Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins

Definitions

• the present invention relates to a printed matter and a laminated laminate using a liquid ink composition that can be used as a laminate gravure ink for flexible packaging or a flexographic ink.
• Gravure inks and flexo inks are widely used for the purpose of imparting aesthetics and functionality to printed materials.
• a gravure or flexographic printed material is used as a packaging material, particularly as a food packaging material, it is generally subjected to lamination.
• various printing materials and lamination processes are used depending on the type of contents and purpose of use.
• Patent Document 1 describes a non-laminating ink composition for flexible packaging containing, as essential components, a polypropylene glycol-containing polyurethane resin and a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group.
• PVC has the following problems, and there are concerns about it as a substance that hinders the recycling of packages.
• the first is the issue of chemical recycling.
• plastics are included in plastic waste discharged as general waste, including chlorinated resins such as polyvinyl chloride and polyvinylidene chloride. Hydrogen chloride is desorbed from these chlorine-based resins in the thermal decomposition process of recycling to generate hydrochloric acid, which causes corrosion of equipment and piping.
• thermal recycling In the method of reusing the energy generated when the waste is incinerated, there is a problem that environmental hormones such as dioxin are discharged when chlorine-based resin is included in the incineration. Therefore, it is desired to develop an ink which does not use chlorine-based materials such as PVC and which has various physical properties required for laminating ink.
• printing inks used for decoration or surface protection are required to have advanced performance and adaptability to various films.
• packaging materials when used as a soft packaging material for foodstuffs or sanitary goods, lamination is generally added.
• various printing materials and lamination processes are used depending on the type of contents and purpose of use.
• printed matter used for flexible packaging generally has a plurality of printed layers, and a printed layer containing a white pigment as a background and a printed layer with a colored pigment that forms a pattern are laminated on a film. The compatibility between the film and each printed layer is also important.
• an ink such as dispersibility, fluidity and printability
• it also has improved adhesion to various substrates, laminate strength, and retort suitability, and is free of chlorine-based resins as a binder. It is by no means easy to improve environmental responsiveness by realizing
• the inventors of the present invention have conducted various studies on the application of various pigments using the techniques described in Patent Documents 2 and 3 to printed matter having a plurality of printed layers and laminated laminates. As a result, it was found that when a white printed layer was formed using a specific white pigment, the white printed layer was tinged with yellow, resulting in loss of whiteness in the white color.
• the problem to be solved by the present invention is to maintain the whiteness of the white printed layer without impairing the basic characteristics of the ink such as dispersibility, fluidity, and stability, and to improve environmental safety.
• the purpose is to provide excellent printed matter.
• the present inventors have made intensive studies in order to solve the above problems, and found that using specific pigments for each of the color printed layer and the white printed layer in a printed matter having a plurality of printed layers is effective for solving the problem. Found it.
• the present invention provides a multilayer printed matter in which a white printed layer having a white pigment and at least one color printed layer having a pigment other than the white pigment are laminated on a film substrate, At least one pigment other than the white pigment contains 200 ppm or more of iron element per 100 parts by mass of the pigment,
• the white pigment relates to printed matter containing less than 200 ppm of elemental iron per 100 parts by weight of white pigment.
• the present invention relates to a laminate having the printed matter.
• the present invention it is possible to obtain a printed matter in which the whiteness of the white printed layer is maintained while having the basic properties of ink such as dispersibility, fluidity, stability and adhesion.
• the printed material of the present invention has excellent ink properties such as dispersibility, fluidity, and stability even if it does not contain a chlorine-based resin as a resin used in the printing ink, so it is excellent in environmental safety. You get a print.
• the liquid ink composition refers to a liquid printing ink, such as gravure ink or flexo ink, which is applied to a printing method using a printing plate, preferably gravure ink or flexo ink.
• the liquid ink of the present invention does not contain an active energy curable component, that is, it is a liquid ink non-reactive to active energy rays.
• Ink used in the following explanation all means “printing ink”.
• parts indicate “mass parts”
• ink total amount indicates the total amount of ink containing all volatile components such as organic solvents
• ink solid content total amount refers to volatile components. indicates the total amount of non-volatile components only, excluding
• the printed matter of the present invention is a multi-layered printed matter in which a white printed layer containing a white pigment and a color printed layer containing at least one pigment other than the white pigment are laminated.
• the white printed layer is formed from a liquid ink composition containing a white pigment
• the color printed layer is formed from a liquid ink composition containing a pigment other than the white pigment.
• a liquid ink composition containing a coloring pigment contains a coloring pigment, a binder resin, an organic solvent, water and various additives as necessary.
• the liquid ink composition forming the color print layer contains at least a pigment (color pigment) other than the white pigment containing 200 ppm or more of iron element per 100 parts by mass of the pigment.
• the coloring pigment used in the color printing layer of the present invention can improve the dispersion stability of the ink using this pigment by subjecting the surface of the pigment particles to iron element introduction treatment.
• the coloring pigment is not particularly limited as long as it is other than the white pigment described later, and examples include inorganic pigments and organic pigments used in general inks, paints, recording agents, and the like.
• organic pigments include condensed polycyclic organic pigments having a cyclic structure having a benzene ring or a heterocyclic ring, and azo pigments. Specific examples of preferred organic pigments are given below.
• azo pigments include C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 112, C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 12, C.I. I. Pigment Red 136, C.I. I. Pigment Red 14, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I.
• Pigment Red 15 C.I. I. Pigment Red 150, C.I. I. Pigment Red 16, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 17, C.I. I. Pigment Red 170, C.I. I. Pigment Red 171, C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 18, C.I. I. Pigment Red 183, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 193, C.I. I.
• Pigment Red 2 C.I. I. Pigment Red 200, C.I. I. Pigment Red 208, C.I. I. Pigment Red 21, C.I. I. Pigment Red 210, C.I. I. Pigment Red 211, C.I. I. Pigment Red 213, C.I. I. Pigment Red 214, C.I. I. Pigment Red 22, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 23, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 242, C.I. I. Pigment Red 243, C.I. I. I.
• Pigment Yellow 154 C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 165, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 167, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 169, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 170, C.I. I. Pigment Yellow 172, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 176, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I.
• Pigment Yellow 183 C.I. I. Pigment Yellow 191, C.I. I. Pigment Yellow 191:1, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 205, C.I. I. Pigment Yellow 206, C.I. I. Pigment Yellow 209, C.I. I. Pigment Yellow 212, C.I. I. Pigment Yellow 214, C.I. I. Pigment Yellow 219, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 4, C.I. I. Pigment Yellow 49, C.I. I. Pigment Yellow 5, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 6, C.I. I.
• Pigment Orange 46 C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 60, C.I. I. Pigment Orange 62, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 74, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 32, C.I. I. Pigment Brown 5, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 17, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 50 may be mentioned, and may be used alone or in combination.
• C.I. I. Pigment Red 57:1 PR57:1
• C.I. I. Pigment Red 146 PR146
• C.I. I. Pigment Yellow 13 PY13
• C.I. I. Pigment Yellow 55 PY55
• C.I. I. Pigment Yellow 83 PY83
• C.I. I. Pigment Yellow 180 PY180
• C.I. I. Pigment Range 13 PO13
• the primary particle size of the azo pigment is, for example, 0.01 to 1.0 ⁇ m, preferably 0.1 to 0.6 ⁇ m.
• the specific surface area of the azo pigment is, for example, 10 to 150 m2/g, preferably 20 to 100 m2/g. When the primary particle size and specific surface area are within the above ranges, the pigment can have excellent coloring power and dispersibility.
• a condensed polycyclic organic pigment can also be mentioned.
• the condensed polycyclic organic pigment means an organic pigment having a cyclic structure having a benzene ring or a heterocyclic ring.
• Examples of condensed polycyclic organic pigments used in the present invention include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:5, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17, C.I.
• Pigment Red 260 and other isoindoline pigments C.I. I. Pigment Red 88, C.I. I. Pigment Red 181, C.I. I. Pigment Red 279, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 38 and other thioindigo pigments, C.I. I. Pigment Red 83, C.I. I. Pigment Red 89, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 182, C.I. I. Pigment Red 216, C.I. I. Pigment Red 226, C.I. I. Pigment Red 251, C.I. I. Pigment Red 263, C.I. I.
• Pigment Blue 60 C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 99, C.I. I. Pigment Yellow 108, C.I. I. Pigment Yellow 123, C.I. I. Pigment Yellow 199, C.I. I. Pigment Violet 31, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 51, C.I. I. Pigment Violet 5:1, C.I. I. Pigment Black 20 and other anthraquinone pigments, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 231 and other quinophthalone pigments, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, C.I. I.
• Pigment Orange 81 C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 270, C.I. I. Pigment Red 272 and other diketopyrrolopyrrole pigments, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 153, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 68, C.I. I. Pigment Red 257, C.I. I. Pigment Red 271, C.I. I. Pigment Green 8, C.I. I. Metal complex pigments such as Pigment Green 10 and the like are included.
• the condensed polycyclic organic pigment used in the present invention a commercially available product may be used, or it may be produced by a known and commonly used method and used. Of course, it may be used by appropriately adding known treatments after production, for example, pigment derivative treatment, surfactant treatment, rosin treatment, and resin treatment may be added before use. Furthermore, the pigment particle size, particle morphology, and particle surface charge may be adjusted and controlled for printing inks, paints, colored moldings, stationery, textile printing, toners, color filters, inkjet inks, and cosmetics.
• the specific surface area according to the method is preferably in the range of 20 to 130 m 2 /g, more preferably in the range of 50 to 100 m 2 /g.
• Non-white inorganic pigments include, for example, carbon black, aluminum particles, mica (mica), bronze powder, chromium vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, Prussian blue, and zircon.
• Aluminum is powder or Although it is in the form of a paste, it is preferable to use it in the form of a paste from the viewpoints of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and density.
• carbon black can be used as carbon black, and usable carbon black is not particularly limited, and oil furnace black, gas furnace black, channel black, channel black, produced by contact method, furnace method, thermal method, etc. Various commercially available products such as acetylene black may be used.
• the particle size of carbon black is, for example, 5 to 200 nm, preferably 20 to 50 nm.
• the nitrogen adsorption specific surface area of carbon black is, for example, 20 to 500 m 2 /g, preferably 30 to 150 m 2 /g.
• Carbon black has a DBP oil absorption of, for example, 20 to 150 cm 3 /100 g, preferably 30 to 120 cm 3 /100 g.
• Volatile content of carbon black is, for example, 0.1 to 10.0%.
• the pH value of carbon black is, for example, 1-10, preferably 2-.
• Examples of the commercially available carbon black include MA7, 8, 11, 77, 100, 100R, 100S, 220, 230, 600, #650, #750, #40, #44B, #44, #45B, # 47, #45, #33, #45L, #47, #50, #52, #2700, #2650, #2600, #200, #2350, #2300, #2200, #1000, #990, #980, #970, #960, #950, #900, #850, #32, #30, #25, #20, #10, #5, CF9, #95, #260 (manufactured by Mitsubishi Chemical Corporation), " Special Black6, 5, 4A, 4, 101, 550, 350, 250, 100", "Printex U, 150T, V, 140V, 140U”, "PrintX P, L6, L, G, ES23, ES22, A, 95 , 90, 85, 80, 75, 60, 55, 45, 40, 35, 300, 30, 3, 25, 200", "Color Black S170, S160,
• a coloring pigment containing 200 ppm or more of iron element per 100 parts by mass of pigment is obtained by adding the above-mentioned coloring pigment to a solvent and stirring to obtain a pigment slurry, and adding an iron compound and an oxidizing agent to the pigment slurry and stirring. It is obtained through a pigment surface treatment step of treating the surface of the pigment and a step of filtering the reaction solution and drying and pulverizing the filtrate.
• Water and/or an organic solvent can be used as the solvent, and methanol, ethanol, n-propanol, i-propanol, etc. can be used as the organic solvent.
• Water is particularly preferred from the point of view of economy.
• the water may be pure water or industrial water, and furthermore, acetate buffer, phosphate buffer, citrate buffer, citrate phosphate buffer, borate buffer, tartrate buffer. You may use buffers, such as.
• the amount of the coloring pigment to be added as a raw material is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the solvent. When the amount added is small, the productivity is low. 2 to 20 parts by mass is more preferable, and 3 to 12 parts by mass is particularly preferable.
• iron compounds iron sulfate, iron chloride, iron fluoride, iron bromide, iron iodide, iron nitrate, iron phosphate, iron borate, iron carbonate, iron acetate, etc. can be used. Iron sulfate, iron chloride, and iron nitrate are preferred from the point of view of economy. As iron, bivalent or trivalent iron can be used. Also, the iron compound may be either an anhydride or a hydrate.
• the temperature in the pigment slurry manufacturing process is preferably 0°C to 100°C.
• the temperature in the pigment surface treatment step is preferably 0° C. to 100° C. Since the reaction rate of the pigment surface treatment reaction is slow at low temperatures and the decomposition of hydrogen peroxide is promoted at high temperatures, 10° C. to 90° C. is preferred. More preferably, 20°C to 80°C is particularly preferred.
• the reaction time for the pigment surface treatment step is preferably 10 minutes to 2 hours.
• the pH of the treatment liquid in the pigment surface treatment step is preferably pH 1 to 7, since iron ions are precipitated due to alkalinity.
• oxidizing agent hydrogen peroxide, permanganate, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, peroxodisulfate, chromic acid, dichromic acid, ozone, etc.
• hydrogen peroxide diluted with water to a concentration of 20 to 50% by mass is preferred.
• the amount of the oxidizing agent to be used may vary depending on the concentration as long as it is suitable for the oxidation reaction.
• the iron compound is preferably added in an amount of 1 to 30% by mass, preferably 2 to 15% by mass, based on the raw condensed polycyclic organic pigment.
• the iron compound and the oxidizing agent may be added to the pigment slurry at the same time or separately. When they are added at the same time, the iron compound and the oxidizing agent may be mixed in advance and then added. When adding them separately, the iron compound may be added first, or the oxidizing agent may be added first. Also, the oxidizing agent may be added dropwise, or may be added all at once.
• iron is introduced onto the surface of the pigment and contains 200 ppm or more of elemental iron per 100 parts by mass of the pigment.
• the surface of the coloring pigment particles of the present invention is covered with an iron-containing compound, and by increasing the hydrophilicity of the particle surface compared to an untreated pigment, the wettability to solvents increases, the wettability increases, and the dispersibility improves. presumed to be excellent.
• the surface-treated coloring pigment preferably contains 200 ppm or more of iron element per 100 parts by mass of the coloring pigment, preferably 230 ppm or more, more preferably 500 ppm or more, and more preferably 1000 ppm or more.
• the upper limit of the iron element contained in the coloring pigment is not particularly limited, but the iron element content is preferably 20000 ppm or less, more preferably 18000 ppm or less, and even more preferably 15000 ppm or less per 100 parts by mass. More specifically, when an azo pigment is used, the iron element content is preferably 200 ppm or more, preferably 500 ppm or more, more preferably 1000 ppm or more, and 3000 ppm or more per 100 parts by mass of the azo pigment.
• the iron element content is preferably 20000 ppm or less, more preferably 18000 ppm or less, and even more preferably 15000 ppm or less per 100 parts by mass of the azo pigment.
• carbon black it preferably contains 200 ppm or more of iron element per 100 parts by mass of carbon black, preferably 500 ppm or more, more preferably 1000 ppm or more, and 3000 ppm or more. It is more preferable.
• the iron element content is preferably 20000 ppm or less, more preferably 18000 ppm or less, and even more preferably 15000 ppm or less per 100 parts by mass of carbon black.
• the iron element is not limited to iron alone (Fe), but may be in the form of iron compounds such as iron oxides (FeO , Fe2O3, etc.) and iron hydroxides (Fe(OH) 2 , Fe(OH) 3 , etc.). may The above content of elemental iron can be measured as the amount of elemental iron even in such an iron compound.
• the amount of iron element contained in the coloring pigment can be measured using an energy dispersive X-ray fluorescent spectrometer, PANalytical Epsilon 5 (manufactured by Spectris Co., Ltd.).
• the color pigment used in the present invention preferably has a base adsorption amount of 0.30 ⁇ mol/m 2 or more per surface area of the pigment in order to enhance dispersibility in a solvent.
• the base adsorption amount per surface area of the pigment is more preferably 0.35 ⁇ mol/m 2 or more, more preferably 0.40 ⁇ mol/m 2 or more, and more preferably 0.50 ⁇ mol/m 2 or more. is more preferably 0.60 ⁇ mol/m 2 or more, more preferably 0.75 ⁇ mol/m 2 or more, and even more preferably 1 ⁇ mol/m 2 or more.
• the upper limit of the base adsorption amount is not particularly limited, but is preferably 2.00 ⁇ mol/m 2 or more.
• the amount of base adsorption contained in the pigment is measured by, for example, adding the pigment to a certain amount of basic solution, allowing the pigment to adsorb the base, and then centrifuging the pigment to settle the pigment and collecting the supernatant solution.
• the amount of base adsorbed per weight of the pigment can be calculated by subtracting the amount of base from the amount of base initially added as the amount of unadsorbed base.
• the base adsorption amount per surface area can be calculated by dividing the base adsorption amount per weight by the nitrogen adsorption specific surface area.
• the amount of the pigment is sufficient to ensure the concentration and coloring power of the liquid ink composition, that is, 1 to 60% by mass of the total mass of the ink, and 10 to 90% by mass of the solid content in the ink. is preferably included in Moreover, a coloring agent can be used individually or in combination of 2 or more types.
• the binder resin is not particularly limited as long as it is usually used for liquid inks such as gravure inks and flexographic inks that are applied to printing methods using printing plates.
• resins include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, polyamide resins, acrylic resins, polyester resins, alkyd resins, Polyvinyl chloride resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, chlorinated rubbers, polyvinyl butyral resins, petroleum resins and the like can be mentioned.
• the ratio of the urethane resin to the total amount of resin in the ink is preferably 50% by mass or more, preferably 60% by mass or more.
• the color printing layer of the present invention uses a coloring pigment containing 200 ppm or more of iron element per 100 parts by mass of the coloring pigment, stable ink dispersibility and fluidity can be obtained regardless of the type of binder resin. be done. Therefore, the safety to the environment and the human body can be improved by using an ink composition that does not use chlorine-based resins such as vinyl chloride-vinyl acetate copolymer resins.
• the polyurethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol and a polyisocyanate.
• a polyol it is preferable to use a polyester polyol, and it is preferable to use a polyester polyol and a polyether polyol.
• the polyester polyol is preferably a polyester polyol obtained by dehydration condensation or polymerization of a low-molecular-weight polyol and a polyvalent carboxylic acid or an anhydride thereof. By introducing an ester group into the polyester polyol to increase the cohesive energy, the lamination strength can be further increased.
• polyester polyol various known compounds having two or more hydroxyl groups that are commonly used for the production of polyester polyols can be used, and one or more of them may be used in combination.
• polyvalent carboxylic acid or an anhydride thereof various known polyvalent carboxylic acids generally used in the production of polyester polyols can be used, and one or more of them may be used in combination.
• Aromatic dicarboxylic acids such as carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and anhydrides of these acids, aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, trimellitic acid and Tricarboxylic acids such as their anhydrides, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid and
• Polyester polyols are polyurethane resins such as polyester polyols obtained by ring-opening polymerization of lactones such as cyclic ester compounds such as polycaprolactone, polyvalerolactone and poly( ⁇ -methyl- ⁇ -valerolactone).
• lactones such as cyclic ester compounds
• Various known polyester polyols generally used in the production of may be used, or one or more of them may be used in combination.
• the number average molecular weight of the polyester polyol is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 7,000, even more preferably in the range of 900 to 6,000. .
• polyether polyol various known polyether polyols that are commonly used in the production of polyurethane resins can be used, and one or more of them may be used in combination.
• examples thereof include polyether polyols of polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide and tetrahydrofuran.
• known general-purpose ones such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used.
• the polyether polyol preferably has a number average molecular weight of 100-3500. If the polyether polyol has a number average molecular weight of less than 100, the polyurethane resin (A) film tends to be hard and the adhesion to the polyester film is lowered. If the number average molecular weight is more than 3,500, the polyurethane resin film tends to be brittle, and the blocking resistance of the ink film is lowered.
• the polyether polyol is preferably contained in the range of 1 to 40% by mass with respect to the polyurethane resin. If the polyether polyol is less than 1 part by mass with respect to 100 parts by mass of the polyurethane resin, the solubility of the polyurethane resin (A) in ketone, ester, and alcohol-based solvents is reduced, resulting in poor adhesion on the high-performance barrier film. tend to decline. In addition, the resolubility of the ink film in the solvent tends to decrease, and the tone reproducibility of the printed matter tends to decrease. On the other hand, if it exceeds 50 parts by mass, the ink film tends to be excessively soft and the anti-blocking property tends to be poor.
• polyurethane resins various known polyols that are generally used in the production of polyurethane resins can be used as combined polyols that are optionally used in polyurethane resins, and one or more of them may be used in combination.
• Diisocyanate compounds used in polyurethane resins include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins.
• Chain extenders used in polyurethane resins include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, 2-hydroxyethylethylenediamine, 2 - hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyropyrethylenediamine, di-2-hydroxypyro Amines having a hydroxyl group in the molecule such as pyrethylenediamine and di-2-hydroxypropylethylenediamine can also be used. These chain extenders can be used alone or in combination of two or more.
• a monovalent active hydrogen compound can also be used as a terminal blocker for the purpose of terminating the reaction.
• examples of such compounds include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol.
• amino acids such as glycine and L-alanine can be used as a reaction terminator, especially when it is desired to introduce a carboxyl group into the polyurethane resin.
• These terminal blocking agents can be used alone or in combination of two or more.
• Polyurethane resins can be prepared, for example, by reacting polypropylene glycol and a polyol used in combination with a diisocyanate compound in a proportion in which the isocyanate groups are excessive to obtain a prepolymer having terminal isocyanate groups, and dissolving the resulting prepolymer in an appropriate solvent, i.e., non- Ester-based solvents such as ethyl acetate, propyl acetate, and butyl acetate, which are commonly used as solvents for toluene-based gravure ink; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methanol, ethanol, isopropyl alcohol, n-butanol, etc.
• an appropriate solvent i.e., non- Ester-based solvents such as ethyl acetate, propyl acetate, and butyl acetate, which are commonly
• the two-step method is preferable for obtaining a uniform polyurethane resin.
• the total (equivalent ratio) of the amino groups of the chain extender and (or) terminal blocker is 1/0.9 to 1.3. is preferred. If the equivalent ratio of the isocyanate group to the amino group is less than 1/1.3, the chain extender and/or the terminal blocker remain unreacted, causing yellowing of the polyurethane resin and odor after printing. may occur. Furthermore, in recent years, from the viewpoint of work environment, it is more preferable not to use aromatic solvents such as toluene and xylene, and ketone solvents.
• the weight average molecular weight of the polyurethane resin thus obtained is preferably within the range of 15,000 to 100,000, more preferably within the range of 15,000 to 80,000.
• the weight-average molecular weight of the polyurethane resin is less than 15,000, the blocking resistance of the resulting ink composition, the strength of the printed film, the oil resistance, etc. tend to be low.
• the viscosity of the resulting ink composition tends to be high and the glossiness of the printed film tends to be low.
• the content of the polyurethane resin used in the liquid ink composition of the present invention in the ink is 4 mass % or more, 5 mass % or more, and 6 mass % or more are preferable. On the other hand, it is preferably 25% by mass or less, preferably 20% by mass or less, and preferably 15% by mass or more from the viewpoint of appropriate ink viscosity and work efficiency during ink production and printing.
• the lower limit of the solid content mass ratio in the ink is preferably 5% by mass, more preferably 10% by mass, more preferably 15% by mass, and 20% by mass. More preferably, it is still more preferably 25% by mass.
• the upper limit of the solid content weight ratio in the ink is preferably 95% by mass, more preferably 90% by mass, more preferably 80% by mass, and more preferably 75% by mass. Preferably, it is more preferably 70% by mass.
• cellulose-based resins include cellulose acetate propionate, cellulose acetate butyrate and other cellulose ester resins, nitrocellulose (also referred to as nitrocellulose), hydroxyalkylcellulose, and carboxyalkylcellulose.
• the cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group and the like. may have a substituent.
• cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable as the cellulose resin.
• the molecular weight a weight average molecular weight of 5,000 to 200,000 is preferable, and 10,000 to 50,000 is more preferable. Further, those having a glass transition temperature of 120° C. to 180° C. are preferable.
• the polyurethane resin (A) of the present invention is used in combination, it can be expected that blocking resistance, scratch resistance and other physical properties of the ink film are improved.
• Nitrocellulose is obtained as a nitric ester obtained by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the 6-membered ring of the anhydride glucopyranose group in natural cellulose with nitric acid groups. preferable.
• polyvinyl butyral resin Dispersibility can be improved by containing a polyvinyl butyral resin as a binder resin.
• a polyvinyl butyral resin (B) known ones can be used without particular limitation.
• a reactant obtained by acetalizing polyvinyl alcohol with butyraldehyde by a known reaction can be used.
• the weight average molecular weight of the polyvinyl butyral resin is preferably 5,000 to 60,000, more preferably 6,000 to 50,000, and even more preferably 7,000 to 40,000.
• the glass transition temperature (hereinafter sometimes referred to as Tg) of the polyvinyl butyral resin is preferably in the range of 50°C to 120°C, more preferably in the range of 55°C to 115°C, more preferably in the range of 60°C to 110°C. preferable.
• the glass transition temperature is obtained by measurement with a differential scanning calorimeter.
• the amount of hydroxyl groups in the polyvinyl butyral resin is preferably in the range of 10-30% by mass, more preferably 15-25% by mass.
• the polyvinyl butyral resin content (solid content of the polyvinyl butyral resin) is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.0% by mass, based on 100% by mass of the ink. Yes, most preferably 0.2 to 3.0% by mass. Adding 0.1% by mass or more of polyvinyl butyral resin tends to maintain the adhesion and transferability of the ink film. can hold
• the lower limit of the solid content weight ratio in the ink is preferably 0.1% by mass, more preferably 0.2% by mass, and most preferably 0.3% by mass.
• the upper limit of the solid content weight ratio in the ink is preferably 16% by mass, more preferably 13% by mass, and most preferably 10% by mass.
• the resin alone can be dispersed, but a dispersant can also be used in combination to further stably disperse the pigment.
• Anionic, nonionic, cationic, and amphoteric surfactants can be used as dispersants.
• a comb-structure polymer compound obtained by adding polyester to polyethyleneimine, or an alkylamine derivative of an ⁇ -olefin maleic acid polymer may be used. Specific examples include Solspers series (ZENECA), Ajisper series (Ajinomoto), Homogenol series (Kao), and the like.
• the dispersant is preferably contained in the ink in an amount of 0.05% by mass or more relative to the total mass of the ink from the viewpoint of ink storage stability, and 5% by mass or less from the viewpoint of lamination suitability, and more preferably 0. .1 to 2% by mass.
• the liquid ink composition further contains a combined resin, extender pigment, pigment dispersant, leveling agent, antifoaming agent, wax, plasticizer, infrared absorber, ultraviolet absorber, fragrance, flame retardant, etc., if necessary. can also be used as a combined resin, extender pigment, pigment dispersant, leveling agent, antifoaming agent, wax, plasticizer, infrared absorber, ultraviolet absorber, fragrance, flame retardant, etc., if necessary. can also
• Organic solvent As the organic solvent used in the liquid ink composition, various organic solvents can be used. For example, aromatic organic solvents such as toluene and xylene; ester solvents such as n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; can be used in mixtures of In recent years, from the viewpoint of work environment, it is more preferable not to use aromatic solvents such as toluene and xylene and ketone solvents.
• aromatic organic solvents such as toluene and xylene
• ester solvents such as n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate
• the liquid ink composition may contain water together with the organic solvent as a volatile component.
• the water content is preferably less than 10% by mass of the total amount of the ink composition.
• Water may be added in advance to the organic solvent to obtain a water-containing organic solvent, or a specific amount of water may be added separately.
• the liquid ink composition is a one-liquid type that does not use a curing agent such as an isocyanate curing agent or a two-liquid type that uses a curing agent, a liquid ink composition with excellent ink dispersibility and fluidity can be obtained.
• a liquid ink composition can be produced by dissolving and/or dispersing a resin, pigment, etc. in an organic solvent.
• an ink can be produced by producing a pigment dispersion by dispersing a pigment in an organic solvent using a polyurethane resin, and blending other compounds into the obtained pigment dispersion as necessary. can.
• the particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the ejection speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to.
• the dispersing machine commonly used roller mills, ball mills, pebble mills, attritors, sand mills and the like can be used.
• the ink contains air bubbles or unexpectedly large particles, it is preferable to remove them by filtration, etc., as this will reduce the quality of the printed matter.
• a conventionally known filter can be used.
• the viscosity of the ink produced by the above method is preferably in the range of 10 mPa ⁇ s or more from the viewpoint of preventing sedimentation of the pigment and appropriately dispersing the pigment, and in the range of 1000 mPa ⁇ s or less from the viewpoint of work efficiency during ink production and printing. preferable.
• the above viscosity is measured at 25° C. with a B-type viscometer manufactured by Tokimec.
• the viscosity of the ink can be adjusted by appropriately selecting the types and amounts of raw materials used, such as polyurethane resins, colorants, and organic solvents. Also, the viscosity of the ink can be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.
• the hues of the liquid ink composition used in the color printing layer include yellow, red, indigo, and black as process basic colors, and red (orange) and grass (grass) as process gamut external colors, depending on the type of pigment used. There are three colors: green) and purple. Further, transparent yellow, peony, vermillion, brown, gold, silver, pearl, almost transparent medium for adjusting color density (including extender pigment if necessary), etc. are prepared as base colors.
• the ink for boiling retort is appropriately selected in consideration of the migration property and heat resistance of the pigment.
• the base ink of each hue is diluted with a diluting solvent to a viscosity and density suitable for gravure printing or flexographic printing, and supplied to each printing unit singly or in combination.
• a liquid ink composition containing a white pigment contains a white pigment, a binder resin, an organic solvent, and optionally water and various additives.
• white pigments examples include titanium oxide, zinc sulfide, lead white, zinc white, litbon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, and silica.
• titanium oxide is preferable from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance, and from the viewpoint of printing performance, the titanium oxide may be treated with silica and/or alumina.
• the white pigment used in the white printed layer of the present invention contains less than 200 ppm of iron element per 100 parts by mass of the white pigment. If it exceeds this range, the white printed layer tends to be yellowish and lose its whiteness. Although the cause of the yellow tint is not clear, it is presumed that the compounds containing iron components are chromatic. Therefore, it is preferable that the amount of iron element is as small as possible, and the iron element is preferably less than 150 ppm, more preferably less than 100 ppm, preferably less than 80 ppm, and less than 60 ppm per 100 parts by mass of the white pigment. is preferably less than 50 ppm, preferably less than 40 ppm, more preferably less than 30 ppm. As such a white pigment, commercially available titanium oxide can be used, and the above-mentioned coloring pigment without surface treatment with an iron compound is applicable.
• the content of the white pigment depends on the desired ink performance, but for white inks that require standard opacity and high plate fogging, the content is usually about 20 to 40% by mass based on the total mass of the ink. On the other hand, in the case of white ink aiming at very high opacity as a required performance, the content may be designed at about 40 to 60% by mass.
• the components other than the white pigment such as the binder resin, the organic solvent, and other additives, may be the same as in the liquid ink composition containing the coloring content described above. can.
• the printed matter of the present invention is a multi-layered printed matter in which a white printed layer and a color printed layer are laminated on a film substrate.
• the white printed layer and the color printed layer can be formed by printing on various film substrates using the liquid ink composition described above, and a gravure printing plate such as an electronic engraving intaglio or an erosion type intaglio is used. While it is useful as an ink for gravure printing or flexographic printing using a flexographic printing plate such as a resin plate, it excludes inks for inkjet systems in which ink is ejected from inkjet nozzles without using a plate.
• the ink droplets ejected from the nozzle directly adhere to the substrate to form a printed matter, whereas the liquid printing ink of the present invention once adheres and transfers the printing ink to the printing plate or printing pattern. After that, only the ink is brought into close contact with the substrate again, and dried as necessary to obtain a printed matter.
• the film substrate is, for example, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polyester resin such as polybutylene naphthalate, nylon 6 , Polyamides such as nylon 66 and nylon 46, polyhydroxycarboxylic acids such as polylactic acid, poly (ethylene succinate), biodegradable resins such as poly (butylene succinate) and other aliphatic polyester resins, polypropylene (CPP: Non-stretched polypropylene film, OPP: biaxially stretched polypropylene film), polyolefins such as polyethylene (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polyimide, polyarylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, ethylene-vinyl Examples include films made of thermoplastic resins such as alcohol cop
• Biomass films are sold by various companies, and for example, sheets listed in the list of certified biomass products described by the Japan Organic Resources Association can be used.
• biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol).
• biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method.
• commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.
• Radiocarbon 14C exists in the atmosphere at a rate of 1 in 1012, and this rate does not change even with carbon dioxide in the atmosphere. Therefore, the carbon of the plant-derived resin contains radioactive carbon 14C. In contrast, the carbon of the fossil fuel-derived resin contains almost no radioactive carbon 14C. Therefore, by measuring the concentration of radioactive carbon 14C in the resin with an accelerator mass spectrometer, the content ratio of the plant-derived resin in the resin, that is, the degree of biomass plasticity can be obtained.
• plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
• plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
• Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866 include, for example, Braskem's product names "SBC818" and "SPB608". "SBF0323HC”, “STN7006”, “SEB853", “SPB681” and the like can be mentioned, and films using these as raw materials can be preferably used.
• films containing biomass polyester, biomass polyethylene terephthalate, etc. having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It has been known.
• the dicarboxylic acid unit of biomass polyester uses the dicarboxylic acid derived from a fossil fuel.
• dicarboxylic acids aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation.
• a difunctional oxycarboxylic acid In addition to the above diol component and dicarboxylic acid component, a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride. It may also be a copolymerized polyester in which a copolymerization component is added as a third component such as at least one polyfunctional compound selected from the group consisting of polycarboxylic acids and tri- or more functional oxycarboxylic acids.
• biomass polyolefin films such as biomass polyethylene films containing polyethylene resins made from biomass-derived ethylene glycol, biomass polyethylene-polypropylene films, etc. Films are also known.
• the polyethylene-based resin is not particularly limited except that the biomass-derived ethylene glycol is used as a part of the raw material.
• ethylene- ⁇ -olefin copolymer containing 90% by mass or more of units ethylene- ⁇ -olefin copolymer containing 90% by mass or more of units), and these can be used alone or in combination of two or more.
• the ⁇ -olefin constituting the copolymer of ethylene and ⁇ -olefin is not particularly limited, and may be 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, or the like having 4 to 10 carbon atoms. 8 ⁇ -olefins.
• Known polyethylene resins such as low density polyethylene resins, medium density polyethylene resins and linear low density polyethylene resins can be used.
• linear low-density polyethylene resin (a copolymer of ethylene and 1-hexene, or ethylene and 1-octene) are preferred, and linear low density polyethylene resins having a density of 0.910 to 0.925 g/cm3 are more preferred.
• Films and sheets containing starch which is a biomass raw material, and polylactic acid are also known. These can be appropriately selected and used depending on the application.
• the biomass film may be a laminate obtained by laminating a plurality of biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film.
• These petroleum-based films and biomass films are produced by laminating vapor-deposited layers of metals such as aluminum, metal oxides such as silica and alumina, using metal foils, etc., using polyvinyl alcohol, ethylene-vinyl alcohol copolymer, A barrier film containing a gas barrier layer such as vinylidene chloride may be used in combination, or may be coated with polyvinyl alcohol or the like. By using such a film, it is possible to obtain a laminate having a high barrier property against water vapor, oxygen, alcohol, inert gas, volatile organic matter (fragrance), and the like.
• these films may be unstretched films or stretched films, and the manufacturing method is not limited.
• a stretching treatment method it is common to melt-extrude a resin into a sheet by an extrusion film-forming method or the like, and then subject the sheet to simultaneous biaxial stretching or sequential biaxial stretching.
• sequential biaxial stretching it is common to first perform longitudinal stretching and then laterally stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
• the thickness of the base film is not particularly limited, but it is usually in the range of 1 to 500 ⁇ m.
• Various surface treatments such as flame treatment and corona discharge treatment may be applied to the surface of the film, if necessary, so that an adhesive layer free from defects such as film tearing and repelling is formed.
• a printing method known printing methods such as gravure printing and flexographic printing can be used, but printing by the gravure printing method is particularly preferable.
• the above printing method that is, after the printing ink is once adhered and transferred to the printing plate or printing pattern, the ink alone is adhered to the substrate again, and if necessary, dried or cured in an oven to fix the printed matter.
• the film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the liquid printing ink of the present invention is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
• the liquid ink composition described above can be preferably used as ink for surface printing, ink for reverse printing, or ink for lamination on a film substrate.
• an overprint varnish layer can be provided separately.
• an anchor coat varnish layer can be separately provided.
• the order in which the color printed layer and the white printed layer are provided is not particularly limited, and may be laminated in the order of film substrate/color printed layer/white printed layer, or film substrate/white printed layer/color printed layer. Layers may be laminated in order.
• the color printed layer can form a pattern with a coloring agent
• the second white printed layer formed with a liquid printing ink containing a white pigment
• the third printed layer can be used as the background of the pattern. can be done.
• the other printed layer may have, for example, a white pigment.
• the laminate of the present invention is a laminate obtained by laminating a plurality of substrates and having a printed layer of the liquid printing ink of the present invention on at least one of the substrates.
• the substrates can be bonded together with an adhesive or laminated by extrusion lamination.
• Base film 1/printed layer/adhesive layer 1/sealant film (2) Base film 1/printed layer/adhesive layer 1/metal deposition unstretched film (3) Base film 1/printed layer/adhesive layer 1/metal vapor deposition stretched film (4) transparent vapor deposition stretched film/printing layer/adhesive layer 1/sealant film (5) base film 1/printing layer/adhesive layer 1/base film 2/adhesive layer 2/sealant film ( 6) Base film 1/printed layer/adhesive layer 1/metal vapor deposition stretched film/adhesive layer 2/sealant film (7) Base film 1/printed layer/adhesive layer 1/transparent vapor deposited stretched film/adhesive layer 2/sealant Film (8) Base film 1/printed layer/adhesive layer 1/metal layer/adhesive layer 2/sealant film
• base film 1/and printed layer corresponds to the above printed matter having a white printed layer and a color printed layer on a film base.
• base film 1 a configuration in which a printed layer is provided on the surface of the base film 1 on the side of the adhesive layer 1 is described, but the surface (surface) of the base film 1 opposite to the adhesive layer 1 A printed layer may be provided on the substrate film 2 , or a configuration in which the printed layer is provided on the base film 2 may be employed.
• Examples of the base film 1 used in configuration (1) include OPP film, PET film, nylon film (hereinafter also referred to as Ny film), and the like. Further, as the base film 1, a film coated for the purpose of improving gas barrier properties, ink receptivity when providing a printing layer described later, and the like may be used. Commercial products of the coated base film 1 include K-OPP film and K-PET film. Examples of sealant films include CPP films and LLDPE films.
• Examples of the base film 1 used in configurations (2) and (3) include OPP films and PET films.
• a VM-CPP film obtained by vapor-depositing a metal such as aluminum on a CPP film may be used as the unstretched metal vapor-deposited film, and a VM-OPP film obtained by vapor-depositing a metal such as aluminum on an OPP film may be used as the stretched metal-deposited film. can be done.
• Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on OPP films, PET films, nylon films, or the like.
• a film obtained by coating the deposition layer may be used.
• Examples of the sealant film include those similar to those of the configuration (1).
• Examples of the base film 1 used in the configuration (5) include PET film and the like. Examples of the base film 2 include a nylon film. Examples of the sealant film include those similar to those of the configuration (1).
• Examples of the base film 1 of configuration (6) include the same ones as those of configurations (2) and (3).
• Examples of the metal-deposited oriented film include VM-OPP film and VM-PET film obtained by subjecting an OPP film or PET film to metal deposition such as aluminum.
• Examples of the sealant film include those similar to those of the configuration (1).
• Examples of the base film 1 of configuration (7) include a PET film and the like.
• Examples of the transparent vapor-deposited stretched film include those similar to those of the configuration (4).
• Examples of the sealant film include those similar to those of the configuration (1).
• Examples of the base film 1 of configuration (8) include a PET film and the like. Aluminum foil etc. are mentioned as a metal layer. Examples of the sealant film include those similar to those of the configuration (1).
• Examples of the base film 1 of configurations (9) and (10) include PET films.
• Examples of the base film 2 include a nylon film. Aluminum foil etc. are mentioned as a metal layer.
• Examples of the sealant film include those similar to those of the configuration (1).
• a known adhesive for film lamination can be appropriately used for the adhesive layer.
• a known anchor coating agent for extrusion lamination can be appropriately used as an adhesion aid. When materials having gas barrier properties are used as these adhesives and anchor coating agents, laminates having particularly excellent barrier properties can be obtained.
• the cured coating film of the adhesive applied at 3 g/m 2 (solid content) has an oxygen barrier property of 300 cc/m 2 /day/atm or less, or a water vapor barrier property of 120 g/m 2 /day/atm or less. It means that it satisfies at least one condition of m 2 /day or less.
• Examples of commercially available products include "PASLIM” series such as PASLIM VM001 and PASLIM J350X manufactured by DIC Corporation, and "Maxieve” manufactured by Mitsubishi Gas Chemical Company.
• the adhesive layer can use any known material without any particular limitation, but preferably contains a cured product of a polyol and an isocyanate compound.
• these polyols and/or isocyanate compounds contain biomass-derived components, a laminate having a high degree of biomass can be obtained, and the environmental load can be reduced.
• adhesion promoters may be contained in advance to either one or both of the polyol composition (A) and the polyisocyanate composition (B), or may be added to the polyol composition (A) and the polyisocyanate composition ( B) may be added when mixing.
• the gas barrier adhesive to be used may be either solvent type or non-solvent type.
• the adhesive of the present invention is applied onto the printed layer surface printed on the first substrate using a roll such as a gravure roll, and heated in an oven or the like. After evaporating the organic solvent, the other substrate is attached to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 80° C., and the aging time is preferably 12 to 240 hours.
• the adhesive of the present invention preheated to about 40° C. to 100° C. is applied onto the surface of the printed layer printed on the first substrate by a gravure roll or the like. After the application using the roll of No. 2, the other substrate is immediately laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.
• the adhesion aid of the present invention is applied onto the surface of the printed layer printed on the first base material using a roll such as a gravure roll, and then dried in an oven or the like. After volatilizing the organic solvent by heating, the laminate of the present invention is obtained by laminating the polymer material melted by an extruder.
• Polyolefin-based resins such as low-density polyethylene resin, linear low-density polyethylene resin, and ethylene-vinyl acetate copolymer resin are preferable as the polymer material to be melted.
• the aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.
• the coating amount of the gas barrier adhesive to be used is appropriately adjusted.
• the solid content is adjusted to 1 g/m 2 or more and 10 g/m 2 or less, preferably 2 g/m 2 or more and 5 g/m 2 or less.
• the coating amount of the adhesive is, for example, 1 g/m 2 or more and 5 g/m 2 or less, preferably 1 g/m 2 or more and 3 g/m 2 or less.
• the coating amount is appropriately adjusted, and is, for example, 0.03 g/m 2 or more and 2 g/m 2 or less (solid content).
• the laminate of the present invention may be used alone or may further contain other films or substrates.
• other substrates in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather can also be used.
• the adhesive used when bonding other substrates may or may not be a gas barrier adhesive as described above.
• the printed matter and laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and the like.
• the layer structure may vary depending on the contents, usage environment, and usage pattern.
• the packaging material of the present invention can be obtained, for example, by using the laminate of the present invention, superimposing the sealant film surfaces of the laminate on each other, and then heat-sealing the peripheral edges.
• the laminate of the present invention is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is sealed, for example, by a side seal type, a two-sided seal type, There are three-side seal type, four-side seal type, envelope seal type, palm-joint seal type, pleated seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-sealing methods. be done.
• the packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use.
• a self-supporting packaging material (standing pouch) or the like is also possible.
• As a heat sealing method known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.
• the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
• the use of the packaging material is not particularly limited, but it can be suitably used for food packaging, pharmaceuticals, sanitary, cosmetics, electronic materials, building materials, industrial materials, and the like.
• Contents to be filled include rice crackers, bean confections, nuts, biscuits, cookies, wafer confections, marshmallows, pies, half-baked cakes, candies, snacks, bread, snack noodles, instant noodles, dried noodles, and pasta.
• aseptic packaged rice, rice porridge, rice porridge, packaged mochi, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, mushrooms, konjac, processed wild plants, jams, peanut cream, salads, frozen Vegetables, processed agricultural products such as processed potatoes, processed hams, bacon, sausages, processed chicken products, processed livestock products such as corned beef, fish hams and sausages, fish paste products, kamaboko, seaweed, tsukudani, bonito flakes, salted fish, Processed marine products such as smoked salmon and cod roe, fruits such as peaches, mandarin oranges, pineapples, apples, pears and cherries, vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes, hamburgers, and meat.
• Frozen and chilled prepared foods such as bowls, fried seafood, gyoza, and croquettes, prepared foods such as chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as infant formula powder, liquid seasonings, and retort pouches
• prepared foods such as chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as infant formula powder, liquid seasonings, and retort pouches
• Examples include foods such as curry and pet food. It can also be used as a packaging material for cigarettes, disposable body warmers, medicines, supplements, infusion packs, vacuum insulation materials, and the like.
• the amount of iron element contained in the pigment was measured using an energy dispersive X-ray fluorescent spectrometer, PANalytical Epsilon 5 (manufactured by Spectris Co., Ltd.).
• the amount of base adsorption per surface area of the pigment was measured by the following method. About 100 mg of the pigment was weighed into a 50 mL polyethylene wide-mouthed bottle together with 15 mL of the base solution for adsorption, and mixed and stirred with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) (750 cpm, 15 minutes). Subsequently, the pigment was sedimented by centrifugation (3500 G, 20 minutes) using a cooling high-speed centrifuge H-2000B (manufactured by Kokusan Co., Ltd.), and then 10 mL of the supernatant was collected.
• a paint shaker manufactured by Toyo Seiki Seisakusho Co., Ltd.
• tetra-n-butylammonium hydroxide solution N/10 (benzene/methanol solution) (manufactured by Kanto Kagaku Co., Ltd.), whose factor value is known, was mixed with acetic acid. It was prepared by diluting with n-propyl (manufactured by Kanto Kagaku 20 Co., Ltd.) to exactly 1/100.
• an acid solution for titration about 95 mg of p-toluenesulfonic acid monohydrate (manufactured by Kanto Chemical Co., Ltd.) is dissolved in 500 mL of n-propyl acetate (manufactured by Kanto Chemical Co., Ltd.), and the above-mentioned adsorption base is dissolved. The solution was used after titration of concentration.
• Pigment Blue 15:3 slurry is transferred to a 5 L stainless steel cup, 2127 parts of ion-exchanged water is added, and iron (II) sulfate heptahydrate (Fujifilm Wako Pure Yaku Co., Ltd.) was added and dissolved, and the temperature was raised to 60°C. Subsequently, 54 parts of 35% hydrogen peroxide solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added and stirred for 2 hours.
• the slurry was subjected to Nutsche filtration, washed with 12 L of hot water at 70° C., and then dried with a constant temperature blow dryer WFO-500 (manufactured by Tokyo Rikakikai Co., Ltd.) (98° C., 18 hours).
• the resulting pigment mass was pulverized to obtain 150 parts of copper phthalocyanine pigment (PB15:3-1).
• the amount of iron element contained in the pigment was 3530 ppm.
• the amount of base adsorption per surface area of the pigment was 0.57 ⁇ mol/m 2 .
• Pigment Blue 15:3 slurry is filtered by Nutsche, washed with 12 L of hot water at 70 ° C., and the filter cake is dried in a constant temperature blow dryer WFO-500 (manufactured by Tokyo Rikaki Co., Ltd.) (98 ° C., 18 hours). bottom.
• the resulting pigment mass was pulverized to obtain 150 parts of copper phthalocyanine pigment (PB15:3-2).
• the amount of iron element contained in the pigment was 155 ppm.
• the amount of base adsorption per surface area of the pigment was 0.0 ⁇ mol/m 2 .
• the coupling reaction was terminated by stirring at 10° C. for 60 minutes to obtain a dye suspension. Subsequently, 77 parts of a 10% Na salt solution of gum rosin (7.7 parts as gum rosin) were added to the resulting dye suspension. After stirring for 30 minutes, a liquid prepared by dissolving 37.4 parts of 72% calcium chloride in 40 parts of water was added, and the mixture was stirred for 60 minutes to complete lake formation. After completion of the lake-forming reaction, the mixture was stirred while being heated at 25° C. for 90 minutes to obtain an aqueous suspension of a calcium lake diazo pigment (C.I. Pigment Red 57:1).
• a calcium lake diazo pigment C.I. Pigment Red 57:1
• the pH of the reaction solution was adjusted to 8.0 with a 25% aqueous solution of caustic soda, 120 parts of 35% aqueous calcium chloride solution was added, and the mixture was stirred for 30 minutes, filtered, washed with water, dried at 110°C for a whole day and night, and pulverized.
• PR57:1-1 consisting of Pigment Red 57:1, was obtained.
• the amount of elemental iron contained in PR57:1-1 was 13780 ppm.
• the amount of base adsorption per surface area of the pigment was 0.80 ⁇ mol/m 2 .
• the coupling reaction was terminated by stirring at 10° C. for 60 minutes to obtain a dye suspension. Subsequently, 77 parts of a 10% Na salt solution of gum rosin (7.7 parts as gum rosin) were added to the resulting dye suspension. After stirring for 30 minutes, a solution obtained by dissolving 37.4 parts of 72% calcium chloride in 40 parts of water and 6.0 parts of iron (II) sulfate heptahydrate were added, and the mixture was stirred for 60 minutes to complete lake formation. . After completion of the lake-forming reaction, the mixture was stirred while being heated at 25° C. for 90 minutes to obtain an aqueous suspension of a calcium lake diazo pigment (C.I. Pigment Red 57:1).
• a calcium lake diazo pigment C.I. Pigment Red 57:1
• the coupling reaction was terminated by stirring at 10° C. for 60 minutes to obtain a dye suspension. Subsequently, 77 parts of a 10% Na salt solution of gum rosin (7.7 parts as gum rosin) were added to the resulting dye suspension. After stirring for 30 minutes, a liquid prepared by dissolving 37.4 parts of 72% calcium chloride in 40 parts of water was added, and the mixture was stirred for 60 minutes to complete lake formation. After completion of the lake-forming reaction, the mixture was stirred while being heated at 25° C. for 90 minutes to obtain an aqueous suspension of a calcium lake diazo pigment (C.I. Pigment Red 57:1).
• a calcium lake diazo pigment C.I. Pigment Red 57:1
• a wet cake of Pigment Red 146 was obtained. After drying the wet cake at 110° C. for a whole day and night, it was pulverized to give C.I.
• a comparative PR146-2 consisting of Pigment Red 146 was obtained. The amount of elemental iron contained in comparative PR146-2 was 61 ppm. Also, the amount of base adsorption per surface area of the pigment was 0.10 ⁇ mol/m 2 .
• the slurry of Pigment Violet 23 was transferred to a 5 L stainless steel cup, and while stirring with a stainless steel anchor blade rotating at 150 rpm, 0.57 parts of iron (II) sulfate heptahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. It was added and dissolved, and the temperature was raised to 60°C. Subsequently, 12.5 parts of 35% hydrogen peroxide solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added, and after stirring for 1 hour, 0.57 parts of iron (II) sulfate heptahydrate was additionally added, Stirred for an additional hour.
• iron (II) sulfate heptahydrate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• the slurry was subjected to Nutsche filtration, washed with 12 L of hot water at 70° C., and then dried with a constant temperature blow dryer WFO-500 (manufactured by Tokyo Rikakikai Co., Ltd.) (98° C., 18 hours).
• the resulting pigment mass was pulverized to obtain 50 parts of a dioxazine pigment (PV23-1).
• the amount of iron element contained in the pigment was 240 ppm.
• the amount of base adsorption per surface area of the pigment was 1.06 ⁇ mol/m 2 .
• CB-1 carbon black-1
• the amount of elemental iron contained in CB-1 was 8590 ppm (0.8590%).
• the amount of base adsorption per surface area of the pigment was 0.69 ⁇ mol/m 2 .
• % urethane prepolymer was prepared, 68.7 parts of ethyl acetate was added thereto to obtain a uniform solution of urethane prepolymer.
• the urethane prepolymer solution was added to a mixture of 7.83 parts of isophoronediamine, 0.11 parts of di-n-butylamine, 136.8 parts of ethyl acetate and 110.7 parts of isopropyl alcohol, and the mixture was heated at 45°C for 5 hours. After reacting with stirring for hours, a polyurethane resin solution P-1 was obtained.
• the resulting polyurethane resin solution P-1 had a resin solid content concentration of 30.4% by weight and a resin solid content Mw of 54,000. 11.4% by weight of polyethylene glycol (15.5 parts) is contained as polyether polyol in polyurethane resin (137.76 parts in total).
• Example 1 Liquid ink composition containing white pigment 30 parts of polyurethane resin solution P1 (solid content: 30%), 1 part of maleic acid resin solution M (solid content: 50%), cellulose acetate propionate resin solution Ca (solid content: 20%), 36 parts of titanium oxide JR-780 (manufactured by Tayka Co., Ltd.), and 30 parts of ethyl acetate, totaling 100 parts, was added to a mixture of Dyno Mill (manufactured by Willie E. Baccophenon). and kneaded to prepare a liquid ink.
• the titanium oxide used in Example 1 was not treated to introduce iron onto the surface of the pigment, and iron was not detected. Also, the amount of base adsorption per surface area of the pigment was 0.0 ⁇ mol/m 2 .
• Examples 2 and 3 and Comparative Examples 1 and 2 For Examples 2 and 3 and Comparative Examples 1 and 2, liquid inks were produced in the same procedure as in Example 1 with the formulations shown in Tables 1-1.
• the titanium oxide used in Example 2 was not treated to introduce iron onto the surface of the pigment, and the amount of elemental iron contained in the titanium oxide of Example 2 was 25 ppm. Also, the amount of base adsorption per surface area of the pigment was 0.0 ⁇ mol/m 2 .
• the obtained liquid ink was evaluated by the following test methods.
• ⁇ Pigment Dispersibility> (Millbase fluidity after kneading) The viscosities of the inks described in Examples and Comparative Examples were measured with a Brookfield viscometer at rotation speeds of 6 rpm and 60 rpm. The TI value was obtained by dividing the viscosity measured at 6 rpm by the viscosity measured at 60 rpm. If the TI value is less than 3.0, it can be used practically. ⁇ : TI value is less than 1.5 ⁇ : TI value is 1.5 or more to less than 3.0 ⁇ : TI value is 3.0 or more (dispersion stability) After allowing the inks described in Examples and Comparative Examples to stand at 25° C. for one week, the degree of separation and sedimentation was evaluated.
• the experimental collars 1 to 3 using untreated titanium oxide were not affected by yellowing and were excellent in pigment dispersibility and dispersion stability.
• Example 4 Liquid ink composition containing color pigment 40 parts of polyurethane resin solution P1 (solid content: 30%), 1 part of maleic acid resin solution M (solid content: 50%), cellulose acetate propionate resin solution Ca (solid content: 20%), 10 parts of the copper phthalocyanine pigment (PB 15:3) obtained in Preparation 1, and 46 parts of ethyl acetate (a total of 100 parts) was added to a Dyno Mill (manufactured by Willie & E. Bacchofenon Co., Ltd.). was kneaded using to prepare a liquid ink.
• Dyno Mill manufactured by Willie & E. Bacchofenon Co., Ltd.
• Examples 5-9 and Comparative Examples 3-6 For Examples 5 to 9 and Comparative Examples 3 to 6, liquid inks were produced in the same manner as in Example 4 with the formulations shown in Tables 2 and 3.
• the pigment dispersibility (millbase fluidity and storage stability after kneading) was evaluated by the same evaluation method as in Example 1 above.
• the viscosities of the liquid inks of Examples 4 to 9 and Comparative Examples 3 to 6 were adjusted to 16 seconds (25°C) with Zahn cup #3 (manufactured by Rigosha) with ethyl acetate, and gravure proofing was performed using a gravure plate with a plate depth of 35 ⁇ m.
• the printed material provided with the printed layer of the liquid ink of Example 1 (printed material prepared for evaluation of yellowness) was formed, and a color printed layer was formed on the white printed layer to produce a printed material.
• the printed material was configured to have a portion where the color printed layer was provided on the white printed layer and a portion where the color printed layer was not provided (a portion where only the white printed layer was provided).
• the OPP film is P2161 (20 ⁇ m) manufactured by Toyobo Co., Ltd.
• the PET film is E5100 (12 ⁇ m) manufactured by Toyobo Co., Ltd.
• the NY film is ON-RT (15 ⁇ m) manufactured by Unitika Ltd.
• Alumina-evaporated transparent PET film IB-PET-PUB (12 ⁇ m) manufactured by Dai Nippon Printing Co., Ltd. was used as the transparent vapor-deposited film.
• Examples 4 to 9 gave excellent results in all evaluations of fluidity, storage stability, and adhesion. Examples 4 to 9, in which the pigment surface was treated to introduce iron elements, exhibited excellent fluidity and dispersion stability even in ink compositions containing no vinyl chloride vinyl acetate copolymer resin.
• Comparative Examples 3 to 6 when a pigment whose surface is not treated with iron element is used, when the ink composition does not contain vinyl chloride vinyl acetate copolymer resin, fluidity and dispersion stability are improved. It was found that the performance of the ink composition not using the chlorine-based resin was inferior due to environmental and human safety concerns. Also in the printed matter of Comparative Examples 3 to 6, the yellowness of the white printed layer (the portion where the color printed layer was not provided) had an effect, and the color of the printed matter changed.

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