WO2023199750A1 - Matériau imprimé et corps en couches stratifié - Google Patents

Matériau imprimé et corps en couches stratifié Download PDF

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Publication number
WO2023199750A1
WO2023199750A1 PCT/JP2023/013051 JP2023013051W WO2023199750A1 WO 2023199750 A1 WO2023199750 A1 WO 2023199750A1 JP 2023013051 W JP2023013051 W JP 2023013051W WO 2023199750 A1 WO2023199750 A1 WO 2023199750A1
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WO
WIPO (PCT)
Prior art keywords
resin
pigment
pigment red
film
ink
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PCT/JP2023/013051
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English (en)
Japanese (ja)
Inventor
瑠璃 青木
朋美 浅見
秀磨 内田
健太郎 永川
Original Assignee
Dic株式会社
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Priority to JP2023562743A priority Critical patent/JPWO2023199750A1/ja
Publication of WO2023199750A1 publication Critical patent/WO2023199750A1/fr

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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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • 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
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to printed matter and laminate laminates using a liquid ink composition that can be used as laminating gravure ink or flexographic ink for flexible packaging.
  • Gravure ink and flexographic ink are widely used for the purpose of imparting cosmetic properties and functionality to printed materials.
  • a printing material subjected to gravure printing or flexography is used as a packaging material, particularly as a food packaging material, it is generally laminated.
  • various printing materials and lamination processes are used depending on the type of content and purpose of use.
  • PVC vinyl chloride-vinyl acetate copolymer resins
  • binders Conventionally, printing inks containing polyurethane resins and vinyl chloride-vinyl acetate copolymer resins (hereinafter referred to as "PVC") as binders have been widely used for such laminated products.
  • PVC vinyl chloride-vinyl acetate copolymer resins
  • These resins are a combination of binders that can achieve both excellent dispersibility and high film properties, and have good printability and the properties required for laminating inks, such as adhesion to substrates, laminating strength, and boiling retortability. It is an essential ink raw material to achieve various physical properties.
  • Patent Document 1 describes a non-tole laminating ink composition for flexible packaging that contains a polypropylene glycol-containing polyurethane resin and a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group as essential components.
  • Plastic waste discharged as general waste includes various plastics, including chlorinated resins such as polyvinyl chloride and polyvinylidene chloride. Hydrogen chloride is released from these chlorinated resins during the thermal decomposition process during recycling, generating hydrochloric acid, which causes corrosion of equipment and piping.
  • the second issue is thermal recycling. In the method of reusing the energy generated when waste is incinerated, if the incineration contains chlorine-based resins, a problem arises in that endocrine disruptors such as dioxins are emitted.
  • Patent Document 2 describes an ink composition that combines a specific polyurethane resin and polyvinyl butyral resin (PVB) as a printing ink that does not use chlorine-based materials.
  • printing inks used for decoration or surface protection are required to have high performance and adaptability to various types of films.
  • a packaging material particularly as a flexible packaging material for food products or sanitary products
  • lamination processing is generally added.
  • various printing materials and lamination processes are used depending on the type of content and purpose of use.
  • printed matter used for flexible packaging materials generally has multiple printed layers, and a printed layer containing a white pigment as a background and a printed layer containing colored pigments that form a pattern are laminated on the film. The compatibility of 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, lamination strength, and retortability, and is free of chlorine resin as a binder. It is by no means easy to improve environmental responsiveness by realizing the following.
  • Patent Document 2 discloses the development of an ink composition for improving various physical properties required for laminating inks without using chlorine-based materials, but there is no study on multiple printing layers. do not have. Therefore, in order to further improve various physical properties such as lamination characteristics, there is a need for development as a printed matter.
  • the problem to be solved by the present invention is to create a printed material that has excellent lamination strength and is environmentally safe without impairing the basic properties of an ink such as dispersibility, fluidity, and stability.
  • the purpose is to provide
  • the present invention relates to a printed matter having a first printed layer not containing polyvinyl butyral resin and a second printed layer containing polyvinyl butyral resin on a film base material.
  • the present invention relates to a laminate having the printed matter.
  • printed matter can be obtained that has the basic properties of an ink such as dispersibility, fluidity, and stability, and has excellent leveling properties and lamination strength.
  • the printed matter of the present invention has excellent ink properties such as dispersibility, fluidity, and stability even without containing chlorine-based resin as the resin used in the printing ink, so it has excellent environmental safety. You can get printed matter.
  • the liquid ink composition refers to a liquid printing ink such as gravure ink or flexo ink that is applied to a printing method using a printing plate, and preferably gravure ink or flexo ink.
  • the liquid ink of the present invention does not contain active energy curable components, that is, it is a liquid ink that is non-reactive with active energy rays.
  • total amount of ink refers to the total amount of ink that includes all volatile components such as organic solvents
  • total amount of ink solids refers to volatile components. Shows the total amount of non-volatile components only, excluding.
  • the printed matter of the present invention is a multilayer printed matter in which a first printed layer and a second printed layer are laminated on a base material.
  • the first printed layer is a white printed layer with a white pigment
  • the second printed layer is a colored printed layer with at least one colorant other than the white pigment, or a colorless layer containing no colorant. It is preferable that the printed layer is .
  • the first printed layer is formed from a first liquid ink composition and the second printed layer is formed from a second liquid ink composition.
  • the second liquid ink composition contains a binder resin, an organic solvent, and if necessary, water and various additives. Moreover, it is preferable that the second liquid ink composition contains a coloring agent other than a white pigment so that the second printing layer forms a color printing layer.
  • the second liquid ink composition may not contain a colorant, and the second printed layer may be a colorless layer.
  • the binder resin contained in the second liquid ink composition contains at least polyvinyl butyral resin.
  • Polyvinyl butyral resin As the polyvinyl butyral resin contained in the second liquid ink composition, any known resin can be used without particular limitation. Generally, a reaction product 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, particularly preferably in the range of 55°C to 115°C, and more preferably in the range of 60 to 110°C. preferable.
  • the glass transition temperature is obtained by measurement using a differential scanning calorimeter.
  • the amount of hydroxyl groups in the polyvinyl butyral resin is preferably in the range of 10 to 30% by mass, more preferably 15 to 25% by mass.
  • the amount of acetyl groups in the polyvinyl butyral resin is preferably 10% by mass or less, and more preferably 8% by mass.
  • the polyvinyl butyral resin content (solid content of 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.
  • the content is most preferably 0.2 to 3.0% by mass. Adding a total amount of polyvinyl butyral resin of 0.1% by mass or more tends to maintain the adhesion and transferability of the ink film, and reducing the total amount to 5% by mass or less improves the ink's lamination strength and boil/retort resistance. can be held.
  • 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 45% by mass, preferably 40% by mass, preferably 30% by mass, preferably 20% by mass, and 15% by mass. More preferably, it is 10% by mass, and most preferably 10% by mass.
  • the second liquid ink composition can improve dispersibility by containing polyvinyl butyral resin. Since the constituent elements of polyvinyl butyral resin are only carbon atoms, hydrogen atoms, and oxygen atoms, the risk of environmental pollution can be reduced during the life cycle of products such as packages using vinyl butyral resin.
  • the total mass of the polyvinyl butyral resin should be 5 to 100% by mass or more based on the total mass of the resin contained in the second liquid ink composition (second printing layer). It is preferably 10 to 75% by mass or more, and even more preferably 15 to 50% by mass or more.
  • the second liquid ink composition of the present invention can contain a binder resin that can be used in combination in the liquid ink technical field.
  • the binder resin that can be used in combination is preferably a resin that does not contain chlorine components from the viewpoint of reducing environmental impact, such as polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, etc.
  • a resin that does not contain chlorine components from the viewpoint of reducing environmental impact such as polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, etc.
  • examples include resins, polyester resins, alkyd resins, rosin resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, petroleum resins, cellulose resins, and the like.
  • Polyurethane resin By using the other binder resin in combination with a urethane resin, adhesion, lamination strength, and retort resistance can be further improved.
  • the polyurethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol and a polyisocyanate.
  • the polyol it is preferable to use polyester polyol and/or polyether polyol.
  • the polyester polyol is preferably a polyester polyol obtained by dehydration condensation or polymerization of a low molecular weight polyol and a polyhydric carboxylic acid or an anhydride thereof. By introducing ester groups into polyester polyols to increase cohesive energy, the laminate strength can be further increased.
  • the low-molecular polyol various known compounds having two or more hydroxyl groups that are commonly used in the production of polyester polyols can be used, and one type or two or more types may be used in combination. Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol , dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and other glycols; 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 , 2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol
  • polyesters having 6 or less carbon atoms and 2 or more carboxyl groups such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, and anhydrides of these acids, etc.
  • 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 acid, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, anhydrides of these acids, etc. can be used.
  • Polyester polyols are polyurethane resins such as polyester polyols obtained by ring-opening polymerization of lactones such as cyclic ester compounds, polycaprolactone, polyvalerolactone, and poly( ⁇ -methyl- ⁇ -valerolactone).
  • lactones such as cyclic ester compounds, polycaprolactone, polyvalerolactone, and poly( ⁇ -methyl- ⁇ -valerolactone).
  • Various known polyester polyols commonly used in the production of polyester polyols may be used, or one type or two or more types 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, and even more preferably in the range of 900 to 6,000. .
  • the number average and weight average molecular weights indicate values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series.
  • TKgel G5000 (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000” (7.8mm I.D. x 30cm) x 1
  • Detector RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL/min Injection volume: 100 ⁇ L (Tetrahydrofuran solution with sample concentration 0.4% by mass) Standard sample: A calibration curve was created using the following standard polystyrene.
  • Examples include polyether polyols of polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran. Specifically, known and commonly used ones such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used.
  • polyether polyol By containing a polyether polyol, the adhesion, especially on a high-performance barrier film, is significantly improved, resulting in excellent blocking resistance and lamination strength.
  • the polyether polyol preferably has a number average molecular weight of 100 to 3,500.
  • the number average molecular weight of the polyether polyol is less than 100, the polyurethane resin film tends to become hard and its adhesion to the polyester film decreases.
  • the number average molecular weight is greater than 3,500, the polyurethane resin film tends to become brittle and the blocking resistance of the ink film decreases.
  • a polyurethane resin that uses a polyester polyol and a polyether polyol as reaction raw materials and has a large mass proportion of the polyester polyol in the total mass of the polyester polyol and polyether polyol. That is, in the polyol structure of the polyurethane resin, by adjusting the mass proportion of the polyester polyol so that the polyester polyol increases, boil resistance, retort resistance, and laminate strength can be further improved. Furthermore, by containing polyether polyol, the dispersibility and fluidity of the ink can be improved, and the effect of improving adhesion can also be obtained.
  • the mass ratio of polyester polyol and polyether polyol in the polyol structure is preferably in the range of 55:45 to 99:1, more preferably in the range of 60:40 to 98:2, and more preferably 70:45 to 99:1. More preferably, the ratio is from 30 to 97:3.
  • polyols commonly used in the production of polyurethane resins can be used as the polyol used in combination with the polyurethane resin as necessary, and one type or two or more types may be used in combination.
  • diisocyanate compound used in the polyurethane resin examples include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. that are commonly used in the production of polyurethane resins.
  • Chain extenders used in polyurethane resins include ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, isophorone diamine, dicyclohexylmethane-4,4'-diamine, and 2-hydroxyethylethylene diamine.
  • a monovalent active hydrogen compound can also be used as a terminal capping agent for the purpose of stopping 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.
  • the polyurethane resin can be produced, for example, by reacting polypropylene glycol and a concomitant polyol with a diisocyanate compound in a proportion in which isocyanate groups are in excess to obtain a prepolymer with terminal isocyanate groups, and then dissolving the obtained prepolymer in an appropriate solvent, that is, a non-containing solvent.
  • Ester solvents such as ethyl acetate, propyl acetate, and butyl acetate, which are commonly used as solvents for toluene-based gravure inks; Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methanol, ethanol, isopropyl alcohol, n-butanol, etc.
  • alcoholic solvent such as methylcyclohexane, ethylcyclohexane
  • hydrocarbon solvent such as methylcyclohexane, ethylcyclohexane
  • the two-step method is preferred in order to obtain a uniform polyurethane resin.
  • the reaction is carried out so that the total (equivalence ratio) of the amino groups of the chain extender and/or end-blocking agent is 1/0.9 to 1.3. It is preferable.
  • the equivalent ratio of isocyanate groups to amino groups is less than 1/1.3, the chain extender and/or end-blocking agent remain unreacted, causing yellowing of the polyurethane resin and odor after printing. It may occur.
  • aromatic solvents such as toluene and xylene or 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 and oil resistance of the printed film tend to be low, and when it exceeds 100,000, , the viscosity of the resulting ink composition tends to be high, and the gloss of the printed film tends to be low.
  • the content of the polyurethane resin in the ink (solid content of the polyurethane resin) used in the liquid ink composition is determined from the viewpoint of ensuring sufficient adhesion of the ink to the printing substrate. It is preferably 1% by mass or more, 3% by mass or more, and 5% by mass or more based on the total mass of the ink. On the other hand, from the viewpoint of appropriate ink viscosity and work efficiency during ink production and printing, the content is preferably 25% by mass or less, preferably 20% by mass or less, and preferably 15% by mass or less.
  • the lower limit of the solid content mass ratio of the polyurethane resin in the ink is preferably 1% by mass, more preferably 5% by mass, more preferably 10% by mass, and 15% by mass. It is more preferable that the amount is 20% 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 most preferably 75% by mass. It is preferably 70% by mass, and more preferably 70% by mass.
  • cellulose resin examples include cellulose acetate propionate, cellulose acetate butyrate and other cellulose ester resins, nitrocellulose (also referred to as nitrified cotton), hydroxyalkylcellulose, and carboxyalkylcellulose.
  • the cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. may have a substituent.
  • cellulose resins cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferred.
  • the weight average molecular weight is preferably 5,000 to 200,000, more preferably 10,000 to 50,000. Further, those having a glass transition temperature of 120°C to 180°C are preferable.
  • Nitrocellulose is a nitric acid ester obtained by reacting natural cellulose with nitric acid and replacing three hydroxyl groups in the six-membered ring of the anhydrous glucopyranose group in natural cellulose with nitric acid groups. preferable.
  • the second liquid ink composition contains at least a polyvinyl butyral resin and a polyurethane resin as binder resins.
  • the total mass of polyvinyl butyral resin and polyurethane resin with respect to the total mass of binder resin is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass. % or more, and even more preferably 95% by mass or more.
  • the colorant used in the second liquid ink composition preferably contains at least a colorant other than white pigment.
  • Examples of the colorant include organic and inorganic pigments and dyes used in general inks, paints, recording materials, and the like.
  • organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthanthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, quinacridone,
  • Examples include lon blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments.
  • non-acid-treated pigments and acid-treated pigments can be used. Specific examples of preferred organic pigments are listed below.
  • black pigments examples include C.I. I. Pigment Black 1, C. I. Pigment Black 6, C. I. Pigment Black 7, C. I. Pigment Black 9, C. I. Pigment Black 20 and the like.
  • blue pigment for example, C.I. I. Pigment Blue 15, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:2, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C. I. Pigment Blue 15:5, C. I. Pigment Blue 15:6, C. I. Pigment Blue 16, C. I. Pigment Blue 17:1, C. I. Pigment Blue 22, C. I. Pigment Blue 24:1, C. I. Pigment Blue 25, C. I. Pigment Blue 26, C. I. Pigment Blue 60, C. I. Pigment Blue 61, C. I. Pigment Blue 62, C. I. Pigment Blue 63, C. I. Pigment Blue 64, C. I. Pigment Blue 75, C. I. Pigment Blue 79, C. I. Pigment Blue 80 and the like.
  • green pigments examples include C.I. I. Pigment Green 1, C. I. Pigment Green 4, C. I. Pigment Green 7, C. I. Pigment Green 8, C. I. Pigment Green 10, C. I. Pigment Green 36 and the like.
  • red pigments examples include C.I. I. Pigment Red 1, C. I. Pigment Red 2, C. I. Pigment Red 3, C. I. Pigment Red 4, C. I. Pigment Red 5, C. I. Pigment Red 6, C. I. Pigment Red 7, C. I. Pigment Red 8, C. I. Pigment Red 9, C. I. Pigment Red 10, C. I. Pigment Red 11, C. I. Pigment Red 12, C. I. Pigment Red 15, C. I. Pigment Red 16, C. I. Pigment Red 17, C. I. Pigment Red 18, C. I. Pigment Red 19, C. I. Pigment Red 20, C. I. Pigment Red 21, C. I. Pigment Red 22, C. I. Pigment Red 23, C. I. Pigment Red 31, C. I.
  • Pigment Red 149 C. I. Pigment Red 150, C. I. Pigment Red 164, C. I. Pigment Red 166, C. I. Pigment Red 168, C. I. Pigment Red 169, C. I. Pigment Red 170, C. I. Pigment Red 171, C. I. Pigment Red 172, C. I. Pigment Red 175, C. I. Pigment Red 176, C. I. Pigment Red 177, C. I. Pigment Red 178, C. I. Pigment Red 179, C. I. Pigment Red 180, C. I. Pigment Red 181, C. I. Pigment Red 182, C. I. Pigment Red 183, C. I. Pigment Red 184, C. I. Pigment Red 185, C.
  • Pigment Red 220 C. I. Pigment Red 221, C. I. Pigment Red 223, C. I. Pigment Red 224, C. I. Pigment Red 226, C. I. Pigment Red 237, C. I. Pigment Red 238, C. I. Pigment Red 239, C. I. Pigment Red 240, C. I. Pigment Red 242, C. I. Pigment Red 245, C. I. Pigment Red 247, C. I. Pigment Red 248, C. I. Pigment Red 251, C. I. Pigment Red 253, C. I. Pigment Red 254, C. I. Pigment Red 255, C. I. Pigment Red 256, C. I. Pigment Red 257, C. I. Pigment Red 258, C. I.
  • Pigment Red 260 C. I. Pigment Red 262, C. I. Pigment Red 263, C. I. Pigment Red 264, C. I. Pigment Red 266, C. I. Pigment Red 268, C. I. Pigment Red 269, C. I. Pigment Red 270, C. I. Pigment Red 271, C. I. Pigment Red 272, C. I. Pigment Red 279, etc.
  • C.I. I. Pigment Violet 1 C. I. Pigment Violet 2, C. I. Pigment Violet 3, C. I. Pigment Violet 3:1, C.I. I. Pigment Violet 3:3, C.I. I. Pigment Violet 5:1, C.I. I. Pigment Violet 13, C. I. Pigment Violet 19 ( ⁇ type, ⁇ type), C.I. I. Pigment Violet 23, C. I. Pigment Violet 25, C. I. Pigment Violet 27, C. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C. I. Pigment Violet 32, C. I. Pigment Violet 36, C. I. Pigment Violet 37, C. I. Pigment Violet 38, C. I. Pigment Violet 42, C. I. Pigment Violet 50, etc.
  • yellow pigments examples include C.I. I. Pigment Yellow 1, C. I. Pigment Yellow 3, C. I. Pigment Yellow 12, C. I. Pigment Yellow 13, C. I. Pigment Yellow 14, Pigment Yellow 17, C. I. Pigment Yellow 24, C. I. Pigment Yellow 42, C. I. Pigment Yellow 55, C. I. Pigment Yellow 62, C. I. Pigment Yellow 65, C. I. Pigment Yellow 74, C. I. Pigment Yellow 83, C. I. Pigment Yellow 86, C. I. Pigment Yellow 93, C. I. Pigment Yellow 94, C. I. Pigment Yellow 95, C. I. Pigment Yellow 109, C. I. Pigment Yellow 110, C. I. Pigment Yellow 117, C. I.
  • orange pigments examples include C.I. I. Pigment Orange 5, C. I. Pigment Orange 13, C. I. Pigment Orange 16, C. I. Pigment Orange 34, C. I. Pigment Orange 36, C. I. Pigment Orange 37, C. I. Pigment O Orange 38, C. I. Pigment Orange 43, C. I. Pigment Orange 51, C. I. Pigment Range 55, C. I. Pigment Orange 59, C. I. Pigment Orange 61, C. I. Pigment Orange 64, C. I. Pigment Orange 71 or C.I. I. Pigment Orange 74 and the like.
  • brown pigments examples include C.I. I. Pigment Brown 23, C. I. Pigment Brown 25 or C.I. I. Pigment Brown 26 and the like.
  • preferred pigments include C.I. I. Pigment Black 7, C.I. as an indigo pigment.
  • Inorganic pigments other than white include, for example, carbon black, aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, deep blue, red iron oxide, yellow iron oxide, iron black, Zircon is an example, and aluminum is in the form of powder or paste, but it is preferable to use it in paste form from the viewpoint of handling and safety, and whether to use leafing or non-leafing is selected as appropriate from the viewpoint of brightness and density. be done.
  • the colorant is used in an amount sufficient to ensure the concentration and coloring power of the second liquid ink composition, that is, 1 to 60% by mass based on the total mass of the ink, and 10 to 90% by weight of solid content in the ink. It is preferably contained in a proportion of % by mass.
  • the coloring agent can be used alone or in combination of two or more types.
  • the second liquid ink composition may be a colorless liquid ink composition that does not contain a colorant.
  • the second liquid ink composition further includes a concomitant resin, an extender pigment, a pigment dispersant, a leveling agent, an antifoaming agent, a wax, a plasticizer, an infrared absorber, an ultraviolet absorber, a fragrance, and a flame retardant, as necessary. It can also include.
  • organic solvent As the organic solvent used in the second liquid ink composition, various organic solvents can be used, such as aromatic organic solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Examples include ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, and alcohol solvents such as n-propanol, inopropanol, n-butanol, and propylene glycol monomethyl ether. A mixture of two or more types can be used. In recent years, from the viewpoint of the working environment, it is more preferable not to use aromatic solvents such as toluene and xylene or ketone solvents.
  • aromatic organic solvents such as toluene and xylene or ketone solvents.
  • the second liquid ink composition may contain water as a volatile component together with the organic solvent.
  • the content of water is preferably less than 10% by mass of the total amount of the ink composition.
  • Water may be added to the organic solvent in advance to form a water-containing organic solvent, or a specific amount of water may be added separately.
  • the second liquid ink composition is a liquid ink composition that has excellent ink dispersibility and fluidity, whether it is a one-component type that does not use a curing agent such as an isocyanate curing agent or a two-component type that uses a curing agent. can get.
  • the particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the crushing media of the dispersion machine, the filling rate of the crushing media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, etc. be able to.
  • the dispersing machine commonly used ones such as a roller mill, ball mill, pebble mill, attritor, and sand mill 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 dispersing it appropriately, and 1000 mPa s or less from the viewpoint of workability efficiency during ink production and printing. preferable.
  • the above viscosity is a viscosity measured at 25° C. using 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, organic solvents, etc.
  • the viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.
  • the hue of the liquid ink composition used in the second printing layer includes five basic process colors: yellow, red, indigo, ink, and white, and external colors in the process gamut. There are three colors: red (orange), grass (green), and purple. Further, base colors such as transparent yellow, peony, vermilion, brown, gold, silver, pearl, and a nearly transparent medium for adjusting color density (including an extender pigment if necessary) are prepared.
  • the ink for boiling retorts is appropriately selected in consideration of pigment migration properties and heat resistance.
  • the base ink of each hue is diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing or flexographic printing, and is supplied to each printing unit either alone or in a mixture.
  • the first liquid ink composition forms a first printing layer (white printing layer) and contains a binder resin, a white pigment, an organic solvent, water as necessary, various additives, and the like.
  • the binder resin contained in the first liquid ink composition does not contain polyvinyl butyral resin.
  • the binder resin is usually used in liquid ink such as gravure ink or flexographic ink that is applied to printing methods using printing plates, and is not particularly limited as long as it is other than polyvinyl butyral resin.
  • the resin include polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, Examples include polyvinyl chloride resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, polyvinyl butyral resin, and petroleum resin.
  • polyurethane resin As the main binder resin, it is preferable to use polyurethane resin as the main binder resin because it has excellent adhesion to film base materials, blocking resistance, lamination suitability, highlight transferability, etc.
  • urethane resin As the main binder, The ratio of the urethane resin to the total amount of resin in the ink is preferably 50% by mass or more, and preferably 60% by mass or more.
  • the polyurethane resin used for the first printing layer 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/or a polyether polyol. things are used.
  • the type of polyol is not particularly limited, but from the viewpoints of boil resistance, retort resistance, and lamination strength, it is preferable that the proportion of polyester polyol is large. It is more preferable to use a polyol consisting of only Specifically, the mass ratio of polyester polyol and polyether polyol in the polyol structure is preferably in the range of 55:45 to 100:0, and preferably in the range of 60:40 to 100:0. is more preferable, and even more preferably in the range of 70:30 to 100:0.
  • diisocyanate compound used in the polyurethane resin various known diisocyanate compounds commonly used in the production of polyurethane resin, such as those used in the first printing layer (first liquid ink composition) described above, can be used. Can be used.
  • the weight average molecular weight of the polyurethane resin is preferably in the range of 15,000 to 100,000, more preferably in the range of 15,000 to 80,000, similar to the polyurethane resin used for the second printing layer. .
  • the weight average molecular weight of the polyurethane resin is less than 15,000, the blocking resistance of the resulting ink composition, the strength and oil resistance of the printed film tend to be low, and when it exceeds 100,000, , the viscosity of the resulting ink composition tends to be high, and the gloss of the printed film tends to be low.
  • the first printing layer preferably uses a polyurethane resin as the main binder, and further uses a cellulose resin and/or a maleic acid resin in combination.
  • a polyurethane resin as the main binder, and further uses a cellulose resin and/or a maleic acid resin in combination.
  • the cellulose resin the same cellulose resin as used for the second printing layer described above can be used.
  • the white pigment examples include titanium oxide, zinc sulfide, lead white, zinc white, lithobon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, silica, and the like.
  • titanium oxide is preferred 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 content of white pigment depends on the desired ink performance, but for white inks that require standard hiding properties and high plate fogging properties, the content is usually about 20 to 40% by mass based on the total ink mass. On the other hand, if the white ink is intended to have extremely high hiding power as a required performance, it may be designed with a content of about 40 to 60% by mass.
  • the same components as in the above-mentioned liquid ink composition (I) can be used as the components other than the white pigment, such as an organic solvent and other additives.
  • Both the second liquid ink composition and the first liquid ink composition preferably do not contain a chlorine-based resin such as vinyl chloride vinyl acetate copolymer. According to the present invention, excellent dispersibility and lamination strength can be obtained with a composition that has less environmental impact.
  • the printed matter of the present invention is a multilayer printed matter in which a first printed layer and a second printed layer are laminated on a film base material.
  • the first printing layer and the second printing layer can be formed by printing on various film base materials using the above-mentioned liquid ink compositions, respectively, and can be formed by gravure printing using electronic engraving intaglio, corrosion type intaglio, etc. While it is useful as an ink for gravure printing using a plate or flexo printing using a flexo printing plate made of a resin plate, it excludes ink for inkjet methods that eject ink from an inkjet nozzle without using a plate. It is something.
  • ink droplets ejected from a nozzle directly adhere to the substrate and form printed matter
  • the printing ink is once adhered to and transferred to the printing plate or printing pattern. After that, only the ink is brought into close contact with the base material again and, if necessary, dried to form a printed matter.
  • the film base material is, for example, a polyester resin such as polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, or nylon 6.
  • PET polyethylene terephthalate
  • polyethylene naphthalate polytrimethylene terephthalate
  • polytrimethylene naphthalate polytrimethylene naphthalate
  • polybutylene terephthalate polybutylene naphthalate
  • nylon 6 polybutylene naphthalate
  • polyamides such as nylon 66 and nylon 46
  • polyhydroxycarboxylic acids such as polylactic acid
  • biodegradable resins such as aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate)
  • polypropylene CPP: Polyolefins such as unoriented polypropylene film, OPP: biaxially oriented polypropylene film
  • polyethylene LLDPE: low density polyethylene film, HDPE: high density polyethylene film
  • polyimide polyarylate, polystyrene, polyacrylonitrile
  • polyvinyl alcohol ethylene-vinyl
  • films made of thermoplastic resins such as alcohol copolymers or mixtures thereof, and laminates thereof. Among them, films made of polyester, polyamide, polyethylene, and polypropylene can be suitably used.
  • Biomass films are sold by various companies, and for example, sheets such as those listed in the list of biomass certified products listed by the Japan Organic Resources Association can be used.
  • a specifically well-known film is one made from biomass-derived ethylene glycol.
  • Biomass-derived ethylene glycol is made from ethanol produced from biomass (biomass ethanol).
  • biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene glycol via ethylene oxide using a conventionally known method.
  • commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Corporation can be suitably used.
  • plant-derived low-density polyethylene that is a biomass plastic with a biomass plastic content defined by ISO16620 or ASTM D6866 of 80% or more, preferably 90% or more
  • plant-derived low-density polyethylene that is a biomass plastic with a biomass plastic content defined by ISO16620 or ASTM D6866 of 80% or more, preferably 90% or more
  • examples of plant-derived low-density polyethylene that is a biomass plastic with a biomass plastic content defined by ISO16620 or ASTM D6866 of 80% or more, preferably 90% or more include the brand names "SBC818" and "SPB608" manufactured by Braskem. Examples include “SBF0323HC”, “STN7006”, “SEB853", “SPB681", etc., and films using these as raw materials can be suitably used.
  • films containing biomass polyester, biomass polyethylene terephthalate, etc. whose diol units are biomass-derived ethylene glycol and dicarboxylic acid units from fossil fuel-derived dicarboxylic acids. It has been known.
  • the dicarboxylic acid unit of the biomass polyester uses dicarboxylic acid derived from fossil fuels.
  • aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation.
  • bifunctional oxycarboxylic acids trifunctional or more polyhydric alcohols, trifunctional or more polycarboxylic acids and/or their anhydrides can be used to form a crosslinked structure. It may also be a copolymerized polyester in which a copolymerized component is added as a third component such as at least one type of polyfunctional compound selected from the group consisting of trifunctional and trifunctional 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. Film is also known.
  • Polyethylene resins are not particularly limited other than using ethylene glycol derived from biomass as a part of the raw material, and can be made of ethylene homopolymers, copolymers of ethylene and ⁇ -olefin with ethylene as the main component (ethylene Examples include ethylene- ⁇ -olefin copolymers 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 include those having 4 or more carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. 8 ⁇ -olefins are mentioned.
  • Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used.
  • linear low-density polyethylene resin (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-hexene, or ethylene and A copolymer with 1-octene) is preferred, and a linear low-density polyethylene resin having a density of 0.910 to 0.925 g/cm3 is more preferred.
  • Films and sheets containing biomass raw materials such as starch and polylactic acid are also known. These can be appropriately selected and used depending on the purpose.
  • the biomass film may be a laminate of multiple biomass films, or a laminate of a conventional petroleum-based film and a biomass film.
  • These petroleum-based films and biomass films are made by laminating vapor-deposited layers of metals such as aluminum, metal oxides such as silica and alumina, using metal foils, etc., or by using polyvinyl alcohol, ethylene-vinyl alcohol copolymers, A barrier film containing a gas barrier layer such as vinylidene chloride may be used in combination, or a coating treatment such as polyvinyl alcohol may be applied.
  • metals such as aluminum, metal oxides such as silica and alumina
  • metal foils such as aluminum, metal oxides such as silica and alumina
  • polyvinyl alcohol ethylene-vinyl alcohol copolymers
  • a barrier film containing a gas barrier layer such as vinylidene chloride may be used in combination, or a coating treatment such as polyvinyl alcohol may be applied.
  • these films may be unstretched films or films that have been subjected to a stretching process, and the manufacturing method thereof is not limited.
  • a stretching treatment method it is common to melt and extrude a resin to form a sheet using an extrusion film forming method or the like, and then perform simultaneous biaxial stretching or sequential biaxial stretching.
  • sequential biaxial stretching it is common to perform longitudinal stretching first and then perform transverse stretching. Specifically, a method that combines 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.
  • the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment, if necessary, so that an adhesive layer free from defects such as film breakage and repellency is formed.
  • printing can be performed by a known printing method such as gravure printing or flexographic printing, but it is particularly preferable to print by a gravure printing method.
  • 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 above-mentioned liquid ink composition can be preferably used as a front printing ink, a back printing ink, or a laminating ink on a film base material.
  • a separate overprint varnish layer can be provided.
  • an anchor coat varnish layer can be provided separately.
  • the order in which the first printed layer and the second printed layer are provided is not particularly limited.
  • the first printing layer may be a color printing layer and the second printing layer may be a white printing layer, and the layers may be laminated in the order of film base material/color printing layer/white printing layer, or film base material/white printing layer.
  • the layer/color printing layer may be laminated in this order.
  • the second printing layer (color printing layer) can form a pattern using a coloring agent, and the first printing layer formed with a liquid printing ink containing a white pigment can be used as the background of the pattern. .
  • a third printing layer may be included as another printing layer, and the other printing layer may include, for example, a white pigment, and in the case of an overprint varnish, a coloring agent (white pigment and Color pigments) may not be included.
  • the laminate of the present invention is obtained by bonding a plurality of base materials together, and has a printed layer of the liquid printing ink of the present invention on at least one of the base materials.
  • the substrates can be bonded together with an adhesive or laminated by extrusion lamination.
  • a more specific structure of the laminate is: (1) Base film 1/Print layer/Adhesive layer 1/Sealant film (2) Base film 1/Print layer/Adhesive layer 1/Metalized unstretched film (3) Base film 1/Print layer/Adhesive layer 1/Metal-deposited stretched film (4) Transparent vapor-deposited stretched film/Printed layer/Adhesive layer 1/Sealant film (5) Base film 1/Printed layer/Adhesive layer 1/Base film 2/Adhesive layer 2/Sealant film ( 6) Base film 1/Printing layer/Adhesive layer 1/Metal-deposited stretched film/Adhesive layer 2/Sealant film (7) Base film 1/Printing layer/Adhesive layer 1/Transparent vapor-deposited stretched film/Adhesive layer 2/Sealant Film (8) Base film 1/Printing layer/Adhesive layer 1/Metal layer/Adhesive layer 2/Sealant film (9)
  • the above-mentioned “base film 1/and printing layer” corresponds to the above-mentioned printed matter having a white printing layer and a color printing layer on the film substrate.
  • the above configurations (1) to (10) a configuration in which a printed layer is provided on the surface of the base film 1 on the adhesive layer 1 side is described, but the surface (surface) on the opposite side to the adhesive layer 1 of the base film 1 A printed layer may be provided on the base film 2, or a printed layer may be provided on the base film 2.
  • Examples of the base film 1 used in configuration (1) include OPP film, PET film, and nylon film (hereinafter also referred to as Ny film). Furthermore, the base film 1 may be coated with a coating for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer, which will be described later.
  • Commercially available coated base films 1 include K-OPP films and K-PET films.
  • Examples of the sealant film include CPP film and LLDPE film.
  • Examples of the base film 1 used in configurations (2) and (3) include OPP films and PET films.
  • As the metal vapor-deposited unstretched film use a VM-CPP film, which is a CPP film on which a metal such as aluminum is vapor-deposited, and as a metal-vapor-deposited stretched film, use a VM-OPP film, which is an OPP film on which a metal such as aluminum is vapor-deposited. I can do it.
  • Examples of the transparent vapor-deposited stretched film used in configuration (4) include OPP films, PET films, nylon films, etc., on which silica or alumina is vapor-deposited.
  • a film coated on the vapor-deposited layer may be used.
  • Examples of the sealant film include those similar to configuration (1).
  • Examples of the base film 1 used in configuration (5) include PET film and the like. Examples of the base film 2 include nylon film and the like. Examples of the sealant film include those similar to configuration (1).
  • Examples of the base film 1 of configuration (6) include those similar to configurations (2) and (3).
  • Examples of the metal vapor-deposited stretched film include VM-OPP film and VM-PET film, which are OPP films and PET films on which a metal such as aluminum is vapor-deposited.
  • Examples of the sealant film include those similar to configuration (1).
  • Examples of the base film 1 of configuration (7) include PET film and the like. Examples of the transparent vapor-deposited stretched film include those similar to configuration (4). Examples of the sealant film include those similar to configuration (1).
  • Examples of the base film 1 of configuration (8) include PET film and the like.
  • Examples of the metal layer include aluminum foil and the like.
  • Examples of the sealant film include those similar to configuration (1).
  • Examples of the base film 1 of configurations (9) and (10) include PET film and the like.
  • Examples of the base film 2 include nylon film and the like.
  • Examples of the metal layer include aluminum foil and the like.
  • Examples of the sealant film include those similar to configuration (1).
  • Adhesive layer For the adhesive layer, a known adhesive for film lamination can be appropriately used. Moreover, when laminating by extrusion lamination, a known anchor coating agent for extrusion lamination can be appropriately used as an adhesion auxiliary agent. When a material having gas barrier properties is used as these adhesives or anchor coating agents, a laminate having particularly excellent barrier properties can be obtained.
  • Particularly preferable adhesives with excellent gas barrier properties are those in which 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. m 2 /day or less, which satisfies at least one of the conditions.
  • Commercially available products include the "PASLIM” series such as PASLIM VM001 and PASLIM J350X manufactured by DIC Corporation, and "Maxive" manufactured by Mitsubishi Gas Chemical Company.
  • the adhesive layer it is preferable to include a cured product of a polyol and an isocyanate compound.
  • these polyols and/or isocyanate compounds contain biomass-derived components, a laminate with a high degree of biomass can be obtained and the environmental load can be reduced.
  • adhesion promoters In addition, adhesion promoters, acid anhydrides, compounds with oxygen scavenging functions, tackifiers, gas barrier adhesives, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, It may contain a lubricant, an antiblocking agent, a coloring agent, a crystal nucleating agent, etc.
  • These various additives may be added in advance to either or both of the polyol composition (A) and the polyisocyanate composition (B), or they may be added to the polyol composition (A) and the polyisocyanate composition (B) in advance. It may be added when mixing with B).
  • the gas barrier adhesive used may be either a solvent type or a solvent-free type.
  • the adhesive of the present invention is applied onto the printed layer surface printed on the first base material using a roll such as a gravure roll, and then heated in an oven etc. After volatilizing the organic solvent, the other base material is bonded 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 which has been preheated to about 40°C to 100°C, is applied to the surface of the printed layer printed on the first base material using a gravure roll, etc. After coating using a roll, the other base material is immediately bonded 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 auxiliary agent of the present invention is applied onto the printed layer surface printed on the first base material using a roll such as a gravure roll, and then heated in an oven or the like. After the organic solvent is volatilized by heating, the laminate of the present invention is obtained by laminating the melted polymer material using an extruder.
  • the polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
  • the aging temperature is preferably room temperature to 70°C, and the aging time is preferably 6 to 240 hours.
  • the amount of gas barrier adhesive to be applied is adjusted as appropriate.
  • the solid content is adjusted to be 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 amount of adhesive applied 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 amount of application is appropriately adjusted, but as an example, it is 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 base materials.
  • porous base materials such as paper, wood, and leather can also be used as other base materials.
  • the adhesive used when bonding other base materials may or may not be a gas barrier adhesive as described above.
  • the printed matter or laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like.
  • the layer structure may change depending on the contents, usage environment, and usage form.
  • the packaging material of the present invention can be obtained, for example, by using the laminate of the present invention, stacking the sealant film surfaces of the laminate facing each other, and then heat-sealing the peripheral edges thereof.
  • the laminate of the present invention is folded or stacked so that the surfaces of the inner layers (the surfaces of the sealant film) are facing each other, and the peripheral edges are sealed, for example, by a side seal type, two-way seal type, Heat-sealing methods include three-sided sealing type, four-sided sealing type, envelope-sticking sealing type, gassho-sticking sealing type, pleated sealing type, flat-bottom sealing type, square-bottom sealing type, gusset type, and other heat-sealing types. It will be done.
  • the packaging material of the present invention can take various forms depending on the contents, usage environment, and usage form. Freestanding packaging materials (standing pouches), etc. are also possible. Heat sealing can be performed by any known method such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing, or the like.
  • the opening is heat-sealed to produce 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 products, cosmetics, electronic materials, building materials, industrial materials, and the like.
  • the contents to be filled include rice crackers, bean sweets, nuts, biscuits/cookies, wafer sweets, marshmallows, pies, half-baked cakes, candy, snack foods such as bread, snack noodles, instant noodles, dry noodles, and pasta.
  • aseptically packaged cooked rice, porridge, rice porridge, wrapped mochi, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, name mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen
  • Processed agricultural products such as vegetables and potato products, processed meat products such as hams, bacon, sausages, processed chicken products, corned beef products, fish meat hams and sausages, fish paste products, kamaboko, seaweed, tsukudani, bonito flakes, salted fish, Processed seafood products such as smoked salmon and mustard cod roe; pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, daikon radish, and potatoes; hamburgers and meat.
  • Prepared foods such as frozen and chilled side dishes such as balls, fried seafood, gyoza, and croquettes, dairy products such as butter, margarine, cheese, cream, instant creamy powder, infant formula powder, liquid seasonings, and retort pouches.
  • dairy products such as butter, margarine, cheese, cream, instant creamy powder, infant formula powder, liquid seasonings, and retort pouches.
  • 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 present invention will be explained in more detail with reference to Examples. Hereinafter, both “parts” and “%” are based on mass.
  • the weight average molecular weight in terms of polystyrene was measured by GPC (gel permeation chromatography) using an HLC8220 system manufactured by Tosoh Corporation under the following conditions. Separation columns: Four TSKgelGMHHR-N manufactured by Tosoh Corporation were used. Column temperature: 40°C. Mobile layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0ml/min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: Differential refractometer. The viscosity was measured at 25° C. using a B-type viscometer manufactured by Tokimec.
  • polyvinyl butyral resin solution B1 A polyvinyl butyral resin (weight average molecular weight 10,000, hydroxyl group content 15% by mass, glass transition point 60°C, acetyl group content 8% by mass) obtained by reacting polyvinyl alcohol with butyraldehyde was made into a 10% solution in isopropyl alcohol. This was designated as polyvinyl butyral resin solution B1.
  • polyvinyl butyral resin solution B2 A polyvinyl butyral resin obtained by reacting polyvinyl alcohol with butyraldehyde (weight average molecular weight 20,000, hydroxyl group content 20% by mass, glass transition point 70°C, acetyl group content 4% by mass) was made into a 10% solution in isopropyl alcohol. This was designated as polyvinyl butyral resin B2.
  • urethane prepolymer solution P1 128.15 parts of ethyl acetate was added to form a homogeneous solution of urethane prepolymer.
  • the urethane prepolymer solution was added to a mixture consisting of 23.87 parts of isophoronediamine, 0.30 parts of cyclohexylamine, 750.3 parts of ethyl acetate, and 376.6 parts of isopropyl alcohol, and the reaction was stirred at 45°C for 5 hours. In this way, a polyurethane resin solution P1 was obtained.
  • the obtained polyurethane resin solution P1 had a resin solid content concentration of 30.3% by mass and a resin solid content Mw of 54,000.
  • urethane prepolymer solution P4 83.7 parts was added to form a homogeneous solution of urethane prepolymer.
  • the urethane prepolymer solution was added to a mixture consisting of 15.99 parts of isophoronediamine, 0.32 parts of cyclohexylamine, 489.7 parts of ethyl acetate, and 245.7 parts of isopropyl alcohol, and the reaction was stirred at 45°C for 5 hours. In this way, a polyurethane resin solution P4 was obtained.
  • the obtained polyurethane resin solution P4 had a resin solid content concentration of 30.3% by mass and a resin solid content Mw of 60,000.
  • the urethane prepolymer solution was added to a mixture consisting of 10.65 parts of isophoronediamine, 0.22 parts of cyclohexylamine, 406.1 parts of ethyl acetate, and 204.1 parts of isopropyl alcohol, and the reaction was stirred at 45°C for 5 hours. In this way, a polyurethane resin solution P3 was obtained.
  • the obtained polyurethane resin solution P3 had a resin solid content concentration of 30.2% by mass and a resin solid content Mw of 65,000.
  • the urethane prepolymer solution was added to a mixture consisting of 10.87 parts of isophoronediamine, 0.22 parts of cyclohexylamine, 406.4 parts of ethyl acetate, and 204.3 parts of isopropyl alcohol, and the reaction was stirred at 45°C for 5 hours. In this way, a polyurethane resin solution P6 was obtained.
  • the obtained polyurethane resin solution P6 had a resin solid content concentration of 30.1% by mass and a resin solid content Mw of 58,000.
  • Adjustment example I-1 30 parts of polyurethane resin solution P1, 25 parts of polyvinyl butyral resin B1 (solid content 10%), 1 part of maleic acid resin solution M, 3 parts of cellulose acetate propionate resin solution Ca, phthalocyanine blue pigment (FASTGEN Blue).
  • Adjustment example II-1 30 parts of polyurethane resin solution P1, 1 part of maleic acid resin solution M, 3 parts of cellulose acetate propionate resin solution Ca, 36 parts of titanium oxide JR-780 (manufactured by Teika Co., Ltd.), and 30 parts of ethyl acetate.
  • a mixture consisting of 100 parts in total was kneaded using a Dyno Mill (manufactured by Willy & Buccophenon) to prepare a liquid ink.
  • Example 1 The viscosity of the liquid ink of Adjustment Example II-1 was adjusted to 16 seconds (25°C) with ethyl acetate using Zahn Cup #3 (manufactured by Rigosha), and coated onto a film using a gravure proofing machine equipped with a gravure plate with a plate depth of 35 ⁇ m. A white printed layer was formed.
  • the viscosity of the liquid ink of Adjustment Example I-1 was adjusted to 16 seconds (25°C) with ethyl acetate using Zahn cup #3 (manufactured by Rigosha), and the viscosity was adjusted to 16 seconds (25°C) using ethyl acetate, and the viscosity was adjusted to 16 seconds (25°C) using ethyl acetate.
  • a color printing layer was formed on the produced white printing layer to produce a multilayer printed matter.
  • Examples 2 to 11, Comparative Examples 1 to 4 For Examples 2 to 11 and Comparative Examples 1 to 4, printed matter was produced in the same manner as in Example 1 using the liquid inks shown in Table 3.
  • TI value is less than 1.5 ⁇ : TI value is 1.5 or more and less than 3.0 ⁇ : TI value is 3.0 or more (viscosity)
  • the viscosity of the first liquid ink and the second liquid ink described in Preparation Example I-1 to Preparation Example II-1 was measured using Zahn Cup #4 (manufactured by Rigosha). If the viscosity is 30 seconds or less, it can be used practically.
  • the obtained laminate was made into a pouch with a size of 120 mm x 120 mm, and the pouch was filled with 70 g of a pseudo food containing vinegar, salad oil, and meat sauce in a weight ratio of 1:1:1 and sealed. After boiling the created pouch at 98° C. for 60 minutes, the contents were taken out and the pouch was washed with water. The bag was cut into a width of 15 mm and a T-peel test was conducted at a pulling speed of 300 mm/min.
  • the produced printed matter has the following order from the Ny film side of the base material: Ny base material (F)/printing ink layer/adhesive layer (Ad)/LLDPE film.
  • ⁇ 3.5N/15mm or more
  • sufficient strength ⁇ : 3.0N/15mm or more - less than 3.5N/15mm
  • practical range ⁇ : 2.0N/15mm or more - less than 3.0N/15mm
  • Slightly insufficient strength ⁇ : Less than 2.0N/15mm, insufficient strength
  • R-CPP unstretched polypropylene film
  • R-CPP unstretched polypropylene film
  • the obtained laminate was made into a pouch with a size of 120 mm x 120 mm, and the pouch was filled with 70 g of a pseudo food containing vinegar, salad oil, and meat sauce in a weight ratio of 1:1:1 and sealed.
  • the created pouch was sterilized in a steam retort at 135° C. for 30 minutes, the contents were taken out and the pouch was washed with water.
  • the bag was cut into a 15 mm width and a T-peel test was conducted at a pulling speed of 300 mm/min.
  • PET film biaxially stretched polyester film
  • the produced printed matter has the following order from the PET film side of the base material: PET base material (F)/printing ink layer/adhesive layer (Ad1)/aluminum foil (AL)/adhesive (Ad2)/R-CPP film.
  • PET base material F
  • Ad1 adhesive layer
  • Ad2 aluminum foil
  • Ad2 adhesive
  • R-CPP film A biaxially stretched polyester film (PET film: E-5100 manufactured by Toyobo Co., Ltd., thickness 12 ⁇ m) was used.
  • PET film E-5100 manufactured by Toyobo Co., Ltd., thickness 12 ⁇ m
  • Leveling property In the printed matter, the densities of 100% and 50% halftone dots of the color printing layer were measured using a reflection densitometer. The leveling property was evaluated based on the concentration ratio obtained by dividing the 50% concentration by the 100% concentration using the following criteria.
  • the first printed layer containing white pigment does not contain polyvinyl butyral resin
  • the second printed layer not containing white pigment uses polyvinyl butyral resin to form a laminate, which improves dispersibility. It has been found that a laminate having excellent laminate strength can be obtained without impairing the basic properties of an ink such as fluidity and stability.
  • the laminates of Examples 1 to 11 are superior in environmental safety because they do not contain chlorine-based resins like Comparative Example 4, and are also superior in leveling properties compared to Comparative Example 4. I understand. It is not clear why Examples 1 to 11 have better leveling properties than Comparative Example 4, but the ink containing butyral has better contact with the film than the ink containing vinyl chloride vinyl acetate copolymer resin. This is thought to be due to the fact that the corners are small and easily wet and spread.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne un matériau imprimé et un corps en couches stratifié comprenant le matériau imprimé. Le matériau imprimé est caractérisé en ce qu'il comporte, sur un matériau de base de film, une couche imprimée blanche ne contenant pas de résine de polybutyral de vinyle, et une couche imprimée en couleur contenant une résine de polybutyral de vinyle. Cette configuration permet d'obtenir un matériau imprimé et un corps en couches comprenant le matériau imprimé, qui présentent une excellente résistance de stratification et sont excellents en termes de sécurité environnementale, sans affecter les caractéristiques de base en tant qu'encre telle que la dispersibilité, l'aptitude à l'écoulement et la stabilité.
PCT/JP2023/013051 2022-04-12 2023-03-30 Matériau imprimé et corps en couches stratifié WO2023199750A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298618A (ja) * 2004-04-09 2005-10-27 Toyo Ink Mfg Co Ltd 軟包装用ノントルラミネートインキ組成物
JP2014062138A (ja) * 2009-03-25 2014-04-10 Toyo Ink Sc Holdings Co Ltd ラミネート用印刷インキ組成物
JP2019173037A (ja) * 2017-11-28 2019-10-10 Dic株式会社 ジオキサジン顔料の製造方法
JP2020084026A (ja) * 2018-11-26 2020-06-04 Dic株式会社 縮合多環系有機顔料及び着色剤
US20210079237A1 (en) * 2017-12-19 2021-03-18 Sun Chemical Corporation High opacity white ink
JP2021080402A (ja) * 2019-11-21 2021-05-27 Ｄｉｃグラフィックス株式会社 リキッド印刷インキ、及び積層体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298618A (ja) * 2004-04-09 2005-10-27 Toyo Ink Mfg Co Ltd 軟包装用ノントルラミネートインキ組成物
JP2014062138A (ja) * 2009-03-25 2014-04-10 Toyo Ink Sc Holdings Co Ltd ラミネート用印刷インキ組成物
JP2019173037A (ja) * 2017-11-28 2019-10-10 Dic株式会社 ジオキサジン顔料の製造方法
US20210079237A1 (en) * 2017-12-19 2021-03-18 Sun Chemical Corporation High opacity white ink
JP2020084026A (ja) * 2018-11-26 2020-06-04 Dic株式会社 縮合多環系有機顔料及び着色剤
JP2021080402A (ja) * 2019-11-21 2021-05-27 Ｄｉｃグラフィックス株式会社 リキッド印刷インキ、及び積層体

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