JP7327702B2 - Detachable film-forming composition - Google Patents

Description

The present invention relates to compositions used to form removable coatings from substrates.

In recent years, the problem of marine plastics has arisen due to the fact that plastics that have been discarded or dumped in the ocean are decomposed in seawater and become finer (microplastics). There are concerns that these microplastics enter the bodies of marine organisms, become concentrated, and affect the health of seabirds and humans through the food chain. One of the ways to improve this marine plastic problem is recycling. Improving the recycling rate of resources such as flexible packaging and plastic bottles will help prevent plastic from entering the ocean. However, in the current recycling, the film printed on the plastic base material does not come off during the recycling process, and when mixed with the plastic, it causes deterioration of hue and deterioration of physical properties, lowering the value of the recycled plastic. exists. If this problem can be solved by making it possible to detach the film from the plastic base material in the recycling process, the value of recycled plastic will increase, leading to the entry of new recycling companies and the development of separate collection by local governments. It is believed that this will improve the recycling rate and improve the marine plastic problem. Therefore, the development of a film-forming material from which the film can be removed in the recycling process is required.
Organic solvent-based printing inks, which are widely used for forming films on plastic substrates, are being replaced by toluene-free and methyl ethyl ketone (MEK)-free ones in consideration of the health of workers and the environment. Therefore, it is necessary to proceed with the development of materials that solve the above problems, taking this fact into consideration.

In the prior art, a method is disclosed in which a film containing a styrene-acrylic acid resin, a phenolic resin, or a styrene-maleic acid resin as a vehicle printed on a heat-shrinkable PET film is removed with alkaline water (Patent Document 1). ). Similarly, a coat layer containing a styrene-maleic acid resin, a rosin-maleic acid resin, or an acrylic acid copolymer resin is placed between the printed layers on the heat-shrinkable PET film, and the coat layer is washed with alkaline water. Desorption methods have been disclosed (Patent Documents 2 and 3). However, these techniques only ensure properties for specific substrates, and are not sufficient from the viewpoint of providing an easy desorption method. In order to provide a method for recycling plastic substrates that can easily remove the film from general-purpose plastic substrates containing polyolefin and easily remove the printed layer from the plastic substrates, there is a need for investigation. There was room.
On the other hand, an organic solvent-based printing ink for releasing alkaline water using a urethane resin having an acid value as a binder resin has also been disclosed (Patent Document 4, Patent Document 5, and Patent Document 6).

Japanese Patent No. 3822738 Japanese Patent No. 4653913 Japanese Patent No. 4451071 Japanese Patent No. 6638802 Japanese Patent No. 6631964 Japanese Patent Application Laid-Open No. 2020-169280

The problem to be solved by the present invention is to simultaneously solve the above-mentioned marine plastic problem and the health and environmental problems of workers. To provide a film-forming material (film-forming composition) capable of easily removing a film layer from a material and forming a film having excellent adhesion to a substrate.

As a result of extensive research to solve the above problems, the inventors have found that the film-forming composition contains a urethane resin having a hydroxyl value and a specific range of weight-average molecular weight and number-average molecular weight. The present inventors have found that the above problems can be solved by using

That is, the present invention includes the following aspects.
[1] A detachable film-forming composition for forming a detachable film on the surface of a substrate A directly or via another layer by treatment with an alkaline solution,
A film-forming composition containing a urethane resin having a hydroxyl value, a weight average molecular weight of 45,000 or more and a number average molecular weight of 10,000 or more.
[2] The film-forming composition according to [1], wherein the urethane resin has an acid value of less than 15.0 mgKOH/g.
[3] The film-forming composition according to [1] or [2], wherein the hydroxyl value is from 1.0 mgKOH/g to 30.0 mgKOH/g.
[4] The film-forming composition according to any one of [1] to [3], wherein the urethane resin contains at least one of polyester polyol and polyether polyol as a constituent component.
[5] The film-forming composition according to any one of [1] to [4], which contains a coloring agent.
[6] The film-forming composition according to [5], which is used as a printing ink.
[7] The film-forming composition of [6], wherein the printing ink is an organic solvent-based ink.
[8] The film-forming composition according to any one of [1] to [5], which is used as a primer or varnish.
[9] A printed matter having a film made of the film-forming composition according to any one of [1] to [8] directly or via another layer on the surface of the substrate A.
[10] The printed matter according to [9], wherein the film is at least one selected from a printed layer, a primer layer, and a varnish layer.
[11] With respect to the printed matter according to [9] or [10], a substrate B is arranged on the surface of the printed layer opposite to the surface on which the substrate A is arranged, and the printed matter and A laminate obtained by laminating the base material B.
[12] A method for producing a recycled base material A obtained by treating the printed matter according to [9] or [10] with an alkaline solution to detach the film from the base material A.
[13] A method for producing a recycled base material A obtained by treating the laminate according to [11] with an alkaline solution to desorb the base material B together with the film.

According to the present invention, a film can be easily removed from a general-purpose plastic substrate by a simple method, and the film layer can be easily removed from the plastic substrate, and a film having excellent adhesion to the substrate can be formed. A film-forming composition can be provided.

The present invention will be described in detail below. It should be noted that the description of the constituent elements described below is an example for describing the present invention, and the present invention is not limited to these contents.

(Film-forming composition)
The film-forming composition of the present invention is used to form a film on the surface of the substrate A directly or via another layer. In addition, in the present invention, the other layer may be a single layer or a plurality of layers.
A film formed from the film-forming composition of the present invention can be removed by treatment with an alkaline solution.
The film-forming composition contains a urethane resin. The urethane resin has a hydroxyl value, a weight average molecular weight of 45,000 or more, and a number average molecular weight of 10,000 or more.
Since the urethane resin has a hydroxyl value, the film can be released by a simple method, and the film layer can be easily removed from the plastic substrate. Hereinafter, this effect may be referred to as peelability.
When the urethane resin has a weight-average molecular weight of 45,000 or more and a number-average molecular weight of 10,000 or more, it is possible to form a film having excellent adhesion to the substrate.

In this specification, having a hydroxyl value means that when measuring the hydroxyl value of a urethane resin by the neutralization titration method of JIS K 0070 (1992), one drop of titration does not reach the end point.
In the present specification, the phrase "having no acid value" means that when the acid value of a urethane resin is measured by the neutralization titration method of JIS K 0070 (1992), titration of one drop reaches the end point.

The film formed from the film-forming composition of the present invention is used to remove from the substrate A a printed layer formed on the surface of the substrate A directly or via another layer.
Here, the printed layer means a layer formed by printing with printing ink.
Methods for removing the printed layer from the base material A include, for example, a method in which the printed layer itself has a detachment function and the printed layer is detached from the base material A (hereinafter also referred to as pattern A method), Another layer is provided between the printed layer and the substrate A, the separate layer has a detachment function, and by detaching the separate layer, the printed layer is also removed from the substrate A. A method of desorption (hereinafter also referred to as pattern B method) and the like can be mentioned.

The film formed from the film-forming composition of the present invention is intended for both the printed layer in the pattern A method and another layer in the pattern B method. More specifically, the film according to the present invention includes both a printed layer and a primer layer and a varnish layer, which will be described later.
That is, the film-forming composition of the present invention can be used in any form of printing ink, primer, or varnish.
The film-forming composition of the present invention may be used to form at least one of the printed layer, the primer layer, and the varnish layer. can be formed with the film-forming composition of the present invention.

Examples of the arrangement configuration of the film and the substrate A according to the present invention include the following cases.
・ Base material A - printed layer (white) - printed layer (color)
・Base material A-primer layer-printing layer (white)-printing layer (color)
・ Base material A - printed layer (white) - printed layer (color) - varnish layer ・ Base material A - primer layer - printed layer (white) - printed layer (color) - varnish layer ・ Base material A - printed layer (color ) - printed layer (white)
・Base material A-primer layer-printing layer (color)-printing layer (white)
・ Base material A - printed layer (color) - printed layer (white) - varnish layer ・ Base material A - primer layer - printed layer (color) - printed layer (white) - varnish layer ・ Base material A - varnish layer ・ Base Material A - printed layer (color)

Here, the base material A represents the base material A described later, and the printed layer (white) uses the film-forming composition of the present invention as a printing ink, and uses a white colorant to be contained in the film-forming composition. The printed layer (color) represents a printed layer formed by printing the film-forming composition using a coloring agent used for ink, and the printed layer (color) uses the film-forming composition of the present invention as a printing ink. A printed layer formed by printing the film-forming composition using a coloring agent other than the coloring agent used in the white ink as a coloring agent to be contained in the film-forming composition, and the primer layer is the primer layer of the present invention. 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.
In the above example, the printed layer is an example in which two layers are laminated, one in which white ink is used and the other in which color ink is used as a coloring agent other than white ink. It is not necessary to form two or more layers, and it may be formed of either one layer of white or color.

<Organic solvent-based composition>
The organic solvent-based composition, which is the film-forming composition of the present invention, is used to form a printed layer that is detached by treatment with an alkaline solution on the surface of the substrate A directly or via another layer.
The organic solvent-based composition contains a urethane resin.
In addition, the organic solvent-based composition contains an organic solvent and, if necessary, a colorant and other components.
The organic solvent-based composition may use raw materials derived from biomass. Due to problems such as the depletion of petroleum resources, petroleum-derived products are preferably replaced by those produced using plants as alternative energy sources and/or using microorganisms. In that case, the organic solvent-based composition can contribute to the reduction of the environmental load by carbon neutrality.

<<Urethane Resin>>
A urethane resin has a hydroxyl value.
Although the hydroxyl value of the urethane resin is not particularly limited, it is preferably 1.0 mgKOH/g or more, preferably 3.0 mgKOH/g or more, and preferably 5.0 mgKOH/g or more from the viewpoint of better releasability. 0 mgKOH/g or more is more preferable, and 10.0 mgKOH/g or more is even more preferable. Moreover, 40.0 mgKOH/g or less is preferable, 35.0 mgKOH/g or less is preferable, 30.0 mgKOH/g or less is preferable, 25.0 mgKOH/g or less is more preferable, and 20.0 mgKOH/g or less is further preferable. Also 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, 8.0 mgKOH / g ~25.0 mg KOH/g is more preferred, and 10.0 mg KOH/g to 20.0 mg KOH/g is more preferred.

The weight average molecular weight of the urethane resin is 45,000 or more. The weight-average molecular weight of the urethane resin is preferably 65,000 or more from the viewpoint of achieving a high level of both releasability and adhesion to the substrate.
Although the upper limit of the weight average molecular weight is not particularly limited, the weight average molecular weight is preferably 200,000 or less, more preferably 150,000 or less.
The number average molecular weight of the urethane resin is 10,000 or more. The number-average molecular weight of the urethane resin is preferably 30,000 or more from the viewpoint of achieving a high level of both releasability and adhesion to the substrate.
Although the upper limit of the number average molecular weight is not particularly limited, the number average molecular weight is preferably 100,000 or less, more preferably 75,000 or less.
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. There may be. The lower limit of the polydispersity is not particularly limited, but the polydispersity may be 1.0 or more, may be 1.2 or more, or may be 1.5 or more.

The acid value of the urethane resin is not particularly limited, but is preferably less than 15.0 mgKOH/g, more preferably 10.0 mgKOH/g or less, from the viewpoint of superior adhesion to the substrate and viscosity stability over time. 5.0 mg KOH/g or less is even more preferred. The urethane resin may or may not have an acid value, but preferably does not have an acid value.
In the present specification, the phrase "having no acid value" means that when the acid value of a urethane resin is measured by the neutralization titration method of JIS K 0070 (1992), titration of one drop reaches the end point.

It is preferable to use a polyester polyol and/or a polyether polyol as a reaction raw material for the urethane resin. In other words, the urethane resin preferably contains at least one of polyester polyol and polyether polyol as a constituent component.
The polyester polyol preferably has a number average molecular weight of 1,000 to 7,000. When the polyester polyol has a number average molecular weight of less than 1,000, the urethane resin film tends to be hard, and the adhesion to the polyester film tends to decrease. If the number-average molecular weight is more than 7,000, the film obtained from the film-forming composition tends to be brittle, and the blocking resistance of the film tends to decrease. On the other hand, the content of the polyester polyol in the urethane resin is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the urethane resin. In addition to the decrease in solubility in alcohol solvents, there is a tendency for the adhesiveness particularly on high-performance barrier films to decrease. In addition, the re-solubility of the film in the solvent tends to decrease, and the tone reproducibility of printed matter tends to decrease. On the other hand, if it exceeds 50 parts by mass, the film tends to be excessively soft and the blocking resistance tends to be poor.
The weight average molecular weight and number average molecular weight of the urethane resin and polyester polyol are values measured under the following conditions by gel permeation chromatography (GPC).

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation are connected in series and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: Create a calibration curve using the following standard polystyrene.
(standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

As said polyester polyol, the thing obtained by well-known esterification reaction of the compound and polybasic acid which have two or more hydroxyl groups can be used, for example.

The compound having two or more hydroxyl groups is used as a chain extender, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, - glycols such as hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 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-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, 2-methyl-1,8-octanediol, etc. aliphatic polyols such as trimethylolpropane, trimethylolethane, pentaerythritol, sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4 Compounds having a number average molecular weight in the range of 50 to 400, such as '-dihydroxydiphenylsulfone, hydrogenated bisphenol A, and aromatic polyols such as hydroquinone, can be used. These chain extenders may be used alone or in combination of two or more.

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, and phthalic acid. Acids, anhydrides of these acids, and the like can be used. These polybasic acids may be used alone or in combination of two or more.

Also, the polyether polyol preferably has a number average molecular weight of 100 to 4,000. Polyether polyols include polyether polyols of polymers or copolymers such as ethylene oxide, propylene oxide and tetrahydrofuran. Specifically, known general-purpose ones such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used, and among them, polyethylene glycol is preferred.
Similarly, when the number average molecular weight of the polyether polyol is less than 100, the film obtained from the film-forming composition tends to be hard and the adhesiveness to the polyester film tends to decrease. If the number-average molecular weight is more than 4,000, the film obtained from the film-forming composition tends to be brittle, and the blocking resistance of the film tends to decrease. The number average molecular weight of the polyether polyol is measured under the same conditions by gel permeation chromatography (GPC) as in the case of the polyester polyol.

Examples of the diisocyanate compound used for producing the urethane resin include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used for producing urethane resins. For example, 1,5-naphthylene 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, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1 , 4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; 5-isocyanato-1-(isocyanomethyl)-1,3 ,3-trimethylcyclohexane;), dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate . These diisocyanate compounds can be used alone or in combination of two or more.

Chain extenders used in the production of the urethane resin include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and 2-hydroxyethyl. Ethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyropyrethylenediamine, di-2 Amines having a hydroxyl group in the molecule, such as -hydroxypyropyrethylenediamine and di-2-hydroxypropylethylenediamine, can also be used. These chain extenders can be used alone or in combination of two or more.

The urethane resin is obtained by, for example, reacting a polyol, a polyisocyanate, a chain extender, and optionally a monovalent active hydrogen compound. For example, a diisocyanate compound is reacted with a diisocyanate compound with a polyester polyol and, if necessary, a combined polyol in such a proportion that the isocyanate groups are excessive to obtain a prepolymer having terminal isocyanate groups, and the resulting prepolymer is placed in an appropriate solvent, i.e., a liquid Ester-based solvents such as ethyl acetate, propyl acetate and butyl acetate, which are commonly used as solvents for ink; ketone-based solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol and n-butanol. Solvent; hydrocarbon solvents such as toluene, xylene, methylcyclohexane, ethylcyclohexane; or a two-step method of reacting with a chain extender and (or) a terminal blocking agent in a mixed solvent thereof, or a polyester polyol and, if necessary, It is produced by a one-step method in which the combined polyol, diisocyanate compound, chain extender and/or terminal blocking agent are reacted together in a suitable solvent among the above. Among these methods, the two-step method is preferable for obtaining a uniform urethane resin. In addition, when producing a urethane resin by a two-step method, the total (equivalent ratio) of the amino groups of the chain extender and (or) terminal blocker is 1/0.9 to 1.3. is preferred. If the equivalent ratio of the isocyanate group to the amino group is less than 1/1.3, the chain extender and (or) the terminal blocking agent remain unreacted, causing yellowing of the urethane resin and odor after printing. may occur.

As a method of imparting a hydroxyl value to a urethane resin, for example, there is a method of using a primary or secondary amine compound having a hydroxy group as a terminal blocking agent when producing a urethane resin. Examples of the amine compound include monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, monoisopropanolamine, diisopropanolamine and the like.

As a method of not imparting an acid value to the urethane resin, for example, a method of using a raw material having no carboxy group in the two-step method or the one-step method described above can be mentioned.
On the other hand, as a method of imparting an acid value to the urethane resin, for example, a method of using a raw material having a carboxy group in the two-step method or the one-step method described above can be mentioned. Raw materials having a carboxy group include, for example, diols having a carboxy group (eg, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid). For example, in the above two-step method or one-step method, a urethane resin having an acid value can be obtained by using a diol having a carboxyl group as a combined polyol.

The amine value of the urethane resin is preferably 10.00 mgKOH/g or less. If the amine value exceeds 10.00 mgKOH/g, the anti-blocking property tends to be poor, and in addition, the two-liquid stability after addition of the curing agent is lowered. It is more preferably in the range of 0 to 5.00 mgKOH/g, still more preferably 0 to 3.50 mgKOH, from the viewpoint of maintaining good blocking resistance and two-liquid stability while maintaining plate fogging resistance, adhesiveness and extrusion lamination strength. /g.

The content of the urethane resin in the composition of the present invention is, for example, in the case of gravure ink used for gravure printing, from the viewpoint of sufficient adhesion of the gravure ink to the substrate to be printed, the solid content relative to the total mass of the ink. 5% by mass or more in terms of minutes, preferably 25% by mass or less from the viewpoint of appropriate ink viscosity and work efficiency during ink production and printing. On the other hand, it is preferably 5% by mass or more and 30% by mass or less in terms of solid content.

<<Organic solvent>>
The organic solvent is not particularly limited, and examples include aromatic hydrocarbons such as toluene, xylene, Solvesso #100 and Solvesso #150, aliphatic hydrocarbons such as hexane, methylcyclohexane, heptane, octane, and decane, and methyl acetate. , ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. Water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, Di)methyl ether, propylene glycol (mono, di)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol (mono, di)methyl ether, and other glycol ether organic solvents can be used. These may be used alone or in combination of two or more.

As the ester-based organic solvent, it is more preferable to contain an ester-based organic solvent having 4 or more carbon atoms from the viewpoint of preventing the plate drying of the organic solvent-based composition of the present invention due to its evaporability. Although the ester-based organic solvent having 4 or more carbon atoms is not limited, ethyl acetate, isopropyl acetate, normal-propyl acetate, and butyl acetate are more preferable, and normal-propyl acetate is particularly preferable.

The content of the ester-based organic solvent in the organic solvent-based 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, and preferably 10% by mass or more. It is 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. Moreover, 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, preferably 35% by mass or less.

The content of the ester organic solvent in the organic solvent-based composition of the present invention is preferably 1 to 60% by mass, preferably 3 to 55% by mass, preferably 5 to 50% by mass, preferably 7 to 45% by mass, 10 to 40% by weight is preferred, 12 to 35% by weight is preferred, 15 to 30% by weight is preferred, 18 to 28% by weight is preferred, 20 to 25% by weight is preferred, and 20 to 23% by weight is preferred.

When the organic solvent-based composition of the present invention is used for gravure ink, an alcohol that does not contain an aromatic hydrocarbon-based organic solvent and has a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is 100 is used. It is preferable to contain. By containing an alcohol having a specific evaporation rate of 100 or less, it is possible to maintain the highlight transfer property with a halftone dot area of 10% or less and improve the highlight. The mechanism has the following two points. First of all,
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.
2) The remaining organic solvent-based composition of the present invention evaporates until it comes into contact with the organic solvent-based composition of the present invention in the ink pan again, and becomes semi-dry. Furthermore, since the solvent evaporates faster, it evaporates first, so the solvent with the slower evaporates remains in the ink pan.
3) At this time, if a solvent with high resin solubility remains, the semi-dried composition is redissolved when it comes into contact with the organic solvent-based composition of the present invention again, and the organic solvent of the present invention is dissolved in the cell. prevent the system composition from hardening.
General-purpose alcohols having a specific evaporation rate of more than 100 when the evaporation rate of butyl acetate is taken as 100 have a high volatilization rate, so the above mechanism tends to be difficult to function.

Secondly, alcohols with a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is 100 have a low ratio of hydroxyl groups (alcohol groups) in one molecule of alcohol, and therefore have a low solubility in urethane resins. tend to increase.
In terms of work hygiene during printing and the toxicity of packaging materials, use ethyl acetate, propyl acetate, isopropanol, normal propanol, etc., and do not use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone. is more preferred.
Among them, a mixture of isopropyl alcohol/ethyl acetate/n-propyl acetate/methylcyclohexane is more preferable from the viewpoint of solubility in urethane resin and nitrocellulose. Moreover, for drying adjustment, glycol ethers can be added as long as they are less than 10% by mass of the total amount of the composition.

<<coloring agent>>
The organic solvent-based composition of the present invention may further contain a colorant.

Examples of the coloring agent used in the organic solvent-based composition of the present invention include inorganic pigments, organic pigments, and dyes used in general inks, paints, recording agents, and the like.
Examples of organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthanthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, quinacridone, Thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethineazo-based, flavanthrone-based, diketopyrrolopyrrole-based, isoindoline-based, indanthrone-based, and carbon black-based pigments can be used. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Ron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, and the like. Both non-acid-treated pigments and acid-treated pigments can be used. Specific examples of preferred organic pigments are given below.

Examples of black pigments include C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 9, C.I. I. Pigment Black 20 and the like.

Examples of the indigo pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:5, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17:1, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 24:1, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and the like.

Examples of green pigments include C.I. I. Pigment Green 1, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 36 and the like.

Examples of red pigments include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 12, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 20, C.I. I. Pigment Red 21, C.I. I. Pigment Red 22, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 38, C.I. I. Pigment Red 41, C.I. I. Pigment Red 43, C.I. I. Pigment Red 46, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 48:4, C.I. I. Pigment Red 48:5, C.I. I. Pigment Red 48:6, C.I. I. Pigment Red 49, C.I. I. Pigment Red 49:1, C.I. I. Pigment Red 49:2, C.I. I. Pigment Red 49:3, C.I. I. Pigment Red 52, C.I. I. Pigment Red 52:1, C.I. I. Pigment Red 52:2, C.I. I. Pigment Red 53, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 53:2, C.I. I. Pigment Red 53:3, C.I. I. Pigment Red 54, C.I. I. Pigment Red 57, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 58, C.I. I. Pigment Red 58:1, C.I. I. Pigment Red 58:2, C.I. I. Pigment Red 58:3, C.I. I. Pigment Red 58:4, C.I. I. Pigment Red 60:1, C.I. I. Pigment Red 63, C.I. I. Pigment Red 63:1, C.I. I. Pigment Red 63:2, C.I. I. Pigment Red 63:3, C.I. I. Pigment Red 64:1, C.I. I. Pigment Red 68, C.I. I. Pigment Red 68, C.I. I. Pigment Red 81:1, C.I. I. Pigment Red 83, C.I. I. Pigment Red 88, C.I. I. Pigment Red 89, C.I. I. Pigment Red 95, C.I. I. Pigment Red 112, C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 136, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I. Pigment Red 171, C.I. I. Pigment Red 172, C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 180, C.I. I. Pigment Red 181, C.I. I. Pigment Red 182, C.I. I. Pigment Red 183, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I. I. Pigment Red 192, C.I. I. Pigment Red 193, C.I. I. Pigment Red 194, C.I. I. pigment red 200,
C. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Pigment Red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 210, C.I. I. Pigment Red 211, C.I. I. Pigment Red 213, C.I. I. Pigment Red 214, C.I. I. Pigment Red 216, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 248, C.I. I. Pigment Red 251, C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 256, C.I. I. Pigment Red 257, C.I. I. Pigment Red 258, C.I. I. Pigment Red 260, C.I. I. Pigment Red 262, C.I. I. Pigment Red 263, C.I. I. Pigment Red 264, C.I. I. Pigment Red 266, C.I. I. Pigment Red 268, C.I. I. Pigment Red 269, C.I. I. Pigment Red 270, C.I. I. Pigment Red 271, C.I. I. Pigment Red 272, C.I. I. Pigment Red 279, and the like.

Examples of purple pigments include C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3:1, C.I. I. Pigment Violet 3:3, C.I. I. Pigment Violet 5:1, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 19 (γ type, β type), C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 38, C.I. I. Pigment Violet 42, C.I. I. Pigment Violet 50, and the like.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like.

Examples of orange pigments include C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 37, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Range 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, or C.I. I. Pigment Orange 74 and the like.

Examples of brown pigments include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, or C.I. I. Pigment Brown 26 and the like.
Among them, as a preferable pigment, C.I. I. Pigment Black 7, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Green 7, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 146, C.I. I. Pigment Red 242, C.I. I. Pigment Red 185, C.I. I. Pigment Red 122, C.I. I. Pigment Red 178, C.I. I. Pigment Red 149, C.I. I. Pigment Red 144, C.I. I. Pigment Red 166, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 139, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 64, etc., and it is preferable to use at least one or two or more selected from these groups.

Examples of inorganic pigments include carbon black, titanium oxide, red iron oxide, aluminum, mica (mica), zinc oxide, barium sulfate, calcium carbonate, and silica. A bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.) obtained by coating glass flakes or massive flakes as a base material with a metal or a metal oxide can also be used. It is preferable to use carbon black for black ink, titanium oxide for white ink, aluminum for gold and silver inks, and mica for pearl ink from the viewpoint of cost and coloring power.

From the viewpoint of ensuring the concentration and coloring power of the organic solvent composition of the present invention, the total content of the pigments is preferably 1% by mass or more, preferably 60%, based on the total amount of the organic solvent composition of the present invention. % by mass or less.

<<Other Ingredients>>
The organic solvent-based composition of the present invention may further contain other components such as binder resins and auxiliary agents.
Binder resins include, for example, cellulosic resins (e.g., nitrocellulose (nitrocellulose)), urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified malein. Resins such as acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, petroleum resins, etc. , itaconic acid, maleic acid, fumaric acid, cinnamic acid or acid anhydrides thereof, polymerizable monomers having a carboxyl group; polymerizable monomers having a sulfonic acid group, such as sulfonated styrene; and sulfones, such as vinylbenzenesulfonamide. (Meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydride) maleic acid resins, terpene-(anhydrous) maleic acid resins, etc., obtained by copolymerizing polymerizable monomers such as polymerizable monomers having an amide group and acid-modified polyolefin resins (excluding the above <<urethane resin>>), and these can be used singly or in combination.

Auxiliaries include waxes such as paraffin waxes, polyethylene waxes, and carnauba waxes for imparting friction resistance and slipperiness; fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide; A silicone-based or non-silicon-based antifoaming agent for suppressing foaming; As the dispersant, a nonionic dispersant is preferred.

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

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 with respect to 100 parts by mass of the coloring agent. More preferably 20 parts by mass or more, 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, 65 parts by mass or less is more preferable, and 60 parts by mass or less is more preferable.

In addition to the above, water, wetting agents, adhesion aids, leveling agents, antistatic agents, viscosity modifiers, metal chelates, trapping agents, antiblocking agents, isocyanate curing agents, and silane coupling agents are also used as necessary. can. The viscosity of the organic solvent-based composition of the present invention is preferably 6 seconds or more, more preferably 10 seconds or more, and even more preferably 13 seconds or more as a numerical value measured at 25° C. using Zahn Cup #3 manufactured by Rigosha. . Also, the time is preferably 25 seconds or less, more preferably 20 seconds or less, and even more preferably 18 seconds or less.

The surface tension of the organic solvent-based composition of the present invention is preferably 25 mN/m or more, more preferably 33 mN/m or more. Moreover, it is preferably 50 mN/m or less, more preferably 43 mN/m or less. By moderately increasing the surface tension of the organic solvent-based composition of the present invention, while maintaining the wettability of the organic solvent-based composition of the present invention to the substrate, dot bridges (adjacent halftone dot portions Stain on the printing surface where halftone dots are connected to each other) can be suppressed, and by appropriately lowering the surface tension of the organic solvent composition of the present invention, the organic solvent composition of the present invention can be applied to the substrate. It can improve wettability and suppress cissing.

When the organic solvent-based 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, etc., which are generally used for producing gravure or flexographic inks. can.

When preparing the organic solvent-based composition of the present invention, from the viewpoint of uniformity, at least part of the urethane resin, the colorant, and at least part of the organic solvent are mixed in advance to form a preliminary composition (kneading base ink) may be prepared.

As in the present invention, the composition to be removed from the substrate includes resist ink, but the purpose of the resist ink is to remove the coating film from the substrate in advance, leaving a part, and to process the substrate. Since the application and purpose are fundamentally different from the film-forming composition of the present invention, which aims to detach the entire film and recycle the substrate, the well-known technique of the present invention is Not applicable.

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

<Primer composition>
When the film-forming composition of the present invention is used to form a primer layer, the primer composition, which is the film-forming composition of the present invention, contains the <<urethane resin>>.
In addition to <<urethane resin>>, the primer composition may contain commercially available binder resins, solvents such as organic solvents and aqueous solvents, and additives without particular limitations.

Binder resins include, for example, cellulosic resins (e.g., nitrocellulose (nitrocellulose)), urethane resins (excluding the above <<urethane resin>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester Resin, (meth)acrylic resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, cyclized rubber, chloride Resins such as rubber, butyral resin, and petroleum resin; polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides; and sulfonic acid groups such as sulfonated styrene. (Meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydride) maleic acid obtained by copolymerizing polymerizable monomers such as polymerizable monomers and polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide Examples include resins, radical copolymer resins such as terpene-(anhydride) maleic acid resins, and acid-modified polyolefin resins, and these can be used singly or in combination.

Any organic solvent may be used as the solvent, and for example, the same organic solvents as those described in the section <<Organic Solvent>> in <Organic Solvent-Based Composition> can be used.

Additives include extender pigments, pigment dispersants, leveling agents, antifoaming agents, waxes, plasticizers, antiblocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants and the like.

When the <<urethane resin>> is contained in the primer layer, the amount of <<urethane resin>> to be added may be appropriately determined within a range that does not impair the properties of the primer layer. It is preferably in the range of 5 to 30% by mass with respect to the total mass of.

Also, primers to which a resin having an acidic group or a low-molecular-weight compound is added can be preferably used. Resins and low-molecular-weight compounds having acidic groups are not particularly limited as long as they can be easily mixed with the aforementioned <<urethane resin>>, which is the main component of the primer, organic solvents, and the like.

Examples of resins having an acidic group include cellulose resins (e.g., nitrocellulose), urethane resins (excluding the above <<urethane resins>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, Ketone resin, polyester resin, (meth)acrylic resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, ring Polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, and sulfones (Meth)acrylic resin, styrene obtained by copolymerizing a polymerizable monomer having an acidic group, such as a polymerizable monomer having a sulfonic acid group such as styrene, a polymerizable monomer having a sulfonamide group such as vinylbenzenesulfonamide, etc. -Resins that are radical copolymers such as (meth)acrylic resins, styrene-(anhydride) maleic acid resins, terpene-(anhydride) maleic acid resins, acid-modified polyolefin resins, etc. (excluding the above binder resins) These can be used singly or in combination.

The low-molecular-weight compound having an acidic group preferably includes 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. Alternatively, a plurality of them can be mixed and used.
Saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, and dodecanoic acid. Unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, and arachidonic acid. , eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, and the like. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid. , salicylic acid, gallic acid, mellitic acid, cinnamic acid, and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid , fumaric acid, maleic acid, azelaic acid, etc. Examples of tricarboxylic acids include aconitic acid, trimer acid, etc. Examples of oxocarboxylic acids include pyruvic acid, oxaloacetic acid, etc. Examples of carboxylic acid derivatives include , amino acids, and nitrocarboxylic acids, and these can be used singly or in combination. Citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc. If so, it is preferable to use substances that can comply with the so-called Swiss Ordinance and comply with various regulations.

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

<Varnish composition>
When the film-forming composition of the present invention is used to form a varnish layer, the varnish composition, which is the film-forming composition of the present invention, contains the <<urethane resin>>.

In addition to <<urethane resin>>, the varnish composition may contain commercially available binder resins, solvents such as organic solvents and aqueous solvents, and additives without particular limitations.

Binder resins include, for example, cellulosic resins (e.g., nitrocellulose (nitrocellulose)), urethane resins (excluding the above <<urethane resin>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester Resin, (meth)acrylic resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, cyclized rubber, chloride Resins such as rubber, butyral resin, and petroleum resin; polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides; and sulfonic acid groups such as sulfonated styrene. (Meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydride) maleic acid obtained by copolymerizing polymerizable monomers such as polymerizable monomers and polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide Examples include resins, radical copolymer resins such as terpene-(anhydride) maleic acid resins, and acid-modified polyolefin resins, and these can be used singly or in combination.

Any organic solvent may be used as the solvent, and for example, the same organic solvent as described in the section <<Organic solvent>> in <Organic solvent-based composition> can be used.

Additives include extender pigments, pigment dispersants, leveling agents, antifoaming agents, waxes, plasticizers, antiblocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants and the like.

When the <<urethane resin>> is contained in the varnish layer, the amount of <<urethane resin>> to be added may be appropriately determined within a range that does not impair the properties of the varnish layer. It is preferably in the range of 5 to 30% by mass with respect to the

Also, a varnish to which a resin having an acidic group or a low-molecular-weight compound is added can be preferably used. Resins and low-molecular-weight compounds having an acidic group are not particularly limited as long as they can be easily mixed with the urethane resin, which is the main component of the varnish, organic solvent, and the like.

Examples of resins having an acidic group include cellulose resins (e.g., nitrocellulose), urethane resins (excluding the above <<urethane resins>>), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, Ketone resin, polyester resin, (meth)acrylic resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, ring Polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, and sulfones (Meth)acrylic resin, styrene obtained by copolymerizing a polymerizable monomer having an acidic group, such as a polymerizable monomer having a sulfonic acid group such as styrene, a polymerizable monomer having a sulfonamide group such as vinylbenzenesulfonamide, etc. -Resins that are radical copolymers such as (meth)acrylic resins, styrene-(anhydride) maleic acid resins, terpene-(anhydride) maleic acid resins, acid-modified polyolefin resins, etc. (excluding the above binder resins) These can be used singly or in combination.

The low-molecular-weight compound having an acidic group preferably includes 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. Alternatively, a plurality of them can be mixed and used.

Saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, and dodecanoic acid. Unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, and arachidonic acid. , eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, and the like. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid. , salicylic acid, gallic acid, mellitic acid, cinnamic acid, and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid , fumaric acid, maleic acid, azelaic acid, etc. Examples of tricarboxylic acids include aconitic acid, trimer acid, etc. Examples of oxocarboxylic acids include pyruvic acid, oxaloacetic acid, etc. Examples of carboxylic acid derivatives include , amino acids, and nitrocarboxylic acids, and these can be used singly or in combination. Citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc. If so, it is preferable to use substances that can comply with the so-called Swiss Ordinance and comply with various regulations.

(Printing on base material)
The film-forming composition of the present invention has excellent adhesion to various substrates, and can be used for printing on paper, synthetic paper, cloth, thermoplastic resin films, plastic products, steel plates, and the like. The film-forming composition of the present invention is useful as an ink for gravure printing using a gravure printing plate such as an electronic engraving intaglio, or flexographic printing using a flexographic printing plate such as a resin plate. On the other hand, it can also be used for an inkjet system in which ink is ejected from an inkjet nozzle without using a plate, but it is not so preferable. That is, in the case of inkjet ink, ink droplets ejected from a nozzle directly adhere to a substrate to form a printed matter. - After transfer, only the ink is brought into close contact with the substrate again, and dried as necessary to produce a printed matter. The film-forming composition of the present invention is suitably used in printing methods such as gravure, flexo, die coater, and roll coater.

The film 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, still more preferably 10 µm or less, and most preferably 5 µm or less.

(Printed matter and laminate)
A printed matter having a film can be obtained by printing the film-forming composition of the present invention on the surface of the substrate A directly or via another layer. This printed matter can also be called a laminate. A laminate can also be obtained by laminating the substrate B on the film side of the printed matter. A laminate having a film, a substrate A and a substrate B may be formed by laminating the film and the substrate B via an adhesive layer.
Embodiments of a printed matter printed using the film-forming composition of the present invention, a laminate constructed using the printed matter, and a laminate having a film formed using the film-forming composition of the present invention Preferred examples include, but are not limited to, the following aspects.

As described above, the mode of forming the film directly on the surface of the substrate A or via another layer is as follows.
<Surface printing>
・ Base material A - printed layer (white) - printed layer (color)
・Base material A-primer layer-printing layer (white)-printing layer (color)
・ Base material A - printed layer (white) - printed layer (color) - varnish layer ・ Base material A - primer layer - printed layer (white) - printed layer (color) - varnish layer ・ Base material A - printed layer (color ) - printed layer (white)
・Base material A-primer layer-printing layer (color)-printing layer (white)
・ Base material A - printed layer (color) - printed layer (white) - varnish layer ・ Base material A - primer layer - printed layer (color) - printed layer (white) - varnish layer

A mode of arranging the film between the base material A and the base material B is as follows.
<Back side printing/Lamination>
・ Base material A - printed layer (white) - printed layer (color) - adhesive layer - base material B
・ Base material A - primer layer - printed layer (white) - printed layer (color) - adhesive layer - base material B
・ Base material A - printed layer (white) - printed layer (color) - varnish layer - adhesive layer - base material B
・ Base material A - primer layer - printed layer (white) - printed layer (color) - varnish layer - adhesive layer - base material B
・ Base material A - printed layer (color) - printed layer (white) - adhesive layer - base material B
・ Base material A - primer layer - printed layer (color) - printed layer (white) - adhesive layer - base material B
・ Base material A - printed layer (color) - printed layer (white) - varnish layer - adhesive layer - base material B
・ Base material A - primer layer - printed layer (color) - printed layer (white) - varnish layer - adhesive layer - base material B
・ Base material A - printed layer (white) - printed layer (color) - resin C layer - base material B
・ Base material A - primer layer - printed layer (white) - printed layer (color) - resin C layer - base material B
・ Base material A - printed layer (white) - printed layer (color) - varnish layer - resin C layer - base material B
・ Base material A - primer layer - printed layer (white) - printed layer (color) - varnish layer - resin C layer - base material B
・ Base material A - printed layer (color) - printed layer (white) - resin C layer - base material B
・ Base material A - primer layer - printed layer (color) - printed layer (white) - resin C layer - base material B
・ Base material A - printed layer (color) - printed layer (white) - varnish layer - resin C layer - base material B
・ Base material A - primer layer - printed layer (color) - printed layer (white) - varnish layer - resin C layer - base material B
・ Base material A - printed layer (white) - printed layer (color) - base material B
・ Base material A - primer layer - printed layer (white) - printed layer (color) - base material B
・ Base material A - printed layer (white) - printed layer (color) - varnish layer - base material B
・ Base material A - primer layer - printed layer (white) - printed layer (color) - varnish layer - base material B
・ Base material A - printed layer (color) - printed layer (white) - base material B
・ Base material A - primer layer - printed layer (color) - printed layer (white) - base material B
・ Base material A - printed layer (color) - printed layer (white) - varnish layer - base material B
・ Base material A - primer layer - printed layer (color) - printed layer (white) - varnish layer - base material B
・ Base material A - varnish layer ・ Base material A - printed layer (color)

The printing layer (white), printing layer (color), primer layer and varnish layer are as described above.
The base material A, the base material B, the adhesive layer, and the resin C layer will be described below.

<Base material A>
As the base material A, a plastic base material is preferable, and polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, Polyester resins such as polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate), polypropylene, polyethylene, etc. Polyolefin resins, polyimide resins, polyarylate resins, or mixtures thereof and films made of thermoplastic resins and laminates thereof. Among them, films and laminates made of polyester, polyamide, polyethylene, and polypropylene are preferable. Polypropylene or polyethylene is more preferable when considering the releasability of the film-forming composition of the present invention. These base films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited. Also, the thickness of the base film is not particularly limited, but it is usually in the range of 1 to 500 μm.

The printing surface of the substrate A is preferably subjected to corona discharge treatment, and silica, alumina or the like may be deposited thereon.

<Base material B>
The substrate B may be the same as the substrate A, and may be the same or different, but is preferably a plastic substrate, more preferably a thermoplastic resin substrate.
When the laminate having the film, substrate A and substrate B is an extrusion laminate, it may be the same as resin C described later. Moreover, it may be laminated with a metal foil layer or a metal foil layer of a deposited film layer.

<Resin C>
Resin C is preferably a thermoplastic resin, more preferably polyolefin, and particularly preferably polypropylene or polyethylene and modified resins thereof.

<Adhesive layer>
As the adhesive for forming the adhesive layer, any commercially available reactive adhesive can be used without particular limitation. A one-part reactive adhesive of polyisocyanate is preferred.
The polyisocyanate composition used in general reactive adhesives is a composition containing a polyisocyanate compound as a main component, especially if it is known as a polyisocyanate compound for reactive adhesives. Can be used without restrictions. Examples of specific polyisocyanate compounds include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and the like. polyisocyanates, compounds obtained by modifying some of the isocyanate groups (NCO groups) of these polyisocyanates with carbodiimide; linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; Compounds obtained by modifying part of the NCO groups of isocyanates with carbodiimide; isocyanurate forms of the various polyisocyanates; allophanate forms derived from the various polyisocyanates; biuret forms derived from the various polyisocyanates; Examples include adducts obtained by modifying isocyanates with trimethylolpropane; and polyisocyanates which are reaction products of the various polyisocyanates described above and polyol components described later.

The polyol composition used in general reactive adhesives is a composition containing a polyol compound as a main component, and any known polyol compound for reactive adhesives can be used without particular limitation. can. Examples of specific polyol compounds include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4 - cyclohexanediol, 1,4-cyclohexanedimethanol, glycols such as triethylene glycol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol; bisphenol A, bisphenol F, hydrogenated bisphenol A, Bisphenol such as hydrogenated bisphenol F; dimer diol, polyester polyol, polyether polyol, polyurethane polyol, polyetherester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyesteramide polyol, acrylic polyol, polycarbonate polyol, Polymer polyols selected from polyhydroxyalkanes, castor oil or mixtures thereof may be mentioned.

Among them, since it is easily dissolved or hydrolyzed by an alkaline solution, it is preferable that one of the constituent components of the reactive adhesive has an ester bond, and the single layer film can be easily formed in a short time in the film removal process described later. can be separated.

Any component of the reactive adhesive having an ester bond specifically means a polyol having a polyol compound such as a polyester polyol, a polyether ester polyol, a polyester (polyurethane) polyol, or an acrylic polyol having an ester bond. A reactive adhesive containing either or both of a composition, a polyol compound having an ester bond, and a polyisocyanate composition having a polyisocyanate compound that is a reaction product of the various polyisocyanates. mentioned.

Reactive adhesives include pigments, silane coupling agents, titanate coupling agents, aluminum coupling agents, adhesion promoters such as epoxy resins, leveling agents, colloidal silica, inorganic fine particles such as alumina sol, poly Methyl methacrylate-based organic fine particles, antifoaming agent, anti-sagging agent, wetting and dispersing agent, viscosity modifier, UV absorber, metal deactivator, peroxide decomposer, flame retardant, reinforcing agent, plasticizer, lubricant Additives such as anti-corrosion agents, anti-rust agents, fluorescent whitening agents, inorganic heat ray absorbers, flame retardants, anti-static agents, and dehydrating agents are sometimes used.

Reactive adhesives include dry lamination adhesives diluted with highly soluble organic solvents for dilution, solvent-free lamination adhesives that contain almost no organic solvents for dilution, and water-based diluents. There are certain water-based adhesives and the like, but any can be used.

The substrate A, the printed layer (white), the printed layer (color), the primer layer, the adhesive layer, the varnish layer, the resin C layer, or the substrate B in the laminate may each have a barrier layer interposed therebetween. Examples of the barrier layer include an inorganic deposition layer and a barrier coat layer, and these may be used alone or in combination.

The inorganic deposition layer is a layer having gas barrier properties to prevent permeation of oxygen gas and water vapor gas, and is a deposition layer made of an inorganic material or an inorganic oxide. Examples of inorganic substances or inorganic oxides include aluminum, alumina, silica and the like, and these can be used singly or in combination of two or more. Two or more inorganic deposition layers may be provided. When two or more inorganic deposition layers are provided, they may have the same composition or may have different compositions.

The barrier coat layer protects the inorganic deposition layer and can improve gas barrier properties against oxygen, water vapor and the like. Such a gas barrier coating layer is obtained, for example, by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel catalyst and a solvent such as water or an organic solvent. It is formed from a resin composition such as a product, a hydrolysis polycondensate of a metal alkoxide, or the like.

(Method for detaching film from substrate A)
According to the present invention, the recycled base material A can be produced by removing the film from the base material A by treating the printed matter or laminate with an alkaline solution.

In addition, the present invention provides a laminate in which a printed matter and a base material B are laminated with a film disposed on the inside via an adhesive layer or the like, and the base material B is detached together with the film by alkaline solution treatment, and recycled. Substrate A can be produced.

The desorption step includes a step of immersing the printed matter or laminate in an alkaline solution while heating and stirring at 20 to 90° C. or ultrasonically vibrating. Heating and stirring and ultrasonic vibration may be performed at the same time. 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, and more preferably perform heating stirring and ultrasonic vibration at the same time.

The alkaline solution used in the desorption step is not limited, but preferably has a pH of 9 or higher, and includes sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium hydrogen carbonate aqueous solution, potassium hydrogen carbonate aqueous solution, sodium dihydrogen carbonate aqueous solution, carbonate Potassium dihydrogen aqueous solution and the like are preferable. Aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous sodium hydrogencarbonate solution, potassium hydrogencarbonate aqueous solution, sodium dihydrogencarbonate aqueous solution, potassium dihydrogencarbonate aqueous solution, etc. are preferably aqueous solutions having a concentration of 0.5% by mass to 10% by mass. More preferred is an aqueous solution with a concentration of 5% by weight to 5% by weight.

Moreover, the alkaline solution may contain a water-soluble organic solvent.
Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol di Butyl 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, triethylene glycol monomethyl ether , triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonylacetone, 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 can be exemplified, and these can be used alone or in combination of two or more. can.

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.
Moreover, the alkaline solution may contain a water-insoluble organic solvent.
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 normal paraffin, benzene, toluene, xylene, Aromatic hydrocarbon solvents such as alkylbenzene; halogenated hydrocarbon solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane and carbon tetrachloride; ester solvents such as methyl acetate, ethyl acetate and butyl acetate , methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, and ether solvents such as ethyl ether and butyl ether, and these can be used alone or in combination of two or more.

Moreover, the alkaline solution may contain a surfactant. Surfactants include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. Among these, anionic surfactants, nonionic surfactants Alternatively, amphoteric surfactants are preferred.

Examples of anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfuric acid ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, and higher alcohol ethers. Sulfuric acid ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples thereof include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, and dibutylphenylphenoldisulfonate.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acid esters. , polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, among others, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid Esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers are preferred.

Other surfactants include silicone-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. spiculisporic acid, rhamnolipids, biosurfactants such as lysolecithin, and the like can also be used.

These surfactants can be used alone or in combination of two or more. When a surfactant is added, the amount added is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, with respect to the total amount of the alkaline solution, and 0.01 to More preferably, it is in the range of 1% by mass.

An alkaline solution is heated to 20 to 90° C. or ultrasonically vibrated, and the target printed matter or laminate is immersed in, for example, a treatment tank. The heating method is not particularly limited, and a known heating method using heat rays, infrared rays, microwaves, or the like can be employed. As for the ultrasonic vibration, for example, a method of attaching an ultrasonic vibrator to the treatment bath and imparting ultrasonic vibration to the warm water or the alkaline solution can be employed.

Moreover, it is preferable that the alkaline solution is stirred during the immersion. Examples of the stirring method include a method of mechanically stirring the dispersion of the printed matter or laminate contained in the processing tank with a stirring blade, a method of stirring with a water jet using a water jet pump, and a bubbling method using an inert gas such as nitrogen gas. and the like, and these may be used together for efficient peeling.

The time for which the printed matter or laminate is immersed in the alkaline solution is generally in the range of 2 minutes to 48 hours, although it depends on the structure of the printed matter. In the present invention, it is not necessary that 100% of the film in the printed material is completely detached from the substrate. , more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

In the desorption step, the number of times of immersion in the alkaline solution may be one or several times. That is, the step of recovering the separated film substrate may be performed after performing the immersion once, or the step of recovering the film substrate may be performed after performing the immersion several times. Further, when the immersion is performed multiple times in the desorption process, the concentration of the alkaline solution may be changed. Further, known steps such as washing with water and drying may be appropriately added during the desorption step.

The film-forming composition of the present invention suppresses the content of solvents that are harmful to health and the environment to a certain level or less, and maintains the same properties for general-purpose plastic substrates as those of conventional film-forming materials. By containing a specific urethane resin, it can be easily detached by alkaline solution treatment, and the film layer can be easily removed from the plastic substrate.In addition, the film layer has excellent adhesion to the substrate. can be formed.

EXAMPLES The contents and effects of the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these. "Parts" and "%" shown below are based on mass.

<Molecular weight measurement method>
The weight average molecular weight and number average molecular weight (converted to polystyrene) by GPC (gel permeation chromatography) in the present invention were measured using an HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: 4 TSKgelGMHHR-N manufactured by Tosoh Corporation are used.
Column temperature: 40°C.
Moving bed: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
Flow rate: 1.0 ml/min.
Sample concentration: 1.0%.
Sample injection volume: 100 microliters.
Detector: differential refractometer.

<Viscosity measurement method>
Viscosity was measured at 25° C. with a B-type viscometer manufactured by Tokimec.

<Hydroxyl value measurement method>
The hydroxyl value was measured according to JIS K 0070-1992.

<Acid value measurement method>
The acid value was measured according to JIS K 0070-1992.

(Synthesis Example 1) Synthesis of Polyurethane (Urethane Resin) 1 2-Methyl-1,3-propanediol and adipic acid were placed in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube. 80.0 parts of polyester polyol (hydroxyl value: 56 mgKOH / g), 20.0 parts of polyethylene glycol (hydroxyl value: 277 mgKOH / g), and isophorone diisocyanate (hereinafter abbreviated as IPDI) 25.4 parts were charged, After reaction was carried out at 90° C. for 20 hours under a nitrogen stream to produce a urethane prepolymer, 83.6 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Then, to a mixture consisting of 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), The urethane prepolymer solution was added and reacted with stirring at 45° C. for 5 hours to obtain polyurethane resin solution 1 containing polyurethane 1 .
The characteristic values of the obtained polyurethane resin solution 1 were as follows.
・ Resin solid content hydroxyl value: 20.2 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 48,300
- Weight average molecular weight of resin solid content: 82,900
・ Resin solid content amine value: 0.40 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 2) Synthesis of polyurethane 2 2-methyl-1,3-propanediol and 3-methyl-1,5- 100.0 parts of a polyester polyol (hydroxyl value: 22 mgKOH/g) made from pentanediol, neopentyl glycol and adipic acid and 9.2 parts of IPDI were charged and reacted at 100°C for 10 hours under a stream of nitrogen to obtain urethane. After the prepolymer was produced, 72.8 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Then, in a mixture consisting of 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, The urethane prepolymer solution was added and reacted with stirring at 45° C. for 5 hours to obtain a polyurethane resin solution 2 containing polyurethane 2 .
The characteristic values of the obtained polyurethane resin solution 2 were as follows.
・ Resin solid content hydroxyl value: 20.8 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 58,600
- Weight average molecular weight of resin solid content: 106,700
・ Resin solid content amine value: 0.30 mg KOH / g
・ Resin solid content concentration: 29.5% by mass

(Synthesis Example 3) Synthesis of Polyurethane 3 Polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, and IPDI 16.8 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. After that, 210.5 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 74.5 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 6.5 parts of IPDA and 15.2 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.2 parts of monoethanolamine (hereinafter abbreviated as MEA) and 0.5 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 3 containing polyurethane 3. Obtained.
The characteristic values of the obtained polyurethane resin solution 3 were as follows.
・ Resin solid content hydroxyl value: 1.5 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 4) Synthesis of Polyurethane 4 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, and IPDI 16.8 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. After that, 210.5 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 74.6 parts of isopropyl alcohol to the urethane prepolymer solution to obtain 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 added. The mixture was reacted with stirring at ℃ for 5 hours. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 4 containing polyurethane 4 .
The properties of the obtained polyurethane resin solution 4 were as follows.
・ Resin solid content hydroxyl value: 2.9 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 5) Synthesis of Polyurethane 5 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, and IPDI 16.8 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. After that, 210.5 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 75.3 parts of isopropyl alcohol to the urethane prepolymer solution to obtain 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 added. The mixture was reacted with stirring at ℃ for 5 hours. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 5 containing polyurethane 5 .
The properties of the obtained polyurethane resin solution 5 were as follows.
・ Resin solid content hydroxyl value: 5.0 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 6) Synthesis of Polyurethane 6 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, and IPDI 16.8 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. After that, 210.5 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 80.2 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 4.0 parts of AEEA and 9.3 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 6 containing polyurethane 6 .
The properties of the obtained polyurethane resin solution 6 were as follows.
・ Resin solid content hydroxyl value: 18.8 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 7) Synthesis of Polyurethane 7 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, and IPDI 22.7 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. After that, 221.0 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 77.7 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 7.0 parts of AEEA and 16.3 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 7 containing polyurethane 7 .
The properties of the obtained polyurethane resin solution 7 were as follows.
・ Resin solid content hydroxyl value: 29.6 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 60,000
- Weight average molecular weight of resin solid content: 120,000
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 8) Synthesis of Polyurethane 8 A polyester polyol (hydroxyl value: 29 mg KOH / g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mg KOH / g) 5.4 parts, dimethylolbutanoic acid (hereinafter abbreviated as DMBA) 2.7 parts, and IPDI 21.4 parts were charged, nitrogen The mixture was allowed to react at 90° C. for 10 hours under an air current to produce a urethane prepolymer, and 217.3 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 79.3 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 6.9 parts of IPDA and 16.1 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 8 containing polyurethane 8 .
The characteristic values of the obtained polyurethane resin solution 8 were as follows.
・ Resin solid content hydroxyl value: 1.7 mg KOH / g
・ Resin solid content acid value: 9.4 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 9) Synthesis of Polyurethane 9 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, DMBA 2.7 parts, and IPDI 21.4 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream. After the urethane prepolymer was produced, 217.3 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 79.5 parts of isopropyl alcohol to the urethane prepolymer solution to make a uniform solution, a mixed solution of 6.5 parts of IPDA, 0.3 parts of AEEA, and 15.9 parts of isopropyl alcohol was added, The mixture was reacted with stirring at ℃ for 5 hours. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 9 containing polyurethane 9 .
The characteristic values of the obtained polyurethane resin solution 9 were as follows.
・ Resin solid content hydroxyl value: 2.7 mg KOH / g
・ Resin solid content acid value: 9.4 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 10) Synthesis of Polyurethane 10 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, DMBA 2.7 parts, and IPDI 21.4 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream. After the urethane prepolymer was produced, 217.3 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, 80.5 parts of isopropyl alcohol was added to the urethane prepolymer solution to make a uniform solution, and then a mixed solution of 5.6 parts of IPDA, 0.8 parts of AEEA, and 14.9 parts of isopropyl alcohol was added. The mixture was reacted with stirring at ℃ for 5 hours. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added, and the mixture was reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 10 containing polyurethane 10 .
The characteristic values of the obtained polyurethane resin solution 10 were as follows.
・ Resin solid content hydroxyl value: 4.8 mg KOH / g
・ Resin solid content acid value: 9.4 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 11) Synthesis of Polyurethane 11 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, DMBA 2.7 parts, and IPDI 21.4 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream. After the urethane prepolymer was produced, 217.3 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 95.4 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 4.2 parts of AEEA and 9.8 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 11 containing polyurethane 11 .
The characteristic values of the obtained polyurethane resin solution 11 were as follows.
・ Resin solid content hydroxyl value: 15.7 mg KOH / g
・ Resin solid content acid value: 9.4 mg KOH / g
・ Number average molecular weight of resin solid content: 15,300
- Weight average molecular weight of resin solid content: 55,600
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 12) Synthesis of Polyurethane 12 A polyester polyol (hydroxyl value: 29 mgKOH/g) 100.0 parts, polyethylene glycol (hydroxyl value: 112 mgKOH/g) 5.4 parts, DMBA 2.7 parts, and IPDI 27.7 parts were charged and reacted at 90°C for 10 hours under a nitrogen stream. After producing a urethane prepolymer, 234.2 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 83.1 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 7.4 parts of AEEA and 17.3 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.3 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 12 containing polyurethane 12 .
The characteristic values of the obtained polyurethane resin solution 10 were as follows.
・ Resin solid content hydroxyl value: 29.5 mg KOH / g
・ Resin solid content acid value: 9.5 mg KOH / g
・ Number average molecular weight of resin solid content: 60,000
- Weight average molecular weight of resin solid content: 120,000
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 13) Synthesis of Polyurethane 13 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 3-methyl-1,5-pentanediol and adipic acid were added as starting materials to a polyester polyol. (Hydroxyl value: 55 mgKOH/g) 100.0 parts of DMBA, 6.7 parts of DMBA, and 38.1 parts of IPDI were charged and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer. 243.9 parts of ethyl acetate was added to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
Next, after adding 109.0 parts of isopropyl alcohol to the urethane prepolymer solution to obtain a uniform solution, a mixed solution of 6.2 parts of AEEA and 14.5 parts of isopropyl alcohol was added, and the mixture was stirred and reacted at 40°C for 5 hours. Ta. After that, a mixed solution of 0.2 parts of MEA and 0.7 parts of isopropyl alcohol was added and reacted with stirring at 40° C. for 2 hours to obtain a polyurethane resin solution 13 containing polyurethane 13 .
The characteristic values of the obtained polyurethane resin solution 13 were as follows.
・ Resin solid content hydroxyl value: 17.9 mg KOH / g
・ Resin solid content acid value: 18.2 mg KOH / g
・ Number average molecular weight of resin solid content: 10,100
- Weight average molecular weight of resin solid content: 30,300
・ Resin solid content amine value: 0.00 mg KOH / g
・ Resin solid content concentration: 30.3% by mass

(Synthesis Example 14) Synthesis of Polyurethane 14 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 2-methyl-1,3-propanediol and adipic acid were added as starting materials to a polyester polyol. (Hydroxyl value: 56 mgKOH/g) 80.0 parts, polyethylene glycol (hydroxyl value: 277 mgKOH/g) 20.0 parts, and IPDI 25.4 parts were charged and reacted at 90°C for 20 hours under a stream of nitrogen to obtain urethane. After the prepolymer was produced, 83.6 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
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 reaction was stirred at 45° C. for 5 hours to produce polyurethane 14. A polyurethane resin solution 14 was obtained.
The characteristic values of the obtained polyurethane resin solution 14 were as follows.
・ Resin solid content hydroxyl value: 0.0 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 48,600
- Weight average molecular weight of resin solid content: 88,000
・ Resin solid content amine value: 2.10 mg KOH / g
・ Resin solid content concentration: 30.2% by mass

(Synthesis Example 15) Synthesis of Polyurethane 15 2-methyl-1,3-propanediol and 3-methyl-1,5- were placed in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube. 100.0 parts of a polyester polyol (hydroxyl value: 22 mgKOH/g) made from pentanediol, neopentyl glycol and adipic acid and 9.2 parts of IPDI were charged and reacted at 100°C for 10 hours under a stream of nitrogen to obtain urethane. After the prepolymer was produced, 72.8 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer (urethane prepolymer solution).
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 reaction was stirred at 45°C for 5 hours to produce polyurethane 15. A polyurethane resin solution 15 was obtained.
The characteristic values of the obtained polyurethane resin solution 15 were as follows.
・ Resin solid content hydroxyl value: 0.0 mg KOH / g
・ Resin solid content acid value: 0.0 mg KOH / g
・ Number average molecular weight of resin solid content: 52,700
- Weight average molecular weight of resin solid content: 95,400
・ Resin solid content amine value: 2.40 mg KOH / g
・ Resin solid content concentration: 29.7% by mass

The properties of the polyurethanes obtained in Synthesis Examples 1 to 15 are summarized in Tables 1 to 3.

(Example 1)
40 parts of N-propyl acetate (normal propyl acetate), 10 parts of ethyl acetate, 11 parts of indigo pigment, 3 parts of vinyl chloride vinyl acetate resin (vinyl chloride/vinyl acetate copolymer resin), 6 parts of isopropyl alcohol, 1 part of dispersant, and 129 parts of the polyurethane resin solution prepared in Synthesis Example 1 was mixed to obtain a mixture.
For 100 parts of the resulting mixture, 42% IPA / EtAc mixed solvent (isopropyl alcohol / ethyl acetate = 50/50 (part/part)) was added to prepare a film-forming composition.

The prepared film-forming composition was subjected to the following evaluations. Table 4 shows the results.

<Evaluation item 1: Viscosity stability>
The resulting film-forming composition was placed in a sealed container and allowed to stand at 25° C. for 24 hours. After being left for 24 hours, the viscosity of the film-forming composition was measured with a Zahn cup #3 and evaluated according to the following evaluation criteria.
[Evaluation criteria]
3: No noticeable increase in viscosity after standing for 24 hours.
2: Remarkable viscosity increase was observed after standing for 24 hours, but the original viscosity was restored by stirring.
1: Remarkable increase in viscosity was observed after standing still for 24 hours, and increase in viscosity was observed even after re-stirring.

<Evaluation Item 2: Substrate Adhesion>
The prepared film-forming composition is printed with a solid pattern of 240 mm long × 80 mm wide on the substrate A using a bar coater #4, and then dried with a dryer to form a printed layer 1, and a printed matter having the following configuration 1 got
<<Composition of printed materials>>
・ Configuration 1: Base material A - printed layer 1
Base material A: Corona-treated polyethylene terephthalate film (Ester E5100, thickness 12 μm, manufactured by Toyobo Co., Ltd.) (PET)

The resulting print was left for 24 hours or immediately, then a 5 cm piece of cellophane tape (made by Nichiban Co., Ltd., 12 mm wide) was attached to the printed surface, and one end of the cellophane tape was quickly peeled off in a direction perpendicular to the printed surface. The residual rate of , was determined visually based on the area ratio.
[Evaluation criteria]
5: The printed film is not peeled off at all.
4: 80% or more of the printed film remained on the film.
3: 50% or more to less than 80% of the printed film remained on the film.
2: Less than 50% of the printed film remained on the film.
1: When sticking the cellophane tape, the printed film peels off from the film to the cellophane tape.

<Evaluation Item 3: Peelability>
The prepared film-forming composition is printed with a solid pattern of 240 mm long × 80 mm wide on the substrate A using a bar coater #4, and then dried with a dryer to form a printed layer 1, and a printed matter having the following configuration 1 got
<<Composition of printed materials>>
・ Configuration 1: Base material A - printed layer 1
Base material A: Corona-treated polyethylene terephthalate film (Ester E5100, thickness 12 μm, manufactured by Toyobo Co., Ltd.) (PET)

<<Alkaline Solution>>
A peeling test was conducted under the following conditions to compare the easiness of peeling under each condition.
・ Sodium hydroxide 1 mass%, surfactant 0.3%, 85 ° C.
・ Sodium hydroxide 1% by mass, no surfactant, 85 ° C.
Here, a nonionic surfactant was used as the surfactant.

<<Peel test conditions>>
The peeling test was evaluated with a treatment time of 15 minutes under each condition. If the film is peeled off within 5 minutes of treatment, it indicates that the performance is quite high.
A test piece obtained by cutting the printed matter into a size of 20 mm×20 mm was immersed in the solution and stirred with a stirrer. After confirming the peeling state after stirring, the printed material was rubbed with a finger, and it was also confirmed whether the coating film was peeled off by rubbing.
The peelability of the ink coating film under the above conditions was evaluated according to the following evaluation criteria.

[Evaluation criteria]
5: Detachment of the ink film was confirmed by stirring within 5 minutes. Completely detached by rubbing 4: Detachment of the ink film was confirmed by stirring for 15 minutes. Completely detached by rubbing 3: Detachment of the ink film was not confirmed by stirring for 15 minutes. Completely detached by rubbing 2: Detachment of the ink film was not confirmed after stirring for 15 minutes. Partially detached by rubbing 1: No detachment of the ink film after stirring for 15 minutes. Detachment has not been confirmed even by rubbing

(Examples 2 to 16 and Comparative Examples 1 to 5)
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 those shown in Tables 4 to 7 below.
The prepared film-forming composition was evaluated in the same manner as in Example 1. The results are shown in Tables 4-7.

The formulations of the film-forming compositions and the evaluation results are shown in Tables 4 to 7 below.

As described above, by using the film-forming composition of the present invention, it is possible to form a film that can be easily detached by treatment with an alkaline solution and that can be easily removed from a plastic substrate. , it is possible to form a film having excellent adhesion to the substrate.

Claims (12)

A detachable film-forming composition for forming a detachable film on the surface of a substrate A directly or via another layer by treatment with an alkaline solution,
Film formation comprising a urethane resin having a hydroxyl value, a weight average molecular weight of 45,000 or more and a number average molecular weight of 10,000 or more, wherein the urethane resin has an acid value of 10.0 mgKOH/g or less . composition. 2. The film-forming composition according to claim 1, wherein the hydroxyl value is from 1.0 mgKOH/g to 30.0 mgKOH/g. 2. The film-forming composition according to claim 1, wherein the urethane resin contains at least one of polyester polyol and polyether polyol as a constituent component. The film-forming composition according to claim 1, which contains a coloring agent. 5. The film-forming composition according to claim 4, which is used as a printing ink. 6. The film-forming composition according to claim 5, wherein the printing ink is an organic solvent-based ink. The film-forming composition according to claim 1, which is used as a primer or varnish. A printed matter having a film comprising the film-forming composition according to any one of claims 1 to 7 directly or via another layer on the surface of a substrate A. 9. The printed matter according to claim 8, wherein the film is at least one selected from a printing layer, a primer layer and a varnish layer. With respect to the printed material according to claim 9, a base material B is arranged on the surface of the printed layer opposite to the surface on which the base material A is arranged, and the printed material and the base material B are laminated. Laminate formed by A method for producing a recycled base material A obtained by treating the printed matter according to claim 9 with an alkaline solution to detach the film from the base material A. A method for producing a recycled base material A obtained by treating the laminate according to claim 10 with an alkaline solution to desorb the base material B together with the film.