Organic solvent-based composition for forming a removable film

Abstract

The present invention provides an organic solvent-based composition that can adhere to a substrate and form a film that can be removed from the substrate by treatment with warm water or an alkaline solution, as well as a laminate having a film formed using this organic solvent-based composition and a method for producing a recycled substrate obtained by removing the film. This problem can be solved by using an organic solvent-based composition having an acid value of 1 to 150 mgKOH / g in the solids. The organic solvent-based composition preferably contains an acidic additive, and the acid value of the acidic additive is preferably 3 to 900 mgKOH / g.

Description

Technical Field

[0001] The present invention relates to an organic solvent-based composition that can be used to form a film that can be releasable from a substrate. Background Art

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

[0003] Furthermore, considering the impact on operator health and the environment, there is a move to replace organic solvent-based printing inks, which are widely used as film-forming materials for plastic substrates, with toluene-free and methyl ethyl ketone (MEK-free) inks. Therefore, the development of materials to address these issues also needs to take this into consideration.

[0004] Prior art discloses methods for removing a coating containing styrene-acrylic resin, phenolic resin, or styrene-maleic acid resin as a coating material printed on a heat-shrinkable PET film using alkaline water (Patent Document 1). Similarly, methods disclose methods for applying a coating containing styrene-maleic acid resin, rosin-maleic acid resin, or an acrylic copolymer resin between the coating layers of the heat-shrinkable PET film and removing the coating using alkaline water (Patent Documents 2 and 3). However, these technologies have limitations, such as ensuring properties only for specific substrates and requiring coatings other than the coating layer, making them unsuitable for recycling general-purpose plastic substrates including polyolefins. On the other hand, organic solvent-based printing inks for alkaline water removal using a urethane resin with an acid value as a binder resin have also been disclosed (Patent Documents 4 and 5). However, when a carbamate resin having an acid value is used as the main binder resin, it is estimated that the adhesion to the substrate is insufficient. In addition, there will be problems such as increasing the viscosity of the resin due to the acid value given to the carbamate resin, and having to use the above-mentioned solvents that have a great impact on health and the environment in order to adjust the viscosity. Therefore, there are still issues in the widespread use of it as a film-forming material that can be removed from the film.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 3822738

[0008] Patent Document 2: Japanese Patent No. 4653913

[0009] Patent Document 3: Japanese Patent No. 4451071

[0010] Patent Document 4: Japanese Patent No. 6638802

[0011] Patent Document 5: Japanese Patent No. 6631964 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] The problem to be solved by the present invention is to provide an organic solvent-based composition that can be adhered to a substrate and can form a film that can be removed from the substrate by treatment with warm water or an alkaline solution, and to provide a laminate having a film formed using the organic solvent-based composition, and a method for producing a recycled substrate obtained by removing the film.

[0014] Means for solving problems

[0015] The inventors have conducted intensive studies to solve the above-mentioned problems and have found that the object can be achieved by adjusting the acid value of the solid content of the organic solvent-based composition to within a specific range.

[0016] That is, the present invention includes the following contents.

[0017] [1] An organic solvent-based composition for forming a film on the surface of a substrate A or on the surface thereof that is removable by treatment with warm water or an alkaline solution, wherein the acid value of the solid content of the organic solvent-based composition is 1 to 150 mgKOH / g.

[0018] [2] The organic solvent-based composition according to [1], which contains an acidic additive.

[0019] [3] The organic solvent-based composition according to [2], wherein the acid value of the acidic additive is 3 to 900 mgKOH / g.

[0020] [4] The organic solvent-based composition according to [2] or [3], wherein the molecular weight of the acidic additive is 50 to 1500.

[0021] [5] The organic solvent-based composition according to any one of [2] to [4], wherein the acidic additive is at least one selected from a resin having an acidic group and an organic acid.

[0022] [6] The organic solvent-based composition according to [5], wherein the acid value of the resin having an acidic group is 3 to 300 mgKOH / g.

[0023] [7] The organic solvent-based composition according to [5] or [6], wherein the resin having an acidic group is at least one selected from rosin-modified maleic acid resin, rosin-modified fumaric acid resin, and styrene-maleic acid (anhydride) resin.

[0024] [8] The organic solvent-based composition according to any one of [1] to [7], which contains a urethane resin or an acrylic resin.

[0025] [9] The organic solvent composition according to any one of [1] to [8], which contains an ester organic solvent having 5 or more carbon atoms.

[0026]

[10] The organic solvent-based composition according to any one of [1] to [9], which contains a colorant.

[0027]

[11] The organic solvent-based composition according to any one of [1] to

[10] , which is used as a printing ink, a primer, or an OPV.

[0028]

[12] A printed article having a film formed by printing the organic solvent-based composition described in any one of [1] to

[11] on the surface of a substrate A or on the surface thereof.

[0029]

[13] A laminated body in which the printed material described in

[12] is laminated in such a manner that the substrate B is arranged on the film side.

[0030]

[14] A method for producing a recycled substrate A, wherein the printed material described in

[12] is treated with warm water or an alkaline solution to remove the film from the substrate A to obtain the recycled substrate A.

[0031]

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

[13] is treated with warm water or an alkaline solution to remove the substrate B together with the film to obtain the recycled substrate A.

[0032] Effects of the Invention

[0033] According to the present invention, a film that can be adhered to and released from a substrate can be formed. In addition, the organic solvent-based composition can be prepared without substantially containing toluene or MEK, which may be harmful to health and the environment. DETAILED DESCRIPTION

[0034] The embodiments of the present invention described below merely illustrate a part of the embodiments of the present invention, and the present invention is not limited to the contents described herein unless it significantly deviates from the gist of the present invention.

[0035] (Organic solvent composition)

[0036] The present invention is an organic solvent-based composition for forming a film on the surface of a substrate A or on the surface thereof that is removable by treatment with warm water or an alkaline solution, wherein the acid value of the solid content of the organic solvent-based composition is 1 to 150 mgKOH / g.

[0037] In this specification, the organic solvent-based composition refers to a composition containing a solvent as an organic solvent and a resin.

[0038] The substrate A will be described later in the section (Printed material and laminated body).

[0039] The releasability using warm water or an alkaline solution will be described in the section (Method of Removing the Film from the Base Material A) described later.

[0040] The formation of the film will be described in the section (Printing on a Substrate) described later.

[0041] The acid value of the solids content of the organic solvent-based composition can be calculated based on the acid value of the raw materials. If calculation is not possible, it can be determined by forming an ink film and measuring it after drying. It should be noted that if the acid value has been published, that value will be used; otherwise, it will be measured in accordance with JIS 0070-1992.

[0042] The acid value in the solid content of the above-mentioned organic solvent-based composition is 1 mgKOH / g or more, but preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, more preferably 35 mgKOH / g or more. In addition, the above-mentioned acid value is 150 mgKOH / g or less, but more preferably 140 mgKOH / g or less, more preferably 130 mgKOH / g or less, more preferably 120 mgKOH / g or less, more preferably 110 mgKOH / g or less, more preferably 100 mgKOH / g or less, more preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, more preferably 70 mgKOH / g or less. By setting it to the above range, it is possible to take into account both the detachability from warm water or alkaline solution and the adhesion to the substrate.

[0043] Furthermore, when emphasis is placed on releasability with warm water or an alkaline solution, the viscosity is preferably 35 mgKOH / g or greater, more preferably 40 mgKOH / g or greater, more preferably 45 mgKOH / g or greater, more preferably 50 mgKOH / g or greater, more preferably 55 mgKOH / g or greater, more preferably 60 mgKOH / g or greater, more preferably 65 mgKOH / g or greater, and more preferably 70 mgKOH / g or greater. When emphasis is placed on adhesion to the substrate, the viscosity is preferably 70 mgKOH / g or less, more preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, and more preferably 35 mgKOH / g or less. When both the releasability from warm water or alkaline solution and the adhesion to the substrate are emphasized, the acid value range is 1 to 150 mgKOH / g, more preferably 1 to 140 mgKOH / g, more preferably 3 to 130 mgKOH / g, more preferably 5 to 120 mgKOH / g, more preferably 10 to 110 mgKOH / g, more preferably 15 to 100 mgKOH / g, more preferably 20 to 90 mgKOH / g, more preferably 25 to 80 mgKOH / g, more preferably 30 to 70 mgKOH / g, and more preferably 35 to 70 mgKOH / g.

[0044] Furthermore, when emphasis is placed on releasability with warm water or an alkaline solution, the content is more preferably 35 to 150 mgKOH / g, more preferably 40 to 150 mgKOH / g, more preferably 45 to 150 mgKOH / g, more preferably 50 to 150 mgKOH / g, more preferably 55 to 150 mgKOH / g, more preferably 60 to 150 mgKOH / g, more preferably 65 to 150 mgKOH / g, and more preferably 70 to 150 mgKOH / g. Furthermore, when emphasis is placed on adhesion to the substrate, the content is more preferably 1 to 70 mgKOH / g, more preferably 1 to 60 mgKOH / g, more preferably 1 to 50 mgKOH / g, more preferably 1 to 40 mgKOH / g, and more preferably 1 to 35 mgKOH / g.

[0045] The organic solvent-based composition of the present invention may further contain an acidic additive and an organic solvent.

[0046] <Acidic additives>

[0047] For example, an organic acid or a resin having an acidic group can be used as the acidic additive.

[0048] The acid value of the acidic additive is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more. In addition, the acid value is preferably 900 mgKOH / g or less, more preferably 850 mgKOH / g or less, more preferably 800 mgKOH / g or less, more preferably 750 mgKOH / g or less, more preferably 700 mgKOH / g or less, more preferably 650 mgKOH / g or less, more preferably 600 mgKOH / g or less, more preferably 550 mgKOH / g or less. By setting it to the above range, it is possible to take into account both the releasability from warm water or alkaline solution and the adhesion to the substrate.

[0049] Furthermore, when emphasis is placed on releasability with warm water or an alkaline solution, the density is preferably 50 mgKOH / g or greater, more preferably 100 mgKOH / g or greater, more preferably 200 mgKOH / g or greater, more preferably 300 mgKOH / g or greater, more preferably 400 mgKOH / g or greater, more preferably 500 mgKOH / g or greater, and particularly preferably 550 mgKOH / g or greater. When emphasis is placed on adhesion to the substrate, the density is preferably 550 mgKOH / g or less, more preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and more preferably 200 mgKOH / g or less.

[0050] When both releasability from warm water or alkaline solution and adhesion to the substrate are emphasized, the acid value range is preferably 1 to 900 mgKOH / g, more preferably 3 to 850 mgKOH / g, more preferably 5 to 800 mgKOH / g, more preferably 10 to 750 mgKOH / g, more preferably 20 to 700 mgKOH / g, more preferably 30 to 650 mgKOH / g, more preferably 40 to 600 mgKOH / g, and more preferably 50 to 550 mgKOH / g.

[0051] When emphasis is placed on releasability with warm water or an alkaline solution, the density is preferably 50 to 900 mgKOH / g, preferably 65 to 900 mgKOH / g, preferably 80 to 900 mgKOH / g, more preferably 100 to 900 mgKOH / g, more preferably 200 to 900 mgKOH / g, more preferably 300 to 900 mgKOH / g, more preferably 400 to 900 mgKOH / g, more preferably 500 to 900 mgKOH / g, and more preferably 550 to 900 mgKOH / g. When emphasis is placed on adhesion to the substrate, the density is preferably 1 to 550 mgKOH / g, more preferably 1 to 500 mgKOH / g, more preferably 1 to 400 mgKOH / g, more preferably 1 to 300 mgKOH / g, and more preferably 1 to 200 mgKOH / g.

[0052] In order to balance the releasability from warm water or alkaline solutions and the adhesion to the substrate, the molecular weight of the acidic additive is preferably 50 or more, preferably 60 or more, preferably 80 or more, preferably 100 or more, preferably 150 or more, preferably 200 or more, preferably 250 or more, and preferably 300 or more. Furthermore, it is preferably 2000 or less, preferably 1800 or less, preferably 1500 or less, preferably 1200 or less, and preferably 1000 or less. The molecular weight range is preferably 50 to 2000, preferably 50 to 1800, preferably 50 to 1500, preferably 60 to 1500, preferably 80 to 1500, preferably 100 to 1500, preferably 150 to 1500, preferably 200 to 1500, preferably 250 to 1500, preferably 300 to 1500, preferably 300 to 1200, and preferably 300 to 1000.

[0053] The organic acid is a low molecular weight organic compound having an acidic group. Examples of the low molecular weight compound having an acidic group include saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives, which can be used alone or in combination.

[0054] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid. Examples of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, and azelaic acid. Examples of tricarboxylic acids include aconitic acid and trimer acid. Examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination. In addition, citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid satisfy the so-called Swiss Ordinance, and it is preferred to use substances that satisfy various restrictions.

[0055] The acid value of the organic acid is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, more preferably 70 mgKOH / g or more, more preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, the acid value is preferably 900 mgKOH / g or less, more preferably 850 mgKOH / g or less, more preferably 800 mgKOH / g or less, more preferably 750 mgKOH / g or less, more preferably 700 mgKOH / g or less, more preferably 650 mgKOH / g or less, more preferably 600 mgKOH / g or less, and more preferably 550 mgKOH / g or less. By setting it within the above range, both the releasability from warm water or alkaline solution and the adhesion to the substrate can be achieved.

[0056] Furthermore, when emphasis is placed on releasability with warm water or an alkaline solution, the density is preferably 100 mgKOH / g or more, more preferably 150 mgKOH / g or more, more preferably 200 mgKOH / g or more, more preferably 250 mgKOH / g or more, more preferably 300 mgKOH / g or more, more preferably 350 mgKOH / g or more, more preferably 400 mgKOH / g or more, more preferably 450 mgKOH / g or more, more preferably 500 mgKOH / g or more, and more preferably 550 mgKOH / g or more. When emphasis is placed on adhesion to the substrate, the density is preferably 550 mgKOH / g or less, more preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and more preferably 200 mgKOH / g or less.

[0057] When both releasability from warm water or alkaline solution and adhesion to the substrate are emphasized, the acid value range is preferably 1 to 900 mgKOH / g, more preferably 3 to 850 mgKOH / g, more preferably 10 to 800 mgKOH / g, more preferably 20 to 750 mgKOH / g, more preferably 30 to 700 mgKOH / g, more preferably 50 to 650 mgKOH / g, more preferably 80 to 600 mgKOH / g, and more preferably 100 to 550 mgKOH / g. When emphasis is placed on releasability with warm water or an alkaline solution, the preferred concentration is 100 to 900 mgKOH / g, more preferably 150 to 900 mgKOH / g, more preferably 200 to 900 mgKOH / g, more preferably 250 to 900 mgKOH / g, more preferably 300 to 900 mgKOH / g, more preferably 350 to 900 mgKOH / g, more preferably 400 to 900 mgKOH / g, more preferably 450 to 900 mgKOH / g, more preferably 500 to 900 mgKOH / g, and more preferably 550 to 900 mgKOH / g. When emphasis is placed on adhesion to the substrate, the preferred concentration is 1 to 550 mgKOH / g, more preferably 1 to 500 mgKOH / g, more preferably 1 to 400 mgKOH / g, more preferably 1 to 300 mgKOH / g, and more preferably 1 to 200 mgKOH / g.

[0058] The number of carbon atoms of the organic acid is preferably 3 or more, preferably 4 or more, preferably 5 or more, preferably 6 or more, preferably 7 or more, and preferably 8 or more. By setting the number of carbon atoms of the organic acid to the above range, the adhesion to the substrate can be improved. In addition, the number of carbon atoms of the organic acid is preferably 20 or less, preferably 18 or less, and preferably 16 or less. By setting the number of carbon atoms of the organic acid to the above range, the dispersibility with the aqueous medium can be improved. The range of the number of carbon atoms of the organic acid is preferably 3 to 20, preferably 3 to 18, preferably 4 to 18, preferably 5 to 18, preferably 6 to 18, preferably 6 to 16, preferably 7 to 16, and preferably 8 to 16.

[0059] When emphasis is placed on releasability from the substrate and water resistance of the film, the solubility of the organic acid in 100 g of water at 25°C is preferably less than 2 g, more preferably less than 1.8 g, further preferably less than 1.5 g, and particularly preferably less than 1.2 g.

[0060] Examples of the resin having an acidic group include cellulose resins, urethane resins (including polyurethane, polyurea, or polyurethane polyurea. The same shall apply hereinafter), polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, petroleum resins, and the like. Resins having acidic groups include (meth)acrylic resins obtained by copolymerizing polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers having sulfonic acid groups such as sulfonated styrene, and polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide, free radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, and terpene-maleic acid (anhydride) resins, and acid-modified polyolefin resins. These resins can be used alone or in combination. More preferred examples of the resins having acidic groups include urethane resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, and styrene-maleic acid (anhydride) resins.

[0061] The acid value of the resin having an acidic group is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. In addition, the acid value is preferably 300 mgKOH / g or less, more preferably 280 mgKOH / g or less, more preferably 260 mgKOH / g or less, more preferably 240 mgKOH / g or less, more preferably 220 mgKOH / g or less, and more preferably 200 mgKOH / g or less. By setting it to the above range, it is possible to take into account both the releasability from warm water or alkaline solution and the adhesion to the substrate.

[0062] Furthermore, when emphasis is placed on releasability with warm water or an alkaline solution, the density is preferably 50 mgKOH / g or greater, more preferably 60 mgKOH / g or greater, more preferably 70 mgKOH / g or greater, more preferably 80 mgKOH / g or greater, more preferably 90 mgKOH / g or greater, and particularly preferably 100 mgKOH / g or greater. When emphasis is placed on adhesion to the substrate, the density is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, more preferably 160 mgKOH / g or less, more preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. When both the releasability from warm water or alkaline solution and the adhesion to the substrate are emphasized, the acid value range is preferably 1 to 300 mgKOH / g, preferably 3 to 300 mgKOH / g, preferably 5 to 280 mgKOH / g, more preferably 10 to 260 mgKOH / g, more preferably 20 to 240 mgKOH / g, more preferably 30 to 220 mgKOH / g, more preferably 40 to 200 mgKOH / g, and more preferably 50 to 200 mgKOH / g.

[0063] When emphasis is placed on releasability with warm water or an alkaline solution, the preferred concentration is 50 to 300 mgKOH / g, more preferably 60 to 300 mgKOH / g, more preferably 70 to 300 mgKOH / g, more preferably 80 to 300 mgKOH / g, more preferably 90 to 300 mgKOH / g, and more preferably 100 to 300 mgKOH / g. When emphasis is placed on adhesion to the substrate, the preferred concentration is 1 to 200 mgKOH / g, more preferably 1 to 180 mgKOH / g, more preferably 1 to 160 mgKOH / g, more preferably 1 to 140 mgKOH / g, more preferably 1 to 120 mgKOH / g, and more preferably 1 to 100 mgKOH / g.

[0064] When the resin having an acidic group is a urethane resin, the weight average molecular weight of the resin having an acidic group is preferably 500 or more, more preferably 1000 or more, more preferably 2000 or more, more preferably 3000 or more, more preferably 4000 or more, more preferably 5000 or more, more preferably 6000 or more, more preferably 7000 or more, more preferably 8000 or more, and more preferably 10000 or more. By setting the weight average molecular weight of the resin having an acidic group within the above range, a balance can be achieved between adhesion to the substrate and releasability with warm water or an alkaline solution.

[0065] Furthermore, when the resin having an acidic group is a urethane resin, the weight average molecular weight of the resin having an acidic group is preferably 100,000 or less, more preferably 50,000 or less, more preferably 40,000 or less, more preferably 30,000 or less, more preferably 25,000 or less, more preferably 20,000 or less, and more preferably 18,000 or less. By setting the weight average molecular weight of the resin having an acidic group within the above range, the viscosity of the organic solvent-based composition of the present invention can be reduced, and a balance can be achieved between adhesion to a substrate and releasability with warm water or an alkaline solution.

[0066] When the resin having an acidic group is a urethane resin, the weight-average molecular weight of the resin having an acidic group is preferably within a range of 500 to 100,000, more preferably 1,000 to 50,000, more preferably 2,000 to 50,000, more preferably 3,000 to 50,000, more preferably 4,000 to 50,000, more preferably 5,000 to 40,000, more preferably 5,000 to 30,000, more preferably 6,000 to 30,000, more preferably 6,000 to 25,000, more preferably 7,000 to 25,000, more preferably 7,000 to 20,000, more preferably 8,000 to 20,000, more preferably 10,000 to 20,000, and more preferably 10,000 to 18,000. By setting the weight-average molecular weight of the resin having an acidic group within the above range, printability can be improved.

[0067] When the resin having an acidic group is a (meth)acrylic resin, the weight average molecular weight of the resin having an acidic group is preferably 1,000 or more, more preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, more preferably 20,000 or more, more preferably 50,000 or more, and more preferably 100,000 or more. By setting the weight average molecular weight of the resin having an acidic group within the above range, a balance can be achieved between adhesion to the substrate and releasability with warm water or an alkaline solution.

[0068] Furthermore, when the resin having an acidic group is a (meth)acrylic resin, the weight average molecular weight of the resin having an acidic group is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. By setting the weight average molecular weight of the resin having an acidic group within the above range, the viscosity of the organic solvent-based composition of the present invention can be reduced, and a balance can be achieved between adhesion to a substrate and releasability with warm water or an alkaline solution.

[0069] When the resin having an acidic group is a (meth)acrylic resin, the weight-average molecular weight of the resin having an acidic group is preferably in the range of 3,000 to 1,000,000, more preferably 5,000 to 500,000, more preferably 10,000 to 200,000, and even more preferably 20,000 to 100,000. By setting the weight-average molecular weight of the resin having an acidic group within the above range, printability can be improved.

[0070] When the resin having an acidic group is a resin having an acid value such as a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin, the weight average molecular weight of the resin having an acidic group is preferably 500 or greater, more preferably 700 or greater, and even more preferably 1000 or greater. By setting the weight average molecular weight of the resin having an acidic group within the above range, a balance can be achieved between adhesion to the substrate and releasability with warm water or an alkaline solution.

[0071] Furthermore, when the resin having an acidic group is a resin having an acid value such as a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin, the weight-average molecular weight of the resin having an acidic group is preferably 50,000 or less, more preferably 30,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 2,000 or less. By setting the weight-average molecular weight of the resin having an acidic group within the above range, the viscosity of the ink can be reduced, and a balance can be achieved between adhesion to the substrate and releasability with warm water or an alkaline solution.

[0072] The weight-average molecular weight of the acidic group-containing resin, when the acidic group-containing resin is a resin having an acid value such as a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin, is preferably 500 to 50,000, more preferably 700 to 520,000, even more preferably 1,000 to 10,000, and even more preferably 1,000 to 5,000. By setting the weight-average molecular weight of the acidic group-containing resin within the above range, printability can be improved.

[0073] When the resin having an acidic group is a styrene-maleic acid (anhydride) resin, the weight average molecular weight of the resin having an acidic group is preferably 500 or more, more preferably 700 or more, and even more preferably 1000 or more. By setting the weight average molecular weight of the resin having an acidic group within the above range, a balance can be achieved between adhesion to the substrate and releasability with warm water or an alkaline solution.

[0074] In addition, when the resin having an acidic group is a styrene-maleic acid (anhydride) resin, the weight average molecular weight of the resin having an acidic group is preferably 100,000 or less, more preferably 70,000 or less, more preferably 50,000 or less, and more preferably 30,000 or less. By setting the weight average molecular weight of the resin having an acidic group within the above range, the viscosity of the organic solvent-based composition of the present invention can be reduced, and a balance can be achieved between adhesion to a substrate and releasability with warm water or an alkaline solution.

[0075] When the resin having an acidic group is a styrene-maleic acid (anhydride) resin, the weight-average molecular weight of the resin having an acidic group is preferably in the range of 500 to 100,000, more preferably 700 to 30,000, more preferably 1,000 to 50,000, and even more preferably 1,000 to 30,000. By setting the weight-average molecular weight of the resin having an acidic group within the above range, printability can be improved.

[0076] From the perspectives of the redissolubility of the organic solvent-based composition of the present invention, suppression of blocking of printed materials, improvement of print density, and adhesion to substrates, the content of the acidic additive as a solid component in the organic solvent-based composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 1.5% by mass or more, more preferably 2% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, and more preferably 50% by mass or less. The range of the content of the acidic additive as a solid component is preferably 0.1 to 60% by mass, more preferably 0.5 to 55% by mass, more preferably 1 to 50% by mass, more preferably 1.5 to 45% by mass, and more preferably 2 to 40% by mass.

[0077] When the acidic additive is an organic acid, the content of the organic acid as a solid content in the organic solvent-based composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.3% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 1.5% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, more preferably 16% by mass or less, more preferably 14% by mass or less, more preferably 12% by mass or less, more preferably 10% by mass or less. The range of the content of the organic acid as a solid content is preferably 0.1 to 20% by mass, more preferably 0.2 to 18% by mass, more preferably 0.3 to 16% by mass, more preferably 0.5 to 14% by mass, more preferably 1 to 12% by mass, more preferably 1.5 to 10% by mass, and more preferably 2 to 10% by mass.

[0078] When the acidic additive is a resin having an acidic group, the content of the resin having an acidic group in the organic solvent-based composition of the present invention, based on solid content, is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 1.5% by mass or more, and more preferably 2% by mass or more, and is preferably 60% by mass or less, more preferably 55% by mass or less, and more preferably 50% by mass or less. The range of the content of the acidic additive based on solid content is preferably 0.1 to 60% by mass, more preferably 0.5 to 55% by mass, more preferably 1 to 50% by mass, more preferably 1.5 to 45% by mass, and more preferably 2 to 40% by mass.

[0079] <Organic Solvents>

[0080] The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, xylene, Solvesso #100, and Solvesso #150; aliphatic hydrocarbons such as hexane, methylcyclohexane, heptane, octane, and decane; and ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. In addition, examples of water-miscible organic solvents include various organic solvents of glycol ethers such as methanol, ethanol, propanol, butanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and ethylene glycol (mono- or di) methyl ether, ethylene glycol (mono- or di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono- or di) methyl ether, diethylene glycol (mono- or di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono- or di) methyl ether, propylene glycol (mono- or di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono- or di) methyl ether. These may be used alone or in combination of two or more.

[0081] As the ester organic solvent, from the viewpoint of preventing the organic solvent-based composition of the present invention from drying out due to its high volatility, it is more preferable to contain an ester organic solvent having 5 or more carbon atoms. The ester organic solvent having 5 or more carbon atoms is not limited, but isopropyl acetate, n-propyl acetate, and butyl acetate are more preferred, and n-propyl acetate is particularly preferred.

[0082] The content of the ester organic solvent in the organic solvent-based composition of the present invention is preferably 1% or more, preferably 3% or more, preferably 5% or more, preferably 7% or more, preferably 10% or more, preferably 12% or more, preferably 15% or more, preferably 18% or more, and preferably 20% or more. Furthermore, it is preferably 35% or less, preferably 32% or less, preferably 30% or less, preferably 28% or less, preferably 25% or less, and preferably 23% or less.

[0083] The content of the ester organic solvent relative to the organic solvent composition of the present invention is preferably 1 to 35%, preferably 3 to 35%, preferably 5 to 32%, preferably 7 to 32%, preferably 10 to 30%, preferably 12 to 30%, preferably 15 to 28%, preferably 18 to 28%, preferably 20 to 25%, and preferably 20 to 23%.

[0084] When the organic solvent-based composition of the present invention is used as a gravure ink, it preferably does not contain an aromatic hydrocarbon organic solvent, but rather contains an alcohol having a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is set to 100. By containing an alcohol having a specific evaporation rate of 100 or less, it is possible to maintain the high gloss transfer property of a dot area of 10% or less and improve the high gloss. The following two points can be cited as the mechanism for this:

[0085] First of all,

[0086] 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.

[0087] 2) The solvent contained in the remaining organic solvent composition of the present invention evaporates before it comes into contact with the organic solvent composition of the present invention in the ink tray again, leaving it in a semi-dry state. Furthermore, since the solvent with the fastest evaporation rate evaporates first, the solvent with the slowest evaporation rate remains in the ink tray.

[0088] 3) At this time, if a solvent with high resin solubility remains, the semi-dried composition will redissolve when it contacts the organic solvent-based composition of the present invention again, thereby preventing the organic solvent-based composition of the present invention from solidifying in the cells.

[0089] In the case of a general-purpose alcohol having a specific evaporation rate exceeding 100 when the evaporation rate of butyl acetate is set to 100, the aforementioned mechanism tends to be less likely to function due to a high volatilization rate.

[0090] Secondly, alcohols having a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is set to 100 tend to increase the solubility of the urethane resin because the ratio of the hydroxyl group (alcohol group) in one alcohol molecule is low.

[0091] Note that, from the perspectives of both hygienic printing operations and toxicity of packaging materials, it is more preferable to use ethyl acetate, propyl acetate, isopropyl alcohol, n-propyl alcohol, etc., and not to use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone.

[0092] Among these, a mixture of isopropyl alcohol / ethyl acetate / n-propyl acetate / methylcyclohexane is more preferred from the viewpoint of solubility in urethane resins and nitrocellulose. Furthermore, glycol ethers may be added to adjust the drying process, as long as the amount is less than 10% by mass of the total composition.

[0093] <Other ingredients>

[0094] Furthermore, the organic solvent-based composition of the present invention may further contain a binder resin, a colorant, an auxiliary agent, and the like.

[0095] Examples of the binder resin include cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, and petroleum resins. These resins can be used in appropriate combinations. Among them, urethane resins, (meth)acrylic resins, rosin resins, and modified products thereof are often used in appropriate combinations.

[0096] For so-called front printing applications in which printing is performed on the surface of the substrate to expose the film, it is preferred to use a carbamate resin, a cellulose resin, a vinyl chloride-vinyl acetate copolymer resin, a polyamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, or a (meth)acrylic resin alone or in combination, and it is more preferred to use a carbamate resin, a (meth)acrylic resin, or a cellulose resin alone or in combination.

[0097] For so-called back printing applications in which a film is arranged between the back side of a substrate and another substrate via an adhesive, it is preferred to use a urethane resin, a cellulose resin, a vinyl chloride-vinyl acetate copolymer resin or a (meth)acrylic resin alone or in combination, and it is more preferred to use a urethane resin alone or in combination.

[0098] The content of the urethane resin in the organic solvent-based composition of the present invention is preferably 5% by mass or more, as converted to solid content, relative to the total mass of the ink, from the viewpoint of ensuring sufficient adhesion of the gravure ink to the printed object, for example, in the case of gravure ink used in gravure printing. From the viewpoint of appropriate ink viscosity and operating efficiency during ink production and printing, it is preferably 25% by mass or less. In the case of flexographic ink used in flexographic printing, it is preferably 5% by mass or more and 30% by mass or less, as converted to solid content, relative to the total mass of the flexographic ink.

[0099] The number average molecular weight of the urethane resin used in the organic solvent-based composition of the present invention is preferably within the range of 15,000 to 100,000. If the number average molecular weight of the urethane resin is less than 15,000, the blocking resistance, lamination strength, chemical resistance, etc. of the resulting ink tend to be low. If the number average molecular weight exceeds 100,000, the viscosity of the resulting ink tends to be high, and a desired print density tends to be impossible to achieve.

[0100] The urethane resin used in the organic solvent-based composition of the present invention preferably uses polyester polyol and / or polyether polyol as a reaction raw material.

[0101] The number average molecular weight of the polyester polyol is preferably 3,000 to 7,000. If the number average molecular weight of the polyester polyol is less than 3,000, the urethane resin film tends to become hard, and adhesion to the polyester film tends to decrease. If the number average molecular weight is greater than 7,000, the urethane resin film tends to become brittle, and the film's blocking resistance tends to decrease. On the other hand, the polyether polyol is preferably 1 to 50 parts by mass relative to 100 parts by mass of the urethane resin. If the polyether polyol is less than 1 part by mass, the solubility of the polyurethane resin in ketone, ester, and alcohol-based solvents decreases, and the adhesion to high-performance barrier films, in particular, tends to decrease. In addition, the re-solubility of the film in the solvent decreases, and the gradation reproducibility of the printed material tends to decrease. Furthermore, if the number average molecular weight is greater than 50 parts by mass, the film becomes too soft, and blocking resistance tends to deteriorate.

[0102] In addition, the number average molecular weight of the said polyester polyol shows the value measured by the gel permeation chromatography (GPC) method under the following conditions.

[0103] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by TOSOH Corporation)

[0104] Chromatographic columns: The following chromatographic columns manufactured by TOSOH Corporation were connected in series and used.

[0105] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 piece

[0106] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 piece

[0107] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 piece

[0108] TSKgel G2000 (7.8mm I.D. x 30cm) x 1 piece

[0109] Detector: RI (differential refractometer)

[0110] Column temperature: 40°C

[0111] Eluent: tetrahydrofuran (THF)

[0112] Flow rate: 1.0 mL / min

[0113] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)

[0114] Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0115] (Standard polystyrene)

[0116] TSKgel Standard Polystyrene A-500, manufactured by TOSOH Corporation

[0117] TSKgel Standard Polystyrene A-1000, manufactured by TOSOH Corporation

[0118] TSKgel Standard Polystyrene A-2500, manufactured by TOSOH Corporation

[0119] TSKgel Standard Polystyrene A-5000, manufactured by TOSOH Corporation

[0120] TSKgel Standard Polystyrene F-1, manufactured by TOSOH Corporation

[0121] TSKgel Standard Polystyrene F-2 manufactured by TOSOH Corporation

[0122] TSKgel Standard Polystyrene F-4, manufactured by TOSOH Corporation

[0123] TSKgel Standard Polystyrene F-10 manufactured by TOSOH Corporation

[0124] TSKgel Standard Polystyrene F-20 manufactured by TOSOH Corporation

[0125] TSKgel Standard Polystyrene F-40 manufactured by TOSOH Corporation

[0126] TSKgel Standard Polystyrene F-80 manufactured by TOSOH Corporation

[0127] TSKgel Standard Polystyrene F-128, manufactured by TOSOH Corporation

[0128] TSKgel Standard Polystyrene F-288, manufactured by TOSOH Corporation

[0129] TSKgel Standard Polystyrene F-550 manufactured by TOSOH Corporation

[0130] For example, polyester polyols obtained by esterifying a compound having two or more hydroxyl groups with a polybasic acid by a known esterification reaction can be used as the polyester polyols.

[0131] The compound having two or more hydroxyl groups is a compound used as a chain extender, and for example, diols such as ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol can be used; 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2- Compounds having a number average molecular weight of 50 to 400 include diols with a branched structure such as isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, and 2-methyl-1,8-octanediol; aliphatic polyols such as trimethylolpropane, trimethylolethane, pentaerythritol, sucrose, methylene glycol, glycerin, and sorbitol; and aromatic polyols such as bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone. These chain extenders may be used alone or in combination of two or more.

[0132] For example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, and anhydrides thereof can be used as the polybasic acid. These polybasic acids can be used alone or in combination of two or more.

[0133] In addition, the number average molecular weight of the above-mentioned polyether polyol is preferably 100 to 4000. Although the details will be described later, as polyether polyols, polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc. can be mentioned. Specifically, it can be polyethylene glycol, polypropylene glycol, poly-1,4-butylene glycol and other well-known and commonly used substances, among which polyethylene glycol is preferred. By containing polyester polyol and / or polyether polyol within the above-mentioned range, the adhesion on the substrate film is significantly improved, and as a result, the blocking resistance and lamination strength become excellent.

[0134] Similarly, if the number average molecular weight of the polyether polyol is less than 100, the urethane resin film tends to become hard, and adhesion to polyester films is likely to be reduced. If the number average molecular weight exceeds 4000, the urethane resin film tends to become brittle, and the film's blocking resistance is likely to be reduced. It should be noted that the number average molecular weight of the polyether polyol is measured using gel permeation chromatography (GPC) under the same conditions as for the polyester polyol.

[0135] Examples of the diisocyanate compound used in the urethane resin in the organic solvent-based composition of the present invention include various well-known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of urethane resins. For example, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diisocyanate Polyacid diisocyanate, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane), dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, bis-chloromethyl-diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, dimer diisocyanate obtained by converting the carboxyl groups of dimer acid into isocyanate groups, and the like. These diisocyanate compounds can be used alone or in combination of two or more.

[0136] As chain extenders used in the urethane resin in the organic solvent-based composition of the present invention, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and the like can be used. In addition, amines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, bis(2-hydroxyethyl)ethylenediamine, bis(2-hydroxy)ethylenediamine, bis(2-hydroxyethyl)propylenediamine, 2-hydroxypropylethylenediamine, bis(2-hydroxypropyl)ethylenediamine, and bis(2-hydroxypropyl)ethylenediamine, can be used. These chain extenders can be used alone or in combination of two or more.

[0137] Furthermore, the amine value of the urethane resin used in the organic solvent-based composition of the present invention is preferably 10.0 mgKOH / g or less. An amine value exceeding 10.0 mgKOH / g tends to deteriorate blocking resistance and reduce the two-liquid stability after the addition of a curing agent. From the perspective of maintaining good blocking resistance and two-liquid stability while maintaining lamination properties, adhesion, and extrusion lamination strength, an amine value of 1.0 to 5.0 mgKOH / g is more preferred, and 1.0 to 3.5 mgKOH / g is even more preferred.

[0138] The (meth)acrylic resin can be obtained by copolymerizing various (meth)acrylate monomers and, if necessary, other polymerizable unsaturated group-containing compounds.

[0139] The monomer constituting the (meth)acrylic resin is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-pentafluoropropyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, and the like. (Meth)acrylic monomers such as ester, glycidyl (meth)acrylate, allyl glycidyl ether, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, (meth)acrylamide, N-monoalkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, 2-aziridinylethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, acrolein, diacetone (meth)acrylamide, and ethyl acetoacetate (meth)acrylate.

[0140] In addition, the above-mentioned "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic" means either or both of acrylic and methacrylic.

[0141] As the compound containing a polymerizable unsaturated group, in addition to the above-mentioned (meth)acrylic monomers, vinyl monomers such as vinyl acetate, vinyl propionate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth)acrylonitrile, styrene, α-methylstyrene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, and N-vinylpyrrolidone can be used. These can be used alone or in combination of two or more.

[0142] The acrylic resins (A1) and (A2) having an acid value can be obtained by copolymerizing a (meth)acrylic monomer having a carboxyl group, such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, mono-2-(2-(meth)acryloyloxy)hydroxyethanol succinate, or mono-2-(2-(meth)acryloyloxy)hydroxyethanol phthalate, for the purpose of introducing one or more hydrophilic groups selected from carboxyl groups and carboxylic acid ester groups obtained by neutralizing carboxyl groups with a basic compound.

[0143] The acrylic resins (A1) and (A2) can be produced, for example, by polymerizing various monomers in the presence of a polymerization initiator at a temperature range of 60°C to 150°C. Examples of polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Examples of polymerization patterns include random copolymers, block copolymers, and graft copolymers.

[0144] Examples of the colorant used in the organic solvent-based composition of the present invention include inorganic pigments, organic pigments, or dyes commonly used in inks, coatings, and recording agents. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrones, diketopyrrolopyrrole pigments, isoindolinone pigments, indanthrone pigments, and carbon black pigments. In addition, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, solid yellow, solid red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone fuchsine, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo red, thioindigo fuchsine, perylene red, perindole orange, isoindolinone yellow, nigrosine, diketopyrrolopyrrole red, daylight fluorescent pigment, etc. can be mentioned. In addition, both non-acidic treatment pigments and acidic treatment pigments can be used. The following is a preferred specific example of an organic pigment.

[0145] Examples of the black pigment include CI Pigment Black 1, CI Pigment Black 6, CI Pigment Black 7, CI Pigment Black 9, and CI Pigment Black 20.

[0146] Examples of the blue pigment include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:5, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 22, CI Pigment Blue 24:1, CI Pigment Blue 25, CI Pigment Blue 26, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Blue 63, CI Pigment Blue 64, CI Pigment Blue 75, CI Pigment Blue 79, and CI Pigment Blue 80.

[0147] Examples of the green pigment include CI Pigment Green 1, CI Pigment Green 4, CI Pigment Green 7, CI Pigment Green 8, CI Pigment Green 10, and CI Pigment Green 36.

[0148] Examples of the red pigment include CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 20, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 38, and CI Pigment Red 4. 1. CI Pigment Red 43, CI Pigment Red 46, CI Pigment Red 48, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 48:5, CI Pigment Red 48:6, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 49:3, CI Pigment Red 52, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53, CI Pigment Red 53:1, CI Pigment Red 53:2, CI Pigment Red 53:3, CI Pigment Red 54, CI Pigment Red CI Pigment Red 57, CI Pigment Red 57:1, CI Pigment Red 58, CI Pigment Red 58:1, CI Pigment Red 58:2, CI Pigment Red 58:3, CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 63:3, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 68, CI Pigment Red 81:1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 89, CI Pigment Red 95, CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red 1 19, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 136, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 147, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 164, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 181, CICI Pigment Red 182, CI Pigment Red 183, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 192, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 211, CI Pigment Red 213, CI Pigment Red 214, CI Pigment Red 216, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 223, CI Pigment Red 224, CI Pigment Red 225 CI Pigment Red 226, CI Pigment Red 237, CI Pigment Red 238, CI Pigment Red 239, CI Pigment Red 240, CI Pigment Red 242, CI Pigment Red 245, CI Pigment Red 247, CI Pigment Red 248, CI Pigment Red 251, CI Pigment Red 253, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 256, CI Pigment Red 257, CI Pigment Red 258, CI Pigment Red 260, CI Pigment Red 262, CI Pigment Red 263, CI Pigment Red 264, CI Pigment Red 266, CI Pigment Red 268, CI Pigment Red 269, CI Pigment Red 270, CI Pigment Red 271, CI Pigment Red 272, CI Pigment Red 279, etc.

[0149] Examples of the violet pigment include CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 3:1, CI Pigment Violet 3:3, CI Pigment Violet 5:1, CI Pigment Violet 13, CI Pigment Violet 19 (γ type, β type), CI Pigment Violet 23, CI Pigment Violet 25, CI Pigment Violet 27, CI Pigment Violet 29, CI Pigment Violet 31, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 37, CI Pigment Violet 38, CI Pigment Violet 42, and CI Pigment Violet 50.

[0150] Examples of yellow pigments include CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 24, CI Pigment Yellow 42, CI Pigment Yellow 55, CI Pigment Yellow 62, CI Pigment Yellow 65, CI Pigment Yellow 74, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 121, CI Pigment Yellow 122, CI Pigment Yellow 123, CI Pigment Yellow 124, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 130, CI Pigment Yellow 131, CI Pigment Yellow 132, CI Pigment Yellow 133, CI Pigment Yellow 134, CI Pigment Yellow 135, CI Pigment Yellow 136, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 140, CI Pigment Yellow 141, CI Pigment Yellow 142 CI Pigment Yellow 120, CI Pigment Yellow 125, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 174, CI Pigment Yellow 180, CI Pigment Yellow 185 and CI Pigment Yellow 213, etc.

[0151] Examples of the orange pigment include CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 37, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 71, and CI Pigment Orange 74.

[0152] Examples of the brown pigment include CI Pigment Brown 23, CI Pigment Brown 25, and CI Pigment Brown 26.

[0153] Among them, preferred pigments include CI Pigment Black 7 for black pigments, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 15:6 for blue pigments, CI Pigment Green 7 for green pigments, and CI Pigment Red 57:1, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 146, CI Pigment Red 242, and CI Pigment Red 57:1. Pigment Red 185, CI Pigment Red 122, CI Pigment Red 178, CI Pigment Red 149, CI Pigment Red 144, CI Pigment Red 166, as for violet pigments, CI Pigment Violet 23 and CI Pigment Violet 37 can be mentioned, as for yellow pigments, CI Pigment Yellow 83, CI Pigment Yellow 14, CI Pigment Yellow 180, CI Pigment Yellow 139 can be mentioned, as for orange pigments, CI Pigment Orange 38, CI Pigment Orange 13, CI Pigment Orange 34, CI Pigment Orange 64, etc. can be mentioned, and it is preferred to use at least one or two or more selected from them.

[0154] The total content of the above pigments is preferably 1% by mass or more and 60% by mass or less in the total amount of the organic solvent-based composition of the present invention from the viewpoint of ensuring the concentration and coloring power of the organic solvent-based composition of the present invention.

[0155] Examples of the auxiliary agents include waxes such as paraffin wax, polyethylene wax, and carnauba wax for imparting friction resistance and slip properties; fatty acid amide compounds such as oleamide, stearamide, and erucamide; silicone and non-silicone defoamers for suppressing foaming during printing; and dispersants. Nonionic dispersants are preferred.

[0156] The acid value of the dispersant is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and even more preferably 20 mgKOH / g or less. Alternatively, it may be, for example, 1 mgKOH / g or more, and even more preferably 3 mgKOH / g or more.

[0157] The acid value of the dispersant is preferably lower than that of the acidic additive. The difference between the acid value of the acidic additive and the acid value of the dispersant is, for example, preferably 1 mgKOH / g or greater, more preferably 3 mgKOH / g or greater. Furthermore, it is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less.

[0158] The content of the dispersant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the colorant, and is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, more preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and more preferably 60 parts by mass or less.

[0159] In addition to the above, water, a wetting agent, an adhesion promoter, a leveling agent, an antistatic agent, a viscosity modifier, a metal chelate, a scavenger, an anti-blocking agent, an isocyanate curing agent, and a silane coupling agent may be used as needed. The viscosity of the liquid ink, as measured at 25°C using a Zahn Cup #4 manufactured by Lihe Co., Ltd., is preferably 6 seconds or greater, more preferably 10 seconds or greater, and even more preferably 13 seconds or greater. Furthermore, it is preferably 25 seconds or less, more preferably 20 seconds or less, and even more preferably 18 seconds or less.

[0160] The surface tension of the organic solvent-based composition of the present invention is preferably 25 mN / m or greater, more preferably 33 mN / m or greater. Furthermore, it is preferably 50 mN / m or less, more preferably 43 mN / m or less. By appropriately increasing the surface tension of the organic solvent-based composition of the present invention, dot bridging (contamination of the printed surface caused by connections between adjacent dots in the mid-tone dot portion) can be suppressed while maintaining the wettability of the organic solvent-based composition of the present invention to the substrate. By appropriately reducing the surface tension of the organic solvent-based composition of the present invention, the wettability of the organic solvent-based composition of the present invention to the substrate can be improved, thereby suppressing craters.

[0161] The organic solvent-based composition of the present invention can be used as a coating such as a printing ink, a primer, an OPV, or a coating, and is preferably used as a printing ink, a primer, or an OPV. The printing ink, primer, or OPV is preferably used for gravure printing or flexographic printing.

[0162] When the organic solvent composition of the present invention is used for gravure printing or flexographic printing, it can be produced using an Eiger mill, a sand mill, a gamma mill, an attritor, or the like, which are commonly used in the production of gravure or flexographic inks.

[0163] When preparing the organic solvent-based composition of the present invention, from the perspective of uniformity, at least a portion of the binder resin, the colorant, at least a portion of the acidic additive, and at least a portion of the organic solvent may be mixed in advance to prepare a preliminary composition (kneaded base ink).

[0164] In addition, as a composition that can be removed from a substrate in the same manner as in the present invention, a resist ink can be cited. This resist ink is an ink for the purpose of removing the coating film from the substrate in advance while leaving a portion thereof and processing the substrate. However, the use and purpose of this resist ink are fundamentally different from the ink of the present invention, which is intended to remove the entire coating film and recycle the substrate, and therefore does not conform to the prior art of the present invention.

[0165] (Printing on substrate)

[0166] The organic solvent-based composition of the present invention has excellent adhesion to various substrates and can be used for printing onto paper, synthetic paper, cloth, thermoplastic resin films, plastic products, steel plates, and the like. It is useful as an ink for gravure printing using an intaglio printing plate based on an electronic engraving plate, or for flexographic printing using a flexographic printing plate based on a resin plate, etc. On the other hand, although it can also be used in an inkjet method in which ink is ejected from an inkjet nozzle without using a plate, this is less preferred. Specifically, in the case of inkjet inks, ink droplets ejected from the nozzle directly adhere to the substrate to form a printed article. However, with the organic solvent-based composition of the present invention, after the printing ink is temporarily adhered and transferred to a printing plate or printed pattern, the ink is simply allowed to adhere to the substrate again and dried as needed to form a printed article.

[0167] The film thickness of the printing ink formed by gravure printing or flexographic printing using the organic solvent-based composition of the present invention is, for example, preferably 10 μm or less, more preferably 5 μm or less.

[0168] Since the organic solvent composition of the present invention contains an acidic additive, it is preferable to thoroughly clean the equipment and materials used immediately after use. Detergents commonly used for cleaning organic solvent compositions can be used as detergents.

[0169] (Printed materials and laminated bodies)

[0170] By printing the organic solvent-based composition of the present invention on the surface or surfaces of substrate A, a printed article having a film can be obtained. By laminating the printed article with substrate B positioned on the film side, a laminate can be obtained. Furthermore, in the laminate, the printed article film and substrate B can be laminated via an adhesive layer.

[0171] The embodiments of the printed article printed using the organic solvent-based composition of the present invention and the laminated body formed using the printed article are not limited, but the following embodiments are preferred.

[0172] <Front printing>

[0173] ■Base material A - film layer (white) - film layer (color)

[0174] ■Base material A - Primer layer - Film layer (white) - Film layer (color)

[0175] ■Base material A - film layer (white) - film layer (color) - OPV layer

[0176] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - OPV layer

[0177] ■Base material A - Film layer (color) - Film layer (white)

[0178] ■Base material A - Primer layer - Film layer (color) - Film layer (white)

[0179] ■Base material A - Film layer (color) - Film layer (white) - OPV layer

[0180] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - OPV layer

[0181] <Back printing, lamination>

[0182] ■Base material A - Film layer (white) - Film layer (color) - Adhesive layer - Base material B

[0183] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - Adhesive layer - Base material B

[0184] ■Base material A - Film layer (white) - Film layer (color) - OPV layer - Adhesive layer - Base material B

[0185] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - OPV layer - Adhesive layer - Base material B

[0186] ■Base material A - Film layer (color) - Film layer (white) - Adhesive layer - Base material B

[0187] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - Adhesive layer - Base material B

[0188] ■Base material A - Film layer (color) - Film layer (white) - OPV layer - Adhesive layer - Base material B

[0189] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - OPV layer - Adhesive layer - Base material B

[0190] ■Base material A - Film layer (white) - Film layer (color) - Resin layer C - Base material B

[0191] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - Resin layer C - Base material B

[0192] ■Base material A - Film layer (white) - Film layer (color) - OPV layer - Resin C layer - Base material B

[0193] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - OPV layer - Resin C layer - Base material B

[0194] ■Base material A - Film layer (color) - Film layer (white) - Resin layer C - Base material B

[0195] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - Resin layer C - Base material B

[0196] ■Base material A - Film layer (color) - Film layer (white) - OPV layer - Resin C layer - Base material B

[0197] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - OPV layer - Resin C layer - Base material B

[0198] ■Base material A - Film layer (white) - Film layer (color) - Base material B

[0199] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - Base material B

[0200] ■Base material A - Film layer (white) - Film layer (color) - OPV layer - Base material B

[0201] ■Base material A - Primer layer - Film layer (white) - Film layer (color) - OPV layer - Base material B

[0202] ■Base material A - Film layer (color) - Film layer (white) - Base material B

[0203] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - Base material B

[0204] ■Base material A - Film layer (color) - Film layer (white) - OPV layer - Base material B

[0205] ■Base material A - Primer layer - Film layer (color) - Film layer (white) - OPV layer - Base material B

[0206] Here, the above-mentioned substrate A represents the substrate A described later, the film layer (white) represents a film layer formed by printing the organic solvent-based composition of the present invention using the colorant used in the above-mentioned white ink as the colorant of the organic solvent-based composition of the present invention, the film layer (color) represents a film layer formed by printing the organic solvent-based composition of the present invention using a colorant other than the colorant used in the above-mentioned white ink as the colorant of the organic solvent-based composition of the present invention, the primer layer represents a layer formed using the primer described later, the adhesive layer represents a layer formed using the adhesive described later, the OPV layer represents a layer formed using the OPV (varnish) described later, the resin C layer represents a layer formed using the resin C described later, and the substrate B represents the substrate B described later.

[0207] In addition, the back printing and lamination structure includes repetition and combination of the above methods, and also includes composite and multi-layer structures.

[0208] As substrate A, preferably a plastic substrate, there can be enumerated films of thermoplastic resins such as polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polyester resins such as polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, poly(ethylene succinate), and aliphatic polyester resins such as poly(butylene succinate), polyolefin resins such as polypropylene and polyethylene, polyimide resins, polyarylate resins, or mixtures thereof, and their laminates. Among them, films and laminates comprising polyester, polyamide, polyethylene, and polypropylene can be suitably used. If the release property of the organic solvent-based composition of the present invention is emphasized, polypropylene or polyethylene is more preferred. These substrate films may be unstretched films or stretched films, and their preparation methods are also not limited. The thickness of the base film is not particularly limited, and may generally be in the range of 1 to 500 μm.

[0209] The printing surface of the substrate A is preferably subjected to a corona discharge treatment, and may also be subjected to vapor deposition of silicon dioxide, aluminum oxide, or the like.

[0210] As the substrate B, the same substrates as the substrate A can be mentioned, and they may be the same or different. However, a plastic substrate is preferred, and a thermoplastic resin substrate is more preferred. When the laminate is extrusion laminated, it may be the same as the resin C described below. Alternatively, it may be laminated with a metal foil or a metal foil layer of a vapor-deposited film layer.

[0211] The resin C is preferably a thermoplastic resin, more preferably a polyolefin, and particularly preferably polypropylene or polyethylene and modified resins thereof.

[0212] The primer used to form the primer layer preferably contains a resin having an acidic group from the perspective of being easily dissolved or hydrolyzed in an alkaline solution. A resin or low-molecular compound having an acidic group may be used alone as the primer. Alternatively, a resin or low-molecular compound having an acidic group may be mixed with a resin not having an acidic group.

[0213] Examples of the resin having an acidic group include cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, and petroleum resins; (meth)acrylic resins obtained by copolymerizing polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid, or anhydrides thereof; polymerizable monomers having sulfonic acid groups such as sulfonated styrene; and polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide; radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, and terpene-maleic acid (anhydride) resins; and acid-modified polyolefin resins. These resins can be used alone or in combination.

[0214] In addition, the primer layer may also use a low molecular weight compound having an acidic group alone or in combination of two or more of a resin having a low acid value and film-forming properties at room temperature.

[0215] Preferred examples of the low molecular weight compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives. These can be used alone or in combination of two or more.

[0216] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and water. Examples of the present invention include salicylic acid, gallic acid, mellitic acid, and cinnamic acid. Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, and azelaic acid. Examples of tricarboxylic acids include aconitic acid and trimer acid. Examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination. In addition, examples of citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid satisfy the so-called Swiss Ordinance, and it is preferred to use substances that satisfy various restrictions.

[0217] As the resin having film-forming properties at room temperature, there are various synthetic resins, for example, polyester, polyvinyl chloride, copolymers of vinyl chloride and other monomers containing unsaturated double bonds, homopolymers of (meth)acrylates, copolymers of (meth)acrylates and other monomers containing unsaturated double bonds, polystyrene, copolymers of styrene monomer and other monomers containing unsaturated double bonds, ketone-formaldehyde condensates, hydrogenated products thereof, multifunctional epoxy resins, polyvinyl acetal, polyurethane, etc. These can be used alone or in combination of one or more selected from them.

[0218] Examples of the polyfunctional epoxy compound include bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, bisphenol S novolac epoxy resin, biphenyl epoxy resin, and naphthalene epoxy resin.

[0219] When a low molecular weight compound having an acidic group is used alone or in combination with a plurality of low molecular weight compounds in the above-mentioned resin having a low acid value and film-forming properties at room temperature, the amount thereof added can be appropriately determined within a range that does not impair the printing adaptability or coating adaptability of the primer solution, preferably in the range of 0.5 to 50% by mass, more preferably in the range of 1.0 to 30% by mass, relative to the solid content of the primer solution.

[0220] When the printed material is, for example, polypropylene (PP), a film-forming resin that has good adhesion to PP and is solid at 50°C and at least one thermoplastic resin selected from ketone-formaldehyde condensates, hydrogenated products thereof, polyesters, vinyl chloride-vinyl acetate copolymers, and polyvinyl acetals can be suitably used. Examples of such ketone-formaldehyde condensates and hydrogenated products include the TEGO (registered trademark) VariPlus series (SK, AP, etc.) manufactured by Evonik Degussa Japan Co., Ltd.; examples of polyesters include the VYLON (registered trademark) series (VYLON 200, etc.) manufactured by Toyobo Co., Ltd.; examples of vinyl chloride-vinyl acetate copolymers include the SOLBIN (registered trademark) series (SOLBIN AL, etc.) manufactured by Nissin Chemical Industry Oil Co., Ltd.; and examples of polyvinyl acetals include the S-LEC (registered trademark) series (S-LEC KS-10, etc.) manufactured by Sekisui Chemical Co., Ltd.

[0221] In order to form a primer layer on a substrate, a solution prepared using the above-mentioned components is applied to the substrate and dried. The coating amount is about 0.1 to 5 μm (dry thickness). If it is less than 0.1 μm, it is difficult to apply evenly, and if it is greater than 5 μm, it is not economical and therefore not practical. Conventional coating methods such as gravure, relief printing, flexographic printing, roller coater, reverse coater, spraying, etc. can be used for coating. The formation of the primer layer and the printing thereon can be continuous (online), or the formation of the primer layer and the printing can be performed separately.

[0222] When printing is performed immediately after primer application using a roll-to-roll printer, blocking can occur, depending on the solubility of the resin used in the primer layer in the ink solvent and the glass transition temperature (Tg) of the resin itself. To prevent this blocking, transparent particles of silica, titanium oxide, or a similar material with a particle size of 0.1 to 10 μm can be added to the primer solvent at a rate of approximately 0.005 to 5% relative to the total amount of primer.

[0223] Furthermore, for the purpose of preventing blocking, the resin solution with a high acid value used in the primer may be neutralized with ammonia or the like before coating to prevent redissolution in the solvent contained in the printing ink.

[0224] The adhesive used to form the adhesive layer is not particularly limited, and any commercially available reactive adhesive can be used. Of these, so-called two-component reactive adhesives of a polyisocyanate composition and a polyol composition, or one-component reactive adhesives of a polyisocyanate are preferred.

[0225] The polyisocyanate composition used in a general reactive adhesive is a composition containing a polyisocyanate compound as a main component. Any composition known as a polyisocyanate compound for a reactive adhesive can be used without particular limitation. Specific examples of polyisocyanate compounds include polyisocyanates having an aromatic structure in their molecular structure, such as toluene diisocyanate, diphenylmethane diisocyanate, polymerized diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate; and compounds in which a portion of the isocyanate groups (NCO groups) of these polyisocyanates are modified with carbodiimide; and polyisocyanates having an alicyclic structure in their molecular structure, such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-(isocyanatomethyl)cyclohexane. Ester; linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; compounds obtained by modifying a portion of the NCO groups of these polyisocyanates with carbodiimide; isocyanurate forms of the above-mentioned various polyisocyanates; allophanate forms derived from the above-mentioned various polyisocyanates; biuret forms derived from the above-mentioned various polyisocyanates; adducts obtained by modifying the above-mentioned various polyisocyanates with trimethylolpropane; polyisocyanates which are reaction products of the above-mentioned various polyisocyanates with a polyol component described later, etc.

[0226] The polyol composition used in a general reactive adhesive is a composition containing a polyol compound as a main component. Any composition known as a polyol compound for reactive adhesives can be used without particular limitation. Specific examples of the polyol compound include glycols such as ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol; and glycerol. , trimethylolpropane, pentaerythritol and other trifunctional or tetrafunctional aliphatic alcohols; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F; polymer polyols selected from dimer, polyester polyols, polyether polyols, polyurethane polyols, polyetherester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, castor oil, or mixtures thereof.

[0227] Among them, it is preferred that any one of the constituent components of the reactive adhesive has an ester bond from the viewpoint of easy dissolution or hydrolysis in an alkaline solution, so that it can be easily separated into a single layer film in a short time in the film removal step described later.

[0228] The so-called reactive adhesive is one in which any one of its constituent components has an ester bond. Specifically, there can be mentioned reactive adhesives containing either or both of a polyol composition and a polyisocyanate composition. The above-mentioned polyol composition contains a polyol compound such as polyester polyol, polyether ester polyol, polyester (polyurethane) polyol, acrylic polyol, etc. having an ester bond. The above-mentioned polyisocyanate composition contains a polyisocyanate compound which is a reaction product of the above-mentioned polyol compound having an ester bond and the above-mentioned various polyisocyanates.

[0229] In addition to the polyol composition and the polyisocyanate composition, a reactive adhesive to which a resin or low-molecular compound having an acidic group is added can also be preferably used. The resin or low-molecular compound having an acidic group can be used without particular limitation as long as it can be easily mixed with the polyol composition and the polyisocyanate composition as the main components of the reactive adhesive (in this case, a solvent described below may be used as needed) and has an acid value.

[0230] Examples of the resin having an acidic group include resins having an acid value such as rosin-modified maleic acid resin and rosin-modified fumaric acid resin; resins in the form of free radical copolymers obtained by copolymerizing polymerizable monomers having carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers having sulfonic acid groups such as sulfonated styrene, polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide, etc.; and acid-modified polyolefin resins. These resins can be used alone or in combination.

[0231] Preferred examples of the low molecular weight compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives. These can be used alone or in combination of two or more.

[0232] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid. Examples of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, and azelaic acid. Examples of tricarboxylic acids include aconitic acid and trimer acid. Examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination. In addition, citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid satisfy the so-called Swiss Ordinance, and it is preferred to use substances that satisfy various restrictions.

[0233] In addition, in reactive adhesives, additives such as pigments, silane coupling agents, titanate coupling agents, aluminum coupling agents, adhesion promoters such as epoxy resins, leveling agents, inorganic fine particles such as colloidal silica and alumina sol, organic fine particles such as polymethyl methacrylate, defoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity regulators, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic heat ray absorbers, fire retardants, antistatic agents, and dehydrating agents are sometimes used.

[0234] In addition, among reactive adhesives, dry laminating adhesives diluted with a highly soluble organic solvent for dilution, solvent-free laminating adhesives that substantially do not contain an organic solvent for dilution, and aqueous adhesives whose diluent is water can all be used. Specifically, the so-called highly soluble organic solvent for dilution includes toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluole, xylene, n-hexane, and cyclohexane. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known to be organic solvents with particularly high solubility. Aqueous adhesives can use water or an organic solvent with affinity for water as a dilution solvent.

[0235] In the reactive adhesive, the mixing ratio of the two-component polyisocyanate composition and the polyol composition is a recommended mixing ratio for commercially available products. Generally, the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the polyisocyanate composition to the hydroxyl group in the polyol composition is generally in the range of 1.0 to 5.0. Of course, combinations in other ranges may also be used.

[0236] The one-component reactive adhesive can be used by applying the polyisocyanate composition alone to a film. The isocyanate groups contained in the polyisocyanate composition react with moisture in the air to crosslink, thereby being used as a laminating adhesive.

[0237] In a laminated film obtained by laminating and bonding with a reactive adhesive, the reactive adhesive is almost always mixed, applied to a first plastic film, and then a second plastic film is laminated on the applied surface, followed by curing and crosslinking through an aging process or the like.

[0238] The reactive adhesive preferably contains the aforementioned resin or low-molecular compound having an acidic group, as it facilitates removal with an alkaline solution. In a two-component reactive adhesive comprising a polyisocyanate composition and a polyol composition, it is preferred to incorporate the aforementioned resin or low-molecular compound into the polyol composition for stability. The amount of the resin or low-molecular compound added can be appropriately determined so as not to impair the adhesiveness and curability of the reactive adhesive. However, it is preferably in the range of 0.5 to 50% by mass, and more preferably in the range of 1.0 to 30% by mass, relative to the solids content of the polyol composition.

[0239] Furthermore, if the reactive adhesive is an ester adhesive such as an ester adhesive, an ester urethane adhesive, or an ether ester adhesive, peeling may occur during the step of immersing the laminate in an alkaline solution while heating and stirring the laminate at 20 to 90°C or subjecting it to ultrasonic vibration. Ether adhesives, on the other hand, may be difficult to peel depending on the situation. In such cases, it is preferable to provide the aforementioned primer layer or to use an ether adhesive containing the aforementioned resin or low-molecular compound having an acidic group.

[0240] The OPV (varnish) used to form the OPV layer is not particularly limited, and any commercially available OPV can be used. The general composition of OPV includes a binder resin, a solvent such as an organic solvent or an aqueous solvent, and additives.

[0241] Examples of the binder resin include cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, petroleum resins and other resins having an acid value; (meth)acrylic resins obtained by copolymerizing polymerizable monomers having a carboxyl group such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or anhydrides thereof; polymerizable monomers having a sulfonic acid group such as sulfonated styrene; polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide; resins in the form of radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, terpene-maleic acid (anhydride) resins; and acid-modified polyolefin resins. These resins can be used in appropriate combinations. Among them, it is preferable to use a (meth)acrylic resin, a urethane resin, a rosin-based resin, and modified products thereof in appropriate combination.

[0242] As long as the solvent is an organic solvent, the above-mentioned organic solvents that can be used in the organic solvent-based composition of the present invention may be mentioned.

[0243] Examples of the additives include extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, anti-blocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc. In addition, a crosslinking agent or a chelating agent may be added to crosslink the printed ink layer itself and increase its hardness.

[0244] Alternatively, OPVs containing resins or low-molecular-weight compounds containing acidic groups can be preferably used. Any resin or low-molecular-weight compound containing an acidic group can be used without particular limitation, as long as it is easily miscible with the binder resin and organic solvent mentioned above, which are the main components of the OPV, and has an acid value.

[0245] Examples of the resin having an acidic group include cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, and petroleum resins; (meth)acrylic resins obtained by copolymerizing polymerizable monomers having carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid, or anhydrides thereof; polymerizable monomers having sulfonic acid groups such as sulfonated styrene; and polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide; radical copolymers such as styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, and terpene-maleic acid (anhydride) resins; and acid-modified polyolefin resins. These resins can be used alone or in combination.

[0246] Preferred examples of the low molecular weight compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives. These may be used alone or in combination of two or more.

[0247] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid. Examples of hydroxy acids include lactic acid, malic acid, and citric acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid. Examples of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, and azelaic acid. Examples of tricarboxylic acids include aconitic acid and trimer acid. Examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination. In addition, citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid satisfy the so-called Swiss Ordinance, and it is preferred to use substances that satisfy various restrictions.

[0248] The OPV preferably contains the resin or low-molecular compound having an acidic group. The amount of the resin or low-molecular compound added can be appropriately determined within a range that does not impair the printability of the OPV. However, the amount is preferably in the range of 0.5 to 50% by mass, and more preferably in the range of 1.0 to 30% by mass, relative to the solids content of the OPV.

[0249] In the laminate, each of the substrate A, film layer (white), film layer (color), primer layer, adhesive layer, OPV layer, resin C layer, or substrate B may be provided with a barrier layer. Examples of the barrier layer include an inorganic vapor-deposited layer and a barrier coating layer, which may be used alone or in combination.

[0250] The inorganic vapor-deposited layer is a gas barrier layer that prevents the permeation of oxygen and water vapor, and is a vapor-deposited layer comprising an inorganic substance or an inorganic oxide. Examples of the inorganic substance or inorganic oxide include aluminum, aluminum oxide, silicon dioxide, and the like, and one or more of these can be used. The inorganic vapor-deposited layer may be provided with two or more layers. When two or more inorganic vapor-deposited layers are provided, each layer may have the same composition or different compositions.

[0251] The inorganic vapor deposition layer can be provided by a conventionally known method. Examples of the method for forming the inorganic vapor deposition layer include physical vapor deposition methods (PVD methods) such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods (CVD methods) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0252] The inorganic vapor-deposited layer preferably has a thickness of 1 to 200 nm. When the inorganic vapor-deposited layer is an aluminum vapor-deposited layer, the thickness is more preferably 1 to 100 nm, more preferably 15 to 60 nm, and even more preferably 10 to 40 nm. When the inorganic vapor-deposited layer is a silicon dioxide or aluminum oxide vapor-deposited layer, the thickness is preferably 1 to 100 nm, more preferably 10 to 50 nm, and even more preferably 20 to 30 nm.

[0253] The barrier coating protects the inorganic deposited layer and improves gas barrier properties against oxygen, water vapor, and the like. Such a barrier coating is formed, for example, from a resin composition such as a hydrolyzate of a metal alkoxide or a hydrolyzed polycondensate of a metal alkoxide, obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer using a sol-gel method in the presence of a sol-gel catalyst, water, an organic solvent, or the like.

[0254] As the metal alkoxide, one or more species represented by the following general formula can be used.

[0255] [Chemistry 1]

[0256]

[0257] (In the above general formula, R 1 、R 2 represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer greater than 0, m represents an integer greater than 1, and n+m represents the atomic valence of M.

[0258] Examples of the metal atom M include silicon, zirconium, titanium, and aluminum. 1 、R 2 Specific examples of the organic group represented by include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. These alkyl groups may be the same or different in the same molecule.

[0259] Specific examples of metal alkoxides include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The metal alkoxides may be used alone or in combination of two or more.

[0260] Examples of water-soluble polymers include polyvinyl alcohol resins and ethylene-vinyl alcohol copolymers. Commercially available water-soluble polymers can be used. Examples of commercially available polyvinyl alcohol resins include RS-110 (manufactured by Kuraray Co., Ltd., RS polymer, saponification degree: 99%, polymerization degree: 1000), Kuraray POVAL LM-20SO (manufactured by Kuraray Co., Ltd., saponification degree: 40%, polymerization degree: 2000), and GOHSENOL NM-14 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 99%, polymerization degree: 1400). Examples of commercially available ethylene-vinyl alcohol copolymers include EVAL EP-F101 (manufactured by Kuraray Co., Ltd., ethylene content: 32 mol%) and SOARNOL D2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene content: 29 mol%).

[0261] Examples of catalysts for the sol-gel method include acids and amine compounds. Suitable amine compounds are tertiary amines that are substantially insoluble in water but soluble in organic solvents. Specifically, for example, N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine can be used. N,N-dimethylbenzylamine is particularly preferred. Examples of acids that can be used include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid.

[0262] Methanol, ethanol, n-propanol, isopropanol, n-butanol, etc. can be used as the organic solvent.

[0263] The gas barrier coating can be formed by applying a resin composition containing these compounds once or multiple times using a conventionally known method such as roller coating with a gravure roll coater, spray coating, spin coating, dipping, brush coating, rod coating, or a size press. More specifically, a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and other components as needed are mixed to prepare a resin composition. A polycondensation reaction gradually proceeds in the resin composition. Then, the resin composition is applied to the inorganic vapor-deposited layer using a conventional method and dried. Drying further promotes the polycondensation reaction of the metal alkoxide and the water-soluble polymer to form a composite polymer layer. It is also preferable to repeat this operation to form a gas barrier coating. Finally, the laminate coated with the resin composition is heated at 20 to 250°C, preferably at 50 to 220°C, for 1 second to 10 minutes. In this way, a gas barrier coating can be formed on the inorganic vapor-deposited layer.

[0264] The thickness of the gas barrier coating is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm. If it is less than 0.01 μm, the improvement of the gas barrier properties is insufficient, while if it is greater than 100 μm, cracks are likely to occur.

[0265] (Method for removing the film from the substrate A)

[0266] In the present invention, the printed material is treated with warm water or an alkaline solution to remove the film from the substrate A, thereby producing a recycled substrate A.

[0267] In the present invention, the laminate obtained by laminating the printed material and substrate B with the film disposed inside via an adhesive layer can be treated with warm water or an alkaline solution to remove the adhesive layer and substrate B together with the film, thereby producing a recycled substrate A.

[0268] The above-mentioned separation process includes a process of immersing the printed material or the laminate in warm water while heating and stirring or ultrasonically vibrating the printed material or the laminate at 70 to 90°C, or a process of immersing the printed material or the laminate in an alkaline solution while heating and stirring or ultrasonically vibrating the printed material or the laminate at 20 to 90°C. The above-mentioned heating and stirring and ultrasonic vibration can also be carried out simultaneously. As the above-mentioned process, it is preferred to immerse the printed material or the laminate in an alkaline solution while heating and stirring or ultrasonically vibrating the printed material or the laminate at 20 to 90°C. The heating temperature is preferably 30°C or higher, preferably 40°C or higher, preferably 50°C or higher, preferably 60°C or higher, and more preferably heating and stirring and ultrasonic vibration are carried out simultaneously.

[0269] The alkaline solution used in the above step is not limited, but preferably has a pH of 9 or higher, and is preferably an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium bicarbonate solution, an aqueous potassium bicarbonate solution, an aqueous sodium dihydrogen carbonate solution, an aqueous potassium dihydrogen carbonate solution, or the like. The aqueous sodium hydroxide solution, the aqueous potassium hydroxide solution, the aqueous sodium bicarbonate solution, the aqueous potassium bicarbonate solution, the aqueous sodium dihydrogen carbonate solution, the aqueous potassium dihydrogen carbonate solution, or the like is preferably an aqueous solution having a concentration of 0.5% to 10% by mass, and more preferably an aqueous solution having a concentration of 1% to 5% by mass.

[0270] In addition, the alkaline solution may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dibutyl ether, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dibutyl ether, triethylene 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 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, di ... Alcohol monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonyl acetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyrate and ethyl lactate, etc., can be used alone or in combination of two or more.

[0271] The content of the water-soluble organic solvent in the alkaline solution is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.

[0272] In addition, the alkaline solution can contain a non-water-soluble organic solvent. As the specific example of the non-water-soluble organic solvent, alcohol solvents such as n-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, octanol, aliphatic hydrocarbon solvents such as hexane, heptane, normal alkanes, aromatic hydrocarbon solvents such as benzene, toluene, xylene, alkylbenzenes, halogenated hydrocarbon solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, carbon tetrachloride, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, ether solvents such as ether, butyl ether can be illustrated, and they can be used alone or in combination of two or more.

[0273] In addition, the alkaline solution may contain a surfactant. Examples of the surfactant include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among them, anionic surfactants, nonionic surfactants, and amphoteric surfactants are preferred.

[0274] Examples of the anionic surfactant include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfuric acid ester salts of higher fatty acid esters, sulfonic acid salts of higher fatty acid esters, sulfuric acid ester salts and sulfonic acid salts of higher alcohol ethers, higher alkylsulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates. Specific examples thereof include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, and dibutylphenylphenol disulfonate.

[0275] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkanolamides, alkyl alkanolamides, acetylenic glycols, oxyethylene adducts of acetylenic glycols, and polyethylene glycol-polypropylene glycol block copolymers. Among these, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkanolamides, acetylenic glycols, oxyethylene adducts of acetylenic glycols, and polyethylene glycol-polypropylene glycol block copolymers are preferred.

[0276] As other surfactants, silicone surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as 4,5-dicarboxy-γ-pentadecalactone (Spiculisporic acid), rhamnolipids, and lysolecithin can also be used.

[0277] These surfactants can be used alone or in combination. When a surfactant is added, the amount thereof is preferably in the range of 0.001 to 2% by mass relative to the total amount of the alkaline solution, more preferably in the range of 0.001 to 1.5% by mass, and even more preferably in the range of 0.01 to 1% by mass.

[0278] The printed material or laminated body to be treated is immersed in a treatment tank, for example, while the warm water is heated to 70-90°C or subjected to ultrasonic vibration, or while the alkaline solution is heated to 20-90°C or subjected to ultrasonic vibration. The heating method is not particularly limited, and known heating methods such as heat rays, infrared rays, and microwaves can be used. Alternatively, ultrasonic vibration can be applied by installing an ultrasonic vibrator in the treatment tank and applying ultrasonic vibration to the warm water or alkaline solution.

[0279] The warm water or alkaline solution is preferably stirred during immersion. Examples of stirring methods include mechanical stirring of the printed material or laminated dispersion contained in the treatment tank using a stirring blade, water flow stirring using a water pump, and bubbling using an inert gas such as nitrogen. These methods may be used in combination for efficient stripping.

[0280] The time for immersing the printed material or laminate in the warm water or alkaline solution varies depending on the composition of the printed material, but is generally between 2 minutes and 48 hours. It should be noted that in the present invention, the printed film need not be completely detached from the substrate. However, it is preferred that 60% or more of the 100% by mass of the film be detached, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.

[0281] In this step, the immersion in the warm water or alkaline solution can be performed once or in multiple times. Specifically, the process of recovering the separated membrane substrate can be performed after a single immersion, or the process of recovering the membrane substrate can be performed after multiple immersions. Furthermore, when multiple immersions are performed in this step, the concentration of the alkaline solution can be varied. Furthermore, it is preferable to appropriately incorporate known steps such as washing and drying during this step.

[0282] As mentioned above, it is speculated that the warm water or alkaline solution used in this separation method acts on the interface between the substrate and the printed film, significantly reducing its adhesion, thereby causing interfacial peeling. On the other hand, since the solubility of the alkaline solution itself is also high, the crosslinked printing ink layer is not dissolved. It is also speculated that even if the printing ink layer itself is crosslinked, since interfacial peeling has also occurred in the present invention, separation and recovery can be carried out efficiently in a short time.

[0283] In the case of a laminate, in order to peel the film by the above-mentioned method, it is preferable to cut the substrate in advance so that warm water or an alkaline solution can easily act on the interface between the substrate and the ink.

[0284] Example

[0285] Hereinafter, the content and effects of the present invention will be described in further detail using Examples, but the present invention is not limited thereto. It should be noted that "parts" shown below represent "parts by mass."

[0286] (Measurement method of acid value)

[0287] If the acid value of the raw material has been measured or is publicly available, the acid value of the ink can be calculated. If it cannot be determined, the acid value of the ink can be determined by forming a film and measuring it after drying. The acid value measurements shown below are based on JIS 0070-1992 or are determined according to this method.

[0288] (Examples 1 to 36, Comparative Examples 1 to 4)

[0289] Examples 1 to 30 (I1 to I30) and Comparative Examples 1 to 4 (RI1 to RI4) were prepared using the following binder resins, pigments, acidic additives, and organic solvents (isopropyl alcohol (IPA), ethyl acetate, and propyl acetate) in the mixing ratios described in Table 1 below.

[0290] <Binder Resin>

[0291] ■Resin 1: Urethane resin (acid value in solid content: 0 mgKOH / g, solid content 30 parts by mass)

[0292] ■Resin 2: Urethane resin (acid value in solid content: 15 mgKOH / g, solid content 30 parts by mass)

[0293] Resin 3: Acrylic resin (solid content acid value: 1 mgKOH / g, solid content 30 parts by mass)

[0294] Resin 4: Acrylic resin (acid value in solid content: 30 mgKOH / g, solid content 30 parts by mass)

[0295] Resin 5: Vinyl chloride-vinyl acetate copolymer resin (resin monomer composition by mass %: vinyl chloride / vinyl acetate / vinyl alcohol = 92 / 3 / 5, hydroxyl value (mgKOH / g) = 64)

[0296] Resin 6: Industrial nitrocellulose H1 / 2 solution (nitrocellulose, solid content 70%, viscosity at 25.0% solution concentration 9.0-14.9% according to JIS K-6703, manufactured by Taihei Chemical Co., Ltd., adjusted to 50% solid content using IPA)

[0297] <Pigment>

[0298] ■White: Titanium oxide pigment (JR600A (manufactured by TAYCA Corporation))

[0299] Blue: Phthalocyanine blue pigment (FASTOGEN BLUE LA5380 blue pigment (manufactured by DIC Corporation))

[0300] <Acidic additives>

[0301] AA1: Stearic acid (acid value: 198 mgKOH / g)

[0302] AA2: Sebacic acid (acid value: 556 mgKOH / g)

[0303] AA3: Citric acid (acid value: 876 mgKOH / g)

[0304] AA4: MALKYD#1 manufactured by Arakawa Chemical Industries, Ltd. (acid value: 30 mgKOH / g, maleated rosin resin)

[0305] AA5: MALKYD #32 manufactured by Arakawa Chemical Industries, Ltd. (acid value: 140 mgKOH / g, maleated rosin resin)

[0306] AA6: HIROS-X X-228 manufactured by Seiko PMC (acid value: 141 mgKOH / g, weight average molecular weight, styrene maleic acid resin)

[0307] [Table 1]

[0308]

[0309] [Table 2]

[0310]

[0311] [Table 3]

[0312]

[0313] [Table 4]

[0314]

[0315] (Examples 37 to 70, Comparative Examples 5 to 8)

[0316] The printing inks of Examples 1 to 30 and Comparative Examples 1 to 4 were used to print a full-size pattern of 240 mm in length and 80 mm in width on substrate A using a Flexoproof 100 test printer (manufactured by Testing Machines, Inc.), and then dried in a dryer to form a film layer 1, thereby obtaining a printed product having the following composition 1. Color printing was performed as needed to form a film layer 2, thereby obtaining a printed product having the following composition 2. The printed products of the obtained Examples and Comparative Examples were evaluated for their blocking resistance, substrate adhesion, ink peelability, and lamination adaptability when using each film using the method described below, and the ink transferability was visually confirmed. The composition and evaluation results of the printed products of each Example and Comparative Example are shown in the following table.

[0317] <Composition of printed materials>

[0318] ■ Structure 1: Base material A - Film layer 1

[0319] ■ Structure 2: Base material A - Film layer 1 - Film layer 2

[0320] <Base Material A>

[0321] ■Corona-treated biaxially stretched polypropylene film (Toyobo Co., Ltd., PYLEN P2161, thickness 20 μm) (OPP)

[0322] ■Corona-treated polyethylene terephthalate film (ESTER E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) (PET)

[0323] <Evaluation Item 1: Blocking Resistance>

[0324] The films were cut into 4 cm × 4 cm sizes so that the printed surface and the non-printed surface of the printed material were in contact with each other, and then overlapped and subjected to a 5 kgf / cm 2 After the film was left standing at 40°C for 12 hours, the state of ink transfer (offset) to the non-printed surface when the film was peeled off was visually judged based on the area ratio (%) of the offset portion.

[0325] A: No transfer to the non-printed surface was observed.

[0326] B: Transfer due to offset was observed although it was slight to less than 5%.

[0327] C: Transfer due to staining was observed in 5% or more and less than 20%.

[0328] D: 20% or more of transfer due to staining was observed.

[0329] <Evaluation Item 2: Adhesion to Substrate>

[0330] After the printed material was left for one day, a transparent tape (12 mm wide, manufactured by Nichiban) was attached to the printed surface. The appearance was visually evaluated based on the area ratio of the remaining printed film when one end of the transparent tape was quickly peeled off perpendicularly to the printed surface.

[0331] A: The printed film did not peel off at all.

[0332] B: 80% or more of the printed film remained on the film.

[0333] C: 50% or more and less than 80% of the printed film remains on the film.

[0334] D: Less than 50% of the printed film remains on the film.

[0335] <Evaluation Item 3: Water Resistance>

[0336] A test piece was cut into a size of 10 mm×10 mm, immersed in 100 g of ion-exchanged water, stirred at 20° C. for 30 minutes, washed with water, and dried, and then the peelability of the printed portion was evaluated.

[0337] A: No peeling.

[0338] B: Fine peeling was observed.

[0339] C: 20 to 30% of the printed portion peeled off.

[0340] D: More than 30% of the printed part peels off

[0341] <Evaluation Item 4: Ink Transferability>

[0342] The ink transfer properties of the printed materials were evaluated.

[0343] A: Visually judged that the film is uniform.

[0344] B: The film was slightly uneven in visual observation.

[0345] C: Whitening was slightly observed in the film in visual judgment.

[0346] D: Whitening was observed in the film in visual judgment.

[0347] <Evaluation Item 5: Ink Peeling Test>

[0348] [Alkaline solution]

[0349] Sodium hydroxide aqueous solution "SH solution": Sodium hydroxide (reagent grade 1) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in ion-exchanged water to prepare a 3% by mass aqueous solution.

[0350] [Peel test conditions]

[0351] The peeling test was evaluated with the treatment time set to 30 minutes under each condition. It should be noted that if peeling occurs within 5 minutes of treatment, it indicates a fairly high performance.

[0352] Examples 25 to 76 and Comparative Examples 4 to 9 were cut into pieces with a size of 10 mm x 10 mm to obtain test pieces. These test pieces were subjected to a peel test under conditions 1 to 3.

[0353] Condition 1: Stirring the sodium hydroxide aqueous solution at 20°C

[0354] Condition 2: Ultrasonic treatment of sodium hydroxide aqueous solution at 20°C

[0355] Condition 3: Stirring the sodium hydroxide aqueous solution at 80°C

[0356] The peelability of the film was evaluated under the above-mentioned conditions.

[0357] A: 90% or more of the ink coating film is separated from the substrate in less than 5 minutes.

[0358] B: 90% or more of the ink coating film is separated from the substrate within 5 minutes or more and less than 15 minutes.

[0359] C: 90% or more of the ink coating film is separated from the substrate within 15 minutes or more and less than 30 minutes.

[0360] D: 50% or more and less than 90% of the ink coating film is detached from the substrate during the 30-minute test.

[0361] E: Less than 50% of the ink coating film is detached from the substrate during the 30-minute test.

[0362] <Evaluation Item 6: Lamination Test Conditions>

[0363] An unstretched polypropylene film (Toyobo Co., Ltd. P-1128, thickness 25 μm) was laminated onto the printed material using a dry laminating adhesive DICDRY LX-401A / SP-60 (DIC) using a dry laminator (DIC Engineering) using an ether-based adhesive. The strength was measured after aging at 40°C for 3 days.

[0364] (Evaluation Criteria)

[0365] A: Lamination strength is 1.0 N / 15 mm or more.

[0366] B: Lamination strength is 0.7 N / 15 mm or more and less than 1.0 N / 15 mm.

[0367] C: Lamination strength is 0.5 N / 15 mm or more and less than 0.7 N / 15 mm.

[0368] D: Lamination strength is less than 0.5 N / 15 mm.

[0369] [Table 5]

[0370]

[0371] [Table 6]

[0372]

[0373] [Table 7]

[0374]

[0375] [Table 8]

[0376]

[0377] [Table 9]

[0378]

[0379] [Table 10]

[0380]

[0381] [Table]1]

[0382]

[0383] [Table 12]

[0384]

[0385] [Table 13]

[0386]

[0387] Note that, C and above in any evaluation item are considered practical levels.

[0388] The above results indicate that, when the acid value of the solid content of the organic solvent-based composition is less than the lower limit of the present invention, the adhesiveness, water resistance, ink transferability, and lamination compatibility are excellent, but the composition does not detach from the substrate. Furthermore, when the acid value of the solid content of the organic solvent-based composition is greater than the upper limit of the present invention, the detachability from the substrate is comparable or better, but the adhesiveness, ink transferability, and lamination compatibility do not reach practical levels.

[0389] In the Examples using the aqueous liquid ink according to the embodiment of the present invention, all evaluation results were above the practical level.

[0390] Based on the above, an organic solvent-based printing ink can be provided. By using the organic solvent-based composition of the present invention, while having physical properties comparable to those of conventional organic solvent-based compositions, the printing ink can also be provided. The printing ink is free of toluene and MEK, and a printed article printed using the printing ink, a laminated body composed of the printed article, and a method for removing the film from the printed article or laminated body can be provided.

Claims

1. An organic solvent-based composition, characterized in that It is used to form a film on the surface of the substrate A or on the surface thereof that is removable by treatment with warm water or an alkaline solution, The acid value of the solid content of the organic solvent-based composition is 1 mgKOH / g to 150 mgKOH / g, The organic solvent composition contains an acidic additive, The acidic additive is an organic acid, The organic acid is at least one selected from citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, eicosanoic acid, and sebacic acid. 2 . The organic solvent-based composition according to claim 1 , comprising a urethane resin or an acrylic resin. The organic solvent composition according to claim 1 or 2, comprising an ester organic solvent having 5 or more carbon atoms. The organic solvent-based composition according to claim 1 or 2, further comprising a colorant. The organic solvent-based composition according to claim 1 or 2, which is used as a printing ink, a primer or an OPV. 6 . A printed article comprising a surface of a substrate A or a film formed by printing the organic solvent-based composition according to claim 1 on the surface of the substrate A. 7 . A laminated body, wherein the printed material according to claim 6 is laminated in a manner such that the substrate B is arranged on the film side.

8. A method for producing a recycled substrate A, wherein the recycled substrate A is obtained by treating the printed material according to claim 6 with warm water or an alkaline solution to remove the film from the substrate A.

9. A method for producing a recycled base material A, wherein the laminate according to claim 7 is treated with warm water or an alkaline solution to remove the base material B together with the film, thereby obtaining the recycled base material A.

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