WO2022014484A1 - Stratifié de papier mousse - Google Patents

Stratifié de papier mousse Download PDF

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Publication number
WO2022014484A1
WO2022014484A1 PCT/JP2021/025927 JP2021025927W WO2022014484A1 WO 2022014484 A1 WO2022014484 A1 WO 2022014484A1 JP 2021025927 W JP2021025927 W JP 2021025927W WO 2022014484 A1 WO2022014484 A1 WO 2022014484A1
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WIPO (PCT)
Prior art keywords
layer
foamed
resin
paper
polyol
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PCT/JP2021/025927
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English (en)
Japanese (ja)
Inventor
光 浦辺
哲哉 佐井
友央 上野
嘉貢 西野
Original Assignee
日清食品ホールディングス株式会社
東洋インキＳｃホールディングス株式会社
東洋インキ株式会社
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Application filed by 日清食品ホールディングス株式会社, 東洋インキＳｃホールディングス株式会社, 東洋インキ株式会社 filed Critical 日清食品ホールディングス株式会社
Priority to CN202180047509.XA priority Critical patent/CN115768625A/zh
Publication of WO2022014484A1 publication Critical patent/WO2022014484A1/fr

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    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the embodiment of the present invention relates to a foamed paper laminate.
  • Effervescent containers are widely used as containers for storing foods containing high-temperature or low-temperature liquids because they have excellent heat insulating properties.
  • foam containers are lacking in products generally called "cup noodles" that can be eaten in a few minutes by simply pouring an appropriate amount of boiling water into instant noodles such as ramen, udon, and soba noodles contained in a container. I can't.
  • Styrofoam containers and foamed paper containers are known as foaming containers for cup noodles, but in recent years, foamed paper containers have been attracting attention from the viewpoint of environmental load and safety.
  • the foamed paper container is manufactured using a foamed paper material having a paper base material and a thermoplastic resin layer that foams by heating at the time of manufacturing the container to form a heat insulating layer.
  • a printing layer including a printing pattern such as a decorative pattern, a company name, and a barcode is formed on the surface of a foamed paper container (foamed paper material). Therefore, it is desirable that the printing layer has excellent foaming followability without hindering foaming when the thermoplastic resin layer of the foamed paper material foams by heating to form a heat insulating layer.
  • the surface (printing surface) of the printed layer in the foamed paper laminate after the thermoplastic resin layer is foamed is smooth, has no cracks or swelling, and has an excellent appearance (hereinafter referred to as “foamed appearance”). It is desirable to have. Further, it is desirable that the printed surface is excellent in various resistances such as friction resistance and heat resistance required for manufacturing the container. Further, in the food field, since a solvent such as ethanol is widely used for disinfection, the printed layer is also required to have solvent resistance such as ethanol resistance.
  • Patent Document 1 and Patent Document 2 include an ink for a foamed paper container (foam cup) containing a binder resin and a pigment as the ink forming the print layer of the foamed paper container, and the binder resin contains a urethane resin. It is disclosed.
  • Patent Documents 3 to 5 disclose environment-friendly inks using biomass resin and laminates using the inks.
  • the printing layer in a foamed paper container is required to have various properties such as abrasion resistance and ethanol resistance, as well as special performance such as heat resistance, foam followability, and foam appearance. Above all, the heat resistance of the printed layer during heat processing is important.
  • the base material expands due to heat processing in the process of forming the foamed layer. Therefore, when the heat resistance of the printed layer is insufficient, troubles such as the printed layer peeling from the base material and depositing on the apparatus are likely to occur in the manufacturing process of the container. Therefore, the printed layer in the foamed paper container is required to have heat resistance that does not peel off from the base material even under the conditions of being heated and the base material expanding.
  • the base material expands with the heat processing that forms the foamed layer.
  • the base material is hardly deformed because the heat treatment is not performed after the print layer is formed. Due to these differences, it is desirable to simply replace the ink component for forming the print layer of the foamed paper container with the environment-friendly ink used for general purposes, such as heat resistance. It is difficult to obtain various characteristics at a sufficiently satisfactory level. Therefore, the development of a foamed paper container using a biomass resin is desired, but as described above, the adoption of a biomass resin has not progressed because the foamed paper container is required to have special performance.
  • the embodiment of the present invention has a printing layer containing a biomass resin, and excellent heat resistance, foaming followability, foaming appearance, and ethanol resistance can be obtained, and a foamed paper container can be obtained.
  • a foamed paper laminate that can be suitably used as a member.
  • the present inventors have diligently studied the resin components constituting the print layer of the foamed paper laminate, and formed a print layer containing a specific biomass resin to achieve heat resistance and foaming. We have found that good results can be obtained in terms of characteristics of the printed layer such as followability, foamed appearance, and ethanol resistance, and have completed the present invention. That is, the present invention relates to the following embodiments, but includes various embodiments without limitation.
  • One embodiment is a foamed paper composed of a base paper, a thermoplastic resin layer (A) provided on one side of the base paper, and a foamed thermoplastic resin layer (B) provided on the other side of the base paper. , And a foamed paper laminate provided with a printing layer provided on the foamed thermoplastic resin layer (B).
  • the print layer contains at least a binder resin and contains The binder resin relates to a foamed paper laminate containing a urethane resin having a structural unit derived from castor oil polyol.
  • the urethane resin preferably further has a structural unit derived from a polyester polyol which is a condensate of a dibasic acid and a diol.
  • the mass ratio (a1) / (a2) of the structural unit (a1) derived from castor oil polyol and the structural unit (a2) derived from polyester polyol is preferably 75/25 to 10/90.
  • the content of the structural unit derived from the polyether polyol is preferably 8% by mass or less based on the total mass of the urethane resin.
  • the weight average molecular weight of the castor oil polyol is preferably 1,000 to 5,000.
  • the binder resin further contains a vinyl chloride / vinyl acetate copolymer, and the content of the vinyl chloride / vinyl acetate copolymer is 5% by mass or more and 50% by mass or less based on the total mass of the binder resin. Is preferable.
  • the elongation rate of the binder resin is preferably 400% to 3,000%.
  • the disclosures of this application relate to the subject matter described in Japanese Patent Application No. 2020-12307 filed on July 17, 2020, the entire disclosure of which is incorporated herein by reference.
  • a foamed paper laminate having a printing layer containing a biomass resin, excellent heat resistance, foaming followability, foaming appearance, and ethanol resistance can be obtained, and can be suitably used as a member of a foamed paper container.
  • FIG. 1 is a perspective view showing a structural example of a foamed paper container provided with a foamed paper laminate according to an embodiment.
  • FIG. 2 is a schematic cross-sectional view showing a part (reference numeral I portion) of the foamed paper container shown in FIG. 1 in an enlarged manner.
  • the foamed paper laminate is formed on a foamed paper having a thermoplastic resin layer (A), a paper base material, and a foamed thermoplastic resin layer (B) in that order, and on the surface of the foamed thermoplastic resin layer (B) of the foamed paper. It has a formed printed layer.
  • the printed layer preferably contains at least a biomass resin as a binder resin, and the biomass resin preferably contains at least a biomass-derived urethane resin.
  • the binder resin comprises a urethane resin having a structural unit derived from castor oil polyol.
  • the urethane resin is a biomass-derived urethane resin obtained by using at least castor oil polyol as a polyol component as a raw material. Details of such a biomass-derived urethane resin will be described later.
  • the foamed thermoplastic resin layer (B) has a number of foamed cells of 1000 cells / 1 cm 2 or more per unit surface area, and is a printed layer after being immersed in ethanol at 25 ° C. for 30 minutes.
  • the residual ratio is preferably 50% by mass or more.
  • the larger the number the smaller the bubbles existing in the foamed layer (B), and the smaller the number. It means that the bubbles existing in the foam layer (B) are large. When the bubbles existing in the foam layer (B) become large, appearance defects such as cracks and swelling of the printed surface are likely to occur.
  • the number of foamed cells per unit surface area of the foamed layer (B) is preferably 1000 cells / 1 cm 2 or more, and more preferably 1250 cells / 1 cm 2 or more.
  • the upper limit of the number of foamed cells is not particularly limited. In one embodiment, the number of foamed cells may be 1600 cells / cm 2 or less from the viewpoint of manufacturing conditions and the like.
  • the "number of foamed cells per unit area” is an independent cell (air bubble) existing in a range partitioned by a certain length in the vertical and horizontal (XY) directions on the surface of the foamed layer (B). It means a value calculated as the number of independent cells per 1 cm 2 by counting the number of. The number of independent cells is determined by removing the printed layer of the foamed paper laminate with a solvent, exposing the surface of the foamed layer (B), and then observing the surface of the foamed layer (B) using an optical microscope. To.
  • the thickness of the foam layer (B) is preferably 500 ⁇ m or more, more preferably 630 ⁇ m or more, from the viewpoint of heat insulating properties. If the thickness of the foamed layer (B) is 500 ⁇ m or more, the foamed paper laminate is formed into a cup-shaped container, and even when hot water of about 100 ° C. is poured into the container, the container is continuously held with bare hands. It becomes easy to hold in. On the other hand, from the viewpoint of resource saving, it is preferable that the amount of resin used is as small as possible. Further, from the viewpoint of heat insulating properties, the heat insulating layer does not need to be thick enough to have excessive quality. Therefore, the thickness of the foamed layer (B) is preferably 950 ⁇ m or less, more preferably 900 ⁇ m or less, and extremely preferably 800 ⁇ m or less.
  • the thickness of the foam layer (B) is preferably 500 to 950 ⁇ m, more preferably 500 to 900 ⁇ m, and even more preferably 500 to 800 ⁇ m.
  • the thickness of the foamed layer (B) is determined by observing the cross section of the foamed paper laminate with an optical micrograph and measuring the height from the upper surface of the paper substrate to the lower surface of the printed layer.
  • the foamed layer (B) of the foamed paper means a state after the thermoplastic resin layer is foamed by heating. That is, the foamed layer (B) is formed by heating and foaming an unexpanded thermoplastic resin layer (foamed thermoplastic resin layer forming layer (B 0)) as a precursor.
  • the foamed paper laminate in order to form the foamed paper laminate, it has a thermoplastic resin layer (A), a paper substrate, and a melting point lower than that of the thermoplastic resin layer (A), and is foamed by heat treatment.
  • a foamed paper material (foamed paper before heating) having a foamed thermoplastic resin layer forming layer (B 0) in sequence can be used.
  • the foamed paper material can be made of a material known in the art.
  • the constituent materials of the foamed paper laminate will be specifically described.
  • the paper base material constituting the foamed paper laminate is not particularly limited.
  • kraft paper or woodfree paper can be used.
  • the basis weight of the paper substrate is preferably 150 to 450 g / m 2 , and more preferably 250 to 400 g / m 2 .
  • the water content contained in the paper substrate is preferably 4 to 10% by mass, more preferably 5 to 8% by mass.
  • thermoplastic resin layer, foam layer forming layer the thermoplastic resin layer (A) and the foamed thermoplastic resin layer forming layer (B 0 ) (hereinafter, also referred to as the foamed layer forming layer (B 0 )) are conventionally known as container materials. It may be a film made of a resin material.
  • a film (thermoplastic resin film) made of at least one thermoplastic resin selected from the group consisting of stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon can be used.
  • a polyethylene film can be preferably used because it is excellent in laminating suitability and foamability.
  • at least one of the thermoplastic resin layer (A) and the foamed layer forming layer (B 0 ) is a film composed of a polyethylene resin derived from biomass.
  • the foamed paper material can be constructed by laminating thermoplastic resin films having different melting points on a paper base material.
  • the water content in the paper substrate evaporates during the heat treatment, and the evaporated water content is extruded to the softened foam layer forming layer (B 0 ) (low Mp resin film) side.
  • the low Mp resin film swells (foams) toward the outside, and a foamed layer (B) is formed.
  • the foam layer (B) thus formed functions as a heat insulating layer in the container.
  • thermoplastic resin layer (A) high Mp resin film
  • a material that does not melt or soften when the low Mp resin film foams by heat treatment is selected for the thermoplastic resin layer (A) (high Mp resin film).
  • the foam paper material is, for example, a high Mp polyethylene film having a melting point of about 125 ° C. to 140 ° C. on one surface (inside of the container) of a paper base material.
  • the low Mp polyethylene film foams to form a foamed layer by heating during the production of a foamed paper container or the like.
  • the high Mp polyethylene film preferably functions as a coating layer. That is, the coating layer can suppress the evaporation of the water content in the paper base material to the outside during the foaming of the low Mp polyethylene film, and can efficiently contribute the water content in the paper base material to the foaming.
  • the material of the foam layer forming layer (B 0 ) preferably contains a low density polyethylene resin (density 910 to 925 kg / m 3 , melting point 105 to 120 ° C.) among the polyethylene resins.
  • the density of the low-density polyethylene resin is more preferably 910 to 922 kg / m 3 , and even more preferably 910 to 918 kg / m 3 .
  • the material of the foam layer forming layer (B 0 ) As the material of the foam layer forming layer (B 0 ), a medium density polyethylene resin (density 925 to 940 kg / m 3 , melting point 115 to 130 ° C.) and a high density polyethylene resin (density 940 to 970 kg / m 3 , melting point 125 to 140).
  • the melt flow rate of the polyethylene resin (hereinafter referred to as “MFR”) is preferably 8 to 28 g / 10 minutes, and preferably 10 to 20 g / 10 minutes. More preferred.
  • a polyethylene film derived from biomass For example, “SHE150 (density 948 kg / m 3 , MFR 1 g / 10 minutes)" manufactured by Braskem Co., Ltd. is used as the thermoplastic resin layer (A), and Braskem Co., Ltd. is used as the material for the foam layer forming layer (B 0). "SBC818 (density 918 kg / m 3 , MFR 8.1 g / 10 minutes)" can be used.
  • the film thickness of the foamed layer forming layer (B 0 ) is preferably 40 ⁇ m or more, and more preferably 60 ⁇ m or more. By adjusting the film thickness to 40 ⁇ m or more, sufficient heat insulating properties can be obtained after the heat treatment.
  • the film thickness of the foam layer forming layer (B 0 ) is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and extremely preferably 80 ⁇ m or less.
  • the printing layer is a coating film obtained by applying an ink composition to the surface of the foamed layer forming layer (B 0) of the foamed paper material.
  • the main component of the coating film constituting the printing layer (that is, the ink composition) is a binder resin, and the binder resin is characterized by containing at least a urethane resin having a structural unit derived from castor oil polyol.
  • the thickness of the printed layer (coating film after drying) is preferably 0.5 to 5.0 ⁇ m from the viewpoint of foaming suppressing power by the printed layer and abrasion resistance.
  • the thickness of the printed layer may be more preferably 0.5 to 4.0 ⁇ m, still more preferably 0.5 to 3.5 ⁇ m.
  • the environmental load can be reduced as compared with the case where the conventional resin derived from petroleum is used.
  • the biomass degree based on the total mass of the binder resin is preferably 10% by mass or more.
  • the print layer may contain a colorant and a binder resin.
  • the biomass content of the colorant and the binder resin in a total of 100 parts by mass is preferably 10% by mass or more. From the viewpoint of building a sound material-cycle society, the higher the biomass level, the more preferable.
  • the biomass degree is more preferably 15% by mass or more.
  • biomass degree means the proportion of biomass-derived raw materials in all the components used as raw materials. For example, it means the ratio of the components derived from biomass in the compound obtained after the synthesis of the binder resin. That is, among the components derived from biomass, if the raw materials are all derived from biomass such as vegetable oil, the degree of biomass is 100%.
  • the ratio of the raw material derived from biomass in the compound is the degree of biomass.
  • the biomass degree can be calculated by converting it into the raw material mass before the reaction, and is a value represented by the following formula (1).
  • Formula (1): Biomass degree 100 ⁇ total mass of biomass-derived components in the compound / total mass of the compound
  • biomass degree is expressed by the following formula.
  • Degree of biomass 100 x (mass of polyol derived from biomass x A%) / mass of urethane resin
  • “mass of urethane resin” is the sum of polyol derived from biomass and diisocyanate derived from petroleum, and is ".
  • the “polyol derived from biomass” is the total of all the polyols derived from biomass used in the urethane resin.
  • At least castor oil polyol is used as the polyol component, so that it is easy to increase the degree of biomass.
  • the degree of biomass can also be determined by measuring the concentration of radioactive carbon (14 C) in the compound using accelerator mass spectrometry or the like. Since no radioactive carbon is present in petroleum-derived compounds, biomass-derived compounds can also be distinguished from petroleum-derived compounds by the degree of biomass.
  • the ink composition contains a binder resin containing a urethane resin having a structural unit derived from castor oil polyol, and a solvent.
  • the ink composition may further comprise a colorant such as a pigment.
  • the ink composition may further contain various additives in addition to the above components, if necessary.
  • the composition of the ink composition will be described.
  • the printed layer does not inhibit the foaming of the foam layer forming layer (B 0) and has excellent foam followability.
  • the foaming of the foam layer forming layer (B 0 ) can be appropriately controlled by the printed layer.
  • the binder resin is the main component of the printing layer (coating film), it is possible to satisfactorily adjust the foaming followability and foaming suppressing power of the printed layer by selecting an appropriate binder resin form. can.
  • the binder resin preferably has an elongation rate of 50 to 4,000%, and more preferably 400 to 3,000%, from the viewpoint of foaming followability.
  • the binder resin preferably has an elongation rate of 50 to 4,000% and a stress of 0.1 mPa or more.
  • the term "elongation rate" described in the present specification refers to a sample having dimensions of 0.3 mm in thickness and 15 mm in width, using a small tensile tester manufactured by Intesco, with a tensile speed of 100 mm / min and a room temperature of 25. It means the value obtained by measuring at ° C.
  • the binder resin preferably has a stress of 0.1 mPa or more, more preferably 1 mPa or more, and even more preferably 5 mPa or more at an elongation rate of 50 to 4,000%.
  • the stress at an elongation rate of 50 to 4,000% is preferably 50 mPa or less, more preferably 40 mPa or less, and even more preferably 30 mPa or less.
  • the stress at an elongation rate of 50 to 4,000% of the binder resin containing the urethane resin may be 0.1 mPa to 50 mPa.
  • the binder resin has an elongation rate and stress in the above range, it becomes easy to obtain good results in terms of foaming appearance in addition to foaming followability. Further, a binder resin having an elongation rate and stress in the above range is preferable from the viewpoint of enhancing ethanol resistance because it is easy to obtain a desired residual rate of the printed layer.
  • the binder resin preferably contains at least a urethane resin from the viewpoint of foaming followability of the printed layer during foaming.
  • urethane resins obtained by reacting a polyol with diisocyanate.
  • a urethane urea resin obtained by extending a chain of a urethane prepolymer obtained by reacting a polyisocyanate with a polyol with an amine compound can be mentioned. That is, the urethane resin is a resin having a urethane bond, but even if it has a urea bond or the like, it is included in the concept.
  • a urethane resin When a urethane resin is used, it is excellent in various resistances such as light resistance, heat resistance, abrasion resistance, and blocking resistance, and is resistant to a low Mp resin film (foam layer forming layer (B 0 )) which is a base material at the time of printing.
  • An ink composition capable of forming a print layer having excellent adhesiveness can be easily formed. Further, by using the urethane resin, even when the ink composition is stored for a long period of time in an environment where heat or light is applied, the friction resistance and blocking resistance of the print layer and the low Mp resin film as a base material are used. Good results can also be obtained in various properties such as adhesiveness to the resin.
  • the urethane resin preferably has a weight average molecular weight in the range of 10,000 to 100,000. More preferably, it is 30,000 to 80,000. When the weight average molecular weight is within the above range, the blocking resistance of the printed layer, the solubility in an organic solvent, and the dispersibility of the pigment can be easily improved.
  • the urethane resin preferably has an amine value.
  • the amine value is preferably 0.5 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g, and even more preferably 3 to 20 mgKOH / g. When the amine value is within the above range, it becomes easy to improve the adhesion.
  • the urethane resin preferably has a glass transition temperature (Tg) of ⁇ 100 ° C. to 0 ° C.
  • Tg glass transition temperature
  • the Tg of the urethane resin may be more preferably ⁇ 10 ° C. or lower, still more preferably ⁇ 25 ° C. or lower.
  • the Tg may be ⁇ 100 ° C. or higher, preferably ⁇ 90 ° C. or higher, more preferably ⁇ 80 ° C. or higher, and even more preferably ⁇ 60 ° C. or higher.
  • a binder resin having a Tg in the above range is preferable from the viewpoint of ethanol resistance because it is easy to obtain a desired residual ratio of the printed layer.
  • the urethane resin is characterized by using a urethane resin derived from biomass, and includes a urethane resin having at least a structural unit (a1) derived from castor oil polyol.
  • Specific embodiments include urethane resins obtained by reacting a polyol containing a castor oil polyol with a diisocyanate.
  • a preferred embodiment is a urethane urea resin obtained by extending a chain of a urethane prepolymer obtained by reacting a polyisocyanate with a polyol containing a castor oil polyol with an amine compound.
  • diisocyanate known aromatic, aliphatic or alicyclic diisocyanates can be used.
  • the castor oil polyol may have a structural unit derived from ricinoleic acid (hereinafter, castor oil fatty acid) which is a component of castor oil.
  • a form in which the structural unit derived from ricinoleic acid is the main component in the total amount of castor oil polyol (50% by mass or more in the total amount of castor oil polyol) is preferable.
  • the structure is not particularly limited as long as the average number of functional groups of the hydroxyl group is 1 to 3, and examples thereof include castor oil and dehydrated castor oil.
  • castor oil fatty acid condensate obtained by condensing castor oil fatty acid with a polyol such as diol as an initiator, and hydrides thereof and the like can be mentioned.
  • These castor oil polyols can be used alone or in admixture of two or more.
  • the urethane resin preferably contains a structural unit derived from castor oil polyol in an amount of 10 to 80% by mass, more preferably 15 to 60% by mass, and more preferably 15 to 40% by mass, based on the resin solid content of the urethane resin. It is more preferable to contain it.
  • a structural unit derived from castor oil polyol is within the above range, it is easy to maintain or improve the dispersion stability of the colorant, the heat resistance of the printed layer, and the blocking resistance.
  • the molecular weight of the castor oil polyol is preferably 500 to 6,000, more preferably 1,000 to 5,000, still more preferably 1,500 to 4,000, and 1,500 to 3,500.
  • the range of is particularly preferable. When the weight average molecular weight is within the above range, it is easy to obtain excellent film strength and excellent adhesion to the foam layer forming layer (B 0) when the foamed paper laminate is formed. Become.
  • the urethane resin preferably contains a structural unit derived from a polyester polyol in addition to a structural unit derived from a castor oil polyol.
  • a structural unit derived from a castor oil polyol in addition to a structural unit derived from a castor oil polyol.
  • the polyester polyol is not limited to the following examples, but for example, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, and azelaic acid. , Sevacinic acid, suberic acid, glutaric acid, 1,4-cyclohexyldicarboxylic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol.
  • the amount of the polyester polyol used is such that the structural unit derived from the polyester polyol is contained in an amount of 15 to 80% by mass with respect to the resin solid content of the urethane resin from the viewpoint of heat resistance, film strength, and blocking resistance in the laminated body. It is preferable, more preferably 25 to 75% by mass.
  • the urethane resin preferably has a structural unit derived from a polyester polyol in addition to a structural unit derived from a castor oil polyol.
  • the polyester polyol is a condensate of the dibasic acid and the diol, and the mass ratio (a1) / (a2) of the structural unit (a1) derived from the castor oil polyol and the structural unit (a2) derived from the polyester polyol is , 75/25 to 10/90, more preferably 60/40 to 25/75, and even more preferably 50/50 to 25/75.
  • the binder resin contains a urethane resin obtained by using only castor oil polyol as a polyol component.
  • the binder resin contains a urethane resin obtained by using a castor oil polyol and a polyester polyol in combination as a polyol component.
  • the binder component may contain the urethane resin of the above embodiment and the urethane resin obtained by using only the polyester polyol as the polyol component.
  • a polyester polyol is used as the polyol component, it is more preferable that the structural unit derived from castor oil polyol and the structural unit derived from polyester polyol coexist in one polymer chain from the viewpoint of ink stability and the like. ..
  • the urethane resin may have a structural unit derived from a polyether polyol.
  • the polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and copolymerized polyetherdiols thereof. These polyether polyols can be used alone or in admixture of two or more.
  • the content of the structural unit derived from the polyether polyol is preferably 8% by mass or less, preferably 5% by mass or less, based on the total mass of the urethane resin. It is more preferably 2% by mass or less, and may be 0% by mass. From the viewpoint of improving the heat resistance of the printed layer, it is extremely preferable that the urethane resin does not contain structural units derived from the polyether polyol.
  • the urethane resin may have a structural unit derived from a small molecule polyhydric alcohol.
  • a structural unit derived from a low molecular weight polyhydric alcohol By introducing a structural unit derived from a low molecular weight polyhydric alcohol, various physical properties required for a resin for printing ink such as pigment dispersibility, resin viscosity, solubility in an organic solvent, and blocking resistance can be adjusted.
  • the low molecular weight polyhydric alcohol is not limited to the following examples, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, and cyclohexanedimethanol.
  • Glycerin 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, hydrogenated bisphenol A, tri Examples thereof include methylolpropane, glycerin, pentaerythritol, and sorbitol. These small molecule polyhydric alcohols are used for the purpose of adjusting the molecular weight of the ink composition of the present invention and the distribution of hard segments and soft segments. These small molecule polyhydric alcohols can be used alone or in admixture of two or more.
  • the amine compound functions as a chain extender for the urethane prepolymer and imparts a urea bond to the urethane resin.
  • Examples of the amine compound include polyamines and amino alcohols.
  • the chain extender can be used alone or in combination of two or more.
  • polyamines examples include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and dimerdiamine obtained by converting the carboxyl group of dimer acid into an amino group.
  • examples thereof include amines having a hydroxyl group in the molecule, methyliminobispropylamine, lauryliminobispropylamine and the like having a tertiary amino group in the molecule.
  • amino alcohols examples include N, N-dimethylethanolamine, N, N-dimethylethanolamine, N, N-dibutylethanolamine, N- ( ⁇ -aminoethyl) ethanolamine, N-methylethanolamine, and N-methyl.
  • reaction solvent For the production of the urethane resin, an organic solvent having no alcohol and / or a hydroxyl group, which is a medium described later, can be used.
  • alcohols include aliphatic alcohols having 1 to 7 carbon atoms such as methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, tertiary butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono.
  • examples thereof include glycol monoethers such as propyl ether, propylene glycol monoisopropyl ether and propylene glycol monobutyl ether.
  • a tertiary alcohol having low reactivity is preferable from the viewpoint of reactivity with the isocyanate group, and examples thereof include tertiary butanol.
  • organic solvent having no hydroxyl group examples include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, cyclic ethers such as tetrahydrofuran and dioxane, toluene and xylene and the like.
  • examples thereof include aromatic hydrocarbons, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethylsulfoxide and dimethylsulfamide. Two or more kinds of these reaction solvents may be mixed and used.
  • the method for producing the urethane resin is not particularly limited, and the urethane resin can be produced by a general chain extension reaction.
  • a castor oil polyol, a polyol other than castor oil polyol, and a diisocyanate are reacted under a solvent-free environment or an organic solvent having no hydroxyl group to produce an isocyanate group-containing prepolymer.
  • the above reaction is carried out at an equivalent ratio in which the isocyanate group of the diisocyanate is excessive with respect to the hydroxyl groups of the castor oil polyol and the polyol other than the castor oil polyol.
  • the isocyanate group-containing prepolymer obtained as described above is dissolved in an organic solvent having no hydroxyl group and / or a tertiary alcohol having low reactivity with the isocyanate group to obtain a prepolymer solution.
  • an organic solvent having no hydroxyl group and / or a tertiary alcohol having low reactivity with the isocyanate group to obtain a prepolymer solution.
  • the previously prepared isocyanate group-containing prepolymer solution is added to the chain extender dissolved in a solvent to cause a chain extension reaction.
  • the solvent used to dissolve the chain extender may be the same as the organic solvent used in the production of the prepolymer.
  • diamines and amino alcohols are preferably used as the chain extender from the viewpoint of reactivity with the isocyanate group-containing prepolymer.
  • the ratio of sardine oil polyol, polyol other than sardine oil polyol, and diisocyanate is the ratio of the number of moles of isocyanate groups of diisocyanate to the number of moles of hydroxyl groups of sardine oil polyols and polyols other than sardine oil polyols. It is preferable to adjust the NCO / OH ratio so as to be in the range of 1.1 to 3.0. When the NCO / OH ratio is within the above range, it is easy to maintain or improve the blocking resistance and the adhesion to the substrate.
  • the above embodiment is characterized by containing a urethane resin as a constituent component of the print layer, but does not exclude the combined use of a binder resin other than the urethane resin.
  • a binder resin other than the urethane resin.
  • Specific examples thereof are acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride / vinyl acetate copolymer, nitrocellulose and the like.
  • the combined use of urethane resin and vinyl chloride / vinyl acetate copolymer and / or nitrocellulose is preferable.
  • the binder resin further contains a vinyl chloride / vinyl acetate copolymer
  • the content is more preferably 70% by mass or more, further preferably 85% by mass or more.
  • the mass ratio of the urethane resin containing the urethane resin to the vinyl chloride / vinyl acetate copolymer is preferably 40:60 to 95: 5, and more preferably 55:45 to 90:10. , 70:30 to 90:10 is extremely preferable.
  • the ink composition may further comprise a colorant.
  • a colorant for example, those used in ordinary ink compositions such as organic pigments, inorganic pigments, and dyes may be used. C.I. I. Pigments can be preferably used.
  • organic pigments examples include azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine-azo-based, dictopyrrolopyrrole-based, and isoindoline-based. Etc. are preferably mentioned.
  • inorganic pigment examples include carbon black, aluminum powder, bronze powder, chrome vermillion, chrome yellow, cadmium yellow, cadmium red, ultramarine, navy blue, red iron oxide, yellow iron oxide, iron black, titanium oxide, zinc oxide and the like. Be done.
  • the dye examples include tartradin lake, Rhodan 6G lake, Victoria pure blue lake, alkaline blue G toner, brilliant green lake, and the like, and coal tar and the like can also be used. Above all, it is preferable to use an organic pigment or an inorganic pigment from the viewpoint of water resistance and the like.
  • the colorant is not particularly limited, and may be an amount sufficient to secure the concentration and coloring power of the ink composition.
  • the content of the colorant is generally 0.5 to 50% by mass with respect to the total mass of the ink composition.
  • the colorant can be used alone or in combination of two or more.
  • the blending amount of the white pigment is preferably in the range of 20 to 50% by mass based on the total mass of the ink composition. From the viewpoint of hiding power, pigment concentration, and light resistance, it is preferable to use titanium dioxide as the white pigment.
  • a colored organic pigment and a colored inorganic pigment such as red iron oxide, prussian blue, ultramarine, carbon black, and graphite can be appropriately selected and used. Organic pigments are preferable from the viewpoint of color development and light resistance.
  • the blending amount of the colored pigment is preferably in the range of 5 to 30% by mass based on the total mass of the ink composition.
  • the ink composition comprises an organic solvent as a liquid medium.
  • organic solvent include, but are not limited to, aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate and isopropyl acetate.
  • organic solvents such as isobutyl acetate, ester organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcohol-based organic solvents, ethylene glycol monopropyl ether and propylene glycol monotyl ether and other glycol ether-based solvents. Can be used, and may be mixed and used. Of these, an organic solvent (non-toluene-based organic solvent) that does not contain aromatic organic solvents such as toluene and xylene is more preferable.
  • the compatibility between the urethane resin and the vinyl chloride copolymer resin, the organic solvent containing the ester-based organic solvent and the alcohol-based organic solvent is preferable, and the mass ratio (ester-based organic solvent) / (alcohol-based organic solvent) of these is 90. It is preferably / 10 to 40/60.
  • the gravure ink may contain water as a liquid medium, but the content thereof is preferably 0.1 to 5% by mass in 100% by mass of the liquid medium.
  • the ink layer and the ink composition may contain additives such as pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, defoaming agents, antistatic agents, viscosity modifiers, chelate crosslinkers, as required.
  • additives such as pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, defoaming agents, antistatic agents, viscosity modifiers, chelate crosslinkers, as required.
  • a trapping agent, an antiblocking agent, a wax component, an isocyanate-based curing agent, a silane coupling agent, or the like can be used.
  • the ink composition can be produced by a known method, for example, the method described in International Publication No. 2009/11800 pamphlet can be used. More specifically, a urethane resin, a vinyl chloride / vinyl acetate copolymer, and an organic solvent having a mass ratio (ester-based organic solvent) / (alcohol-based organic solvent) of 90/10 to 40/60 are sand milled. Dispersion treatment is performed with another bead mill for about 5 to 60 minutes, and a urethane resin, the above-mentioned organic solvent, a leveling agent and other additives are further added to the obtained dispersion, and the mixture is uniformly stirred to obtain an ink composition. be able to.
  • One embodiment relates to a method for manufacturing a foamed paper laminate. That is, one embodiment includes a foam paper having a thermoplastic resin layer (A), a paper base material, and a foam layer (B) in that order, and a printing layer formed on the surface of the foam layer (B) of the foam paper.
  • the present invention relates to a method for producing a foamed paper laminate having the above. More preferably, in the configuration of the foamed paper laminate, the number of foamed cells per unit surface area of the foamed layer (B) is 1000 cells / 1 cm 2 or more, and printing is performed after immersion in ethanol at 25 ° C. for 30 minutes.
  • the present invention relates to a method for producing a foamed paper laminate having a layer residual ratio of 50% by mass or more.
  • the method for producing the foamed paper laminate is described in the following steps (i) to (iv), that is, (i) the thermoplastic resin layer (A), the paper substrate, and the melting point lower than that of the thermoplastic resin layer (A).
  • a foamed paper material having sequentially having a foamed layer forming layer (B 0), which foams by heating.
  • (Ii) Preparing an ink composition containing a binder resin containing a urethane resin and a medium.
  • Applying the ink composition to the surface of the foam layer forming layer (B 0) of the foam paper material to form a print layer.
  • the foamed paper material having the printed layer is heated to foam the foamed layer forming layer (B 0 ) of the foamed paper material to form the foamed layer (B).
  • each step relating to (i) preparation of foamed paper material, (ii) preparation of ink composition, (iii) formation of printing layer, and (iv) formation of foamed layer (B) by heating is the same. It can be carried out according to a method well known in the technical field. Hereinafter, each step will be described.
  • Step (i): Preparation of foam paper material The preparation of the foamed paper material can be carried out, for example, according to the extrusion laminating method.
  • the constituent materials of the paper base material, the thermoplastic resin layer (A), and the foamed layer forming layer (B 0 ) constituting the foamed paper material are as described above.
  • the extrusion laminating method a well-known method such as a single laminating method, a tandem laminating method, a sandwich laminating method, and a coextrusion laminating method can be appropriately selected.
  • polyethylene resins having different melting points can be preferably used as the constituent materials of the thermoplastic resin layer (A) and the foamed layer forming layer (B 0).
  • the foam layer forming layer (B 0 ) is formed by using a polyethylene resin (low Mp polyethylene resin) having an Mp lower than the melting point (Mp) of the polyethylene resin constituting the thermoplastic resin layer (A).
  • a low Mp polyethylene resin is extruded into a film on one side of the paper substrate and a high Mp polyethylene resin is extruded into a film on the other surface of the paper substrate through a T-die extruder.
  • Mp melting point
  • the temperature of the polyethylene resin at the time of laminating is preferably 300 to 350 ° C, more preferably 320 ° C to 340 ° C. Within this temperature range, sufficient lamination strength can be realized between each polyethylene resin layer (A, B 0) and the paper substrate. It is preferable to control the surface temperature of the cooling roll that passes after laminating in the range of 10 to 50 ° C.
  • the laminating speed is preferably 50 to 130 m / min, more preferably 60 to 110 m / min. If the laminating speed is too slow, the productivity will be low, while if the laminating speed is too fast, the neck-in tends to reduce the yield.
  • Neck-in is a phenomenon in which the width of the extruded polyethylene resin film is smaller than the effective width of the T-die when the polyethylene resin is extruded into a film by a T-die extruder. At this time, both ends of the film are thicker than the central portion. When the thickness of both ends deviates from the standard, it is common to cut and remove both ends, but when the neck-in is severe, the area deviating from the standard increases and the yield decreases.
  • the air gap is preferably 300 mm or less, more preferably 200 mm or less. If the air gap is widened too much, the polyethylene resin will neck in and the yield will tend to decrease.
  • the air gap refers to the distance from the T-die extrusion port to the nip roll. It is preferable to surface-treat the polyethylene resin with ozone gas and / or oxygen gas while the polyethylene resin passes through the air gap. By performing the surface treatment using ozone gas and / or oxygen gas, the formation of an oxide film can be promoted and the adhesive force with the base material layer can be improved.
  • the amount of ozone gas and / or oxygen gas to be treated is not particularly limited, but 0.5 mg / m 2 or more is preferable from the viewpoint of promoting the oxidation of the polyethylene resin.
  • Step (ii): Preparation of ink composition The specific composition, production, and the like of the ink composition are as described above in the embodiment of the ink composition.
  • the binder resin is characterized by being a urethane resin produced by using at least castor oil polyol as a polyol component.
  • a biomass-derived urethane resin preferably has a stress of 0.1 mPa to 50 mPa at an elongation rate of 50 to 4,000%.
  • the formation of the print layer (iii) is not particularly limited, and a well-known technique can be applied.
  • a coater such as a bar coater, a roll coater, or a reverse roll coater may be used.
  • various printing methods can be applied.
  • the ink composition of the embodiment described above can be preferably used.
  • the print layer preferably comprises a plurality of layers.
  • the print layer may have a base layer that covers the entire surface of the foam layer forming layer (B 0 ) and a print pattern provided on at least a part of the surface of the base layer.
  • the base layer is composed of a white ink composition and the print pattern is formed of a color ink composition.
  • the thickness of the printed layer is preferably adjusted so that the film thickness of the dry coating film is 0.5 to 5 ⁇ m from the viewpoint of the foaming suppressing force of the printed layer and the friction resistance. ..
  • the film thickness of the printed layer (dry coating film) may be more preferably 0.5 to 4 ⁇ m, still more preferably 0.5 to 3.5 ⁇ m.
  • the print layer may include a plurality of layers and may have a transparent layer as the outermost layer thereof.
  • the lucidum can be configured using a pigment-free clear ink composition.
  • the appropriate heating temperature and heating time vary depending on the characteristics of the paper substrate used and the thermoplastic resin film.
  • a person skilled in the art can determine the combination conditions of the optimum heating temperature and heating time according to the material such as the thermoplastic resin film used.
  • the heat treatment is generally carried out in the molding process of the container. If the heating temperature during the heat treatment is too low, sufficient foamability cannot be obtained, and if the heating temperature is too high, the foaming cells are combined and swelling is likely to occur.
  • the heating temperature may be preferably 100 to 125 ° C, more preferably 110 to 120 ° C.
  • the heating time can be appropriately adjusted according to the heating temperature, but is preferably 3 to 10 minutes, more preferably 5 to 7 minutes.
  • the heating temperature is 110 to 123 ° C. It is preferable to adjust the heating time to 5 to 7 minutes. It is more preferable to adjust the heating temperature to 115 to 121 ° C. and the heating time to 5 to 7 minutes.
  • Any means such as hot air, electric heat, and electron beam can be used as the heating means.
  • a large amount of heat treatment can be carried out inexpensively by heating with hot air, electric heat, or the like in a tunnel provided with a transport means by a conveyor.
  • FIG. 1 is a perspective view showing the structure of a foamed paper container 10A obtained by performing a heat treatment after assembling and molding the container.
  • the foamed paper container 10A is composed of a container body member 10 made of a foamed paper laminate and a bottom plate member 12.
  • the high Mp resin film forms the inner wall surface 10a of the container
  • the printing layer on the low Mp resin film forms the outer wall surface 10b of the container.
  • FIG. 2 is a schematic cross-sectional view showing an enlarged reference numeral I portion of the container body member of the foam paper container shown in FIG.
  • the container body member (foamed paper laminate) 10 includes a high Mp resin film 20, a paper base material 30, and a low Mp resin film (foamed layer) 40 after foaming, in order from the inner wall surface 10a side (see FIG. 1) of the container. And a print layer 50, and the print layer 50 has a base layer 50a and a print pattern 50b.
  • Molding of foamed paper containers can be carried out by applying well-known technology. For example, a foamed paper laminate (foamed paper laminate before heating) on which a print layer is first formed is punched into a predetermined shape along a mold to obtain a container body member. Similarly, the bottom plate material is punched into a predetermined shape to obtain a bottom plate member. Next, the container body member and the bottom plate member are assembled and molded into the shape of the container by using a conventional container manufacturing apparatus. In the assembly and molding of the container by the container manufacturing apparatus, the high Mp resin film of the container body member forms the inner wall surface, the low Mp resin film forms the outer wall surface, and the laminated surface of the bottom plate member is on the inside. To carry out.
  • the low Mp resin film can be foamed to form a foamed layer (heat insulating layer), and a foamed paper container having heat insulating properties can be obtained. can.
  • one surface of the paper base material is made of medium-density or high-density polyethylene film. It is preferable to laminate the other surface (outer wall surface of the container) with a low-density polyethylene film.
  • the thickness of each film laminated on the paper substrate is not particularly limited. However, the thickness of the low Mp resin film constituting the outer wall surface of the container body is appropriately set so that the foamed film has a sufficient thickness to function as a heat insulating layer when the film is foamed. Is preferable.
  • the thickness of the film laminated on the paper substrate may be 40 to 150 ⁇ m.
  • the thickness of the film laminated on the paper substrate is not particularly limited. However, it is preferable to appropriately set the thickness of the film so that the permeability resistance of the contents is ensured when used as a heat-insulating foamed paper container. Since the thickness of the film to be laminated on the paper substrate varies depending on the resin material of the film used, it is desirable to be appropriately set by those skilled in the art in consideration of the characteristics of the resin material.
  • Binder resin (1) Raw material for urethane resin (castor oil polyol and other raw materials)
  • the castor oil polyols used in the synthesis of the following urethane resins are various commercially available polyols and polyols obtained by synthesizing according to a known method shown in JP-A-2005-320437.
  • the raw materials not described as "biomass-derived” in the raw materials described below are raw materials not derived from biomass.
  • IPDA isophoronediamine
  • IBPA iminobispropylamine
  • AEA N- (2-hydroxyethyl) ethylenediamine
  • IPA ethyl / 2-propanol
  • the mixture was added and then reacted at 80 ° C. for 1 hour to obtain a urethane resin solution PU1 (solid content 30%) having a weight average molecular weight of 65,000.
  • the weight average molecular weight of the urethane resin was measured as follows. (Weight average molecular weight) As a pretreatment, all the amino groups at both ends of the urethane resin are reacted with ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate. Then, for the pretreated urethane resin, Polystyrene GPC LF-604 (manufactured by Shodex) was used as a column, and gel permeation chromatography equipped with an RI detector (manufactured by GPC Shodex, GPC-104) was used as a developing solvent in tetrahydrofuran (GPC-104). The polystyrene-equivalent molecular weight when using THF) was obtained.
  • urethane resin solution solid content 30%
  • the gravure ink W1 is an ink using PU1 (a urethane resin having a structural unit derived from castor oil polyol and a structural unit derived from polyester polyol in one polymer chain).
  • the gravure ink 20 is an ink in which PU8 (urethane resin having a structural unit derived from castor oil polyol) and PU14 (urethane resin having a structural unit derived from polyester polyol) are used in combination. Therefore, from the viewpoint of ink stability, it can be seen that the urethane resin in which the structural unit derived from castor oil polyol and the structural unit derived from polyester polyol coexist in the polymer chain is preferable.
  • foamed paper laminate (1) Production example of foamed paper material
  • the foamed paper material is (step 1) a water vapor blocking layer obtained by extruding and laminating a medium density polyethylene resin (M) on one side of a paper base material. Then, the low-density polyethylene resin (L) was extruded and laminated on the other surface (non-laminated surface) of the paper substrate (step 2).
  • step 1 and step 2 Various conditions in step 1 and step 2 are as follows.
  • Paper substrate Moisture content 23 kg / m 3 , Basis weight 300 kg / m 3
  • Air gap 130 mm
  • Thickness 40 ⁇ m (thickness of the central part of the polyethylene resin layer)
  • Step 2 Low density polyethylene resin (L); Extrusion temperature (T die outlet temperature) described later: 310 ° C. Pick-up speed (lamination speed): 60 m / min Air gap: 130 mm Thickness: 50 ⁇ m
  • the low-density polyethylene resin (L) used in the above step 2 is a foam layer forming layer (B 0 ).
  • low-density polyethylene resin (L) low-density polyethylene resins (L2) and (L3) are used in Examples 23 and 24 and Comparative Example 2, and low-density polyethylene resin (L1) is used in other cases for foaming.
  • Manufactured paper material Details of the low-density polyethylene resins (L1), (L2) and (L3) are as follows. Low-density polyethylene resin (L1): Toso Co., Ltd.
  • MEK methyl ethyl ketone
  • NPAC n-propyl acetate
  • IPA 40: 40: 20 (mass ratio).
  • Dilute to (25 ° C., Zahn cup No. 3) and use a gravure printing machine with a corrosion of 30 ⁇ m on a low-density polyethylene resin (L1) as a foam paper material at a printing speed of 100 m / min to achieve a film thickness of 1.
  • L1 low-density polyethylene resin
  • the thickness of the printed layer was determined from a scanning electron microscope (SEM) photograph (magnification of 5000) of the cross section of the foamed paper laminate. The print layer was measured at any five points, and the average value thereof was taken as the film thickness of the print layer.
  • SEM scanning electron microscope
  • Example 2 Examples 2 to 25, Comparative Examples 1 to 3
  • Table 4 printing was performed in the same manner as in Example 1 except that each printing ink was used, and a printing layer having a film thickness of 1.5 ⁇ m was formed.
  • the film thickness of the print layer was 2.5 ⁇ m because the overprinting was performed.
  • the low-density polyethylene resin (L2) was used instead of the low-density polyethylene resin (L1), and in Example 24, the low-density polyethylene resin (L1) was replaced with the low-density polyethylene resin (L1). L3) was used.
  • the foam paper laminate (after foaming) is reheated to improve the heat resistance. evaluated. Specifically, first, with respect to the foam paper laminates of Examples 1 to 25 and Comparative Examples 1 to 3, an aluminum foil cut to the same size as the print layer was superposed on the surface of the print layer (coating film). Next, using a heat seal tester heated to 140 ° C., the aluminum foil portion was pressed at a pressure of 2 kg / cm 2 for 1 second.
  • the evaluation criteria are as follows. (Evaluation criteria) 5: No ink adhesion to the aluminum foil (ink adhesion cannot be confirmed). 4: Ink adhesion to the aluminum foil is confirmed, but it is less than 3%. 3: Ink adhesion to the aluminum foil is 3% or more and less than 10%. 2: Ink adhesion to aluminum foil is 10% or more and less than 30%. 1: Ink adhesion to aluminum foil is 30% or more.
  • the evaluation criteria are as follows. (Evaluation criteria) 5: Ink peeling is less than 30%. 4: Ink peeling is 30% or more and less than 40%. 3: Ink peeling is 40% or more and less than 60%. 2: Ink peeling is 60% or more and less than 70%. 1: Ink peeling is 70% or more.
  • the thickness of the foam layer and the number of foam cells of the foam paper laminate were measured according to the method described below.
  • the thickness of the foamed layer is 500 ⁇ m or more, and the number of foamed cells is 1250 cells / 1 cm 2 or more, so that sufficient heat insulating properties are obtained in practical use. I was able to confirm that it was possible.
  • the foam sheet laminate of Comparative Example 3 although the thickness of the foamed layer was greater than 500 [mu] m, a number of foamed cells is less than 1000/1 cm 2, not possible to obtain sufficient heat insulating property in a practical rice field.
  • the printed layer of the foamed paper laminate was removed with methyl ethyl ketone (MEK) to expose the surface of the foamed thermoplastic resin layer (foamed layer).
  • MEK methyl ethyl ketone
  • the surface of the foam layer was observed using an optical microscope (AZ100M manufactured by Nikon Corporation) (magnification 25 times), and an independent cell existing within a range partitioned by a certain length in the vertical and horizontal (XY) directions. The number of independent cells was obtained, and the value calculated as the number of independent cells per 1 cm 2 was obtained. Observation was performed at any 5 points, and the average value of these was taken as the number of foamed cells.
  • the film thickness of the foam layer was determined by observing the cross section of the foam paper laminate with an optical micrograph and measuring the height from the upper surface of the paper substrate to the lower surface of the print layer. Further, the film thickness before foaming corresponds to the film thickness of the foamed layer forming layer. Therefore, the value obtained by measuring the film thickness of the low-density polyethylene resin formed as the foam layer forming layer was used.
  • the present invention has a printed layer containing a biomass resin, excellent heat resistance, foaming followability, foaming appearance, and ethanol resistance are obtained, and is suitable as a member of a foamed paper container. It can be seen that a usable foamed paper laminate can be provided.

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Abstract

L'invention concerne un stratifié de papier mousse comprenant : un papier mousse composé d'un papier de base, d'une couche de résine thermoplastique (A) disposée sur une surface du papier de base et d'une couche de résine thermoplastique expansée (B) disposée sur l'autre surface du papier de base ; et une couche d'impression disposée sur la couche de résine thermoplastique expansée (B), la couche d'impression contenant au moins une résine liante et la résine liante contenant une résine d'uréthane ayant un motif structurel dérivé du polyol d'huile de ricin.
PCT/JP2021/025927 2020-07-17 2021-07-09 Stratifié de papier mousse WO2022014484A1 (fr)

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JP2015231870A (ja) * 2014-05-13 2015-12-24 凸版印刷株式会社 蓋材とそれを用いた包装容器
JP2018058955A (ja) * 2016-10-03 2018-04-12 Ｄｉｃグラフィックス株式会社 発泡カップ用水性フレキソインキ及び発泡カップ
JP2018109131A (ja) * 2017-01-06 2018-07-12 東洋インキＳｃホールディングス株式会社 グラビアインキ、それを用いた印刷物および積層体
JP2019214669A (ja) * 2018-06-12 2019-12-19 サカタインクス株式会社 ラミネート用印刷インキ組成物
JP2020055575A (ja) * 2018-09-28 2020-04-09 大日本印刷株式会社 包装材料及び包装製品

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