JP6482502B2 - Solvent-type gravure printing ink composition for front-printing paper, printed coating, laminate, method for producing laminate, paper container, label, lid material, paper bag, paper product - Google Patents

Description

  The present invention relates to a solvent-type gravure printing ink composition for surface printing on a paper substrate.

  Conventionally, as a gravure printing ink composition that can be printed on a film substrate or a paper substrate, one having a polyamide resin or a nitrified cotton resin as a main component is known.

Patent Document 1 describes a gravure printing ink for publications containing a polyamide resin modified with a metal resin acid salt, and has been proposed to have good paper permeability, gloss and color developability. However, since the amount of polyamide used is as high as 15 to 100% by weight based on the resin acid metal salt, the stability of the varnish deteriorates, and undesirable phenomena such as thickening occur over time.
Further, since the compatibility with the solvent is poor and a large amount of solvent is used, it is necessary to set the solid content of the resin acid salt low, so that the gloss and printing density during printing tend to be low. Furthermore, since a modified resin acid salt obtained by reacting a polyamide resin and a metal resin acid salt is used, there is a problem that restrictions due to an amine value and an acid value increase in designing the resin.

  Patent Document 2 discloses a method of using a pigment or a pigment preparation used for packaging gravure printing and flexographic printing, in which a nonionic surfactant is added immediately before pigment isolation and nitrocellulose is used as a binder. Although described, it is merely a proposal for the use of pigments or pigment preparations for use in packaging gravure and flexographic printing and only uses nitrocellulose as a binder for printing on paper or film.

  Patent Document 3 uses not a polyamide resin modified with a resin acid metal salt as in Patent Document 1, but a mixture obtained by adding a polyamide resin to a resin acid metal salt obtained by reacting two or more kinds of metal compounds of modified rosin. In addition, a varnish composition for publishing gravure printing ink in which the polyamide resin contains a polyamide resin as small as 0.5 to 10% by weight based on the resin acid metal salt is described, and the balance between gloss and dryness of the printed matter is excellent Although a modified rosin is prepared, a resin acid metal salt is prepared by reacting two or more kinds of metal compounds therewith, and then a polyamide resin is added and reacted, resulting in a complicated process. End up.

The nitrocellulose resin is a nitro group-substituted cellulose in which a part of the hydroxyl groups of the cellulose skeleton is nitrated, and the cellulose skeleton is a biomass material.
Polyamide resins, on the other hand, are obtained from polymerized fatty acids as raw materials and are obtained by polymerizing unsaturated fatty acids or esters thereof derived from dry or semi-dry oils such as vegetable oils and animal oils, and many unsaturated fatty acids having 18 carbon atoms are used. Polymerized fatty acids derived from vegetable oil are biomass materials.
Here, biomass is defined as an organic resource derived from renewable organisms excluding fossil resources. Therefore, if it is a biomass material, it is considered to be the same amount of carbon dioxide absorbed from the atmosphere as the plant grows, and even if it is incinerated, the carbon dioxide generated is counted as zero (carbon neutral), reducing the environmental burden. And contribute to global warming.
In Patent Documents 1 to 3, polyamide resins and nitrocellulose resins are mainly used for paper applications, but there is no description or suggestion about water resistance, heat resistance, and degree of biomass.

  In addition, Patent Document 4 was selected from an acrylic resin, a styrene-acrylic acid copolymer, a styrene-maleic acid resin, and a rosin-maleic acid resin as a fiber-based resin containing nitrocellulose. An easily separable laminate printing ink composition containing one or more kinds and a fibrous resin is described, and a nitrified cotton of a fibrous resin is used as a compatible resin and used for a foamed polystyrene sheet. When used as a printing ink, a resin selected from styrene-acrylic acid copolymer, styrene-maleic acid resin, and rosin-maleic acid resin has an appropriate swelling property with respect to water, making it easy to peel off from the sheet. However, it is difficult to apply the main acrylic resin to a paper substrate.

  Patent Document 5 describes a printing ink containing an acrylic resin, a cellulose resin and a low-volatile solvent, suppresses the precipitation of the cellulose resin during the printing process, improves the ink stability, and further improves the plastic film. Although it has been proposed to be excellent in adhesion, heat resistance, blocking resistance, etc., although the adhesion to the film is improved, the ink coating strength (heat resistance) decreases, and printing on paper There is no description or suggestion, and application to a paper substrate is not sufficient. In particular, the adhesion to uncoated paper without a coating layer is poor.

  Although it has been proposed to apply a cellulose-based resin to a film substrate as in Patent Documents 4 and 5, it is generally known that a nitrocellulose resin is used for application to a paper substrate. It is what was done. However, with the nitrocellulose resin alone, when the overprinting is performed, the subsequent ink does not satisfactorily ride on the previously printed ink coating film, resulting in poor transfer and poor appearance as a printed matter. In order to improve this, Patent Document 6 describes a printing ink composition for solvent-borne gravure printing paper containing an acrylic resin having a specific acid value and a nitrocellulose resin, and is applied to a paper substrate. Patent Document 7 describes a printing ink composition for solvent-type gravure printing for paper containing a nitrocellulose resin and a rosin resin, and has a good ink transfer property in printing and excellent color tone reproducibility. Ink transfer property in overprinting on paper and excellent in versatility, Patent Document 8 discloses a solvent-based gravure printing ink composition for paper containing styrene-maleic acid half ester copolymer and nitrocellulose resin In which the ink transfer property in the overprinting on the paper substrate is good, the dot reproducibility is excellent, and the odor is low. Patent Document 9 includes a nitrocellulose resin and a polymerized rosin. A solvent-type gravure printing ink composition for paper is described, which has a high pigment concentration in the ink, can be printed using a shallow plate cylinder, and can reduce the amount of generated organic solvent .

  Although the said patent documents 6-9 use a nitrocellulose resin as a paper use, there exists room for improvement in water resistance, and there is no description or suggestion about the biomass degree in an ink coating film.

  On the other hand, from the viewpoint of environmental problems such as air pollution due to organic solvents, safety and health problems in the work environment, and disaster prevention, water-based gravure ink compositions have been studied for a long time in the field of printing inks and paints by removing organic solvents and making them water-based. I came. Patent Document 10 describes an aqueous gravure ink composition for paper containers containing a styrene-acrylic emulsion having a core / shell structure, which is an ink having a solvent composition containing as little or no volatile organic compound as possible. Patent Document 11 describes an aqueous coating composition for paper containers containing a styrene-acrylic aqueous resin obtained by emulsion polymerization and 2-ethyl-1,3-hexanediol, and reduces the lower alcohol as much as possible. However, those having good drying properties and printability, Patent Document 12 discloses an aqueous gravure printing ink for paper containers containing a styrene-maleic acid half ester copolymer resin and 2-ethyl-1,3-hexanediol. The composition is described, the pigment concentration in the ink is high, printing can be performed using a shallow plate cylinder, and lower alcohol is used as much as possible. Even if it is made dry, the printability is improved. Patent Document 13 contains a water-soluble resin (such as acrylic), a water-based resin (such as styrene-acrylic), glycol ethers, and biomass-derived alcohol. A water-based gravure printing ink composition for paper containers is described, and it has been proposed that the amount of volatile organic compounds and carbon dioxide emitted can be reduced, and the drying property and printability are improved.

  In Patent Documents 10 to 13, water-soluble resins are used for paper containers, but synthetic resins such as styrene-acrylic resins are used, and the printing speed must be reduced due to the poor drying characteristic of aqueous printing. In addition, the halftone dots of the printed matter are blurred and the desired hue cannot be obtained, or the plate is jammed due to poor re-solubility in water or water / alcohol solvents, plate cylinder stains, doctor lines, plate fogging. Therefore, improvement is desired. Moreover, there is room for improvement in heat resistance, and there is no description or suggestion about the degree of biomass in the ink coating.

  Regarding the degree of biomass, Patent Document 14 describes that the degree of biomass is 50 to 95% in a label printed with a polyamide resin using a biomass material as a synthetic material and a label printing ink composition containing nitrocellulose. As a result, petroleum resources can be conserved and the amount of carbon dioxide produced when polyamide resin using biomass materials is incinerated is close to the amount of carbon dioxide originally taken from the atmosphere. The amount of excess carbon dioxide that is discharged when petroleum-derived materials are incinerated can be suppressed. However, it is mainly composed of polyamide resin and is applied to the label of plastic base material. Although it uses a small amount of nitrocellulose, it is difficult to apply to paper base material, and the heat resistance and water resistance are also described. There is no suggestion.

  As a packaging material, it has long been known to use metal chelates in order to improve various resistances. Patent Document 15 describes a one-pack type ink containing nitrified cotton, alkyl titanate, plasticizer, and other resin components, having good adhesion to a film, water resistance, oil resistance, and boiling resistance Patent Document 16 describes a one-component reactive coating composition containing a hydroxyl group-containing resin (such as nitrified cotton), titanium chelate, and alcohol, which has good adhesion and can form a high-strength film. Patent Document 17 discloses a printing ink vehicle in which a specific polyamide resin is blended with nitrified cotton and a chelating agent, and has excellent heat resistance and adhesion. Patent Document 18 discloses polymerized fatty acid, polyamine, modified polydimethyl A polyamide resin for printing ink obtained by condensation polymerization of siloxane and rosin ester is described, and can be used for surface printing special gravure printing ink. In which a small amount of nitrocellulose and an organometallic coordination compound are used in combination, heat seal heat resistance, drying property, high water resistance, and excellent adhesion to a film, Patent Document 19 , A printing ink composition for paper gravure rotation containing nitrified cotton, metal chelate compound, and plastic component, which has good adhesion to film or coated paper, and is suitable for laminating polyethylene layer on the printed surface after printing. What has been proposed.

  Although the said patent documents 15-19 use metal chelate and various tolerance improves, there is no description or suggestion about a biomass degree.

  Examples of the packaging material using paper as a base material include paper containers such as the above-mentioned paper containers and liquid paper containers, labels, lid materials, paper bags, burger wraps, and the like. There are also decorative paper and wall materials for building materials, which are produced by gravure printing.

  As an example of a container using paper as a base material, as in Patent Documents 20 to 22, a film is thermally bonded to the inner surface of a tray and integrated to form a container, and water resistance is given. , Packaging materials, packaging bags, packaging containers, and lid materials using a base material in which an isocyanate compound resin is impregnated into a paper base material are described, and can impart water resistance, heat resistance, paper strength and rigidity, Patent Documents No. 24 describes a paper outer container in which a paperboard substrate impregnated with a resin is molded, and has excellent water resistance, heat resistance, shape retention, and buckling strength. Patent Document 25 discloses a blank sheet having water resistance. A water retention container for cut flowers is described, which has water resistance and suppresses water spillage. Patent Document 26 discloses a composite comprising paper as a base material and at least an innermost layer and an outermost layer with a thermoplastic synthetic resin layer. A paper container using a sheet is described, Patent Document 27 describes a paper container in which paper is used as a base material, and an inner surface resin film and an outer surface resin film are laminated on an inner surface and an outer surface, respectively, and has barrier properties, water resistance, retort sterilization resistance, and Patent Document 28 describes a paper container in which paper is used as a base material, and an inner surface resin film and an outer surface resin film are laminated on an inner surface and an outer surface, respectively, and has barrier properties, water resistance, and retort resistance. Patent Document 29 describes a paper box formed from a laminated sheet in which a thermoplastic resin layer is provided on the front and back surfaces of the paper layer, and has a steaming effect by heating in a microwave oven. However, in Patent Documents 20 to 29, a film made of a synthetic resin is laminated on a paper base in advance or impregnated with a synthetic resin. To be those with the ink to the printing, and ink coating, not to impart water resistance and heat resistance by the ink coating, also no description or suggestion of biomass degree in the ink coating.

  In Patent Document 30, a coating film is formed on a paper base material with a coating agent comprising an ethylene (meth) acrylic acid copolymer neutralized ammonia and an ethylene (meth) acrylic acid copolymer alkali metal neutralized product. Paper containers are described, and those with oil resistance, water resistance and water vapor barrier properties have been proposed, but the binder is a synthetic resin ethylene (meth) acrylic acid copolymer, and the biomass in the coating film There is no mention or suggestion of degree.

  As a label based on paper, in Patent Document 31, a resin layer (alkali desorption layer) crosslinked with an acrylic ester, an acrylic copolymer and a crosslinking agent is formed, and a printed layer is further formed thereon. An alkali-releasable label having a layer is described and has water resistance when used by being affixed to a container or the like. Layers, printing layers, etc. have been proposed for separation and separation, but the printing layer is a printing layer with a nitrocellulose / polyamide printing ink, and the overcoat layer is only described as an overcoat layer made of a nitrocellulose resin, Details are unknown and the water resistance is not sufficient. There is no description or suggestion about the degree of biomass in the ink coating.

  As a cover material using paper as a base material, Patent Document 32 describes a cover material in which a paper layer, an adhesive layer, a vapor deposition layer of metal or metal oxide, a polyester film, an anchor coat layer, and a thermal adhesive layer are sequentially laminated. Patent Document 33 describes a surface material including a paper layer and a cover material including at least an innermost layer of a sealant layer, and strengthens the base material strength of the hot water cutting portion. A material that does not cause inadvertent breakage of the base material that hinders work and peeling work. Patent Document 34 discloses that one waterproof layer is an aluminum layer made of aluminum foil, and the other waterproof layer is made of a synthetic resin. A lid for food containers having a base material layer made of paper disposed between layers is described, has water resistance, and can be easily opened by passing through a straw. Patent Document 35 and Patent Document 36 disclose a gas barrier. Group with layer A heat sealing lid material in which a layer, an anchor coating agent layer, and a thermal adhesive layer formed by applying a thermal adhesive are sequentially laminated, and a paper layer or a protective film layer is provided on the gas barrier layer side through the adhesive layer. Although it may be laminated and does not require a special baking process and has a thermal adhesive layer with good friction resistance, a printing layer is not essential as the outermost layer, and the water resistance of the printing layer is There is no description or suggestion about the property and heat resistance, and naturally there is no description or suggestion about the biomass degree in the ink coating film.

  Patent Document 37 discloses a packaging container in which a neutral paper is preliminarily impregnated with an impregnation resin with an isocyanate compound and then heat-treated and then a heat-treated paper is laminated on one or both sides with a plastic film having water vapor-permeable fine holes. A lid has been described, and water vapor permeates but moisture other than water vapor has been proposed, but a paper base is impregnated with a synthetic resin beforehand, and ink is printed to form an ink coating. The ink coating does not impart water resistance or heat resistance, and there is no description or suggestion about the degree of biomass in the ink coating.

  Patent Document 38 describes a cover material in which a paper material layer and a resin film layer are laminated, printed on the upper surface of the paper material layer, and further provided with a water-resistant varnish layer. Although it has been proposed to have excellent curl suppression, the water-resistant varnish layer is made of a water-resistant varnish with silicon added, the heat resistance is not sufficient, and the degree of biomass in the varnish coating is described and suggested There is no.

  Patent Document 39 describes a food container lid in which a heat-resistant coating layer is laminated on the outermost layer of a paper layer, and a curling is proposed, but the heat-resistant coating layer is an acrylate-based synthetic resin, There is no description or suggestion about the degree of biomass in the coating.

  As a paper bag based on paper, Patent Document 40 describes a lidded handbag having a lid on the upper surface of the handbag, and both the bag and the lid are made of paper having water resistance and biodegradability. In addition, paper has been proposed that protects the baggage in a paper bag from rain, etc., and has a function that allows easy loading and unloading of the bag, and also has biodegradability. Paper with water resistance and biodegradability is There is only a description of a biodegradable cardboard impregnated with a waterproofing agent, and a paper base material is impregnated with a fluorine-based waterproofing agent in advance, and an ink is printed to form an ink coating. It does not impart heat resistance or heat resistance, and naturally there is no description or suggestion about the degree of biomass in the ink coating film.

  As a decorative paper, Patent Document 41 describes an aqueous matte coating agent in which a component comprising a water-soluble or water-dispersible binder resin and a polymer fine particle matting agent is diluted in water. Has been proposed to form a coating film with excellent properties, scratch resistance, solvent resistance, stain resistance, etc., but it is a water-based synthetic resin, which is quite thick as a coating film and difficult to print In addition, there is room for improvement in heat resistance, and there is no description or suggestion about the degree of biomass in the coating film.

  As a paper paint for producing a paper product, Patent Document 42 describes a paper paint containing liquid paraffin, sucrose fatty acid ester, and a water-soluble resin, and applied to the surface of paper. Paper packaging containers with zeolite added are described, and those that can improve antibacterial properties, water resistance and oil resistance have been proposed, but they are water-based synthetic resins, and because of the poor drying characteristic of water-based printing, printing Speed must be reduced and improvements are desired. Moreover, there is room for improvement in heat resistance, and there is no description or suggestion about the degree of biomass in the paint film.

In addition, global warming countermeasures should be addressed globally. At the 21st Conference of the Parties to the Framework Convention on Climate Change (COP21) held in 2015, reduction targets for each country were submitted. Japan has submitted a draft commitment to reduce greenhouse gases by 26% by 2030 compared to 2013. Under these circumstances, companies that deal with foodstuffs should consider measures to reduce the disposal of foodstuffs themselves, explore whether waste can be reduced and used, and consider whether transportation distances can be reduced. Is important. In recent years, it has been emphasized how to improve the corporate image by proposing "environmentally friendly" products as an important business strategy for companies. Because packaging materials used for daily necessities and foods are familiar to general consumers and can be directly touched with the contents of the product, it is also important how to appeal as an “environmentally friendly” package. .
Therefore, there is a solvent-based gravure printing ink composition that can be used as a variety of packaging materials and materials for paper, and can be used as packaging and materials that are “environmentally friendly” without increasing the environmental burden. It was desired.

Japanese Examined Patent Publication No. 6-21260 JP-A-6-157934 JP 2005-255871 A JP 2000-313833 A JP 2008-163231 A JP 2012-111901 A JP 2012-193250 A JP 2014-58653 A JP, 2006-50286, A JP 2011-144334 A JP 2012-97235 A JP 2013-35967 A JP2013-142150A JP 2013-181125 A Japanese Patent Publication No. 45-29005 Japanese Patent Publication No. 47-29571 JP-A-5-295313 JP-A-7-258593 JP 2000-319568 A JP-A-11-236028 JP 2000-355318 A JP 2000-355365 A JP 2001-212920 A JP 2002-104369 A JP 2005-96875 A JP 2006-273396 A JP 2012-81999 A JP 2012-91809 A Japanese Patent Laid-Open No. 2006-94204 JP 2004-59657 A JP 2002-11819 A JP 2004-115089 A JP 2013-23238 A JP 2013-234004 A Japanese Patent Laid-Open No. 2015-37966 Japanese Patent Laid-Open No. 2006-94208 JP 2001-212920 A JP 2003-432 A JP 2004-106858 A JP 2004-196363 A JP-A-10-251556 Japanese Patent No. 4551992

  Accordingly, the present invention is a solvent-based gravure printing ink composition for paper that does not increase the environmental burden, and the ink composition is prepared on a paper substrate to form a printed coating film. It is an object of the present invention to provide a solvent-type gravure printing ink composition for surface printing paper having a biomass degree higher than that of a conventional solvent-type gravure printing ink for paper.

  The present inventors are a solvent-type gravure printing ink composition for paper containing a biomass material nitrocellulose resin, biomass-derived polyamide resin, and a chelate, wherein the ink composition is formed on a paper substrate. When it was set as the coating film, it discovered that the said objective can be achieved when the biomass degree (a pigment is not included) in this printing coating film is 26-85 mass%, and came to complete this invention.

That is, the present invention
(1) A solvent-type gravure printing ink composition for surface printing paper containing a nitrocellulose resin, a biomass-derived polyamide resin and a chelate,
The biomass-derived polyamide resin is at least one selected from tall oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, wheat oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, corn oil fatty acid, and rice bran oil fatty acid It is a polyamide resin having a number average molecular weight of 1,000 to 3,000 using a dimer acid generated from a plant-derived fatty acid, and a softening point of 90 to 130 ° C.
The total content of the nitrocellulose resin and the biomass-derived polyamide resin is 5 to 15% by mass in the ink composition,
The content ratio of the nitrocellulose resin and the biomass-derived polyamide resin is 1 / 0.5 to 1/4,
The chelate is titanium acetylacetonate, and is contained in an ink composition in an amount of 0.1 to 3% by mass,
When a printed film is formed on the paper base material layer using the solvent-type gravure printing ink composition for front cover paper, the degree of biomass (excluding pigment) in the printed film is 60% by mass or more. A solvent-type gravure printing ink composition for front-printing paper, characterized by being 73.8 % by mass or less ,
(2) The solvent-type gravure printing ink composition for cover paper according to (1), wherein the biomass-derived polyamide resin is a polyamide resin having a softening point of 90 to 107 ° C.
(3) On a paper base material layer, it is a printing film created using the solvent-type gravure printing ink composition for surface printing paper according to (1) or (2),
The degree of biomass (excluding pigment) in the printed film is 60% by mass or more and 73.8 % by mass or less ,
(4) A laminate having a printed layer comprising the printed coating film according to (3) on one of the paper substrate layer and the paper substrate layer,
(5) Using the solvent-type gravure printing ink composition for cover paper according to (1) or (2),
Including a gravure printing step of creating a printing layer comprising the solvent-type gravure printing ink composition for a front-printing paper on a paper base layer;
A method for producing a laminate, wherein the degree of biomass (not including pigment) in the printed layer is 60% by mass or more and 73.8 % by mass or less ,
(6) A paper container produced using the laminate according to (4),
(7) A label produced using the laminate according to (4),
(8) A lid material produced using the laminate according to (4),
(9) A paper bag produced using the laminate according to (4),
(10) A paper product produced using the laminate according to (4),
It is about.

  According to the present invention, there is provided a solvent-based gravure printing ink composition for paper that does not increase the environmental load, and the ink composition is formed on a paper substrate to form a printed coating film. It is possible to provide a solvent-type gravure printing ink composition for surface printing paper having a biomass degree higher than that of a conventional solvent-type gravure printing ink for paper.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. The present embodiment is merely one form for carrying out the present invention, and the present invention is not limited by the present embodiment, and various modifications and embodiments are possible without departing from the gist of the present invention. Is possible.

  The solvent-type gravure printing ink composition for surface printing paper of the present invention (hereinafter also simply referred to as “ink composition”) contains a nitrocellulose resin, a biomass-derived polyamide resin and a chelate, and the nitrocellulose resin and biomass. The content of the derived polyamide resin is 5 to 40% by mass in the ink composition, and the content ratio of the nitrocellulose resin and the biomass-derived polyamide resin is from 1 / 0.4 to 1 / 9.5. It is a solvent-type gravure printing ink composition for front-printing paper, and the printing film is formed on the paper substrate layer using the solvent-type gravure printing ink composition for front-printing paper. It is preferable that the degree of biomass (not including pigment) in the coating film is 26 to 85% by mass.

  The biomass-derived polyamide resin is a polyamide resin manufactured from a biomass (biologically renewable resource) material, and uses a biomass material as an acid component or an amine component or both components as a raw material of the polyamide resin. This is a manufactured polyamide resin.

Examples of the acid component include polymerized fatty acids, which may partially include aliphatic, alicyclic and aromatic dicarboxylic acids and aliphatic monocarboxylic acids. Polymerized fatty acid is a dimerization of plant-derived fatty acid, and as plant-derived fatty acid, it was used in cooking residual foods (dark oil, alkaline oil cake) and food and beverages discharged during the production of edible oil. Fatty acids obtained by collecting, separating, distilling, and refining waste edible oils, such as tall oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, wheat oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, corn oil Fatty acids and rice bran oil fatty acids are preferred, and tall oil fatty acids and rice bran oil fatty acids are more preferred. Many of these plant-derived fatty acids mainly have 8 to 24 carbon atoms, but the most utilized are unsaturated fatty acids having 18 carbon atoms, and a dimer acid having 36 carbon atoms is preferred. However, the structure of this dimer acid is not single, and may be a mixture of acyclic, monocyclic and polycyclic. In addition, commercially available dimer acid may also contain a small amount of monomeric acid (1 to 15% by mass), trimer acid (20% by mass or less), and the like.
Dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, maleic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aromatics such as isophthalic acid and terephthalic acid. And dicarboxylic acids.
Examples of the monocarboxylic acid include acetic acid, propionic acid, stearic acid, oleic acid, linoleic acid, plant-derived fatty acid and the like.
As the plant-derived fatty acid, among tall oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, wheat oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, corn oil fatty acid and rice bran oil fatty acid, tall oil fatty acid, soybean oil fatty acid, Cottonseed oil fatty acid, rapeseed oil fatty acid, wheat oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, corn oil fatty acid are obtained from imported soybeans, cottonseed, rapeseed, etc., but rice bran oil fatty acid is from domestically produced rice From the viewpoint of food mileage, rice bran oil fatty acid is very small in food mileage and does not place a great burden on the global environment. Here, food mileage means that the longer the distance between the production area and the consumption area, the higher the energy consumption required for transporting foods and the greater the carbon dioxide emissions. It is a concept that has been proposed as an indicator of The food mileage can be expressed by a numerical value calculated by L × W, where L is the transport distance when the product is transported from the production area to the sales place, and W is the weight of the product. The food mileage becomes smaller if the production area and the sales area of the product are close, and the food mileage becomes larger if the same product is transported from a farther production area. It also leads to local pond consumption efforts.
Therefore, companies that handle foodstuffs, especially distribution companies that handle rice products such as bento and rice balls (convenience stores, supermarkets, etc.), do not discard the rice bran produced when the rice is milled, and extract the rice bran extracted from the rice bran. The production and use of oil fatty acids and dimer acids are very effective from the viewpoint of reducing environmental impact, food mileage, and local pond consumption.

Examples of the amine component include aliphatic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, and xylylenediamine, and aromatic polyamines such as diaminophenylmethane, phenylenediamine, triaminobenzene, triaminophenol, and tetraaminobenzene. , Alicyclic polyamines such as isophorone diamine and diaminodicyclohexyl methane, and heterocyclic amines such as piperazine.
Mono- and di-alkylamines such as butylamine, octylamine and diethylamine, monoamines such as mono- and di-alkanolamines such as monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine and aminoethylethanolamine May be.

  As a method for synthesizing a biomass-derived polyamide resin, the acid component and the amine component are preferably reacted at a reaction temperature of 160 to 250 ° C. in an inert gas atmosphere, and is preferably 180 to 230 ° C. More preferred. In particular, it is preferable to use dimer acid generated from rice bran oil fatty acid or tall oil fatty acid as the acid component.

The acid value of the biomass-derived polyamide resin is preferably 0 to 20 KOHmg / g, and the total amine value is preferably 1 to 15 KOHmg / g.
The softening point is preferably 80 to 200 ° C, more preferably 90 to 130 ° C.
The number average molecular weight is preferably 1,000 to 3,000, and more preferably 1,500 to 2,500. When the number average molecular weight is less than 1,000, the viscosity does not increase, resulting in a low viscosity ink. When the number average molecular weight exceeds 3,000, the solubility is insufficient and the solution becomes cloudy.
The acid value is a value measured according to JIS K5601.
The total amine value is a value measured by ASTM D2074.
The softening point is a value measured by the ring and ball method according to JIS K2207.
The number average molecular weight is a value measured by GPC method (polystyrene conversion).

The nitrocellulose resin is a nitro group-substituted cellulose resin in which a part of hydroxyl groups of the cellulose skeleton is nitrated. The cellulose skeleton of the nitrocellulose resin is a biomass material.
As the nitrocellulose resin used in the gravure printing ink composition of the present invention, a general nitrocellulose resin can be used without any problem, and among them, an average of 1.3 to 1 per glucose unit constituting the cellulose skeleton. It is preferably one substituted with 2.7 nitro groups.

The content ratio of the nitrocellulose resin and the biomass-derived polyamide resin is preferably 1 / 0.4 to 1 / 9.5, and more preferably 1 / 0.5 to 1/9. When the content ratio of the biomass-derived polyamide resin is smaller than 0.4 with respect to the nitrocellulose resin 1, the water resistance is inferior. When the content ratio of the biomass-derived polyamide resin is larger than 9.5 with respect to the nitrocellulose resin 1, the heat resistance is inferior.
The total amount of the ink composition is preferably 5 to 40% by mass, and more preferably 6 to 35% by mass.

  The chelate is preferably a metal chelate or a phosphorus chelate, and the metal atom in the metal chelate is preferably titanium, zirconium, or hafnium, and preferably titanium or zirconium. Examples of the titanium system include titanium acylate, titanium alkoxide, titanium chelate (complex), and the like. Examples of the zirconium series include zirconium acylate, zirconium alkoxide, zirconium chelate (complex) and the like. Of these, titanium acetylacetonate and diisopropoxybis (acetylacetonato) titanium are preferable. Moreover, the metal chelate represented by Formula (1) is also preferably used. Chelates are very effective in improving heat resistance.

式（１）中のＲ^１〜Ｒ^４は、それぞれ独立に炭素数１〜１８個のアルキル基が好ましく、それぞれ独立に炭素数１〜１０個のアルキル基がより好ましく、それぞれ独立に炭素数１〜８個のアルキル基がさらに好ましい。これらは、高い架橋反応性が得られる点で特に好ましい。炭素数が１８個を超えると、反応性が乏しくなり好ましくない。Ｍは、周期表第４族の中から選ばれる何れかの金属原子であることが好ましく、チタン、ジルコニウム、ハフニウムがより好ましく、チタンまたはジルコニウムが特に好ましい。

R ^{1 to} R ⁴ in the formula (1) are each independently preferably an alkyl group having 1 to 18 carbon atoms, more preferably independently an alkyl group having 1 to 10 carbon atoms, and each independently having 1 carbon atom. More preferred are -8 alkyl groups. These are particularly preferable in that high crosslinking reactivity can be obtained. When the number of carbon atoms exceeds 18, the reactivity becomes poor, which is not preferable. M is preferably any metal atom selected from Group 4 of the periodic table, more preferably titanium, zirconium or hafnium, and particularly preferably titanium or zirconium.

Examples of M that is titanium include tetramethoxide titanium, tetraethoxide titanium, tetra n-propoxide titanium, tetraisopropoxide titanium, tetra n-butoxide titanium, tetraisobutoxide titanium, diisopropoxide di-n-butoxide titanium. Di-tert-butoxydiisopropoxide titanium, tetra-sec-butoxide titanium, tetra-tert-butoxide titanium, tetra-2-ethylhexoside titanium, tetraoctyloxide titanium, tetraisooctyloxide titanium, tetrastearyl alkoxide titanium Etc. Examples of M as zirconium include tetramethoxide zirconium, tetraethoxide zirconium, tetra n-propoxide zirconium, tetraisopropoxide zirconium, tetra n-butoxide zirconium, tetraisobutoxide zirconium, diisopropoxide di- Examples include butoxide zirconium, di tert-butoxy diisopropoxide zirconium, tetra sec-butoxide zirconium, tetra tert-butoxide zirconium, tetra 2-ethylhexoside zirconium, tetraisooctyloxide zirconium, tetrastearyl alkoxide zirconium and the like. Among them, tetra n-propoxide titanium, tetraisopropoxide titanium, tetra n-butoxide titanium, tetraisobutoxide titanium, tetra 2-ethylhexoside titanium, tetraoctyloxide titanium, tetraisooctyloxide titanium, tetra n-propoxide zirconium, tetraisopropoxide zirconium, tetra n-butoxide zirconium, tetraisobutoxide zirconium, tetra-2-ethylhexoside zirconium, tetraoctyloxide zirconium and tetraisooctyloxide zirconium are more preferable.
The metal chelate represented by the formula (1) is a metal chelate that does not contain acetylacetone or the like as a ligand, and therefore has less odor and excellent stability as an ink. These can be used alone or in admixture of two or more.

  The chelate content in the ink composition is preferably 0.1 to 5 mass%, more preferably 1 to 3 mass%. If the chelate content is less than 0.1% by mass, the effect of heat resistance cannot be obtained. When the content of the chelate is larger than 5% by mass, yellowing is likely to occur.

The solvent-type gravure printing ink composition for front cover paper of the present invention may contain an organic solvent. Any organic solvent may be used as long as it dissolves or disperses the resin in the solvent, and those usually used in gravure printing are preferable.
Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, isopropyl alcohol (IPA), normal propyl alcohol, Alcohol solvents such as 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester systems such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate Solvent, acetone, methyl ethyl ketone (MEK), ketone solvents such as methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Examples include glycol ether solvents such as recall dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and esterified products thereof. Acetates are selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Such as monoethyl ether acetate. Further, it may be a biomass-derived solvent such as biomass ethanol or biomass ethyl acetate.

  The content of the organic solvent is preferably 10 to 95% by mass in the ink composition, and more preferably 20 to 85% by mass. If the amount is less than 10% by mass, sufficient printability cannot be obtained. If the amount is more than 95% by mass, the solid content decreases and the density decreases.

  Furthermore, in the ink composition of the present invention, coloring materials, inorganic fillers, organic fillers, antifoaming agents, for the purpose of improving required physical properties such as design properties, applications, hues, ink stability, and printability, A leveling agent, an antiblocking agent, a wax, a pigment dispersant, an antistatic agent, a release agent, a slip agent, a plasticizer, a tackifier, and the like can also be contained. Any known and commonly used one can be appropriately selected within a range that does not impair the printability and the properties of the ink composition. Moreover, what is derived from biomass is preferable.

  The color material can contain a pigment, a dye, or a mixture thereof. Examples of the pigment include titanium oxide, petal, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, carbon black and other inorganic pigments, phthalocyanine-based, insoluble azo-based, condensed azo Organic pigments such as organic, dioxazine, anthraquinone, quinacridone, perylene, perinone, and thioindigo, and various other fluorescent pigments, metal powder pigments, extender pigments, and the like. These pigments may be used alone or in combination of two or more. As the dye, those which are dissolved or dispersed in a solvent are preferable, and one kind or a combination of two or more kinds may be used. Among these, it is preferable to use a pigment from the viewpoint of durability. Since it can contain a coloring material, it is very useful in terms of color variation and design.

The printed coating film is formed on the paper base layer by a printing method or the like which will be described later on the ink composition, but the organic solvent contained in the ink composition is volatilized in the drying process at the time of printing. As a result, a resin component, a pigment component, and the like remain as solids on the paper base material layer, and this is referred to as a printed coating film in this specification. At this time, it is preferable that the biomass degree (a pigment is not included) in a printed coating film is 26-85 mass%. The larger the degree of biomass, the more effective the environmental load is reduced, which is preferable.
Here, the degree of biomass (not including pigment) is the biomass-derived solid content contained in the resin solid component excluding the solid content of the pigment component in the printed coating film for the printed coating film prepared on the paper substrate layer. The ratio is expressed by the following formula (2).
Biomass degree (%) = (biomass-derived resin solid content / resin solid content) × 100 (2)

  The production of the printed coating film is preferably a gravure printing method from the viewpoint of high quality and high productivity. In particular, a gravure printing method using a multicolor gravure printing machine is more preferable.

  It is preferable that the laminated body of this invention has a printing layer which consists of the said printing coating film in one of a paper base material layer and a paper base material layer.

  The paper base layer preferably includes at least one selected from coated paper, uncoated paper, and a paper base material on which a plastic film, an aluminum foil, a vapor deposition film, and the like are bonded. The paper base material may be laminated by a method using a thermoplastic resin or the like by dry lamination, non-solvent lamination or extrusion lamination, a method of bonding through an adhesive or the like, or a combination of these appropriately It may be a thing. Moreover, the laminated body which provided heat sealability can also be used as a paper base material. Examples of methods for imparting heat-sealability include known sealant film bonding, resin coating by extrusion lamination, heat-sealable resin processing by heat-sealant or hot-melt coating or co-extrusion, and the like. A layer to which heat sealability is imparted by a method is also referred to as a heat seal layer. Although there will be no restriction | limiting in particular if the thickness of a paper base material layer is in the range which does not have trouble in printability, winding-up property, etc., 5-800 micrometers is preferable and 6-600 micrometers is more preferable.

  It is preferable that the manufacturing method of a laminated body includes the gravure printing process which creates the printing layer which consists of a printing coating film in one of a paper base material layer and a paper base material layer. In particular, the gravure printing process is preferably a printing process by a multicolor gravure printing machine.

  The laminate of the present invention is for packaging, food preservation, agriculture, civil engineering, fishery, automotive interior and exterior use, marine use, daily necessities, building material interior and exterior use, housing equipment use, medical / medical equipment use, and pharmaceutical use. It can be used for household appliances, furniture, stationery and office supplies, sales promotion, commercial use, and electrical and electronics industries.

  The paper container of the present invention is preferably prepared using the laminate. Forms of bottles and boxes such as paper containers and trays for food packaging, cups, dishes, bottles, tetra packs, gable tops, bricks, carton cans, cake boxes, etc. Can be preferably used.

  The label of the present invention is preferably produced using the laminate. It can be preferably used in the form of a label attached to a glass bottle, a metal can, a plastic bottle, another container, or a body-wound label.

  The lid member of the present invention is preferably prepared using the laminate. It can be preferably used as a form of a lid material to be a sealed container by closely contacting with a bottomed cylindrical container such as a plastic container for food or daily necessities, a glass container, a metal can or a paper can. The close contact with the container may be performed through human hand, but a machine such as an automatic sealing device may be used. These may be selected as appropriate depending on the type, form and size of the food, quantity, container to be sealed, equipment, environment, etc., and sticking or bonding with heat seal (hot pressure seal), face seal, adhesive, etc. It may be performed by a method using such as. Moreover, it can use preferably as forms, such as a cover body for closing the upper part of a paper container by fitting etc.

  The paper bag of the present invention is preferably prepared using the laminate. It can be preferably used in the form of a packaging bag or a handbag for food or daily necessities. As a form of the packaging bag, it can be preferably used as a form such as a two-side seal, a three-side seal, a four-side seal, a pillow seal, a standing pouch, an envelope attachment, a gusset, and a fusing seal.

  The paper product of the present invention is preferably prepared using the laminate. It can be preferably used as a form for wrapping contents such as burger wrap for food, a wrapping paper for daily necessities, a decorative paper for building materials, and the like.

  Both forms can greatly contribute to reducing the environmental burden as packaging the contents, and reach directly to the general consumer. Therefore, as an "environmentally friendly" company, consider the environment and actively work on the environment. You can appeal what you are promoting.

  The ink composition can be produced by a known method by uniformly dissolving or dispersing a pigment, resin, chelate, various additives and the like in a solvent. Dissolver or disperser is various agitators or dispersers such as dissolver, roll mill, ball mill, bead mill, sand mill, attritor, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, wet jet mill, kneader, homomixer, etc. You can use the machine. These devices may be used alone or in combination of two or more. When air bubbles and coarse particles are contained in each composition, it is preferable to remove them using a known filter or centrifuge in order to reduce printability and print quality.

  The viscosity of the ink composition is not particularly limited as long as it does not interfere with printing. Considering the production suitability and handling of each composition used in gravure printing and flexographic printing, it is preferably 10 to 1,000 mPa · s at 25 ° C. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone plate viscometer.

  Ink compositions used in gravure printing and flexographic printing can be applied as they are, but depending on the coating conditions and coating effect, Zahn Cup # 3 (manufactured by Chugai Co., Ltd.) can be used as a diluent solvent. Can be used after adjusting to a desired viscosity. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C.

  The dilution solvent may be any one as long as it can be used by adjusting the viscosity of the ink composition, and examples thereof include organic solvents, and commercially available ones can also be used. Examples of commercially available products include CN104 (non-toluene solvent) (manufactured by Tokyo Ink Co., Ltd.).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these. In addition, the part in an Example and a comparative example represents a mass part, and% represents the mass%.

[Production of varnish]
Varnish 1 (Production Example 1)
20 parts of nitrocellulose resin (solid content 70%, biomass degree 49%), polyamide resin using biomass material (solid content 100%, rice bran-derived dimer acid used, biomass degree 80%), 8 parts of methylcyclohexane, Varnish 1 was prepared by charging, dissolving and mixing 22 parts of isopropyl alcohol and 7 parts of ethyl acetate.

Varnish 2 (Production Example 2)
Nitrocellulose resin (solid content 70%, biomass degree 49%) 15 parts, polyamide resin using biomass material (solid content 100%, rice bran-derived dimer acid used, biomass degree 80%) 10.5 parts, cyclohexane 45 parts Then, 22.5 parts of isopropyl alcohol and 7 parts of acetic acid-n-propyl were charged and dissolved and mixed to prepare varnish 2.

Varnish 3 (Production Example 3)
7 parts of nitrocellulose resin (solid content 70%, biomass degree 49%), polyamide resin using biomass material (solid content 100%, rice bran-derived dimer acid used, biomass degree 80%) 19.5 parts, methylcyclohexane 44 Parts, 10 parts of methanol, 12.5 parts of isopropyl alcohol, and 7 parts of ethyl acetate were dissolved, mixed, and varnish 3 was prepared.

Varnish 4 (Production Example 4)
Nitrocellulose resin (solid content 70%, biomass degree 49%) 3.5 parts, biomass material polyamide resin (solid content 100%, rice bran-derived dimer acid used, biomass degree 80%) 22.5 parts, methyl Varnish 4 was prepared by charging 45 parts of cyclohexane, 10 parts of methanol, 12 parts of isopropyl alcohol and 7 parts of ethyl acetate, and dissolving and mixing them.

Varnish 5 (Production Example 5)
7 parts of nitrocellulose resin (solid content 70%, biomass degree 49%), polyamide resin using biomass material (solid content 100%, using tall oil-derived dimer acid, biomass degree 67%), 19.5 parts of methylcyclohexane 44 parts, 10 parts of methanol, 12.5 parts of isopropyl alcohol, and 7 parts of ethyl acetate were charged, dissolved and mixed to prepare varnish 5.

Varnish 6 (Production Example 6)
Varnish 6 was prepared by charging 19 parts of methylcyclohexane, 25 parts of isopropyl alcohol, and 30 parts of ethyl acetate into 26 parts of nitrocellulose resin (solid content: 70%, biomass degree: 49%).

Varnish 7 (Production Example 7)
Polyamide resin using biomass material (solid content 100%, rice bran-derived dimer acid used, biomass degree 80%) is charged with 42 parts of methylcyclohexane, 10 parts of methanol, 11 parts of isopropyl alcohol and 7 parts of ethyl acetate and dissolved. And varnish 7 was prepared.

[Preparation of ink composition]
Ink 1 (Example 1)
60 parts of the varnish 1 produced in Production Example 1 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 1 was prepared by preparing a mixed solution with 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 2 (Example 2)
60 parts of varnish 2 produced in Production Example 2 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 2 was prepared by preparing a mixed solution with 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 3 (Example 3)
60 parts of varnish 3 produced in Production Example 3 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 3 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 4 (Example 4)
60 parts of the varnish 4 produced in Production Example 4 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol, and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 4 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 5 (Example 5)
60 parts of the varnish 3 produced in Production Example 3 was charged with 10 parts of yellow pigment (Pigment Yellow 14), 6 parts of isopropyl alcohol, and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 5 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 6 (Example 6)
60 parts of varnish 3 produced in Production Example 3 was charged with 10 parts of indigo pigment (Pigment Blue 15: 4), 6 parts of isopropyl alcohol and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 6 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 7 (Example 7)
60 parts of varnish 3 produced in Production Example 3 was charged with 10 parts of black pigment (Pigment Black 7), 6 parts of isopropyl alcohol, and 10 parts of methylcyclohexane, and kneaded with a paint shaker to produce a mill base. Ink 7 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 8 (Example 8)
60 parts of varnish 5 produced in Production Example 5 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol, and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 8 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 9 (Comparative Example 1)
60 parts of the varnish 6 produced in Production Example 6 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 9 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 10 (Comparative Example 2)
60 parts of varnish 7 produced in Production Example 7 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol, and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. Ink 10 was prepared by preparing a mixed solution of 3 parts of titanium acetyl acetate (metal chelate), 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 3 parts of ethyl acetate and adding to the mill base and mixing.

Ink 11 (Comparative Example 3)
60 parts of varnish 2 produced in Production Example 2 was charged with 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol and 10 parts of methylcyclohexane, and kneaded with a paint shaker to prepare a mill base. A mixed solution was prepared with 5 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 6 parts of ethyl acetate, and added to the mill base and mixed to prepare ink 11.

Ink 12 (Comparative Example 4)
23 parts of varnish 6 produced in Production Example 6, 37 parts of acrylic resin varnish (solid content 45%, biomass degree 0%), 10 parts of red pigment (Pigment Red 48: 3), 6 parts of isopropyl alcohol, 10 parts of ethyl acetate The part was prepared and kneaded with a paint shaker to prepare a mill base. A mixed solution was prepared with 3 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 8 parts of ethyl acetate, added to the mill base, and mixed to prepare ink 12.

Ink 13 (Comparative Example 5)
12 parts of varnish 6 produced in Production Example 6, 4 parts of butyral resin (solid content 100%, biomass degree 0%), 10 parts of red pigment (Pigment Red 48: 3) and 6 parts of isopropyl alcohol were added to a paint shaker. To prepare a mill base. A mixed solution was prepared with 4 parts of titanium acetyl acetate (metal chelate), 21 parts of ethyl acetate, and 43 parts of isopropyl alcohol, and added to the mill base and mixed to prepare ink 13.

Ink 14 (Reference Example 1)
50 parts of the varnish 6 produced in Production Example 6 was charged with 10 parts of red pigment (Pigment Red 48: 3) and 6 parts of isopropyl alcohol, and kneaded with a paint shaker to prepare a mill base. A mixed solution was prepared with 18 parts of methylcyclohexane, 3 parts of isopropyl alcohol, and 13 parts of ethyl acetate, added to the mill base, and mixed to prepare ink 14.

[Preparation of coating composition]
Ink 15 (Example 9)
A mixed solution was prepared from 50 parts of the varnish 3 prepared in Production Example 3, 3 parts of titanium acetyl acetate (metal chelate), 28 parts of methylcyclohexane, 14 parts of isopropyl alcohol, and 5 parts of ethyl acetate, and added to the mill base. And ink 15 was prepared.

The materials used are as follows.
Nitrocellulose resin: Biomass degree 49%, mixture of RS1 / 16 70 parts and isopropyl alcohol 30 parts (manufactured by TNC), solid content 70%
Polyamide resin using biomass material: Rice bran-derived dimer acid used, biomass degree 80%, softening point 107 ° C, number average molecular weight 2,500, solid content 100%
Polyamide resin using biomass material: Use of tall oil-derived dimer acid, biomass degree 67%, softening point 105 ° C, number average molecular weight 2,000, solid content 100%
Acrylic resin varnish: Biomass degree 0%, Dianal GR-5679 (manufactured by Mitsubishi Rayon Co., Ltd.), solid content 45%
Butyral resin: 0% biomass, Mobital B 16H (manufactured by Kuraray Co., Ltd.), solid content 100%

Using a five-color machine gravure printing machine, ink 1 (abbreviation: ink 1) is printed on a 150 g / m ² coated paper (abbreviation: coated paper) with the first unit, and wound to produce a laminate 1. did. At this time, ink 1 was diluted with CN104 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.). As a result, the laminate 1 became a laminate having a configuration of “ink 1 / coated paper”.

  Laminate 2 was produced under the same conditions as laminate 1 except that ink 1 was changed to ink 2 (abbreviation: ink 2). At this time, ink 2 was diluted with CN104. As a result, the laminate 2 became a laminate having a configuration of “ink 2 / coated paper”.

  Laminate 3 was produced under the same conditions as laminate 1 except that ink 1 was changed to ink 3 (abbreviation: ink 3). At this time, ink 3 was diluted with CN104. As a result, the laminate 3 became a laminate having a configuration of “ink 3 / coated paper”.

  A laminate 4 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 4 (abbreviation: ink 4). At this time, the ink 4 was diluted with CN104. As a result, the laminate 4 became a laminate having a configuration of “ink 4 / coated paper”.

  Laminate 5 was produced under the same conditions as laminate 1 except that ink 1 was changed to ink 8 (abbreviation: ink 8). At this time, the ink 8 was diluted with CN104. As a result, the laminate 5 became a laminate having a configuration of “ink 8 / coated paper”.

Using a five-color gravure printing machine, print ink 5 on the first unit, ink 3 on the second unit, ink 6 on the third unit, and ink 7 on the fourth unit on 150 g / m ² of coated paper. , Wound up, and laminated body 6 was produced. At this time, inks 5, 3, 6, and 7 were diluted with CN104. As a result, the laminate 6 became a laminate having a configuration of “ink 7, ink 6, ink 3, ink 5 / coated paper”.

Using a five-color gravure printing machine, on a coated paper for labeling of 60 g / m ² , ink 7 is printed in the first unit, and ink 15 (abbreviation: ink 15) is printed in the second unit. 7 was produced. At this time, inks 7 and 15 were diluted with CN104. As a result, the laminate 7 became a laminate having a configuration of “ink 15 / ink 7 / coated paper”.

  Using a five-color machine gravure printing machine, on the surface of the paper / aluminum foil / easy peel film laminated base paper, the ink 7 is printed in the first unit and the ink 15 is printed in the second unit. Produced. At this time, inks 7 and 15 were diluted with CN104. As a result, the laminate 8 became a laminate having a configuration of “ink 15 / ink 7 / paper / aluminum foil / easy peel film”.

Using a five-color gravure printing machine, on the coated paper of 60 g / m ² , print the ink 6 with the first unit, the ink 7 with the second unit, the ink 15 with the third unit, wind up, and ink 15 layers A polyethylene terephthalate film (abbreviation: PET) with a thickness of 12 μm is bonded to the opposite surface by a dry laminating method using a urethane-based adhesive (abbreviation: DL), and a hot melt adhesive (X40A) , Manufactured by Tokyo Ink Co., Ltd., abbreviated name: HM), was subjected to gravure coating so as to be 25 g / m ² , thereby preparing a laminate 9. At this time, inks 6, 7, and 15 were diluted with CN104. As a result, the laminate 9 became a laminate having a configuration of “ink 15 / ink 7 / ink 6 / coated paper / DL / PET / HM”.

  Using a 5-color gravure printing machine, print the ink 6 on the first unit and the ink 15 on the second unit on the opposite side of the polyethylene coated wrap paper (abbreviation: PE coated paper). The laminated body 10 was produced. At this time, inks 6 and 15 were diluted with CN104. Thereby, the laminated body 10 became a laminated body having a configuration of “ink 15 / ink 6 / coated paper / PE (coated paper / PE layer is PE coated paper)”.

  Using a five-color gravure printing machine, on the corona-treated surface of milk carton paper (abbreviation: milk carton paper, polyethylene resin coat, single-sided corona treatment) with a thickness of 0.5 mm, the first unit uses ink 5 and the second unit uses Ink 3, ink 6 in the third unit, and ink 7 in the fourth unit were printed, wound up, and a laminate 11 was produced. At this time, inks 5, 3, 6, and 7 were diluted with CN104. As a result, the laminate 11 became a laminate having a configuration of “ink 7 / ink 6 / ink 3 / ink 5 / PE / coated paper / PE (PE / coated paper / PE layer is milk carton paper)”. .

  A laminate 12 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 14 (abbreviation: ink 14). At this time, the ink 14 was diluted with CN104. As a result, the laminate 12 became a laminate having a configuration of “ink 14 / coated paper”.

  A laminate 13 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 9 (abbreviation: ink 9). At this time, the ink 9 was diluted with CN104. As a result, the laminate 13 became a laminate having a configuration of “ink 9 / coated paper”.

  A laminate 14 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 10 (abbreviation: ink 10). At this time, the ink 10 was diluted with CN104. As a result, the laminate 14 became a laminate having a configuration of “ink 10 / coated paper”.

  A laminate 15 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 11 (abbreviation: ink 11). At this time, the ink 11 was diluted with CN104. As a result, the laminate 15 became a laminate having a configuration of “ink 11 / coated paper”.

  A laminate 16 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 12 (abbreviation: ink 12). At this time, the ink 12 was diluted with CN104. As a result, the laminate 16 became a laminate having a configuration of “ink 12 / coated paper”.

  A laminate 17 was produced under the same conditions as the laminate 1 except that the ink 1 was changed to the ink 13 (abbreviation: ink 13). At this time, the ink 13 was diluted with CN104. As a result, the laminate 17 became a laminate having the configuration of “ink 13 / coated paper”.

  About the laminated bodies 1-17, the biomass degree, heat resistance, adhesiveness, and water resistance of the printed coating film were evaluated, and the results are shown in Table 1.

<Biomass degree>
The biomass degree was calculated by the following formula (2).
Biomass degree (%) = (biomass-derived resin solid content / resin solid content) × 100 (2)

<Heat resistance>
About the printing surface of each obtained laminated body, when it heat-sealed by 150 degreeC and the load of 3 kgf / cm < ² > for 2 second, the peeling condition of the printing surface was observed visually and evaluated. It was judged that the heat resistance was good when the printed surface did not peel from the paper substrate surface. About the peeling condition of the printing surface, it evaluated in three steps, (circle): It does not peel at all, (triangle | delta): Some peeling is seen (no problem in practical use), x: Many peeling.

<Adhesion>
Adhesive tape (28 mm, manufactured by Nichiban Co., Ltd.) is applied to the solid portion of the printed surface of each laminate that has a halftone dot concentration of 100%. Were visually observed and evaluated. Those having a small degree of being taken on the adhesive tape were judged to have good adhesion. The degree of removal to the adhesive tape was evaluated in three stages: ○: not taken at all, Δ: some taken, ×: almost taken.

<Water resistance>
About the solid part of the dot density of 100% of the printing surface of each obtained laminated body, water was dripped and left still, and the penetration | invasion state of the water drop was visually observed and evaluated after 1 hour. Those with less penetration were judged to have good water resistance. The water droplet penetration was evaluated in three stages: ○: no penetration, no change, Δ: slight penetration, x: stain due to penetration.

According to Table 1, it is clear that the laminates of Examples 10 to 20 are excellent in heat resistance and water resistance of the printed surface, and have good adhesion between the printed surface and the paper base material layer. Moreover, the biomass degree of a printing coating film is higher than the reference example 2 which is a prior art example, and there is also little environmental impact. Furthermore, since the laminated bodies of Examples 10 to 13 and 15 to 20 are polyamide resins using dimer acid derived from rice bran, they are very effective from the viewpoint of food mileage. On the other hand, since the comparative example 6 is only a nitrocellulose resin, water resistance is inferior. Since the comparative example 7 is only the polyamide resin which uses biomass material, although the degree of biomass is high, heat resistance is inferior. Since Comparative Example 8 does not contain a chelate, the heat resistance is inferior. Although the comparative example 9 contains the nitrocellulose and acrylic resin which are the examples similar to the cited reference 6, a biomass degree is low and heat resistance and water resistance are inferior. Comparative Example 10 contains nitrocellulose, a metal chelate, and a butyral resin as a plastic component similar to Cited Document 19, but has poor water resistance.
For companies that handle foodstuffs, especially distributors that handle rice products, polyamide resin that generates and uses dimer acid derived from rice bran from rice bran that is generated and disposed of when rice is milled. Because it can produce printed materials consisting of, it can appeal about environmental load reduction, food mileage reduction, and local production for local consumption. Furthermore, since it can be applied by gravure printing, it is not limited to food packaging applications, but is used for food preservation, agriculture, civil engineering, fishing, automobile interior and exterior applications, ship applications, daily necessities applications, building materials interior and exterior applications, and residential equipment. Various types of paper containers such as uses, medical / medical equipment use, pharmaceutical use, household appliance use, furniture use, stationery / office supplies use, sales promotion use, commercial use, electrical electronics industry use and industrial material use Widely applicable to labels, lids, paper bags, paper products, etc.

Claims (10)

A solvent-type gravure printing ink composition for surface printing paper containing a nitrocellulose resin, a biomass-derived polyamide resin and a chelate,
The biomass-derived polyamide resin is at least one selected from tall oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, wheat oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, corn oil fatty acid, and rice bran oil fatty acid It is a polyamide resin having a number average molecular weight of 1,000 to 3,000 using a dimer acid generated from a plant-derived fatty acid, and a softening point of 90 to 130 ° C.
The total content of the nitrocellulose resin and the biomass-derived polyamide resin is 5 to 15% by mass in the ink composition,
The content ratio of the nitrocellulose resin and the biomass-derived polyamide resin is 1 / 0.5 to 1/4,
The chelate is titanium acetylacetonate, and is contained in an ink composition in an amount of 0.1 to 3% by mass,
When a printed film is formed on the paper base material layer using the solvent-type gravure printing ink composition for front cover paper, the degree of biomass (excluding pigment) in the printed film is 60% by mass or more. A solvent-type gravure printing ink composition for surface printing paper, characterized by being 73.8 % by mass or less .   The solvent-type gravure printing ink composition for cover paper according to claim 1, wherein the biomass-derived polyamide resin is a polyamide resin having a softening point of 90 to 107 ° C. On the paper base material layer, a printed coating film produced using the solvent-type gravure printing ink composition for surface printing paper according to claim 1 or 2,
A print film having a biomass degree (not including a pigment) in the print film of 60% by mass or more and 73.8 % by mass or less .   A laminate having a printed layer comprising the printed coating film according to claim 3 on one of a paper substrate layer and a paper substrate layer. Using the solvent-type gravure printing ink composition for surface printing paper according to claim 1 or 2,
Including a gravure printing step of creating a printing layer comprising the solvent-type gravure printing ink composition for a front-printing paper on a paper base layer;
A method for producing a laminate, wherein a degree of biomass (not including a pigment) in the printed layer is 60% by mass or more and 73.8 % by mass or less .   A paper container produced using the laminate according to claim 4.   A label produced by using the laminate according to claim 4.   A lid material produced using the laminate according to claim 4.   A paper bag produced using the laminate according to claim 4.   A paper product produced using the laminate according to claim 4.