JP6996259B2 - Liquid ink composition - Google Patents

Description

The present invention relates to a liquid ink composition mainly used for front printing of flexible packaging materials, and can be used for either gravure or flexographic printing methods, and in addition, the liquid ink is used. Regarding printed matter.

The liquid ink composition used for the front printing of flexible packaging materials mainly by the gravure printing method or the flexographic printing method uses a polyamide resin as a main component. In recent years, the use of aromatic solvents such as toluene and ketone solvents such as methyl ethyl ketone have been restricted from the viewpoints of both work hygiene during printing and harmfulness of packaging materials. Along with this, from the viewpoint of printability, the detoluene-type liquid ink contains aromatics as solvents, acetates such as ethyl acetate and propyl acetate instead of ketone solvents, and alcohols such as isopropyl alcohol and normal propyl alcohol. Solvents, non-aromatic hydrocarbon solvents such as methylcyclohexane or mixed solvents thereof tend to be used.

However, when a non-aromatic solvent is used, the friction resistance, oil resistance, heat resistance, printability, and viscosity stability required for the surface printing ink are inferior to those of the conventional toluene ink. Improvement is an issue.
On the other hand, liquid inks using a vitrified cotton / polyamide resin or a mixed resin system of vitrified cotton / urethane resin, and inks in which the polyamide resin uses a thermoplastic polyamide resin obtained by the reaction of dimer acid and diamine are disclosed. , Vegetable fatty acids such as tall oil fatty acids or synthetic oil fatty acids are used as reaction raw materials for dimer acid (for example, Patent Documents 1 and 2).
However, although there is a description of various vegetable fatty acids as the reaction raw material of the dimer acid, there is no description of the superiority of using rice bran fatty acid. The liquid ink composition of the present invention realizes an ink composition that sufficiently maintains abrasion resistance, oil resistance, heat resistance, printability, and viscosity stability even if it is a non-toluene solvent composition. In addition, the use of rice bran fatty acid as a raw material is desired from the viewpoint of carbon offset and saving of fossil resources.

Japanese Unexamined Patent Publication No. 2016-029122 Japanese Unexamined Patent Publication No. 2005-171167

An object of the present invention is to provide a liquid ink composition for gravure inks and flexographic inks, which are excellent in abrasion resistance, oil resistance, heat resistance, printability, and viscosity stability. Another object of the present invention is to provide a printed matter using the ink composition.

As a result of diligent studies to solve the above problems, the liquid ink composition of the present invention contains a thermoplastic polyamide resin, a fibrous resin, an organic solvent, and a plasticizer using a specific vegetable fatty acid as a reaction raw material. As a result, we found that friction resistance, oil resistance, heat resistance, printability, and viscosity stability were improved, and completed the invention.

That is, the present invention is characterized by containing a thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material, a fibrous resin (B), an organic solvent (C) and a plasticizer (D). Regarding things.

Further, in the present invention, the plasticizer (D) is at least one selected from the group consisting of a citric acid ester-based plasticizer, a sulfonamide-based plasticizer, a phosphoric acid ester-based plasticizer, an epoxidized soybean oil, and a fatty oil. As described above, the present invention relates to a liquid ink composition containing 0.01 to 10.0% by mass of the total amount of the composition.

The present invention also relates to a liquid ink composition further containing a chelate cross-linking agent (E).

The present invention also relates to a liquid ink composition further containing a colorant (F).

The present invention also relates to a liquid ink composition in which the organic solvent (C) does not contain an aromatic organic solvent and / or a ketone solvent.

The present invention also relates to a printed matter obtained by printing the liquid ink composition.

INDUSTRIAL APPLICABILITY According to the present invention, a liquid ink composition for gravure inks and flexo inks having excellent abrasion resistance, oil resistance, heat resistance, printability, and viscosity stability can be obtained.

The liquid ink composition of the present invention is characterized by containing a thermoplastic polyamide resin (A), a fibrous resin (B), an organic solvent (C) and a plasticizer (D) using rice bran fatty acid as a reaction raw material. It is something to do.

The liquid ink composition of the present invention requires a thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material.
The polyamide resin is generally a polycondensate of a polycarboxylic acid such as a polymerized fatty acid or various vegetable fatty acids and a polyamine. Examples of the polymerized fatty acid include dimer acid and hydrogenated dimer acid. Examples of various vegetable fatty acids include tall oil fatty acid, palm oil fatty acid, palm oil fatty acid, soybean oil fatty acid, cocoa fatty acid, and mixed fatty acids of these natural fats and oils. In the present invention, rice bran fatty acid is used as a reaction raw material. It is something to do.

Examples of the polyamine include aliphatic polyamines, alicyclic polyamines, and aromatic polyamines, and examples of the aliphatic polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexane, piperazin, and N-amino. Examples of the alicyclic polyamine include ethyl piperazine, isophorodiamine, bisaminomethylcyclohexane and the like, and examples of the aromatic polyamine include metaxylenediamine. Above all, from the viewpoint of solubility, it is preferable to use an aliphatic diamine or an alicyclic diamine.

The thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material has a number average molecular weight of 1000 to 30,000, an acid value of 15 or less, and an amine from the viewpoint of maintaining high gloss and blocking resistance of the liquid ink composition of the present invention. A value of 5 or less, a softening point of 90 to 150 ° C., and a number average molecular weight of 1000 to 30,000 are preferable, and a softening point of 100 to 130 ° C. and a number average molecular weight of 1000 to 20,000 are more preferable.
When the number average molecular weight is smaller than 1000, the blocking resistance and heat resistance tend to decrease, and when it exceeds 30,000, the low temperature flexibility tends to decrease.
The blending amount of the thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material is preferably 10 to 70% by mass with respect to the total solid content in the ink composition.

Further, the liquid ink composition of the present invention requires a fibrin-based resin (B). As a typical example of the fibrin-based resin (B), vitrified cotton can be mentioned. The vitrified cotton can improve the dispersibility of the pigment and can react with the metal chelate compound described later to improve the heat resistance and oil resistance of the printing ink coating film. The nitrified cotton used in the liquid ink composition of the present invention preferably has a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 30 to 500, more preferably a nitrogen content of 10 to 13% by mass and an average degree of polymerization. It is 45 to 290. The blending amount of nitrified cotton is preferably 1 to 50% by mass with respect to the total solid content in the ink composition.

The organic solvent (C) that can be used in the liquid ink composition of the present invention is not particularly limited, but for example, aromatic hydrocarbons such as toluene, xylene, Solbesso # 100 and Solbesso # 150, hexane, methylcyclohexane, and the like. Examples thereof include aliphatic hydrocarbon-based solvents such as heptane, octane and decane, and ester-based organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate and butyl propionate. Also, as water-mixable organic solvents, alcohol-based solvents such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) Examples thereof include various glycol ether-based organic solvents such as di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. It is more preferable not to use an aromatic solvent such as toluene or a ketone solvent such as methyl ethyl ketone from the viewpoints of both work hygiene at the time of printing and harmfulness of the packaging material. Above all, a mixed solution of isopropyl alcohol / ethyl acetate / normal propyl acetate / methylcyclohexane is more preferable from the viewpoint of solubility in polyamide resin and nitrified cotton. Further, glycol ethers can be added as long as it is less than 10% by mass of the total amount of the composition for drying adjustment.

Further, the liquid ink composition of the present invention requires a plasticizer (D) in order to enhance the fluidity, adhesiveness, and abrasion resistance of the composition. In the case of a polycondensation polymer such as a polyamide resin, by adding the plasticizer (D), thickening can be suppressed, and the flexibility and flexibility of the ink dry film after printing can be maintained.
Examples of the plasticizer (D) include fatty oils such as castor oil, phthalates such as dioctylphthalate, phosphate esters, fatty acid esters such as adipic acid esters and sebacic acid esters, polyesters, and epoxys. Examples thereof include epoxy systems such as chemical vegetable oils, citrate esters such as tributyl acetylcitrate, and sulfonic acid amide systems such as N-butylbenzene sulphonamide and N-ethyltoluene sulphonamide. Of these, citric acid esters, epoxidized vegetable oils, phosphoric acid esters and sulfonic acid amides are preferable.
The blending amount of the plasticizer (D) is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and 0.5 to 3.0% of the total amount of the composition. It is more preferable if it is by mass%. These plasticizers (D) may be used alone or in combination of two or more.

Further, the liquid ink composition of the present invention may be added with a chelate cross-linking agent (E). The chelate cross-linking agent (E) is intended for improving the cohesive force, and a chelate-type metal organic compound is preferable. As the metal chelate compound, an organic titanium-based compound, an organic zirconium-based compound, or an organoaluminum-based compound can be used. If a chelate-type metal-organic compound is used, the cross-linking reaction can be completed without heating, but a stable cross-linking reaction can be obtained in which hydrolysis at room temperature is unlikely to occur, especially when an amine is present in the molecule. The effect is great.
The titanium chelate has a Ti—OC bond in one molecule, and by having this alkoxy group, it has a role of strengthening the intramolecular or intramolecular cross-linking bond of the resin. Examples of the titanium chelate include titanium alkoxide and titanium acylate. Examples of the titanium alkoxide include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate, and tetrastearyl titanate, as well as triethanolamine titanate, titanium acetyl acetate, and titanium ethyl acet acetate. , Titanium lactate, octylene glycol titanate, titanium tetraacetyl acetate, titanium phosphate compound and the like. Among the organic titanium compounds, titanium phosphate compounds and titanium acetyl acetate are preferable.
The blending amount of the chelate cross-linking agent (E) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, based on the total amount of the composition.

Examples of the colorant (F) used in the liquid ink composition of the present invention include organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like. Organic pigments include azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindoleinone-based, quinophthalone-based, azomethine-azo-based, dictopyrrolopyrrole-based, and isoindoline-based. Pigments can be mentioned. Copper phthalocyanine for indigo ink and C.I. for transparent yellow ink in terms of cost and light resistance. I. It is preferable to use Pigment No Yellow 83.

For example, Pigment C.I. I. As numbers, Black7, Y12, Y13, Y14, Y17, Y83, Y74, Y-154, Y180, R57: 1, R122, R48: 1, R48: 2, R48: 3, R53: 1, R146, R-150. , R-166, R170, R184, R185, V19, V23, V32, O13, O16, O34, G7, G36, B15: 3, B15: 4, W6 and the like.

Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, mica (mica) and the like. It is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver ink, and mica (mica) for pearl ink from the viewpoint of cost and coloring power. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether reefing or non-reefing is used is appropriately selected from the viewpoint of luminance and concentration. The amount of the colorant is sufficient to secure the concentration and coloring power of the ink, that is, 1 to 50% by mass with respect to the total mass of the ink composition, and 1 to 40% by mass with respect to the total solid content in the ink composition. It is preferable that it is contained in the ratio of. In addition, the colorant can be used alone or in combination of two or more.

(Normal manufacturing method)
The liquid ink composition of the present invention is necessary, for example, by adding nitrified cotton and an organic solvent (C) previously dissolved in an organic solvent to a thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material. Additives such as plasticizer (D), chelate crosslinker (E), colorant (F), other polyethylene wax, amide wax, extender pigment, antistatic agent, antiblocking agent, ink fluidity and dispersion. A surface active agent for improving the properties or a resin compatible with the polyamide resin is used in combination as long as thickening and gelation do not occur over time, and is usually used for ball mills, attritors, sand mills, triple rolls, etc. It is produced by kneading using the printing ink manufacturing apparatus of. In particular, the addition of an antistatic agent is effective in suppressing static electricity troubles during printing called whiskers, which are likely to occur when an ester solvent or a ketone solvent is used.

Examples of the resin that can be used in combination with the thermoplastic polyamide resin (A) using the rice bran fatty acid as a reaction raw material include chlorinated polyethylene, chlorinated polypropylene, chlorinated polyolefin such as chlorinated ethylene / propylene, ethylene / vinyl acetate copolymer or a resin thereof. Chlorinated resin, vinyl chloride / vinyl acetate copolymer, rosin resin and its modified products, ketone resin, cellulose resin such as cellulose acetate propionate and cellulose acetate butyrate, urethane modified ketone resin, urethane resin, urethane Examples thereof include urea resin and maleic acid-modified resin.
It is also possible to mix and use a thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material, a polyamide resin derived from a vegetable fatty acid such as tall oil, and a polyamide resin derived from a synthetic fatty acid.

The present invention provides a printed matter obtained by printing the liquid ink described above.

The present invention will be described in more detail with reference to Examples. Hereinafter, both "part" and "%" are based on the mass standard.
The measurement of the number average molecular weight (polystyrene equivalent) Mn by GPC (gel permeation chromatography) in the present invention was carried out using the HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: Uses 4 TSKgelGMHR-N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: Differential refractometer.

[Preparation of dimer acid (X) using rice bran fatty acid as a reaction material]
Add 100 parts of rice bran fatty acid (acid value 200, iodine value 108), 6 parts of montmorillonite clay, 0.1 part of lithium hydroxide, 0.1 part of calcium hydroxide and 1 part of water to the autoclave. The inside of the system was made into a nitrogen atmosphere, and after sealing, the pressure was maintained at 0.5 MPa while stirring, and the mixture was heated at 230 ° C. for 3 hours. Then, the reaction product was cooled to 130 ° C., 1 part of 75% phosphoric acid was added, and the mixture was treated for 1 hour. The solid matter was removed by pressure filtration to obtain a tax product. The product was guided to a flow-down membrane still and the monomeric acid was removed under the conditions of a pressure of 0.1 kPa and a temperature of 200 ° C.
The obtained dimer acid (X) was measured by GPC (gel permeation chromatography), and it was confirmed that the dimer component was 75%.

[Preparation of thermoplastic polyamide resin (A) using rice bran fatty acid as a reaction raw material]
In a four-necked flask equipped with a stirrer, a thermometer, a recirculation cooler and a nitrogen gas introduction tube, 100 parts of dimer acid (X) derived from the rice bran fatty acid obtained above, rice bran fatty acid (acid 100S; Bosso Oil and Fat Co., Ltd.) (Manufactured by) 1 part, 5 parts of sebacic acid, 10 parts of ethylenediamine, 5 parts of hexamethylenediamine, and 0.24 parts of triphenylphosphine are added to create a nitrogen atmosphere in the system, and further, 200 parts while stirring for homogenization under a nitrogen stream. The temperature is slowly raised to ° C. Subsequently, a dehydration condensation was carried out at 200 ° C. for 5 hours with stirring to obtain a dimer acid-modified polyamide resin composition derived from rice bran fatty acid having a softening point of 125 ° C., an amine value of 2, an acid value of 8, and a number average molecular weight of 11,000. Obtained.

[Preparation of thermoplastic polyamide resin (T) using tall fatty acid as a reaction raw material]
In a four-necked flask equipped with a stirrer, thermometer, recirculation cooler and nitrogen gas introduction tube, 100 parts of dimer acid (Haridimer 270S; manufactured by Harima Chemicals Co., Ltd.), tall oil fatty acid (Hartall FA-1; Harima Chemicals Co., Ltd.) (Manufactured by Co., Ltd.) 1 part, 5 parts of sebacic acid, 10 parts of ethylenediamine, 5 parts of hexamethylenediamine, and 0.24 parts of triphenylphosphine are added to create a nitrogen atmosphere in the system, and further, stirring for homogenization under a nitrogen stream is performed. While slowly raising the temperature to 200 ° C. Subsequently, by performing dehydration condensation at 200 ° C. for 5 hours with stirring, a dimer acid-modified polyamide resin composition derived from a toll fatty acid having a softening point of 123 ° C., an amine value of 2, an acid value of 8, and a number average molecular weight of 10,000 (a dimer acid-modified polyamide resin composition ( T) was obtained.

[Preparation of nitrified cotton varnish liquid (S)]
Industrial vitrified cotton H1 / 2 (nitrocellulose, non-volatile content 70%, viscosity 9.0-14.9% at a solution concentration of 25.0% by JIS K-6703, manufactured by Taihei Chemicals Limited) in 37.5 parts , 62.5 parts of a mixed solution of isopropyl alcohol / ethyl acetate / normal propyl acetate / methyl cyclohexane (ratio of 25/25/13/10 by weight) was added and sufficiently mixed to prepare a nitrocellulose varnish solution (S). ..

Examples 1 to 16, Comparative Example 1
[Ink preparation method]
The mixture mixed at the blending ratios shown in Tables 1 and 2 was kneaded using a mighty mill (manufactured by Inoue Seisakusho Co., Ltd.) to prepare the indigo inks shown in Examples 1 to 16 and Comparative Example 1, respectively. The following evaluations were carried out.

[Viscosity measurement]
The indigo inks shown in Tables 1 and 2 were used in Zahn Cup No. 1 manufactured by Rigosha, respectively. Viscosity was measured at a liquid temperature of 25 ° C. immediately after ink production using No. 4. The measured value is preferably 12 to 18 seconds.

[Viscosity stability]
The indigo inks shown in Tables 1 and 2 were collected in glass bottles and stored at 50 ° C. for 28 days. After that, the viscosity was measured and the change in viscosity from before storage was evaluated.
If the evaluation standard is 3 or more, it is within the practical range.
(Evaluation criteria)
5: No change in viscosity Viscosity change is less than 2 seconds 4: Viscosity change is slight Viscosity difference is 2 seconds or more and less than 5 seconds 3: Viscosity change is slightly more Viscosity difference is 5 seconds or more and less than 10 seconds 2: Viscosity change is large Difference is 10 seconds or more and less than 15 seconds 1: Viscosity change is very large Viscosity difference is 15 seconds or more

〔Oil resistance〕
The indigo ink shown in Tables 1 and 2 was applied to a biaxially stretched polypropylene film (FOR thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) having a corona discharge treatment on one side with a bar coater # 10, and left for 24 hours. I made a printed matter.
Next, 2 cc of soybean white squeezed oil was applied to this printed surface with a cotton swab, and then left in an oven at 40 ° C. for 24 hours. After that, the soybean white squeezed oil-applied portion was rubbed with a dry rolling pin, and the condition of the printed surface was visually evaluated.
(Evaluation criteria)
5: The printed film does not separate from the film at all.
4: As the area ratio of the printed film, less than 20% is detached from the film.
3: The area ratio of the printing film is 20% or more and less than 40% is the film.
Although it departs from, it is within the practical range.
2: As the area ratio of the printing film, 40% or more and less than 60% is the film.
Eliminate from.
1: As the area ratio of the printed surface, 60% or more is detached from the film.

〔Heat-resistant〕
The indigo ink shown in Tables 1 and 2 was applied to a biaxially stretched polypropylene film (FOR thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) having a corona discharge treatment on one side with a bar coater # 10, and left for 24 hours. I made a printed matter.
Next, the aluminum foil is superposed on this printed surface, thermocompression bonded using a heat seal tester at a temperature of 180 ° C., a load of 2 kg / cm ² , and a crimping time of 1 second, cooled to room temperature of 25 ° C., and then the aluminum foil is placed. It was peeled off and the condition of the printed surface was visually evaluated.
(Evaluation criteria)
5: The print film does not peel off from the film at all.
4: As the area ratio of the printed film, less than 20% is peeled off from the film.
3: The area ratio of the printing film is 20% or more and less than 40% is the film.
Although it peels off from, it is within the practical range.
2: As the area ratio of the printing film, 40% or more and less than 60% is the film.
Peel off from.
1: As the area ratio of the printed surface, 60% or more is peeled off from the film.

〔Adhesiveness〕
The indigo ink shown in Tables 1 and 2 was applied to a biaxially stretched polypropylene film (FOR thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) having a corona discharge treatment on one side with a bar coater # 10, and left for 24 hours. I made a printed matter.
Next, after attaching cellophane tape (manufactured by Nichiban Co., Ltd.) to this printed surface, the tape was quickly peeled off and the state of the printed surface was visually evaluated.
(Evaluation criteria)
5: The print film does not peel off from the film at all.
4: As the area ratio of the printed film, less than 20% is peeled off from the film.
3: The area ratio of the printing film is 20% or more and less than 40% is the film.
Although it peels off from, it is within the practical range.
2: As the area ratio of the printing film, 40% or more and less than 60% is the film.
Peel off from.
1: As the area ratio of the printed surface, 60% or more is peeled off from the film.

[Abrasion resistance]
The indigo ink shown in Tables 1 and 2 was applied to a biaxially stretched polypropylene film (FOR thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) having a corona discharge treatment on one side with a bar coater # 10, and left for 24 hours. I made a printed matter.
Then, using a Sutherland type wear tester, the material was rubbed with white woodfree paper 100 times under a load of 2 pounds, and the degree of indigo ink removal was visually evaluated.
(Evaluation criteria)
5: The rubbed white woodfree paper does not get any color.
4: The rubbed white wood-free paper is colored to a medium degree of "5" and "3".
3: The rubbed white high-quality paper is lightly colored, but it is within the practical range.
2: The rubbed white woodfree paper is colored to a medium degree of evaluation "3" and "1".
1: The rubbed white woodfree paper gets a dark color.

[Printability test: Cassoulet test]
The indigo inks shown in Tables 1 and 2 were diluted with the same ratio of mixed organic solvent used for ink preparation, and diluted with Zahn Cup No. 3 manufactured by Rigosha for 16 seconds. A biaxially stretched polypropylene film (Futamura Chemical Co., Ltd. FOR) that was subjected to corona discharge treatment on one side using an MD type gravure printing machine (manufactured by Fuji Machinery Co., Ltd.) equipped with a laser gravure plate having a plate depth of 25 μm. Printing was performed on the treated surface having a thickness of 20 μm). Then, the degree of ink transfer (cassoulet degree) to the printed portion of the printed matter was evaluated. The blur test was evaluated at a printing speed of 300 m / min with a circumference of 600 mmφ of the gravure plate.
(Evaluation criteria)
5: There is no cassoulet.
4: Very slight blurring occurs.
3: A little blurring occurs, which is within the practical range.
2: Cassoulet can be noticeably confirmed.
1: Frequent cassoulet.

[Blocking resistance]
5 kg using a permanent strain tester (manufactured by Tester Sangyo Co., Ltd.) by combining each printed surface and non-printed surface of a good printed matter with a rating of "5" in the printed matter when printed under the above-mentioned blur test conditions. It was tightened at a pressure of / cm ² and peeled by hand at 40 ° C. after 1 day, and the blocking resistance was evaluated from the degree of ink peeling and the strength of peeling resistance.
If the evaluation standard is 3 or more, it is within the practical range.
(Evaluation criteria)
5: There is no peeling of the printed film, and no peeling resistance is felt.
4: There is no peeling of the printed film, but no peeling resistance is felt.
3: There is no peeling of the printed film, but peeling resistance is felt.
2: Peeling of the printing film is observed, and stains are remarkably generated.
1: The print film is almost peeled off, and the peeling resistance is strongly felt.

The raw materials in the table are as follows.
-Nitrocellulose H1 / 2 (nitrocellulose, non-volatile content 70%, viscosity 9.0-14.9% at a solution concentration of 25.0% by JIS K-6703, manufactured by Taihei Chemicals Limited)
-Fastogen Blue 5380 (manufactured by DIC Corporation): C.I. I. Pig.
No. = B-15: 3
-Citric acid ester-based ATBC plasticizer: Tributyl acetyl citrate (tributyl = 2-acetoxy-1,2,3-propanetricarboxylate, manufactured by Asahi Kasei Finechem Co., Ltd.) Epoxidized soybean oil Sunsoyzer E-2000H: CAS No. 8013-07-8
Sibercizer C6 plasticizer manufactured by Shin Nihon Rika Co., Ltd .: N-ethylo / p-toluenesulfonamide, Merck manufactured phosphoric acid ester-based TOP plasticizer: Tris (2-ethylhexyl) phosphate, Daihachi Chemical Industry Co., Ltd. ) Titanium TAA chelating agent (BORICA): Titanium acetylacetonate CAS: 17927-27-9

From the above results, the liquid ink composition of the present invention can have abrasion resistance, oil resistance, heat resistance, printability and viscosity stability.

The liquid ink composition of the present invention is an environmentally friendly gravure ink or flexo ink from the viewpoint of carbon offset and saving of fossil resources, such as food packaging materials such as bread, rice cake and rice cake packaging, retort food packaging materials, and so on. It can be widely used in flexible packaging for industrial products such as snack packaging materials, liquid containers, sanitary, cosmetics, and electronic parts.

Claims (5)

Thermoplastic polyamide resin (A), fibrin-based resin (B), which uses rice bran fatty acid as a reaction raw material,
It contains an organic solvent (C) and a plasticizer (D), and the blending amount of the thermoplastic polyamide resin (A) is 10 to 70% by mass with respect to the total solid content in the ink composition.
Further, it contains a chelate cross-linking agent (E).
A liquid ink composition characterized by the fact that The plasticizer (D) is at least one selected from the group consisting of a citrate ester-based plasticizer, a sulfonamide-based plasticizer, a phosphoric acid ester-based plasticizer, an epoxidized soybean oil, and a fatty oil, and is a composition. The liquid ink composition according to claim 1, which contains 0.01 to 10.0% by mass of the total amount. The liquid ink composition according to claim 1 or 2 , further comprising a colorant (F). The liquid ink composition according to any one of claims 1 to 3 , wherein the organic solvent (C) does not contain an aromatic organic solvent and / or a ketone solvent. A printed matter obtained by printing the liquid ink according to any one of claims 1 to 4 .