Peeling agent composition

Abstract

To provide a peeling agent composition which is excellent in removal performance for various functional layers and ink films formed on a plastic substrate, and is less likely to cause damage such as whitening of the plastic substrate due to removal of the functional layers or ink cleaning.SOLUTION: There is provided a peeling agent composition containing: a compound represented by the general formula (A): [In the formula (A), R1 is C8-22 alkyl group or C8-22 alkenyl group, and R2 to R4 independently represent C1-3 alkyl group or a group represented by the general formula (B):-(A1O)n-H; (in the formula (B), A1O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents the number of a specific repeating unit of A1O). At least one of R2 to R4 is a group represented by the general formula (B), Xm- represents a counter ion, and m is an integer of 1 to 3.]; and an inorganic basic compound and / or an organic basic compound.SELECTED DRAWING: None

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 the functional layer. [Background technology]

[0002] Conventionally, waste plastic has been disposed of by landfilling, dumping at sea, incineration, etc., but securing landfill sites is becoming difficult, and dumping at sea poses environmental problems because plastic does not decompose. In addition, while it is possible to use the plastic as heat by incineration, there is a problem that the carbon dioxide gas emitted contributes to global warming.

[0003] In light of the recent heightening of environmental concerns, there is a need for recycling, such as reusing and regenerating waste plastics, and research and development into this field is being actively carried out. In addition, since most plastics are produced using fossil fuels, there is a need to develop recycling methods in order to make effective use of resources.

[0004] Polyester films, which are a type of plastic film, are useful as substrate films and are often used as laminated films having various functional layers laminated on one or both sides. The functional layers in such laminated films include various functional layers such as a hard coat layer, a tacky adhesive layer, a decorative layer, a light-shielding layer, a polarizing layer, and an ultraviolet-shielding layer, and materials corresponding to the functional layers are laminated on the polyester film.

[0005] Conventionally, such laminated films have hardly been reused after use, but have been discarded or incinerated. In addition, even if an attempt is made to re-melt a laminated film having a laminated functional layer as is and recycle it, there are problems such as the generation of an unpleasant odor during extrusion and the decrease in the melt viscosity of the polymer, which causes breakage during film formation, because the material constituting the functional layer is mixed into the molten polymer. In addition, even if a film can be formed, there is a problem that deterioration in quality due to discoloration of the obtained film or contamination with foreign matter is unavoidable.

[0006] Furthermore, even if the functional layer was physically peeled off or removed and the recovered polymer was melt-extruded, there was a problem that the functional layer remaining in the molten polymer would clog 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 a film can be formed, 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 adopt a roll-to-roll method.

[0008] Therefore, JP 2022-095599 A (Patent Document 1) discloses a functional layer remover for polyester films 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] In addition, 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 an ink film printed on a plastic substrate. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] JP 2022-095599 A [Patent Document 2] International Publication No. 2022 / 044941 Summary of the Invention [Problem to be solved by the invention]

[0011] However, conventional functional layer removers and ink cleaners did 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 could cause damage to the plastic substrate, such as whitening.

[0012] The present invention has been made in consideration of the problems associated with the above-mentioned conventional techniques, and has an object to provide a release agent composition that has excellent removal performance for various functional layers and ink films formed on plastic substrates, and is less likely to cause damage to the plastic substrate, such as whitening, due to functional layer removal or ink washing. [Means for solving the problem]

[0013] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above object, and as a result have found that a release agent composition containing a quaternary ammonium compound having at least one alkyl group or alkyleneoxy group having a hydroxyl group at a terminal, and an inorganic basic compound and / or an organic basic compound has excellent removal performance for various functional layers (e.g., release layers and adhesive layers made of a cured silicone resin) and ink films formed on plastic substrates, and is less likely to damage (e.g., whiten) the plastic substrate, and have thus completed the present invention.

[0014] That is, the present invention provides the following aspects. [1] The following general formula (A):

[0015] [ka]

[0016] [In general formula (A), R 1 represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms; R 2 ~R 4each independently represents an alkyl group having 1 to 3 carbon atoms or the following general formula (B): -(A 1 O) n -H (B) (In general formula (B), A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents A 1 represents the number of repeating units of A, which is an integer from 1 to 6 and exists in a plurality of cases where n is 2 or more; 1 O may be the same or different. R represents a group represented by 2 ~R 4 At least one of X is a group represented by the general formula (B), m- represents a counter ion, and m is an integer of 1 to 3. and an inorganic basic compound and / or an organic basic compound. [2] R in the above general formula (A) 2 ~R 4 one of which is a group represented by general formula (B) and the rest are an alkyl group having 1 to 3 carbon atoms. [3] The stripping composition according to [1] or [2], which contains at least an inorganic basic compound. [4] The following general formula (C): R 5 -(A 2 O) p -H (C) [In general formula (C), R 5 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 p represents A 2 represents the number of repeating units of A, which is an integer from 1 to 100, and when p is 2 or more, a plurality of A 2 O may be the same or different. The stripping composition according to any one of [1] to [3], further comprising a compound represented by the following formula: Effect of the Invention

[0017] 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 washing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below based on preferred embodiments thereof.

[0019] The stripping composition of the present invention is represented by the following general formula (A):

[0020] [ka]

[0021] [In general formula (A), R 1 represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms; R 2 ~R 4 each independently represents an alkyl group having 1 to 3 carbon atoms or the following general formula (B): -(A 1 O) n -H (B) (In general formula (B), A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents A 1 represents the number of repeating units of A, which is an integer from 1 to 6 and exists in a plurality of cases where n is 2 or more; 1 O may be the same or different. R represents a group represented by 2 ~R 4 At least one of X is a group represented by the following formula (B): m- represents a counter ion, and m is an integer of 1 to 3. and an inorganic basic compound and / or an organic basic compound.

[0022] The release agent composition of the present invention is a compound represented by the following general formula (C): R 5 -(A 2 O) p -H (C) [In general formula (C), R 5 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 p represents A 2 represents the number of repeating units of A, which is an integer from 1 to 100, and when p is 2 or more, a plurality of A 2 O may be the same or different. It is preferable that the compound further contains a compound represented by the following formula:

[0023] (Compound represented by general formula (A)) The compound represented by the general formula (A) used in the present invention is a quaternary ammonium compound having at least one alkyl group or alkyleneoxy group having a hydroxyl group at its terminal.

[0024] In the general formula (A), R 1 represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms. Of these, from the viewpoint of improving the removability of the functional layer or the ink film, an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 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. The alkyl group and alkenyl group may be linear or branched, but is preferably linear, and is more preferably a linear alkyl group.

[0025] In the general formula (A), R 2 ~R 4 each independently represents an alkyl group having 1 to 3 carbon atoms or a group represented by the general formula (B). 2 ~R 4 At least one of R is a group represented by the general formula (B). 2 ~R 4At least one of R is a group represented by the general formula (B), which provides excellent removal performance for various functional layers and ink films. Furthermore, in the general formula (A), from the viewpoint of excellent removal performance for ink films and release layers, R 2 ~R 4 It is preferable that one of them is a group represented by the above formula (B), and the remaining is an alkyl group having 1 to 3 carbon atoms.

[0026] In the general formula (B), A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms. 1 represents the number of repeating units of A and is an integer of 1 to 6. When n is 2 or more, 1 The O's may be the same or different.

[0027] In the general formula (A), R 2 ~R 4 When one of them is a group represented by general formula (B) (and the rest are alkyl groups having 1 to 3 carbon atoms), n in general formula (B) is an integer of 1 to 6, and is preferably an integer of 1 to 3 from the viewpoint of ease of synthesis of the compound represented by general formula (A).

[0028] In addition, in the general formula (A), R 2 ~R 4 When two or more of the general formula (B) are groups represented by the general formula (B), n in the two or more general formulas (B) is each independently an integer of 1 to 6. From the viewpoint of improving the removal performance of the compound represented by the general formula (A) for various functional layers and ink films, it is preferable that n in at least one of the general formulas (B) is an integer of 1 to 3 (n in the remaining general formulas (B) may be an integer of 1 to 3 or an integer of 4 to 6), and it is more preferable that n in all of the general formulas (B) is an integer of 1 to 3.

[0029] In the general formula (A), X m-represents a counter ion, and m is the valence of the counter ion. The counter ion is not particularly limited and may be an inorganic anion or an organic anion. Examples of inorganic anions include nitrate ions, phosphate ions, borate ions, and sulfate ions. Examples of organic anions include organic carboxylate ions, organic sulfonate ions, phosphate ester ions, alkyl carbonate ions, and anionic polymers. These counter ions may be used alone or in combination of two or more.

[0030] The method for synthesizing such a compound represented by the general formula (A) is not particularly limited, and a known synthesis method can be adopted in which an alkylene oxide having 2 to 4 carbon atoms is added to a primary to tertiary amine compound containing an alkyl group or alkenyl group having a predetermined number of carbon atoms.

[0031] For example, a primary amine compound containing an alkyl or alkenyl group having a predetermined carbon number is charged into a pressure-resistant reaction vessel, a predetermined amount of alkylene oxide is introduced, and the vessel is heated to 70 to 160°C to carry out an addition reaction, synthesizing an alkylene oxide 2-mol adduct of the primary amine compound as an intermediate compound. Next, this intermediate compound is neutralized with an acid, and then a predetermined amount of alkylene oxide is introduced and the vessel is heated to 70 to 140°C to carry out an addition reaction, thereby producing the target compound (R 2 ~R 4 are all groups represented by general formula (B).

[0032] In addition, a tertiary amine compound containing an alkyl group or alkenyl group having a predetermined carbon number is charged into a pressure-resistant reaction vessel, and the tertiary amine compound is neutralized with an acid. Then, a predetermined amount of alkylene oxide is introduced and the mixture is heated to 70 to 140° C. to carry out an addition reaction, thereby obtaining the target compound (R 2 ~R 4 a compound in which one of the groups is a group represented by general formula (B) and the remaining groups are alkyl groups having 1 to 3 carbon atoms can be obtained.

[0033] (Basic compounds) The release agent composition of the present invention contains an inorganic basic compound and / or an organic basic compound. In the release agent composition of the present invention, the inorganic basic compound and the organic basic compound adjust the release agent composition to be alkaline, and it is sufficient to contain either one of them, but from the viewpoint of improving the removal performance for various functional layers and ink films, it is preferable that the release agent composition contains at least an inorganic basic compound, and it is more preferable that the release agent composition contains both an inorganic basic compound and an organic basic compound.

[0034] Examples of inorganic basic compounds used in the present invention include ammonia; hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; phosphates of alkali metals such as trisodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, tripotassium phosphate, potassium pyrophosphate, and potassium tripolyphosphate; and silicates of alkali metals such as sodium orthosilicate, sodium metasilicate, and potassium silicate. These inorganic basic compounds may be used alone or in combination of two or more. Among these inorganic basic compounds, hydroxides of alkali metals are preferred, and sodium hydroxide and potassium hydroxide are more preferred from the viewpoint of availability, and it is particularly preferred to use potassium hydroxide and sodium hydroxide in combination from the viewpoint of improving the removal performance and handling for various functional layers and ink films.

[0035] 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 (9-hydrate) (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.

[0036] Examples of organic basic compounds used in the present invention include organic amine compounds such as N,N-bis(2-hydroxyethyl)-N-cyclohexylamine, diazabicycloundecene, diazabicyclononene, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 1-amino-2-propanol, and triisopropanolamine. These organic amine compounds may be used alone or in combination of two or more. Among these organic amine compounds, from the viewpoint of availability, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine are preferred, and from the viewpoint of improving the removal performance for various functional layers and ink films, monoethanolamine is more preferred.

[0037] In the present invention, as such an organic basic compound, commercially available organic basic compounds such as monoethanolamine (manufactured by Mitsui Fine Chemicals, Inc.), diethanolamine (manufactured by Mitsui Fine Chemicals, Inc.), triethanolamine (manufactured by Mitsui Fine Chemicals, Inc.), and monoisopropanolamine (manufactured by Mitsui Fine Chemicals, Inc.) can be appropriately used.

[0038] (Compound represented by general formula (C)) The compound represented by the general formula (C) used in the present invention is a compound in which an alkyl group or an alkyleneoxy group having a hydroxyl group at a terminal is bonded to an alkyl group or an alkenyl group which may have a hydroxyl group, and functions as a nonionic surfactant.

[0039] In the general formula (C), R 5represents 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 viewpoint of improving the removability of various functional layers and ink films, an alkyl group having 10 to 18 carbon atoms, a hydroxyalkyl group having 10 to 18 carbon atoms, an alkenyl group having 10 to 18 carbon atoms, or a hydroxyalkenyl group having 10 to 18 carbon atoms is preferred, and an alkyl group having 10 to 16 carbon atoms, a hydroxyalkyl group having 10 to 16 carbon atoms, an alkenyl group having 10 to 16 carbon atoms, or a hydroxyalkenyl group having 10 to 16 carbon atoms is more preferred. The alkyl group, the hydroxyalkyl group, the alkenyl group, and the hydroxyalkenyl group may be linear or branched, but are preferably linear, and are more preferably linear alkyl groups.

[0040] In the general formula (C), A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and may be a chain consisting of one type of these alkyleneoxy groups or a mixed chain consisting of two or more types. 2 From 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.

[0041] In the general formula (C), p is A 2 It represents the number of repeating units of A and is an integer from 1 to 100. From the viewpoint of improving the removal performance for various functional layers and ink films, it is preferably an integer from 4 to 50, and more preferably an integer from 4 to 20. In addition, when p is 2 or more, a plurality of A 2 The O's may be the same or different.

[0042] There is no particular limitation on the method for synthesizing the compound represented by the general formula (C), 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. 5 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.

[0043] [Removal Agent Composition] The stripping agent composition of the present invention contains the compound represented by the general formula (A) and the inorganic basic compound and / or the organic basic compound, and preferably further contains the compound represented by the general formula (C).

[0044] In the present invention, a mixture of the compound represented by the general formula (A), the inorganic basic compound and / or the organic basic compound, and the compound represented by the general formula (C) contained as necessary can be used as it is as a stripping agent composition, but from the viewpoint of dissolution and improvement of flowability, water or an organic solvent may be added thereto.

[0045] 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, and benzyl alcohol; 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol ethyl ether acetate. Examples of the glycol ethers include diethylene 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, and tripropylene glycol monomethyl ether; and glycols such as ethylene glycol, propylene glycol, 1,3-butanediol, hexylene glycol, diethylene glycol, and dipropylene glycol.

[0046] In the release agent composition of the present invention, the content of the compound represented by the general formula (A) is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and even more preferably 0.1 to 20 mass%, based on the total mass of the release agent composition, from the viewpoints of improving the removability of various functional layers and ink films and suppressing damage such as whitening of plastic substrates.

[0047] With regard to the content of the inorganic basic compound and / or the organic basic compound, from the viewpoints of improving the removability for various functional layers and ink films and suppressing damage such as whitening of plastic substrates, the total content of the inorganic basic compound and the organic basic compound is preferably 0.05 to 30 mass%, more preferably 0.1 to 20 mass%, and even more preferably 0.1 to 15 mass%, relative to the entire release agent composition.

[0048] Furthermore, when the inorganic basic compound and the organic basic compound are used in combination, the mass ratio of the inorganic basic compound to the organic basic compound is preferably inorganic basic compound / organic basic compound=1 / 0.1 to 1 / 1, and more preferably inorganic basic compound / organic basic compound=1 / 0.2 to 1 / 1, from the viewpoints of improving the removal performance for various functional layers and ink films and suppressing damage such as whitening of plastic substrates.

[0049] From the viewpoint of improving the removal performance for various functional layers and ink films, the mass ratio of the compound represented by the general formula (A) (compound (A)) to the total amount of the inorganic basic compound and the organic basic compound is preferably compound (A) / basic compound=5 / 1 to 5 / 100, more preferably compound (A) / basic compound=5 / 1 to 5 / 50, and even more preferably compound (A) / basic compound=5 / 1 to 5 / 20.

[0050] Furthermore, the content of the compound represented by the general formula (C) is preferably 0.01 to 30 mass %, and more preferably 0.1 to 20 mass %, of the entire release agent composition, from the viewpoint of improving the removal performance for various functional layers and ink films.

[0051] (Other Ingredients) The release agent composition of the present invention may contain known components that can be added to 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, and defoamers.

[0052] (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 for various functional layers and ink films and improving the removal performance for inorganic foreign matter. 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, aminomethylglycine diacetic acid, etc.; organic acid salts such as citric acid, tartaric acid, gluconic acid, etc.; polyelectrolyte compounds such as polyacrylic acid, polyacrylic acid / maleic acid copolymer, and their salts; phosphoric acid compounds such as tripolyphosphate, orthophosphate, pyrophosphate, etc.; 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.

[0053] (Antioxidants) Examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants.

[0054] (rust inhibitor) Examples of the rust inhibitor include inorganic rust inhibitors such as chromates, molybdates, and sodium nitrite.

[0055] (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.

[0056] (Viscosity modifier) Examples of the viscosity modifier include polymer compounds and layered inorganic particles.

[0057] (Antifoaming agent) Examples of the antifoaming agent include fluorine-based compounds, silicone-based compounds, polyether-based compounds, and acetylene glycol-based compounds.

[0058] (Removal method) Next, a method for removing a functional layer or an ink film using the stripping composition of the present invention will be described.

[0059] In the method for removing a functional layer or an ink film using the release agent composition of the present invention, the functional layer or ink film of a laminated film is brought into contact with the release agent composition of the present invention. Examples of the method for bringing the functional layer or ink film into contact with the release agent composition include a method for immersing the functional layer or ink film in a release agent tank containing a release agent composition in a solution state (immersion method), a method for applying the release agent composition in a solution state to the surface of the functional layer or ink film (application method), and a method for spraying the release agent composition in a solution state or a vaporized release agent composition onto the surface of the functional layer or ink film (spray method). In the immersion method, ultrasonic treatment may be performed in the release agent tank (ultrasonic treatment method). Among these methods, the immersion method and the ultrasonic treatment method are preferred from the viewpoint of the permeability of the release agent composition into the functional layer or ink film.

[0060] In the immersion method, the temperature of the release agent composition during immersion (immersion temperature) is not particularly limited, but from the viewpoint of low viscosity of the release agent composition and easy penetration of the release agent composition into the functional layer or ink film, it is preferably room temperature (20°C) or higher, and from the viewpoint of improving the removal performance for various functional layers and ink films, it is more preferably 40°C or higher, further preferably 60°C or higher, and particularly preferably 70°C or higher. In addition, 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 immersion temperature can also be adopted in methods other than the immersion method.

[0061] In the immersion method, the immersion time in the release agent composition is not particularly limited, but from the viewpoint of improving the removability of various functional layers and ink films 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.

[0062] (Ultrasonic Treatment Method) The frequency of the ultrasonic waves in the ultrasonic treatment method is not particularly limited, but from the viewpoint of improving the removal performance for various functional layers and ink films and finely dividing the 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 amplitude of the ultrasonic waves is not particularly limited, but from the viewpoint of improving the removal performance for various functional layers and ink films and finely dividing the peeled functional layers, it is preferably 1 to 100 μm, and more preferably 5 to 80 μm. The immersion temperature and immersion time in the ultrasonic treatment method are the same as those in the immersion method.

[0063] There are no particular limitations on the ultrasonic processing device used in such an ultrasonic processing method, but examples include horn type and sweep type devices. When removing a functional layer or ink film over a wide area, a sweep type device is preferred, and when removing a functional layer or ink film over a narrow area, a horn type device is preferred. EXAMPLES

[0064] 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.

[0065] [Compound represented by general formula (A)] The compounds represented by the following general formula (A) (hereinafter abbreviated as "compound (A)") used in the examples and comparative examples were synthesized by the following method. In addition, R in the following general formula (A) in the compounds (A1) to (A11) obtained in each synthesis example 1 ~R 4 and X m- is shown in Table 1.

[0066] [ka]

[0067] [Table 1]

[0068] (Synthesis Example A1) In a pressure-resistant reaction vessel, 100 g of N,N-dimethyldodecylamine (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), 207 g of ion-exchanged water, and 47 g of 60% nitric acid were charged and heated to 85-95°C, after which the inside of the pressure-resistant reaction vessel was replaced with nitrogen. Then, 23 g of ethylene oxide was blown in, and the mixture was aged at 85-95°C for 6 hours to obtain the target compound (A1).

[0069] (Synthesis example A2) The target compound (A2) was obtained in the same manner as in Synthesis Example A1, except that 27 g of 85% phosphoric acid was used instead of 60% nitric acid.

[0070] (Synthesis example A3) The target compound (A3) was obtained in the same manner as in Synthesis Example A1, except that 15 g of boric acid was used instead of 60% nitric acid.

[0071] (Synthesis example A4) In a pressure-resistant reaction vessel, 100 g of dodecylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved at 40°C was charged, and the inside of the pressure-resistant reaction vessel was replaced with nitrogen, and then heated to 120-130°C. Then, 48 g of ethylene oxide was blown in, and the mixture was aged at 120-130°C for 6 hours to obtain an intermediate compound which is an ethylene oxide 2 mole adduct of dodecylamine. After cooling this intermediate compound to 90°C, 207 g of ion-exchanged water was added, and further 54 g of 60% nitric acid was added and mixed, and the mixture was heated to 85-95°C, and then the inside of the pressure-resistant reaction vessel was replaced with nitrogen. Then, 26 g of ethylene oxide was blown in, and the mixture was aged at 85-95°C for 6 hours to obtain the target compound (A4).

[0072] (Synthesis example A5) The target compound (A5) was obtained in the same manner as in Synthesis Example A1, except that 30 g of propylene oxide was used instead of ethylene oxide.

[0073] (Synthesis example A6) In the same manner as in Synthesis Example A4, an intermediate compound, which is an ethylene oxide 2 mole adduct of dodecylamine, was obtained. After cooling this intermediate compound to 60°C, 148g was charged into a reaction vessel, and 114g of dimethyl sulfate was added dropwise while heating to 85-95°C. After completion of the dropwise addition, the mixture was aged at 85-95°C for 6 hours, and 207g of ion-exchanged water was added and mixed to obtain the target compound (A6).

[0074] (Synthesis example A7) The target compound (A7) was obtained in the same manner as in Synthesis Example A1, except that 100 g of N,N-dimethyl-n-octylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of N,N-dimethyldodecylamine, the amount of 60% nitric acid was changed to 64 g, and the amount of ethylene oxide was changed to 31 g.

[0075] (Synthesis example A8) In a pressure-resistant reaction vessel, 100 g of N,N-dimethyl-n-octadecylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved at 30°C was charged instead of N,N-dimethyldodecylamine, the amount of 60% nitric acid was changed to 34 g, and the amount of ethylene oxide was changed to 16 g. The target compound (A8) was obtained in the same manner as in Synthesis Example A1.

[0076] (Synthesis example A9) An intermediate compound, which is an ethylene oxide 2-mol adduct of oleylamine, was obtained in the same manner as in Synthesis Example A4, except that 100 g of oleylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dodecylamine, and the amount of ethylene oxide was changed to 33 g. Thereafter, the target compound (A9) was obtained in the same manner as in Synthesis Example A4, except that an ethylene oxide 2-mol adduct of oleylamine was used instead of an ethylene oxide 2-mol adduct of dodecylamine as an intermediate compound, the amount of 60% nitric acid was changed to 37 g, and the amount of ethylene oxide was changed to 18 g.

[0077] (Synthesis Example A10) An intermediate compound, which is an ethylene oxide 2-mol adduct of dodecylamine, was obtained in the same manner as in Synthesis Example A4. After cooling this intermediate compound to 90°C, 0.15g of potassium hydroxide was added as a catalyst, and the inside of the pressure-resistant reaction vessel 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, 190g of ethylene oxide was blown in while heating to 120-130°C, and the mixture was aged at 120-130°C for 6 hours to obtain an intermediate compound, which is an ethylene oxide 10-mol adduct of dodecylamine. Then, the target compound (A10) was obtained in the same manner as in Synthesis Example A4, except that an ethylene oxide 10-mol adduct of dodecylamine was used instead of an ethylene oxide 2-mol adduct of dodecylamine as the intermediate compound, and 163g of p-toluenesulfonic acid was used instead of 60% nitric acid.

[0078] (Synthesis Example A11) The target compound (A11) was obtained in the same manner as in Synthesis Example A10, except that 63 g of propylene oxide was used instead of 190 g of ethylene oxide.

[0079] [Compound represented by formula (C)] The compounds represented by the following general formula (C) (hereinafter abbreviated as "compound (C)") used in the examples and comparative examples were synthesized by the following method. In addition, R in the following general formula (C) in the compounds (C1) to (C5) obtained in each synthesis example 5 , A 2 O and p are shown in Table 2. R 5 -(A 2 O) p -H (C)

[0080] [Table 2]

[0081] (Synthesis example C1) In a pressure-resistant reaction vessel, 100 g of decyl alcohol (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide were charged, and the inside of the pressure-resistant reaction vessel 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, 139 g of ethylene oxide was introduced while heating to 120-130°C, and the mixture was aged at the same temperature for 3 hours to obtain the target compound (C1).

[0082] (Synthesis Example C2) In a pressure-resistant reaction vessel, 100 g of dodecyl alcohol (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide were charged, and the inside of the pressure-resistant reaction vessel 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, 94 g of propylene oxide was introduced while heating to 120-130°C, and the mixture was aged at the same temperature for 12 hours, and further, 213 g of ethylene oxide was introduced while heating to 120-130°C, and the mixture was aged at the same temperature for 3 hours to obtain the target compound (C2).

[0083] (Synthesis Example C3) The target compound (C3) was obtained in the same manner as in Synthesis Example C2, except that the amount of propylene oxide was changed to 281 g and the amount of ethylene oxide was changed to 71 g.

[0084] (Synthesis example C4) The target compound (C4) was obtained in the same manner as in Synthesis Example C1, except that 100 g of dodecyl alcohol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of decyl alcohol and the amount of ethylene oxide was changed to 284 g.

[0085] (Synthesis example C5) In a heat-resistant reaction vessel, 100 g of octadecyl alcohol (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of potassium hydroxide were charged, and the temperature was raised to 70°C, after which the inside of the pressure-resistant reaction vessel 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, 322 g of propylene oxide was introduced while heating to 120-130°C, and the mixture was aged at the same temperature for 12 hours, and further, 976 g of ethylene oxide was introduced while heating to 120-130°C, and the mixture was aged at the same temperature for 3 hours to obtain the target compound (C5).

[0086] [Chelating Agent] Diethylenetriaminepentaacetic acid (a reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the chelating agent.

[0087] [Other compounds (a)] Compounds similar to the compound (A) used in the Comparative Examples (hereinafter, abbreviated as "compound (a)") were synthesized by the following method. In addition, in the compounds (a1) to (a3) ​​and compound (a4) obtained in each Synthesis Example, R in the general formula (A) was 1 ~R 4 and X m- The corresponding groups and counterions are shown in Table 3.

[0088] [Table 3]

[0089] (Synthesis Example a1) A reaction vessel was charged with 100 g of N,N-dimethyldodecylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), heated to 85-95°C while introducing nitrogen, and 99 g of benzyl chloride (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise at the same temperature. After completion of the addition, the mixture was aged at 85-95°C for 6 hours, and then 207 g of ion-exchanged water was added and mixed to obtain the target compound (a1).

[0090] (Synthesis example a2) An intermediate compound, which is an ethylene oxide 2-mol adduct of dodecylamine, was obtained in the same manner as in Synthesis Example A4. After cooling this intermediate compound to 90°C, 0.15g of potassium hydroxide was added as a catalyst, and the inside of the pressure-resistant reaction vessel was replaced with nitrogen. Next, after dehydration under reduced pressure at 120°C for 1 hour, 428g of ethylene oxide was blown in and aged at 120 to 130°C for 6 hours to obtain an intermediate compound, which is an ethylene oxide 20-mol adduct of dodecylamine. Thereafter, the target compound (a2) was obtained in the same manner as in Synthesis Example A4, except that an ethylene oxide 20-mol adduct of dodecylamine was used instead of an ethylene oxide 2-mol adduct of dodecylamine as the intermediate compound.

[0091] (Synthesis example a3) An intermediate compound, which is an ethylene oxide 2 mole adduct of hexylamine, was obtained in the same manner as in Synthesis Example A4, except that 100 g of hexylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dodecylamine, and the amount of ethylene oxide was changed to 87 g. After cooling this intermediate compound to 60°C, 187 g was charged into a reaction vessel, and 254 g of diethyl sulfate was added dropwise while heating to 85 to 95°C. After the dropwise addition was completed, the mixture was aged at 85 to 95°C for 6 hours, and 207 g of ion-exchanged water was added and mixed to obtain the target compound (a3).

[0092] (Compound (a4)) Tetrahexylammonium chloride (reagent, manufactured by Sigma-Aldrich) was used as compound (a4).

[0093] (Examples 1 to 28 and Comparative Examples 1 to 11) [Preparation of Stripping Composition] The types of compound (A) or compound (a), inorganic basic compound, organic basic compound, compound (C) and chelating agent shown in Table 4 were dissolved in water to the concentrations shown in Table 4 to prepare stripper compositions.

[0094] [Performance evaluation of stripping agent composition] 1. Ink film removal performance (Preparation of printed film) A hybrid UV-curable ink (Toyo Ink Co., Ltd.'s "F-DK-HS ink") was solid-colored (printed) to a thickness of approximately 1 μm on a 10 cm x 10 cm area of ​​the surface of a 25 μm-thick polyethylene terephthalate film (AS ONE Corporation's "Lumirror(R) Film") using a manual screen printer (Tsujii Senki Kogyo Co., Ltd.). The colored polyethylene terephthalate film was then exposed to UV light from a 120 W / cm metal hydride lamp using a conveyor-type UV device (Eye Graphics Co., Ltd.'s "ECS-4011GX / N") with an integrated light output of 1000 mj / cm. 2 The ink was cured by irradiation so as to obtain a printed film.

[0095] (Performance evaluation test) The printed film cut to 5 cm x 5 cm was immersed in 100 ml of the stripping composition placed in a SUS container under the conditions shown in Table 4, and then dried at 70°C for 30 minutes. The surface of the printed film after drying 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 5 and 6. 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: Less than 50% ink removal rate.

[0096] 2. Release layer removal performance (Preparation of release film) One side of a 25 μm thick polyethylene terephthalate film (As One Corporation's "Lumirror(R) Film") was coated with a 5 wt % aqueous solution of polyvinyl alcohol resin (Mitsubishi Chemical Corporation's "GH-17R") using a bar coater (Tester Sangyo Co., Ltd.'s "PI-1210 AUTO FILM APPLICATOR") so that the thickness after drying would be 0.5 μm, and then dried in an oven at 120°C for 5 minutes.

[0097] Using the bar coater, a 5% by mass toluene solution of curable silicone resin ("LTC-310" manufactured by Dow-Toray Industries, Inc., curing agent: SRX211) was coated on the surface of the polyvinyl alcohol resin layer of the dried film so that the thickness after drying would be 1 μm, and then the coating was dried in an oven at 100° C. for 5 minutes to produce a release film with a release layer (cured silicone resin layer).

[0098] (Performance evaluation test) The release film cut to 5 cm x 5 cm was immersed in 100 ml of the release agent composition contained in a SUS container under the conditions shown in Table 4, 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, Shimadzu Corporation's "EDX-7000"), and the Si removal rate was calculated using the following formula and evaluated according to the following criteria. The results are shown in Tables 5 and 6. 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%.

[0099] 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 above method so that the thickness after drying was 5 μm, and then dried in an oven at 85°C for 10 minutes to prepare a ceramic green sheet.

[0100] (Performance evaluation test) The release film was peeled off from the ceramic green sheet, and the obtained release film was cut to 5 cm x 5 cm, immersed in 100 ml of the release agent composition contained in a SUS container under the conditions shown in Table 4, and then dried at 70°C for 30 minutes. The number of inorganic foreign matter particles on the release film after drying was counted, and the inorganic foreign matter removal rate was calculated using the following formula and evaluated according to the following criteria. The results are shown in Tables 5 and 6. Inorganic foreign matter removal rate [%] = (1 - number of inorganic foreign matter after immersion / number of inorganic foreign matter 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 is less than 50%.

[0101] 4.Adhesive layer removal performance (Performance evaluation test) A commercially available adhesive sheet ("PET75-H-120(10)" manufactured by Nichiei Shinka Co., Ltd., thickness of polyethylene terephthalate: 75 μm, thickness of acrylic adhesive layer: 10 μm) cut to 5 cm x 5 cm was immersed in 100 ml of the release agent composition contained in a SUS container under the conditions shown in Table 4, and then dried at 70°C for 30 minutes. The adhesive sheet after drying was touched with a finger and the adhesion was evaluated according to the following criteria. The results are shown in Tables 5 and 6. A:No stickiness. B: Weak adhesion is observed. C: Strong adhesion is observed.

[0102] 5. Damage to plastic substrates (Evaluation test) The film after the evaluation test in 2. Release layer removability was visually observed, and damage to the plastic substrate was evaluated according to the following criteria. A: No bleaching. B: Partly cloudy. C: The entire surface is whitened.

[0103] [Table 4]

[0104] [Table 5]

[0105] [Table 6]

[0106] As shown in Table 5, the release agent composition (Examples 1 to 28) containing the compound (A) represented by the general formula (A) and an inorganic basic compound and / or an organic basic compound can sufficiently peel off the functional layers (ink film, release layer, adhesive layer) of the printed film, release film, and adhesive sheet, and can sufficiently remove inorganic foreign matter from the release film peeled off from the ceramic green sheet, and it was confirmed that the plastic substrate after peeling is not damaged and can be recycled. In addition, as shown in Example 5, it was found that the inorganic foreign matter removal performance is improved by blending a chelating agent in the release agent composition.

[0107] On the other hand, as shown in Table 6, it was found that the release agent compositions not containing the compound (A) represented by the general formula (A) (Comparative Examples 1 to 9) and the release agent compositions not containing an inorganic basic compound and an organic basic compound (Comparative Examples 10 to 11) were inferior in the removal performance of the ink film, the release layer, the adhesive layer, and inorganic foreign matter. [Industrial Applicability]

[0108] As described above, 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 washing.

[0109] Therefore, the release agent composition of the present invention is useful as a release agent for recycling plastic materials, since it is possible to remove functional layers and ink films from a laminate film having various functional layers and ink films laminated on a plastic substrate without damaging the plastic substrate when recycling the laminate film.

Claims

1. The following general formula (A): 【Chemistry 1】 [In general formula (A), R １ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms; R ２ ~R ４ each independently represents an alkyl group having 1 to 3 carbon atoms or the following general formula (B): -(A １ O) ｎ -H (B) (In general formula (B), A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents A １ represents the number of repeating units of A, which is an integer from 1 to 6, and when n is 2 or more, a plurality of A １ O may be the same or different. R represents a group represented by ２ ~R ４ At least one of X is a group represented by the general formula (B), ｍ－ represents a counter ion, and m is an integer of 1 to 3. and an inorganic basic compound and / or an organic basic compound.

2. R in the general formula (A) ２ ~R ４ The stripping composition according to claim 1, wherein one of the above is a group represented by formula (B) and the remaining is an alkyl group having 1 to 3 carbon atoms.

3. 2. The stripping composition according to claim 1, which contains at least an inorganic basic compound.

4. The following general formula (C): R ５ -(A ２ O) ｐ -H (C) [In general formula (C), R ５ 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; p represents A ２ represents the number of repeating units of A, which is an integer from 1 to 100, and when p is 2 or more, a plurality of A ２ O may be the same or different.

2. The stripping composition according to claim 1, further comprising a compound represented by the following formula:

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