Removable film-forming composition

Abstract

The present invention provides a film-forming composition that can easily remove a film layer from a general-purpose plastic substrate using a simple method. The film-forming composition of the present invention is a removable film-forming composition used to form a film on the surface of a substrate (A) directly or through another layer that is removable by treatment in an alkaline solution. The film-forming composition contains a urethane resin having a hydroxyl value and no acid value. The hydroxyl value of the film-forming composition is preferably 1.0 mgKOH / g to 30.0 mgKOH / g.

Description

Technical Field

[0001] The present invention relates to a composition for forming a film that can be releasable from a substrate. Background Art

[0002] In recent years, the problem of marine plastics, caused by the decomposition and micronization of discarded and discarded plastics in seawater (microplasticization), has become increasingly prominent. These microplastics enter the bodies of marine organisms and become concentrated, raising concerns about their impact on the health of seabirds and humans through the food chain. One way to improve the problem of marine plastics is recycling. Increasing the recycling rate of resources such as flexible packaging materials and plastic bottles is related to preventing the influx of plastics into the ocean. However, in current recycling, the film printed on the plastic substrate is not separated during the recycling process, but is mixed into the plastic, causing a deterioration in color tone and a reduction in physical properties, which has the problem of reducing the value of recycled plastics. If this problem can be solved by achieving the separation of the film from the plastic substrate during the recycling process, the value of the recycled plastic will increase, leading to the entry of new recycling companies and the improvement of classified recycling by autonomous groups. Therefore, it is believed that by increasing the recycling rate, the problem of marine plastics will be improved. Therefore, it is required to develop a film-forming material that can separate the film during the recycling process.

[0003] Furthermore, considering the impact on worker health and the environment, there is a push to replace organic solvent-based printing inks, which are widely used as film-forming materials for plastic substrates, with toluene-free and methyl ethyl ketone (MEK-free) inks. Therefore, materials that address these issues also need to be developed with this in mind.

[0004] Prior art discloses a method for removing a printed film containing a styrene-acrylic resin, phenolic resin, or styrene-maleic acid resin as a carrier, printed on a heat-shrinkable PET film, using alkaline water (Patent Document 1). Similarly, methods disclose a coating containing a styrene-maleic acid resin, a rosin-maleic acid resin, or an acrylic copolymer resin, placed between the printed layer and the heat-shrinkable PET film, and removing the coating using alkaline water (Patent Documents 2 and 3). However, these techniques only guarantee properties for specific substrates and are insufficient from the perspective of providing an easy removal method. There is still room for research to provide a recycling method for plastic substrates that can easily remove the printed layer from a general-purpose plastic substrate including a polyolefin by a simple method.

[0005] On the other hand, organic solvent-based printing inks for alkaline water release using a urethane resin having an acid value as a binder resin have been disclosed (Patent Documents 4, 5, and 6).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent No. 3822738

[0009] Patent Document 2: Japanese Patent No. 4653913

[0010] Patent Document 3: Japanese Patent No. 4451071

[0011] Patent Document 4: Japanese Patent No. 6638802

[0012] Patent Document 5: Japanese Patent No. 6631964

[0013] Patent Document 6: Japanese Patent Application Laid-Open No. 2020-169280 Summary of the Invention

[0014] Problems to be solved by the invention

[0015] The problem to be solved by the present invention is to provide a film-forming material (film-forming composition) in order to simultaneously solve the above-mentioned marine plastic problem and the problems caused to the health of workers and the environment, which can form a film that can be detached from a general plastic substrate using a simple method, the film layer can be easily removed from the plastic substrate, and has excellent adhesion to the substrate.

[0016] Means for solving problems

[0017] The inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by including a urethane resin having a hydroxyl value and no acid value in a film-forming composition, thereby completing the present invention.

[0018] That is, the present invention includes the following aspects.

[0019] [1] A film-forming composition, which is a removable film-forming composition for forming a film on the surface of a substrate A, directly or through another layer, that is removable by treatment in an alkaline solution.

[0020] The film-forming composition contains a urethane resin having a hydroxyl value and no acid value.

[0021] [2] The film-forming composition according to [1], wherein the hydroxyl value is 1.0 mgKOH / g to 30.0 mgKOH / g.

[0022] [3] The film-forming composition according to [1] or [2], wherein the urethane resin contains at least one of a polyester polyol and a polyether polyol as a constituent component.

[0023] [4] The film-forming composition according to any one of [1] to [3], which contains a colorant.

[0024] [5] The film-forming composition according to [4], which is used as a printing ink.

[0025] [6] The film-forming composition according to [5], wherein the printing ink is an organic solvent-based ink.

[0026] [7] The film-forming composition according to any one of [1] to [4], which is used as a primer or a clear coat.

[0027] [8] A printed article having a film comprising the film-forming composition according to any one of [1] to [7] on the surface of a substrate A, directly or via another layer.

[0028] [9] The printed matter according to [8], wherein the film is at least one selected from a printed layer, a primer layer, and a varnish layer.

[0029]

[10] A laminated body obtained by arranging a substrate B on the surface of the printed material described in [8] or [9] opposite to the surface on which the substrate A is arranged, and laminating the printed material and the substrate B.

[0030]

[11] A method for producing a recycled substrate A, wherein the printed matter described in [8] or [9] is treated with an alkaline solution to remove the film from the substrate A, thereby obtaining the recycled substrate A.

[0031]

[12] A method for producing a recycled substrate A, wherein the laminate described in

[10] is treated with an alkaline solution to remove the substrate B together with the film, thereby obtaining the recycled substrate A.

[0032] Effects of the Invention

[0033] According to the present invention, a film-forming composition can be provided that can form a film that can be easily removed from a general-purpose plastic substrate, can be easily removed from the plastic substrate, and has excellent adhesion to the substrate. DETAILED DESCRIPTION

[0034] The present invention will be described in detail below. It should be noted that the description of the constituent elements described below is for illustration purposes only and the present invention is not limited thereto.

[0035] (Film-forming composition)

[0036] The film-forming composition of the present invention is used to form a film directly or via another layer on the surface of the substrate A. In the present invention, the other layer may be a single layer or a plurality of layers.

[0037] The film formed using the film-forming composition of the present invention can be removed by treatment in an alkaline solution.

[0038] The film-forming composition contains a urethane resin. The urethane resin has a hydroxyl value and no acid value.

[0039] By providing the urethane resin with a hydroxyl value, the film can be removed by a simple method, and the film layer can be easily removed from the plastic substrate. Hereinafter, this effect may be referred to as releasability.

[0040] By making the urethane resin have no acid value, a film having excellent adhesion to the substrate can be formed.

[0041] Here, the term "having a hydroxyl value" as used in this specification means that the hydroxyl value of the urethane resin does not reach an end point with a single drop of titration when the hydroxyl value of the urethane resin is measured by the neutralization titration method of JIS K 0070 (1992).

[0042] In this specification, the phrase "having no acid value" means that the end point is reached by titration with one drop when the acid value of the urethane resin is measured by the neutralization titration method of JIS K 0070 (1992).

[0043] The film formed from the film-forming composition of the present invention is used to remove a printed layer formed on the surface of the substrate A directly or through another layer from the substrate A.

[0044] Here, the printed layer refers to a layer formed by printing printing ink.

[0045] As methods for removing the printed layer from substrate A, for example, there can be cited a method in which the printed layer itself has a detachment function and the printed layer is detached from substrate A (hereinafter also referred to as mode A method); a method in which another layer is provided between the printed layer and substrate A, the other layer has a detachment function, and the printed layer is detached from substrate A together with the printed layer by detaching the other layer (hereinafter also referred to as mode B method), etc.

[0046] The film formed from the film-forming composition of the present invention also includes the printed layer in the method of Mode A and the other layer in the method of Mode B. More specifically, the film of the present invention also includes the printed layer and any of the primer layer and clear coat layer described below.

[0047] That is, the film-forming composition of the present invention can be used in any form of a printing ink, a primer, or a varnish.

[0048] The film-forming composition of the present invention may be used to form at least one of the printed layer, primer layer, and clear coat layer. Of these layers, one or more layers may be formed using the film-forming composition of the present invention.

[0049] As an example of the arrangement structure of the film and the substrate A of the present invention, the following can be mentioned.

[0050] Substrate A - Printing layer (white) - Printing layer (color)

[0051] Substrate A - Primer layer - Printing layer (white) - Printing layer (color)

[0052] Substrate A - Printing layer (white) - Printing layer (color) - Varnish layer

[0053] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Clear varnish layer

[0054] Substrate A - Printing layer (color) - Printing layer (white)

[0055] Substrate A - Primer layer - Printing layer (color) - Printing layer (white)

[0056] Substrate A - Printing layer (color) - Printing layer (white) - Varnish layer

[0057] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Clear varnish layer

[0058] ·Substrate A-Varnish layer

[0059] Substrate A-printing layer (color)

[0060] Here, substrate A represents substrate A described later, a printed layer (white) represents a printed layer formed by printing the film-forming composition of the present invention as a printing ink and a colorant used in white ink as a colorant contained in the film-forming composition, a printed layer (color) represents a printed layer formed by printing the film-forming composition of the present invention as a printing ink and a colorant other than the colorant used in white ink as a colorant contained in the film-forming composition, a primer layer represents a layer formed using the film-forming composition of the present invention as a primer described later, and a varnish layer represents a layer formed using the film-forming composition of the present invention as a varnish described later.

[0061] It should be noted that in the above examples, the printed layer can be stacked in two layers, one in which white ink is used and the other in which colored ink is used as a colorant other than white ink. However, the printed layer does not need to be formed in two or more layers like this, and can also be formed in any one layer of white or colored.

[0062] <Organic solvent-based composition>

[0063] The organic solvent-based composition as the film-forming composition of the present invention is used to form a printed layer on the surface of the substrate A directly or through another layer, which is removable by treatment in an alkaline solution.

[0064] The organic solvent-based composition contains a urethane resin.

[0065] The organic solvent-based composition contains an organic solvent and, if necessary, a colorant and other components.

[0066] Organic solvent-based compositions can use biomass-derived raw materials. Considering issues such as the depletion of petroleum resources, petroleum-derived products are preferably replaced with products produced from plants and / or microorganisms, which serve as alternative energy sources. In this case, organic solvent-based compositions can contribute to reducing environmental burdens through carbon neutrality.

[0067] Urethane resin

[0068] Urethane resin has a hydroxyl value and does not have an acid value.

[0069] The hydroxyl value of the urethane resin is not particularly limited. However, from the perspective of achieving superior releasability, the hydroxyl value is preferably 1.0 mgKOH / g or higher, preferably 3.0 mgKOH / g or higher, preferably 5.0 mgKOH / g or higher, more preferably 8.0 mgKOH / g or higher, and even more preferably 10.0 mgKOH / g or higher. Furthermore, the hydroxyl value is preferably 40.0 mgKOH / g or lower, preferably 35.0 mgKOH / g or lower, preferably 30.0 mgKOH / g or lower, more preferably 25.0 mgKOH / g or lower, and even more preferably 20.0 mgKOH / g or lower. Furthermore, it is preferably 1.0 mgKOH / g to 40.0 mgKOH / g, more preferably 3.0 mgKOH / g to 35.0 mgKOH / g, more preferably 5.0 mgKOH / g to 30.0 mgKOH / g, more preferably 8.0 mgKOH / g to 25.0 mgKOH / g, and more preferably 10.0 mgKOH / g to 20.0 mgKOH / g.

[0070] The weight average molecular weight of the urethane resin is not particularly limited, but is preferably 45,000 or greater from the perspective of achieving superior releasability, and is more preferably 65,000 or greater from the perspective of achieving a high balance between releasability and adhesion to the substrate. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 200,000 or less, and more preferably 150,000 or less.

[0071] The number average molecular weight of the urethane resin is not particularly limited, but is preferably 10,000 or greater from the perspective of achieving superior releasability, and is more preferably 30,000 or greater from the perspective of achieving a high balance between releasability and adhesion to the substrate. The upper limit of the number average molecular weight is not particularly limited, but is preferably 100,000 or less, and more preferably 75,000 or less.

[0072] The polydispersity (weight average molecular weight / number average molecular weight) of the urethane resin is not particularly limited, but may be 5.0 or less, 4.0 or less, or 3.0 or less. The lower limit of the polydispersity is not particularly limited, but may be 1.0 or more, 1.2 or more, or 1.5 or more.

[0073] The urethane resin preferably uses polyester polyol and / or polyether polyol as its reaction raw material. In other words, the urethane resin preferably contains at least one of polyester polyol and polyether polyol as a constituent component.

[0074] The number average molecular weight of the polyester polyol is preferably 1000 to 7000. If the number average molecular weight of the polyester polyol is less than 1000, the urethane resin film tends to become hard, and the adhesion to the polyester film is likely to be reduced. If the number average molecular weight is greater than 7000, the film obtained using the film-forming composition tends to become brittle, and the blocking resistance of the film tends to be reduced. On the other hand, the content of the polyester polyol in the urethane resin is preferably 1 to 50 parts by mass relative to 100 parts by mass of the urethane resin. If the polyether polyol content is less than 1 part by mass, the solubility of the urethane resin in ketone, ester, and alcohol solvents decreases, and the adhesion to high-performance barrier films, in particular, tends to decrease. In addition, the re-solubility of the film in the solvent decreases, and the gradation reproducibility of the printed material tends to decrease. In addition, if the content is greater than 50 parts by mass, the film is too soft and tends to deteriorate in blocking resistance.

[0075] In addition, the weight average molecular weight and number average molecular weight of a urethane resin and a polyester polyol show the value measured by the gel permeation chromatography (GPC) method under the following conditions.

[0076] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by TOSOH Corporation)

[0077] Chromatographic columns: The following chromatographic columns manufactured by TOSOH Corporation were connected in series and used.

[0078] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 piece

[0079] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 piece

[0080] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 piece

[0081] TSKgel G2000 (7.8mm I.D. x 30cm) x 1 piece

[0082] Detector: RI (differential refractometer)

[0083] Column temperature: 40°C

[0084] Eluent: tetrahydrofuran (THF)

[0085] Flow rate: 1.0 mL / min

[0086] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)

[0087] Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0088] (Standard polystyrene)

[0089] TSKgel Standard Polystyrene A-500, manufactured by TOSOH Corporation

[0090] TSKgel Standard Polystyrene A-1000, manufactured by TOSOH Corporation

[0091] TSKgel Standard Polystyrene A-2500, manufactured by TOSOH Corporation

[0092] TSKgel Standard Polystyrene A-5000, manufactured by TOSOH Corporation

[0093] TSKgel Standard Polystyrene F-1, manufactured by TOSOH Corporation

[0094] TSKgel Standard Polystyrene F-2 manufactured by TOSOH Corporation

[0095] TSKgel Standard Polystyrene F-4, manufactured by TOSOH Corporation

[0096] TSKgel Standard Polystyrene F-10 manufactured by TOSOH Corporation

[0097] TSKgel Standard Polystyrene F-20 manufactured by TOSOH Corporation

[0098] TSKgel Standard Polystyrene F-40 manufactured by TOSOH Corporation

[0099] TSKgel Standard Polystyrene F-80 manufactured by TOSOH Corporation

[0100] TSKgel Standard Polystyrene F-128, manufactured by TOSOH Corporation

[0101] TSKgel Standard Polystyrene F-288, manufactured by TOSOH Corporation

[0102] TSKgel Standard Polystyrene F-550 manufactured by TOSOH Corporation

[0103] For example, polyester polyols obtained by subjecting a compound having two or more hydroxyl groups and a polybasic acid to a known esterification reaction can be used as the polyester polyols.

[0104] The compound having two or more hydroxyl groups is a compound used as a chain extender, and for example, diols such as ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol can be used; 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2- Compounds with a number average molecular weight of 50 to 400 include diols with a branched structure, such as isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, and 2-methyl-1,8-octanediol; aliphatic polyols, such as trimethylolpropane, trimethylolethane, pentaerythritol, sucrose, methylene glycol, glycerin, and sorbitol; and aromatic polyols, such as bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone. These chain extenders may be used alone or in combination of two or more.

[0105] Examples of the polybasic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, and anhydrides thereof. These polybasic acids may be used alone or in combination of two or more.

[0106] The number average molecular weight of the polyether polyol is preferably 100 to 4000. Examples of the polyether polyol include polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, and the like. Specifically, known and commonly used compounds such as polyethylene glycol, polypropylene glycol, and polybutylene glycol are exemplified, with polyethylene glycol being preferred.

[0107] Similarly, if the number average molecular weight of the polyether polyol is less than 100, the film formed using the film-forming composition tends to be hard, and adhesion to polyester films is likely to be reduced. If the number average molecular weight exceeds 4000, the film formed using the film-forming composition tends to be brittle, and the blocking resistance of the film is likely to be reduced. The number average molecular weight of the polyether polyol is measured using gel permeation chromatography (GPC) under the same conditions as for the polyester polyol.

[0108] Examples of the diisocyanate compound used in the production of the urethane resin include various well-known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of urethane resins. For example, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylidene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimer Acid diisocyanate, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane;), dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, bis-chloromethyl-diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, dimer diisocyanate obtained by converting the carboxyl groups of dimer acid into isocyanate groups, and the like. These diisocyanate compounds can be used alone or in combination of two or more.

[0109] As chain extenders used in the production of the above-mentioned urethane resin, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, etc. can be used. In addition, amines having hydroxyl groups in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, bis(2-hydroxyethyl)ethylenediamine, bis(2-hydroxy)ethylenediamine, bis(2-hydroxyethyl)propylenediamine, 2-hydroxypropylethylenediamine, bis(2-hydroxypropyl)ethylenediamine, and bis(2-hydroxypropyl)ethylenediamine, can also be used. These chain extenders can be used alone or in combination of two or more.

[0110] The urethane resin can be obtained, for example, by reacting a polyol, a polyisocyanate, a chain extender, and, if necessary, a monovalent active hydrogen compound. For example, it can be produced by a two-stage process or a one-stage process. In the two-stage process, a polyester polyol and, if necessary, a combined polyol are reacted with a diisocyanate compound in a ratio in which the isocyanate groups are in excess to obtain a prepolymer having terminal isocyanate groups. The resulting prepolymer is then reacted with a chain extender and / or a capping agent in an appropriate solvent, i.e., an ester solvent commonly used as a solvent for liquid ink, such as ethyl acetate, propyl acetate, or butyl acetate; a ketone solvent such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an alcohol solvent such as methanol, ethanol, isopropanol, or n-butanol; a hydrocarbon solvent such as toluene, xylene, methylcyclohexane, or ethylcyclohexane; or a mixed solvent thereof. In the one-stage process, a polyester polyol and, if necessary, a combined polyol, a diisocyanate compound, a chain extender, and / or a capping agent are reacted all at once in an appropriate solvent. Among these methods, a two-stage process is preferred for obtaining a uniform urethane resin. Furthermore, when producing a urethane resin using the two-stage process, the reaction is preferably conducted so that the total (equivalent ratio) of the amino groups of the chain extender and / or end-capping agent is between 1 / 0.9 and 1.3. If the equivalent ratio of isocyanate groups to amino groups is less than 1 / 1.3, the chain extender and / or end-capping agent may remain unreacted, causing the urethane resin to yellow and generating a post-printing odor.

[0111] As a method for imparting a hydroxyl value to a urethane resin, for example, a method of using a primary or secondary amine compound having a hydroxyl group as a capping agent during the production of the urethane resin can be mentioned. Examples of such amine compounds include monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, monoisopropanolamine, and diisopropanolamine.

[0112] As a method for not imparting an acid value to the urethane resin, for example, there can be mentioned a method of using a raw material having no carboxyl group in the above-mentioned two-stage method or one-stage method.

[0113] On the other hand, methods for imparting an acid value to a urethane resin include, for example, using a raw material having a carboxyl group in the aforementioned two-stage method or one-stage method. Examples of raw materials having a carboxyl group include diols having a carboxyl group (e.g., 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid). For example, in the aforementioned two-stage method or one-stage method, using a diol having a carboxyl group as a co-polyol can yield a urethane resin having an acid value.

[0114] The amine value of the urethane resin is preferably 10.0 mgKOH / g or less. If the amine value exceeds 10.0 mgKOH / g, blocking resistance tends to deteriorate, and the two-liquid stability after the addition of the curing agent decreases. From the perspective of maintaining good blocking resistance and two-liquid stability while maintaining plate-forming properties, adhesion, and extrusion lamination strength, the amine value is more preferably in the range of 0 to 5.00 mgKOH / g, and even more preferably in the range of 0 to 3.50 mgKOH / g.

[0115] Regarding the content of the urethane resin in the composition of the present invention, for example, in the case of gravure ink used for gravure printing, from the viewpoint of ensuring sufficient adhesion of the gravure ink to the printed object, the content is preferably 5% by mass or more, calculated as solid content, relative to the total mass of the ink, and from the viewpoint of appropriate ink viscosity and operational efficiency during ink production and printing, it is preferably 25% by mass or less. In the case of flexographic ink used for flexographic printing, the content is preferably 5% by mass or more and 30% by mass or less, calculated as solid content, relative to the total mass of the flexographic ink.

[0116] <<Organic solvent>>

[0117] The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, xylene, Solvesso #100, and Solvesso #150; aliphatic hydrocarbons such as hexane, methylcyclohexane, heptane, octane, and decane; and ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. In addition, examples of water-miscible organic solvents include various organic solvents of alcohols such as methanol, ethanol, propanol, butanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and glycol ethers such as ethylene glycol (mono- or di) methyl ether, ethylene glycol (mono- or di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono- or di) methyl ether, diethylene glycol (mono- or di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono- or di) methyl ether, propylene glycol (mono- or di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono- or di) methyl ether. These can be used alone or in combination of two or more.

[0118] As the ester organic solvent, from the viewpoint of preventing the drying of the organic solvent-based composition of the present invention due to its high volatility, it is more preferable to contain an ester organic solvent having 4 or more carbon atoms. The ester organic solvent having 4 or more carbon atoms is not limited, but ethyl acetate, isopropyl acetate, n-propyl acetate, and butyl acetate are more preferred, and n-propyl acetate is particularly preferred.

[0119] The content of the ester organic solvent relative to the organic solvent composition of the present invention is preferably 1% by mass or more, preferably 3% by mass or more, preferably 5% by mass or more, preferably 7% by mass or more, preferably 10% by mass or more, preferably 12% by mass or more, preferably 15% by mass or more, preferably 18% by mass or more, and preferably 20% by mass or more. Furthermore, it is preferably 60% by mass or less, preferably 55% by mass or less, preferably 50% by mass or less, preferably 45% by mass or less, preferably 40% by mass or less, and preferably 35% by mass or less.

[0120] The content of the ester organic solvent relative to the organic solvent composition of the present invention is preferably 1 to 60 mass %, preferably 3 to 55 mass %, preferably 5 to 50 mass %, preferably 7 to 45 mass %, preferably 10 to 40 mass %, preferably 12 to 35 mass %, preferably 15 to 30 mass %, preferably 18 to 28 mass %, preferably 20 to 25 mass %, and preferably 20 to 23 mass %.

[0121] When the organic solvent composition of the present invention is used as a gravure ink, it is preferred that the composition not contain an aromatic hydrocarbon organic solvent but contain an alcohol having a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is set to 100. By containing an alcohol having a specific evaporation rate of 100 or less, it is possible to maintain the high gloss transfer property of a dot area of ​​10% or less and improve the high gloss. The following two points can be cited as the mechanism for this:

[0122] First things first:

[0123] 1) After the organic solvent-based composition of the present invention is transferred to the substrate, half of the organic solvent-based composition of the present invention remains in the cells of the gravure plate.

[0124] 2) The solvent contained in the remaining organic solvent composition of the present invention evaporates before it comes into contact with the organic solvent composition of the present invention in the ink tray again, leaving it in a semi-dry state. Furthermore, since the solvent with the fastest evaporation rate evaporates first, the solvent with the slowest evaporation rate remains in the ink tray.

[0125] 3) At this time, if a solvent with high resin solubility remains, the semi-dried composition will redissolve when it contacts the organic solvent-based composition of the present invention again, thereby preventing the organic solvent-based composition of the present invention from solidifying in the cells.

[0126] In the case of a general-purpose alcohol having a specific evaporation rate exceeding 100 when the evaporation rate of butyl acetate is set to 100, the aforementioned mechanism tends to be less likely to function due to a high volatilization rate.

[0127] Secondly, alcohols having a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is set to 100 tend to increase the solubility of the urethane resin because the ratio of the hydroxyl group (alcohol group) in one alcohol molecule is low.

[0128] Note that, from the perspectives of both hygienic printing operations and toxicity of packaging materials, it is more preferable to use ethyl acetate, propyl acetate, isopropyl alcohol, n-propyl alcohol, etc., and not to use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone.

[0129] Among these, a mixture of isopropyl alcohol / ethyl acetate / n-propyl acetate / methylcyclohexane is more preferred from the viewpoint of solubility in urethane resins and nitrocellulose. Furthermore, glycol ethers may be added to adjust the drying process, as long as the amount is less than 10% by mass of the total composition.

[0130] Colorants

[0131] The organic solvent-based composition of the present invention may further contain a colorant.

[0132] Examples of the colorant used in the organic solvent-based composition of the present invention include inorganic pigments, organic pigments, and dyes commonly used in inks, coatings, and recording agents.

[0133] Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, perylene pigments, pyrenone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthronone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, indanthrone pigments, and carbon black pigments. In addition, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, solid yellow, solid red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone fuchsine, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo red, thioindigo fuchsine, perylene red, pyrene orange, isoindolinone yellow, nigrosine, diketopyrrolopyrrole red, daylight fluorescent pigments, etc. In addition, both non-acid-treated pigments and acid-treated pigments can be used. Specific examples preferred as organic pigments are given below.

[0134] Examples of the black pigment include CI Pigment Black 1, CI Pigment Black 6, CI Pigment Black 7, CI Pigment Black 9, and CI Pigment Black 20.

[0135] Examples of the blue pigment include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:5, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 22, CI Pigment Blue 24:1, CI Pigment Blue 25, CI Pigment Blue 26, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Blue 63, CI Pigment Blue 64, CI Pigment Blue 75, CI Pigment Blue 79, and CI Pigment Blue 80.

[0136] Examples of the green pigment include CI Pigment Green 1, CI Pigment Green 4, CI Pigment Green 7, CI Pigment Green 8, CI Pigment Green 10, and CI Pigment Green 36.

[0137] Examples of the red pigment include CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 20, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 38, and CI Pigment Red 4. 1. CI Pigment Red 43, CI Pigment Red 46, CI Pigment Red 48, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 48:5, CI Pigment Red 48:6, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 49:3, CI Pigment Red 52, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53, CI Pigment Red 53:1, CI Pigment Red 53:2, CI Pigment Red 53:3, CI Pigment Red 54, CI Pigment Red CI Pigment Red 57, CI Pigment Red 57:1, CI Pigment Red 58, CI Pigment Red 58:1, CI Pigment Red 58:2, CI Pigment Red 58:3, CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 63:3, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 68, CI Pigment Red 81:1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 89, CI Pigment Red 95, CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red 1 19, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 136, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 147, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 164, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 181, CICI Pigment Red 182, CI Pigment Red 183, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 192, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 211, CI Pigment Red 213, CI Pigment Red 214, CI Pigment Red 216, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 223, CI Pigment Red 224, CI Pigment Red 225 CI Pigment Red 226, CI Pigment Red 237, CI Pigment Red 238, CI Pigment Red 239, CI Pigment Red 240, CI Pigment Red 242, CI Pigment Red 245, CI Pigment Red 247, CI Pigment Red 248, CI Pigment Red 251, CI Pigment Red 253, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 256, CI Pigment Red 257, CI Pigment Red 258, CI Pigment Red 260, CI Pigment Red 262, CI Pigment Red 263, CI Pigment Red 264, CI Pigment Red 266, CI Pigment Red 268, CI Pigment Red 269, CI Pigment Red 270, CI Pigment Red 271, CI Pigment Red 272, CI Pigment Red 279, etc.

[0138] Examples of the violet pigment include CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 3:1, CI Pigment Violet 3:3, CI Pigment Violet 5:1, CI Pigment Violet 13, CI Pigment Violet 19 (γ type, β type), CI Pigment Violet 23, CI Pigment Violet 25, CI Pigment Violet 27, CI Pigment Violet 29, CI Pigment Violet 31, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 37, CI Pigment Violet 38, CI Pigment Violet 42, and CI Pigment Violet 50.

[0139] Examples of yellow pigments include CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 24, CI Pigment Yellow 42, CI Pigment Yellow 55, CI Pigment Yellow 62, CI Pigment Yellow 65, CI Pigment Yellow 74, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 121, CI Pigment Yellow 122, CI Pigment Yellow 123, CI Pigment Yellow 124, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 130, CI Pigment Yellow 131, CI Pigment Yellow 132, CI Pigment Yellow 133, CI Pigment Yellow 134, CI Pigment Yellow 135 CI Pigment Yellow 120, CI Pigment Yellow 125, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 174, CI Pigment Yellow 180, CI Pigment Yellow 185 and CI Pigment Yellow 213, etc.

[0140] Examples of the orange pigment include CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 37, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 71, and CI Pigment Orange 74.

[0141] Examples of the brown pigment include CI Pigment Brown 23, CI Pigment Brown 25, and CI Pigment Brown 26.

[0142] Among them, preferred pigments include CI Pigment Black 7 for black pigments, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 15:6 for blue pigments, CI Pigment Green 7 for green pigments, and CI Pigment Red 57:1, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 146, CI Pigment Red 242, and CI Pigment Red 57:1. Pigment Red 185, CI Pigment Red 122, CI Pigment Red 178, CI Pigment Red 149, CI Pigment Red 144, CI Pigment Red 166, as for violet pigments, CI Pigment Violet 23 and CI Pigment Violet 37 can be mentioned, as for yellow pigments, CI Pigment Yellow 83, CI Pigment Yellow 14, CI Pigment Yellow 180, CI Pigment Yellow 139 can be mentioned, as for orange pigments, CI Pigment Orange 38, CI Pigment Orange 13, CI Pigment Orange 34, CI Pigment Orange 64, etc. can be mentioned, and it is preferred to use at least one or two or more selected from them.

[0143] Examples of inorganic pigments include carbon black, titanium oxide, red iron oxide, aluminum, mica, zinc oxide, barium sulfate, calcium carbonate, and silicon dioxide. In addition, shimmering pigments (Metashine; Nippon Sheet Glass Co., Ltd.) made by coating a glass sheet or block-shaped sheet with a metal or metal oxide can be used. From the perspectives of cost and coloring power, it is preferred to use carbon black for black ink, titanium oxide for white ink, aluminum for gold and silver inks, and mica for pearlescent inks.

[0144] The total content of the pigments is preferably 1% by mass or more and 60% by mass or less of the total amount of the organic solvent-based composition of the present invention from the viewpoint of ensuring the concentration and coloring power of the organic solvent-based composition of the present invention.

[0145] <<Other ingredients>>

[0146] The organic solvent-based composition of the present invention may further contain other components such as a binder resin and an auxiliary agent.

[0147] Examples of the binder resin include cellulose resins (e.g., nitrocellulose), urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth) acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, petroleum resins, and resins such as itaconic acid, maleic acid, fumaric acid, meat (Meth)acrylic resins obtained by copolymerizing polymerizable monomers such as cinnamic acid or its anhydrides having a carboxyl group, polymerizable monomers such as sulfonated styrene, polymerizable monomers having a sulfonic acid group, such as vinylbenzenesulfonamide, etc., resins as free radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, terpene-maleic acid (anhydride) resins, acid-modified polyolefin resins, etc. (excluding the above-mentioned "urethane resins"), and these may be used alone or in combination of multiple types.

[0148] As auxiliary agents, suitable examples include waxes such as paraffin wax, polyethylene wax, and carnauba wax for imparting friction resistance and slip properties; fatty acid amide compounds such as oleamide, stearamide, and erucamide; silicone and non-silicone defoamers for suppressing foaming during printing; and dispersants. Nonionic dispersants are preferred.

[0149] The acid value of the dispersant is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and even more preferably 20 mgKOH / g or less. Alternatively, it may be, for example, 1 mgKOH / g or more, and further preferably 3 mgKOH / g or more.

[0150] The content of the dispersant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the colorant, and is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, more preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and more preferably 60 parts by mass or less.

[0151] In addition to the above, water, a wetting agent, an adhesion promoter, a leveling agent, an antistatic agent, a viscosity modifier, a metal chelate, a scavenger, an antiblocking agent, an isocyanate curing agent, and a silane coupling agent may be used as needed. The viscosity of the organic solvent-based composition of the present invention, as measured at 25°C using a No. 3 Zahn cup manufactured by Lihe Co., Ltd., is preferably 6 seconds or greater, more preferably 10 seconds or greater, and even more preferably 13 seconds or greater. Furthermore, it is preferably 25 seconds or less, more preferably 20 seconds or less, and even more preferably 18 seconds or less.

[0152] The surface tension of the organic solvent-based composition of the present invention is preferably 25 mN / m or greater, more preferably 33 mN / m or greater. Furthermore, it is preferably 50 mN / m or less, more preferably 43 mN / m or less. By appropriately increasing the surface tension of the organic solvent-based composition of the present invention, dot bridging (contamination of the printed surface caused by connections between adjacent dots in the mid-tone dot portion) can be suppressed while maintaining the wettability of the organic solvent-based composition of the present invention to the substrate. By appropriately reducing the surface tension of the organic solvent-based composition of the present invention, the wettability of the organic solvent-based composition of the present invention to the substrate can be improved, thereby suppressing craters.

[0153] When the organic solvent composition of the present invention is used for gravure printing or flexographic printing, it can be produced using an Eiger mill, a sand mill, a gamma mill, an attritor, or the like, which are commonly used in the production of gravure or flexographic inks.

[0154] When preparing the organic solvent-based composition of the present invention, from the viewpoint of uniformity, at least a portion of the urethane resin, the colorant, and at least a portion of the organic solvent may be mixed in advance to prepare a preliminary composition (milling base ink).

[0155] It should be noted that as a composition that can be removed from the substrate in the same manner as in the present invention, a resist ink can be cited. The purpose of this resist ink is to remove the coating film from the substrate in advance while leaving a portion thereof and then process the substrate. Its use and purpose are fundamentally different from the film-forming composition of the present invention, which is intended to remove the entire film and recycle the substrate, and therefore does not conform to the known art of the present invention.

[0156] The film-forming composition of the present invention can also be used as a primer composition for forming a primer layer.

[0157] <Primer composition>

[0158] When the film-forming composition of the present invention is used to form a primer layer, the primer composition contains the above-mentioned <<urethane resin>>, and the primer composition is the film-forming composition of the present invention.

[0159] The primer composition may contain, in addition to the urethane resin, a commercially available binder resin, a solvent such as an organic solvent or an aqueous solvent, and additives without particular limitation.

[0160] Examples of the binder resin include cellulose resins (e.g., nitrocellulose), urethane resins (excluding the above-mentioned <<urethane resin>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins. Resins such as styrene-maleic acid (anhydride) resins, terpene-maleic acid (anhydride) resins, and acid-modified polyolefin resins, which are obtained by copolymerizing polymerizable monomers such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers such as sulfonic acid groups such as sulfonated styrene, and polymerizable monomers such as vinylbenzenesulfonamide, which are free radical copolymers, and acid-modified polyolefin resins, can be used alone or in combination.

[0161] The solvent may be an organic solvent, and for example, the same organic solvents as those described in the "Organic Solvent" column of the "Organic Solvent-Based Composition" can be used.

[0162] Examples of the additives include extender pigments, pigment dispersants, leveling agents, defoaming agents, waxes, plasticizers, anti-blocking agents, infrared absorbers, ultraviolet absorbers, fragrances, and flame retardants.

[0163] When the primer layer contains the above-mentioned <<urethane resin>>, the amount of the <<urethane resin>> added may be appropriately determined within a range that does not impair the properties of the primer layer, and is preferably in the range of 5 to 30% by mass relative to the total mass of the primer layer composition.

[0164] Alternatively, a primer containing a resin or low-molecular-weight compound having an acidic group may be preferably used. The resin or low-molecular-weight compound having an acidic group may be used without particular limitation as long as it can be easily mixed with the aforementioned <<urethane resin>> and organic solvent, which are the main components of the primer.

[0165] Examples of the resin having an acidic group include cellulose resins (e.g., nitrocellulose), urethane resins (excluding the above-mentioned <<urethane resin>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, petroleum resins, and the like, to which an acid value is imparted. , (meth)acrylic resins obtained by copolymerizing polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers having sulfonic acid groups such as sulfonated styrene, polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide, etc., resins as free radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, terpene-maleic acid (anhydride) resins, acid-modified polyolefin resins, etc. (excluding the above-mentioned binder resins), which can be used alone or in combination of multiple types.

[0166] Preferred examples of the low-molecular compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives. These can be used alone or in combination of two or more.

[0167] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid. Examples of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, and azelaic acid. Examples of tricarboxylic acids include aconitic acid and trimer acid. Examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination. In addition, citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid satisfy the so-called Swiss Ordinance, and it is preferred to use substances that satisfy various restrictions.

[0168] The film-forming composition of the present invention can also be used as a varnish composition for forming a varnish layer.

[0169] <Varnish composition>

[0170] When the film-forming composition of the present invention is used to form a clear coat layer, the clear coat composition contains the above-mentioned <<urethane resin>>, and the clear coat composition is the film-forming composition of the present invention.

[0171] The varnish composition may contain, in addition to the urethane resin, a commercially available binder resin, a solvent such as an organic solvent or an aqueous solvent, and additives without particular limitation.

[0172] Examples of the binder resin include cellulose resins (e.g., nitrocellulose), urethane resins (excluding the above-mentioned <<urethane resin>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins. Resins such as styrene-maleic acid (anhydride) resins, terpene-maleic acid (anhydride) resins, and acid-modified polyolefin resins, which are obtained by copolymerizing polymerizable monomers such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers such as sulfonic acid groups such as sulfonated styrene, and polymerizable monomers such as vinylbenzenesulfonamide, which are free radical copolymers, and acid-modified polyolefin resins, can be used alone or in combination.

[0173] The solvent may be an organic solvent, and for example, the same organic solvents as those described in the "Organic Solvent" column of the "Organic Solvent-Based Composition" can be used.

[0174] Examples of the additives include extender pigments, pigment dispersants, leveling agents, defoaming agents, waxes, plasticizers, anti-blocking agents, infrared absorbers, ultraviolet absorbers, fragrances, and flame retardants.

[0175] When the clear coat layer contains the urethane resin, the amount of the urethane resin added may be appropriately determined within a range that does not impair the properties of the clear coat layer, and is preferably in the range of 5 to 30% by mass based on the clear coat layer composition.

[0176] In addition, varnishes to which resins or low-molecular-weight compounds having acidic groups are added may also be preferably used. As resins or low-molecular-weight compounds having acidic groups, any resins or low-molecular-weight compounds may be used without particular limitation as long as they can be easily mixed with the above-mentioned urethane resins, organic solvents, etc., which are the main components of the varnish.

[0177] Examples of the resin having an acidic group include cellulose resins (e.g., nitrocellulose), urethane resins (excluding the above-mentioned <<urethane resin>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, petroleum resins, and the like, to which an acid value is imparted. , (meth)acrylic resins obtained by copolymerizing polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers having sulfonic acid groups such as sulfonated styrene, polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide, etc., resins as free radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, terpene-maleic acid (anhydride) resins, acid-modified polyolefin resins, etc. (excluding the above-mentioned binder resins), which can be used alone or in combination of multiple types.

[0178] Preferred examples of the low-molecular compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives. These can be used alone or in combination of two or more.

[0179] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid. Examples of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, and azelaic acid. Examples of tricarboxylic acids include aconitic acid and trimer acid. Examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination. In addition, citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid satisfy the so-called Swiss Ordinance, and it is preferred to use substances that satisfy various restrictions.

[0180] (Printing on substrate)

[0181] The film-forming composition of the present invention has excellent adhesion to various base materials and can be used for printing to paper, synthetic paper, cloth, thermoplastic resin film, plastic products, steel plates, etc. The film-forming composition of the present invention is useful as an intaglio printing using an intaglio printing plate based on an electronic engraving gravure or a flexographic printing ink using a flexographic printing plate based on a resin plate. On the other hand, although it can also be used for an inkjet method that ejects ink from an inkjet nozzle without using a plate, it is less preferred. That is, in the case of an inkjet ink, the ink droplets ejected from the nozzle directly adhere to the base material and form a printed matter, but for the film-forming composition of the present invention, after the printing ink is temporarily adhered and transferred to a printing plate or a printed pattern, only the ink is again adhered to the base material, and it is dried as needed to make a printed matter. The film-forming composition of the present invention can be suitably used for printing methods such as gravure, flexographic plates, die coaters, and roller coaters.

[0182] The thickness of the film formed using the film-forming composition of the present invention is, for example, preferably 30 μm or less, more preferably 20 μm or less, further preferably 10 μm or less, and most preferably 5 μm or less.

[0183] (Printed materials and laminated bodies)

[0184] By printing the film-forming composition of the present invention directly or via another layer on the surface of substrate A, a printed material having a film can be obtained. This printed material can also be referred to as a laminate. A laminate having substrate A and a film can also be obtained by laminating the laminate in a form in which substrate B is arranged on the film side. In the laminate having a film, substrate A, and substrate B, the film and substrate B can be laminated via an adhesive layer.

[0185] Embodiments of the printed article printed using the film-forming composition of the present invention, the laminated body formed using the printed article, and the laminated body having a film formed using the film-forming composition of the present invention are not limited, but the following embodiments are preferably mentioned.

[0186] As described above, a method for forming a film on the surface of the substrate A directly or via another layer is as follows.

[0187] <Print>

[0188] Substrate A - Printing layer (white) - Printing layer (color)

[0189] Substrate A - Primer layer - Printing layer (white) - Printing layer (color)

[0190] Substrate A - Printing layer (white) - Printing layer (color) - Varnish layer

[0191] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Clear varnish layer

[0192] Substrate A - Printing layer (color) - Printing layer (white)

[0193] Substrate A - Primer layer - Printing layer (color) - Printing layer (white)

[0194] Substrate A - Printing layer (color) - Printing layer (white) - Varnish layer

[0195] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Clear varnish layer

[0196] The following is a method for disposing the film between the substrate A and the substrate B.

[0197] <Inside printing, lamination>

[0198] Substrate A - Printing layer (white) - Printing layer (color) - Adhesive layer - Substrate B

[0199] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Adhesive layer - Substrate B

[0200] Substrate A - Printing layer (white) - Printing layer (color) - Varnish layer - Adhesive layer - Substrate B

[0201] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Clear coat layer - Adhesive layer - Substrate B

[0202] Substrate A - Printing layer (color) - Printing layer (white) - Adhesive layer - Substrate B

[0203] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Adhesive layer - Substrate B

[0204] Substrate A - Printing layer (color) - Printing layer (white) - Varnish layer - Adhesive layer - Substrate B

[0205] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Clear coat layer - Adhesive layer - Substrate B

[0206] Substrate A - Printing layer (white) - Printing layer (color) - Resin layer C - Substrate B

[0207] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Resin C layer - Substrate B

[0208] Substrate A - Printing layer (white) - Printing layer (color) - Varnish layer - Resin C layer - Substrate B

[0209] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Clear coat layer - Resin C layer - Substrate B

[0210] Substrate A - Printing layer (color) - Printing layer (white) - Resin layer C - Substrate B

[0211] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Resin C layer - Substrate B

[0212] Substrate A - Printing layer (color) - Printing layer (white) - Varnish layer - Resin C layer - Substrate B

[0213] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Clear coat layer - Resin C layer - Substrate B

[0214] Substrate A - Printing layer (white) - Printing layer (color) - Substrate B

[0215] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Substrate B

[0216] Substrate A - Printing layer (white) - Printing layer (color) - Varnish layer - Substrate B

[0217] Substrate A - Primer layer - Printing layer (white) - Printing layer (color) - Clear coat layer - Substrate B

[0218] Substrate A - Printing layer (color) - Printing layer (white) - Substrate B

[0219] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Substrate B

[0220] Substrate A - Printing layer (color) - Printing layer (white) - Varnish layer - Substrate B

[0221] Substrate A - Primer layer - Printing layer (color) - Printing layer (white) - Clear coat layer - Substrate B

[0222] ·Substrate A-Varnish layer

[0223] Substrate A-printing layer (color)

[0224] The printing layer (white), printing layer (color), primer layer and clear coat layer are shown above.

[0225] Hereinafter, the substrate A, the substrate B, the adhesive layer, and the resin C layer will be described.

[0226] <Base Material A>

[0227] As substrate A, preferably a plastic substrate, there can be mentioned films of thermoplastic resins such as polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polyester resins such as polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, poly(ethylene succinate), and aliphatic polyester resins such as poly(butylene succinate), polyolefin resins such as polypropylene and polyethylene, polyimide resins, polyarylate resins, or mixtures thereof, and their laminates. Among them, films and laminates comprising polyester, polyamide, polyethylene, and polypropylene can be suitably used. If the release property of the film-forming composition of the present invention is emphasized, polypropylene or polyethylene is more preferred. These substrate films may be unstretched films or stretched films, and their preparation methods are also not limited. The thickness of the base film is not particularly limited, and may generally be in the range of 1 to 500 μm.

[0228] The printing surface of the substrate A is preferably subjected to a corona discharge treatment, and may also be subjected to vapor deposition of silicon dioxide, aluminum oxide, or the like.

[0229] <Base material B>

[0230] Examples of the substrate B include the same substrates as those for the substrate A. The substrates may be the same as or different from the substrate A. However, a plastic substrate is preferred, and a thermoplastic resin substrate is more preferred.

[0231] When the laminate comprising the film, substrate A, and substrate B is extrusion laminated, the resin may be the same as the resin C described later. Alternatively, a metal foil or a metal foil layer of a vapor-deposited film layer may be laminated.

[0232] Resin C

[0233] The resin C is preferably a thermoplastic resin, more preferably a polyolefin, and particularly preferably polypropylene or polyethylene and modified resins thereof.

[0234] Adhesive layer

[0235] The adhesive used to form the adhesive layer is not particularly limited, and any commercially available reactive adhesive can be used. Of these, so-called two-component reactive adhesives of a polyisocyanate composition and a polyol composition, or one-component reactive adhesives of a polyisocyanate are preferred.

[0236] The polyisocyanate composition used in a general reactive adhesive is a composition containing a polyisocyanate compound as a main component. As long as it is a substance known as a polyisocyanate compound for a reactive adhesive, it can be used without particular limitation. Specific examples of polyisocyanate compounds include polyisocyanates having an aromatic structure in their molecular structure, such as toluene diisocyanate, diphenylmethane diisocyanate, polymerized diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate; compounds in which a part of the isocyanate group (NCO group) of these polyisocyanates is modified with carbodiimide; polyisocyanates having an alicyclic structure in their molecular structure, such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-(isocyanatomethyl)cyclohexane. Ester; linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; compounds obtained by modifying a portion of the NCO groups of these polyisocyanates with carbodiimide; isocyanurate forms of the above-mentioned various polyisocyanates; allophanate forms derived from the above-mentioned various polyisocyanates; biuret forms derived from the above-mentioned various polyisocyanates; adducts obtained by modifying the above-mentioned various polyisocyanates with trimethylolpropane; polyisocyanates which are reaction products of the above-mentioned various polyisocyanates with the polyol component described later, etc.

[0237] The polyol composition used in a general reactive adhesive is a composition containing a polyol compound as a main component. Any known polyol compound for use in reactive adhesives can be used without particular limitation. Specific examples of the polyol compound include ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol. diols; trifunctional or tetrafunctional aliphatic alcohols such as glycerol, trimethylolpropane, and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; polymer polyols selected from dimer, polyester polyols, polyether polyols, polyurethane polyols, polyetherester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, castor oil, or mixtures thereof.

[0238] Among them, it is preferred that any one of the constituent components of the reactive adhesive has an ester bond from the viewpoint of easy dissolution or hydrolysis in an alkaline solution, so that it can be easily separated into a single layer film in a short time in the film removal step described later.

[0239] The so-called reactive adhesive in which any one of its constituent components has an ester bond, specifically, includes a reactive adhesive containing either or both of the following polyol composition, wherein the polyol composition comprises a polyol compound such as a polyester polyol, polyether ester polyol, polyester (polyurethane) polyol, or acrylic polyol having an ester bond, and the following polyisocyanate composition comprises a polyisocyanate compound which is a reaction product of the above-mentioned polyol compound having an ester bond and the above-mentioned various polyisocyanates.

[0240] In reactive adhesives, additives such as pigments, silane coupling agents, titanate coupling agents, aluminum coupling agents, adhesion promoters such as epoxy resins, leveling agents, inorganic fine particles such as colloidal silica and alumina sol, organic fine particles such as polymethyl methacrylate, defoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity regulators, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic heat ray absorbers, fire retardants, antistatic agents, and dehydrating agents are sometimes used.

[0241] Reactive adhesives include dry laminating adhesives diluted with a highly soluble organic solvent for dilution, solvent-free laminating adhesives containing substantially no organic solvent for dilution, and aqueous adhesives using water as a diluent.

[0242] In the laminate, a barrier layer may be interposed between each of the substrate A, printed layer (white), printed layer (color), primer layer, adhesive layer, varnish layer, resin C layer, or substrate B. Examples of the barrier layer include an inorganic vapor-deposited layer and a barrier coating layer, which may be used alone or in combination.

[0243] The inorganic vapor-deposited layer is a gas barrier layer that prevents the permeation of oxygen and water vapor, and is a vapor-deposited layer comprising an inorganic substance or an inorganic oxide. Examples of the inorganic substance or inorganic oxide include aluminum, aluminum oxide, silicon dioxide, and the like, and one or more of these can be used. Two or more inorganic vapor-deposited layers may be provided. When two or more inorganic vapor-deposited layers are provided, each may have the same composition or different compositions.

[0244] The barrier coating protects the inorganic deposited layer and improves gas barrier properties against oxygen, water vapor, and the like. Such a gas barrier coating is formed, for example, from a resin composition such as a hydrolyzate of a metal alkoxide or a hydrolyzed polycondensate of a metal alkoxide, obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer using a sol-gel method in the presence of a sol-gel catalyst, water, an organic solvent, or the like.

[0245] (Method for removing the film from the substrate A)

[0246] In the present invention, the printed material or laminate is treated with an alkaline solution to remove the film from the substrate A, thereby producing a recycled substrate A.

[0247] In the present invention, a laminate obtained by laminating a printed material and a substrate B with an adhesive layer or the like disposed inside thereof can be treated with an alkaline solution to remove the substrate B together with the film, thereby producing a recycled substrate A.

[0248] The removal step includes immersing the printed material or laminate in an alkaline solution while heating and stirring at 20 to 90°C or while ultrasonically vibrating. Heating and stirring and ultrasonic vibration may also be performed simultaneously. The heating temperature is preferably 30°C or higher, preferably 40°C or higher, preferably 50°C or higher, and preferably 60°C or higher. More preferably, heating and stirring and ultrasonic vibration are performed simultaneously.

[0249] The alkaline solution used in the desorption step is not limited, but preferably has a pH of 9 or higher, and is preferably an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium bicarbonate solution, an aqueous potassium bicarbonate solution, an aqueous sodium dihydrogen carbonate solution, an aqueous potassium dihydrogen carbonate solution, or the like. The aqueous sodium hydroxide solution, the aqueous potassium hydroxide solution, the aqueous sodium bicarbonate solution, the aqueous potassium bicarbonate solution, the aqueous sodium dihydrogen carbonate solution, the aqueous potassium dihydrogen carbonate solution, or the like is preferably an aqueous solution having a concentration of 0.5% to 10% by mass, and more preferably an aqueous solution having a concentration of 1% to 5% by mass.

[0250] In addition, the alkaline solution may contain a water-soluble organic solvent.

[0251] Examples of the water-soluble organic solvent include methanol, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dibutyl ether, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dibutyl ether, and triethylene glycol. Monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonyl acetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyrate and ethyl lactate, etc., can be used alone or in combination of two or more.

[0252] The content of the water-soluble organic solvent in the alkaline solution is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass.

[0253] In addition, the alkaline solution may contain a water-insoluble organic solvent.

[0254] Specific examples of water-insoluble organic solvents include alcohol solvents such as n-butanol, 2-butanol, isobutanol, and octanol; aliphatic hydrocarbon solvents such as hexane, heptane, and n-alkanes; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and alkylbenzenes; halogenated hydrocarbon solvents such as dichloromethane, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, and carbon tetrachloride; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; and ether solvents such as diethyl ether and dibutyl ether. These solvents can be used alone or in combination of two or more.

[0255] The alkaline solution may contain a surfactant. Examples of the surfactant include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among them, anionic surfactants, nonionic surfactants, and amphoteric surfactants are preferred.

[0256] Examples of the anionic surfactant include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfuric acid ester salts of higher fatty acid esters, sulfonic acid salts of higher fatty acid esters, sulfuric acid ester salts and sulfonic acid salts of higher alcohol ethers, higher alkylsulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates. Specific examples thereof include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, and dibutylphenylphenol disulfonate.

[0257] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkanolamides, alkyl alkanolamides, acetylenic glycols, oxyethylene adducts of acetylenic glycols, and polyethylene glycol-polypropylene glycol block copolymers. Among these, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkanolamides, acetylenic glycols, oxyethylene adducts of acetylenic glycols, and polyethylene glycol-polypropylene glycol block copolymers are preferred.

[0258] As other surfactants, silicone surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as 4,5-dicarboxy-γ-pentadecalactone (Spiculisporic acid), rhamnolipids, and lysolecithin can also be used.

[0259] These surfactants can be used alone or in combination of two or more. When a surfactant is added, the amount thereof is preferably in the range of 0.001 to 2% by mass relative to the total amount of the alkaline solution, more preferably in the range of 0.001 to 1.5% by mass, and even more preferably in the range of 0.01 to 1% by mass.

[0260] The printed material or laminated material to be treated is immersed in, for example, a treatment tank while the alkaline solution is heated or ultrasonically vibrated at 20-90°C. The heating method is not particularly limited, and known heating methods such as heat rays, infrared rays, and microwaves can be used. Ultrasonic vibration can be applied, for example, by installing an ultrasonic vibrator in the treatment tank and applying ultrasonic vibration to the warm water or alkaline solution.

[0261] The alkaline solution is preferably stirred during immersion. Examples of stirring methods include mechanical stirring of the printed material or the dispersion of the laminate contained in the treatment tank using a stirring blade, water flow stirring using a water pump, and bubbling using an inert gas such as nitrogen. These methods may be used in combination for efficient stripping.

[0262] The time for immersing the printed material or laminate in the alkaline solution varies depending on the composition of the printed material, but is generally between 2 minutes and 48 hours. It should be noted that in the present invention, the printed film need not be completely detached from the substrate. However, it is preferred that 60% by mass or more of the 100% by mass film be detached, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0263] During the separation process, the immersion in the alkaline solution may be performed once or in multiple times. Specifically, the process of recovering the separated membrane substrate may be performed after a single immersion, or after multiple immersions. Furthermore, when multiple immersions are performed during the separation process, the concentration of the alkaline solution may be varied. Furthermore, it is preferred that known steps such as washing and drying be appropriately incorporated into the separation process.

[0264] The film-forming composition of the present invention suppresses the content of solvents that are harmful to health and the environment to a certain amount or less, and while maintaining the properties for general-purpose plastic substrates as those of conventional film-forming materials, by further containing a specific urethane resin, it can form a film layer that can be easily detached by treatment with an alkaline solution, can be easily removed from the plastic substrate, and has excellent adhesion to the substrate.

[0265] Example

[0266] Hereinafter, the content and effects of the present invention will be described in further detail using examples, but the present invention is not limited thereto. It should be noted that "parts" and "%" shown below are based on mass.

[0267] <Molecular weight measurement method>

[0268] In addition, the measurement of the weight average molecular weight and the number average molecular weight (polystyrene conversion) by GPC (gel permeation chromatography) of the present invention was performed using an HLC8220 system manufactured by TOSOH Corporation under the following conditions.

[0269] Separation columns: Four TSKgelGMHHR-N columns manufactured by TOSOH Corporation were used.

[0270] Column temperature: 40℃.

[0271] Mobile phase: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.

[0272] Flow rate: 1.0 ml / min.

[0273] Sample concentration: 1.0%.

[0274] Sample injection volume: 100 μl.

[0275] Detector: Differential refractometer.

[0276] <Viscosity measurement method>

[0277] The viscosity was measured at 25° C. using a B-type viscometer manufactured by TOKIMEC Corporation.

[0278] <Hydroxy value measurement method>

[0279] The hydroxyl value was measured in accordance with JIS K 0070-1992.

[0280] <Acid value measurement method>

[0281] The acid value was measured in accordance with JIS K 0070-1992.

[0282] (Synthesis Example 1) Synthesis of Polyurethane (Urethane Resin) 1

[0283] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 80.0 parts of a polyester polyol (hydroxyl value: 56 mgKOH / g) prepared from 2-methyl-1,3-propanediol and adipic acid, 20.0 parts of polyethylene glycol (hydroxyl value: 277 mgKOH / g), and 25.4 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI) were added. The mixture was reacted at 90°C for 20 hours under a nitrogen stream to produce a urethane prepolymer. 83.6 parts of ethyl acetate was then added to the mixture to prepare a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0284] Then, the above-mentioned urethane prepolymer solution was added to a mixture containing 110.1 parts of ethyl acetate, 104.9 parts of isopropyl alcohol, 2.7 parts of isophoronediamine (hereinafter abbreviated as IPDA) and 0.3 parts of diethanolamine (hereinafter abbreviated as DEA), and the mixture was stirred and reacted at 45°C for 5 hours to obtain a polyurethane resin solution 1 containing polyurethane 1.

[0285] The characteristic values ​​of the obtained polyurethane resin solution 1 are shown below.

[0286] Resin solid content hydroxyl value: 20.2mgKOH / g

[0287] Resin solid content acid value: 0.0mgKOH / g

[0288] Number average molecular weight of resin solid content: 48300

[0289] Weight average molecular weight of resin solid content: 82900

[0290] Amine value of resin solid content: 0.40mgKOH / g

[0291] Resin solid content concentration: 30.3% by mass

[0292] (Synthesis Example 2) Synthesis of Polyurethane 2

[0293] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 22 mgKOH / g) prepared from 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and adipic acid, and 9.2 parts of IPDI were added. The mixture was reacted at 100°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 72.8 parts of ethyl acetate was then added to the mixture to prepare a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0294] Then, the above-mentioned urethane prepolymer solution was added to a mixture containing 96.6 parts of ethyl acetate, 91.2 parts of isopropyl alcohol, 2.2 parts of 2-(2-aminoethylamino)ethanol (hereinafter abbreviated as AEEA) and 0.3 parts of DEA, and the mixture was stirred and reacted at 45°C for 5 hours to obtain a polyurethane resin solution 2 containing polyurethane 2.

[0295] The characteristic values ​​of the obtained polyurethane resin solution 2 are shown below.

[0296] Resin solid content hydroxyl value: 20.8mgKOH / g

[0297] Resin solid content acid value: 0.0mgKOH / g

[0298] Number average molecular weight of resin solid content: 58600

[0299] Weight average molecular weight of resin solid content: 106700

[0300] Amine value of resin solid content: 0.30mgKOH / g

[0301] Resin solid content concentration: 29.5% by mass

[0302] (Synthesis Example 3) Synthesis of Polyurethane 3

[0303] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 29 mgKOH / g) prepared from neopentyl glycol, propylene glycol, and adipic acid, 5.4 parts of polyethylene glycol (hydroxyl value: 112 mgKOH / g), and 16.8 parts of IPDI were added, and the mixture was reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 210.5 parts of ethyl acetate was then added to the mixture to produce a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0304] Next, 74.5 parts of isopropyl alcohol was added to the urethane prepolymer solution to form a uniform solution. A mixed solution of 6.5 parts of IPDA and 15.2 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.2 parts of monoethanolamine (hereinafter abbreviated as MEA) and 0.5 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours to obtain a polyurethane resin solution 3 containing polyurethane 3.

[0305] The characteristic values ​​of the obtained polyurethane resin solution 3 are shown below.

[0306] Resin solid content hydroxyl value: 1.5mgKOH / g

[0307] Resin solid content acid value: 0.0mgKOH / g

[0308] Number average molecular weight of resin solid content: 15300

[0309] Weight average molecular weight of resin solid content: 55600

[0310] Resin solid content amine value: 0.00mgKOH / g

[0311] Resin solid content concentration: 30.3% by mass

[0312] (Synthesis Example 4) Synthesis of Polyurethane 4

[0313] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 29 mgKOH / g) prepared from neopentyl glycol, propylene glycol, and adipic acid, 5.4 parts of polyethylene glycol (hydroxyl value: 112 mgKOH / g), and 16.8 parts of IPDI were added, and the mixture was reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 210.5 parts of ethyl acetate was then added to the mixture to produce a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0314] Next, 74.6 parts of isopropyl alcohol was added to the urethane prepolymer solution to form a uniform solution. A mixed solution of 6.1 parts of IPDA, 0.3 parts of AEEA, and 14.9 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours to obtain a polyurethane resin solution 4 containing polyurethane 4.

[0315] The properties of the obtained polyurethane resin solution 4 are shown below.

[0316] Resin solid content hydroxyl value: 2.9mgKOH / g

[0317] Resin solid content acid value: 0.0mgKOH / g

[0318] Number average molecular weight of resin solid content: 15300

[0319] Weight average molecular weight of resin solid content: 55600

[0320] Resin solid content amine value: 0.00mgKOH / g

[0321] Resin solid content concentration: 30.3% by mass

[0322] (Synthesis Example 5) Synthesis of Polyurethane 5

[0323] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 29 mgKOH / g) prepared from neopentyl glycol, propylene glycol, and adipic acid, 5.4 parts of polyethylene glycol (hydroxyl value: 112 mgKOH / g), and 16.8 parts of IPDI were added, and the mixture was reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 210.5 parts of ethyl acetate was then added to the mixture to produce a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0324] Next, 75.3 parts of isopropyl alcohol was added to the urethane prepolymer solution to form a uniform solution. A mixed solution of 5.3 parts of IPDA, 0.8 parts of AEEA, and 14.2 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours to obtain a polyurethane resin solution 5 containing polyurethane 5.

[0325] The properties of the obtained polyurethane resin solution 5 are shown below.

[0326] Resin solid content hydroxyl value: 5.0mgKOH / g

[0327] Resin solid content acid value: 0.0mgKOH / g

[0328] Number average molecular weight of resin solid content: 15300

[0329] Weight average molecular weight of resin solid content: 55600

[0330] Resin solid content amine value: 0.00mgKOH / g

[0331] Resin solid content concentration: 30.3% by mass

[0332] (Synthesis Example 6) Synthesis of Polyurethane 6

[0333] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 29 mgKOH / g) prepared from neopentyl glycol, propylene glycol, and adipic acid, 5.4 parts of polyethylene glycol (hydroxyl value: 112 mgKOH / g), and 16.8 parts of IPDI were added, and the mixture was reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 210.5 parts of ethyl acetate was then added to the mixture to produce a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0334] Next, 80.2 parts of isopropyl alcohol was added to the urethane prepolymer solution to form a uniform solution. A mixed solution of 4.0 parts of AEEA and 9.3 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours to obtain a polyurethane resin solution 6 containing polyurethane 6.

[0335] The properties of the obtained polyurethane resin solution 6 are shown below.

[0336] Resin solid content hydroxyl value: 18.8mgKOH / g

[0337] Resin solid content acid value: 0.0mgKOH / g

[0338] Number average molecular weight of resin solid content: 15300

[0339] Weight average molecular weight of resin solid content: 55600

[0340] Resin solid content amine value: 0.00mgKOH / g

[0341] Resin solid content concentration: 30.3% by mass

[0342] (Synthesis Example 7) Synthesis of Polyurethane 7

[0343] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 29 mgKOH / g) prepared from neopentyl glycol, propylene glycol, and adipic acid, 5.4 parts of polyethylene glycol (hydroxyl value: 112 mgKOH / g), and 22.7 parts of IPDI were added, and the mixture was reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 221.0 parts of ethyl acetate was then added to the mixture to produce a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0344] Next, 77.7 parts of isopropyl alcohol was added to the urethane prepolymer solution to form a uniform solution. A mixed solution of 7.0 parts of AEEA and 16.3 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours to obtain polyurethane resin solution 7 containing polyurethane 7.

[0345] The properties of the obtained polyurethane resin solution 7 are shown below.

[0346] Resin solid content hydroxyl value: 29.6mgKOH / g

[0347] Resin solid content acid value: 0.0mgKOH / g

[0348] Number average molecular weight of resin solid content: 60,000

[0349] Weight average molecular weight of resin solid content: 120,000

[0350] Resin solid content amine value: 0.00mgKOH / g

[0351] Resin solid content concentration: 30.3% by mass

[0352] (Synthesis Example 8) Synthesis of Polyurethane 8

[0353] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 29 mgKOH / g) prepared from neopentyl glycol, propylene glycol, and adipic acid, 5.4 parts of polyethylene glycol (hydroxyl value: 112 mgKOH / g), 2.7 parts of dimethylolbutyric acid (hereinafter abbreviated as DMBA), and 21.4 parts of IPDI were added, and the mixture was reacted at 90° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer. 217.3 parts of ethyl acetate was then added to the mixture to prepare a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0354] Next, 95.4 parts of isopropyl alcohol was added to the urethane prepolymer solution to prepare a uniform solution. A mixed solution of 4.2 parts of AEEA and 9.8 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours, thereby obtaining a polyurethane resin solution 8 containing polyurethane 8.

[0355] The characteristic values ​​of the obtained polyurethane resin solution 8 are shown below.

[0356] Resin solid content hydroxyl value: 15.7mgKOH / g

[0357] Resin solid content acid value: 9.4mgKOH / g

[0358] Number average molecular weight of resin solid content: 15300

[0359] Weight average molecular weight of resin solid content: 55600

[0360] Resin solid content amine value: 0.00mgKOH / g

[0361] Resin solid content concentration: 30.3% by mass

[0362] (Synthesis Example 9) Synthesis of Polyurethane 9

[0363] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 55 mgKOH / g) prepared from 3-methyl-1,5-pentanediol and adipic acid, 6.7 parts of DMBA, and 38.1 parts of IPDI were added, and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 243.9 parts of ethyl acetate was then added to the flask to prepare a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0364] Next, 109.0 parts of isopropyl alcohol was added to the urethane prepolymer solution to prepare a uniform solution. A mixed solution of 6.2 parts of AEEA and 14.5 parts of isopropyl alcohol was then added, and the mixture was stirred and reacted at 40°C for 5 hours. Subsequently, a mixed solution of 0.2 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 2 hours, thereby obtaining a polyurethane resin solution 9 containing polyurethane 9.

[0365] The characteristic values ​​of the obtained polyurethane resin solution 9 are shown below.

[0366] Resin solid content hydroxyl value: 17.9mgKOH / g

[0367] Resin solid content acid value: 18.2mgKOH / g

[0368] Number average molecular weight of resin solid content: 10100

[0369] Weight average molecular weight of resin solid content: 30300

[0370] Resin solid content amine value: 0.00mgKOH / g

[0371] Resin solid content concentration: 30.3% by mass

[0372] (Synthesis Example 10) Synthesis of Polyurethane 10

[0373] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 80.0 parts of a polyester polyol (hydroxyl value: 56 mgKOH / g) prepared from 2-methyl-1,3-propanediol and adipic acid, 20.0 parts of polyethylene glycol (hydroxyl value: 277 mgKOH / g), and 25.4 parts of IPDI were added. The mixture was reacted at 90°C for 20 hours under a nitrogen stream to produce a urethane prepolymer. 83.6 parts of ethyl acetate was then added to the mixture to prepare a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0374] Next, the urethane prepolymer solution was added to a mixture of 113.3 parts of ethyl acetate, 106.0 parts of isopropyl alcohol, and 4.9 parts of IPDA, and the mixture was stirred and reacted at 45° C. for 5 hours to obtain a polyurethane resin solution 10 containing polyurethane 10 .

[0375] The characteristic values ​​of the obtained polyurethane resin solution 10 are shown below.

[0376] Resin solid content hydroxyl value: 0.0mgKOH / g

[0377] Resin solid content acid value: 0.0mgKOH / g

[0378] Number average molecular weight of resin solid content: 48600

[0379] Weight average molecular weight of resin solid content: 88,000

[0380] Amine value of resin solid content: 2.10mgKOH / g

[0381] Resin solid content concentration: 30.2% by mass

[0382] (Synthesis Example 11) Synthesis of Polyurethane 11

[0383] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 100.0 parts of a polyester polyol (hydroxyl value: 22 mgKOH / g) prepared from 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and adipic acid, and 9.2 parts of IPDI were added. The mixture was reacted at 100°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 72.8 parts of ethyl acetate was then added to the mixture to prepare a uniform solution of the urethane prepolymer (urethane prepolymer solution).

[0384] Next, the urethane prepolymer solution was added to a mixture of 99.1 parts of ethyl acetate, 92.6 parts of isopropyl alcohol, and 4.2 parts of IPDA, and the mixture was stirred and reacted at 45° C. for 5 hours to obtain a polyurethane resin solution 11 containing polyurethane 11.

[0385] The characteristic values ​​of the obtained polyurethane resin solution 11 are shown below.

[0386] ■Resin solid content hydroxyl value: 0.0mgKOH / g

[0387] ■Acid value of resin solid content: 0.0mgKOH / g

[0388] ■Number average molecular weight of resin solid content: 52700

[0389] ■Weight average molecular weight of resin solid content: 95400

[0390] ■Amine value of resin solid content: 2.40mgKOH / g

[0391] Resin solid content concentration: 29.7% by mass

[0392] The properties of the polyurethanes obtained in Synthesis Examples 1 to 11 are summarized in Tables 1 and 2.

[0393] [Table 1]

[0394]

[0395] [Table 2]

[0396]

[0397] (Example 1)

[0398] 40 parts of n-propyl acetate (n-propyl acetate), 10 parts of ethyl acetate, 11 parts of blue pigment, 3 parts of vinyl chloride-vinyl acetate copolymer resin, 6 parts of isopropyl alcohol, 1 part of dispersant, and 29 parts of polyurethane resin solution 1 prepared in Synthesis Example 1 were mixed to obtain a mixture.

[0399] To 100 parts of the obtained mixture, a 42% IPA / EtAc mixed solvent (isopropyl alcohol / ethyl acetate = 50 / 50 (part / part)) was added so that the reaction time measured with a No. 3 Zahn cup (manufactured by Riko Co., Ltd.) was about 15 seconds (25°C) to prepare a film-forming composition.

[0400] The prepared film-forming composition was used for the following evaluation. The results are shown in Table 3.

[0401] <Evaluation Item 1: Viscosity Stability>

[0402] The obtained film-forming composition was placed in a sealed container and allowed to stand for 24 hours at 25° C. The viscosity of the film-forming composition after standing for 24 hours was measured using a No. 3 Zahn cup and evaluated according to the following evaluation criteria.

[0403] [Evaluation Criteria]

[0404] 3: No significant viscosity increase was observed after standing for 24 hours.

[0405] 2: After standing for 24 hours, a significant increase in viscosity was observed, but the viscosity returned to its original value by stirring.

[0406] 1: A significant viscosity increase was observed after standing for 24 hours, and the viscosity increase was observed even after further stirring.

[0407] <Evaluation Item 2: Adhesion to Substrate>

[0408] The prepared film-forming composition was printed on a substrate A in a solid pattern of 240 mm in length and 80 mm in width using a bar coater #4, and then dried in a dryer to form a printed layer 1. A printed article having the following structure 1 was obtained.

[0409] <<Composition of printed materials>>

[0410] Configuration 1: Substrate A-Printing layer 1

[0411] Substrate A: Corona-treated polyethylene terephthalate film (Ester E5100 manufactured by Toyobo Co., Ltd., thickness 12 μm) (PET)

[0412] The printed material was immediately or after 24 hours of standing, and a 5 cm layer of transparent tape (12 mm wide, manufactured by Nichiban) was affixed to the printed surface. One end of the transparent tape was quickly peeled off at right angles to the printed surface. The remaining percentage of the printed film at this time was visually evaluated based on the area ratio.

[0413] [Evaluation Criteria]

[0414] 5: The printed film is not peeled off at all.

[0415] 4: More than 80% of the printed film remains on the film.

[0416] 3: 50% or more and less than 80% of the printed film remains on the film.

[0417] 2: Less than 50% of the printed film remains on the film.

[0418] 1: When applying the transparent tape, the printed film peels off from the film to the transparent tape.

[0419] <Evaluation Item 3: Peelability>

[0420] The prepared film-forming composition was printed on a substrate A in a solid pattern of 240 mm in length and 80 mm in width using a bar coater #4, and then dried in a dryer to form a printed layer 1, thereby obtaining a printed article having the following structure 1.

[0421] <<Composition of printed materials>>

[0422] Configuration 1: Substrate A-Printing layer 1

[0423] Substrate A: Corona-treated polyethylene terephthalate film (Ester E5100 manufactured by Toyobo Co., Ltd., thickness 12 μm) (PET)

[0424] <<Alkaline solution>>

[0425] A peeling test was performed under the following conditions, and the ease of peeling under each condition was compared.

[0426] ·Sodium hydroxide 1% by mass, surfactant 0.3%, 85°C

[0427] 1% sodium hydroxide by mass, no surfactant, 85°C

[0428] Here, the surfactant used is a nonionic surfactant.

[0429] <<Peel test conditions>>

[0430] In the peeling test, the treatment time under each condition was set to 15 minutes for evaluation. It should be noted that if peeling occurs within 5 minutes of treatment, it shows a very high performance.

[0431] Cut the printed material into 20 mm x 20 mm pieces, immerse the resulting test piece in the solution, and stir with a stirrer. After stirring, check for peeling. Then, rub the printed material with your fingers to check if the coating peels off due to friction.

[0432] The releasability of the ink coating film under the above-mentioned conditions was evaluated according to the following evaluation criteria.

[0433] [Evaluation Criteria]

[0434] 5: Check for detachment of the ink film while stirring for 5 minutes or less. It detaches completely upon rubbing.

[0435] 4: Check for detachment of the ink coating after stirring for 15 minutes. It detaches completely upon rubbing.

[0436] 3: No detachment of the ink coating was observed after 15 minutes of stirring. The ink coating completely detached upon rubbing.

[0437] 2: No detachment of the ink coating was observed after 15 minutes of stirring. Partial detachment occurred upon rubbing.

[0438] 1: No detachment of the ink coating was observed after 15 minutes of stirring. No detachment was observed even after rubbing.

[0439] (Examples 2 to 11 and Comparative Examples 1 to 6)

[0440] A film-forming composition was prepared in the same manner as in Example 1, except that the formulation of the film-forming composition was changed to the formulation described in Table 3 or Table 4 below.

[0441] The prepared film-forming composition was evaluated in the same manner as in Example 1. The results are shown in Tables 3 to 5.

[0442] The formulations of the film-forming compositions and the evaluation results are shown in Tables 3 to 5 below.

[0443] [Table 3]

[0444]

[0445] [Table 4]

[0446]

[0447] [Table 5]

[0448]

[0449] The above results show that the film-forming composition of the present invention can form a film that can be easily removed by treatment in an alkaline solution, the film layer can be easily removed from the plastic substrate, and a film having excellent adhesion to the substrate can be formed.

Claims

1. A film-forming composition, which is a removable film-forming composition for forming a film on the surface of a substrate A directly or through another layer that is removable by treatment in an alkaline solution. The film-forming composition contains a urethane resin having a hydroxyl value and no acid value.

2. The film-forming composition according to claim 1, wherein The hydroxyl value is 1.0 mgKOH / g to 30.0 mgKOH / g.

3. The film-forming composition according to claim 1, wherein The urethane resin contains at least one of a polyester polyol and a polyether polyol as a constituent component. The film-forming composition according to claim 1 , further comprising a colorant. The film-forming composition according to claim 4 , which is used as a printing ink. The film-forming composition according to claim 5 , wherein The printing ink is an organic solvent ink, a water-based ink or a UV ink. The film-forming composition according to claim 1 , which is used as a primer or a clear coat.

8. The film-forming composition according to claim 1, wherein The urethane resin is obtained by reacting a polyol, a polyisocyanate, and a chain extender.

9. The film-forming composition according to claim 1, wherein The hydroxyl value is 1.0 mgKOH / g to 25.0 mgKOH / g.

10. The film-forming composition according to claim 1, wherein The hydroxyl value is 10.0 mgKOH / g to 25.0 mgKOH / g.

11. The film-forming composition according to claim 1, wherein The amine value of the urethane resin is less than 2.10 mgKOH / g.

12. The film-forming composition according to claim 1, wherein The urethane resin has a weight average molecular weight of 45,000 or more.

13. The film-forming composition according to claim 1, wherein The film-forming composition does not contain any urethane resin other than the urethane resin. The film-forming composition according to claim 1 , which is used for forming a film that is removable by treatment in an alkaline solution. 15 . A printed article comprising a film comprising the film-forming composition according to claim 1 on a surface of a substrate A, directly or via another layer.

16. The printed matter according to claim 15, wherein The film is at least one selected from a printing layer, a primer layer, and a varnish layer. 17 . A laminated body obtained by placing a substrate B on the surface of the printed material according to claim 16 opposite to the surface on which the substrate A is arranged, and laminating the printed material and the substrate B.

18. A method for producing a recycled substrate A, wherein the recycled substrate A is obtained by treating the printed matter according to claim 16 with an alkaline solution to remove the film from the substrate A.

19. A method for producing a recycled base material A, wherein the recycled base material A is obtained by treating the laminate according to claim 17 with an alkaline solution to remove the base material B together with the film.

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