Processing liquid, separation and recovery method, manufacturing method for molding materials, and manufacturing method for molded articles

Abstract

To provide a processing solution for separating and recovering a plastic substrate from a laminate comprising at least a release layer on the plastic substrate, a method for separating and recovering the plastic substrate, and methods for manufacturing molding materials and molded articles, characterized by providing a high-grade recycled plastic substrate with excellent release properties of the release layer and superior ability to suppress reattachment during prolonged processing.SOLUTION: The above problem is solved by a treatment solution for separating and recovering a plastic substrate from a laminate comprising at least a release layer on the plastic substrate, and the treatment solution contains a basic compound and oils and / or oil decomposition products.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a treatment liquid for separating and recovering a plastic substrate from a laminate having at least a release layer on the plastic substrate, a separation and recovery method, a method for producing a molding material, and a method for producing a molded article. [Background technology]

[0002] In recent years, packaging, plastic bottles, and other plastic products made from plastic film have been discarded and dumped into the ocean as litter, causing environmental pollution. These plastic products decompose in seawater and become submicron-sized fragments (microplastics), which float in the seawater. These microplastics are ingested by marine organisms such as fish and become concentrated in their bodies, raising concerns that they may affect the health of seabirds and humans that consume these marine organisms as food.

[0003] Examples of the plastic products include food packaging packages made of single-layer or multi-layer plastic film. Various plastic substrates, such as polyester, nylon (NY), polypropylene (PP), and polyethylene (PE), are used as film substrates in such food packaging packages. These film substrates are printed with printing ink and then made into bags to form packages. Alternatively, they are bonded to other film substrates or heat-melting resin substrates via adhesives or the like, and then made into bags and heat-sealed to form packages. However, because such food packaging contains coloring components, they can only be recycled by downcycling as is, and have not yet achieved the recycling of plastics.

[0004] Regarding material recycling of such multi-layered packaging materials, for example, Patent Document 1 discloses a technology for removing printed layers from laminates with not only single-layer (surface-printed) structures but also multi-layer structures by treating a laminate having a detachment layer containing a polyurethane resin with a predetermined acid value with an alkaline aqueous solution. Patent Document 2 discloses a technique for removing ink from a film using a cleaning solution that is basic and contains a cationic or anionic surfactant.

[0005] Furthermore, Patent Document 3 discloses a technology for removing ink from a film by using a treatment liquid containing a nonionic surfactant and crushing the target printed matter while feeding it under pressure. Similarly, Patent Document 4 discloses a technique for removing ink from a film with excellent workability, using a treatment liquid containing a nonionic surfactant and an antifoaming agent in combination. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6638802 [Patent Document 2] International Publication No. 2013 / 144400 [Patent Document 3] Patent No. 7004124 [Patent Document 4] Patent No. 7263661 Summary of the Invention [Problem to be solved by the invention]

[0007] However, in the ink removal process described in Patent Document 1, if the amount of packaging material treated with the alkaline aqueous solution is increased in order to improve productivity, the ink removability decreases, and furthermore, the printed layer and adhesive layer that were separated and removed become finely dispersed and reattach to the plastic substrate. Note that "reattachment" refers to the process in which impurities such as the printed layer and adhesive layer that have peeled off the substrate are finely dispersed by agitation and reattach to the substrate, which can cause discoloration of the recovered plastic substrate and a deterioration in the properties of the recycled material. Furthermore, when a treatment liquid containing a cationic or anionic surfactant as described in Patent Document 2 is used, bubbles are generated during the process of immersing a laminate in the treatment liquid to remove the colored layer. The generated bubbles then embrace components derived from the colored layer (especially highly lipophilic components) to form micelles, which then rise to the surface of the treatment liquid. Meanwhile, plastic substrates with low specific gravity also rise to the surface of the treatment liquid, causing the components derived from the colored layer and the plastic substrate to congregate on the surface of the treatment liquid, further increasing the problem of re-adhesion to the plastic substrate.

[0008] Furthermore, the ink removal process described in Patent Document 3 uses a treatment liquid containing a nonionic surfactant that generates relatively little foaming. Furthermore, Patent Document 4 uses a defoaming agent in combination to suppress re-adhesion of impurities due to foaming. However, while both methods are excellent at suppressing re-adhesion in the short period of time until impurities such as colored layers peel off, when performing continuous treatment, there are cases in which re-adhesion cannot be sufficiently suppressed if the plastic substrate is immersed in a treatment liquid containing fine impurity fragments for a long period of time and coexists with the impurity fragments.

[0009] Therefore, an object of the present invention is to provide a treatment liquid for separating and recovering a plastic substrate from a laminate having at least a detachment layer on a plastic substrate, which is excellent in the detachment property of the detachment layer and the ability to inhibit reattachment during long-term treatment, and which can produce a high-quality recycled plastic substrate; a method for separating and recovering the plastic substrate; and a method for producing a molding material and a molded article. [Means for solving the problem]

[0010] That is, the present invention relates to the following [1] to

[10] .

[0011] [1] A treatment solution for separating and recovering a plastic substrate from a laminate having at least a release layer on a plastic substrate, A treatment liquid comprising a basic compound and fats and / or fat decomposition products.

[0012] [2] The treatment liquid according to [1], wherein the fats and / or fat decomposition products are at least one selected from the group consisting of vegetable fats and oils, animal fats and oils, decomposition products of vegetable fats and oils, and decomposition products of animal fats and oils.

[0013] [3] The treatment liquid according to [1] or [2], wherein the number of carbon atoms in the fatty acids constituting the fats and / or fat decomposition products is 1 to 24.

[0014] [4] The treatment liquid according to any one of [1] to [3], wherein the total content of fats and oils and decomposition products thereof is 0.05 to 10.00 mass % in 100 mass % of the treatment liquid.

[0015] [5] The treatment liquid according to any one of [1] to [4], further comprising a surfactant (excluding fat and oil decomposition products), wherein the surfactant is at least one selected from the group consisting of anionic surfactants, nonionic surfactants, and amphoteric surfactants.

[0016] [6] The treatment liquid according to [5], wherein the content of the surfactant (excluding fat and oil decomposition products) is 0.01 to 5.0 mass % in 100 mass % of the treatment liquid.

[0017] [7] The treatment liquid according to any one of [1] to [6], further comprising an antifoaming agent.

[0018] [8] A method for separating and recovering a plastic substrate, comprising the steps of contacting a laminate having at least a detachment layer on a plastic substrate with the treatment liquid according to any one of [1] to [7] to detach the detachment layer, and separating and recovering the plastic substrate.

[0019] [9] [8] A method for producing a molding material using a plastic substrate separated and recovered by the separation and recovery method described in the plastic substrate is a polyolefin substrate, A method for producing a molding material, wherein the molding material contains the separated and recovered plastic base material in an amount of 70% by mass or more relative to 100% by mass of the molding material.

[0020]

[10] [9] A method for producing a molded body, comprising: heat-molding the molding material produced by the method described in [9]. [Effects of the Invention]

[0021] The present invention can provide a treatment liquid for separating and recovering a plastic substrate from a laminate having at least a detachment layer on a plastic substrate, which is excellent in detachability of the detachment layer and in inhibiting reattachment during long-term treatment, and which can produce a high-quality recycled plastic substrate; a method for separating and recovering a plastic substrate using the treatment liquid; and a method for producing a molding material and a molded article. DETAILED DESCRIPTION OF THE INVENTION

[0022] The following describes in detail the embodiments of the present invention. However, the following description of the embodiments or requirements is merely an example of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist of the present invention.

[0023] The present invention relates to a treatment liquid for separating and recovering a plastic substrate from a laminate having at least a detachment layer on the plastic substrate, the treatment liquid comprising a basic compound and fats and / or fat decomposition products.

[0024] The treatment solution of the present invention contains fats and / or fat decomposition products, which promotes the detachment of the detachment layer from the plastic substrate, and furthermore, the alkylene moieties of the fats and oils or the alkyl moieties of the fatty acids in the fat decomposition products tightly surround the finely dispersed impurity components derived from the detachment layer (for example, highly lipophilic components derived from petrochemical raw materials such as inks and adhesives) to form a micellar structure, which is thought to prevent the re-adhesion of such components to the plastic substrate, but this is merely one consideration and does not limit the present invention in any way. As a result, even after long-term continuous treatment, plastic substrates with little coloring or staining can be recovered and recycled into high-quality recycled materials.

[0025] <Processing liquid> The treatment liquid of the present invention is used to separate and recover a plastic substrate from a laminate comprising at least a release layer on the plastic substrate. In the present invention, "detachment" refers to the detachment layer being dissolved or swelled by the treatment liquid and peeled off, thereby detaching from the substrate, and includes both cases: (1) when the detachment layer is dissolved and detached from the substrate, and (2) when the detachment layer is not dissolved but is detached from the substrate by neutralization, swelling, etc.

[0026] The treatment liquid of the present invention may contain a basic compound and fats and / or fat decomposition products, and may swell and dissolve the detachment layer, and may be appropriately selected taking into consideration the ease of detachment of the detachment layer described below. Examples of the medium for such a treatment liquid include water, organic solvents, and fluorine-based solvents, but water is preferred from the viewpoints of environmental friendliness and maintaining the properties of recycled materials made from recovered plastic substrates. It is also preferred that the treatment liquid be heated before use.

[0027] [Basic compounds] The basic compound is not particularly limited, and examples thereof include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)), ammonia, barium hydroxide (Ba(OH)), and sodium carbonate (NaCO). More preferably, the basic compound is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide. The content of the basic compound in the treatment liquid is preferably 0.5 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 3 to 15 mass %, based on the mass of the entire treatment liquid. When the content of the basic compound is within the above range, the treatment liquid can retain sufficient basicity to remove the detachment layer described below by dissolving or swelling it, thereby recovering the plastic substrate, which is preferable from the viewpoint of releasability.

[0028] [Oils and fats] Fats and oils are primarily composed of triacylglycerol, a compound formed by the combination of glycerin and fatty acids. Their main role is to prevent the re-adhesion of fine impurities, which are generated by the detachment of the detached layer, to the plastic substrate. Fats and oils are broadly divided into those containing a high amount of unsaturated fatty acids, which are commonly found in vegetable oils and marine animal oils, and those containing a high amount of saturated fatty acids, which are commonly found in land animal oils. Examples of fats and oils include vegetable fats and oils such as soybean oil, linseed oil, rapeseed oil, safflower oil, sunflower oil, cottonseed oil, rice oil, corn oil, grapeseed oil, olive oil, palm oil, sesame oil, perilla oil, coconut oil, and margarine; marine animal fats and oils such as fish oil, liver oil, and whale oil; and terrestrial animal fats and oils such as heptagonal, lard, horse oil, bone oil, and dairy fat (butter fat). One or more selected from the group consisting of soybean oil, linseed oil, rapeseed oil, safflower oil, sunflower oil, palm oil, olive oil, margarine, fish oil, lard, and dairy fat are preferred. Although not particularly limited, from the viewpoint of workability when added to an aqueous solution, vegetable oil or fish oil that is liquid at room temperature is preferred, and vegetable oil is more preferred. The number of carbon atoms of the fatty acids constituting the oil or fat is preferably 1 to 24, more preferably 4 to 24, more preferably 8 to 24, and even more preferably 10 to 20, from the viewpoint of efficiently micellizing impurity components.

[0029] [Oil and fat decomposition products] Decomposition of fats and oils proceeds easily under heating conditions in a basic solution, and fats and oils are decomposed into glycerin and fatty acids (called saponification), which are fat and oil decomposition products. Fat and oil decomposition products preferably contain fatty acids.

[0030] 〔fatty acid〕 The number of carbon atoms in the fatty acid is preferably 4 or more, more preferably 8 or more, and even more preferably 10 or more. Fatty acids can be broadly classified into saturated fatty acids, monounsaturated fatty acids, and polyunsaturated fatty acids depending on the number of double bonds in the molecule, and preferably contain unsaturated fatty acids and / or monounsaturated fatty acids, more preferably contain monounsaturated fatty acids. Specific examples of fatty acids include acetic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)-linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, and melissic acid. The fatty acids in the fat and oil hydrolysate are usually a mixture of two or more types, but one type may be used alone. From the viewpoint of efficiently micellizing impurities, the number of carbon atoms of the fatty acids constituting the fat and oil hydrolysate is preferably 1 to 24, more preferably 4 to 24, more preferably 8 to 24, and even more preferably 10 to 20.

[0031] [Glycerin] Glycerin is classified as a trihydric alcohol and is also produced as a decomposition product of fats and oils. Glycerin is highly hydrophilic, odorless, and miscible with water. Even when used alone, glycerin is thought to contribute to the prevention of reattachment of impurities due to its amphiphilic properties. However, when used together with fatty acids, the fatty acids further encapsulate the micellized impurities, providing a synergistic effect of preventing reattachment. In addition, aqueous solutions containing glycerin can be stabilized at low temperatures by lowering their freezing point.

[0032] The total content of fats and oil decomposition products (including the case where the fats and oil decomposition products are 0) is preferably 0.05 to 10.00 mass%, more preferably 0.1 to 10.00 mass%, preferably 0.25 to 5.0 mass%, and even more preferably 0.5 to 3.0 mass% in 100 mass% of the treatment liquid, from the viewpoint of micellizing a large amount of impurity components derived from the detachment layer.

[0033] [Surfactants] The treatment liquid of the present invention preferably further contains a surfactant (excluding fat and oil decomposition products). Examples of surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. The treatment liquid preferably contains at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and amphoteric surfactants, and more preferably contains a nonionic surfactant. The surfactant mainly plays a role in improving the releasability of the release layer. This is thought to be because the surfactant action makes it easier for the treatment liquid to penetrate into the release layer of the primer layer, printed layer, adhesive layer, etc., thereby promoting release. In addition, the surfactant is thought to adsorb to the released components and the surface of the substrate, preventing the finely dispersed printed layer, etc. from re-adhering.

[0034] The surfactant preferably has an HLB value of 7 or more. An HLB value of 7 or more provides excellent detachment and re-adhesion properties of the detachment layer. The surfactant preferably has an HLB value of 8 or more, more preferably 10 or more. The surfactant preferably has an HLB value of 20 or less, more preferably 19 or less, and even more preferably 17 or less. An HLB value of 20 or less is preferred because it provides excellent foam suppression.

[0035] The HLB value is an index value relating to the affinity of a surfactant for water and oil, and is calculated by dividing the HLB value into two equal parts: a substance with no hydrophilic groups has an HLB value of 0 and a substance with only hydrophilic groups has an HLB value of 20. The concept of HLB was proposed by William Griffin of the Atlas Powder Company in 1949, and several methods for determining it by calculation have been proposed, but in this invention the HLB value can be calculated using the Griffin method using the following formula. Formula) HLB = 20 × [(molecular weight of hydrophilic group contained in surfactant) / (molecular weight of surfactant)]

[0036] These surfactants may be used alone or in combination of two or more. The total content of surfactants in the treatment liquid is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.3 to 5% by mass, based on 100% by mass of the treatment liquid. A surfactant content of 0.1% by mass or more in the treatment liquid is preferred because it provides excellent deinking and re-adhesion properties, and a surfactant content of 10% by mass or less is preferred from the viewpoint of suppressing foaming.

[0037] [Anionic surfactants] The anionic surfactant is preferably a non-soap type, and examples thereof include sulfonic acid type anionic surfactants, sulfate ester type anionic surfactants, carboxylic acid type anionic surfactants, and phosphate ester type anionic surfactants.

[0038] [Sulfonic acid-based anionic surfactants] Examples of the sulfonic acid-based anionic surfactant include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, alkylene oxide adduct of sulfonic acid, and salts thereof.Specific examples include hexane sulfonic acid, octane sulfonic acid, decane sulfonic acid, dodecane sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, octyl benzene sulfonic acid, dodecyl benzene sulfonic acid, dinitro benzene sulfonic acid, lauryl dodecyl phenyl ether disulfonic acid, etc.

[0039] [Sulfate ester-based anionic surfactants] Examples of the sulfate ester-based anionic surfactant include sulfate esters (alkyl ether sulfate esters), alkylene oxide adducts of sulfate esters, and salts thereof. Specific examples include lauryl sulfate, myristyl sulfate, and polyoxyethylene lauryl ether sulfate.

[0040] [Carboxylic acid-based anionic surfactants] Examples of the carboxylic acid-based anionic surfactant include alkylbenzene carboxylic acids, alkylene oxide adducts of carboxylic acids, and salts thereof. Specific examples include polyoxyethylene lauryl ether acetic acid and polyoxyethylene tridecyl ether acetic acid.

[0041] [Phosphate ester-based anionic surfactants] Examples of the phosphate ester-based anionic surfactant include phosphate esters (alkyl ether phosphate esters), alkylene oxide adducts of phosphate esters, and salts thereof. Specific examples include octyl phosphate ester, lauryl phosphate ester, tridecyl phosphate ester, myristyl phosphate ester, cetyl phosphate ester, stearyl phosphate ester, polyoxyethylene octyl ether phosphate ester, and polyoxyethylene lauryl ether phosphate ester.

[0042] The anionic surfactant preferably has an alkyl group having 2 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms, and more preferably has an alkyl group having 8 to 18 carbon atoms. The alkyl group or alkenyl group may be linear or branched. When the anionic surfactant is an alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide being preferred. The number of moles of alkylene oxide added is preferably 1 to 12 moles, more preferably 1 to 8 moles, per mole of alcohol or alkylphenol. This range is preferred because it provides excellent releasability.

[0043] Examples of salts constituting the anionic surfactants include metal salts of sodium, potassium, magnesium, calcium, etc. These salts may be used alone or in combination of two or more. Among these, from the viewpoint of releasability and reattachment, preferred anionic surfactants are sulfonate types and phosphate types, and more preferred are alkyl sulfonates, polyoxyalkylene alkyl ether sulfonates, polyoxyalkylene alkyl ether phosphates, etc.

[0044] [Nonionic surfactants] The nonionic surfactant is not particularly limited, but is preferably an alkylene oxide adduct in which an alkylene oxide (hereinafter also referred to as AO) is added. More preferably, it is a compound obtained by adding an alkylene oxide to an alcohol having active hydrogen, a compound obtained by adding an alkylene oxide to an amine, or a compound obtained by adding an alkylene oxide to a fatty acid. The addition may be either random addition or block addition. The alkylene oxide preferably has 2 to 4 carbon atoms. The nonionic surfactant is more preferably an alcohol-based nonionic surfactant in which an alkylene oxide having 2 to 4 carbon atoms is added to an alcohol.

[0045] [Alcohol-based nonionic surfactant] Examples of alcohol-based nonionic surfactants include alkylene oxide adducts of primary or secondary alcohols having a total of 8 to 24 carbon atoms, and alkylene oxide adducts of alkylphenols having a total of 8 to 12 carbon atoms. The primary or secondary alcohols having a total of 8 to 24 carbon atoms may be saturated or unsaturated. Examples of the primary or secondary alcohol having a total of 8 to 24 carbon atoms include lauryl alcohol, stearyl alcohol, oleyl alcohol, dodecyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, and myristyl alcohol. Examples of alkylene oxides added to alcohols include ethylene oxide, propylene oxide, and butylene oxide, and it is preferable to use ethylene oxide as an essential component. The number of moles of alkylene oxide added is preferably 1 to 100 moles, more preferably 2 to 50 moles, per mole of alcohol or alkylphenol. The above range is preferred because it provides excellent elimination properties.

[0046] [Fatty acid-based nonionic surfactant] The fatty acid-based nonionic surfactant is not particularly limited in structure, and examples thereof include alkylene oxide adducts of higher fatty acids having a total of 10 to 24 carbon atoms, oils and fats composed of esters of the above-mentioned saturated or unsaturated higher fatty acids having a total of 10 to 24 carbon atoms and glycerin, and alkylene oxide adducts of mixtures of the above-mentioned oils and fats and polyhydric alcohols having 2 to 10 carbon atoms. The above-mentioned higher fatty acids having a total of 10 to 24 carbon atoms may be saturated or unsaturated. Examples of the higher fatty acids having a total of 10 to 24 carbon atoms include saturated higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid; and unsaturated higher fatty acids such as palmitoleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, erucic acid, and ricinoleic acid. Examples of dihydric to decahydric polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, polyglycerin, sorbitol, sorbitan, and sucrose. The type and number of moles of alkylene oxide added are the same as those described above in the section on [Alcohol-based nonionic surfactants].

[0047] [Amine-based nonionic surfactant] Examples of amine-based nonionic surfactants include AO adducts of saturated or unsaturated primary or secondary amines having a total of 8 to 36 carbon atoms. Examples of amines include 2-ethylhexylamine, di-2-ethylhexylamine, laurylamine, dilaurylamine, tetradecylamine, ditetradecylamine, hexadecylamine, dihexadecylamine, stearylamine, distearylamine, oleylamine, and dioleylamine. The type and number of moles of AO added are the same as those described above.

[0048] [Amphoteric surfactants] Examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, polyoctyl polyaminoethyl glycine, and imidazoline derivatives.

[0049] [Cationic surfactants] Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts. Specific examples include stearylamine acetate, trimethyl coconut ammonium chloride, trimethyl beef tallow ammonium chloride, dimethyldioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, lauryl pyridinium chloride, lauryl pyridinium bromide, lauryl pyridinium disulfate, cetyl pyridinium bromide, 4-alkylmercaptopyridine, poly(vinylpyridine)-dodecyl bromide, and dodecylbenzyl triethyl ammonium chloride.

[0050] [Antifoaming agent] The treatment liquid of the present invention preferably further contains an antifoaming agent. Antifoaming agents generally have extremely high lipophilicity and an HLB value in the range of 1 to 3. By using an antifoaming agent in combination with the above-mentioned nonionic surfactant having an HLB value of 7 or more, good antifoaming properties can be achieved without reducing detachment and reattachment properties, and foaming caused by the surfactant can be suppressed. Examples of the antifoaming agent include silicone compounds and non-silicone compounds.

[0051] (Silicone compounds) Examples of the silicone-based compound include emulsion type, self-emulsifying type, oil type, oil compound type, and solvent type. Emulsion-type antifoaming agents are silicone-based antifoaming agents in which a silicone oil compound is emulsified with an activator to form an O / W emulsion. Examples include "KM-89" and "KM-98" manufactured by Shin-Etsu Chemical Co., Ltd., "FC2913" and "SILFOAM SE47" manufactured by Asahi Kasei Wacker Silicone, and "BYK-015" and "BYK-1640" manufactured by BYK Japan. Self-emulsifying types are silicone-based defoamers that contain 100% active ingredients and become emulsified when diluted and mixed with water. Examples include "KS-540" and "X-50-1176" manufactured by Shin-Etsu Chemical Co., Ltd., and "SILFOAM SD670" and "SILFOAM SD850" manufactured by Asahi Kasei Wacker Silicone. Oil-type defoamers are 100% silicone oil defoamers that do not contain solvents or additives. Examples include "KM-89" and "KM-98" manufactured by Shin-Etsu Chemical Co., Ltd., "AK350" and "AK12500" manufactured by Asahi Kasei Wacker Silicone, and "BYK-1770" manufactured by BYK Japan. Oil compound types are silicone-based defoamers that combine silica particles with silicone oil. Examples include "KM-89" and "KM-98" manufactured by Shin-Etsu Chemical Co., Ltd., "SILFOAM SC370" and "PULPSIL22274VP" manufactured by Asahi Kasei Wacker Silicone, and "BYK-017" and "BYK-018" manufactured by BYK Japan. Solvent-type antifoaming agents are silicone-based antifoaming agents in which silicone oil is dissolved in a solvent, and examples include "KM-89" and "KM-98" manufactured by Shin-Etsu Chemical Co., Ltd., and "BYK-019" and "BYK-025" manufactured by BYK Japan.

[0052] (non-silicone compounds) Examples of the non-silicone compounds include fatty acid ester compounds, urea resin compounds, paraffin compounds, polyoxyalkylene glycol compounds, acrylic ester copolymers, ester polymers, ether polymers, amide polymers, emulsions of mineral oils, polysiloxane adducts, fluorine compounds, vinyl polymers, acetylene alcohol, acrylic polymers, special vinyl polymers, ethylene glycol, and higher alcohols (octyl alcohol, cyclohexanol, etc.).

[0053] One type of defoaming agent may be used alone, or two or more types may be used in combination. The content of the defoaming agent in the treatment liquid is preferably in the range of 0.01 to 5 mass%, and more preferably in the range of 0.03 to 3 mass%, based on 100 mass% of the treatment liquid. When the content of the defoaming agent is 0.01 mass% or more, excellent foam suppression is achieved, and when it is 5 mass% or less, excellent deinking properties and re-adhesion properties are achieved. From the viewpoints of having good alkali resistance and being less likely to reduce deinking and re-adhesion properties when combined with a surfactant, the defoaming agent is preferably at least one selected from the group consisting of emulsion-type silicone compounds, self-emulsifying silicone compounds, and non-silicone compounds.

[0054] <Laminate> The treatment liquid of the present invention is used to separate and recover a plastic substrate from a laminate having at least a release layer on the plastic substrate. The release layer in contact with the plastic substrate is removed by the treatment liquid of the present invention, making it possible to recover and recycle the plastic substrate.

[0055] <Detachment layer> The detachment layer may be any layer that can be detached from the plastic substrate by a treatment liquid containing a basic compound, and is preferably a layer containing a water-soluble resin or a compound having an acidic group that has a high affinity with basic compounds, and more preferably a layer containing a compound having an acidic group. The release layer is a layer in contact with the plastic substrate layer, and is, for example, at least one layer selected from the group consisting of a primer layer, a printed layer, and an adhesive layer. That is, at least one layer selected from the group consisting of a primer layer, a printed layer, and an adhesive layer is preferably a layer containing a water-soluble resin and / or a compound having an acidic group, more preferably a layer containing a compound having an acidic group. The compound having an acidic group may be a resin or a low-molecular-weight compound. These water-soluble resins or compounds having an acidic group may be used alone or in combination of two or more.

[0056] At least one layer selected from the group consisting of the primer layer, the printing layer, and the adhesive layer may contain a resin component (hereinafter also referred to as a binder resin) constituting the layer, which may include a water-soluble resin or a resin having an acidic group, or may contain a binder resin and a low molecular weight compound having an acidic group. Below, the cases where the release layer is a primer layer, a printed layer, and an adhesive layer will be described.

[0057] [Primer layer] When a printed layer is present, the primer layer is used for the purpose of controlling the releasability, adhesiveness, design properties, etc. of the printed layer. When the release layer is a primer layer, the primer layer is disposed in contact with the plastic substrate and serves to release the plastic substrate by dissolution with the treatment liquid, peeling, etc. The primer layer preferably contains a water-soluble resin or a compound having an acidic group (however, excluding water-soluble resins).

[0058] (Water-soluble resin) The water-soluble resin may be any resin that swells or dissolves in water and can be removed from the plastic substrate. The water may be heated to a temperature of about 25 to 100°C. This allows the primer layer to be removed with water (including warm water). Such resins can be selected from known resins as long as they do not impair water solubility, and examples thereof include water-soluble polyester resins, water-soluble polyamide resins, water-soluble polyimide resins, water-soluble acrylic resins, water-soluble polyurethane resins, water-soluble polyallylamine resins, water-soluble phenolic resins, water-soluble epoxy resins, water-soluble phenoxy resins, water-soluble urea resins, water-soluble melamine resins, polyvinyl alcohol resins, and modified products of these resins. These can be used alone or in combination of two or more. Among these, polyvinyl alcohol (PVA) resins are preferred from the viewpoints of availability and release properties. When the water-soluble resin has film-forming properties, the water-soluble resin may be used as the binder resin constituting the primer layer.

[0059] The polyvinyl alcohol resin may be unmodified polyvinyl alcohol, modified polyvinyl alcohol obtained by copolymerizing various monomers during the production of a vinyl ester resin and then saponifying the copolymer, or various post-modified polyvinyl alcohols obtained by introducing various functional groups into unmodified polyvinyl alcohol by post-modification. Modified polyvinyl alcohols may also be used. These modifications may be carried out to the extent that the water solubility of the polyvinyl alcohol resin is not impaired. These resins may be used alone or in combination of two or more.

[0060] Preferred examples of polyvinyl alcohol resins include resins containing structural units having primary hydroxyl groups in their side chains and ethylene-modified polyvinyl alcohol resins. Among these, polyvinyl alcohol resins containing structural units having primary hydroxyl groups in their side chains are preferred because of their excellent melt moldability and water solubility. The number of primary hydroxyl groups in these structural units is usually 1 to 5, preferably 1 to 2, and more preferably 1. Furthermore, it is preferred that the structural units have secondary hydroxyl groups in addition to the primary hydroxyl groups.

[0061] The saponification degree of the polyvinyl alcohol resin (measured in accordance with JIS K 6726) is usually 60 to 100 mol%. The preferred range of the saponification degree varies depending on the modified species. For example, in the case of an unmodified polyvinyl alcohol resin, it is usually 60 to 99.9 mol%, preferably 70 to 99.0 mol%, and more preferably 75 to 98.5%. The saponification degree of a modified polyvinyl alcohol resin containing a 1,2-diol structural unit in a side chain is usually 60 to 99.9 mol%, preferably 65 to 99.8 mol%, and more preferably 70 to 99.5 mol%. If the saponification degree is too low, water solubility tends to decrease. The saponification degree of an ethylene-modified polyvinyl alcohol resin modified with a small amount of ethylene is usually 60 mol% or more, preferably 70 to 99.5 mol%, and particularly preferably 75 to 99.0 mol%. A saponification degree within the above range is preferred because it provides excellent water solubility and good releasability, and also provides excellent coating properties when forming a primer layer.

[0062] The average degree of polymerization of the polyvinyl alcohol resin (measured in accordance with JIS K 6726) is usually 100 to 3,000, preferably 150 to 2,000, more preferably 180 to 1,000, and particularly preferably 200 to 800.

[0063] (Compounds with an acidic group) The compound having an acidic group may be a resin having an acidic group or a low molecular weight compound having an acidic group, which allows the primer layer to be removed by the above-mentioned basic aqueous solution.

[0064] Examples of resins having an acidic group include cellulose resins, urethane resins, polyamide resins, vinyl chloride / vinyl acetate copolymers, ketone resins, polyester resins, and (meth)acrylic resins. Examples of the acidic group include a carboxy group, a phosphate group, a sulfo group, a sulfino group, or an ester or salt thereof. Furthermore, as the resin having an acidic group, a rosin-modified resin having an acid value, such as maleic rosin or fumaric rosin, can be used. Furthermore, examples of resins having an acidic group that can be used include radical copolymers such as styrene-(meth)acrylic resin, styrene-maleic (anhydride) resin, and terpene-maleic (anhydride) resin, which are copolymerized with polymerizable monomers having an acidic group, such as polymerizable monomers having a carboxy group, such as itaconic acid, maleic acid, fumaric acid, and cinnamic acid; polymerizable monomers that are acid anhydrides, such as itaconic acid anhydride and maleic acid anhydride; polymerizable monomers having a sulfonic acid group, such as sulfonated styrene; and polymerizable monomers having a sulfonamide group, such as vinylbenzenesulfonamide; and acid-modified polyolefin resins. These may be used alone or in combination of two or more.

[0065] A low-molecular-weight compound having an acidic group refers to a compound that does not have a molecular weight distribution and has a molecular weight of 1,000 or less. Examples of such compounds include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid; hydroxy acids such as lactic acid, malic acid, and citric acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, and cinnamic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, and maleic acid; tricarboxylic acids such as aconitic acid; oxocarboxylic acids such as pyruvic acid and oxaloacetic acid; carboxylic acid derivatives such as amino acids and nitrocarboxylic acids; and acid anhydrides such as trimellitic anhydride and pyromellitic anhydride. The low molecular weight compound having an acidic group can be used in combination with the above-mentioned resin having an acidic group or a known binder resin that constitutes a known primer layer to form a primer layer.

[0066] From the viewpoint of printability, the primer layer preferably contains one or more resins selected from the group consisting of urethane resins having acidic groups, acrylic resins having acidic groups, and rosin-modified resins.

[0067] [Urethane resin having an acidic group] The urethane resin having an acidic group is not particularly limited, and examples thereof include a urethane resin obtained by reacting a polyol having an acidic group with a polyisocyanate, a resin obtained by acid-modifying the hydroxyl groups in a urethane resin obtained by reacting a polyol with a polyisocyanate, and a resin obtained by acid-modifying the amino groups in a urethane urea resin obtained by reacting a polyamine with the isocyanate groups in a urethane resin obtained by reacting a polyol with a polyisocyanate. Furthermore, as the urethane resin having an acidic group, a resin obtained by reacting a polyol containing a hydroxy acid with a polyisocyanate may be used. By using a hydroxy acid as the polyol, an acid value derived from the carboxy group can be imparted to the urethane resin, thereby improving the releasing property. Furthermore, when the urethane resin having an acidic group has an isocyanate group, a polyamine may be reacted with a portion of the isocyanate group to introduce a urea bond, thereby forming a urethane urea.

[0068] <Polyol> Polyol is a general term for compounds having at least two hydroxyl groups in one molecule. The number-average molecular weight of the polyol is preferably 500 to 10,000, more preferably 1,000 to 5,000. The number-average molecular weight is calculated from the hydroxyl value of the polyol, and the hydroxyl value refers to a value measured according to JIS K0070. When the number-average molecular weight of the polyol is 500 or more, the flexibility of the primer layer is excellent and the adhesion to the plastic substrate is improved. When the number-average molecular weight is 10,000 or less, the blocking resistance to the plastic substrate is excellent.

[0069] The polyol is not particularly limited, and more preferably, at least one polyol selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols is used. The polyol may further include other polyols such as dimer diols, hydrogenated dimer diols, and castor oil-modified polyols. That is, the urethane resin preferably contains a structural unit derived from at least one polyol selected from the group consisting of polyester polyol, polyether polyol, and polycarbonate polyol, and more preferably contains a structural unit derived from a polyester polyol, since the ester bond site of the polyester polyol is hydrolyzed by alkali to improve the releasability. The content of the polyol-derived structural units is preferably 10 to 75 mass%, more preferably 15 to 70 mass%, and even more preferably 20 to 65 mass%, based on the total amount of the urethane resin. The content of the polyester polyol-derived structural units is preferably 5 mass% or more, more preferably 30 mass% or more, even more preferably 60 mass% or more, and particularly preferably 80 mass% or more, based on the total amount of the polyol-derived structural units.

[0070] Hydroxy acids The polyol may contain a hydroxy acid. The hydroxy acid refers to a compound having both a hydroxyl group, which is an active hydrogen group, and an acidic functional group in one molecule. The acidic functional group refers to a functional group that can be neutralized with potassium hydroxide when measuring the acid value, and specific examples include a carboxy group and a sulfonic acid group, with a carboxy group being preferred. As such a hydroxy acid, for example, a dimethylolalkanoic acid such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, or 2,2-dimethylolvaleric acid is preferably used.

[0071] <Polyisocyanate> The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates. Preferably, it contains a diisocyanate or triisocyanate, and more preferably, it contains an aromatic, aliphatic, or alicyclic diisocyanate. These may be used alone or in combination of two or more.

[0072] Polyamines The polyamine for forming the urethane urea is not particularly limited, but is preferably a diamine compound. Furthermore, a diamine having a hydroxyl group may be used because it can introduce a hydroxyl group into the urethane resin.

[0073] The acid value of the urethane resin having acidic groups is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. An acid value of 15 mgKOH / g or more is preferred because it improves releasability with the treatment solution, and 70 mgKOH / g or less is preferred because it improves substrate adhesion and retort resistance. The hydroxyl value of the urethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. An acid value of 1 mgKOH / g or more is preferred because it improves releasability with the treatment solution, and 35 mgKOH / g or less is preferred because it improves substrate adhesion.

[0074] The mass-average molecular weight of the urethane resin having an acidic group is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and even more preferably 15,000 to 50,000. The molecular weight distribution (Mw / Mn) of the urethane resin is preferably 6 or less. Mw represents the mass-average molecular weight, and Mn represents the number-average molecular weight. A molecular weight distribution of 6 or less results in excellent releasability, drying properties of the primer composition, and retort resistance. Furthermore, the smaller the molecular weight distribution, i.e., the sharper the molecular weight distribution, the more uniform the dissolution and peeling action by the treatment liquid occurs, improving the releasability of the plastic substrate. The molecular weight distribution is more preferably 5 or less, and even more preferably 4 or less. The molecular weight distribution is also preferably 1.5 or more, more preferably 1.2 or more. In this specification, Mw, Mn and molecular weight distribution (Mw / Mn) are values ​​calculated as polystyrene by gel permeation chromatography (GPC).

[0075] The urethane resin having an acidic group may have an amino group. When the urethane resin has an amino group, the amine value is preferably 0.1 to 20 mg KOH / g, and more preferably 1 to 10 mg KOH / g. When the amine value is within the above range, excellent adhesion to substrates is achieved.

[0076] The number of urethane bonds in the urethane resin having acidic groups is preferably 1 to 3 mmol / g, more preferably 1.5 to 2 mmol / g. The number of urea bonds in the urethane resin having acidic groups is preferably 0 to 3 mmol / g, more preferably 0.2 to 1 mmol / g. The total number of urethane bonds and urea bonds in the urethane resin having acidic groups is preferably 1 to 6 mmol / g, more preferably 1.7 to 3 mmol / g. By setting the number of urethane bonds and the number of urea bonds of the urethane resin having an acidic group within the above ranges, the releasability and the adhesion to the substrate are improved.

[0077] [Acrylic resin having an acidic group] Examples of acrylic resins having an acidic group include polymers obtained by polymerizing a monomer containing a (meth)acrylic monomer having an acidic group such as (meth)acrylic acid or maleic acid; and resins obtained by polymerizing a monomer containing a (meth)acrylic monomer having a hydroxyl group or a glycidyl group, and then modifying the functional group to introduce a carboxyl group (e.g., maleic anhydride-modified resin). The acid value of the acrylic resin having an acidic group is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more.

[0078] [Rosin-modified resin] Rosin-modified resins are resins prepared using rosin as one of the raw materials. Rosin contains a mixture of resin acids, such as abietic acid, palustric acid, isopimaric acid, and levopimaric acid. These resin acids contain hydrophilic, chemically active carboxyl groups, some of which contain conjugated double bonds. Therefore, various rosin-modified resins have been prepared by combining polyhydric alcohols and polybasic acids and subjecting them to condensation polymerization; adding resols, which are condensates of phenols, to the benzene rings contained in the rosin skeleton; or performing a Diels-Alder reaction with dienophiles such as maleic anhydride and maleic acid to add maleic acid or maleic anhydride skeletons. Various types of such rosin-modified resins are commercially available, and they can be obtained and used.

[0079] Examples of rosin-modified resins include maleated rosin, fumarated rosin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, rosin-modified phenolic resin, rosin-modified alkyd resin, and rosin-modified polyester resin. Any of these rosin-modified resins may be used in the present invention, but among these, those containing in their structure a moiety derived from at least one selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride are preferably used. A resin "containing in its structure a moiety derived from at least one selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride" is one prepared using at least one selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride as part of a raw material, and means, for example, a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin obtained by condensation polymerization of maleic acid or fumaric acid as part of a polybasic acid, a maleated rosin or fumarated rosin having a structure in which maleic acid, maleic anhydride, fumaric acid, or fumaric anhydride is added as a dienophile by a Diels-Alder reaction, or a resin obtained by further polymerizing other chemical species using the functional groups contained in these.

[0080] The acid value of the rosin-modified resin is preferably 10 to 400 mgKOH / g, and more preferably 100 to 300 mgKOH / g.

[0081] (Other ingredients) The primer layer may contain a resin other than the water-soluble resin or the compound having an acidic group. Examples of such resins include cellulose resins, polyamide resins, vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer resins and vinyl chloride-acrylic copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, acrylic resins, styrene resins, dammar resins, styrene-acrylic copolymer resins, polyester resins, alkyd resins, terpene resins, phenol-modified terpene resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyral, polyacetal resins, petroleum resins, and modified resins thereof. These resins may be used alone or in combination of two or more. Among these, the primer layer preferably contains at least one resin selected from the group consisting of cellulose resin, vinyl chloride resin, rosin resin, and acrylic resin, and more preferably contains vinyl chloride resin or acrylic resin. The mass ratio of the urethane resin having an acidic group to the other resin (urethane resin having an acidic group:other resin) is preferably 95:5 to 50:50. When the mass ratio is within this range, when the printed layer peels off together with the primer layer in a basic aqueous solution, the printed layer peels off in the form of a thin film, which is preferable because it is easy to recover.

[0082] The primer layer may contain an extender pigment. Examples of the extender pigment include silica, barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, zinc oxide, zirconium oxide, and other metal oxides. Among these, silica is preferred, and hydrophilic silica is more preferred. The average particle size of the extender pigment is preferably 0.5 to 10 μm, more preferably 1 to 8 μm. The content of the extender pigment in the primer layer is preferably 0.5 to 10 mass %, more preferably 1 to 5 mass %. When the average particle size and the content of the extender pigment are within the above ranges, the wettability of the printing layer is improved, resulting in improved image quality.

[0083] The primer layer may be a layer in which the above-described urethane resin having an acidic group is crosslinked with a curing agent. By introducing a crosslinked structure into the primer layer, penetration and bleeding of the printing layer formed on the primer layer are suppressed, and excellent image quality can be achieved. Examples of the curing agent include polyisocyanates. The polyisocyanates are not particularly limited and can be selected from conventionally known polyisocyanates, such as aliphatic polyisocyanates and araliphatic polyisocyanates. These may be used alone or in combination of two or more.

[0084] The primer layer may further contain known additives, such as dispersants, wetting agents, adhesion promoters, leveling agents, antifoaming agents, antistatic agents, viscosity modifiers, metal chelates, trapping agents, antiblocking agents, wax components other than those mentioned above, and silane coupling agents.

[0085] The thickness of the primer layer is preferably in the range of 0.5 to 3.0 μm, more preferably 0.6 to 2.0 μm, and even more preferably 0.8 to 1.5 μm, and can be formed using a known method.

[0086] [Print layer] The printed layer is a layer on which any printed pattern is formed for the purpose of decoration, aesthetic impression, indication of contents, expiration date, manufacturer or seller, etc., and includes a solid printed layer. When the release layer is a printed layer, the printed layer is disposed in contact with the plastic substrate and serves to release the plastic substrate by dissolution, peeling, or the like using a treatment liquid. The printed layer preferably contains a water-soluble resin or a compound having an acidic group (excluding water-soluble resins), and a colorant. Furthermore, the method for forming the printed layer is not limited, and it can be formed using a known method. From the viewpoint of printability, the print layer preferably contains one or more of a urethane resin having an acidic group, an acrylic resin having an acidic group, and a rosin-modified resin. The embodiments of the water-soluble resin and the compound having an acidic group, as well as the urethane resin having an acidic group, the acrylic resin having an acidic group, and the rosin-modified resin, can be referenced from the descriptions of (water-soluble resin), (compound having an acidic group), [urethane resin having an acidic group], [acrylic resin having an acidic group], and [rosin-modified resin] in the section [Primer layer] described above.

[0087] (coloring agent) The printed layer may be colored or colorless, and preferably contains a known colorant used in printing inks and paints. The colorant is not particularly limited, and may be an inorganic pigment, an organic pigment, a dye, a metal powder that imparts metallic luster, a near-infrared absorbing material, or an ultraviolet absorbing material. Examples of inorganic pigments include colored pigments such as titanium oxide, red iron oxide, Prussian blue, ultramarine, carbon black, and graphite; and extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. Suitable organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. The pigments are not limited to these, and any pigment listed by its generic name in the Color Index can be used as appropriate. Among these, since the treatment solution of the present invention contains a basic compound, a pigment that is alkali-resistant and does not dissolve in a basic aqueous solution is preferred. Preventing the dissolution of the pigment makes it easier to reuse the basic aqueous solution. The alkali resistance of a pigment is generally estimated from the skeleton or structure of the pigment. Examples of alkali-resistant pigments include inorganic pigments, CI Pigment Blue 15, and CI Pigment Yellow 83. When the pigment is titanium oxide, the content of titanium oxide in the printed layer is preferably 20 to 80% by mass, more preferably 30 to 75% by mass. When the pigment is one or more selected from the group consisting of inorganic pigments other than titanium oxide, extender pigments, and organic pigments, the content of each of these pigments is preferably 0.5 to 60% by mass, more preferably 10 to 50% by mass, based on 100% by mass of the printed layer.

[0088] (Other ingredients) The print layer may contain a pigment derivative and / or a resin-type dispersant as a dispersant for the colorant. The pigment derivative is a compound in which a substituent has been introduced into the pigment skeleton, and the content of the pigment derivative is preferably 0.01 to 10 mass %, more preferably 0.05 to 6 mass %, and even more preferably 0.1 to 4 mass %, based on the mass of the colorant. A pigment derivative content of 0.01 mass % or more provides excellent releasability from plastic substrates, while a content of 10 mass % or less can suppress reattachment of the printed layer. The resin-type dispersant functions to adsorb to the colorant and stabilize its dispersion in printing ink, etc., and can be appropriately selected from known resin-type dispersants. The content of the resin-type dispersant is preferably 0.01 to 30 mass%, more preferably 0.05 to 20 mass%, and even more preferably 0.1 to 10 mass%, based on the mass of the colorant. When the content of the resin-type dispersant is 0.01 mass% or more, excellent releasability from the plastic substrate is achieved, and when it is 30 mass% or less, excellent water resistance of the printed layer is achieved.

[0089] The print layer may contain a resin other than the water-soluble resin or the compound containing an acidic group. Examples of such resins include fibrous materials such as nitrocellulose and cellulose acetate propionate, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, acrylic, urethane resin and acrylic urethane, polyamide, polybutyral, cyclized rubber, and chlorinated rubber. These resins may be used alone or in combination.

[0090] The thickness of the printing layer is preferably 0.1 μm or more and 100 μm or less, more preferably 0.1 μm or more and 10 μm or less, and even more preferably 1 μm or more and 5 μm or less.

[0091] [Adhesive layer] When the release layer is an adhesive layer, the adhesive layer is disposed in contact with the plastic substrate and serves to release the plastic substrate by dissolution, peeling, or the like with a treatment liquid. The adhesive layer preferably contains a compound having an acidic group (excluding water-soluble resins). When the adhesive layer contains a resin having an acidic group or a low-molecular compound having an acidic group, the adhesive layer can be released using the basic aqueous solution described above. The description of (Compound having an acidic group) in the section [Primer layer] above can be applied to the embodiments of the compound having an acidic group, resin having an acidic group, and low molecular weight compound having an acidic group. The method for forming the adhesive layer is not limited, and the adhesive layer can be formed using a known method.

[0092] From the viewpoint of releasability, the adhesive layer may be a cured product of an adhesive containing a polyester polyol having an acidic group and at least one polyisocyanate selected from the group consisting of an aliphatic polyisocyanate and an araliphatic polyisocyanate. The cured product corresponds to a resin having an acidic group. The adhesive layer may also be a cured product of an adhesive containing a polyester polyol, at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanates and araliphatic polyisocyanates, and a low molecular weight compound having an acidic group.

[0093] (polyester polyol) The polyester polyol may have an acidic group and may be appropriately selected from known polyester polyols. When a basic aqueous solution is used as the treatment liquid, the polyester polyol preferably contains an ester bond having a high affinity with the basic compound, thereby improving the release property. The polyester polyol may be used alone or in combination of two or more.

[0094] The polyester polyol is not particularly limited, but polyester polyols obtained by reacting a carboxyl group component with a hydroxyl group component; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone) are preferably used. Examples of the carboxyl group component include dibasic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, and itaconic anhydride, or dialkyl esters thereof, or mixtures thereof. Examples of the hydroxyl group component include diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, glycerin, 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, 1,9-nonanediol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, polyurethane polyol, and mixtures thereof. The above carboxyl group components and hydroxyl group components may be used in combination of two or more kinds.

[0095] The polyester polyol may be a polyester urethane polyol obtained by reacting a polyisocyanate with a hydroxyl group in a polyol. The polyester polyol having a urethane bond exhibits excellent heat resistance and adhesiveness. Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0096] The polyester polyol may also be an acid anhydride-modified product obtained by reacting an acid anhydride with a hydroxyl group in the polyol, thereby introducing a carboxyl group, which is an acidic group, into the polyester polyol. Examples of acid anhydrides include pyromellitic anhydride, mellitic anhydride, trimellitic anhydride, and trimellitic ester anhydrides. Examples of trimellitic ester anhydrides include ethylene glycol bisanhydrotrimellitate and propylene glycol bisanhydrotrimellitate.

[0097] The acid value of the polyester polyol is preferably 5.0 mgKOH / g or more, more preferably 10.0 mgKOH / g or more. The acid value of the polyester polyol is preferably 100 mgKOH / g or less, more preferably 80 mgKOH / g or less. When the acid value of the polyester polyol is within the above range, upon contact with a treatment liquid that is a basic aqueous solution, the basic aqueous solution penetrates and decomposes the polyester polyol, resulting in better release properties. When the adhesive contains a plurality of polyester polyols, the acid value of the entire polyester polyols can be determined from the acid value of each polyester polyol and its mass ratio.

[0098] The number average molecular weight (Mn) of the polyester polyol is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and particularly preferably 7,000 to 15,000. When the number average molecular weight of the polyester polyol is 3,000 or more, not only coatability but also sufficient retort suitability can be exhibited, and when it is 20,000 or less, not only coatability but also releasability are improved, which is preferable.

[0099] In order to satisfy the various physical properties required of packaging materials, the polyester polyol component may contain a combination of multiple polyester polyol components, for example, a polyester polyol having a number average molecular weight of 5,000 to 20,000, and may further contain a polyester polyol having a number average molecular weight of less than 3,000 in order to improve adhesion to substrates. The content of polyester polyol having a number average molecular weight of less than 3,000 is preferably 0 to 30 mass %, more preferably 0 to 20 mass %, based on the total mass of polyester polyol. When it is 30 mass % or less, retort resistance can be maintained.

[0100] (Other polyols) The adhesive constituting the adhesive layer may contain a polyol other than polyester polyol. The polyol that may be contained other than polyester polyol is not particularly limited, and examples thereof include polycarbonate polyol, polycaprolactone polyol, polyether polyol, polyolefin polyol, acrylic polyol, silicone polyol, castor oil-based polyol, and fluorine-based polyol.

[0101] (Polyisocyanate) The polyisocyanate to be combined with the polyester polyol described above to form the adhesive layer is preferably at least one selected from the group consisting of known aliphatic polyisocyanates and araliphatic polyisocyanates.

[0102] Examples of aliphatic polyisocyanates include acyclic aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,2-butylene diisocyanate; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter referred to as isophorone diisocyanate); and polyisocyanates such as allophanate type, nurate type, biuret type, and adduct type derivatives derived from the above diisocyanates, or complexes thereof. The derivatives are preferably nurate type and adduct type, more preferably adduct type. As the aliphatic polyisocyanate, polyisocyanates derived from hexamethylene diisocyanate (hereinafter also referred to as HDI), which can easily ensure a balance between releasability and laminate properties, are preferred.

[0103] Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof; and polyisocyanates such as allophanate type, nurate type, biuret type, or adduct type derivatives derived from the above araliphatic diisocyanates, or complexes thereof.

[0104] (Other polyisocyanates) The adhesive may contain polyisocyanates other than aliphatic polyisocyanates and araliphatic polyisocyanates, as long as the effects of the present invention are not impaired. Examples of such polyisocyanates include aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; and polyisocyanates such as derivatives of the above diisocyanates or complexes thereof.

[0105] The polyol and polyisocyanate may be mixed in such a manner that the molar ratio (NCO / OH) of the isocyanate groups in the polyisocyanate to the hydroxyl groups in the polyol is 0.3 to 10.0. The molar ratio (NCO / OH) is preferably 0.3 to 7.0, and more preferably 0.5 to 5.0.

[0106] (Other ingredients) The adhesive layer may contain, in addition to a silane coupling agent, a phosphorus oxygen acid or a derivative thereof, a leveling agent, an antifoaming agent, and a reaction accelerator, inorganic fillers (e.g., silica, alumina, mica, talc, aluminum flakes, glass flakes), layered inorganic compounds, stabilizers (e.g., antioxidants, heat stabilizers, ultraviolet absorbers, and hydrolysis inhibitors), rust inhibitors, thickeners, plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, nucleating agents, and catalysts for adjusting the curing reaction.

[0107] <Plastic substrate> The laminate used in the present invention has a plastic substrate. Examples of plastic substrates used in the present invention include substrates containing polyolefin resin, polyester resin, polyamide resin, polystyrene resin, vinyl chloride resin, vinyl acetate resin, ABS resin, acrylic resin, acetal resin, polycarbonate resin, polyvinyl alcohol resin, cellulose-based plastics, and aluminum foil. From the viewpoint of reuse as a recycled substrate, substrates containing polyolefin resin and polyester resin are particularly preferred, and polyolefin substrates containing polyolefin resin are more preferred.

[0108] The thickness of the plastic substrate is not particularly limited and may be appropriately selected depending on the application. The thickness is preferably 5 to 1000 μm, more preferably 10 to 300 μm, even more preferably 10 to 100 μm, and particularly preferably 12 to 50 μm.

[0109] The plastic substrate may also have an aluminum foil, a metal vapor deposition layer of aluminum or the like, or a metal oxide vapor deposition layer of silica, alumina or the like as a gas barrier substrate. From an economical standpoint, the thickness of the aluminum foil is preferably in the range of 3 to 50 μm. The aluminum foil, aluminum vapor deposition layer, and alumina vapor deposition layer dissolve and are released in a basic aqueous solution, and therefore function as the aforementioned release layer, enabling adjacent plastic substrates to be separated.

[0110] The plastic substrate may be made of a single resin, or may be made of the same or different multiple layers laminated together directly or via an adhesive layer. Hereinafter, a plastic substrate made of a single layer or multiple layers will also be referred to as a plastic substrate layer. Also, a polyolefin substrate made of a single layer or multiple layers will also be referred to as a polyolefin substrate layer.

[0111] <Polyolefin base material> In particular, polyolefin substrates have a low specific gravity and float to the surface of the treatment liquid, so components (especially highly lipophilic components) that have been detached from the detachment layer are prone to reattachment. However, by using the treatment liquid of the present invention, it is possible to achieve both detachment properties and the ability to prevent reattachment. Examples of polyolefin substrate layers include plastic substrates such as polyethylene (PE) and biaxially oriented polypropylene (OPP), as well as sealant substrates such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), acid-modified polyethylene, cold-stretched polypropylene (CPP), aluminum-deposited polypropylene (VMOPP), acid-modified polypropylene, and copolymer polypropylene. The thickness of the polyolefin substrate layer is not particularly limited and may be appropriately selected depending on the application, but is preferably 5 to 200 μm, more preferably 10 to 150 μm.

[0112] <Polyester base material> Examples of polyester substrates include biaxially oriented polyester (PET), aluminum-deposited polyester (VMPET), and shrink polyester (shrink PET). The thickness of the polyester substrate layer is not particularly limited and may be appropriately selected depending on the application, but is preferably 5 to 1000 μm, and more preferably 10 to 100 μm.

[0113] <Laminate structure> The laminate of the present invention only needs to have a partial structure including at least a release layer on a plastic substrate, and may further include other layers.

[0114] Specific examples of the laminate include the following structures. (1) A laminate comprising a plastic substrate layer and a printed layer in this order, the printed layer being a release layer. (2) A laminate comprising a plastic layer, a primer layer, and a printed layer in this order, wherein the primer layer is a release layer. (3) A laminate comprising a first substrate layer, a printed layer, an adhesive layer, and a second substrate layer in this order, wherein at least one of the printed layer and the adhesive layer is a detachable layer, and the substrate in contact with the detachable layer is a plastic substrate. (4) A laminate comprising a first substrate layer, a primer layer, a printing layer, an adhesive layer, and a second substrate layer in this order, wherein at least one of the primer layer and the adhesive layer is a release layer, and the substrate in contact with the release layer is a plastic substrate. (5) A laminate comprising a first substrate layer, an adhesive layer, and a second substrate layer in this order, wherein the adhesive layer is a release layer and at least one of the substrates is a plastic substrate. (6) A laminate comprising a first substrate layer, a vapor deposition layer, a printing layer, an adhesive layer, and a second substrate layer in this order, wherein at least one of the vapor deposition layer and the adhesive layer is a detachable layer, and the substrate in contact with the detachable layer is a plastic substrate.

[0115] Examples of laminate structures of the present invention are given below, but the present invention is not limited to these. In the examples below, " / " indicates the boundary between layers. In the structures below, the "substrate layer" does not have to be a single layer, but may be a laminate in which multiple substrates are stacked. Plastic substrate layer / detachable printing layer ·Plastic substrate layer / Removable primer layer / Printing layer Plastic substrate layer / detachable printing layer / detachable adhesive layer / plastic substrate layer Plastic substrate layer / Removable primer layer / Printing layer / Removable adhesive layer / Plastic substrate layer Plastic substrate layer / printing layer / detachable adhesive layer / plastic substrate layer Plastic substrate layer / detachable adhesive layer / plastic substrate layer Plastic substrate layer / Removable primer layer / Printed layer / Removable adhesive layer / Vapor deposition layer / Plastic substrate layer

[0116] <Separation and collection method> The method for separating and recovering plastic substrates of the present invention includes a step of contacting a laminate having at least a detachment layer on a plastic substrate with a treatment liquid containing a basic compound and fats and / or fats and oil decomposition products by immersion or the like to detach the detachment layer, and separating and recovering the plastic substrate layer.

[0117] Since the plastic substrate separation and recovery method of the present invention aims to use the plastic substrate after separation and recovery as a molding material, a preferred embodiment is one in which a certain amount of the detached layer is detached from a laminate having at least the detached layer. Specifically, at the end of the treatment, it is preferable that 50% by mass or more of the detached layer is detached in the area or film thickness direction out of 100% by mass of the detached layer, and the detached ratio is more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0118] The treatment liquid penetrates the edge of the laminate, contacts the detachment layer, and dissolves or swells the detachment layer, thereby separating the plastic substrate from the detachment layer. Therefore, in order to efficiently promote detachment, it is preferable that the laminate is cut or crushed so that the detachment layer is exposed on the cross section when immersed in the treatment liquid. In such a case, the substrate layer can be detached in a shorter time.

[0119] The temperature of the treatment liquid when the laminate is immersed is preferably in the range of 25 to 120°C, more preferably 30 to 120°C, and particularly preferably 30 to 80°C. The immersion time of the laminate in the treatment liquid is preferably in the range of 1 minute to 24 hours, more preferably 1 minute to 12 hours, and preferably 1 minute to 6 hours. The amount of treatment liquid used is preferably in the range of 50,000 to 100,000 times, and more preferably 10 to 10,000 times, the mass of the laminate, and it is preferable to stir or circulate the treatment liquid to improve the desorption efficiency. The rotation speed is preferably 80 to 5,000 rpm, and more preferably 80 to 4,000 rpm.

[0120] After the release layer is released from the laminate and the plastic substrate is recovered, the plastic substrate is preferably washed with water and dried to obtain a recycled substrate.

[0121] In the method for separating and recovering plastic substrates of the present invention, the median diameter of the impurity components derived from the detachment layer is preferably 1 μm or more. By ensuring that the median diameter of the impurity components derived from the detachment layer is 1 μm or more, the impurity components are prevented from reattaching to the substrate, and a recycled material with higher performance can be obtained. The median diameter of the impurity components derived from the detachment layer is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and particularly preferably 20 μm or more. The median diameter of the impurity components derived from the detachment layer is preferably 1000 μm or less, more preferably 800 μm or less. A median diameter of 1000 μm or less is preferred because it facilitates separation of the impurity components derived from the detachment layer from the substrate after detachment.

[0122] In the present invention, the volume-based median diameter (D50) and span value A of the impurity components derived from the detachment layer are measured using a laser diffraction particle size distribution analyzer. The span value A is expressed by the following formula. A=(D90-D10) / D50 D10: Volumetric particle size obtained by laser diffraction particle size distribution measurement of the detached printing layer components Cumulative 10% diameter of distribution D90: Volumetric particle size obtained by laser diffraction particle size distribution measurement of the detached printing layer components Cumulative 90% diameter of distribution

[0123] The span value A represents the particle size distribution width of the impurity components derived from the detachment layer; the larger the value, the wider the particle size distribution width, and the more likely it is to contain fine printed layer components that are likely to re-adhere to the substrate. The span value A is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less. A span value of 10 or less is preferable because it can suppress redeposition of impurity components originating from the detachment layer.

[0124] <Method of manufacturing molding material> A molding material can be produced by melt-kneading the plastic substrate recovered by the above-described separation and recovery method. The method for producing a molding material of the present invention preferably includes the following steps 1 to 3. When the molding material includes a masterbatch, the method may further include the following step 4. (Step 1) A step of crushing the laminate and immersing it in a treatment liquid to remove the plastic substrate from the laminate. (Step 2) A step of washing the plastic substrate obtained in step 1 with water. (Step 3) A step of melting and kneading the plastic base material obtained in Step 2 to obtain recycled resin. (Step 4) A step of mixing the masterbatch with the recycled resin obtained in step 3

[0125] The method for crushing the laminate in step 1 is not particularly limited, and examples thereof include methods using a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, and hammer mill. Step 2 may further include a drying step, if necessary. Step 2 makes it possible to obtain a recycled substrate (also called a recycled plastic substrate).

[0126] The melt-kneading step in step 3 involves adding various additives as needed, mixing using a Henschel mixer, tumbler, disperser, or the like, and then mixing and dispersing using a batch mixer such as a kneader, roll mill, super mixer, Henschel mixer, Schuggie mixer, vertical granulator, high-speed mixer, Farmatrix, ball mill, steel mill, sand mill, vibration mill, attritor, or Banbury mixer, a twin-screw extruder, a single-screw extruder, or a rotor-type twin-screw kneader. This results in a recycled resin, which is a resin composition. The shape of the recycled resin is not particularly limited and may be in the form of pellets, powder, granules, or beads. A twin-screw extruder is preferably used for the melt-kneading step.

[0127] [Masterbatch] The molding material may further contain a masterbatch. The masterbatch is not particularly limited as long as it is compatible with the recycled resin, and generally, a mixture of a thermoplastic resin such as a polyethylene resin or a polypropylene resin and a colorant can be used. The thermoplastic resin contained in the masterbatch may be used alone or in combination of two or more types. The masterbatch in the present invention may contain, within the scope not impairing the effects of the present invention, a metallic soap of an alkali metal, alkaline earth metal, or zinc, hydrotalcite, a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, an antistatic agent, a flame retardant such as a halogen-based, phosphorus-based, or metal oxide, a lubricant such as ethylene bisalkylamide, an antioxidant, an ultraviolet absorber, or a filler.

[0128] <Formed body> A formed body can be obtained by thermoforming a molding material obtained by the above-described manufacturing method. The thermoforming method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, and compression molding. The molding material produced using the plastic substrate recovered by the separation and recovery method of the present invention is of high quality because the printing layer, adhesive layer, etc. are detached, and reattachment of the detached components is suppressed. It can be used in various fields such as home appliances, stationery, automotive parts, toys and sports goods, materials for medical and construction materials.

Examples

[0129] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the present invention, "parts" and "%" represent parts by mass and mass%, respectively, unless otherwise noted.

[0130] <Molecular weight and molecular weight distribution> The mass average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured by GPC (gel permeation chromatography) and determined as the converted molecular weight using polystyrene as a standard substance. The measurement conditions are shown below. GPC apparatus: Shodex GPC-104 manufactured by Showa Denko KK Columns: The following columns were connected in series and used. Two Shodex LF-404 manufactured by Showa Denko KK Shodex LF-G manufactured by Showa Denko KK Detector: RI (differential refractometer) Measurement conditions: Column temperature 40°C Eluent: Tetrahydrofuran Flow rate: 0.3 mL / min

[0131] <Acid value, hydroxyl value> The acid value and hydroxyl value were measured according to the method described in JIS K 0070 (1992).

[0132] <FT-IR measurement> The FT-IR measurements were carried out under the following conditions. Equipment manufacturer: Thermo Scientific Instrument name: Nicolet iS50 FT-IR Spectrometer Measurement mode: ATR method Crystal: Diamond ·Resolution: 4cm-1 Number of times accumulated: 32

[0133] <Production of primer composition and printing ink resin> [Synthesis Example 1-1] (Polyurethane Resin P1) Into a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet pipe, a stirrer, and a thermometer, 152.2 parts of PPA (a polyester polyol having a number average molecular weight of 2,000, composed of a polycondensate of propylene glycol and adipic acid), 15.2 parts of PPG (a polyether polyol having a number average molecular weight of 2,000, composed of polypropylene glycol), 13.6 parts of BD (1,4-butanediol), 99.8 parts of IPDI (isophorone diisocyanate), and 200 parts of NPAC (normal propyl acetate) were charged while introducing nitrogen gas, and the mixture was allowed to react at 90°C for 5 hours to obtain a urethane prepolymer solution having isocyanate groups at its terminals. Next, a mixture of 19.2 parts of AEA (2-(2-aminoethylamino)ethanol) and 350 parts of IPA (isopropyl alcohol) was added dropwise to the obtained urethane prepolymer solution at room temperature over 60 minutes, and then the mixture was allowed to react at 70°C for 3 hours to obtain a polyurethane resin solution. NPAC was added to the resulting polyurethane resin solution to adjust the solid content, yielding a solution of polyurethane resin P1 with a solid content concentration of 30%, a mass average molecular weight of 27,000, Mw / Mn=3.1, and an acid value of 0.0 mgKOH / g.

[0134] [Synthesis Example 1-2] (Polyurethane Resin P2) Into a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet pipe, a stirrer, and a thermometer, 135.7 parts of PPA (a polyester polyol having a number average molecular weight of 2,000, composed of a polycondensate of propylene glycol and adipic acid), 13.6 parts of PPG (a polyether polyol having a number average molecular weight of 2,000, composed of polypropylene glycol), 28.3 parts of DMPA (2,2-dimethylolpropanoic acid), 105.7 parts of IPDI (isophorone diisocyanate), and 200 parts of NPAC (normal propyl acetate) were charged while introducing nitrogen gas, and the mixture was allowed to react at 90°C for 5 hours to obtain a urethane prepolymer solution having isocyanate groups at its terminals. Next, a mixture of 16.7 parts of AEA (2-(2-aminoethylamino)ethanol) and 350 parts of IPA (isopropyl alcohol) was added dropwise to the obtained urethane prepolymer solution at room temperature over 60 minutes, and then the mixture was allowed to react at 70°C for 3 hours to obtain a polyurethane resin solution. NPAC was added to the resulting polyurethane resin solution to adjust the solid content, yielding a solution of polyurethane resin P2 with a solid content concentration of 30%, a mass average molecular weight of 30,000, Mw / Mn=3.0, and an acid value of 39.3 mgKOH / g.

[0135] [Synthesis Example 1-3] (Polyurethane Resin P3) Into a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet pipe, a stirrer, and a thermometer, 108.6 parts of PPA (a polyester polyol composed of a polycondensate of propylene glycol and adipic acid and having a number average molecular weight of 2,000), 40.7 parts of PEG (a polyether polyol composed of polyethylene glycol and having a number average molecular weight of 2,000), 28.3 parts of DMPA (2,2-dimethylolpropanoic acid), 105.7 parts of IPDI, and 200 parts of NPAC were charged while introducing nitrogen gas, and the mixture was reacted at 90°C for 5 hours to obtain a prepolymer solution having an isocyanate group at the end. Next, a mixture of 16.7 parts of AEA and 150 parts of IPA was added dropwise to the resulting urethane prepolymer solution at room temperature over 60 minutes, and then 10.0 parts of 28% aqueous ammonia and 690 parts of ion-exchanged water were gradually added to neutralize the carboxyl groups in the resin, thereby making it water-soluble. Next, NPAC and IPA were distilled off under reduced pressure to obtain an aqueous solution of polyurethane resin P3 having a solids concentration of 30%, a mass average molecular weight of 32,000, Mw / Mn=3.3, and an acid value of 39.3 mgKOH / g (note that the acid value of P3 is the value before neutralization).

[0136] [Synthesis Example 1-4] (Acrylic Resin P4) Into a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer, 70 parts of styrene, 23 parts of acrylic acid, 7 parts of 2-hydroxyethyl methacrylate, 40 parts of EA (ethyl acetate), and 40 parts of IPA were charged while introducing nitrogen gas, and the temperature was raised to 90°C. 1 part of AIBN (azobisisobutyronitrile) and 15 parts of EA were added and a polymerization reaction was carried out for 4 hours, and then 0.1 part of AIBN and 3 parts of EA were added and the reaction was carried out for 2 hours, thereby obtaining an acrylic resin solution. EA was added to the obtained acrylic resin solution to adjust the solid content, and acrylic resin P4 having a solid content concentration of 30.0%, a mass average molecular weight of 27,000, an acid value of 179.1 mgKOH / g, and a hydroxyl value of 30.2 mgKOH / g was obtained.

[0137] <Composition for forming primer layer> [Production Example 1-1] (Primer Composition A1) 87 parts of polyurethane resin P2 solution, 5 parts of EA, 5 parts of IPA, and 3 parts of silica particles (P-73 manufactured by Mizusawa Chemicals, Inc.: hydrophilic silica particles with an average particle size of 3.8 μm) were mixed and stirred using a disper to obtain primer composition A1.

[0138] [Production Examples 1-2 to 1-4] (Primer Compositions A2 to A4) Primer compositions A2 to A4 were obtained in the same manner as in Production Example 1-1, except that the raw materials and compounding ratios were changed to those shown in Table 1.

[0139] <Printing ink manufacturing> [Manufacturing Example 2-1] (Printing Ink R1) 10 parts of indigo pigment PB15 (CI Pigment Blue 15), 25 parts of polyurethane resin P1 solution, 5 parts of PVC (vinyl chloride-vinyl acetate copolymer resin (Nissin Chemical's Solvine TAO, 30% solids, EA solution)), 10 parts of EA, and 10 parts of IPA were mixed and stirred, and dispersed for 20 minutes using a sand mill as a bead mill. 20 parts of polyurethane resin P1 solution, 10 parts of EA, and 10 parts of IPA were then mixed and stirred to obtain printing ink R1.

[0140] [Manufacturing Examples 2-2 to 2-3] (Printing Ink R2 to 2-3) Printing inks R2 to R3 were obtained in the same manner as Ink Production Example 2-1, except that the raw materials and blending ratios shown in Table 3 were used. The blending amounts in Table 1 are the total of blending during dispersion and post-blending.

[0141] [Table 1]

[0142] The abbreviations in Table 1 are listed below. Maleated rosin resin: Arakawa Chemical's Marquid No. 32 (acid value 130 mg KOH / g, solids concentration 100%) diluted with ethyl acetate to a solids concentration of 30% PVA resin: Kuraray Poval 5-88 (saponification degree 86.5-89.0%), 15% solids aqueous solution PB15: CI Pigment Blue 15 PVC resin: vinyl chloride-vinyl acetate copolymer resin (Nissin Chemical Solvin TAO, 30% solids, EA solution) EA: Ethyl acetate IPA: Isopropyl alcohol

[0143] <Production of polyols used in adhesives> [Synthesis Example 2-1] (Polyester polyol B1) A reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet tube was charged with 124 parts of ethylene glycol, 212 parts of neopentyl glycol, 368 parts of 1,6-hexanediol, 645 parts of isophthalic acid, 36 parts of adipic acid, and 265 parts of sebacic acid. The mixture was heated to 250°C with stirring under a nitrogen stream to carry out an esterification reaction. The reaction was continued until a predetermined amount of water was distilled and the acid value reached 5 or less. The pressure was then gradually reduced, and the deglycolization reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. Subsequently, 35 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150°C for approximately 2 hours to obtain a polyester polyurethane polyol. 12.0 parts of ethylene glycol bis-anhydrotrimellitate was added to 100 parts of this polyester polyurethane polyol, and the mixture was allowed to react at 180°C for approximately 2 hours. The mixture was then diluted with ethyl acetate to a solids concentration of 50%, yielding a solution of partially acid-modified polyester polyol B1 with a number average molecular weight of 9,000 and an acid value of 30.3 mgKOH / g.

[0144] [Synthesis Example 2-2] (Polyester polyol B2) A reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet tube was charged with 58 parts of ethylene glycol, 412 parts of diethylene glycol, 343 parts of neopentyl glycol, 517 parts of isophthalic acid, and 393 parts of adipic acid. The mixture was heated to 250 °C while stirring under a nitrogen stream to carry out an esterification reaction. After a predetermined amount of water was distilled and the reaction was continued until the acid value reached 5 or less, the pressure was gradually reduced and the deglycolization reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. 4.0 parts of trimellitic anhydride were added to 100 parts of this polyester polyol, and the reaction was carried out at 180 °C for approximately 2 hours. The mixture was then diluted with ethyl acetate to a solids concentration of 50%, yielding a solution of partially acid-modified polyester polyol B2 with a number average molecular weight of 2,000 and an acid value of 23.5 mgKOH / g.

[0145] <Preparation of Polyisocyanate> [Preparation Example 1] (Polyisocyanate C1) Coronate 2785 (biuret type polyisocyanate derived from hexamethylene diisocyanate, manufactured by Tosoh Corporation) was diluted with ethyl acetate to adjust the solid concentration to 50% and NCO%=9.6%, to obtain a solution of polyisocyanate C1.

[0146] <Adhesive manufacturing> [Manufacturing Example 3-1] (Adhesive D1) 90 parts of polyester polyol B1 solution, 10 parts of polyester polyol B2 solution, and 8 parts of polyisocyanate C1 solution were blended, and EA was added to prepare an adhesive solution with a solids concentration of 30%.

[0147] [Manufacturing Example 3-2] (Adhesive D2) 90 parts of polyester polyol B1 solution, 10 parts of polyester polyol B2 solution, and 8 parts of polyisocyanate C1 solution were blended, and EA was added to prepare an adhesive solution with a solids concentration of 5%.

[0148] <Production of laminate> The method for producing the laminate is described below. The primer composition and printing ink were each diluted with a mixed solvent of EA / IPA (mass ratio 70 / 30) to a viscosity of 15 seconds (25°C, Zahn cup #3 (manufactured by Rigo Co., Ltd.) before use. The thickness of the primer layer and the printing layer were each adjusted to about 1.5 μm.

[0149] [Manufacturing Example 4-1] (Laminate S1) The diluted primer composition A1 and printing ink R1 were printed in that order onto LLDPE (one-sided corona-treated low-density polyethylene film, 30 μm thick) using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50°C to obtain a laminate S1 having a configuration of polyolefin base layer (LLDPE) / detachable primer layer (A1) / printing layer (R1).

[0150] [Manufacturing example 4-2~13, 16] (laminate S2~13, 16) Laminates S2 to 13 and 16 were obtained in the same manner as in Production Example 4-1, except that the substrate, primer composition, and printing ink were changed as shown in Table 2. For S16, the printing ink was printed directly onto the substrate without using a primer composition.

[0151] [Manufacturing Example 4-14] (Laminate S14) Adhesive D1 is applied to AL foil (soft aluminum film) using a dry laminating machine at a coating amount of 2 g / m after drying. 2 After coating and drying, a LLDPE (low density polyethylene film, thickness 40 μm) was laminated to obtain a laminate. Next, the diluted primer composition A1 and printing ink R1 were printed onto the soft aluminum film surface using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50°C to obtain a laminate S14 having a configuration of printing layer (R1) / detachable primer layer (A1) / soft aluminum substrate layer (AL) / polyethylene substrate layer (LLDPE).

[0152] [Manufacturing Example 4-15] (Laminate S15) Adhesive D2 was applied to double-sided treated OPP (double-sided corona-treated stretched polypropylene film, 30 μm thick) using a gravure coater equipped with a gravure plate with a plate depth of 15 μm, and the film was dried at 80°C to form an adhesive layer. LDPE was extrusion-laminated onto the adhesive layer at a melt temperature of 310°C, thereby laminating it with the vapor-deposited surface of VMOPP. Next, adhesive D2 was applied to the aluminum (VM) surface of the VMOPP using a gravure coater equipped with a gravure plate with a plate depth of 15 μm, and dried at 80°C to form an adhesive layer. LDPE was extrusion laminated onto the adhesive layer at 310°C, and the CPP was then pressed and laminated. Next, the diluted primer composition A1 and printing ink R1 were printed onto the side of the OPP that had not been coated with D2 using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50°C to obtain a laminate S15 having a configuration of detachable printing layer (R1) / polyolefin base layer (double-sided treated OPP) / adhesive layer (D1) / vapor-deposited polyester base layer (VMPET) / adhesive layer (D1) / polyolefin base layer (CPP).

[0153] [Manufacturing Example 4-17] (Laminate L1) The diluted primer composition A1 and printing ink R1 were printed in that order onto the corona-treated surface of OPP (one-sided corona-treated stretched polypropylene film, 30 μm thick) using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and then dried at 50°C to obtain a laminate having a configuration of OPP / A1 / R1. Next, adhesive D1 was applied to the printed layer of the obtained laminate using a dry laminator in an amount of 2 g / m2 after drying. 2 After applying and drying the mixture to form a laminate, it was laminated with CPP to obtain a laminate L1 having a structure of polyolefin substrate layer (OPP) / detachable primer layer (A1) / printed layer (R1) / adhesive layer (D1) / polyolefin substrate layer (CPP).

[0154] [Manufacturing Examples 4-18 to 25, 32] (Laminates L2 to 9, 16) Laminates L2 to L9 and L16 were obtained in the same manner as in Production Example 4-16, except that the substrate, primer composition, printing ink, and adhesive were changed as shown in Table 2. For S16, the printing ink was printed directly onto the substrate without using a primer composition.

[0155] [Manufacturing Example 4-26] (Laminate L10) The diluted primer composition A1 and printing ink R1 were printed in that order onto NY (nylon film, thickness 15 μm) using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and then dried at 50°C to obtain a laminate having a configuration of NY / A1 / R1. Next, adhesive D1 was applied to the printed layer of the obtained laminate using a dry laminator in an amount of 2 g / m2 after drying.2 After applying and drying the mixture until it reached the desired thickness, it was laminated with VMPET (aluminum vapor-deposited polyester film, thickness 15 μm) to obtain a laminate consisting of polyamide substrate layer (NY) / detachable primer layer (A1) / printed layer (R1) / adhesive layer (D1) / vapor-deposited polyester substrate layer (VMPET). Next, adhesive D1 was applied to the VMPET surface of the obtained laminate using a dry laminator in an amount of 2 g / m2 after drying. 2 After that, the mixture was applied and dried so that the composition was as shown in the figure, and then laminated with LLDPE to obtain a laminate L10 having a structure of polyamide substrate layer (NY) / primer layer (A1) / printed layer (R1) / adhesive layer (D1) / deposited polyester substrate layer (VMPET) / adhesive layer (D1) / polyolefin substrate layer (LLDPE).

[0156] [Manufacturing Examples 4-27 to 4-29] (Laminates L11 to L13) Laminates L11 to L13 were obtained in the same manner as in Production Example 4-25, except that the substrate, primer composition, printing ink, and adhesive were changed to those shown in Table 2.

[0157] [Manufacturing Example 4-30] (Laminate L14) The diluted primer composition A1 and printing ink R1 were printed in that order onto the OPP using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50°C to obtain a laminate consisting of an olefin base layer (OPP) / primer layer (A1) / printing layer (R1). Next, adhesive D2 was applied to the printed layer of the obtained laminate using a gravure coater equipped with a gravure plate with a plate depth of 15 μm, and dried at 80°C to form an adhesive layer. LDPE was extrusion laminated onto the adhesive layer at a melt temperature of 310°C to adhere it to the vapor-deposited surface of the VMPET, obtaining a laminate. Next, adhesive D2 was applied to the PET surface of the VMPET using a gravure coater equipped with a gravure plate with a plate depth of 15 μm, and dried at 80°C to form an adhesive layer. LDPE was extrusion laminated onto the adhesive layer at 310°C to press-bond and laminate it with the CPP, obtaining laminate L14, which had a configuration of polyolefin base layer (OPP) / primer layer (A1) / printing layer (R1) / adhesive layer (D2) / vapor-deposited polyester base layer (VMPET) / adhesive layer (D2) / polyolefin base layer (CPP).

[0158] [Manufacturing Example 4-31] (Laminate L15) A laminate L15 was obtained in the same manner as in Production Example 4-29, except that the substrate and adhesive were changed to those shown in Table 2.

[0159] [Table 2]

[0160] The abbreviations in Table 2 are as follows: HSOPP: One-sided heat-sealable polyolefin film, 30 μm thick Anti-fogging OPP: Double-sided anti-fogging polyolefin film, 30 μm thick CPP: Unstretched polypropylene film, thickness 40 μm PET: Biaxially oriented polyester film, thickness 12 μm NY: Nylon film, thickness 15 μm WLLDPE: Milky white polyethylene film, thickness 60 μm OPP: Corona-treated biaxially oriented polypropylene film, 30 μm thick VMPET: Aluminum vapor-deposited polyester film, 15 μm Barrier PET: transparent vapor-deposited polyester film, 12 μm

[0161] <Production of processing solution> [Production Example 5-1] (Treatment Solution T1) 1.0 part of safflower oil as an oil and fat, 2.0 parts of sodium hydroxide, and 97.0 parts of water were blended and stirred with a disper to obtain a treatment liquid T1.

[0162] [Production Examples 5-2 to 5-7] (Treatment Solutions T2 to T7) Treatment solutions T2 to T7 were obtained in the same manner as in Production Example 5-1, except that the oils and basic compounds were changed to those shown in Table 3.

[0163] [Production Example 5-8] (Treatment Solution T8) 1.0 part of POE alkyl ether (polyoxyethylene lauryl ether, POE addition number: 12, HLB: 13.9) as a surfactant, 0.1 part of BYK-1650 (manufactured by BYK Japan, silicone emulsion type defoamer, solids concentration 27.5%) as an antifoaming agent, 1.0 part of palm oil as an oil and fat, 2.0 parts of sodium hydroxide, and 95.9 parts of water were mixed and stirred with a disper to obtain treatment liquid T8.

[0164] [Production Examples 5-9 to 5-15] (Treatment Solutions T9 to T15) Treatment solutions T9 to T15 were obtained in the same manner as in Production Example 5-8, except that the oils and surfactants were changed to the blending compositions shown in Table 3.

[0165] [Table 3]

[0166] [Production Example 5-16] (Treatment Solution T16) 1.0 part of oleic acid as a fatty acid, which is a fat and oil decomposition product, 2.0 parts of sodium hydroxide, and 97.0 parts of water were mixed and stirred with a disper to obtain a treated liquid T16.

[0167] [Production Examples 5-17 to 5-22] (Treatment Solutions T17 to T22) Treatment solutions T17 to T22 were obtained in the same manner as in Production Example 5-16, except that the composition was changed to that shown in Table 4.

[0168] [Production Example 5-23] (Treatment solution T23) 1.0 part of POE alkyl ether (polyoxyethylene lauryl ether, POE addition number: 12, HLB: 13.9) as a surfactant, 0.1 part of BYK-1650 (manufactured by BYK Japan, silicone emulsion type defoamer, solids concentration 27.5%) as an antifoaming agent, 1.0 part of oleic acid as a fatty acid which is an oil and fat decomposition product, 2.0 parts of sodium hydroxide, and 95.9 parts of water were mixed and stirred with a disper to obtain treatment liquid T23.

[0169] [Production Examples 5-24 to 5-35] (Processing Solutions T24 to T35) Treatment solutions T24 to T35 were obtained in the same manner as in Production Example 5-23, except that the composition was changed to that shown in Table 4.

[0170] [Table 4]

[0171] The abbreviations in Tables 3 and 4 are shown below. Nonionic surfactant: POE alkyl ether (polyoxyethylene lauryl ether, POE addition number: 12, HLB: 13.9) Anionic surfactant: Polyoxyethylene lauryl ether phosphate: POE addition number: 4, HLB: 10.0 Defoamer: BYK-1650: BYK Japan, silicone oil compound, solids concentration >97% Safflower oil: safflower oil (number of carbon chains of fatty acids that make up the oil: 16-18) manufactured by J Oil Mills Co., Ltd. Palm oil: Delica Premier palm oil, manufactured by Nisshin Oillio Group Co., Ltd. (number of carbon chains of fatty acids that make up the oil: 16-18) Soybean oil: manufactured by J Oil Mills Co., Ltd., soybean oil (number of carbon chains of fatty acids that make up the oil: 14 to 20) Rapeseed oil: J Oil Mills Co., Ltd., salad oil (number of carbon chains of fatty acids that make up the oil: 14-18) Margarine: J Oil Mills, Rama Butter Flavor (number of carbon chains of fatty acids that make up the oil: 10-20) Butter: Snow Brand Hokkaido Butter, manufactured by Megmilk Snow Brand Co., Ltd. (number of carbon chains of fatty acids that make up the oil and fat: 4 to 20) Oleic acid: Fujifilm Wako Pure Chemical Industries, Ltd., standard content 98.0%+, CH3(CH2)7CH=CH(CH2)7COOH, molecular weight 282.46 Linoleic acid: Fujifilm Wako Pure Chemical Industries, Ltd., standard content 98.0+%, CH3(CH2)3(CH2CH=CH)2(CH2)7COOH, molecular weight 280.45 Linolenic acid: Fujifilm Wako Pure Chemical Industries, Ltd., standard content 98.0+%, CH3(CH2CH=CH)3(CH2)7COOH, molecular weight 278.43 Stearic acid: Fujifilm Wako Pure Chemical Industries, Ltd., standard content 95.0%+, CH3(CH2) 16 COOH, molecular weight 284.47 Butyric acid: Fujifilm Wako Pure Chemical Industries, Ltd., standard content 98.0+%, CH3(CH2)2COOH, molecular weight 88.11 Caprylic acid: Fujifilm Wako Pure Chemical Industries, Ltd., standard content 98.0%+, CH3(CH2)6COOH, molecular weight 144.21

[0172] <Separation and recovery of laminated body> [Example 1] 200 g of treatment solution T1 and 8 g of a sample cut into a 1 cm x 1 cm size from packaging material S1 were placed in a 1000 mL stainless steel beaker and stirred at 70 °C and 1500 rpm. The separation and recovery state of the laminate was evaluated as follows.

[0173] [Examples 2 to 100, Comparative Examples 1 to 8] The separation and recovery state of the laminate was evaluated in the same manner as in Example 1, except that the materials shown in Tables 5 to 7 were used. The results are shown in Tables 5 to 7.

[0174] <Evaluation of laminate> (Removal properties of the detachment layer) The detachment of the detachment layer was evaluated for the laminate having a plastic substrate on which the detachment layer was formed using the following method. Samples were prepared by taking samples of the substrate 15 minutes, 30 minutes, and 1 hour after the start of stirring, rinsing with water, and drying. 1. Ten samples of the obtained substrates were taken, and the removal rate (area) of the printed layer was visually confirmed. 2. Three plastic substrates that come into contact with the primer and three sealant substrates that come into contact with the adhesive were taken out, and for each, 18 locations, three on each side, were examined using FT-IR to check for the presence or absence of absorption peaks of the primer and adhesive. A (Excellent): 15 minutes after stirring began, 90% or more of the printed layer peeled off from the substrate, and no absorption peak was observed in any of the 18 locations for either the primer or adhesive. B (Good): 90% or more of the printed layer peeled off from the substrate 30 minutes after the start of stirring, and no absorption peak was observed in any of the 18 locations for either the primer or the adhesive. C (Acceptable): 90% or more of the printed layer peeled off from the substrate one hour after stirring began, and no absorption peak was observed in any of the 18 locations for either the primer or adhesive. D (Fail): 90% or more of the printed layer does not peel off from the substrate one hour after stirring begins, and an absorption peak of either the primer or adhesive is observed in one or more of the 18 locations.

[0175] (Reattachment of impurities from the detached layer) In the evaluation of the detachment properties of the detachment layer, the substrates were stirred under the above stirring conditions for 1, 12, and 24 hours, and then the detached substrates were collected, washed with water, and dried. Ten substrates were sampled, and the ten substrates were stacked and measured for color value L using a spectrophotometer (X-rite eXact, manufactured by X-rite). * x , a * x , b * x was measured. Similarly, for the plastic substrate itself, which is the substrate to be printed, the detached substrate was collected, and 10 substrates were stacked and the color value L* y , a * y , b * y was measured. The color difference ΔE before and after stirring for 1 hour was calculated using the formula below, and the re-adhesion was evaluated according to the following criteria. (Formula)ΔE=((L * x -L * y ) 2 +(a * x -a * y ) 2 +(b * x -b * y ) 2 ) 1 / 2 A (Excellent): ΔE is less than 5 B (Good): ΔE is 5 or more and less than 15 C (Acceptable): ΔE is 15 or more and less than 20 D (not allowed): Other than A~C

[0176] (foaming) Stirring was temporarily stopped 10 minutes after the start of stirring, and the height of the liquid surface (above the bubbles) was visually observed and evaluated according to the following criteria: The height of 450 mL refers to the volume scale marked on the beaker, and the higher the number, the higher the liquid surface, i.e., the more bubbles were generated. A (Excellent): The height of the liquid surface (above the bubbles) during stirring is less than 450 mL B (Good): The liquid level (above the bubbles) during stirring is 450 mL or more and less than 600 mL C (Acceptable): The height of the liquid surface (above the bubbles) during stirring is 600 mL or more and less than 900 mL D (Not acceptable): The liquid level (above the bubbles) during stirring is 900 mL or more.

[0177] (Haze evaluation of recycled materials) (Examples 1 to 85, 88 to 100) The detached polyolefin substrate was recovered, washed with water, dried, and then extruded at 220°C using a single-screw extruder and pelletized to obtain recycled resin pellets. The recycled resin was then extruded using a T-die film molding machine to produce a recycled film with a thickness of 40 μm. Regarding the coloration of the recycled film, the total light transmittance was measured using a haze meter (SH7000, manufactured by Nippon Denshi Kogyo Co., Ltd.) and evaluated according to the following criteria. A (Excellent): Total light transmittance is 70% or more B (Good): Total light transmittance is 50% or more and less than 70% C (Acceptable): Total light transmittance is 30% or more but less than 50% D (unacceptable): Total light transmittance is less than 30%

[0178] Example 86 The detached polyester substrate was recovered, washed with water, dried, and then extruded at 260°C using a single-screw extruder. After a pelletizing process, recycled resin pellets were obtained. The recycled resin was extruded using a T-die film molding machine to produce a recycled film with a thickness of 40 μm. Regarding the coloration of the recycled film, the total light transmittance was measured using a haze meter (SH7000, manufactured by Nippon Denshi Kogyo Co., Ltd.) and evaluated according to the following criteria. A (Excellent): Total light transmittance is 70% or more B (Good): Total light transmittance is 50% or more and less than 70% C (Acceptable): Total light transmittance is 30% or more but less than 50% D (unacceptable): Total light transmittance is less than 30%

[0179] Example 87 The detached nylon substrate was recovered, washed with water, dried, and then extruded at 260°C using a single-screw extruder. After a pelletizing process, recycled resin pellets were obtained. The recycled resin was then extruded using a T-die film molding machine to produce a recycled film with a thickness of 40 μm. Regarding the coloration of the recycled film, the total light transmittance was measured using a haze meter (SH7000, manufactured by Nippon Denshi Kogyo Co., Ltd.) and evaluated according to the following criteria. A (Excellent): Total light transmittance is 70% or more B (Good): Total light transmittance is 50% or more and less than 70% C (Acceptable): Total light transmittance is 30% or more but less than 50% D (unacceptable): Total light transmittance is less than 30%

[0180] [Table 5]

[0181] [Table 6]

[0182] [Table 7]

[0183] The above evaluation results show that the treatment liquid of the present invention can easily remove printed layers and adhesive layers from packaging materials, can suppress re-adhesion of plastic substrates that remain after a long or continuous de-inking process, and can produce high-quality recycled substrates with little re-adhesion of printed layers and adhesive layers, as well as high-quality molding materials with little coloration.

Claims

1. A treatment solution for separating and recovering a plastic substrate from a laminate having at least a release layer on a plastic substrate, A treatment liquid comprising a basic compound and fats and / or fat decomposition products.

2. The treatment liquid according to claim 1, wherein the fats and / or fat decomposition products are at least one selected from the group consisting of vegetable fats and oils, animal fats and oils, decomposition products of vegetable fats and oils, and decomposition products of animal fats and oils.

3. The treatment liquid according to claim 1, wherein the number of carbon atoms in the fatty acids constituting the fats and / or fats and / or fat decomposition products is 1 to 24.

4. The treatment liquid according to claim 1, wherein the total content of the fats and oils and fat decomposition products is 0.05 to 10.00 mass% in 100 mass% of the treatment liquid.

5. The treatment liquid according to claim 1, further comprising a surfactant (excluding fat and oil decomposition products), wherein the surfactant comprises at least one selected from the group consisting of anionic surfactants, nonionic surfactants, and amphoteric surfactants.

6. The treatment liquid according to claim 5, wherein the content of the surfactant (excluding fat and oil decomposition products) is 0.01 to 5.0 mass % in 100 mass % of the treatment liquid.

7. The treatment solution according to claim 1 , further comprising an antifoaming agent.

8. A method for separating and recovering a plastic substrate, comprising the steps of contacting a laminate having at least a detachment layer on a plastic substrate with the treatment liquid according to any one of claims 1 to 7 to detach the detachment layer, and separating and recovering the plastic substrate.

9. A method for producing a molding material using a plastic substrate separated and recovered by the separation and recovery method according to claim 8, the plastic substrate is a polyolefin substrate, A method for producing a molding material, wherein the molding material contains the separated and recovered plastic base material in an amount of 70% by mass or more based on 100% by mass of the molding material.

10. A method for producing a molded article, comprising hot molding a molding material produced by the method according to claim 9.

Images