroxyl group is bonded to an acetylene alcohol, and functions as a nonionic surfactant.
[0066] In the general formula (3), A 3 O represents an alkyleneoxy group having 2 to 4 carbon atoms. 3 O) j and (A 3 O) k ) may be composed of one type of alkyleneoxy group or may be a mixed chain composed of two or more types of alkyleneoxy groups.
[0067] Also, A 3From the viewpoint of antifoaming properties, O is preferably an ethyleneoxy group (hereinafter abbreviated as "EO") alone or a mixed chain of an ethyleneoxy group and a propyleneoxy group (hereinafter abbreviated as "PO") (hereinafter abbreviated as "EO / PO"), more preferably an EO / PO mixed chain. The molar ratio of EO to PO in the EO / PO mixed chain is preferably EO / PO=10 / 90 to 90 / 10, more preferably EO / PO=25 / 75 to 75 / 25.
[0068] In the general formula (3), j and k are each independently selected from the group consisting of A 3 represents the average number of repeating units of O, and each is independently a number equal to or greater than 0. Furthermore, the total number of j and k (j+k) is a number from 1 to 30, and is preferably a number from 4 to 10 from the viewpoint of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers. 3 When there are multiple O's, they may be the same or different.
[0069] There are no particular limitations on the method for synthesizing such a compound represented by the general formula (3), and any known synthesis method can be used in which an alkylene oxide having 2 to 4 carbon atoms is added to an acetylene alcohol. For example, the target compound can be obtained by charging an acetylene alcohol and an alkali catalyst into a pressure-resistant reaction vessel, dehydrating the mixture under reduced pressure while heating to 100°C, and then introducing an equivalent amount of alkylene oxide to be added, and heating to 120 to 150°C to carry out an addition reaction.
[0070] <Anionic surfactants (D)> The anionic surfactant (D) used in the present invention is at least one selected from the group consisting of compounds represented by the general formula (4), compounds represented by the general formula (5), and compounds represented by the general formula (6).
[0071] (Compound represented by general formula (4)) The compound represented by the general formula (4) is a compound in which an alkyl group or alkyleneoxy group having a hydroxyl group is bonded to a higher alcohol, and the higher alcohol is further sulfated, and functions as an anionic surfactant.
[0072] In the general formula (4), R 3 represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms. Of these, from the viewpoints of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers, an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms is preferred, and an alkyl group having 10 to 16 carbon atoms or an alkenyl group having 10 to 16 carbon atoms is more preferred. Furthermore, the alkyl group and alkenyl group may be linear or branched, but are preferably linear, and are more preferably linear alkyl groups.
[0073] In the general formula (4), A 4 O represents an alkyleneoxy group having 2 to 4 carbon atoms. 4 O) p may be composed of one type of alkyleneoxy group or a mixed chain composed of two or more types of alkyleneoxy groups.
[0074] Also, A 4 From the viewpoint of antifoaming properties, EO is preferably EO alone or an EO / PO mixed chain, more preferably an EO / PO mixed chain. The molar ratio of EO to PO in the EO / PO mixed chain is preferably EO / PO=10 / 90 to 90 / 10, more preferably EO / PO=25 / 75 to 75 / 25.
[0075] In the general formula (4), p is A 4 represents the average number of repeating units of O, and is a number from 0 to 10, and is preferably a number from 0 to 5 from the viewpoint of improving the removal performance for various functional layers and ink films, and the removal of stains derived from the contents of used polyethylene terephthalate containers. 4When there are multiple O's, they may be the same or different.
[0076] In the general formula (4), M represents an alkali metal, an alkaline earth metal, ammonium, or a basic group. Furthermore, x represents the valence of M and is an integer of 1 to 3. Examples of the alkali metal include sodium and potassium, examples of the alkaline earth metal include calcium and magnesium, and examples of the basic group include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Among these, alkali metals, ammonium, and alkanolamines are preferred from the viewpoints of solubility and stability.
[0077] There is no particular limitation on the method for synthesizing such a compound represented by the general formula (4). For example, a method for synthesizing a compound represented by the general formula (4) is to add an alkylene oxide having 2 to 4 carbon atoms to a higher alcohol, and then add a sulfite group (-SO3 - For example, a known synthesis method for introducing the R 3 The target compound can be obtained by adding a higher alcohol having the formula (I) and an alkali catalyst, dehydrating the mixture under reduced pressure while heating to 100°C, introducing an equivalent amount of alkylene oxide to be added, and heating to 120 to 150°C to carry out an addition reaction, followed by introducing sulfamic acid and reacting the resulting mixture.
[0078] (Compound represented by general formula (5)) The compound represented by the general formula (5) is a compound obtained by reacting an alkylene oxide adduct of a higher alcohol with a phosphoric acid oxidizing agent, and functions as an anionic surfactant.
[0079] In the general formula (5), R 4represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. Of these, from the viewpoints of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains from the contents of used polyethylene terephthalate containers, an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms is preferred, and an alkyl group having 4 to 16 carbon atoms or an alkenyl group having 4 to 16 carbon atoms is more preferred. Furthermore, the alkyl group and alkenyl group may be linear or branched, but are preferably linear, and are more preferably linear alkyl groups.
[0080] In the general formula (5), R 5 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or hydrogen. Of these, from the viewpoints of improving the removal performance for various functional layers and ink films, and improving the performance of removing stains from the contents of used polyethylene terephthalate containers, an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms is preferred, and an alkyl group having 4 to 16 carbon atoms or an alkenyl group having 4 to 16 carbon atoms is more preferred. Furthermore, the alkyl group and alkenyl group may be linear or branched, but are preferably linear, and are more preferably linear alkyl groups.
[0081] In the general formula (5), A 5 O represents an alkyleneoxy group having 2 to 4 carbon atoms. 5 O) q and (A 5 O) r may be composed of one type of alkyleneoxy group or a mixed chain composed of two or more types of alkyleneoxy groups.
[0082] Also, A 5 From the viewpoint of antifoaming properties, EO is preferably EO alone or an EO / PO mixed chain, more preferably an EO / PO mixed chain. The molar ratio of EO to PO in the EO / PO mixed chain is preferably EO / PO=10 / 90 to 90 / 10, more preferably EO / PO=25 / 75 to 75 / 25.
[0083] In the general formula (5), q and r are each independently selected from the group consisting of A 5 represents the average number of repeating units of q and r, and each is independently a number equal to or greater than 0. Furthermore, the total number of q and r (q+r) is a number from 0 to 20, and is preferably a number from 0 to 10 from the viewpoint of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains from the contents of used polyethylene terephthalate containers. 5 When there are multiple O's, they may be the same or different.
[0084] In the general formula (5), M represents an alkali metal, an alkaline earth metal, ammonium, or a basic group. y represents the valence of M and is an integer of 1 to 3. Examples of the alkali metal include sodium and potassium, examples of the alkaline earth metal include calcium and magnesium, and examples of the basic group include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Of these, alkali metals, ammonium, and alkanolamines are preferred from the viewpoints of solubility and stability.
[0085] There is no particular limitation on the method for synthesizing such a compound represented by the general formula (5). For example, a method for synthesizing a compound represented by the general formula (5) is to add an alkylene oxide having 2 to 4 carbon atoms to a higher alcohol, and then add a phosphate ion (>PO4 3- For example, a known synthesis method for introducing the R 4 and a higher alcohol having the formula R 5 A higher alcohol having the formula (I) and an alkali catalyst are charged, and the mixture is dehydrated under reduced pressure while heated to 100°C. Then, an equivalent amount of alkylene oxide to be added is introduced, and the mixture is heated to 120 to 150°C to carry out an addition reaction. After obtaining an alkylene oxide adduct of a higher alcohol, the adduct is mixed with phosphoric anhydride and reacted to obtain the target compound.
[0086] (Compound represented by general formula (6)) The compound represented by the general formula (6) is a compound in which a higher aliphatic compound is neutralized with a basic compound, and functions as an anionic surfactant.
[0087] In the general formula (6), R 6 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms. Of these, an alkyl group having 8 to 16 carbon atoms or an alkenyl group having 8 to 16 carbon atoms is more preferred from the viewpoint of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains from the contents of used polyethylene terephthalate containers. Furthermore, the alkyl group and alkenyl group may be linear or branched, but are preferably linear, and are more preferably linear alkyl groups.
[0088] In the general formula (6), M represents an alkali metal, an alkaline earth metal, ammonium, or a basic group. Furthermore, z represents the valence of M and is an integer of 1 to 3. Examples of the alkali metal include sodium and potassium, examples of the alkaline earth metal include calcium and magnesium, and examples of the basic group include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Among these, alkali metals, ammonium, and alkanolamines are preferred from the viewpoints of solubility and stability.
[0089] <Removal Agent Composition> The release agent composition of the present invention contains an amine-based nonionic surfactant (A), which is a compound represented by the general formula (1), and the inorganic basic compound (B), and preferably further contains at least one nonionic surfactant (C) selected from the group consisting of compounds represented by the general formula (2) and compounds represented by the general formula (3), and / or at least one anionic surfactant (D) selected from the group consisting of compounds represented by the general formula (4), compounds represented by the general formula (5), and compounds represented by the general formula (6).
[0090] In the present invention, a mixture of the amine-based nonionic surfactant (A), the inorganic basic compound (B), and the nonionic surfactant (C) and / or the anionic surfactant (D) contained as needed can be used as a release agent composition as is, but from the viewpoint of dissolution and improving fluidity, water or an organic solvent may be added thereto before use.
[0091] The organic solvent is not particularly limited, and examples thereof include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, benzyl alcohol, phenoxyethanol, and phenoxypropanol; 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethyl ether, methyl ... Examples of the glycol ethers include ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-n-hexyl ether, diethylene glycol dibutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and dibenzyl glycol; glycols such as ethylene glycol, propylene glycol, 1,3-butanediol, hexylene glycol, diethylene glycol, and dipropylene glycol; and terpenes such as d-limonene and terpineol.
[0092] In the release agent composition of the present invention, the content of the amine-based nonionic surfactant (A) is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 20% by mass, based on the total mass of the release agent composition, from the viewpoints of improving the removal performance for various functional layers and ink films, improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers, and suppressing damage such as whitening of plastic substrates.
[0093] The content of the inorganic basic compound (B) is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.1 to 15% by mass, based on the total mass of the release agent composition, from the viewpoints of improving the removal performance for various functional layers and ink films, improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers, and suppressing damage such as whitening of plastic substrates.
[0094] Furthermore, the mass ratio of the amine-based nonionic surfactant (A) to the inorganic basic compound (B) is preferably (A) / (B)=5 / 1 to 5 / 100, more preferably 5 / 1 to 5 / 50, and even more preferably 5 / 1 to 5 / 20, from the viewpoints of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers.
[0095] The content of the nonionic surfactant (C) is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total mass of the release agent composition, from the viewpoints of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers.
[0096] Furthermore, the content of the anionic surfactant (D) is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, based on the total mass of the release agent composition, from the viewpoints of improving the removal performance for various functional layers and ink films, and improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers.
[0097] <Other ingredients> The release agent composition of the present invention may contain known components that can be incorporated into functional layer release agent compositions in the field of plastic material recycling, within the scope of not impairing the effects of the present invention. Such components are not particularly limited, but examples thereof include chelating agents, antioxidants, rust inhibitors, preservatives, viscosity modifiers, antifoaming agents, etc.
[0098] (chelating agent) In the release agent composition of the present invention, it is preferable to incorporate a chelating agent from the viewpoint of improving the removal performance of various functional layers and ink films, and improving the removal performance of stains derived from the contents of used polyethylene terephthalate containers. Examples of such chelating agents include aminocarboxylic acid derivatives and their salts, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminepentaacetic acid, iminodisuccinic acid, aspartic acid diacetic acid, and aminomethylglycine diacetic acid; salts of organic acids, such as citric acid, tartaric acid, and gluconic acid; polymer electrolyte compounds, such as polyacrylic acid, polyacrylic acid / maleic acid copolymers, and their salts; phosphoric acid compounds, such as tripolyphosphate, orthophosphate, and pyrophosphate; phosphonic acid compounds, such as 1-hydroxyethane-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and their salts; and aluminosilicates, such as A-type zeolite and B-type zeolite. Among these, nitrilotriacetate, ethylenediaminetetraacetate, triethylenetetraminepentaacetic acid, tripolyphosphate, 1-hydroxyethane-1,1-diphosphonic acid and salts thereof are preferred.
[0099] (antioxidant) Examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants.
[0100] (rust inhibitor) Examples of the rust inhibitor include inorganic rust inhibitors such as chromates, molybdates, and sodium nitrite.
[0101] (preservatives) Examples of preservatives include paraben-based preservatives, benzoic acid, sodium benzoate, sorbic acid, propionate-based preservatives, dehydroacetic acid, sulfur dioxide, and sodium pyrosulfite-based preservatives.
[0102] (Viscosity modifier) Examples of viscosity modifiers include polymer compounds and layered inorganic particles.
[0103] (Antifoaming agent) Examples of the antifoaming agent include fluorine-based compounds, silicone-based compounds, polyether-based compounds, and acetylene glycol-based compounds.
[0104] <Removal method> Next, a method for removing a functional layer or an ink film using the stripping composition of the present invention and a method for removing stains derived from the contents of a used polyethylene terephthalate container will be described.
[0105] In the method for removing a functional layer or ink film using the release agent composition of the present invention and the method for removing stains derived from the contents of a used polyethylene terephthalate container, the functional layer or ink film of a laminate film or the soiled portion derived from the contents of a used polyethylene terephthalate container is contacted with the release agent composition of the present invention. Methods for contacting the functional layer, ink film, or soiled portion derived from the contents with the release agent composition include a method of immersing the functional layer, ink film, or used polyethylene terephthalate container in a release agent tank containing a release agent composition in solution (immersion method), a method of applying the release agent composition in solution to the surface of the functional layer or ink film or the surface of the soiled portion derived from the contents of a used polyethylene terephthalate container (application method), and a method of spraying the release agent composition in solution or vaporized release agent composition onto the surface of the functional layer, ink film, or the surface of the soiled portion derived from the contents of a used polyethylene terephthalate container (spray method). Furthermore, in the immersion method, ultrasonic treatment may be performed in the release agent tank (ultrasonic treatment method). Of these methods, the immersion method and ultrasonic treatment method are preferred from the viewpoint of the penetration of the release agent composition into the functional layer, the ink film, and the soiled portion derived from the contents of the used polyethylene terephthalate container.
[0106] In the immersion method, the temperature of the release agent composition during immersion (immersion temperature) is not particularly limited. However, from the viewpoint of low viscosity of the release agent composition and easy penetration of the release agent composition into the functional layer, ink film, and soiled areas originating from the contents of the used polyethylene terephthalate container, a temperature of room temperature (20°C) or higher is preferred. From the viewpoint of improving the removal performance of various functional layers and ink films and improving the performance of removing soiling originating from the contents of the used polyethylene terephthalate container, a temperature of 40°C or higher is more preferred, 60°C or higher is even more preferred, and 70°C or higher is particularly preferred. Furthermore, from the viewpoint of preventing evaporation of the release agent composition, the immersion temperature is preferably below the boiling point of the release agent composition. For example, in a release agent composition containing water as a solvent, the immersion temperature is preferably 100°C or lower, more preferably 90°C or lower. The above-mentioned immersion temperatures can also be used in methods other than the immersion method.
[0107] In the immersion method, the immersion time in the release agent composition is not particularly limited, but from the viewpoints of improving the removal performance for various functional layers and ink films, improving the removal performance for stains derived from the contents of used polyethylene terephthalate containers, and suppressing damage such as whitening of plastic substrates, the immersion time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes, and even more preferably 1 to 10 minutes.
[0108] (Ultrasonic treatment method) The ultrasonic frequency used in the ultrasonic treatment method is not particularly limited, but from the viewpoints of improving the removal performance of various functional layers and ink films, improving the removal performance of dirt derived from the contents of used polyethylene terephthalate containers, and miniaturizing peeled functional layers, it is preferably 5 to 3000 kHz, more preferably 15 to 500 kHz, and even more preferably 15 to 100 kHz. The ultrasonic amplitude is also not particularly limited, but from the viewpoints of improving the removal performance of various functional layers and ink films, improving the removal performance of dirt derived from the contents of used polyethylene terephthalate containers, and miniaturizing peeled functional layers, it is preferably 1 to 100 μm, more preferably 5 to 80 μm. The immersion temperature and immersion time used in the ultrasonic treatment method are the same as those used in the immersion method.
[0109] There are no particular limitations on the ultrasonic treatment device used in such an ultrasonic treatment method, but examples include horn-type and sweep-type devices. When removing a wide range of functional layers, ink films, or stains derived from the contents, a sweep-type device is preferred, and when removing a narrow range of functional layers, ink films, or stains derived from the contents, a horn-type device is preferred. [Example]
[0110] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.
[0111] [Compound represented by general formula (1)] The compound represented by the following general formula (1) (hereinafter abbreviated as "compound (A1)") used in the examples and comparative examples was synthesized by the following method. In addition, in the compounds (A1-1) to (A1-13) obtained in each synthesis example, R in the following general formula (1) 1 , (A 1 O) m , (A 1 O) n and m+n are shown in Table 1.
[0112] [ka]
[0113] [Table 1]
[0114] (Synthesis Example A1-1) A pressure-resistant reactor was charged with 100 g of octylamine (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Then, 68.1 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain an intermediate compound, which was an octylamine-ethylene oxide 2-mol adduct. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, after which 68.1 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain the target compound (A1-1).
[0115] (Synthesis Example A1-2) A pressure-resistant reactor was charged with 100 g of octylamine (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, and then the reactor was heated to 120 to 130° C. Then, 68.1 g of ethylene oxide was blown into the reactor, and the mixture was aged at 120 to 130° C. for 6 hours to obtain the target compound (A1-2).
[0116] (Synthesis Example A1-3) In the same manner as in Synthesis Example A1-1, an intermediate compound, an octylamine ethylene oxide 2 mole adduct, was obtained. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the pressure-resistant reactor was purged with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 272.3 g of ethylene oxide was blown in, and the mixture was aged at 120-130°C for 6 hours to obtain the target compound (A1-3).
[0117] (Synthesis Example A1-4) In the same manner as in Synthesis Example A1-1, an intermediate compound, an octylamine ethylene oxide 2-mol adduct, was obtained. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the pressure-resistant reactor was purged with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 612.8 g of ethylene oxide was blown in, and the mixture was aged at 120-130°C for 6 hours to obtain the target compound (A1-4).
[0118] (Synthesis Example A1-5) In the same manner as in Synthesis Example A1-1, an intermediate compound, an octylamine ethylene oxide 2 mole adduct, was obtained. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the pressure-resistant reactor was purged with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 953.2 g of ethylene oxide was blown in, and the mixture was aged at 120-130°C for 6 hours to obtain the target compound (A1-5).
[0119] (Synthesis Example A1-6) In the same manner as in Synthesis Example A1-1, an intermediate compound, an octylamine ethylene oxide 2 mole adduct, was obtained. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the pressure-resistant reactor was purged with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 1293.6 g of ethylene oxide was blown in, and the mixture was aged at 120-130°C for 6 hours to obtain the target compound (A1-6).
[0120] (Synthesis Example A1-7) A pressure-resistant reactor was charged with 100 g of octylamine (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, and then the mixture was heated to 120 to 130° C. Then, 89.9 g of propylene oxide was blown in, and the mixture was aged at 120 to 130° C. for 12 hours to obtain the target compound (A1-7).
[0121] (Synthesis Example A1-8) In the same manner as in Synthesis Example A1-1, an intermediate compound, an octylamine ethylene oxide 2-mol adduct, was obtained. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the pressure-resistant reactor was purged with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 89.9 g of propylene oxide was blown in at 120-130°C, and the mixture was aged at the same temperature for 12 hours to obtain the target compound (A1-8).
[0122] (Synthesis Example A1-9) An intermediate compound, an octylamine ethylene oxide 2-mol adduct, was obtained in the same manner as in Synthesis Example A1-1. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the pressure-resistant reactor was purged with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 102.1 g of ethylene oxide was blown in at 120-130°C and aged at the same temperature for 6 hours. After that, 224.8 g of propylene oxide was blown in at 120-130°C and aged at the same temperature for 12 hours to obtain the target compound (A1-9).
[0123] (Synthesis Example A1-10) A pressure-resistant reactor was charged with 100 g of n-butyldiethanolamine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, after which it was heated to 120-130° C. Then, 54.6 g of ethylene oxide was blown in, and the mixture was aged at 120-130° C. for 6 hours to obtain the target compound (A1-10).
[0124] (Synthesis Example A1-11) A pressure-resistant reactor was charged with 100 g of dodecylamine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Then, 47.5 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain an intermediate compound, which was an ethylene oxide 2-mol adduct of dodecylamine. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, and then 47.5 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain the target compound (A1-11).
[0125] (Synthesis Example A1-12) A pressure-resistant reactor was charged with 100 g of octadecylamine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Then, 32.7 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain an intermediate compound, which was an ethylene oxide 2-mol adduct of octadecylamine. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, after which 32.7 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain the target compound (A1-12).
[0126] (Synthesis Example A1-13) A pressure-resistant reactor was charged with 100 g of oleylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Then, 32.9 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain an intermediate compound, which was an ethylene oxide 2-mol adduct of oleylamine. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, after which 32.9 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain the target compound (A1-13).
[0127] [Compound represented by general formula (2)] The compound represented by the following general formula (2) (hereinafter abbreviated as "compound (C2)") used in the examples and comparative examples was synthesized by the following method. In addition, in the compounds (C2-1) to (C2-14) obtained in each synthesis example, R in the following general formula (2) 2 , (A 2 O) i and i are shown in Table 2.
[0128] [ka]
[0129] [Table 2]
[0130] (Synthesis Example C2-1) A pressure-resistant reactor was charged with 100 g of decyl alcohol (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, and then heated to 120-130°C. 139 g of ethylene oxide was then blown in, and the mixture was aged at the same temperature for 6 hours to obtain the target compound (C2-1).
[0131] (Synthesis Example C2-2) The target compound (C2-2) was obtained in the same manner as in Synthesis Example C2-1, except that the amount of ethylene oxide was changed to 28 g.
[0132] (Synthesis Example C2-3) The target compound (C2-3) was obtained in the same manner as in Synthesis Example C2-1, except that the amount of ethylene oxide was changed to 111 g.
[0133] (Synthesis Example C2-4) The target compound (C2-4) was obtained in the same manner as in Synthesis Example C2-1, except that the amount of ethylene oxide was changed to 445 g.
[0134] (Synthesis Example C2-5) The target compound (C2-5) was obtained in the same manner as in Synthesis Example C2-1, except that the amount of ethylene oxide was changed to 1279 g.
[0135] (Synthesis Example C2-6) The target compound (C2-6) was obtained in the same manner as in Synthesis Example C2-1, except that the amount of ethylene oxide was changed to 2502 g.
[0136] (Synthesis Example C2-7) The target compound (C2-7) was obtained in the same manner as in Synthesis Example C2-1, except that 147 g of propylene oxide was used instead of ethylene oxide.
[0137] (Synthesis Example C2-8) A pressure-resistant reactor was charged with 100 g of decyl alcohol (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, and then heated to 120-130°C. 59 g of propylene oxide was then blown in, and the mixture was aged at the same temperature for 12 hours. 400 g of ethylene oxide was then blown in at 120-130°C, and the mixture was aged at the same temperature for 6 hours to obtain the target compound (C2-8).
[0138] (Synthesis Example C2-9) The target compound (C2-9) was obtained in the same manner as in Synthesis Example C2-8, except that the amount of propylene oxide was changed to 528 g and the amount of ethylene oxide was changed to 44 g.
[0139] (Synthesis Example C2-10) The target compound (C2-10) was obtained in the same manner as in Synthesis Example C2-8, except that the amount of propylene oxide was changed to 176 g and the amount of ethylene oxide was changed to 311 g.
[0140] (Synthesis Example C2-11) The target compound (C2-11) was obtained in the same manner as in Synthesis Example C2-8, except that the amount of propylene oxide was changed to 410 g and the amount of ethylene oxide was changed to 133 g.
[0141] (Synthesis Example C2-12) The target compound (C2-12) was obtained in the same manner as in Synthesis Example C2-1, except that 100 g of octadecyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of decyl alcohol and the amount of ethylene oxide was changed to 81 g.
[0142] (Synthesis Example C2-13) The target compound (C2-13) was obtained in the same manner as in Synthesis Example C2-1, except that 100 g of 2-ethylhexyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of decyl alcohol and the amount of ethylene oxide was changed to 169 g.
[0143] (Synthesis Example C2-14) The target compound (C2-14) was obtained in the same manner as in Synthesis Example C2-1, except that 100 g of behenyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of decyl alcohol and the amount of ethylene oxide was changed to 67 g.
[0144] [Compound represented by general formula (3)] In the examples and comparative examples, the compounds represented by the following general formula (3) (hereinafter abbreviated as "compound (C3)") were the following commercially available products and compounds synthesized by the following methods. In addition, in the following compounds (C3-1) to (C3-6), (A 3 O) j , (A 3 O) k and j+k are shown in Table 3.
[0145] [ka]
[0146] [Table 3]
[0147] (Compound (C3-1)) Acetylenol E40 (manufactured by Kawaken Fine Chemicals Co., Ltd.) was used as the compound (C3-1).
[0148] (Compound (C3-2)) Acetylenol E13T (manufactured by Kawaken Fine Chemicals Co., Ltd.) was used as the compound (C3-2).
[0149] (Compound (C3-3)) Acetylenol E100 (manufactured by Kawaken Fine Chemicals Co., Ltd.) was used as the compound (C3-3).
[0150] (Compound (C3-4)) As the compound (C3-4), Olfine 1030W (manufactured by Nissin Chemical Industry Co., Ltd.) was used.
[0151] (Synthesis Example C3-5) A pressure-resistant reactor was charged with 100 g of 2,4,7,9-tetramethyl-5-decyne-4,7,diol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, and then heated to 120-130°C. Then, 103 g of propylene oxide was blown in, and the mixture was aged at the same temperature for 12 hours to obtain the target compound (C3-5).
[0152] (Synthesis Example C3-6) A pressure-resistant reactor was charged with 100 g of 2,4,7,9-tetramethyl-5-decyne-4,7,diol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, and then heated to 120-130°C. 103 g of propylene oxide was then blown in, and the mixture was aged at the same temperature for 12 hours. 117 g of ethylene oxide was then blown in at 120-130°C, and the mixture was aged at the same temperature for 6 hours to obtain the target compound (C3-6).
[0153] [Compound represented by general formula (4)] The compound represented by the following general formula (4) (hereinafter abbreviated as "compound (D4)") used in the examples and comparative examples was synthesized by the following method. In addition, in the compounds (D4-1) to (D4-8) obtained in each synthesis example, R in the following general formula (4) 3 , (A 4 O) p , p, x and M x+ is shown in Table 4.
[0154] [ka]
[0155] [Table 4]
[0156] (Synthesis Example D4-1) A heat-resistant reaction vessel was charged with 100 g of 2-ethylhexyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide, followed by nitrogen substitution. Dehydration was carried out under reduced pressure at 100°C, followed by heating to 120-130°C. Then, 101 g of ethylene oxide was blown in, and the mixture was aged at the same temperature for 6 hours. 262.2 g of the resulting reaction product was added to the reaction vessel, dehydration was carried out at 110°C while blowing in nitrogen, and then the mixture was heated to 120-130°C. 37 g of sulfamic acid was added, and the mixture was reacted for 3 hours. After that, 885 g of ion-exchanged water and 64.0 g of 48% sodium hydroxide were added, followed by neutralization, to obtain the target compound (D4-1).
[0157] (Synthesis Example D4-2) 100 g of 2-ethylhexyl alcohol was placed in a reaction vessel, and after dehydration at 110°C while introducing nitrogen, the mixture was heated to 120-130°C. 74 g of sulfamic acid was added thereto, and the mixture was reacted for 3 hours. After that, 546 g of ion-exchanged water and 64.0 g of 48% sodium hydroxide were added, and the mixture was neutralized to obtain the target compound (D4-2).
[0158] (Synthesis Example D4-3) The target compound (D4-3) was obtained in the same manner as in Synthesis Example D4-1, except that the amount of ethylene oxide was changed to 169 g and the amount of ion-exchanged water was changed to 1110 g.
[0159] (Synthesis Example D4-4) The target compound (D4-4) was obtained in the same manner as in Synthesis Example D4-1, except that the amount of ethylene oxide was changed to 338 g and the amount of ion-exchanged water was changed to 1673 g.
[0160] (Synthesis Example D4-5) The target compound (D4-5) was obtained in the same manner as in Synthesis Example D4-1, except that ethylene oxide was replaced with 134 g of propylene oxide and the amount of ion-exchanged water was changed to 992 g.
[0161] (Synthesis Example D4-6) A pressure-resistant reactor was charged with 100 g of 2-ethylhexyl alcohol and 0.2 g of potassium hydroxide, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, and then heated to 120-130°C. Then, 45 g of propylene oxide was blown in, and the mixture was aged at the same temperature for 12 hours. Then, 68 g of ethylene oxide was blown in at 120-130°C, and the mixture was aged at the same temperature for 6 hours. 276.2 g of the resulting reaction mixture was added to the reactor, dehydrated at 110°C while blowing in nitrogen, and then heated to 120-130°C. 74.6 g of sulfamic acid was added, and the mixture was reacted for 3 hours. Then, 920 g of ion-exchanged water and 64.0 g of 48% sodium hydroxide were added, and the mixture was neutralized to obtain the target compound (D4-6).
[0162] (Synthesis Example D4-7) The target compound (D4-7) was obtained in the same manner as in Synthesis Example D4-1, except that dodecyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl alcohol, the amount of ethylene oxide was changed to 71 g, the amount of sulfamic acid was changed to 52.1 g, the amount of ion-exchanged water was changed to 719 g, and the amount of 48% sodium hydroxide was changed to 44.8 g.
[0163] (Synthesis Example D4-8) The target compound (D4-8) was obtained in the same manner as in Synthesis Example D4-1, except that octadecyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl alcohol, the amount of ethylene oxide was changed to 49 g, the amount of sulfamic acid was changed to 35.9 g, the amount of ion-exchanged water was changed to 599 g, and the amount of 48% sodium hydroxide was changed to 30.8 g.
[0164] [Compound represented by general formula (5)] The compound represented by the following general formula (5) (hereinafter abbreviated as "compound (D5)") used in the examples and comparative examples was synthesized by the following method. In addition, in the compounds (D5-1) to (D5-6) obtained in each synthesis example, R in the following general formula (5) 4 , R 5 , (A 5 O) q , (A 5 O) r , q+r, y and M y+ is shown in Table 5.
[0165] [ka]
[0166] [Table 5]
[0167] (Synthesis Example D5-1) A reaction vessel was charged with 136.4 g of 2-ethylhexyl acid phosphate ("JP-508" manufactured by Johoku Chemical Industry Co., Ltd.) and 167 g of ion-exchanged water, and the mixture was neutralized with 25.6 g of 48% sodium hydroxide to obtain the target compound (D5-1).
[0168] (Synthesis Example D5-2) The target compound (D5-2) was obtained in the same manner as in Synthesis Example D5-1, except that 202.7 g of ethyl acid phosphate ("JP-502" manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl acid phosphate, the amount of ion-exchanged water was changed to 142 g, and the amount of 48% sodium hydroxide was changed to 72.3 g.
[0169] (Synthesis Example D5-3) The target compound (D5-3) was obtained in the same manner as in Synthesis Example D5-1, except that 163.9 g of butyl acid phosphate ("JP-504" manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl acid phosphate, the amount of ion-exchanged water was changed to 157 g, and the amount of 48% sodium hydroxide was changed to 45.0 g.
[0170] (Synthesis Example D5-4) The target compound (D5-4) was obtained in the same manner as in Synthesis Example D5-1, except that 123.6 g of isotridecyl acid phosphate ("JP-513" manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl acid phosphate, the amount of ion-exchanged water was changed to 171 g, and the amount of 48% sodium hydroxide was changed to 16.6 g.
[0171] (Synthesis Example D5-5) The target compound (D5-5) was obtained in the same manner as in Synthesis Example D5-1, except that 118 g of oleyl acid phosphate ("JP-518-O" manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl acid phosphate, the amount of ion-exchanged water was changed to 174 g, and the amount of 48% sodium hydroxide was changed to 12.4 g.
[0172] (Synthesis Example D5-6) The target compound (D5-6) was obtained in the same manner as in Synthesis Example D5-1, except that 140 g of butoxyethyl acid phosphate ("JP-506H" manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl acid phosphate, the amount of ion-exchanged water was changed to 165 g, and the amount of 48% sodium hydroxide was changed to 28.2 g.
[0173] [Compound represented by general formula (6)] In the examples and comparative examples, the following commercially available products were used as the compound represented by the following general formula (6) (hereinafter abbreviated as "compound (D6)"). In addition, in the following compounds (D6-1) to (D6-3), R in the following general formula (6) was 6 , z and M z+ is shown in Table 6.
[0174] [ka]
[0175] [Table 6]
[0176] (Compound (D6-1)) Sodium laurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as compound (D6-1).
[0177] (Compound (D6-2)) Sodium octanoate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the compound (D6-2).
[0178] (Compound (D6-3)) Sodium stearate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as compound (D6-3).
[0179] [Other compounds (a)] In the comparative examples, the following commercially available products and compounds synthesized by the following methods were used as compounds similar to the compound (A1) (hereinafter abbreviated as "compound (a1)"). In addition, in the compounds (a1-1) to (a1-4) obtained in each synthesis example, R in the general formula (1) was 1 , (A 1 O) m , (A 1 O) n and m+n are shown in Table 7.
[0180] [Table 7]
[0181] (Compound (a1-1)) Octylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the compound (a1-1).
[0182] (Synthesis example a1-2) A pressure-resistant reactor was charged with 100 g of octylamine (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Then, 68.1 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain an intermediate compound, which was an octylamine-ethylene oxide 2-mol adduct. After cooling this intermediate compound to 90°C, 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, after which 1974.5 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130°C for 6 hours to obtain the target compound (a1-2).
[0183] (Synthesis Example a1-3) A pressure-resistant reactor was charged with 100 g of N-methyldiethanolamine (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide, and the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, and then the mixture was heated to 120 to 130° C. Then, 73.9 g of ethylene oxide was blown in, and the mixture was aged at 120 to 130° C. for 6 hours to obtain the target compound (a1-3).
[0184] (Synthesis Example a1-4) A pressure-resistant reactor was charged with 100 g of behenylamine (Nissan Amine VB-S manufactured by NOF Corporation) and 0.2 g of potassium hydroxide. The atmosphere inside the pressure-resistant reactor was purged with nitrogen and then heated to 120-130°C. 50.3 g of ethylene oxide was then blown in, and the mixture was aged at 120-130°C for 6 hours to obtain an intermediate compound, which was an ethylene oxide 2-mol adduct of behenylamine. This intermediate compound was then cooled to 90°C, and 0.2 g of potassium hydroxide was added as a catalyst, and the atmosphere inside the pressure-resistant reactor was purged with nitrogen. Next, the mixture was dehydrated under reduced pressure at 120°C for 1 hour, after which 50.3 g of ethylene oxide was blown in, and the mixture was aged at 120-130°C for 6 hours to obtain the target compound (a1-4).
[0185] (Examples 1 to 68 and Comparative Examples 1 to 8) [Preparation of Stripping Composition] Amine-based nonionic surfactant (A) (compound (A1) or compound (a1)), inorganic basic compound (B), nonionic surfactant (C) (compound (C2) or compound (C3)), and anionic surfactant (D) (compound (D4), compound (D5), or compound (D6)) of the type shown in Tables 8 to 11 were dissolved in water to the concentrations shown in Tables 8 to 11 to prepare stripper compositions.
[0186] [Performance Evaluation of Stripping Agent Composition] 1. Ink film removal performance (Production of printing film) A hybrid UV-curable ink (F-DK-HS ink, manufactured by Toyo Ink Co., Ltd.) was solid-printed to a thickness of approximately 1 μm over a 10 cm x 10 cm area on the surface of a 25 μm-thick polyethylene terephthalate film (Lumirror® Film, manufactured by AS ONE Corporation) using a manual screen printer (manufactured by Tsujii Senki Kogyo Co., Ltd.). The printed polyethylene terephthalate film was then irradiated with UV light using a 120 W / cm metal hydride lamp in a conveyor-type UV device (manufactured by iGraphics Co., Ltd., ECS-4011GX / N) at an integrated dose of 1000 mJ / cm. 2 The ink was cured by irradiation so as to form a printed film.
[0187] (Performance evaluation test) The printed film cut to a size of 5 cm x 5 cm was immersed in 100 ml of the stripping composition placed in a stainless steel container under the conditions shown in Tables 8 to 11, and then dried at 70°C for 30 minutes. After drying, the surface of the printed film was photographed using a digital camera (Canon Inc.'s "IXY200"). Using the photograph obtained, the ink film area was determined by image processing, and the ink removal rate was calculated using the following formula and evaluated according to the following criteria. The results are shown in Tables 12 to 15. Ink removal rate [%] = (1 - ink film area after immersion / ink film area before immersion) x 100 A: 100% ink removal rate. B: Ink removal rate is 75% or more but less than 100%. C: Ink removal rate is 50% or more but less than 75%. D: Ink removal rate less than 50%.
[0188] 2. Release layer removal performance (Preparation of release film) One side of a 25 μm thick polyethylene terephthalate film ("Lumirror(R) Film" manufactured by AS ONE Corporation) was coated with a 5 wt % aqueous solution of polyvinyl alcohol resin ("GH-17R" manufactured by Mitsubishi Chemical Corporation) using a bar coater ("PI-1210 AUTO FILM APPLICATOR" manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying would be 0.5 μm, and the film was then dried in an oven at 120°C for 5 minutes.
[0189] After drying, a 5% by mass toluene solution of curable silicone resin ("LTC-310" manufactured by Dow-Toray Industries, Inc., curing agent: SRX211) was coated onto the surface of the polyvinyl alcohol resin layer of the film using the bar coater so that the thickness after drying would be 1 μm, and then dried in an oven at 100°C for 5 minutes to produce a release film with a release layer (cured silicone resin layer).
[0190] (Performance evaluation test) The release film cut to a size of 5 cm x 5 cm was immersed in 100 ml of the release agent composition placed in a stainless steel container under the conditions shown in Tables 8 to 11, and then dried at 70°C for 30 minutes. The Si element in the release film after drying was quantitatively analyzed using an X-ray fluorescence analyzer (XRF, "EDX-7000" manufactured by Shimadzu Corporation), and the Si removal rate was calculated using the following formula and evaluated according to the following criteria. The results are shown in Tables 12 to 15. Si removal rate [%] = (1 - amount of Si element after immersion / amount of Si element before immersion) x 100 A:Si removal rate of 90% or more and 100% or less. B: Si removal rate is 75% or more but less than 90%. C:Si removal rate is 50% or more but less than 75%. D: Si removal rate less than 50%.
[0191] 3.Inorganic foreign matter removal performance (Preparation of ceramic green sheets) A ceramic slurry was prepared by adding 100 parts by mass of ceramic powder (barium titanate (reagent) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 10 parts by mass of an acrylic polymer to isopropyl alcohol so that the slurry viscosity was 300 to 500 mPa·s. This ceramic slurry was uniformly applied to the surface of the release layer (cured silicone resin layer) of the release film prepared by the method described above so that the thickness after drying would be 5 μm, and the coating was dried in an oven at 85°C for 10 minutes to produce a ceramic green sheet.
[0192] (Performance evaluation test) The release film was peeled from the ceramic green sheet, and the resulting release film was cut into a 5 cm x 5 cm piece. The piece was immersed in 100 ml of the release agent composition placed in a SUS container under the conditions shown in Tables 8 to 11, and then dried at 70°C for 30 minutes. After drying, the number of inorganic foreign particles on the release film was counted, and the inorganic foreign particle removal rate was calculated using the following formula and evaluated according to the following criteria. The results are shown in Tables 12 to 15. Inorganic foreign matter removal rate [%] = (1 - number of inorganic foreign matters after immersion / number of inorganic foreign matters before immersion) x 100 A: Inorganic foreign matter removal rate of 90% or more and 100% or less. B: Inorganic foreign matter removal rate is 75% or more but less than 90%. C: Inorganic foreign matter removal rate is 50% or more but less than 75%. D: Inorganic foreign matter removal rate less than 50%.
[0193] 4.Adhesive layer removal performance (Preparing the adhesive sheet) A commercially available adhesive sheet ("PET75-H-120(10)" manufactured by Nichiei Shinka Co., Ltd., polyethylene terephthalate thickness: 75 μm, acrylic adhesive layer thickness: 10 μm) was used.
[0194] (Performance evaluation test) The PSA sheet cut into 5 cm x 5 cm pieces was immersed in 100 ml of the release agent composition placed in a SUS container under the conditions shown in Tables 8 to 11, and then dried at 70°C for 30 minutes. After drying, the PSA sheet was touched with a finger, and the adhesive layer removal performance was evaluated based on the adhesiveness rating according to the following criteria. The results are shown in Tables 12 to 15. A: No stickiness. B: Weak adhesion was observed. C: Strong adhesion was observed.
[0195] 5.Oil removal performance (Preparation of simulated contaminated test specimens) Polyethylene terephthalate containers collected by local governments were cut into 5 x 5 cm plates and immersed in soybean oil (reagent: Fujifilm Wako Pure Chemical Industries, Ltd.) filled in a 200 ml glass bottle at 60°C for 14 days to prepare simulated contamination test pieces.
[0196] (Performance evaluation test) The simulated soiled test piece was immersed in 100 ml of the stripper composition placed in a stainless steel container under the conditions shown in Tables 8 to 11, after which the soybean oil adhering to the test piece was wiped off and the oil removal performance was evaluated according to the following criteria. The results are shown in Tables 12 to 15. A: I was able to wipe it all off. B: About 80% was wiped off. C: About half of the soybean oil remained. D: I couldn't wipe it off.
[0197] 6. Damage to plastic substrates After the evaluation test in 2. Release Layer Removability, the film was visually observed and evaluated for damage to the plastic substrate according to the following criteria. A: No bleaching. B: Partly cloudy. C: The entire surface is bleached.
[0198] [Table 8]
[0199] [Table 9]
[0200] [Table 10]
[0201] [Table 11]
[0202] [Table 12]
[0203] [Table 13]
[0204] [Table 14]
[0205] [Table 15]
[0206] As shown in Tables 12 to 14, the release agent compositions (Examples 1 to 68) containing the amine-based nonionic surfactant (A), which is a compound represented by the general formula (1), and the inorganic basic compound (B) were able to sufficiently peel the functional layers (ink film, release layer, adhesive layer) of printed films, release films, and pressure-sensitive adhesive sheets, sufficiently remove inorganic foreign matter from release films peeled from ceramic green sheets, and sufficiently remove oil stains adhering to polyethylene terephthalate. Furthermore, it was confirmed that the plastic substrates left undamaged after peeling were recyclable.
[0207] On the other hand, as shown in Table 15, it was found that the release agent compositions containing an amine-based nonionic surfactant other than the compound represented by the general formula (1) (Comparative Examples 1 to 4), the release agent composition not containing the amine-based nonionic surfactant (A) (Comparative Example 5), and the release agent compositions not containing the inorganic basic compound component (B) (Comparative Examples 7 and 8) were inferior in the performance of removing oil stains adhering to ink films, release layers, adhesive layers, inorganic foreign matter, and polyethylene terephthalate. [Industrial Applicability]
[0208] As explained above, according to the present invention, it is possible to sufficiently remove various functional layers (for example, release layers and adhesive layers made of a cured silicone resin) and ink films formed on a plastic substrate, and it is also possible to suppress damage to the plastic substrate, such as whitening, caused by functional layer removal or ink washing. Therefore, when recycling a laminate film in which various functional layers and ink films are laminated on a plastic substrate, the release agent composition of the present invention is capable of removing functional layers and ink films from the laminate film without damaging the plastic substrate, and is therefore useful as a release agent for recycling plastic materials.
[0209] Furthermore, according to the present invention, it is possible to sufficiently remove stains derived from the contents of used polyethylene terephthalate containers. Therefore, the release agent composition of the present invention can efficiently remove stains such as oils and fats derived from the contents when recycling used polyethylene terephthalate bottles (PET bottles), and is therefore also useful as a release agent for recycling used polyethylene terephthalate bottles.
Claims
1. The following general formula (1): 【Chemistry 1】 [In general formula (1), R １ represents an alkyl group having 4 to 18 carbon atoms or an alkenyl group having 4 to 18 carbon atoms; A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n and m represent A １ represents the average number of repeating units of A, B, C, and D, each independently being a number of 0 or more, and n+m being a number of 1 to 50; １ When a plurality of O's are present, they may be the same or different. and an inorganic basic compound (B).
2. The following general formula (2): 【Chemistry 2】 [In general formula (2), R ２ represents an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a hydroxyalkenyl group having 8 to 22 carbon atoms; A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and i represents A ２ represents the average number of repeating units of A, B, C, D, E, F ... ２ When a plurality of O's are present, they may be the same or different. and a compound represented by the following general formula (3): 【Transformation 3】 [In general formula (3), A ３ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and j and k represent A ３ represents the average number of repeating units of O, each independently being a number of 0 or more, j+k being a number of 1 to 30, A ３ When a plurality of O's are present, they may be the same or different. A compound represented by 2. The stripping composition according to claim 1, further comprising at least one nonionic surfactant (C) selected from the group consisting of:
3. The following general formula (4): 【Chemistry 4】 [In general formula (4), R ３ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms; A ４ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and p represents A ４ represents the average number of repeating units of A, B, C, D, E, F ... ４ When a plurality of O's are present, they may be the same or different, M represents an alkali metal, an alkaline earth metal, ammonium or a basic group, and x represents the valence of M and is an integer of 1 to 3. a compound represented by the following general formula (5): 【Transformation 5】 [In general formula (5), R ４ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, R ５ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or hydrogen; A ５ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and q and r represent A ５ represents the average number of repeating units of O, each independently being a number of 0 or more, and q+r being a number of 0 to 20; ５ When a plurality of O's are present, they may be the same or different, M represents an alkali metal, an alkaline earth metal, ammonium or a basic group, and y represents the valence of M and is an integer of 1 to 3. and a compound represented by the following general formula (6): 【Transformation 6】 [In general formula (6), R ６ represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms; M represents an alkali metal, an alkaline earth metal, ammonium, or a basic group; z represents the valence of M and is an integer of 1 to 3. A compound represented by 3. The stripping composition according to claim 1, further comprising at least one anionic surfactant (D) selected from the group consisting of:
Citation Information
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