Organic solvent-based composition for forming a peelable film

Abstract

The present invention addresses the problem of providing: an organic solvent-based composition which can be adhered to a base material and from which it is possible to form a coating that is detachable from the base material when being treated with warm water or an alkaline solution; a laminate having a coating formed using the organic solvent-based composition; and a method for producing a recycled base material obtained through detaching of the coating. Said problem can be solved by an organic solvent-based composition in which an acid value of a solid content thereof is 1-150 mgKOH / g. The organic solvent-based composition preferably contains an acidic additive. The acid value of said acidic additive is preferably 3-900 mgKOH / g.

Description

Technical Field

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

Background Art

[0002] In recent years, the problem of marine plastics has become apparent due to plastics discarded or dumped into the ocean being decomposed in seawater and becoming finer (microplastics). There is concern that this microplastic enters the bodies of marine organisms, accumulates, and affects the health of seabirds and humans through the food chain. One way to improve this marine plastic problem is recycling. Improving the recycling rate of resources such as flexible packaging materials and plastic bottles leads to preventing plastics from entering the ocean. However, in current recycling, the film printed on the plastic substrate does not detach in the recycling process, mixes into the plastic, causing deterioration of hue and reduction of physical properties, and there is a problem of reducing the value of recycled plastics. If it is possible to detach the film from the plastic substrate in the recycling process and solve this problem, the value of recycled plastics will be improved, leading to the entry of new recycling operators and the improvement of the separate collection system by local governments. Thus, it is considered that the marine plastic problem will be improved by increasing the recycling rate. Therefore, there is a demand for the development of a film-forming material in which the film can be detached in the recycling process. In addition, since the organic solvent-based printing ink, which is a widely used film-forming material for plastic substrates, is being replaced by toluene-free and methyl ethyl ketone (MEK)-free ones in consideration of the impact on the health of workers and the environment, it is necessary to develop materials that solve the above problems in consideration of this fact.

[0003] In the prior art, a method of detaching a film containing a styrene-acrylic resin, a phenol resin, or a styrene-maleic resin printed on a heat-shrinkable PET film as a vehicle with alkaline water has been disclosed (Patent Document 1). Similarly, a method has been disclosed in which a coat layer containing a styrene-maleic resin, a rosin-maleic resin, or an acrylic acid copolymer resin is disposed between film layers on a heat-shrinkable PET film, and the coat layer is detached with alkaline water (Patent Documents 2 and 3). However, these technologies have limitations such as only guaranteeing characteristics for specific substrates and requiring a coat layer separate from the film layer, and are not suitable for recycling general-purpose plastic substrates containing polyolefin. On the other hand, an organic solvent-based printing ink for alkaline water detachment using a urethane resin having an acid value as a binder resin has also been disclosed (Patent Documents 4 and 5). However, when a urethane resin having an acid value is used as the main binder resin, it is assumed that the adhesion to the substrate is not sufficient, and problems such as an increase in the viscosity of the resin due to imparting an acid value to the urethane resin and the necessity of using a solvent that has a large impact on health and the environment for viscosity adjustment also occur. Therefore, there are still problems for general use as a film-forming material from which the film can be detached.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide an organic solvent-based composition that can adhere to a substrate and form a film that can be detached from the substrate by treatment with warm water or an alkaline solution, a laminate having a film formed using the organic solvent-based composition, and a method for producing a recycled substrate obtained by detaching the film.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the inventors have found that this can be achieved by adjusting the acid value in the solid content of the organic solvent-based composition within a specific range.

[0007] That is, the present invention includes the following. [1] An organic solvent-based composition for forming a film that detaches by treatment with warm water or an alkaline solution on the surface or on the surface of substrate A, wherein the acid value in the solid content of the organic solvent-based composition is 1 to 150 mgKOH / g. An organic solvent-based composition characterized by this. [2] The organic solvent-based composition according to [1], which contains an acidic additive. [3] The organic solvent-based composition according to [2], wherein the acid value of the acidic additive is 3 to 900 mgKOH / g. [4] The organic solvent-based composition according to any one of [2] or [3], wherein the molecular weight of the acidic additive is 50 to 1500. [5] The organic solvent-based composition according to any one of [2] to [4], wherein the acidic additive is at least one selected from the group consisting of a resin having an acidic group and an organic acid. [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. [7] The organic solvent-based composition according to [5] or [6], wherein the resin having an acidic group is at least one selected from the group consisting of a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, and a styrene-(anhydrous) maleic acid resin. [8] The organic solvent-based composition according to any one of [1] to [7], which contains a urethane resin or an acrylic resin. [9] The organic solvent-based composition according to any one of [1] to [8], which contains an ester-based organic solvent having 5 or more carbon atoms.

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

[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.

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

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

[13] A laminate formed by laminating a substrate B on the film side of the printed matter according to

[12] .

[14] A method for producing a recycled substrate A, which is obtained by detaching the film from the substrate A by treating the printed matter according to

[12] with warm water or an alkaline solution.

[15] A method for producing a recycled substrate A, which is obtained by detaching the substrate B together with the film by treating the laminate according to

[13] with warm water or an alkaline solution. [Effect of the Invention]

[0008] According to the present invention, it becomes possible to form a film that adheres to and detaches from a substrate. Further, the organic solvent-based composition can be prepared without substantially containing toluene and MEK, which may be harmful to health and the environment. [Embodiments for Carrying Out the Invention]

[0009] The embodiments of the present invention shown below only represent some embodiments of the present invention, and are not limited only to the described content as long as the gist is not significantly deviated.

[0010] (Organic Solvent-Based Composition) The present invention is an organic solvent-based composition for forming a film that detaches by treatment with warm water or an alkaline solution on the surface or on the surface of a substrate A, and the acid value in the solid content of the organic solvent-based composition is 1 to 150 mgKOH / g. It is an organic solvent-based composition characterized by this. In this specification, the organic solvent-based composition refers to a composition containing a solvent of an organic solvent and a resin. Substrate A will be described in the section (printed matter and laminate) described later. The releasability in warm water or an alkaline solution will be described in the section (method for peeling the film from Substrate A) described later. The formation of the film will be described in the section (printing on the substrate) described later.

[0011] Also, the acid value in the solid content of the organic solvent-based composition can be determined by calculation from the acid value of the raw materials. If this cannot be done, an ink film is prepared and measured after drying to obtain it. In addition, if the acid value is publicly available, that value is used, and if it is not publicly available, it is measured based on JIS0070-1992.

[0012] The acid value in the solid content of the organic solvent-based composition is 1 mgKOH / g or more, 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. Also, the acid value is 150 mgKOH / g or less, 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 the above range, it is possible to achieve both the releasability in warm water or an alkaline solution and the adhesion to the substrate.

[0013] When emphasizing the detachability in warm water or an alkaline solution, it is preferably 35 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 45 mgKOH / g or more, yet more preferably 50 mgKOH / g or more, even more preferably 55 mgKOH / g or more, still even more preferably 60 mgKOH / g or more, yet even more preferably 65 mgKOH / g or more, and most preferably 70 mgKOH / g or more. When emphasizing the adhesion to the substrate, it is preferably 70 mgKOH / g or less, more preferably 60 mgKOH / g or less, still more preferably 50 mgKOH / g or less, yet more preferably 40 mgKOH / g or less, and even more preferably 35 mgKOH / g or less. When emphasizing both the detachability in warm water or an alkaline solution and the adhesion to the substrate, the acid value range is 1 to 150 mgKOH / g, but more preferably 1 to 140 mgKOH / g, still more preferably 3 to 130 mgKOH / g, yet more preferably 5 to 120 mgKOH / g, even more preferably 10 to 110 mgKOH / g, still even more preferably 15 to 100 mgKOH / g, yet even more preferably 20 to 90 mgKOH / g, more preferably 25 to 80 mgKOH / g, still more preferably 30 to 70 mgKOH / g, and most preferably 35 to 70 mgKOH / g.

[0014] When emphasizing the detachability in warm water or an alkaline solution, it is more preferably 35 to 150 mgKOH / g, more preferably 40 to 150 mgKOH / g, still more preferably 45 to 150 mgKOH / g, yet more preferably 50 to 150 mgKOH / g, even more preferably 55 to 150 mgKOH / g, still even more preferably 60 to 150 mgKOH / g, yet even more preferably 65 to 150 mgKOH / g, and most preferably 70 to 150 mgKOH / g. When emphasizing the adhesion to the substrate, it is more preferably 1 to 70 mgKOH / g, more preferably 1 to 60 mgKOH / g, still more preferably 1 to 50 mgKOH / g, yet more preferably 1 to 40 mgKOH / g, and even more preferably 1 to 35 mgKOH / g. The organic solvent-based composition of the present invention can further contain an acidic additive and an organic solvent.

[0015] <Acidic additive> As the acidic additive, for example, an organic acid or a resin having an acidic group can be used. The acid value of the acidic additive is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more. Also, the acid value is preferably 900 mgKOH / g or less, more preferably 850 mgKOH / g or less, still more preferably 800 mgKOH / g or less, still more preferably 750 mgKOH / g or less, still more preferably 700 mgKOH / g or less, still more preferably 650 mgKOH / g or less, still more preferably 600 mgKOH / g or less, still more preferably 550 mgKOH / g or less. By setting the range as above, it is possible to achieve both the desorbability in warm water or an alkaline solution and the adhesion to the substrate.

[0016] When emphasizing the desorbability in warm water or an alkaline solution, 50 mgKOH / g or more is preferable, more preferably 100 mgKOH / g or more, still more preferably 200 mgKOH / g or more, still more preferably 300 mgKOH / g or more, still more preferably 400 mgKOH / g or more, still more preferably 500 mgKOH / g or more, and particularly preferably 550 mgKOH / g or more. When emphasizing the adhesion to the substrate, 550 mgKOH / g or less is preferable, more preferably 500 mgKOH / g or less, still more preferably 400 mgKOH / g or less, still more preferably 300 mgKOH / g or less, still more preferably 200 mgKOH / g or less. When emphasizing both the desorbability in warm water or an alkaline solution and the adhesion to the substrate, the acid value range is preferably 1 - 900 mgKOH / g, more preferably 3 - 850 mgKOH / g, still more preferably 5 - 800 mgKOH / g, still more preferably 10 - 750 mgKOH / g, still more preferably 20 - 700 mgKOH / g, still more preferably 30 - 650 mgKOH / g, still more preferably 40 - 600 mgKOH / g, still more preferably 50 - 550 mgKOH / g.

[0017] When emphasis is placed on the detachability in warm water or an alkaline solution, it is preferably 50 to 900 mgKOH / g, more preferably 65 to 900 mgKOH / g, still more preferably 80 to 900 mgKOH / g, even more preferably 100 to 900 mgKOH / g, still even more preferably 200 to 900 mgKOH / g, yet even more preferably 300 to 900 mgKOH / g, still yet even more preferably 400 to 900 mgKOH / g, even still more preferably 500 to 900 mgKOH / g, and most preferably 550 to 900 mgKOH / g. When emphasis is placed on the adhesion to the substrate, it is preferably 1 to 550 mgKOH / g, more preferably 1 to 500 mgKOH / g, still more preferably 1 to 400 mgKOH / g, even more preferably 1 to 300 mgKOH / g, and most preferably 1 to 200 mgKOH / g.

[0018] When the molecular weight of the acidic additive is to balance the detachability in warm water or an alkaline solution and the adhesion to the substrate, it is preferably 50 or more, more preferably 60 or more, still more preferably 80 or more, even more preferably 100 or more, still even more preferably 150 or more, yet even more preferably 200 or more, still yet even more preferably 250 or more, and most preferably 300 or more. Also, it is preferably 2000 or less, more preferably 1800 or less, still more preferably 1500 or less, even more preferably 1200 or less, and most preferably 1000 or less. As the range of the molecular weight, 50 to 2000 is preferred, 50 to 1800 is preferred, 50 to 1500 is preferred, 60 to 1500 is preferred, 80 to 1500 is preferred, 100 to 1500 is preferred, 150 to 1500 is preferred, 200 to 1500 is preferred, 250 to 1500 is preferred, 300 to 1500 is preferred, 300 to 1200 is preferred, and 300 to 1000 is preferred.

[0019] The organic acid refers to a low-molecular organic compound having an acidic group. Preferred examples of the low-molecular compound having an acidic group include saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, etc., and these can be used singly or in combination of two or more.

[0020] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, dodecanoic acid, etc. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc. Examples of hydroxy acids include lactic acid, malic acid, citric acid, etc. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, etc. 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, azelaic acid, etc. Examples of tricarboxylic acids include aconitic acid, trimer acid, etc. Examples of oxocarboxylic acids include pyruvic acid, oxaloacetic acid, etc. Examples of carboxylic acid derivatives include amino acids, nitrocarboxylic acids. These can be used alone or in a mixture of two or more. Also, if it is citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc., it can comply with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.

[0021] The acid value of the organic acid is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more, still more preferably 60 mgKOH / g or more, still more preferably 70 mgKOH / g or more, still more preferably 80 mgKOH / g or more, still more preferably 90 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Further, the acid value is preferably 900 mgKOH / g or less, more preferably 850 mgKOH / g or less, still more preferably 800 mgKOH / g or less, still more preferably 750 mgKOH / g or less, still more preferably 700 mgKOH / g or less, still more preferably 650 mgKOH / g or less, still more preferably 600 mgKOH / g or less, and more preferably 550 mgKOH / g or less. By setting it within the above range, it is possible to achieve both the desorbability in warm water or an alkaline solution and the adhesion to the substrate.

[0022] When emphasizing the desorbability in warm water or an alkaline solution, 100 mgKOH / g or more is preferable, more preferably 150 mgKOH / g or more, still more preferably 200 mgKOH / g or more, still more preferably 250 mgKOH / g or more, still more preferably 300 mgKOH / g or more, still more preferably 350 mgKOH / g or more, still more preferably 400 mgKOH / g or more, still more preferably 450 mgKOH / g or more, still more preferably 500 mgKOH / g or more, and still more preferably 550 mgKOH / g or more. When emphasizing the adhesion to the substrate, 550 mgKOH / g or less is preferable, more preferably 500 mgKOH / g or less, still more preferably 400 mgKOH / g or less, still more preferably 300 mgKOH / g or less, and still more preferably 200 mgKOH / g or less.

[0023] When both the detachability in warm water or an alkaline solution and the adhesion to the substrate are emphasized, the acid value preferably ranges from 1 to 900 mgKOH / g, more preferably from 3 to 850 mgKOH / g, still more preferably from 10 to 800 mgKOH / g, yet more preferably from 20 to 750 mgKOH / g, still more preferably from 30 to 700 mgKOH / g, yet more preferably from 50 to 650 mgKOH / g, still more preferably from 80 to 600 mgKOH / g, and most preferably from 100 to 550 mgKOH / g. When the detachability in warm water or an alkaline solution is emphasized, it preferably ranges from 100 to 900 mgKOH / g, more preferably from 150 to 900 mgKOH / g, still more preferably from 200 to 900 mgKOH / g, yet more preferably from 250 to 900 mgKOH / g, still more preferably from 300 to 900 mgKOH / g, yet more preferably from 350 to 900 mgKOH / g, still more preferably from 400 to 900 mgKOH / g, yet more preferably from 450 to 900 mgKOH / g, still more preferably from 500 to 900 mgKOH / g, and most preferably from 550 to 900 mgKOH / g. When the adhesion to the substrate is emphasized, it preferably ranges from 1 to 550 mgKOH / g, more preferably from 1 to 500 mgKOH / g, still more preferably from 1 to 400 mgKOH / g, yet more preferably from 1 to 300 mgKOH / g, and most preferably from 1 to 200 mgKOH / g.

[0024] The number of carbon atoms of the organic acid is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, yet more preferably 6 or more, still more preferably 7 or more, and most preferably 8 or more. By setting the number of carbon atoms of the organic acid within the above range, the adhesion to the substrate can be enhanced. Also, the number of carbon atoms of the organic acid is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less. By setting the number of carbon atoms of the organic acid within the above range, the dispersibility in an aqueous medium can be enhanced. The range of the number of carbon atoms of the organic acid is preferably from 3 to 20, more preferably from 3 to 18, still more preferably from 4 to 18, yet more preferably from 5 to 18, still more preferably from 6 to 18, yet more preferably from 6 to 16, still more preferably from 7 to 16, and most preferably from 8 to 16.

[0025] When attaching importance to the detachability from the substrate and the 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, still more preferably less than 1.5 g, and particularly preferably less than 1.2 g.

[0026] Examples of the resin having the acidic group include resins having an acid value such as cellulose resins, urethane resins (including polyurethanes, polyureas or polyurethane-polyureas; 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 and rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, petroleum resins, etc., and polymerizable monomers having a carboxyl group such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide, etc. Resins which are radical copolymers such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydrous)maleic acid resins, terpene-(anhydrous)maleic acid resins, etc. obtained by copolymerizing the polymerizable monomers having an acidic group, and acid-modified polyolefin resins, etc. may be mentioned, and these may be used alone or in admixture of two or more. As the resin having the acidic group, urethane resins, (meth)acrylic resins, resins having an acid value such as rosin-modified maleic acid resins and rosin-modified fumaric acid resins, and styrene-(anhydrous)maleic acid resins are more preferable.

[0027] The acid value of the resin having the acidic group is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. Further, the acid value is preferably 300 mgKOH / g or less, more preferably 280 mgKOH / g or less, still more preferably 260 mgKOH / g or less, still more preferably 240 mgKOH / g or less, still more preferably 220 mgKOH / g or less, and still more preferably 200 mgKOH / g or less. By setting the range as above, it is possible to achieve both the releasability in warm water or an alkaline solution and the adhesion to the substrate.

[0028] When importance is attached to the releasability in warm water or an alkaline solution, 50 mgKOH / g or more is preferable, 60 mgKOH / g or more is more preferable, 70 mgKOH / g or more is still more preferable, 80 mgKOH / g or more is still more preferable, 90 mgKOH / g or more is still more preferable, and 100 mgKOH / g or more is particularly preferable. When importance is attached to the adhesion to the substrate, 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 160 mgKOH / g or less is still more preferable, 140 mgKOH / g or less is still more preferable, 120 mgKOH / g or less is still more preferable, and 100 mgKOH / g or less is still more preferable. When both the releasability in warm water or an 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.

[0029] When emphasizing the removability in warm water or an alkaline solution, 50 to 300 mgKOH / g is preferable, 60 to 300 mgKOH / g is more preferable, 70 to 300 mgKOH / g is more preferable, 80 to 300 mgKOH / g is more preferable, 90 to 300 mgKOH / g is more preferable, and 100 to 300 mgKOH / g is more preferable. When emphasizing the adhesion to the substrate, 1 to 200 mgKOH / g is preferable, 1 to 180 mgKOH / g is more preferable, 1 to 160 mgKOH / g is more preferable, 1 to 140 mgKOH / g is more preferable, 1 to 120 mgKOH / g is more preferable, and 1 to 100 mgKOH / g is more preferable.

[0030] When the resin having the acidic group is a urethane resin, the weight average molecular weight of the resin having the 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 the acidic group within the above range, it is possible to balance the adhesion to the substrate and the removability in warm water or an alkaline solution.

[0031] When the resin having the acidic group is a urethane resin, the weight average molecular weight of the resin having the acidic group is preferably 100000 or less, more preferably 50000 or less, more preferably 40000 or less, more preferably 30000 or less, more preferably 25000 or less, more preferably 20000 or less, and more preferably 18000 or less. By setting the weight average molecular weight of the resin having the acidic group within the above range, the organic solvent-based composition of the present invention can be made to have a lower viscosity, and furthermore, the balance between the adhesion to the substrate and the removability in warm water or an alkaline solution can be achieved. When the resin having the acidic group is a urethane resin, the range of the weight average molecular weight of the resin having the acidic group is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 50,000, still more preferably from 3,000 to 50,000, still more preferably from 4,000 to 50,000, still more preferably from 5,000 to 40,000, still more preferably from 5,000 to 30,000, still more preferably from 6,000 to 30,000, still more preferably from 6,000 to 25,000, still more preferably from 7,000 to 25,000, still more preferably from 7,000 to 20,000, still more preferably from 8,000 to 20,000, still more preferably from 10,000 to 20,000, and still more preferably from 10,000 to 18,000. By setting the weight average molecular weight of the resin having the acidic group within the above range, printability can be improved.

[0032] When the resin having the acidic group is a (meth)acrylic resin, the weight average molecular weight of the resin having the acidic group is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 20,000 or more, still more preferably 50,000 or more, and still more preferably 100,000 or more. By setting the weight average molecular weight of the resin having the acidic group within the above range, the balance between adhesion to the substrate and detachability in warm water or an alkaline solution can be achieved.

[0033] When the resin having the acidic group is a (meth)acrylic resin, the weight average molecular weight of the resin having the acidic group is preferably 1,000,000 or less, more preferably 500,000 or less, and still more preferably 200,000 or less. By setting the weight average molecular weight of the resin having the acidic group within the above range, the organic solvent-based composition of the present invention can be made to have a lower viscosity, and furthermore, the balance between adhesion to the substrate and detachability in warm water or an alkaline solution can be achieved.

[0034] When the resin having the acidic group is a (meth)acrylic resin, the range of the weight average molecular weight of the resin having the acidic group is preferably from 3,000 to 1,000,000, more preferably from 5,000 to 500,000, still more preferably from 10,000 to 200,000, and even more preferably from 20,000 to 100,000. By setting the weight average molecular weight of the resin having the acidic group within the above range, the printing suitability can be improved.

[0035] When the resin having the 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 the acidic group is preferably 500 or more, more preferably 700 or more, and still more preferably 1,000 or more. By setting the weight average molecular weight of the resin having the acidic group within the above range, the balance between the adhesion to the substrate and the detachability in warm water or an alkaline solution can be achieved.

[0036] When the resin having the 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 the acidic group is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 10,000 or less, even more preferably 5,000 or less, and still more preferably 2,000 or less. By setting the weight average molecular weight of the resin having the acidic group within the above range, the viscosity of the ink can be reduced, and the balance between the adhesion to the substrate and the detachability in warm water or an alkaline solution can be achieved.

[0037] When the resin having the 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 range of the weight average molecular weight of the resin having the acidic group is preferably from 500 to 50,000, more preferably from 700 to 520,000, still more preferably from 1,000 to 10,000, and even more preferably from 1,000 to 5,000. By setting the weight average molecular weight of the resin having the acidic group within the above range, the printing suitability can be improved. When the resin having the acidic group is a styrene-(anhydrous) maleic acid resin, the weight average molecular weight of the resin having the acidic group is preferably 500 or more, more preferably 700 or more, and still more preferably 1000 or more. By setting the weight average molecular weight of the resin having the acidic group within the above range, it is possible to balance the adhesion to the substrate and the detachability in warm water or an alkaline solution. When the resin having the acidic group is a styrene-(anhydrous) maleic acid resin, the weight average molecular weight of the resin having the acidic group is preferably 100000 or less, more preferably 70000 or less, still more preferably 50000 or less, and still more preferably 30000 or less. By setting the weight average molecular weight of the resin having the acidic group within the above range, the organic solvent-based composition of the present invention can be made to have a lower viscosity, and further, the balance between the adhesion to the substrate and the detachability in warm water or an alkaline solution can be achieved.

[0038] When the resin having the acidic group is a styrene-(anhydrous) maleic acid resin, the range of the weight average molecular weight of the resin having the acidic group is preferably from 500 to 100000, more preferably from 700 to 30000, still more preferably from 1000 to 50000, and still more preferably from 1000 to 30000. By setting the weight average molecular weight of the resin having the acidic group within the above range, the printing suitability can be improved.

[0039] From the viewpoints of the redissolubility of the organic solvent-based composition of the present invention, the suppression of blocking of the printed matter, the improvement of the printing density, and the adhesion to the substrate, the content of the acidic additive as a solid content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less in the organic solvent-based composition of the present invention. The range of the content of the acidic additive as a solid content is preferably from 0.1 to 60% by mass, more preferably from 0.5 to 55% by mass, still more preferably from 1 to 50% by mass, still more preferably from 1.5 to 45% by mass, and still more preferably from 2 to 40% by mass.

[0040] When the acidic additive is an organic acid, the content as the solid content of the organic acid is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 16% by mass or less, still more preferably 14% by mass or less, still more preferably 12% by mass or less, and still more preferably 10% by mass or less in the organic solvent-based composition of the present invention. As the range of the content as the solid content of the above organic acid, 0.1 to 20% by mass is preferable, 0.2 to 18% by mass is more preferable, 0.3 to 16% by mass is still more preferable, 0.5 to 14% by mass is still more preferable, 1 to 12% by mass is still more preferable, 1.5 to 10% by mass is still more preferable, and 2 to 10% by mass is still more preferable.

[0041] When the acidic additive is a resin having an acidic group, the content as the solid content of the resin having an acidic group is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less in the organic solvent-based composition of the present invention. As the range of the content as the solid content of the above acidic additive, 0.1 to 60% by mass is preferable, 0.5 to 55% by mass is more preferable, 1 to 50% by mass is still more preferable, 1.5 to 45% by mass is still more preferable, and 2 to 40% by mass is still more preferable.

[0042] <Organic solvent> The organic solvent is not particularly limited. For example, aromatic hydrocarbon-based solvents such as toluene, xylene, Solvesso #100, and Solvesso #150; aliphatic hydrocarbon-based solvents such as hexane, methylcyclohexane, heptane, octane, and decane; and various ester-based organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. In addition, water-miscible organic solvents include alcohol-based solvents such as methanol, ethanol, propanol, butanol, and isopropyl alcohol; ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; and various glycol ether-based organic solvents such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. These can be used alone or in combination of two or more.

[0043] From the viewpoint of preventing the semi-drying of the organic solvent-based composition of the present invention due to the easy evaporation of the ester-based organic solvent, it is more preferable to contain an ester-based organic solvent having 5 or more carbon atoms. The ester-based organic solvent having 5 or more carbon atoms is not limited, but isopropyl acetate, normal propyl acetate, and butyl acetate are more preferable, and normal propyl acetate is particularly preferable.

[0044] The content of the ester-based 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. Further, 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.

[0045] The content of the ester-based organic solvent in the organic solvent-based 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%.

[0046] When the organic solvent-based composition of the present invention is used for gravure ink applications, it preferably does not contain an aromatic hydrocarbon-based organic solvent and contains an alcohol having a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is 100. By containing an alcohol having a specific evaporation rate of 100 or less, it is possible to maintain the highlight transfer property with a dot area of 10% or less and improve the highlight. The mechanism is as follows: First, 1) After the organic solvent-based composition of the present invention is transferred to the substrate, half of the organic solvent-based composition of the present invention remains in the cells of the gravure plate. 2) The remaining organic solvent-based composition of the present invention evaporates the solvent it contains until it comes into contact again with the organic solvent-based composition in the ink pan and becomes semi-dry. Further, since it evaporates from the solvent with a high evaporation rate, the solvent with a slow evaporation rate remains in the ink pan. 3) At this time, if a solvent with high resin solubility remains, when the semi-dry composition comes into contact again with the organic solvent-based composition of the present invention, it redissolves, preventing the organic solvent-based composition of the present invention from solidifying in the cells. In general-purpose alcohols with a specific evaporation rate exceeding 100 when the evaporation rate of butyl acetate is set to 100, the above-described mechanism tends to be difficult to function because of their high volatility. Second, alcohols with a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is set to 100 tend to enhance the solubility of the urethane resin because the ratio of hydroxyl groups (alcohol groups) in one molecule of the alcohol is low. In addition, from the perspectives of both work hygiene during printing and the harmfulness of packaging materials, it is more preferable to use ethyl acetate, propyl acetate, isopropanol, normal propanol, etc., and not to use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone. Among them, from the perspective of solubility in urethane resin and nitrocellulose, a mixed solution of isopropyl alcohol / ethyl acetate / normal propyl acetate / methylcyclohexane is more preferable. Also, glycol ethers can be added if the amount is less than 10% by mass of the total amount of the composition for drying adjustment.

[0047] <Other components> Furthermore, the organic solvent-based composition of the present invention may further contain a binder resin, a colorant, an auxiliary agent, or the like. Examples of the binder resin include cellulose-based 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, etc., and these can be used in appropriate combinations. Among them, urethane resins, (meth)acrylic resins, rosin-based resins and their modified products, etc. are often used in appropriate combinations.

[0048] For so-called surface printing applications where a film is exposed by printing on the front side of the substrate, it is preferable to use a urethane resin, a cellulose-based resin, a vinyl chloride-vinyl acetate copolymer resin, a polyamide resin, a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin, or a (meth)acrylic resin alone or in combination. It is more preferable to use a urethane resin, a (meth)acrylic resin or a cellulose-based resin alone or in combination.

[0049] For so-called back printing applications where a film is disposed between the substrate and another substrate through an adhesive by printing on the back side of the substrate, it is preferable to use a urethane resin, a cellulose-based resin, a vinyl chloride-vinyl acetate copolymer resin or a (meth)acrylic resin alone or in combination. It is more preferable to use a urethane resin alone or in combination.

[0050] In the organic solvent-based composition of the present invention, the content of the urethane resin is, for example, in the case of gravure ink used for gravure printing, 5% by mass or more in terms of solid content based on the total mass of the ink from the viewpoint of ensuring sufficient adhesiveness of the gravure ink to the printing object, and preferably 25% by mass or less from the viewpoints of appropriate ink viscosity and work efficiency during ink production and printing. In the case of flexo ink used for flexographic printing, it is preferably 5% by mass or more and 30% by mass or less in terms of solid content based on the total mass of the flexo ink.

[0051] The number average molecular weight of the urethane resin used in the organic solvent-based composition of the present invention is preferably in the range of 15,000 to 100,000. When the number average molecular weight of the urethane resin is less than 15,000, the blocking resistance, laminate strength, chemical resistance, etc. of the resulting ink tend to be low. When it exceeds 100,000, the viscosity of the resulting ink tends to be high and a predetermined printing density cannot be obtained.

[0052] As the reaction raw material of the urethane resin used in the organic solvent-based composition of the present invention, it is preferable to use a polyester polyol and / or a polyether polyol.

[0053] It is preferable that the number average molecular weight of the polyester polyol is 3,000 to 7,000. If the number average molecular weight of the polyester polyol is less than 3,000, the film of the urethane resin tends to become hard and the adhesiveness to the polyester film is likely to decrease. When the number average molecular weight is greater than 7,000, the film of the urethane resin tends to become fragile and the blocking resistance of the film is likely to decrease. On the other hand, it is preferable that the polyether polyol is 1 to 50 parts by mass with respect to 100 parts by mass of the urethane resin. When the polyether polyol is less than 1 part by mass, in addition to the decrease in the solubility of the polyurethane resin in ketone, ester, and alcohol solvents, the adhesiveness particularly on a high-functional barrier film tends to decrease. Also, the redissolvability of the film in the solvent decreases, and the tone reproducibility of the printed matter tends to decrease. Also, when it exceeds 50 parts by mass, the film becomes excessively soft and tends to have poor blocking resistance.

[0054] In addition, the number average molecular weight of the polyester polyol indicates a value measured under the following conditions by the gel permeation chromatography (GPC) method. Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 piece Detector: RI (differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was created using the following standard polystyrene. (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0055] As the polyester polyol, for example, a compound obtained by a known esterification reaction between a compound having two or more hydroxyl groups and a polybasic acid can be used.

[0056] The compound having two or more hydroxyl groups is used as a chain extender. For example, glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; glycols having a branched structure such as 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol; aliphatic polyols such as trimethylolpropane, trimethylolethane, pentaerythritol, sucrose, methylene glycol, glycerin, sorbitol; aromatic polyols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc., compounds having a number average molecular weight in the range of 50 to 400 can be used. These chain extenders may be used alone or in combination of two or more.

[0057] As the polybasic acid, 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, anhydrides of these acids, etc. can be used. These polybasic acids may be used alone or in combination of two or more.

[0058] In addition, the polyether polyol preferably has a number average molecular weight of 100 to 4,000. Details will be described later. Examples of the polyether polyol include polyether polyols that are polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc. Specifically, well-known general-purpose ones such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used, and among them, polyethylene glycol is preferable. By containing the polyester polyol and / or the polyether polyol within the above range, the adhesion on the base film is significantly improved, and as a result, the blocking resistance and the laminate strength become excellent.

[0059] Similarly, when the number average molecular weight of the polyether polyol is less than 100, the film of the urethane resin tends to become hard and the adhesiveness to the polyester film is likely to decrease. When the number average molecular weight is greater than 4,000, the film of the urethane resin tends to become fragile and the blocking resistance of the film is likely to decrease. Incidentally, the number average molecular weight of the polyether polyol was measured under the same conditions by the gel permeation chromatography (GPC) method, similar to the polyester polyol.

[0060] Examples of the diisocyanate compound used for the urethane resin in the organic solvent-based composition of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. generally used for the production of urethane resins. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimer 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, tolylene diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and dimer diisocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group. These diisocyanate compounds can be used alone or in admixture of two or more.

[0061] As the chain extender used for the urethane resin in the organic solvent-based composition of the present invention, in addition to ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, etc., amines having a hydroxyl group in the molecule such as 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, 2-hydroxyethyl propylenediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethyl propylenediamine, 2-hydroxypyrropyl ethylenediamine, di-2-hydroxypyrropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine can also be used. These chain extenders can be used alone or in combination of two or more.

[0062] 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. When the amine value exceeds 10.0 mgKOH / g, the blocking resistance tends to be poor, and in addition, the two-component stability after adding the curing agent decreases. From the viewpoint of maintaining good blocking resistance and two-component stability while retaining plate fogging property, adhesiveness, and extrusion lamination strength, the range of 1.0 to 5.0 mgKOH / g is more preferable, and further preferably the range of 1.0 to 3.5 mgKOH / g.

[0063] (The (meth)acrylic resin is obtained by copolymerizing various (meth)acrylate monomers and, if necessary, other polymerizable unsaturated group-containing compounds.

[0064] The monomers constituting the (meth)acrylic resin are not particularly limited. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (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, dicyclopentanyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-pentafluoropropyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, 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-methylol (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, acetoacetoxyethyl (meth)acrylate and other (meth)acrylic monomers can be used. In addition, the term "(meth)acrylate" refers to either one or both of acrylate and methacrylate, and the term "(meth)acrylic" refers to either one or both of acrylic and methacrylic.

[0065] As the polymerizable unsaturated group-containing compound, in addition to the (meth)acrylic monomer, 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, N-vinylpyrrolidone, etc. can also be used. These can be used alone or in combination of two or more kinds.

[0066] In addition, the acrylic resins (A1) and (A2) having an acid value can be obtained by copolymerizing (meth)acrylic monomers having a carboxyl group such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, β-(meth)acryloyloxyethyl hydrogen succinate, β-(meth)acryloyloxyethyl hydrogen phthalate, etc. for the purpose of introducing one or more hydrophilic groups selected from the group consisting of a carboxyl group and a carboxylate group in which the carboxyl group is neutralized by a basic compound. The acrylic resins (A1) and (A2) can be produced, for example, by polymerizing various monomers in a temperature range of 60°C to 150°C in the presence of a polymerization initiator. Examples of the polymerization method include bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, etc. Examples of the polymerization mode include random copolymer, block copolymer, graft copolymer, etc.

[0067] Examples of the colorant used in the organic solvent-based composition of the present invention include inorganic pigments, organic pigments, or dyes used in general inks, paints, and recording agents. Examples of organic pigments include soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, ansanthrone-based, dianthraquinonyl-based, anthrapyrimidine-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine azo-based, flavanthrone-based, diketopyrrolopyrrole-based, isoindoline-based, indanthrone-based, carbon black-based pigments, and the like. Further, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo Bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, and the like can be mentioned. Also, either unacid-treated pigments or acid-treated pigments can be used. Specific examples of preferred organic pigments are given below.

[0068] Examples of the black pigment include, for example, C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7, C.I. Pigment Black 9, C.I. Pigment Black 20, and the like.

[0069] Examples of blue pigments include C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 22, C.I. Pigment Blue 24:1, C.I. Pigment Blue 25, C.I. Pigment Blue 26, C.I. Pigment Blue 60, C.I. Pigment Blue 61, C.I. Pigment Blue 62, C.I. Pigment Blue 63, C.I. Pigment Blue 64, C.I. Pigment Blue 75, C.I. Pigment Blue 79, C.I. Pigment Blue 80, and the like.

[0070] Examples of green pigments include C.I. Pigment Green 1, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 10, C.I. Pigment Green 36, and the like.

[0071] Examples of red pigments include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 20, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 38, C.I. Pigment Red 41, C.I. Pigment Red 43, C.I. Pigment Red 46, C.I. Pigment Red 48, C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 48:5, C.I. Pigment Red 48:6, C.I. Pigment Red 49, C.I. Pigment Red 49:1, C.I. Pigment Red 49:2, C.I. Pigment Red 49:3, C.I. Pigment Red 52, C.I. Pigment Red 52:1, C.I. Pigment Red 52:2, C.I. Pigment Red 53, C.I. Pigment Red 53:1, C.I. Pigment Red 53:2, C.I. Pigment Red 53:3, C.I. Pigment Red 54, C.I. Pigment Red 57, C.I. Pigment Red 57:1, C.I. Pigment Red 58, C.I. Pigment Red 58:1, C.I. Pigment Red 58:2, C.I. Pigment Red 58:3, C.I. Pigment Red 58:4, C.I. Pigment Red 60:1, C.I. Pigment Red 63, C.I. Pigment Red 63:1, C.I. Pigment Red 63:2, C.I. Pigment Red 63:3, C.I. Pigment Red 64:1, C.I. Pigment Red 68, C.I. Pigment Red 68, C.I. Pigment Red 81:1, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 89, C.I. Pigment Red 95, C.I. Pigment Red 112, C.I. Pigment Red 114, C.I. Pigment Red 119, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 136, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 147, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 164, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 169, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 172, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 181, C.I. Pigment Red 182, C.I. Pigment Red 183, C.I. Pigment Red 184, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 188, C.I. Pigment Red 190, C.I. Pigment Red 192, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 200,. C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 210, C.I. Pigment Red 211, C.I. Pigment Red 213, C.I. Pigment Red 214, C.I. Pigment Red 216, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 223, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 237, C.I. Pigment Red 238, C.I. Pigment Red 239, C.I. Pigment Red 240, C.I. Pigment Red 242, C.I. Pigment Red 245, C.I. Pigment Red 247, C.I. Pigment Red 248, C.I. Pigment Red 251, C.I. Pigment Red 253, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 256, C.I. Pigment Red 257, C.I. Pigment Red 258, C.I. Pigment Red 260, C.I. Pigment Red 262, C.I. Pigment Red 263, C.I. Pigment Red 264, C.I. Pigment Red 266, C.I. Pigment Red 268, C.I. Pigment Red 269, C.I. Pigment Red 270, C.I. Pigment Red 271, C.I. Pigment Red 272, C.I. Pigment Red 279, etc. can be mentioned.

[0072] Examples of purple pigments include, for example, C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3:1, C.I. Pigment Violet 3:3, C.I. Pigment Violet 5:1, C.I. Pigment Violet 13, C.I. Pigment Violet 19 (γ-type, β-type), C.I. Pigment Violet 23, C.I. Pigment Violet 25, C.I. Pigment Violet 27, C.I. Pigment Violet 29, C.I. Pigment Violet 31, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 37, C.I. Pigment Violet 38, C.I. Pigment Violet 42, C.I. Pigment Violet 50, and the like.

[0073] Examples of yellow pigments include, for example, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, Pigment Yellow 17, C.I. Pigment Yellow 24, C.I. Pigment Yellow 42, C.I. Pigment Yellow 55, C.I. Pigment Yellow 62, C.I. Pigment Yellow 65, C.I. Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 120, Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 174, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 213, etc.

[0074] Examples of orange pigments include, for example, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 16, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 37, C.I. Pigment Orange 38, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 71, or C.I. Pigment Orange 74, etc.

[0075] Examples of the brown pigment include C.I. Pigment Brown 23, C.I. Pigment Brown 25, or C.I. Pigment Brown 26. Among them, preferred pigments include C.I. Pigment Black 7 as the black pigment, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6 as the blue pigments, C.I. Pigment Green 7 as the green pigment, C.I. Pigment Red 57:1, C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 146, C.I. Pigment Red 242, C.I. Pigment Red 185, C.I. Pigment Red 122, C.I. Pigment Red 178, C.I. Pigment Red 149, C.I. Pigment Red 144, C.I. Pigment Red 166 as the red pigments, C.I. Pigment Violet 23, C.I. Pigment Violet 37 as the purple pigments, C.I. Pigment Yellow 83, C.I. Pigment Yellow 14, C.I. Pigment Yellow 180, C.I. Pigment Yellow 139 as the yellow pigments, C.I. Pigment Orange 38, C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Orange 64 as the orange pigments, etc. It is preferable to use at least one or two or more selected from these groups.

[0076] From the viewpoints of ensuring the concentration and coloring power of the organic solvent-based composition of the present invention, the total content ratio of the pigments is preferably 1% by mass or more and preferably 60% by mass or less in the total amount of the organic solvent-based composition of the present invention.

[0077] As the auxiliary agent, waxes such as paraffin wax, polyethylene wax, and carnauba wax for imparting abrasion resistance, slipperiness, etc.; fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide; silicone-based and non-silicone-based defoaming agents for suppressing foaming during printing; dispersants, etc. can also be appropriately used. As the dispersant, a nonionic dispersant is preferred.

[0078] 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. Also, for example, it may be 1 mgKOH / g or more, and further 3 mgKOH / g or more.

[0079] The acid value of the dispersant is preferably smaller than the acid value of the acidic additive. The difference between the acid value of the acidic additive and the acid value of the dispersant is preferably, for example, 1 mgKOH / g or more, more preferably 3 mgKOH / g or more. Also, it is preferably 30 mgKOH / g or less, and more preferably 20 mgKOH / g or less.

[0080] 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, 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 with respect to 100 parts by mass of the colorant.

[0081] In addition to the above, water, wetting agents, adhesion aids, leveling agents, antistatic agents, viscosity modifiers, metal chelates, trapping agents, antiblocking agents, isocyanate-based curing agents, and silane coupling agents can also be used as required. The viscosity of the liquid ink, as a value measured at 25°C using a Rheonik Zahn cup #4 manufactured by Rheonik Co., Ltd., is preferably 6 seconds or more, more preferably 10 seconds or more, and even more preferably 13 seconds or more. Also, it is preferably 25 seconds or less, more preferably 20 seconds or less, and even more preferably 18 seconds or less.

[0082] The surface tension of the organic solvent-based composition of the present invention is preferably 25 mN / m or more, more preferably 33 mN / m or more. Also, 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, it is possible to suppress dot bridging (staining of the printed surface where adjacent halftone dots are connected at the halftone dot portion) while maintaining the wettability of the organic solvent-based composition of the present invention to the substrate. By appropriately lowering the surface tension of the organic solvent-based composition of the present invention, it is possible to enhance the wettability of the organic solvent-based composition of the present invention to the substrate and suppress repellency.

[0083] The organic solvent-based composition of the present invention can be used as a coating such as printing ink, primer, OPV, or paint, and is preferably used as printing ink, primer, or OPV. As printing ink, primer, or OPV, it is preferably used for gravure printing or flexographic printing applications.

[0084] When the organic solvent-based composition of the present invention is used for gravure printing or flexographic printing applications, it can be produced using an Eiger mill, sand mill, gamma mill, attritor, etc., which are generally used in the production of gravure or flexographic inks.

[0085] When preparing the organic solvent-based composition of the present invention, from the viewpoint of uniformity, at least a part of the binder resin, the colorant, at least a part of the acidic additive, and at least a part of the organic solvent may be mixed in advance to prepare a preliminary composition (ground meat base ink).

[0086] Also, resist ink can be mentioned as a composition removed from the substrate in the same manner as the present invention. However, the resist ink is for the purpose of removing a part of the coating film from the substrate in advance and processing the substrate, and its use and purpose are fundamentally different from those of the ink of the present invention, which aims to remove the entire film and recycle the substrate, so it does not fall under the well-known technology of the present invention.

[0087] (Printing on a substrate) The organic solvent-based composition of the present invention has excellent adhesion to various substrates and can be used for printing on paper, synthetic paper, cloth, thermoplastic resin films, plastic products, steel plates, etc. It is useful as an ink for gravure printing using a gravure printing plate such as an electron engraved intaglio plate or for flexographic printing using a flexographic printing plate such as a resin plate. On the other hand, it can also be used for an inkjet method in which ink is ejected from an inkjet nozzle without using a plate, but this is not very preferable. That is, in the case of inkjet ink, the ink droplets ejected from the nozzle directly adhere to the substrate to form a printed matter, whereas the organic solvent-based composition of the present invention once adheres and transfers the printing ink to a printing plate or a printing pattern, and then only the ink adheres to the substrate again and is dried as necessary to obtain a printed matter.

[0088] The film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the organic solvent-based composition of the present invention is preferably, for example, 10 μm or less, and more preferably 5 μm or less.

[0089] In addition, the organic solvent-based composition of the present invention contains an acidic additive, and it is preferable to wash the equipment used immediately after use. As the cleaning agent, a cleaning agent generally used for cleaning the organic solvent-based composition can be used.

[0090] (Printed matter and laminate) A printed matter having a film can be obtained by printing the organic solvent-based composition of the present invention on the surface or on the surface of substrate A. A laminate can be obtained by laminating substrate B in such a manner that it is disposed on the film side of the printed matter. Further, in the laminate, the film of the printed matter and substrate B may be laminated via an adhesive layer. As embodiments of the printed matter printed using the organic solvent-based composition of the present invention and the laminate constituted by using the printed matter, although not limited, the following forms are preferably mentioned.

[0091] <Sheet printing> · Substrate A - Film layer (white) - Film layer (color) ·Substrate A - Primer layer - Film layer (white) - Film layer (color) ·Substrate A - Film layer (white) - Film layer (color) - OPV layer ·Substrate A - Primer layer - Film layer (white) - Film layer (color) - OPV layer ·Substrate A - Film layer (color) - Film layer (white) ·Substrate A - Primer layer - Film layer (color) - Film layer (white) ·Substrate A - Film layer (color) - Film layer (white) - OPV layer ·Substrate A - Primer layer - Film layer (color) - Film layer (white) - OPV layer

[0092] <Back coating · Lamination> ·Substrate A - Film layer (white) - Film layer (color) - Adhesive layer - Substrate B ·Substrate A - Primer layer - Film layer (white) - Film layer (color) - Adhesive layer - Substrate B ·Substrate A - Film layer (white) - Film layer (color) - OPV layer - Adhesive layer - Substrate B ·Substrate A - Primer layer - Film layer (white) - Film layer (color) - OPV layer - Adhesive layer - Substrate B ·Substrate A - Film layer (color) - Film layer (white) - Adhesive layer - Substrate B ·Substrate A - Primer layer - Film layer (color) - Film layer (white) - Adhesive layer - Substrate B ·Substrate A - Film layer (color) - Film layer (white) - OPV layer - Adhesive layer - Substrate B ·Substrate A - Primer layer - Film layer (color) - Film layer (white) - OPV layer - Adhesive layer - Substrate B ·Substrate A - Film layer (white) - Film layer (color) - Resin C layer - Substrate B ·Substrate A - Primer layer - Film layer (white) - Film layer (color) - Resin C layer - Substrate B ·Substrate A - Film layer (white) - Film layer (color) - OPV layer - Resin C layer - Substrate B ·Substrate A - Primer layer - Film layer (white) - Film layer (color) - OPV layer - Resin C layer - Substrate B ·Substrate A - Film layer (color) - Film layer (white) - Resin C layer - Substrate B ·Substrate A - Primer layer - Film layer (color) - Film layer (white) - Resin C layer - Substrate B · Substrate A - Film layer (Color) - Film layer (White) - OPV layer - Resin C layer - Substrate B · Substrate A - Primer layer - Film layer (Color) - Film layer (White) - OPV layer - Resin C layer - Substrate B · Substrate A - Film layer (White) - Film layer (Color) - Substrate B · Substrate A - Primer layer - Film layer (White) - Film layer (Color) - Substrate B · Substrate A - Film layer (White) - Film layer (Color) - OPV layer - Substrate B · Substrate A - Primer layer - Film layer (White) - Film layer (Color) - OPV layer - Substrate B · Substrate A - Film layer (Color) - Film layer (White) - Substrate B · Substrate A - Primer layer - Film layer (Color) - Film layer (White) - Substrate B · Substrate A - Film layer (Color) - Film layer (White) - OPV layer - Substrate B · Substrate A - Primer layer - Film layer (Color) - Film layer (White) - OPV layer - Substrate B

[0093] Here, the substrate A represents the substrate A described later, the film layer (White) represents the film layer formed by printing the organic solvent-based composition of the present invention using the colorant used in the white ink described above as the colorant of the organic solvent-based composition of the present invention, the film layer (Color) represents the film layer formed by printing the organic solvent-based composition of the present invention using a colorant other than the colorant used in the white ink described above as the colorant of the organic solvent-based composition of the present invention, the primer layer represents the layer formed using the primer described later, the adhesive layer represents the layer formed using the adhesive described later, the OPV layer represents the layer formed using the OPV (overprint varnish) described later, the resin C layer represents the layer formed using the resin C described later, and the substrate B represents the substrate B described later.

[0094] Also, the configuration of the back printing and lamination includes repetitions and combinations of the above forms, and also includes composite and multi-layer configurations.

[0095] As the base material A, a plastic base material is preferable. Examples include polyamide resins such as nylon 6, nylon 66, and nylon 46; polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; polyhydroxycarboxylic acids such as polylactic acid; biodegradable resins such as aliphatic polyester resins like poly(ethylene succinate) and poly(butylene succinate); polyolefin resins such as polypropylene and polyethylene; thermoplastic resins such as polyimide resins, polyarylate resins, or mixtures thereof. Among these, films made of polyester, polyamide, polyethylene, or polypropylene and laminates thereof can be preferably used. When emphasizing the releasability of the organic solvent-based composition of the present invention, polypropylene or polyethylene is more preferable. These base material films can be either unstretched films or stretched films, and their manufacturing methods are not limited. Also, the thickness of the base material film is not particularly limited, but usually, a range of 1 to 500 μm is sufficient.

[0096] It is preferable that the printing surface of the base material A is subjected to corona discharge treatment, and silica, alumina, etc. may be deposited.

[0097] As the base material B, the same materials as those of the base material A can be mentioned, and they can be the same or different, but a plastic base material is preferable, and a thermoplastic resin base material is more preferable. When the laminate is an extrusion laminate, it may be the same as the resin C described later. Also, it may be laminated with a metal foil or a metal foil layer of a vapor deposition film layer.

[0098] The resin C is preferably a thermoplastic resin, more preferably a polyolefin, and particularly preferably polypropylene or polyethylene and modified resins thereof. As a primer for forming a primer layer, since it is easily dissolved or hydrolyzed by an alkaline solution, it preferably contains a resin having an acidic group. A resin having an acidic group or a low molecular compound can be used alone as the primer. Further, a resin having an acidic group or a low molecular compound can be mixed and used with a resin having no acidic group.

[0099] Examples of the resin having an acidic group include resins having an acid value such as cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins and rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, petroleum resins, etc., and polymerizable monomers having a carboxyl group such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide, etc. Resins which are radical copolymers such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydrous)maleic acid resins, terpene-(anhydrous)maleic acid resins, etc. obtained by copolymerizing these polymerizable monomers having an acidic group, and acid-modified polyolefin resins, etc. are mentioned, and these can be used singly or in combination of two or more.

[0100] Further, the primer layer can also be used by mixing one or more low molecular compounds having an acidic group with a resin having a low acid value and film-forming property at normal temperature.

[0101] Preferred examples of the low molecular compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, etc., and these can be used singly or in combination of two or more.

[0102] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, dodecanoic acid, etc. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc. Examples of hydroxy acids include lactic acid, malic acid, citric acid, etc. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, etc. 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, azelaic acid, etc. Examples of tricarboxylic acids include aconitic acid, trimer acid, etc. Examples of oxocarboxylic acids include pyruvic acid, oxaloacetic acid, etc. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in a mixture of one or more of them. Also, if it is citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc., it can comply with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.

[0103] Examples of the resin having film-forming properties at normal temperature include various synthetic resins. For example, polyester, a copolymer of polyvinyl chloride or vinyl chloride and another monomer containing an unsaturated double bond, a homopolymer of (meth)acrylic acid ester or a copolymer of (meth)acrylic acid ester and another monomer containing an unsaturated double bond, polystyrene or a copolymer of styrene monomer and another monomer containing an unsaturated double bond, a ketone-formaldehyde condensate or its hydrogenated product, a polyfunctional epoxy resin, polyvinyl acetal, polyurethane, etc. These can be used alone or in combination of one or more selected from these.

[0104] Examples of the polyfunctional epoxy compound include bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, bisphenol S novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, and the like. When using a resin having a low acid value and film-forming properties at room temperature by mixing one or more low molecular weight compounds having an acidic group, the addition amount may be appropriately determined within a range that does not impair the printability or coatability of the primer solution, but is generally preferably in the range of 0.5 to 50% by mass, more preferably in the range of 1.0 to 30% by mass, based on the solid content of the primer solution.

[0105] When the object to be printed is, for example, polypropylene (PP), as the resin having film-forming properties, at least one thermoplastic resin selected from the group consisting of a ketone-formaldehyde condensate or its hydrogenated product, polyester, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetal, which has good adhesion to PP itself and is solid at 50°C, is preferably used. Examples of such a ketone-formaldehyde condensate or its hydrogenated product include Evonik Degussa Japan Co., Ltd.'s TEGO (registered trademark) VariPlus series (SK, AP, etc.), examples of polyester include Toyobo Co., Ltd.'s BYRON (registered trademark) series (BYRON 200, etc.), examples of vinyl chloride-vinyl acetate copolymer include Nisshin Chemical Industry Co., Ltd.'s Solvain (registered trademark) series (Solvain AL, etc.), and examples of polyvinyl acetal include Sekisui Chemical Co., Ltd.'s Esrec (registered trademark) series (Esrec KS-10, etc.).

[0106] To form a primer layer on a substrate, a solution adjusted using each of the above components is applied to the substrate and dried. The coating amount is about 0.1 to 5 μm (dry thickness). However, if it is less than 0.1, it is difficult to apply uniformly, and if it exceeds 5 μm, it is uneconomical and not practical. For coating, ordinary coating methods such as gravure, letterpress, flexo, roll coater, reverse coater, spray method, etc. are used. The formation of the primer layer and printing thereon can be continuous (inline) or the formation of the primer layer and printing can be performed separately.

[0107] When printing is carried out inline immediately after primer coating using a printing machine such as roll-to-roll, depending on the re-solubility of the resin used in the primer layer in the ink solvent and the glass transition point (Tg) of the resin itself, so-called blocking occurs where the printed surface sticks to the back surface of the substrate. To prevent such blocking, transparent particles with a particle size of 0.1 μm to 10 μm such as silica and titanium oxide can be mixed into the primer solvent in an amount of about 0.005 to 5% based on the total amount of the primer as an anti-blocking agent.

[0108] Also, for the purpose of preventing blocking, the resin solution with a high acid value used in the primer can be neutralized in advance with ammonia or the like before coating to prevent re-solubility in the solvent contained in the printing ink.

[0109] As the adhesive for forming the adhesive layer, any commercially available reactive adhesive can be used without particular limitation. Among them, a so-called two-component type of polyisocyanate composition and polyol composition or a one-component type reactive adhesive of polyisocyanate is preferable. The polyisocyanate composition used in a general reactive adhesive is a composition containing a polyisocyanate compound as a main component, and any polyisocyanate compound known as a polyisocyanate compound for reactive adhesives can be used without particular limitation. Examples of specific polyisocyanate compounds include, for example, polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, etc.; compounds obtained by modifying a part of the isocyanate groups (NCO groups) of these polyisocyanates with carbodiimide; polyisocyanates having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, etc.; linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, etc., and compounds obtained by modifying a part of the NCO groups of these polyisocyanates with carbodiimide; isocyanurate bodies of the above various polyisocyanates; allophanate bodies derived from the above various polyisocyanates; biuret bodies derived from the above various polyisocyanates; adduct bodies obtained by modifying the above various polyisocyanates with trimethylolpropane; polyisocyanates which are reaction products of the above various polyisocyanates and a polyol component described later, etc.

[0110] The polyol composition used in a general reactive adhesive is a composition containing a polyol compound as a main component, and it can be used without particular limitation as long as it is known as a polyol compound for reactive adhesives. Examples of specific polyol compounds include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol and other glycols; glycerin, trimethylolpropane, pentaerythritol and other trifunctional or tetrafunctional aliphatic alcohols; bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F and other bisphenols; dimer diol, and polymer polyols selected from polyester polyols, polyether polyols, polyurethane polyols, polyether ester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil or mixtures thereof can be mentioned.

[0111] Among them, since it is easily dissolved or hydrolyzed by an alkaline solution, it is preferable that any of the constituent components of the reactive adhesive has an ester bond, and it can be easily separated into a single-layer film in a short time in the film detachment step described later.

[0112] When any of the components of the reactive adhesive has an ester bond, specifically, it refers to a polyol composition having a polyol compound such as a polyester polyol, a polyether ester polyol, a polyester (polyurethane) polyol, an acrylic polyol, etc. having an ester bond, or a polyisocyanate composition having a polyisocyanate compound which is a reaction product of the polyol compound having the ester bond and the various polyisocyanates, or a reactive adhesive containing either or both of them.

[0113] In addition to the above polyol composition and polyisocyanate composition, a reactive adhesive to which a resin or a low-molecular compound having an acidic group is added can also be preferably used. As the resin or low-molecular compound having an acidic group, it can be easily mixed with the above polyol composition and polyisocyanate composition which are the main components of the reactive adhesive (in this case, a solvent described later may be used if necessary), and any resin or low-molecular compound having an acid value can be used without particular limitation.

[0114] 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; radical copolymers such as (meth)acrylic resin, styrene-(meth)acrylic resin, styrene-(anhydrous)maleic acid resin, terpene-(anhydrous)maleic acid resin, etc. obtained by copolymerizing a polymerizable monomer having an acidic group such as a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, a polymerizable monomer having a sulfonic acid group such as sulfonated styrene, a polymerizable monomer having a sulfonamide group such as vinylbenzenesulfonamide; and acid-modified polyolefin resins, etc. These can be used singly or in combination of two or more.

[0115] Examples of the low-molecular compound having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives, and these can be used alone or in combination of two or more.

[0116] Examples of the saturated fatty acid include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, dodecanoic acid, etc. Examples of the unsaturated fatty acid include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc. Examples of the hydroxy acid include lactic acid, malic acid, citric acid, etc. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, etc. Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, azelaic acid, etc. Examples of the tricarboxylic acid include aconitic acid, trimer acid, etc. Examples of the oxocarboxylic acid include pyruvic acid, oxaloacetic acid, etc. Examples of the carboxylic acid derivative include amino acid, nitrocarboxylic acid, etc., and these can be used alone or in combination of two or more. Further, if it is citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc., it can comply with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.

[0117] In addition, additives such as pigments, silane coupling agents, titanate coupling agents, coupling agents such as aluminum-based ones, adhesion promoters such as epoxy resins, leveling agents, inorganic fine particles such as colloidal silica and alumina sol, organic fine particles of polymethyl methacrylate, defoaming agents, anti-sagging agents, wetting dispersants, viscosity modifiers, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust preventives, fluorescent brighteners, inorganic heat ray absorbers, flameproof agents, antistatic agents, dehydrating agents, etc. may also be used in the reactive adhesive.

[0118] Also, there are reactive adhesives such as dry laminating adhesives diluted with highly soluble organic solvents for dilution, solventless laminating adhesives containing almost no organic solvents for dilution, and aqueous adhesives with water as the diluent, etc., and any of them can be used. Specifically, highly soluble organic solvents for dilution include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-15 hexane, cyclohexane, etc. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly known as highly soluble organic solvents. For aqueous adhesives, water and organic solvents having an affinity for water can be used as diluents.

[0119] In the above reactive adhesive, the mixing ratio of the two-component type of the polyisocyanate composition and the polyol composition is the recommended mixing ratio for commercial products. Generally, the equivalent ratio of the isocyanate groups in the polyisocyanate composition to the hydroxyl groups in the polyol composition [isocyanate groups / hydroxyl groups] is often in the range of 1.0 to 5.0. Of course, there may also be cases where it is mixed and used in other ranges. The one-component adhesive of the reactive adhesive is used by applying the polyisocyanate composition alone to a film, and the isocyanate groups contained in the polyisocyanate composition react with moisture in the air and crosslink to be used as a laminating adhesive. In a laminated film laminated with a reactive adhesive, the reactive adhesive is, for example, after mixing the reactive adhesive, applied to a first plastic film, and then a second plastic film is laminated on the coated surface, and then it is almost always cured and crosslinked through an aging process or the like.

[0120] Among them, the reactive adhesive preferably contains a resin or low molecular compound having the acidic group because it is easily desorbed by an alkaline solution. In a two-component reactive adhesive of a polyisocyanate composition and a polyol composition, it is preferable from the viewpoint of stability that the resin or low molecular compound having the acidic group is blended in the polyol composition. The addition amount may be appropriately determined within a range that does not impair the adhesiveness and curability of the reactive adhesive, but is generally preferably in the range of 0.5 to 50% by mass, more preferably in the range of 1.0 to 30% by mass, based on the solid content of the polyol composition.

[0121] Further, as the reactive adhesive, as long as it is an ester-based adhesive such as an ester-based adhesive, an ester urethane-based adhesive, or an ether ester-based adhesive, delamination occurs in the step of immersing the laminate in an alkaline solution while heating and stirring or ultrasonically vibrating the laminate at 20 to 90°C. On the other hand, the ether-based adhesive may be difficult to delaminate in some cases. In that case, it is preferable to provide the aforementioned primer layer or to use an ether-based adhesive containing a resin or low molecular compound having the acidic group.

[0122] As the OPV (overprint varnish) for forming the OPV layer, any commercially available OPV can be used without particular limitation. A general composition of the OPV includes a binder resin, a solvent such as an organic solvent or an aqueous solvent, and additives.

[0123] Examples of the binder resin include resin having an acid value such as cellulose resin, urethane resin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin, ketone resin, polyester resin, (meth)acrylic resin, rosin-modified maleic acid resin and rosin-modified fumaric acid resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, cyclized rubber, chlorinated rubber, butyral resin, petroleum resin, etc., polymerizable monomers having a carboxyl group such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide, etc., (meth)acrylic resin, styrene-(meth)acrylic resin, styrene-(anhydrous)maleic acid resin, terpene-(anhydrous)maleic acid resin, etc. which are radical copolymers obtained by copolymerizing polymerizable monomers having an acidic group, and acid-modified polyolefin resin, etc. These can be used in appropriate combinations. Among them, it is preferable to use (meth)acrylic resin, urethane resin, rosin-based resin and its modified products, etc. in appropriate combinations.

[0124] Examples of the solvent include the organic solvents usable in the organic solvent-based composition of the present invention as long as they are organic solvents.

[0125] Examples of the additive include extender pigment, pigment dispersant, leveling agent, defoaming agent, wax, plasticizer, anti-blocking agent, infrared absorber, ultraviolet absorber, fragrance, flame retardant, etc. In addition, there are also those in which a crosslinking agent or a chelating agent is further added to crosslink the printing ink layer itself to increase the hardness.

[0126] In addition, OPV added with a resin or a low molecular compound having an acidic group can also be preferably used. As the resin or the low molecular compound having an acidic group, it can be easily mixed with the binder resin, the organic solvent, etc. which are the main components of OPV, and can be used without particular limitation as long as it is a resin or a low molecular compound having an acid value. Examples of the resin having the acidic group include resins having an acid value such as cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins and rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, petroleum resins, etc., polymerizable monomers having a carboxyl group such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their acid anhydrides, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide, etc., (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydrous)maleic acid resins, terpene-(anhydrous)maleic acid resins, etc., which are radical copolymers obtained by copolymerizing a polymerizable monomer having an acidic group, and acid-modified polyolefin resins, etc. These can be used alone or in combination of two or more.

[0127] Examples of the low molecular compound having the acidic group preferably include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, etc. These can be used alone or in combination of two or more.

[0128] Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, capric acid, undecanoic acid, dodecanoic acid, etc. Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc. Examples of hydroxy acids include lactic acid, malic acid, citric acid, etc. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, etc. 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, azelaic acid, etc. Examples of tricarboxylic acids include aconitic acid, trimer acid, etc. Examples of oxocarboxylic acids include pyruvic acid, oxaloacetic acid, etc. Examples of carboxylic acid derivatives include amino acids and nitrocarboxylic acids. These can be used alone or in combination of two or more. Also, citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc. can comply with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.

[0129] Among them, the OPV preferably contains a resin or a low molecular compound having the acidic group. The addition amount may be appropriately determined within a range that does not impair the printability of the OPV, but is preferably in the range of 0.5 to 50% by mass, more preferably in the range of 1.0 to 30% by mass, based on the solid content of the OPV.

[0130] The base material A, the white film layer, the color film layer, the primer layer, the adhesive layer, the OPV layer, the resin C layer, or the base material B in the laminate may each be provided with a barrier layer. Examples of the barrier layer include an inorganic vapor deposition layer and a barrier coating layer, and these may be used alone or in combination of two or more.

[0131] The inorganic vapor deposition layer is a layer having a gas barrier property that prevents the permeation of oxygen gas and water vapor gas, and is a vapor deposition layer made of an inorganic substance or an inorganic oxide. Examples of the inorganic substance or inorganic oxide include aluminum, alumina, silica, etc., and one or more of these can be used in combination. Two or more inorganic vapor deposition layers may be provided. When two or more inorganic vapor deposition layers are provided, they may have the same composition or different compositions.

[0132] 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 (Physical Vapor Deposition method (PVD method)) such as vacuum vapor deposition method, sputtering method, and ion plating method, and chemical vapor deposition methods (Chemical Vapor Deposition method (CVD method)) such as plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photo chemical vapor deposition method.

[0133] The film thickness of the inorganic vapor deposition layer is preferably 1 to 200 nm. When the inorganic vapor deposition layer is an aluminum vapor deposition layer, its film thickness is more preferably 1 to 100 nm, still more preferably 15 to 60 nm, and still more preferably 10 to 40 nm. When the inorganic vapor deposition layer is a silica or alumina vapor deposition layer, its film thickness is preferably 1 to 100 nm, more preferably 10 to 50 nm, and more preferably 20 to 30 nm.

[0134] The barrier coat layer can protect the inorganic vapor deposition layer and enhance the gas barrier property against gases such as oxygen and water vapor. Such a barrier coat layer is formed from a resin composition such as a hydrolyzate of a metal alkoxide, a hydrolytic polycondensate of a metal alkoxide, etc., which are obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by the sol-gel method in the presence of a solvent such as a sol-gel method catalyst, water or an organic solvent.

[0135] As the metal alkoxide, one or more represented by the following general formula can be used.

[0136] [Chemical formula] (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 of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.) Examples of the metal atom M include silicon, zirconium, titanium, aluminum, etc. Specific examples of the organic group represented by R 1 , R 2 include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and i-butyl group. In the same molecule, these alkyl groups may be the same or different.) Specific examples of the metal alkoxide 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 alkoxide can be used alone or in combination of two or more.)

[0137] Examples of the water-soluble polymer include polyvinyl alcohol-based resins and ethylene-vinyl alcohol copolymers. Commercially available products may be used as the water-soluble polymer. Examples of commercially available polyvinyl alcohol-based resins include RS-110 (manufactured by Kuraray Co., Ltd., RS polymer, saponification degree: 99%, polymerization degree: 1,000), Kuraray Poval LM-20SO (manufactured by Kuraray Co., Ltd., saponification degree: 40%, polymerization degree: 2,000), Gosenol NM-14 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 99%, polymerization degree: 1,400), etc. Examples of commercially available ethylene-vinyl alcohol copolymers include Eval EP-F101 (manufactured by Kuraray Co., Ltd., ethylene content: 32 mol%), Soanol D2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene content: 29 mol%), etc.)

[0138] Examples of the sol-gel method catalyst include acid or amine compounds. As the amine compound, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is preferable. Specifically, for example, N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In particular, N,N-dimethylbenzylamine is preferable. As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid can be used.

[0139] As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used. The gas barrier coating layer is formed by applying a resin composition containing these compounds one or more times by conventionally known means such as roll coating with a gravure roll coater, spray coating, spin coating, dipping, brushing, bar coating, an applicator, etc. More specifically, a resin composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent, and other components as necessary. In the resin composition, the polycondensation reaction gradually proceeds. Next, the resin composition is applied onto the inorganic vapor deposition layer by a conventional method and dried. By drying, the polycondensation reaction of the metal alkoxide and the water-soluble polymer further proceeds, and a layer of a composite polymer is formed. It is also preferable to repeat this operation to form the gas barrier coating layer. Finally, the laminate coated with the resin composition is heated at 20 to 250 °C, preferably 50 to 220 °C for 1 second to 10 minutes. Thereby, a gas barrier coating layer can be formed on the inorganic vapor deposition layer.

[0140] The film thickness of the gas barrier coating layer 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 property is not sufficient, and if it is more than 100 μm, cracks are likely to occur.

[0141] (Method for detaching the film from Substrate A) In the present invention, for the printed matter, a film can be detached from the base material A by treatment with warm water or an alkaline solution, and the recycled base material A can be produced.

[0142] Further, in the present invention, for a laminate in which the printed matter and the base material B are laminated with the film disposed inside via an adhesive layer, the adhesive layer and the base material B can be detached together with the film by treatment with warm water or an alkaline solution, and the recycled base material A can be produced. As the detachment step, there is a step of immersing the printed matter or the laminate in warm water while heating and stirring or ultrasonically vibrating at 70 to 90°C, or a step of immersing in an alkaline solution while heating and stirring or ultrasonically vibrating at 20 to 90°C. The heating and stirring and the ultrasonic vibration may be performed simultaneously. As the step, a step of immersing in an alkaline solution while heating and stirring or ultrasonically vibrating at 20 to 90°C is preferable. As the heating temperature, 30°C or higher is preferable, 40°C or higher is preferable, 50°C or higher is preferable, 60°C or higher is preferable, and it is more preferable to perform the heating and stirring and the ultrasonic vibration simultaneously.

[0143] The alkaline solution used in the above step is not particularly limited, but a pH of 9 or higher is preferable, and an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium hydrogen carbonate solution, an aqueous potassium hydrogen carbonate solution, an aqueous sodium dihydrogen carbonate solution, an aqueous potassium dihydrogen carbonate solution, etc. are preferable. An aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium hydrogen carbonate solution, an aqueous potassium hydrogen carbonate solution, an aqueous sodium dihydrogen carbonate solution, an aqueous potassium dihydrogen carbonate solution, etc. are preferably aqueous solutions having a concentration of 0.5% by mass to 10% by mass, and more preferably aqueous solutions having a concentration of 1% by mass to 5% by mass.

[0144] The alkaline solution may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol 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 monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonylacetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyrate, and ethyl lactate. These can be used alone or in combination of two or more kinds.

[0145] The content ratio 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. Further, the alkaline solution may contain a water-insoluble organic solvent. Specific examples of the water-insoluble organic solvent include alcohol solvents such as n-butanol, 2-butanol, isobutanol, and octanol; aliphatic hydrocarbon solvents such as hexane, heptane, and normal paraffin; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and alkylbenzene; halogenated hydrocarbon solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, and carbon tetrachloride; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; and ether solvents such as ethyl ether and butyl ether. These can be used alone or in combination of two or more.

[0146] Further, the alkaline solution may contain a surfactant. Examples of the surfactant include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, anionic surfactants, nonionic surfactants, or amphoteric surfactants are preferred.

[0147] Examples of the anionic surfactant include, for example, alkylbenzene sulfonates, alkylphenyl sulfonates, alkylnaphthalene sulfonates, higher fatty acid salts, sulfate esters of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfate esters and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples thereof include dodecylbenzene sulfonate, isopropylnaphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfonate, etc.

[0148] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl amine, polyoxyethylene fatty acid amide, fatty acid alkanol amide, alkyl alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer, etc. Among these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer are preferable.

[0149] As other surfactants, silicone surfactants such as polyoxyethylene adduct of polysiloxane; fluorine surfactants such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, oxyethylene perfluoroalkyl ether; biosurfactants such as spiculisporic acid, rhamnolipid, lysophosphatidylcholine can also be used.

[0150] These surfactants can be used alone or in combination of two or more. When adding a surfactant, the addition amount is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, and even more preferably in the range of 0.01 to 1% by mass based on the total amount of the alkaline solution.

[0151] The warm water is heated or ultrasonically vibrated at 70 to 90°C, or the alkaline solution is heated or ultrasonically vibrated at 20 to 90°C, and for example, in a treatment tank, the target printed matter or laminate is immersed. The heating method is not particularly limited, and known heating methods such as by heat rays, infrared rays, microwaves, etc. can be adopted. Also, for ultrasonic vibration, for example, a method of attaching an ultrasonic vibrator to the treatment tank and applying ultrasonic vibration to the warm water or alkaline solution can be adopted.

[0152] Also, it is preferable that the warm water or alkaline solution is stirred during immersion. Examples of the stirring method include a method of mechanically stirring the dispersion of the printed matter or laminate accommodated in the treatment tank with a stirring blade, a method of water flow stirring with a water flow pump, a bubbling method with an inert gas such as nitrogen gas, etc., and these may be used in combination to efficiently peel.

[0153] The time for immersing the printed matter or the laminate in the warm water or alkaline solution generally ranges from 2 minutes to 48 hours, although it depends on the composition of the printed matter. In the present invention, it is not necessary for the film on the printed matter to be completely detached from the substrate by 100%, but it is preferable that 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more of the film is detached out of 100% by mass of the film.

[0154] In this step, the number of times of immersion in the warm water or alkaline solution may be once or divided into several times. That is, after performing the immersion once, a step of recovering the separated film substrate may be performed, or after performing the immersion several times, a step of recovering the film substrate may be performed. Also, when performing multiple immersions in this step, the concentration of the alkaline solution may be changed. Also, it is preferable to appropriately add known steps such as water washing and drying during this step. The hot water or alkaline solution used in this separation method is presumed to cause interfacial peeling by acting on the interface between the substrate and the printed film and significantly reducing their adhesion, as described above. On the other hand, since the solubility of the alkaline solution itself is also high, the uncrosslinked printed ink layer also dissolves. Even when the printed ink layer itself is crosslinked, in the present invention, since interfacial peeling is caused, it is presumed that separation and recovery can be efficiently performed in a short time.

[0155] In the case of a laminate, in order to peel the film by the above method, it is preferable to cut the substrate in advance so that hot water or an alkaline solution easily acts on the interface between the substrate and the ink.

Examples

[0156] Hereinafter, the content and effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Note that "parts" shown below represents "parts by mass".

[0157] (Method for measuring acid value) If the acid value of the raw material is measured or published, the acid value of the ink can be obtained by calculation. If this is not possible, the acid value of the ink can be obtained by creating a film and measuring it after drying. The acid value measurement shown below is based on JIS0070-1992 or obtained according to this method.

[0158] (Examples 1 to 36, Comparative Examples 1 to 4) The following binder resins, pigments, acidic additives and organic solvents (isopropyl alcohol (IPA), ethyl acetate, propyl acetate) were used in the mixing ratios shown in Table 1 below to prepare Examples 1 to 30 (I1 to I30) and Comparative Examples 1 to 4 (RI1 to RI4).

[0159] <Binder resin> · Resin 1: Urethane resin (acid value in solid content: 0 mgKOH / g, solid content 30 parts by mass) · Resin 2: Urethane resin (acid value in solid content: 15 mgKOH / g, solid content 30 parts by mass) · Resin 3: Acrylic resin (acid value in solid content: 1 mg KOH / g, solid content 30 parts by mass) · Resin 4: Acrylic resin (acid value in solid content: 30 mg KOH / g, solid content 30 parts by mass) · Resin 5: Vinyl chloride - vinyl acetate copolymer resin ( Resin monomer composition by mass% is vinyl chloride / vinyl acetate / vinyl alcohol = 92 / 3 / 5 , hydroxyl value (mg KOH / g) = 64)) · Resin 6: Industrial nitrocellulose H1 / 2 solution (nitrocellulose, solid content 70%, viscosity at 25.0% solution concentration according to JIS K - 6703 is 9.0 - 14.9%, product of Taihei Chemical Products Co., Ltd., adjusted to 50% solid content with IPA)

[0160] <Pigment> · White: Titanium oxide - based pigment (JR600A (manufactured by Teika Co., Ltd.)) · Blue: Phthalocyanine - based blue pigment (FASTOGEN BLUE LA5380 blue pigment (manufactured by DIC Corporation))

[0161] <Acidic additive> AA1: Stearic acid (acid value: 198 mg KOH / g) AA2: Sebacic acid (acid value: 556 mg KOH / g) AA3: Citric acid (acid value: 876 mg KOH / g) AA4: Marukid #1 manufactured by Arakawa Chemical Industries Co., Ltd. (acid value: 30 mg KOH / g, Weight-average molecular weight: 3300, maleated rosin resin) AA5: Marukid #32 manufactured by Arakawa Chemical Industries Co., Ltd. (acid value: 140 mg KOH / g, Weight-average molecular weight: 1300, maleated rosin resin) AA6: Hi - Ross - X X - 228 manufactured by Seiko PMC Co., Ltd. (acid value: 141 mg KOH / g, weight - average molecular weight :14000~18000 , styrene - maleic acid resin)

[0162]

Table 1

[0163]

Table 2

[0164]

Table 3

[0165]

Table 4

[0166] (Examples 37 to 70, Comparative Examples 5 to 8) The printed inks of Examples 1 to 30 and Comparative Examples 1 to 4 prepared were used to print a solid pattern of 240 mm in length and 80 mm in width on Substrate A using a Flexoproof 100 test printing machine (manufactured by Testing Machines, Inc.). After printing, it was dried with a dryer to form a film layer 1, and a printed matter having the following Configuration 1 was obtained. If necessary, overprinting was performed to form a film layer 2, and a printed matter having the following Configuration 2 was obtained. Regarding the printed matters of the obtained Examples and Comparative Examples, the blocking resistance, substrate adhesion, ink peelability, and laminating suitability when using each film were evaluated by the methods described later, and the ink transferability was visually confirmed. The configurations and evaluation results of the printed matters of each Example and Comparative Example are shown in the following table.

[0167] <Configuration of Printed Matter> · Configuration 1: Substrate A - Film Layer 1 · Configuration 2: Substrate A - Film Layer 1 - Film Layer 2

[0168] <Substrate A> · Corona-treated biaxially oriented polypropylene film (Pyren P2161, thickness 20 μm, manufactured by Toyobo Co., Ltd.) (OPP) · Corona-treated polyethylene terephthalate film (Ester E5102, thickness 12 μm, manufactured by Toyobo Co., Ltd.) (PET)

[0169] <Evaluation Item 1: Blocking Resistance> The film was cut into a size of 4 cm × 4 cm so that the printed surface and the non-printed surface of the printed matter were in contact, then they were overlapped, a load of 5 Kgf / cm 2 was applied, and after leaving it in an environment of 40 °C for 12 hours, when the film was peeled off, the state of ink transfer (back transfer) to the non-printed surface was visually judged based on the area ratio (%) of the back transfer part. A: No transfer to the non-printed surface is seen at all. B: Although it is slightly less than 5%, transfer due to back transfer is seen. C: Transfer due to back transfer of 5% or more and less than 20% is seen. D: Transfer due to back transfer of 20% or more is seen.

[0170] <Evaluation Item 2: Substrate Adhesion> After leaving the printed matter for one day, cellophane tape (12 mm wide, made by Nichiban) was attached to the printed surface, and when one end of the cellophane tape was quickly peeled off in a direction perpendicular to the printed surface, the residual rate of the printed film was visually judged based on the area ratio by observing the appearance. A: The printed film does not peel off at all. B: 80% or more of the printed film remained on the film. C: 50% or more and less than 80% of the printed film remained on the film. D: Less than 50% of the printed film remained on the film.

[0171] <Evaluation Item 3: Water Resistance> It was cut into a size of 10 mm × 10 mm to obtain test pieces. These were 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 part was evaluated. A: No peeling. B: Fine peeling is seen. C: 20 - 30% of the printed part is peeled off. D: More than 30% of the printed part is peeled off

[0172] <Evaluation Item 4: Ink Transferability> The ink transferability when the printed matter was created was evaluated. A: The film is uniform in visual judgment. B: In visual inspection, the film is slightly non-uniform. C: In visual inspection, slight film peeling is observed. D: In visual inspection, film peeling is observed.

[0173] <Evaluation Item 5: Ink Peeling Test> [Alkaline Solution] 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 mass% aqueous solution. [Peeling Test Conditions] The peeling test was evaluated with a treatment time of 30 minutes under each condition. Note that peeling within 5 minutes indicates a very high performance. Examples 25 to 76 and Comparative Examples 4 to 9 were cut into 10 mm × 10 mm sizes to obtain test pieces. These test pieces were subjected to the peeling test under Conditions 1 to 3. Condition 1: Stirring treatment of sodium hydroxide aqueous solution at 20°C Condition 2: Ultrasonic treatment of sodium hydroxide aqueous solution at 20°C Condition 3: Stirring treatment of sodium hydroxide aqueous solution at 80°C The peelability of the film under the above conditions was evaluated. A: More than 90% of the ink coating film peeled off from the substrate in less than 5 minutes. B: More than 90% of the ink coating film peeled off from the substrate in 5 minutes or more and less than 15 minutes. C: More than 90% of the ink coating film peeled off from the substrate in 15 minutes or more and less than 30 minutes. D: In the 30-minute test, 50% or more and less than 90% of the ink coating film peeled off from the substrate. E: In the 30-minute test, less than 50% of the ink coating film peeled off from the substrate.

[0174] <Evaluation Item 6: Lamination Test Conditions> An ether-based adhesive was used for the above-mentioned printed matter, and a dry laminate film (P-1128, thickness 25 μm, manufactured by Toyobo Co., Ltd.) was laminated with a dry laminating machine (manufactured by DIC Engineering Co., Ltd.) using a dry laminate adhesive Dick Dry LX-401A / SP-60 (manufactured by DIC). The strength was measured after aging at 40°C for 3 days. (Evaluation Criteria) A: The laminate strength is 1.0 N / 15 mm or more. B: The laminate strength is 0.7 N / 15 mm or more and less than 1.0 N / 15 mm. C: The laminate strength is 0.5 N / 15 mm or more and less than 0.7 N / 15 mm. D: The laminate strength is less than 0.5 N / 15 mm.

[0175]

Table 5

[0176]

Table 6

[0177]

Table 7

[0178]

Table 8

[0179]

Table 9

[0180]

Table 10

[0181]

Table 11

[0182]

Table 12

[0183]

Table 13

[0184] Moreover, in any evaluation item, C or higher is the practical level. From the above results, when the acid value in the solid content of the organic solvent-based composition is below the lower limit value of the present invention, although the adhesion, water resistance, ink transferability, and lamination suitability are excellent, it was found that it does not peel off from the substrate. Also, when the acid value in the solid content of the organic solvent-based composition exceeds the upper limit value of the present invention, although the peelability from the substrate is equal to or better, it was found that the adhesion, ink transferability, and lamination suitability do not reach the practical level. In the examples using the aqueous liquid ink having the embodiment of the present invention, all evaluation results are at or above the practical level. In addition, Examples 4 to 6, 10 to 12, 16 to 18, 22 to 24, 28 to 30, 34 to 36, 40 to 42, 46 to 48, 52 to 54, 60, 62, 68, 76 to 78, 82 to 84, and 88 to 90, 96, 98 and 106 are respectively regarded as Reference Examples 1 to 42.

[0185] From the above, by using the organic solvent-based composition of the present invention, it has physical properties equivalent to those of conventional organic solvent-based compositions, and the film can be peeled off from the plastic substrate by treatment with an alkaline solution, and a toluene- and MEK-free organic solvent-based printing ink, a printed matter printed using the printing ink, a laminate composed of the printed matter, and a method for peeling off a film or the like from the printed matter or laminate can be provided.

Claims

1. A composition containing a solvent of an organic solvent and a resin for forming a film that detaches by treatment with an alkaline solution on the surface or on the surface of substrate A, containing an acidic additive having a molecular weight or weight average molecular weight of 50 to 1500, and having an acid value of 15 to 114 mgKOH / g in the solid content of the composition.

2. The composition according to claim 1, wherein the acid value of the acidic additive is 3 to 900 mgKOH / g.

3. The composition according to any one of claims 1 to 3, wherein the acidic additive is at least one selected from the group consisting of a resin having an acidic group and an organic acid.

4. The composition according to claim 3, wherein the acid value of the resin having an acidic group is 3 to 300 mgKOH / g.

5. The composition according to claim 3 or 4, wherein the resin having an acidic group is at least one selected from the group consisting of a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, and a styrene-(anhydrous) maleic acid resin.

6. The composition according to any one of claims 1 to 5, containing a urethane resin or an acrylic resin.

7. The composition according to any one of claims 1 to 6, containing an ester-based organic solvent having 5 or more carbon atoms.

8. The composition according to any one of claims 1 to 7, containing a colorant.

9. The composition according to any one of claims 1 to 8, used as a printing ink, a primer, or an OPV.

10. A printed matter having a film formed by printing the composition according to any one of claims 1 to 9 on the surface or on the surface of substrate A.

11. A laminate formed by laminating substrate B on the film side of the printed matter according to claim 10.

12. A method for manufacturing a recycled substrate A obtained by detaching the film from the substrate A by treating the printed matter according to claim 11 with an alkaline solution.

13. A method for manufacturing a recycled substrate A obtained by detaching the substrate B together with the film by treating the laminate according to claim 11 with an alkaline solution.

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