TW202136434A - Detachable aqueous ink and method for detaching same - Google Patents

Abstract

In order to simultaneously combat two environmental problems, i.e., the marine plastic problem and global warming, the present invention addresses the problem of providing: an aqueous ink that allows an ink coating film to be detached from a base material; printed matter printed using the aqueous ink; a laminate configured from the printed matter; and a method for detaching the ink coating film, etc., from the printed matter or the laminate. The abovementioned problem is solved by an aqueous liquid ink for forming an ink coating film that can be detached from a base material A by warm water or an alkali solution, wherein the aqueous liquid ink is characterized in that the acid value of the solids fraction of the aqueous liquid ink is 3-150 mg KOH/g.

Description

Detachable water-based ink and its detachment method

The present invention relates to an aqueous liquid ink that can be used to form an ink coating film that can be detached from a substrate, a printed matter printed by using the aqueous liquid ink, a laminate composed of the printed matter, and the release of the ink from the printed matter or laminate Methods such as film coating.

In recent years, two environmental issues surrounding the earth have attracted attention. One is the ocean plastic problem, and the other is global warming. The problem of marine plastics is caused by the decomposition of plastic discarded into the ocean in the seawater to become finer (microplasticization). It is worried that this kind of microplastics will enter marine organisms, be concentrated, and affect the health of seabirds and humans through the food chain. One way to improve this marine plastic problem is recycling. Increasing the recycling rate of resources such as flexible packaging materials or PET bottles will help prevent plastics from mixing into the ocean. However, current recycling has the following problem. In the recycling step, the ink coating film printed on the plastic substrate cannot be detached, because it is mixed in the plastic and the hue deteriorates or the physical properties decrease, which reduces the price of the recycled plastic. If the ink coating film can be detached and this problem can be solved, the price of recycled plastic will increase, which will facilitate the addition of new recycling companies or the preparation of separate recycling by the local government. Therefore, it is believed that the problem of marine plastics can be improved by increasing the recycling rate, and therefore, the development of inks from which the coating film is detached in the recycling step is sought.

Global warming is an environmental problem caused by the release of greenhouse gases such as carbon dioxide or organic solvent vapor into the air. Printing inks are no exception, and it is necessary to switch from conventional organic solvent-based inks to water-based inks. In addition, by switching from an organic solvent-based ink to a water-based ink, the effect of improving the working environment can also be obtained.

In the conventional technology, the release mechanism using water-based gravure ink (Patent Document 1) and a water-based primer (Patent Document 2) has been proposed for surface printing (a form in which the ink coating film is provided on the outermost layer). However, the current situation is that there is no report of an ink coating film that can be used for general-purpose substrates and has the same physical properties as conventional water-based inks.

In addition, a recycling method of a laminated substrate using an organic solvent-based ink is advocated for use in backside printing or lamination (a form in which the ink coating film is provided between the substrate layers) (Patent Document 3 and Patent Document 4). However, the physical properties of organic solvents are very different from the resins required in water-based inks and cannot be simply deployed horizontally. Therefore, the recycling of substrates using water-based inks including back-side printing or lamination applications has not been achieved. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2001-350411 Patent Document 2: Japanese Patent No. 6388131 Patent Document 3: Japanese Patent No. 6631964 Patent Document 4: Japanese Patent No. 6638802

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide: an aqueous ink whose purpose is to simultaneously deal with the above two environmental problems and the ink coating film can be detached from the substrate, a printed matter printed with the aqueous ink, and a laminate composed of the printed matter , And the method of detaching the ink coating film from the printed matter or laminate. [Means to solve the problem]

As a result of intensive research by the inventors to solve the above-mentioned problems, they found that by adding acidic additives to the aqueous liquid ink composition, the physical properties equivalent to those of conventional aqueous inks can be obtained, and the film can be removed by alkaline solution treatment. Release the ink coating film. That is, the present invention relates to: 1. A water-based liquid ink, which is used to form a warm water or alkaline solution detachable ink coating film on the substrate A, and the acid value of the solid component of the water-based liquid ink is 3 to 150 mgKOH/g. 2. The aqueous liquid ink as in item 1 above, which further contains acidic additives and an aqueous medium. 3. The water-based liquid ink of item 1 or item 2 above, which further contains a colorant. 4. The aqueous liquid ink of item 2 or item 3 above, wherein the acid value of the acidic additive is 3 to 900 mgKOH/g. 5. The aqueous liquid ink according to any one of items 2 to 4 above, wherein the acidic additive is an organic acid. 6. The water-based liquid ink according to item 5 above, wherein the number of carbon atoms of the organic acid is 3-20. 7. The aqueous liquid ink of item 5 above, wherein the number of carbon atoms of the organic acid is 6-18. 8. The aqueous liquid ink according to any one of the above 2 to 4, wherein the acidic additive is a resin having an acid group. 9. The aqueous liquid ink of item 8 above, wherein the acid value of the resin with acid groups is 3 to 300 mgKOH/g. 10. A printed matter, which is formed by printing the aqueous liquid ink of any one of items 1 to 9 above directly or via other layers on the substrate A. 11. A laminated body in which the above-mentioned printed matter and the substrate B are laminated with the ink coating film arranged on the inner side. 12. A method for manufacturing a recycled substrate A, which is obtained by treating the above-mentioned printed matter with warm water or alkaline solution to release the ink coating film from the substrate A. 13. A method for manufacturing a recycled base material A, which is a laminate in which the above-mentioned printed matter and base material B are arranged with an ink coating film on the inside, and treated with warm water or alkaline solution , Obtained by detaching the adhesive layer and substrate B together with the ink coating film. [Effects of the invention]

As long as the water-based liquid ink of the present invention, the printed matter printed with the water-based ink, and the laminate composed of the printed matter have physical properties equivalent to those of conventional water-based liquid inks, the ink coating film can be separated from the film.

The embodiments of the present invention shown below only show a part of the embodiments of the present invention, and are not limited to the contents described as long as they do not greatly deviate from the gist. (Ink composition) The present invention is an aqueous liquid ink, which is used to form a warm water or alkaline water detachable ink coating film on the substrate A, and is characterized by the acid in the solid component of the aqueous liquid ink The value is 3 to 150 mgKOH/g. The releasability of warm water or alkaline water will be described in the following paragraph (Method of Detachment of Ink Coating Film from Substrate A). In addition, the formation of the ink coating film will be described in the paragraph (printing to substrate) described later. In addition, the acid value in the solid content of the above-mentioned aqueous liquid ink can be obtained by calculating from the acid value of the raw material. If it cannot be obtained by this method, it can be obtained by making an ink film and measuring after drying. . In addition, the acid value uses this value at the time of publication, and when it is not disclosed, it is measured in accordance with JIS0070-1992.

The acid value in the solid component of the aqueous liquid ink is 3 mgKOH/g or more, preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, It is more preferably 20 mgKOH/g or more, more preferably 25 mgKOH/g or more, more preferably 30 mgKOH/g or more, and still more preferably 35 mgKOH/g or more. In addition, the acid value is 150 mgKOH/g or less, 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, and even more preferably 70 mgKOH/g or less. By setting it in the above range, it is possible to have both the releasability of warm water or alkaline solution and the adhesion to the base material.

In addition, when attaching importance to the release of warm water or alkaline water, it is preferably 35 mgKOH/g or more, more preferably 40 mgKOH/g or more, more preferably 45 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 55 mgKOH /g or more, more preferably 60 mgKOH/g or more, more preferably 65 mgKOH/g or more, and still more preferably 70 mgKOH/g or more. When attaching importance to the adhesion to the substrate, it is preferably 70mgKOH/g or less, more preferably 60mgKOH/g or less, more preferably 50mgKOH/g or less, more preferably 40mgKOH/g or less, more preferably 35mgKOH/g or less . When both warm water or alkaline solution detachability and adhesion to the substrate are important, the range of acid value is 3～150mgKOH/g, more preferably 3～140mgKOH/g, more preferably 5～130mgKOH/ g, more preferably 10 to 120 mgKOH/g, more preferably 15 to 110 mgKOH/g, more preferably 20 to 100 mgKOH/g, more preferably 25 to 90 mgKOH/g, more preferably 30 to 80 mgKOH/g, more preferably 35～70mgKOH/g.

In addition, when attaching importance to the desorption of warm water or alkaline water, it is more preferably 35 to 150 mgKOH/g, more preferably 40 to 150 mgKOH/g, more preferably 45 to 150 mgKOH/g, and more preferably 50 to 150 mgKOH/g, It is more preferably 55 to 150 mgKOH/g, more preferably 60 to 150 mgKOH/g, still more preferably 65 to 150 mgKOH/g, and even more preferably 70 to 150 mgKOH/g. In addition, when attaching importance to the adhesion to the substrate, it is more preferably 3 to 70 mgKOH/g, more preferably 3 to 60 mgKOH/g, more preferably 3 to 50 mgKOH/g, more preferably 3 to 40 mgKOH/g, and more Preferably, it is 3 to 35 mgKOH/g. The aqueous liquid ink of the present invention may further contain acidic additives and an aqueous medium.

＜Acid Additives＞ As the above-mentioned acidic additive, for example, a low-molecular compound having an acid group or a resin having an acid group can be used. The acid value of the above acidic additives is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more. In addition, the acid value is preferably 900 mgKOH/g or less, more preferably 850 mgKOH/g or less, more preferably 800 mgKOH/g or less, more preferably 750 mgKOH/g or less, more preferably 700 mgKOH/g or less, and more preferably 650 mgKOH/g or less. g or less, more preferably 600 mgKOH/g or less, more preferably 550 mgKOH/g or less. By setting it in the above range, it is possible to have both the releasability of warm water or alkaline solution and the adhesion to the base material.

In addition, when attaching importance to the release of warm water or alkaline water, it is preferably 50 mgKOH/g or more, more preferably 100 mgKOH/g or more, more preferably 200 mgKOH/g or more, more preferably 300 mgKOH/g or more, and more preferably 400 mgKOH /g or more, more preferably 500mgKOH/g or more, particularly preferably 550mgKOH/g or more. When attaching importance to the adhesion to the substrate, it is preferably 550mgKOH/g or less, more preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, more preferably 300mgKOH/g or less, more preferably 200mgKOH/g or less . When both warm water or alkaline solution releasability and adhesion to the substrate are important, the acid value range is preferably 3 to 900 mgKOH/g, more preferably 5 to 850 mgKOH/g, and more preferably 7 to 800 mgKOH/g, more preferably 10 to 750 mgKOH/g, more preferably 20 to 700 mgKOH/g, more preferably 30 to 650 mgKOH/g, still more preferably 40 to 600 mgKOH/g, more preferably 50 to 550 mgKOH/g.

In addition, when attaching importance to warm water or alkaline water releasability, it is preferably 50 to 900 mgKOH/g, more preferably 100 to 900 mgKOH/g, more preferably 200 to 900 mgKOH/g, and more preferably 300 to 900 mgKOH/g, It is more preferably 400 to 900 mgKOH/g, more preferably 500 to 900 mgKOH/g, and still more preferably 550 to 900 mgKOH/g. In addition, when attaching importance to the adhesion to the substrate, it is preferably 3 to 550 mgKOH/g, more preferably 3 to 500 mgKOH/g, more preferably 3 to 400 mgKOH/g, more preferably 3 to 300 mgKOH/g, and more Preferably, it is 3 to 200 mgKOH/g. As the above-mentioned low-molecular compound having an acid group, preferably, a low-molecular compound having a carboxyl group, a phosphoric acid group, a sulfonic acid group, a sulfinic acid group, etc. or an ester or salt thereof as an acid group, more preferably Saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, organic phosphoric acid, organic phosphoric acid derivatives, organic sulfonic acids, organic sulfonic acid derivatives , Organic sulfinic acid, organic sulfinic acid derivatives and other organic acids, which can be used singly or in plural.

Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid; examples of unsaturated fatty acids include oleic acid and linoleic acid. Acid, linolenic acid, arachidic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc.; examples of hydroxy acids include lactic acid, malic acid, citric acid, etc.; as aromatic carboxylic acids, Examples: 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.; as Examples of tricarboxylic acids include: aconitic acid, trimer acid, etc.; examples of oxocarboxylic acid include: pyruvic acid, acid oxalic acid, etc.; examples of carboxylic acid derivatives include: amino acid and nitrocarboxylic acid , It can be used singly or in plural. Also, if it is citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, oleostearic acid , Arachidic acid, sebacic acid, etc., can correspond to the so-called Swiss Ordinance (Swiss Ordinance), it is better to use substances corresponding to various regulations. As the above-mentioned organic phosphoric acid, organic phosphoric acid derivative, organic sulfonic acid, organic sulfonic acid derivative, organic sulfinic acid, and organic sulfinic acid derivative, preferably: monoalkyl phosphoric acid, dialkyl phosphoric acid, trialkyl phosphoric acid , Monoalkyl phosphoric acid derivatives, dialkyl phosphoric acid derivatives, trialkyl phosphoric acid derivatives, monophenyl phosphoric acid, diphenyl phosphoric acid, triphenyl phosphoric acid, monophenyl phosphoric acid derivatives, diphenyl phosphoric acid derivatives , Triphenylphosphoric acid derivatives, monoalkylsulfonic acid, dialkylsulfonic acid, trialkylsulfonic acid, monoalkylsulfonic acid derivatives, dialkylsulfonic acid derivatives, trialkylsulfonic acid derivatives, Monophenylsulfonic acid, diphenylsulfonic acid, triphenylsulfonic acid, monophenylsulfonic acid derivatives, diphenylsulfonic acid derivatives, triphenylsulfonic acid derivatives, monoalkylsulfinic acid, two Alkylsulfinic acid, trialkylsulfinic acid, monoalkylsulfinic acid derivatives, dialkylsulfinic acid derivatives, trialkylsulfinic acid derivatives, monophenylsulfinic acid, diphenyl Sulfinic acid, triphenylsulfinic acid, monophenylsulfinic acid derivatives, diphenylsulfinic acid derivatives, triphenylsulfinic acid derivatives.

The acid value of the above organic acid is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 40 mgKOH /g or more, more preferably 50mgKOH/g or more, more preferably 60mgKOH/g or more, more preferably 70mgKOH/g or more, more preferably 80mgKOH/g or more, more preferably 90mgKOH/g or more, and particularly preferably 100mgKOH/g above. In addition, the acid value is preferably 900 mgKOH/g or less, more preferably 850 mgKOH/g or less, more preferably 800 mgKOH/g or less, more preferably 750 mgKOH/g or less, more preferably 700 mgKOH/g or less, and more preferably 650 mgKOH/g or less. g or less, more preferably 600 mgKOH/g or less, more preferably 550 mgKOH/g or less. By setting it in the above range, it is possible to have both the releasability of warm water or alkaline solution and the adhesion to the base material.

In addition, when attaching importance to the release of warm water or alkaline water, it is preferably 100 mgKOH/g or more, more preferably 150 mgKOH/g or more, more preferably 200 mgKOH/g or more, more preferably 250 mgKOH/g or more, and more preferably 300 mgKOH /g or more, more preferably 350 mgKOH/g or more, more preferably 400 mgKOH/g or more, more preferably 450 mgKOH/g or more, more preferably 500 mgKOH/g or more, more preferably 550 mgKOH/g or more. When attaching importance to the adhesion to the substrate, it is preferably 550mgKOH/g or less, more preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, more preferably 300mgKOH/g or less, more preferably 200mgKOH/g or less .

When both warm water or alkaline solution releasability and adhesion to the substrate are important, the acid value range is preferably 3 to 900 mgKOH/g, more preferably 10 to 850 mgKOH/g, and more preferably 20 to 800 mgKOH/g, more preferably 30 to 750 mgKOH/g, more preferably 40 to 700 mgKOH/g, more preferably 60 to 650 mgKOH/g, more preferably 80 to 600 mgKOH/g, more preferably 100 to 550 mgKOH/g. In addition, when attaching importance to warm water or alkaline water releasability, it is preferably 100 to 900 mgKOH/g, more preferably 150 to 900 mgKOH/g, more preferably 200 to 900 mgKOH/g, and even more preferably 250 to 900 mgKOH/g, More preferably, it is 300-900mgKOH/g, more preferably 350-900mgKOH/g, more preferably 400-900mgKOH/g, more preferably 450-900mgKOH/g, more preferably 500-900mgKOH/g, more preferably 550- 900mgKOH/g. In addition, when attaching importance to the adhesion to the substrate, it is preferably 3 to 550 mgKOH/g, more preferably 3 to 500 mgKOH/g, more preferably 3 to 400 mgKOH/g, more preferably 3 to 300 mgKOH/g, and more Preferably, it is 3 to 200 mgKOH/g.

The number of carbon atoms of the organic acid is preferably 3 or more, more preferably 4 or more, more preferably 5 or more, preferably 6 or more, preferably 7 or more, and preferably 8 or more. By setting the number of carbon atoms of the organic acid in the above range, the adhesion to the substrate can be improved. In addition, the number of carbon atoms of the organic acid is preferably 20 or less, more preferably 18 or less, and more preferably 16 or less. By setting the number of carbon atoms of the organic acid in the above range, the dispersibility with an aqueous medium can be improved. The range of the number of carbon atoms of the organic acid is preferably 3 to 20, preferably 3 to 18, preferably 4 to 18, preferably 5 to 18, preferably 6 to 18, preferably 6 ~16, preferably 7-16, preferably 8-16. Regarding the solubility of the above-mentioned organic acid in 100 g of water at 25° C., when releasability from the substrate and the water resistance of the ink coating film are important, it is preferably less than 2 g, more preferably less than 1.8 g, and still more preferably less than Up to 1.5g, particularly preferably less than 1.2g.

As the resin having an acid group, for example, a cellulose resin having a carboxyl group, a phosphoric acid group, a sulfonic acid group, a sulfinic acid group or the like or an ester or salt thereof as an acid group, a urethane resin (urethane resin) ), polyamide resin, vinyl chloride/vinyl acetate copolymer, ketone resin, polyester resin, (meth)acrylic resin, rosin-modified maleic acid resin or rosin-modified fumaric acid resin, etc. Resins with acid value; or polymerizable monomers with carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, sulfonated styrene, etc., having sulfonic acid groups Polymerizable monomers, vinylbenzene sulfonamides and other polymerizable monomers having sulfonamide groups, etc. (meth)acrylic resins, styrene-(methyl) Base) acrylic resin, styrene-(anhydrous) maleic acid resin, terpene-(anhydrous) maleic acid resin and other free radical copolymer resins, or acid-modified polyolefin resins, etc. Use this singly or in a mixture of plural numbers. As the above-mentioned resin having an acid group, more preferred are resins having acid value such as urethane resin, (meth)acrylic resin, rosin-modified maleic acid resin or rosin-modified fumaric acid resin, and styrene -(Anhydrous) maleic acid resin.

The acid value of the resin having an acid group is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, more It is preferably 40 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more. In addition, the acid value is preferably 300 mgKOH/g or less, more preferably 280 mgKOH/g or less, more preferably 260 mgKOH/g or less, more preferably 240 mgKOH/g or less, more preferably 220 mgKOH/g or less, and more preferably 200 mgKOH/g or less. g or less. By setting it in the above range, it is possible to have both the releasability of warm water or alkaline solution and the adhesion to the base material. In addition, when attaching importance to the detachability of warm water or alkaline water, it is preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more, more preferably 70 mgKOH/g or more, more preferably 80 mgKOH/g or more, and more preferably 90 mgKOH /g or more, more preferably 100mgKOH/g or more. When attaching importance to the adhesion to the substrate, it is preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, more preferably 160mgKOH/g or less, more preferably 140mgKOH/g or less, more preferably 120mgKOH/g or less , More preferably 100mgKOH/g or less. When both warm water or alkaline solution releasability and adhesion to the substrate are important, the acid value range is preferably 3 to 300 mgKOH/g, preferably 10 to 280 mgKOH/g, and more preferably 20 to 260 mgKOH/g, more preferably 30 to 240 mgKOH/g, more preferably 40 to 220 mgKOH/g, still more preferably 50 to 200 mgKOH/g.

In addition, when attaching importance to warm water or alkaline water releasability, it is preferably 50 to 300 mgKOH/g, more preferably 60 to 300 mgKOH/g, more preferably 70 to 300 mgKOH/g, and more preferably 80 to 300 mgKOH/g, More preferably, it is 90 to 300 mgKOH/g, and still more preferably 100 to 300 mgKOH/g. In addition, when attaching importance to the adhesion to the substrate, it is preferably 3 to 200 mgKOH/g, more preferably 3 to 180 mgKOH/g, more preferably 3 to 160 mgKOH/g, more preferably 3 to 140 mgKOH/g, and more It is preferably 3 to 120 mgKOH/g, more preferably 3 to 100 mgKOH/g.

Regarding the weight average molecular weight of the resin having an acid group, when the resin having an acid group is a urethane resin, it is preferably 500 or more, more preferably 1000 or more, more preferably 2000 or more, more preferably 3000 or more, and more It is preferably 4,000 or more, more preferably 5,000 or more, more preferably 6,000 or more, more preferably 7,000 or more, still more preferably 8,000 or more, and even more preferably 10,000 or more. By setting the weight average molecular weight of the resin having an acid group in the above range, the adhesion to the substrate and the deinking property during alkaline solution treatment can be balanced. In addition, the weight average molecular weight of the resin having an acid group is preferably 100,000 or less, more preferably 50,000 or less, more preferably 40,000 or less, more preferably 30,000 or less, more preferably 25,000 or less, more preferably 20,000 or less, more preferably Below 18000. By setting the weight average molecular weight of the resin having an acid group in the above range, the viscosity of the ink can be lowered, and further, the adhesion to the substrate can be balanced with the deinking property during alkaline solution treatment. The range of the weight average molecular weight of the resin having an acid group is preferably 500 to 100,000, more preferably 1,000 to 50,000, more preferably 2,000 to 50,000, more preferably 3,000 to 50,000, more preferably 4,000 to 50,000, more preferably Preferably it is 5000～40,000, more preferably 5000～30000, more preferably 6000～30000, more preferably 6000～25000, more preferably 7000～25000, still more preferably 7000～20000, more preferably 8000～20000, more preferably It is 10,000 to 20,000, more preferably 10,000 to 18,000. By setting the weight average molecular weight of the resin having an acid group in the above range, the printability can be improved.

Regarding the weight average molecular weight of the resin having an acid group, when the resin having an acid group is a (meth)acrylic resin, it is preferably 1000 or more, more preferably 3000 or more, more preferably 5000 or more, and more preferably 10000 Above, more preferably 20,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more. By setting the weight average molecular weight of the resin having an acid group in the above range, the adhesion to the substrate and the deinking property during alkaline solution treatment can be balanced. In addition, the weight average molecular weight of the resin having an acid group is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. By setting the weight average molecular weight of the resin having an acid group in the above range, the viscosity of the ink can be lowered, and further, the adhesion to the substrate can be balanced with the deinking property during alkaline solution treatment. The range of the weight average molecular weight of the resin having an acid group is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, more preferably 10,000 to 200,000, and even more preferably 20,000 to 100,000. By setting the weight average molecular weight of the resin having an acid group in the above range, the printability can be improved.

Regarding the weight average molecular weight of the resin having an acid group, when the resin having an acid group is a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin and other resins having an acid value, it is preferably 500 or more, more preferably 700 or more, still more preferably 1,000 or more. By setting the weight average molecular weight of the resin having an acid group in the above range, the adhesion to the substrate and the deinking property during alkaline solution treatment can be balanced. In addition, the weight average molecular weight of the resin having an acid group is preferably 50,000 or less, more preferably 30,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, and more preferably 2,000 or less. By setting the weight average molecular weight of the resin having an acid group in the above range, the viscosity of the ink can be lowered, and further, the adhesion to the substrate can be balanced with the deinking property during alkaline solution treatment.

The range of the weight average molecular weight of the resin having an acid group is preferably 500 to 50,000, more preferably 700 to 520,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 5,000. By setting the weight average molecular weight of the resin having an acid group in the above range, the printability can be improved. Regarding the weight average molecular weight of the acid group-containing resin, when the acid group-containing resin is a styrene-(anhydrous) maleic acid resin, it is preferably 500 or more, more preferably 700 or more, and more preferably 1000 above. By setting the weight average molecular weight of the resin having an acid group in the above range, the adhesion to the substrate and the deinking property during alkaline solution treatment can be balanced. It can achieve a balance of deinking performance when treated with alkali. In addition, the weight average molecular weight of the resin having an acid group is preferably 100,000 or less, more preferably 70,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

By setting the weight average molecular weight of the resin having an acid group in the above range, the viscosity of the ink can be lowered, and further, the adhesion to the substrate can be balanced with the deinking property during alkaline solution treatment. The range of the weight average molecular weight of the resin having an acid group is preferably 500 to 100,000, more preferably 700 to 30,000, more preferably 1,000 to 50,000, and even more preferably 1,000 to 30,000. By setting the weight average molecular weight of the resin having an acid group in the above range, the printability can be improved. In addition, part or all of the acid groups of the acidic additives may form a salt with a basic compound described later in the aqueous liquid ink in advance or in the aqueous liquid ink. The basic compound described later neutralizes the acid group of the above-mentioned acidic additive, thereby improving water solubility or water dispersibility.

Regarding the solid content of acid additives, from the viewpoints of the re-dissolvability of the aqueous liquid ink, the inhibition of the adhesion of the printed matter, the improvement of the printing density, and the adhesion to the substrate, in the above-mentioned aqueous liquid ink , Preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 1.5% by mass or more, more preferably 2% by mass or more, preferably 60% by mass or less, more It is preferably 55% by mass or less, and more preferably 50% by mass or less. The range of the solid content of the acidic additives is preferably 0.1-60% by mass, more preferably 0.5-55% by mass, more preferably 1-50% by mass, and still more preferably 1.5-45% by mass , More preferably 2-40% by mass.

When the acidic additive is an organic acid, the solid content of the organic acid in the aqueous liquid ink is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.3% by mass Above, more preferably 0.5% by mass or more, more preferably 1% by mass or more, 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, It is more preferably 16% by mass or less, more preferably 14% by mass or less, still more preferably 12% by mass or less, and still more preferably 10% by mass or less. The range of the solid content of the organic acid is preferably from 0.1 to 20% by mass, more preferably from 0.2 to 18% by mass, more preferably from 0.3 to 16% by mass, even more preferably from 0.5 to 14% by mass, It is more preferably from 1 to 12% by mass, more preferably from 1.5 to 10% by mass, and even more preferably from 2 to 10% by mass.

When the acidic additive is a resin having an acid group, the content of the solid content of the resin having an acid group in the aqueous liquid ink is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, It is more preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, more preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less. The range of the solid content of the acidic additives is preferably 0.1-60% by mass, more preferably 0.5-55% by mass, more preferably 1-50% by mass, and still more preferably 1.5-45% by mass , More preferably 2-40% by mass.

＜Aqueous medium＞ Examples of the above-mentioned aqueous medium include: water, hydrophilic organic solvents, a mixture of water and hydrophilic organic solvents, etc. From the viewpoint of safety or burden on the environment, water or water and hydrophilic organic solvents are preferred. The mixture is more preferably water.

As the above-mentioned hydrophilic organic solvent, one kind or two or more kinds can be used, and one mixed with water is preferred. Examples include: monovalent alcohol solvents such as methanol, ethanol, n-propanol, and 2-propanol; ethylene glycol, Diethylene glycol, propylene glycol, polyalkylene glycol, glycerin and other polyvalent alcohol solvents; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl carbitol and other ether solvents; Amine solvents such as N-methyl-2-pyrrolidone are preferably monovalent alcohols, and among them, 2-propanol is most preferred.

When the above-mentioned aqueous medium contains water and a hydrophilic organic solvent, the water content in the aqueous medium is preferably 70% by mass or more, more preferably 75% by mass or more, more preferably 80% by mass or more, and more preferably 85% Mass% or more, more preferably 90 mass% or more, for example, 100 mass% or less, and further, 95 mass% or less may also be allowed.

＜Other ingredients＞ In addition, the aqueous liquid ink of the present invention may further contain a binder resin, a basic compound, a coloring agent, an organic solvent (not including the above-mentioned aqueous medium), an auxiliary agent, and the like. Examples of binder resins include cellulose resins such as nitrocellulose, urethane resins, polyamide resins, vinyl chloride/vinyl acetate copolymers, rosin resins and their modifications, ketone resins, cellulose resins, Polyester resin, (meth)acrylic resin, etc., can be used in appropriate combination. Among them, urethane resins, (meth)acrylic resins, rosin-based resins, and modified products thereof are commonly used in appropriate combinations. The above-mentioned binder resin may be dispersed in the above-mentioned aqueous medium in advance.

In the above water-based method, an emulsifier may also be used as needed. In addition, when dissolving or dispersing in water, machines such as a homogenizer may be used as needed.

Examples of the emulsifier include: polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene-poly Non-ionic emulsifiers such as oxypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfuric acid Anionic emulsifiers such as sodium salt, alkane sulfonate sodium salt, and alkyl diphenyl ether sulfonate sodium salt; cationic emulsifier such as alkyl amine salt, alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, etc. Wait. Among them, from the viewpoint of storage stability, an anionic or nonionic emulsifier is preferred. In addition, the above-mentioned resin having an acid group can also be used as the above-mentioned binder resin. The basic compound includes at least one selected from the group consisting of basic metal compounds and organic amines.

Examples of the above-mentioned basic metal compounds include: metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and magnesium hydroxide; metal chlorides such as sodium chloride and potassium chloride; copper sulfate, etc. Metal sulfates, etc.

啉等環狀胺等。 上述鹼性化合物較佳為至少含有胺，更佳為至少含有氨。Examples of the above-mentioned amines include: ammonia; primary amines such as monomethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine; secondary amines such as dimethylamine, ethylmethylamine, and diethylamine Amine; trimethylamine, triethylamine, tripropylamine, dimethylethylamine, methyldiisopropylamine, diisopropylethylamine, diethylethanolamine, triethanolamine and other tertiary amines; ethylenediamine, tetramethylethylenediamine Amines and other amines;

Cyclic amines such as morpholino. The above-mentioned basic compound preferably contains at least amine, and more preferably contains at least ammonia.

(dioxazine)系、異吲哚啉酮(isoindolinone)系、喹酞酮(quinophthalone)系、偶氮甲鹼偶氮(azomethine azo)系、黃士酮(flavanthrone)系、吡咯并吡咯二酮(diketopyrrolopyrrole)系、異吲哚啉(isoindoline)系、靛蒽醌(indanthrone)系、炭黑系等顏料。又，例如可列舉：洋紅6B(Carmine 6B)、金光紅C(Lake Red C)、永固紅2B(Permanent Red 2B)、偶氮縮合黃(Disazo Yellow)、吡唑橙(Pyrazolone Orange)、洋紅FB(Carmine FB)、克勞莫夫塔爾黃(Chromophthal Yellow)、克勞莫夫塔爾紅(Chromophthal Red)、酞青藍(Phthalocyanine Blue)、酞青綠(Phthalocyanine Green)、二

紫(Dioxazine Violet)、喹吖酮品紅(Quinacridone Magenta)、喹吖酮紅(Quinacridone Red)、靛蒽醌藍(Indanthrone Blue)、嘧啶黃(Pyrimidine Yellow)、硫靛棗紅(Thioindigo Bordeaux)、硫靛品紅(Thioindigo Magenta)、苝紅(Perylene Red)、芘酮橙(Perinone Orange)、異吲哚啉酮黃(Isoindolinone Yellow)、苯胺黑(Aniline Black)、吡咯并吡咯二酮紅(Diketopyrrolopyrrole Red)、日光螢光顏料等。又，亦可使用未經酸性處理之顏料、酸性處理顏料之任一者。以下，列舉作為有機顏料之較佳的具體例。Examples of the coloring agent used in the aqueous liquid printing ink of the present invention include inorganic pigments, organic pigments, or dyes used in ordinary inks, paints, and recording agents. Examples of organic pigments include: soluble azo series, insoluble azo series, azo series, phthalocyanine series, halogenated phthalocyanine series, anthraquinone series, anthanthrone series, Dianthraquinone series, anthrapyrimidine series, perylene series, perinone series, quinacridone series, thioindigo series, two

(dioxazine) series, isoindolinone series, quinophthalone series, azomethine azo series, flavanthrone series, diketopyrrolopyrrole ) Series, isoindoline series, indanthrone series, carbon black series and other pigments. Also, for example, Carmine 6B (Carmine 6B), Lake Red C (Lake Red C), Permanent Red 2B (Permanent Red 2B), Disazo Yellow (Disazo Yellow), Pyrazolone Orange (Pyrazolone Orange), Magenta FB (Carmine FB), Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, two

Violet, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indanthrone Blue, Pyrimidine Yellow, Thioindigo Bordeaux, Sulfur Thioindigo Magenta, Perylene Red, Perinone Orange, Isoindolinone Yellow, Aniline Black, Diketopyrrolopyrrole Red ), daylight fluorescent pigments, etc. In addition, any one of a pigment that has not been acid-treated or an acid-treated pigment may be used. Hereinafter, preferred specific examples of organic pigments are listed.

As a black pigment, 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, etc. are mentioned, for example.

Examples of blue pigments include: CIPigment Blue 15, CIPigment Blue 15:1, CIPigment Blue 15: 2, CIPigment Blue 15: 3, CIPigment Blue 15: 4, CIPigment Blue 15: 5, CI Pigment Blue 15: 6, CIPigment Blue 16, CIPigment Blue 17:1, CIPigment Blue 22, CIPigment Blue 24:1, CIPigment Blue 25, CIPigment Blue 26, CIPigment Blue 60, CIPigment Blue 61, CIPigment Blue 62, CIPigment Blue 63, CIPigment Blue 64, CIPigment Blue 75, CIPigment Blue 79, CIPigment Blue 80, etc.

As a green pigment, 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, etc. are mentioned, for example.

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

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

As yellow pigments, for example, CIPigment Yellow 1, CIPigment Yellow 3, CIPigment Yellow 12, CIPigment Yellow 13, CIPigment Yellow 14, Pigment Yellow 17, CIPigment Yellow 24, CIPigment Yellow 42, CIPigment Yellow 55, CIPigment Yellow 62, CIPigment Yellow 65, CIPigment Yellow 74, CIPigment Yellow 83, CIPigment Yellow 86, CIPigment Yellow 93, CIPigment Yellow 94, CIPigment Yellow 95, CIPigment Yellow 109, CIPigment Yellow 110, CIPigment Yellow 117, CIPigment Yellow 120, Pigment Yellow 125, CIPigment Yellow 128, CIPigment Yellow 129, CIPigment Yellow 137, Yellow 138, CIPigment Yellow 139, CIPigment Yellow 147, CIPigment Yellow 148, CI Pigment Yellow 150, CIPigment Yellow 151, CIPigment Yellow 153, CIPigment Yellow 154, CIPigment Yellow 155, CIPigment Yellow 166, CIPigment Yellow 168, CIPigment Yellow 174, CIPigment Yellow 180, CIPigment Yellow 185 and CI Pigment Yellow 213 and so on.

As orange pigments, for example, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 16, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 37, CIPigment Orange 38, CIPigment Orange 43, CIPigment Orange 51, CIPigment Orange 55, CIPigment Orange 59, CIPigment Orange 61, CIPigment Orange 64, CIPigment Orange 71, or CIPigment Orange 74, etc.

As a brown pigment, C.I.Pigment Brown 23, C.I.Pigment Brown 25, or C.I.Pigment Brown 26, etc. are mentioned, for example. Among them, as a preferred pigment, as a black pigment, CIPigment Black 7 can be cited; as a blue pigment, CIPigment Blue 15, CIPigment Blue 15:1, CIPigment Blue 15: 2, CIPigment Blue 15: 3 , CIPigment Blue 15:4, CIPigment Blue 15:6; as green pigments, CIPigment Green 7 can be cited; as red pigments, CIPigment Red 57:1, CIPigment Red 48:1, and CIPigment Red 48 ：2, CIPigment Red 48:3, CIPigment Red 146, CIPigment Red 242, CIPigment Red 185, CIPigment Red 122, CIPigment Red 178, CIPigment Red 149, CIPigment Red 144, CIPigment Red 166; As purple pigments, CIPigment Violet 23 and CIPigment Violet 37 can be cited; as yellow pigments, CIPigment Yellow 83, CIPigment Yellow 14, CIPigment Yellow 180, and CIPigment Yellow 139 can be cited; as orange pigments, CIPigment can be cited Orange 38, CIPigment Orange 13, CIPigment Orange 34, CIPigment Orange 64, etc., it is preferable to use at least one or two or more selected from the group.

Regarding the total content of the above-mentioned pigments, from the viewpoint of ensuring ink concentration and coloring power, it is preferably 1% by mass or more in the total ink, and more preferably 60% by mass or less. Examples of the above-mentioned organic solvents include aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc. Ester solvent. Moreover, if it is an aqueous solvent, the solvent which mixed water-soluble alcoholic solvent etc. with water as a main component is mentioned. From the perspective of the actual state of the environment, a mixture of alcohol-based solvents or ester-based solvents is the most suitable. Water may also be contained in this solvent. Among the alcohol solvents, ethanol, n-propanol, and isopropanol are the best. Among the ester solvents, ethyl acetate, n-propyl acetate, and isopropyl acetate are the best. A single solvent of the ester system, and further, an ink formed of only a single solvent.

As the above-mentioned additives, waxes such as paraffin wax, polyethylene wax, carnauba wax, etc. used to impart friction resistance, slip properties, etc.; Amine compound; silicon-based and non-silicon-based defoaming agent used to inhibit foaming during printing; dispersing agents can also be used appropriately. As the above-mentioned dispersing agent, a nonionic dispersing agent is preferable. The acid value of the above dispersant is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, and still more preferably 20 mgKOH/g or less. In addition, it may be, for example, 1 mgKOH/g or more, and further 3 mgKOH/g or more. The acid value of the above-mentioned dispersant is preferably smaller than the acid value of the above-mentioned acidic additive. The difference between the acid value of the acidic additive and the acid value of the dispersant is, for example, preferably 1 mgKOH/g or more, and more preferably 3 mgKOH/g or more. Moreover, 30 mgKOH/g or less is preferable, and 20 mgKOH/g or less is more preferable.

Regarding the content of the dispersant, relative to 100 parts by mass of the colorant, it 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, and more preferably 65 parts by mass Parts by mass or less, more preferably 60 parts by mass or less. In addition to the above, wetting agents, adhesive adjuvants, leveling agents, antistatic agents, viscosity regulators, metal chelating agents, trapping agents, anti-blocking agents, isocyanate-based hardeners, and silane coupling agents can also be used as needed. . The viscosity of the above-mentioned aqueous liquid ink is a value measured at 25°C using Zahn cup #4 manufactured by Rigakusha, preferably 6 seconds or more, more preferably 10 seconds or more, and still more preferably 13 seconds or more. Furthermore, it is preferably 25 seconds or less, more preferably 20 seconds or less, and still more preferably 18 seconds or less.

The surface tension of the above-mentioned aqueous liquid ink is preferably 25 mN/m or more, more preferably 33 mN/m or more. Furthermore, it is preferably 50 mN/m or less, more preferably 43 mN/ or less. By appropriately increasing the surface tension of the ink, the wettability of the ink to the substrate can be maintained, and at the same time, the dot bridge (dot bridge, in the halftone dot part, the printing surface formed by connecting adjacent dots can be connected to each other). Smudge), by appropriately reducing the surface tension of the ink, the wettability of the ink to the substrate can be improved, and shrinkage can be suppressed. The water-based liquid ink of the present invention can be carried out using Eiger Mill, sand mill, Gamma Mill, attritor, etc., which are commonly used in the manufacture of gravure and flexographic printing inks. manufacture. When preparing the aqueous liquid ink of the present invention, from the viewpoint of uniformity, at least a part of the above-mentioned binder resin, the above-mentioned colorant, at least a part of the above-mentioned acidic additives, and the above-mentioned basic compound At least a part of the above-mentioned dispersant, and at least a part of the above-mentioned aqueous medium are mixed to prepare a preliminary composition (mixed base ink). In addition, as the ink to be removed from the substrate in the same manner as in the present invention, photoresist inks can be cited, but the purpose of this photoresist ink is to "leave a part of the coating film from the substrate in advance and process the substrate", and " The ink of the present invention, which aims to detach the entire ink coating film and recycle the substrate, is fundamentally different in use and purpose, and therefore does not conform to the well-known technology of the present invention.

(Printed to substrate) The water-based liquid ink of the present invention has excellent adhesion to various substrates, and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc. Ink for gravure printing of gravure printing plates, or flexographic printing using flexographic printing plates made of resin plates, etc., on the other hand, although it can also be used to eject ink from inkjet nozzles without using a plate The inkjet method, but not very good. That is, in the case of inkjet inks, the ink droplets ejected from the nozzles directly adhere to the substrate to form a printed matter. In contrast, the aqueous liquid ink of the present invention temporarily adheres and transfers the printing ink to After the printing plate or the pattern is printed, only the ink is adhered to the base material again, and then dried as necessary to make a printed matter. The film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the aqueous liquid ink of the present invention is, for example, preferably 10 μm or less, more preferably 5 μm or less.

In addition, the aqueous liquid ink of the present invention contains acidic additives, and the used substrate is preferably fully washed immediately after use. As the detergent, detergents commonly used in the washing of water-based inks can be used.

(Printed matter and laminated body) The aqueous liquid ink of the present invention can be printed on the substrate directly or via other layers. The embodiments of the printed matter printed using the aqueous liquid ink of the present invention and the laminate formed using the printed matter are not limited, but the following forms are preferably cited.

＜Surface printing＞ ･Substrate A-Ink coating layer (white)-Ink coating layer (color) Substrate A- Primer layer-Ink coating layer (white)-Ink coating layer (color) ･Substrate A-Ink Coating layer (white)-ink coating layer (color)-OPV layer ･ substrate A-primer layer-ink coating layer (white)-ink coating layer (color)-OPV layer ･ substrate A-ink Coating layer (color)-Ink coating layer (white) ･Substrate A-Primer layer-Ink coating layer (color)-Ink coating layer (white) Substrate A-Ink coating layer (color) -Ink coating layer (white)-OPV layer ･Substrate A- Primer layer-Ink coating layer (color)-Ink coating layer (white)-OPV layer

＜Back printing･Layer＞ ･Substrate A-Ink coating layer (white)-Ink coating layer (color)-Adhesive layer-Substrate B ･Substrate A-Primer layer-Ink coating layer (white)-Ink coating layer( Color)-Adhesive layer-Substrate B ･Substrate A-Ink coating layer (white)-Ink coating layer (color)-OPV layer-Adhesive layer-Substrate B ･Substrate A-Primer layer- Ink coating layer (white)-ink coating layer (color)-OPV layer-adhesive layer-substrate B ･ substrate A-ink coating layer (color)-ink coating layer (white)-adhesive layer -Substrate B ･Substrate A- Primer layer-Ink coating layer (color)-Ink coating layer (white)-Adhesive layer-Substrate B ･Substrate A-Ink coating layer (color)-Ink Coating layer (white)-OPV layer-adhesive layer-substrate B ･ substrate A-primer layer-ink coating layer (color)-ink coating layer (white)-OPV layer-adhesive layer-base Material B ･Substrate A-Ink coating layer (white)-Ink coating layer (color)-Resin C layer-Substrate B ･Substrate A- Primer layer-Ink coating layer (white)-Ink coating film Layer (color)-resin C layer-substrate B ･ substrate A-ink coating layer (white)-ink coating layer (color)-OPV layer-resin C layer-substrate B ･ substrate A-primer Layer-Ink coating layer (white)-Ink coating layer (color)-OPV layer-Resin C layer-Substrate B ･Substrate A-Ink coating layer (color)-Ink coating layer (white)-Resin Layer C-Substrate B ･Substrate A-Primer Layer-Ink Coating Layer (Color)-Ink Coating Layer (White)-Resin C Layer-Substrate B ･Substrate A-Ink Coating Layer (Color) -Ink coating layer (white)-OPV layer-Resin C layer-Substrate B ･Substrate A-Primer layer-Ink coating layer (color)-Ink coating layer (white)-OPV layer-Resin C layer -Substrate B ･Substrate A- Ink coating layer (white)-Ink coating layer (color)-Substrate B ･Substrate A- Primer layer-Ink coating layer (white)-Ink coating layer ( Color)-Substrate B ･Substrate A-Ink coating layer (white)-Ink coating layer (color)-OPV layer-Substrate B ･Substrate A-Primer layer-Ink coating layer (white)- Ink coating layer (color)-OPV layer-substrate B ･ substrate A-ink coating layer (color)-ink coating layer (white)-substrate B ･ substrate A-primer layer-ink coating Layer (color)-ink coating layer (white)-substrate B ･ substrate A-ink coating layer (color)-ink coating layer (white)-OPV layer-substrate B substrate A-primer Layer-ink coating layer (color)-ink coating layer (white)-OPV layer-substrate B

Here, the above-mentioned substrate A refers to the substrate A described later, and the ink coating film layer (white) refers to printing "the aqueous liquid ink of the present invention using the coloring agent used in the white ink as the coloring agent of the aqueous liquid ink of the present invention "The ink coating film layer formed, and the ink coating film layer (color) means printing "the water-based liquid ink of the present invention using a coloring agent other than the coloring agent used in the white ink as the coloring agent of the water-based liquid ink of the present invention "The ink coating film layer formed, the primer layer means the layer formed using the primer described below, the adhesive layer means the layer formed using the adhesive described below, and the OPV layer means the layer formed using the OPV (varnish) described below , The resin C layer means a layer formed using the resin C described later, and the substrate B means the substrate B described later.

In addition, the backside printing/layer structure includes the repetition and combination of the above-mentioned forms, as well as composite and multilayer structures. The base material A is preferably a plastic base material, and examples thereof include polyamide resins such as nylon 6, nylon 66, and nylon 46; polyethylene terephthalate (PET), polyethylene naphthalate Diester, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate and other polyester resins; polylactic acid and other polyhydroxycarboxylates Acid; poly(ethylene succinate), poly(butylene succinate) and other aliphatic polyester resins and other biodegradable resins; polypropylene, polyethylene and other polyolefin resins; polyimide resins, Films or laminates made of thermoplastic resins such as polyarylate resins or mixtures of these, among them, films or laminates made of polyester, polyamide, polyethylene, or polypropylene can be preferably used If the releasability of the ink of the present invention is important, polypropylene or polyethylene is more preferable. These base films may be unstretched films or stretched films, and their production methods are also not limited. In addition, the thickness of the base film is also not particularly limited, and it may usually be in the range of 1 to 500 μm. For the printing surface of the substrate A, corona discharge treatment is preferred, and silica, alumina, etc. may also be vapor-deposited. As the substrate B, those that are the same as the substrate A, which may be the same or different, are preferably a plastic substrate, and more preferably a thermoplastic resin substrate. When the above-mentioned laminate is an extrusion laminate, it may be the same as the resin C described later. In addition, it may be laminated with a metal foil or a metal foil of a vapor-deposited film layer.

As the resin C, a thermoplastic resin is preferred, polyolefin is more preferred, and polypropylene or polyethylene and modified resins thereof are particularly preferred. As the primer for forming the primer layer, it is preferable to contain a resin having an acid group in terms of being easily dissolved or hydrolyzed by an alkaline solution. The resin with acid group or low molecular compound can be used alone in the primer. In addition, a resin having an acid group or a low-molecular compound can be mixed with a resin having no acid group and used. Examples of resins having acid groups include cellulose resins, urethane resins, polyamide resins, vinyl chloride/vinyl acetate copolymers, ketone resins, polyester resins, (meth)acrylic resins, and rosin. Resins with acid value such as modified maleic acid resin or rosin-modified fumaric acid resin; or itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, etc. Polymerizable monomers having carboxyl groups, polymerizable monomers having sulfonic acid groups such as sulfonated styrene, polymerizable monomers having sulfonamide groups such as vinylbenzene sulfonamide, etc. make polymerizable monomers having acid groups Free radicals such as (meth)acrylic resin, styrene-(meth)acrylic resin, styrene-(anhydrous) maleic acid resin, terpene-(anhydrous) maleic acid resin, etc. Copolymer resins, or acid-modified polyolefin resins, etc., can be used singly or in plural. In addition, the primer layer can also be used by mixing single or multiple low-molecular compounds with acid groups in a resin with low acid value and film-forming properties at room temperature. As the above-mentioned low-molecular compound having an acid group, preferably, a low-molecular compound having a carboxyl group, a phosphoric acid group, a sulfonic acid group, a sulfinic acid group, etc. or an ester or salt thereof as an acid group, more preferably Saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, organic phosphoric acid, organic phosphoric acid derivatives, organic sulfonic acids, organic sulfonic acid derivatives , Organic sulfinic acid, organic sulfinic acid derivatives and other organic acids, which can be used singly or in plural.

Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid; examples of unsaturated fatty acids include oleic acid and linoleic acid. Acid, linolenic acid, arachidic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc.; examples of hydroxy acids include lactic acid, malic acid, citric acid, etc.; as aromatic carboxylic acids, Examples: 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.; as Examples of tricarboxylic acids include: aconitic acid, trimer acid, etc.; examples of oxocarboxylic acid include: pyruvic acid, acid oxalic acid, etc.; examples of carboxylic acid derivatives include: amino acid and nitrocarboxylic acid , It can be used singly or in plural. Also, if it is citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, oleostearic acid , Arachidic acid, sebacic acid, etc., can correspond to the so-called Swiss Ordinance (Swiss Ordinance), it is better to use substances corresponding to various regulations. As the above-mentioned organic phosphoric acid, organic phosphoric acid derivative, organic sulfonic acid, organic sulfonic acid derivative, organic sulfinic acid, and organic sulfinic acid derivative, preferably: monoalkyl phosphoric acid, dialkyl phosphoric acid, trialkyl phosphoric acid , Monoalkyl phosphoric acid derivatives, dialkyl phosphoric acid derivatives, trialkyl phosphoric acid derivatives, monophenyl phosphoric acid, diphenyl phosphoric acid, triphenyl phosphoric acid, monophenyl phosphoric acid derivatives, diphenyl phosphoric acid derivatives , Triphenylphosphoric acid derivatives, monoalkylsulfonic acid, dialkylsulfonic acid, trialkylsulfonic acid, monoalkylsulfonic acid derivatives, dialkylsulfonic acid derivatives, trialkylsulfonic acid derivatives, Monophenylsulfonic acid, diphenylsulfonic acid, triphenylsulfonic acid, monophenylsulfonic acid derivatives, diphenylsulfonic acid derivatives, triphenylsulfonic acid derivatives, monoalkylsulfinic acid, two Alkylsulfinic acid, trialkylsulfinic acid, monoalkylsulfinic acid derivatives, dialkylsulfinic acid derivatives, trialkylsulfinic acid derivatives, monophenylsulfinic acid, diphenyl Sulfinic acid, triphenylsulfinic acid, monophenylsulfinic acid derivatives, diphenylsulfinic acid derivatives, triphenylsulfinic acid derivatives.

As the above-mentioned resin having film-forming properties at room temperature, there are various synthetic resins, for example, polyester, polyvinyl chloride or copolymers of vinyl chloride and other monomers containing unsaturated double bonds, and (meth)acrylates Copolymers of monomers or (meth)acrylates and other monomers containing unsaturated double bonds, copolymers of polystyrene or styrene monomers and other monomers containing unsaturated double bonds, ketone-formaldehyde condensation Or its hydrogenated product, polyfunctional epoxy resin, polyvinyl acetal, polyurethane, etc., and these can be used alone, or one or more selected from them can be used in combination. Examples of polyfunctional epoxy compounds include: bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, bisphenol S novolac type epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin. Epoxy and so on. When mixing single or multiple low-molecular compounds with acid groups in the above-mentioned resins with low acid value and film-forming properties at room temperature, the amount of addition does not impair the printability or coating suitability of the primer solution. The range may be appropriately determined, and in general, it is preferably in the range of 0.5 to 50% by mass relative to the solid content of the primer solution, and more preferably in the range of 1.0 to 30% by mass.

When the printed object is polypropylene (PP), for example, as a resin with film-forming properties, the following thermoplastic resins are preferably used, namely: their own good adhesion to PP, selected from ketone-formaldehyde condensates or their hydrogenation Thermoplastic resin that is at least one of the group consisting of polyester, polyester, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetal, and is solid at 50°C. Examples of such ketone-formaldehyde condensates or hydrogenated products thereof include: Evonik Degussa Japan (Co., Ltd.) TEGO (registered trademark) VariPlus series (SK, AP, etc.); examples of polyester include: manufactured by Toyobo Co., Ltd. Vylon (registered trademark) series (Vylon 200, etc.); as vinyl chloride-vinyl acetate copolymers, examples include: SOLBIN (registered trademark) series (SOLBIN AL, etc.) manufactured by Nissin Chemical Industry Co., Ltd.; as polyethylene Examples of acetals include: S-LEC (registered trademark) series (S-LEC KS-10, etc.) manufactured by Sekisui Chemical Industry Co., Ltd. Regarding the formation of the primer layer on the substrate, a solution prepared using the above-mentioned components is applied to the substrate and dried. The coating amount is about 0.1-5um (dry thickness). If it is less than 0.1, it will be difficult to apply uniformly. If it exceeds 5um, it is not economical and therefore not practical. Coating can use common coating methods, such as gravure, relief, flexo, roll coater, reverse coater, spray method, etc. The formation of the primer layer and printing on it can be performed continuously (in-line), or the formation and printing of the primer layer can be performed separately. When a roll-to-roll printer is used to perform online printing immediately after the primer is applied, the resin used in the primer can be re-solubilized in the ink solvent and the glass transition point (Tg ), there will be so-called adhesion between the printed surface and the back of the substrate. In order to prevent such adhesion, as an anti-blocking agent, about 0.005 to 5% of the total amount of the primer, such as silicon dioxide or titanium oxide and other transparent particles with a particle size of 0.1um to 10um, can be mixed with the primer solvent middle. In addition, for the purpose of preventing blocking, it is also possible to neutralize it with ammonia or the like before coating the resin solution with high acid value used in the primer to prevent the re-solubility of the solvent contained in the printing ink.

The adhesive used to form the adhesive layer is not particularly limited. It can be used as long as it is a commercially available reactive adhesive. Among them, the so-called two-component type of polyisocyanate composition and polyol composition, or poly A one-component reactive adhesive of isocyanate is preferred. The polyisocyanate composition used in a general reactive adhesive is a composition containing a polyisocyanate compound as a main component, and it is not particularly limited as long as it is known as a polyisocyanate compound used as a reactive adhesive. use. Examples of specific polyisocyanate compounds include, for example, toluene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, Polyisocyanates with aromatic structures in the molecular structure such as xylene diisocyanate, compounds in which part of the isocyanate groups (NCO groups) of these polyisocyanates are modified with carbodiimide; isophorone diisocyanate, 4,4'- Methylene bis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane and other polyisocyanates with alicyclic structure in the molecular structure; 1,6-hexamethylene diisocyanate, 1 , 5-Pentamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and other linear aliphatic polyisocyanates, and part of the NCO group of these polyisocyanates is modified with carbodiimide The compound; the trimeric isocyanate of the above-mentioned various polyisocyanates; the alloformate derived from the above-mentioned various polyisocyanates; the biuret derived from the above-mentioned various polyisocyanates; the above-mentioned various polyisocyanates are trimethylol Adducts modified from propane; polyisocyanates as reaction products of the various polyisocyanates described above and polyol components described below.

The polyol composition used in a general reactive adhesive is a composition containing a polyol compound as the main component. As long as it is a polyol compound known to be used as a reactive adhesive, it can be used without particular restrictions. . 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- Pentylene glycol, 1,6-hexanediol, neopentyl glycol, methyl pentane glycol, dimethyl butanediol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, triethylene glycol Glycol, dipropylene glycol, trimethylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol and other glycols; glycerol, triethylene glycol Tri-functional or 4-functional aliphatic alcohols such as methyl propane and neopentyl erythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; selected from dimer diols, or poly Ester polyol, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol Polymer polyols in alcohols, polyhydroxyalkanes, castor oil, or mixtures of these.

Among them, in terms of being 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 can be easily separated in a short time in the ink coating release step described later. Into a single layer film. Any one of the components of the reactive adhesive has an ester bond. Specifically, a reactive adhesive containing one or both of the following components can be mentioned. The composition system contains a polyester polyol having an ester bond, Polyether ester polyols, polyester (polyurethane) polyols, acrylic polyols, and other polyol compounds, or polyisocyanate compounds, which are reaction products of polyol compounds having the above ester bonds and various polyisocyanates described above The polyisocyanate composition. Furthermore, in addition to the above-mentioned polyol composition or the above-mentioned polyisocyanate composition, a reactive adhesive to which a resin having an acid group or a low-molecular compound is added can also be preferably used. As the resin or low molecular compound having an acid group, as long as it can be easily mixed with the above-mentioned polyol composition or the above-mentioned polyisocyanate composition as the main component of the reactive adhesive (in this case, if necessary, it can also be used Solvents mentioned later) and resins or low-molecular compounds having an acid value can be used without particular restrictions.

Examples of the resin having an acid group include resins having an acid value such as rosin-modified maleic acid resin or rosin-modified fumaric acid resin; or acrylic acid, methacrylic acid, itaconic acid, Polymerizable monomers with carboxyl groups such as maleic acid, fumaric acid, cinnamic acid or their anhydrides, polymerizable monomers with sulfonic acid groups such as sulfonated styrene, vinylbenzene sulfonamide, etc. (Meth) acrylic resin, styrene-(meth)acrylic resin, styrene-(anhydrous) maleic resin obtained by copolymerization of polymerizable monomer with acid group such as polymerizable monomer with sulfonamide group Radical copolymer resins such as diacid resins, terpene-(anhydrous) maleic acid resins; or acid-modified polyolefin resins, etc., can be used singly or in plural. As the above-mentioned low-molecular compound having an acid group, preferably, a low-molecular compound having a carboxyl group, a phosphoric acid group, a sulfonic acid group, a sulfinic acid group, etc. or an ester or salt thereof as an acid group, more preferably Saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, organic phosphoric acid, organic phosphoric acid derivatives, organic sulfonic acids, organic sulfonic acid derivatives , Organic sulfinic acid, organic sulfinic acid derivatives and other organic acids, which can be used singly or in plural. Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid; examples of unsaturated fatty acids include oleic acid and linoleic acid. Acid, linolenic acid, arachidic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc.; examples of hydroxy acids include lactic acid, malic acid, citric acid, etc.; as aromatic carboxylic acids, Examples: 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.; as Examples of tricarboxylic acids include: aconitic acid, trimer acid, etc.; examples of oxocarboxylic acid include: pyruvic acid, acid oxalic acid, etc.; examples of carboxylic acid derivatives include: amino acid and nitrocarboxylic acid , It can be used singly or in plural. Also, if it is citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, oleostearic acid , Arachidic acid, sebacic acid, etc., can correspond to the so-called Swiss Ordinance (Swiss Ordinance), it is better to use substances corresponding to various regulations. As the above-mentioned organic phosphoric acid, organic phosphoric acid derivative, organic sulfonic acid, organic sulfonic acid derivative, organic sulfinic acid, and organic sulfinic acid derivative, preferably: monoalkyl phosphoric acid, dialkyl phosphoric acid, trialkyl phosphoric acid , Monoalkyl phosphoric acid derivatives, dialkyl phosphoric acid derivatives, trialkyl phosphoric acid derivatives, monophenyl phosphoric acid, diphenyl phosphoric acid, triphenyl phosphoric acid, monophenyl phosphoric acid derivatives, diphenyl phosphoric acid derivatives , Triphenylphosphoric acid derivatives, monoalkylsulfonic acid, dialkylsulfonic acid, trialkylsulfonic acid, monoalkylsulfonic acid derivatives, dialkylsulfonic acid derivatives, trialkylsulfonic acid derivatives, Monophenylsulfonic acid, diphenylsulfonic acid, triphenylsulfonic acid, monophenylsulfonic acid derivatives, diphenylsulfonic acid derivatives, triphenylsulfonic acid derivatives, monoalkylsulfinic acid, two Alkylsulfinic acid, trialkylsulfinic acid, monoalkylsulfinic acid derivatives, dialkylsulfinic acid derivatives, trialkylsulfinic acid derivatives, monophenylsulfinic acid, diphenyl Sulfinic acid, triphenylsulfinic acid, monophenylsulfinic acid derivatives, diphenylsulfinic acid derivatives, triphenylsulfinic acid derivatives.

In addition, pigments, silane coupling agents, titanate coupling agents, aluminum coupling agents, epoxy resins and other adhesion promoters, leveling agents, colloidal silica, and oxidizing agents are also used in reactive adhesives. Inorganic particles such as aluminum sol, polymethylmethacrylate-based organic particles, defoamers, sag inhibitors, wetting and dispersing agents, viscosity modifiers, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants In the case of additives such as additives, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent whitening agents, inorganic heat ray absorbers, flame retardants, antistatic agents, dehydrating agents, etc. In addition, reactive adhesives include dry-type laminating adhesives diluted with a highly soluble organic solvent for dilution, solvent-free laminating adhesives that hardly contain organic solvents for dilution, and water-based adhesives where the diluent is water. And so on, can be used. Specific examples of organic solvents with high solubility for dilution include toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluene, Xylene, n-15 hexane, cyclohexane, etc. Among them, toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly known as organic solvents with high solubility. Aqueous adhesives can use water and organic solvents with affinity for water as the diluting solvent.

In the above-mentioned reactive adhesive, the blending ratio of the two-component type of the above-mentioned polyisocyanate composition and the above-mentioned polyol composition, if it is a commercially available product, is based on the recommended blending ratio. Generally speaking, the above-mentioned polyisocyanate The equivalent ratio of the isocyanate group in the isocyanate composition to the hydroxyl group in the polyol composition [isocyanate group/hydroxyl group] is often in the range of 1.0 to 5.0. Of course, there are also cases where it is blended and used in a range outside the above-mentioned range. Regarding the one-component adhesive of the reactive adhesive, the above-mentioned polyisocyanate composition is applied to the film alone, and the isocyanate group contained in the polyisocyanate composition reacts with moisture in the air to be cross-linked, thereby being used as Laminated adhesive. In the laminated film laminated by the reactive adhesive, the above-mentioned reactive adhesive is almost always mixed with the reactive adhesive and then coated on the first plastic film, and then the second plastic film is layered on the coated area After that, curing and cross-linking are carried out through an aging step and the like. Among the above-mentioned reactive adhesives, since detachment caused by an alkaline solution becomes easy to occur, it is preferable to contain the above-mentioned resin or low-molecular compound having an acid group. Among the two-component reactive adhesives of polyisocyanate composition and polyol composition, in terms of the stability of blending into the polyol composition, the above-mentioned resin or low-molecular compound having an acid group is preferred . In addition, the amount of addition may be appropriately determined within a range that does not impair the adhesiveness or curability of the reactive adhesive. In general, it is preferably 0.5-50 mass relative to the solid content of the polyol composition. The range of% is more preferably the range of 1.0-30% by mass.

In addition, as the reactive adhesive, as long as it is an ester-based adhesive, an ester amine-ester-based adhesive, an ether-ester-based adhesive, etc., the laminate is heated and stirred at 20 to 90°C or super In the step of immersing the laminate in an alkaline solution while sonic vibration, peeling occurs. On the other hand, ether-based adhesives may be difficult to peel off depending on the situation. In this case, it is better to provide the above-mentioned primer layer, or to use the above-mentioned acid group-containing resin or low Molecular compound person. There are no particular restrictions on the OPV (finishing varnish) used to form the OPV layer, and it can be used as long as it is commercially available OPV. The usual composition of OPV includes binder resin, organic solvents or water-based solvents and other solvents, additives, etc. Examples of the above-mentioned binder resins include cellulose resins such as nitrocellulose, urethane resins, polyamide resins, vinyl chloride/vinyl acetate copolymers, rosin resins and their modifications, ketone resins, and cellulose resins. , Polyester resin, (meth)acrylic resin, etc., which can be used in appropriate combination. Among them, it is preferable to use (meth)acrylic resin, urethane resin, rosin-based resin, and modified products thereof in an appropriate combination.

If the above-mentioned solvent is an organic solvent, for example, aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether ethyl Ester solvents such as acid esters, alcoholic solvents such as n-propanol, isopropanol, n-butanol, and propylene glycol monomethyl ether. Moreover, if it is an aqueous solvent, the solvent obtained by mixing water-soluble alcoholic solvent etc. with water as a main component is mentioned. Examples of the above-mentioned additives include extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, anti-blocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, and the like. In addition, there are also those that further add a cross-linking agent or a chelating agent to cross-link the printing ink layer itself to increase the hardness. In addition, OPV added with resins with acid groups or low-molecular-weight compounds can also be preferably used. As resins or low-molecular compounds having an acid group, any resin or low-molecular compound that can be easily mixed with the above-mentioned binder resin or organic solvent as the main component of OPV and has an acid value can be used without particular limitation . Examples of the resin having an acid group include: cellulose resins, urethane resins, and polyamides having carboxyl groups, phosphoric acid groups, sulfonic acid groups, sulfinic acid groups, etc. as acid groups or esters or salts thereof. Amine resin, vinyl chloride/vinyl acetate copolymer, ketone resin, polyester resin, (meth)acrylic resin, rosin modified maleic acid resin or rosin modified fumaric acid resin, etc. have acid value Resins; or polymerizable monomers with carboxyl groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid or their anhydrides, or polymerizable monomers with sulfonic acid groups such as sulfonated styrene , Vinylbenzenesulfonamide and other polymerizable monomers with sulfonamide groups, etc. (meth)acrylic resins, styrene-(meth)acrylic resins, which are copolymerized with polymerizable monomers with acid groups, etc. Free-radical copolymer resins such as styrene-(anhydrous) maleic acid resin, terpene-(anhydrous) maleic acid resin, or acid-modified polyolefin resin, etc., can be single or plural Mixed use.

As the above-mentioned low-molecular compound having an acid group, preferably, a low-molecular compound having a carboxyl group, a phosphoric acid group, a sulfonic acid group, a sulfinic acid group, etc. or an ester or salt thereof as an acid group, more preferably Saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, carboxylic acid derivatives, organic phosphoric acid, organic phosphoric acid derivatives, organic sulfonic acids, organic sulfonic acid derivatives , Organic sulfinic acid, organic sulfinic acid derivatives and other organic acids, which can be used singly or in plural. Examples of saturated fatty acids include lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, capric acid, undecanoic acid, and dodecanoic acid; examples of unsaturated fatty acids include oleic acid and linoleic acid. Acid, linolenic acid, arachidic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, etc.; examples of hydroxy acids include lactic acid, malic acid, citric acid, etc.; as aromatic carboxylic acids, Examples: 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.; as Examples of tricarboxylic acids include: aconitic acid, trimer acid, etc.; examples of oxocarboxylic acid include: pyruvic acid, acid oxalic acid, etc.; examples of carboxylic acid derivatives include: amino acid and nitrocarboxylic acid , It can be used singly or in plural. Also, if it is citric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, oleostearic acid , Arachidic acid, sebacic acid, etc., can correspond to the so-called Swiss Ordinance (Swiss Ordinance), it is better to use substances corresponding to various regulations. As the above-mentioned organic phosphoric acid, organic phosphoric acid derivative, organic sulfonic acid, organic sulfonic acid derivative, organic sulfinic acid, and organic sulfinic acid derivative, preferably: monoalkyl phosphoric acid, dialkyl phosphoric acid, trialkyl phosphoric acid , Monoalkyl phosphoric acid derivatives, dialkyl phosphoric acid derivatives, trialkyl phosphoric acid derivatives, monophenyl phosphoric acid, diphenyl phosphoric acid, triphenyl phosphoric acid, monophenyl phosphoric acid derivatives, diphenyl phosphoric acid derivatives , Triphenylphosphoric acid derivatives, monoalkylsulfonic acid, dialkylsulfonic acid, trialkylsulfonic acid, monoalkylsulfonic acid derivatives, dialkylsulfonic acid derivatives, trialkylsulfonic acid derivatives, Monophenylsulfonic acid, diphenylsulfonic acid, triphenylsulfonic acid, monophenylsulfonic acid derivatives, diphenylsulfonic acid derivatives, triphenylsulfonic acid derivatives, monoalkylsulfinic acid, two Alkylsulfinic acid, trialkylsulfinic acid, monoalkylsulfinic acid derivatives, dialkylsulfinic acid derivatives, trialkylsulfinic acid derivatives, monophenylsulfinic acid, diphenyl Sulfinic acid, triphenylsulfinic acid, monophenylsulfinic acid derivatives, diphenylsulfinic acid derivatives, triphenylsulfinic acid derivatives.

The OPV preferably contains the resin or low-molecular compound having an acid group. The addition amount may be appropriately determined within a range that does not impair the printability of OPV. Generally speaking, it is preferably in the range of 0.5-50% by mass relative to the solid content of OPV, and more preferably 1.0-30% by mass. % Range.

(Method for separating ink coating film from substrate A) In the present invention, the above-mentioned printed matter can be treated with warm water or alkaline solution to release the ink coating film from the base material A, thereby manufacturing the recycled base material A.

In addition, the present invention can be a laminate formed by laminating the above-mentioned printed matter and the substrate B with the ink coating film arranged on the inner side of the adhesive layer, and treat the adhesive layer and the substrate B with warm water or alkaline solution. It is released together with the ink coating film, thereby manufacturing a recycled base material A. The detachment step includes the following steps: the printing or the laminate is heated and stirred at 70 to 90°C or ultrasonic vibration, while being immersed in warm water; or heated and stirred at 20 to 90°C. Or ultrasonic vibration, while immersing in alkaline solution. The heating and stirring and ultrasonic vibration can be performed simultaneously. The above-mentioned step is preferably a step of immersing in an alkaline solution while heating and stirring at 20 to 90°C or ultrasonic vibration. The heating temperature is preferably 30°C or higher, preferably 40°C or higher, preferably 50°C or higher, preferably 60°C or higher, and more preferably heating stirring and ultrasonic vibration are performed simultaneously. The alkaline solution used in the above steps is not limited, preferably pH 9 or higher, preferably sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium dihydrogen carbonate aqueous solution, dicarbonate Potassium hydrogen aqueous solution, etc. Sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium dihydrogen carbonate aqueous solution, potassium dihydrogen carbonate aqueous solution, etc. are preferably an aqueous solution with a concentration of 0.5% to 10% by mass, more preferably a concentration An aqueous solution of 1% to 5% by mass.

Moreover, the said alkaline solution may contain a water-soluble organic solvent. As the above-mentioned water-soluble organic solvent, for example, methanol, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether (methoxaloxol), ethylene glycol monoethyl ether (celoxol), ethylene glycol monomethyl ether can be exemplified. Butyl ether (butyrethoxy), ethylene glycol dibutyl ether, diethylene glycol monomethyl ether (methcarbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (calar Diethylene glycol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butylcarbitol), diethylene glycol dibutyl ether, triethylene glycol monomethyl ether, Triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methylene dimethyl diether (dimethyl formal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetone acetone , Acetone, ethylene glycol monomethyl ether acetate (methyl cellulose acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether Acetate (carbitol acetate), ethyl hydroxyisobutyrate, ethyl lactate, etc., can be used alone or in combination of two or more.

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. Moreover, the said alkaline solution may contain a water-insoluble organic solvent. Specific examples of the above-mentioned water-insoluble organic solvent include: alcohol-based solvents such as n-butanol, 2-butanol, isobutanol, and octanol; aliphatic hydrocarbon-based solvents such as hexane, heptane, and n-alkane; benzene , Toluene, xylene, alkylbenzene and other aromatic hydrocarbon solvents; dichloromethane, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, carbon tetrachloride and other halogenated hydrocarbon solvents; methyl acetate Ester solvents such as ester, ethyl acetate, and butyl acetate; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; ether solvents such as diethyl ether and butyl ether, which can be used alone or in combination of two Used above. Furthermore, the above-mentioned alkaline solution may also contain a surfactant. As the surfactant, various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be cited. Among them, anionic surfactants and nonionic surfactants are preferred. Surfactant.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, and sulfate ester salt of higher fatty acid ester. , Sulfonates of higher fatty acid esters, sulfates 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 of these include: dodecyl benzene sulfonate, isopropyl naphthalene sulfonate, monobutyl phenyl phenol sulfonate Acid salt, monobutyl biphenyl sulfonate, dibutyl phenyl phenol disulfonate, etc. Examples of the aforementioned nonionic surfactant include: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitol fatty acid ester, polyoxyethylene sorbitol fat 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 alkylamine, polyoxyethylene fatty acid amide, Fatty acid alkanol amides, alkyl alkanol amides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol polypropylene glycol block copolymers, etc. Among them, poly(ethylene glycol) is preferred. Oxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitol fatty acid ester, polyoxyethylene Oxyethylene sorbitol fatty acid ester, fatty acid alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer.

As other surfactants, polysiloxane-based surfactants such as polysiloxane oxyethylene adducts can also be used; such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, oxyethylene perfluoro Alkyl ether-like fluorine-based surfactants; such as spiculisporic acid, rhamnolipid, and lysolecithin-like biological surfactants. These surfactants may be used alone, or two or more of them may be mixed and used. When adding the surfactant, the amount added is preferably in the range of 0.001 to 2% by mass relative to the total amount of the alkaline solution, more preferably in the range of 0.001 to 1.5% by mass, and still more preferably in the range of 0.01 to 1% by mass . In the state of heating or ultrasonic vibration at 70 to 90°C, for example, in a processing tank, immersing the target printed matter or laminate in the above-mentioned warm water; or in the state of heating or ultrasonic vibration at 20 to 90°C For example, in a processing tank, the printed matter or laminate to be the object is immersed in the above-mentioned alkaline solution. The heating method is not particularly limited, and known heating methods such as heat rays, infrared rays, and microwaves can be used. In addition, the ultrasonic vibration may be, for example, a method of installing an ultrasonic vibrator in the treatment tank and applying ultrasonic vibration to the above-mentioned warm water or alkaline solution. Furthermore, it is preferable to stir the above-mentioned warm water or alkaline solution during immersion. Examples of the stirring method include: a method of mechanically stirring the dispersion of printed matter or laminate contained in a processing tank with a stirring blade, a method of stirring with water using mercury, and a method of using inert gas such as nitrogen. In order to perform peeling efficiently, the bubble method etc. can also be used together.

The time for immersing the printed matter or the laminate in the warm water or alkaline solution also depends on the composition of the printed matter, but it is usually in the range of 2 minutes to 48 hours. Furthermore, in the present invention, it is not necessary for 100% of the ink coating film in the printed matter to be completely separated from the substrate, preferably 60% by mass or more of the 100% by mass of the ink coating film, more preferably 70% by mass or more, It is still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. In this step, the number of times of immersion in the above-mentioned warm water or alkaline solution can be performed once or several times. That is, the step of "recovering the separated membrane substrate after performing one immersion number of times" may be implemented, or the step of "recovering the above-mentioned membrane substrate after performing multiple immersion times". In addition, when the immersion is performed multiple times in this step, the concentration of the alkaline solution may be changed. Moreover, it is preferable to appropriately add a well-known step such as water washing or drying between these steps. Regarding the warm water or alkaline solution used in this separation method, as described above, it is presumed that by acting on the interface between the substrate and the printing ink coating film, the adhesion is significantly reduced, and the interface peeling occurs. On the other hand, since the solubility of the alkaline solution itself is also high, the printing ink layer that has not been cross-linked also dissolves. In addition, when the printing ink layer itself is crosslinked, since interface peeling occurs in the present invention, it is estimated that separation and recovery can also be performed efficiently in a short time. In the case of a laminate, in order to peel off the ink coating film by the above-mentioned method, it is preferable to cut off the substrate in advance, and make it easy for warm water or alkaline solution to act on the interface between the substrate and the ink in advance. [Example]

The content and effects of the present invention will be further described in detail by the following examples, but the present invention is not limited by them. Furthermore, "parts" shown below means "parts by mass". (Method of measuring acid value) If the acid value of the raw material is measured or announced, the acid value of the ink can be calculated by calculation. If it cannot be calculated, the acid value of the ink can be obtained by forming an ink film and measuring after drying. Out of acid value. The measurement of the acid value shown below is based on JIS0070-1992 or obtained by this method.

(Examples 1-24) The printing inks of Examples 1 to 24 were prepared by using the following binder resins, pigments, acid additives, and isopropyl alcohol (IPA), ethanol, and water according to the blending ratios described in Tables 1 to 3 below. (Printing inks I1～I24).

＜Adhesive resin＞ ･Resin 1: Water-based styrene-acrylic resin emulsion (acid value in solid content: 68mgKOH/g, solid content 40 parts by mass) Resin 2: Water-based urethane resin emulsion (acid value in solid content: 23mgKOH/g , Weight average molecular weight 17000, solid content 40 mass parts) Resin 3: Water-based urethane resin emulsion (solid content acid value: 2mgKOH/g, weight average molecular weight 18000, solid content 40 mass parts)

＜Pigment＞ ･White: Titanium oxide pigment (JR600A (manufactured by TAYCA)) Blue: Phthalocyanine blue pigment (FASTOGEN BLUE LA5380 blue pigment (manufactured by DIC))

＜Acid Additives＞ AA1: Stearic acid (acid value: 198mgKOH/g) AA2: sebacic acid (acid value: 556mgKOH/g) AA3: citric acid (acid value: 876mgKOH/g) AA4: Hiros X X-436( manufactured by Starlight PMC) Acid value: 33mgKOH/g, 40% emulsion solution of styrene acrylic resin) AA5: MALKYD#32-30WS manufactured by Arakawa Chemical Industry Co., Ltd. (Acid value: 140mgKOH/g, 30% aqueous solution of fumaric rosin resin) AA6: Starlight Hiros X X-200 manufactured by PMC (acid value: 190mgKOH/g, weight average molecular weight 12,000, styrene maleic acid resin) The above-mentioned AA1, AA2, AA3, and AA6 are neutralized with ammonia to prepare aqueous solutions. In addition, let AA1aq-AA6aq be AA1aq-AA6aq which prepared AA1-AA6 to 20% of solid content using ion-exchange water.

[Table 1] Example No. 1 2 3 4 5 6 7 8 9 10 Printing ink I1 I2 I3 I4 I5 I6 I7 I8 I9 I10 Adhesive resin Resin 1 50 50 50 50 50 50 Resin 2 50 50 50 50 Resin 3 pigment White 10 10 10 10 10 10 Blue 20 20 20 20 Solvent IPA 5 5 5 5 5 5 3 3 3 3 Ethanol 10 10 10 10 10 10 water 25 25 25 25 25 25 27 27 27 27 Acid additives AA1aq 10 10 AA2aq 10 10 AA3aq 10 10 AA4aq 10 10 AA5aq 10 AA6aq 10 Total 110 110 110 110 110 110 110 110 110 110 Acid value of solid content (mgKOH/g) 55 77 97 44 51 54 20 37 53 13

[Table 2] Example No. 11 12 13 14 15 16 17 18 19 20 Printing ink I11 I12 I13 I14 I15 I16 I17 I18 I19 I20 Adhesive resin Resin 1 Resin 2 50 50 50 50 50 50 50 50 Resin 3 50 50 pigment White Blue 20 20 20 20 20 20 20 20 10 10 Solvent IPA 3 3 3 3 3 3 3 3 3 3 Ethanol water 27 27 27 27 27 27 27 27 37 37 Acid additives AA1aq 10 10 AA2aq 10 10 AA3aq 10 AA4aq 10 AA5aq 10 10 AA6aq 10 10 Total 110 110 110 110 110 110 110 110 110 110 Acid value of solid content (mgKOH/g) 18 20 39 71 101 twenty four 34 38 20 52

[table 3] Example No. twenty one twenty two twenty three twenty four Printing ink I21 I22 I23 I24 Adhesive resin Resin 1 Resin 2 Resin 3 50 50 50 50 pigment White Blue 10 10 10 10 Solvent IPA 3 3 3 3 Ethanol water 37 37 37 37 Acid additives AA1aq AA2aq AA3aq 10 AA4aq 10 AA5aq 10 AA6aq 10 Total 110 110 110 110 Acid value of solid content (mgKOH/g) 81 5 15 19

(Comparative Examples 1～2) In the same manner as in Examples 1 to 24, Comparative Examples 1 to 2 were prepared with the blending ratios shown in Table 4 below.

[Table 4] Comparative example No. 1 2 Printing ink RI1 RI2 Adhesive resin Resin 1 Resin 2 Resin 50 50 pigment White Blue 10 10 Solvent IPA 3 3 Ethanol water 37 37 Acid additives AA1aq AA2aq AA3aq 40 AA4aq 1.5 AA5aq AA6aq Total 101.5 140 Acid value of solid content (mgKOH/g) 2.7 185

(Examples 25 to 76, Comparative Examples 3 to 8) Using Flexoproof 100 Testing Machine (manufactured by Testing Machines, Inc.), the prepared printing inks of Examples 1-24 and Comparative Examples 1-2 were printed on the substrate A into a full-plate pattern of 240 mm in length × 80 mm in width, It was dried with a dryer to form the ink coating layer 1 to obtain a printed matter of the following composition 1. If necessary, printing is repeated to form the ink coating layer 2 to obtain a printed matter of the following composition 2. Regarding the obtained printed matter of the Examples and Comparative Examples, the anti-blocking properties, substrate adhesion, ink releasability, and lamination suitability of each film during use were evaluated by the method described below, and the ink transferability was visually confirmed. The composition and evaluation results of the printed matter of each example and comparative example are shown in the following table.

＜The composition of printed matter＞ ･Constitution 1: Substrate A-Ink coating film layer 1 ･Constitution 2: Substrate A-Ink coating film layer 1-Ink coating film layer 2

＜Substrate A＞ ･Corona-treated polypropylene biaxially stretched film (PYLEN P2161 made by Toyobo Co., Ltd., thickness 20μm) (OPP) ･Corona-treated polyterephthalate film (ESTEL E5102, made by Toyobo Co., Ltd., thickness 12μm) )(PET)

<Evaluation Item 1: Anti-adhesion property> The film was cut into 4cm × 4cm size, the printed surface and the non-printed surface of the printed material and then contacting overlap, applying a load 5Kgf / cm ^2, and allowed to stand at ambient 40 ℃ for 12 hours , Then peel off the film, and visually judge the state of ink transfer to the non-printing surface (adhesion to the back) based on the area ratio (%) of the part stuck to the back surface. A: No transfer to the non-printing surface is observed at all. B: Only less than 5%, and transfer due to sticking to the back is observed. C: 5% to less than 20% of the transfer caused by sticking to the back is observed. D: Transfer caused by adhesion to the back surface of more than 20% is observed.

<Evaluation item 2: Adhesion to substrate> After leaving the printed matter for 1 day, attach a cellophane tape (made by Nichiban, width 12mm) on the printing surface. The residual rate of the printed film when one end of the cellophane tape is quickly peeled off in the direction perpendicular to the printing surface is calculated as The area ratio was used as a reference, and the appearance was judged visually. A: The printed film is not peeled off at all. B: More than 80% of the printed film remains on the film. C: More than 50% to less than 80% of the printed film remains on the film. D: Less than 50% of the printed film remains on the film.

<Evaluation item 3: Water resistance> Cut into a size of 10mm×10mm to obtain a test piece. This was 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: Not stripped. B: A slight peeling is observed. C: 20-30% peeling of the printing department. D: more than 30% of the printing department peeled off

<Evaluation item 4: Ink transferability> The ink transferability at the time of making the above-mentioned printed matter was evaluated. A: In visual judgment, the ink coating film is uniform. B: In the visual judgment, the ink coating film is slightly uneven. C: In the visual judgment, some peeling was observed on the ink coating film. D: In the visual judgment, peeling was observed in the ink coating film.

<Evaluation item 5: Ink peeling test> [Alkaline solution] Aqueous sodium hydroxide solution "SH solution": Dissolve sodium hydroxide (reagent grade 1) manufactured by Wako Pure Chemicals in ion-exchange water to prepare a 3% by mass aqueous solution. [Peel test conditions] The peel test is evaluated by setting the processing time in each condition to 30 minutes. Furthermore, if it peels off within 5 minutes of treatment, it shows quite high performance. Cut Examples 25 to 76 and Comparative Examples 4 to 9 into a size of 10 mm×10 mm to obtain test pieces. These test pieces were subjected to a peel test under conditions 1 to 3. Condition 1: Use sodium hydroxide aqueous solution for stirring treatment at 20°C Condition 2: Use sodium hydroxide aqueous solution for stirring treatment at 80°C Condition 3: Use sodium hydroxide aqueous solution for ultrasonic treatment at 20°C Evaluate the peeling of the ink coating under the above conditions sex. A: More than 90% of the ink coating is separated from the substrate in less than 1 minute. B: More than 90% of the ink coating film separated from the substrate for more than 1 minute and less than 5 minutes. C: More than 90% of the ink coating film is separated from the substrate for more than 5 minutes and less than 30 minutes. D: In a 30-minute test, more than 50 to less than 90% of the ink coating is separated from the substrate. E: In the 30-minute test, less than 50% of the ink coating film did not detach from the substrate.

<Evaluation item 6: Build-up test conditions> The ether-based adhesive was used for the above-mentioned printed matter, and the dry laminate adhesive DICDRY LX-401A/SP-60 (manufactured by DIC) was used to laminate an unstretched polypropylene film (manufactured by Toyobo Co., Ltd.) by a dry-layer laminator (manufactured by DIC Engineering) P-1128, thickness 25m), after aging at 40°C for 3 days, the strength was measured. (Evaluation Criteria) A: The laminated strength is 1.0N/15mm or more. B: The laminated strength is above 0.7N/15mm to less than 1.0N/15mm. C: The laminate strength is 0.5N/15mm or more to less than 0.7N/15mm. D: The build-up strength has not reached 0.5N/15mm.

[table 5] Example No. 25 26 27 28 29 30 31 32 33 34 Substrate A OPP Ink coating layer 1 I1 I2 I3 I4 I5 I6 I7 I8 I9 I10 Ink coating layer 2 Anti-blocking A A A A A A A A A A Tightness A B B A A A A B B A Water resistance A A B A A A A A B A Ink transferability A A A A A A A A A A Peel test condition 1 B A A B A A B A A B Peel test condition 2 A A A A A A B A A A Peel test condition 3 A A A A A A A A A A Build-up suitability B B B B B B A A A A

[Table 6] Example No. 35 36 37 38 39 40 41 42 43 44 Substrate A OPP Ink coating layer 1 I11 I12 I13 I14 I15 I16 I17 I18 I19 I20 Ink coating layer 2 Anti-blocking A A A A A A A A A A Tightness A A A B B A A A A B Water resistance A A A A B A A A A A Ink transferability A A A A A A A A A A Peel test condition 1 B B B A A B B A B A Peel test condition 2 B B A A A B B A B A Peel test condition 3 A A A A A A A A A A Build-up suitability A A A A A A A A A A

[Table 7] Example No. 45 46 47 48 49 50 51 52 53 54 Substrate A OPP PET Ink coating layer 1 I21 I22 I23 I24 I1 I1 I1 I2 I3 I4 Ink coating layer 2 I24 RI1 Anti-blocking A A A A A A A A A A Tightness B A A A A A A B B A Water resistance B A A A A A A A B A Ink transferability A A A A A A A A A A Peel test condition 1 A B B B B C B A A B Peel test condition 2 A B B B A B A A A A Peel test condition 3 A A A A A B A A A A Build-up suitability A A A A B A B B B B

[Table 8] Example No. 55 56 57 58 59 60 61 62 63 64 Substrate A PET Ink coating layer 1 I5 I6 I7 I8 I9 I10 I11 I12 I13 I14 Ink coating layer 2 Anti-blocking A A A A A A A A A A Tightness A A A A A A A A A B Water resistance A A A A B A A A A A Ink transferability A A A A A A A A A A Peel test condition 1 A A B A A B B B B A Peel test condition 2 A A B A A B B B A A Peel test condition 3 A A A A A A A A A A Build-up suitability B B A A A A A A A A

[Table 9] Example No. 65 66 67 68 69 70 71 72 73 74 Substrate A PET Ink coating layer 1 I15 I16 I17 I18 I19 I20 I21 I22 I23 I24 Ink coating layer 2 Anti-blocking A A A A A A A A A A Tightness B A A A A A B A A A Water resistance B A A A A A B A A A Ink transferability A A A A A A A A A A Peel test condition 1 A B B A B A A B B B Peel test condition 2 A B B A B A A B B B Peel test condition 3 A A A A A A A A A A Build-up suitability A A A A A A A A A A

[Table 10] Example No. 75 76 Substrate A PET Ink coating layer 1 I1 I1 Ink coating layer 2 I24 RI1 Anti-blocking A A Tightness A A Water resistance A A Ink transferability A A Peel test condition 1 B C Peel test condition 2 A B Peel test condition 3 A B Build-up suitability B A

[Table 11] Comparative example No. 3 4 5 6 7 8 Substrate A OPP PET Ink coating layer 1 RI1 RI2 RI1 RI1 RI2 RI1 Ink coating layer 2 RI2 RI2 Anti-blocking A A A A A A Tightness A D D A D D Water resistance A D D A D D Ink transferability A D D A D D Peel test condition 1 E A D E A D Peel test condition 2 E A D E A D Peel test condition 3 E A D E A D Build-up suitability A C C A C C

Furthermore, in all evaluation items, C or higher is a practical level. From the above results, it can be seen that when the acid value of the solid component of the aqueous liquid ink is lower than the lower limit of the present invention, although it is excellent in adhesion, water resistance, ink transferability, and lamination suitability, it does not detach from the substrate. In addition, it can be seen that when the acid value of the solid component in the aqueous liquid ink exceeds the upper limit of the present invention, the releasability from the substrate is equal or more, but the adhesion, water resistance, ink transferability, and stackability are not good. Reach practical level. In the examples using the water-based liquid ink according to the embodiment of the present invention, all the evaluation results are above the practical level. It can be seen from the above that by using the aqueous liquid of the present invention, an ink coating film that has the same level of physical properties as conventional aqueous liquid inks and can be easily released under the set release conditions can be formed on a plastic substrate.

without

without

Claims (13)

An aqueous liquid ink, which is used to form a warm water or alkaline solution detachable ink coating film on the substrate A. The acid value of the solid component of the aqueous liquid ink is 3 to 150 mgKOH/g. Such as the aqueous liquid ink of claim 1, which further contains acidic additives and an aqueous medium. Such as the aqueous liquid ink of claim 1 or 2, which further contains a colorant. Such as the water-based liquid ink of claim 2 or 3, wherein the acid value of the above-mentioned acidic additive is 3 to 900 mgKOH/g. The aqueous liquid ink according to any one of claims 2 to 4, wherein the acidic additive is an organic acid. The aqueous liquid ink of claim 5, wherein the number of carbon atoms of the organic acid is 3-20. The aqueous liquid ink of claim 5, wherein the number of carbon atoms of the organic acid is 6-18. The aqueous liquid ink according to any one of claims 2 to 4, wherein the acidic additive is a resin having an acid group. The aqueous liquid ink of claim 8, wherein the acid value of the resin having an acid group is 3 to 300 mgKOH/g. A printed matter, which is formed by printing the aqueous liquid ink of any one of claims 1 to 9 directly or via other layers on a substrate A. A laminated body in which the above-mentioned printed matter and the base material B are laminated so that the ink coating film is arranged on the inner side. A method for manufacturing a recycled substrate A, which is obtained by treating the above-mentioned printed matter with warm water or an alkaline solution to release the ink coating film from the substrate A. A method for manufacturing a recycled substrate A. The recycled substrate A is a laminate in which the printed matter and the substrate B are laminated with the ink coating film arranged on the inside, and treated with warm water or alkaline solution to make The adhesive layer and the substrate B are detached together with the ink coating film.