WO2023173685A1 - 一种可生物堆肥降解的透明改性生物基材料,在自粘应用领域实现与薄膜材料相同的性能 - Google Patents

一种可生物堆肥降解的透明改性生物基材料,在自粘应用领域实现与薄膜材料相同的性能 Download PDF

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WO2023173685A1
WO2023173685A1 PCT/CN2022/114871 CN2022114871W WO2023173685A1 WO 2023173685 A1 WO2023173685 A1 WO 2023173685A1 CN 2022114871 W CN2022114871 W CN 2022114871W WO 2023173685 A1 WO2023173685 A1 WO 2023173685A1
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bio
oil
label
based material
cellulose
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PCT/CN2022/114871
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English (en)
French (fr)
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黄素朴
杨森
张顺伟
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嘉兴市豪能科技股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18Block or graft polymers
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions

Definitions

  • the present disclosure relates to the field of degradable and compostable bio-based materials, specifically to transparent modified bio-based materials that can achieve the same performance as plastic film substrates, and more specifically to the field of label printing technology.
  • Biobased material has good tensile strength, gloss, transparency and printability. It also has good heat resistance and can be used for high-temperature sterilization together with food. Films made of bio-based materials are easy to biodegrade and have little impact on the environment, but they are easy to tear and absorb water and soften. Since most beer and other beverage labels have very high water resistance requirements, the widespread use of such degradable materials as label substrates is affected.
  • the substrate is impregnated with a suspension of inorganic nanoparticles or the surface is sprayed with a superhydrophobic coating containing inorganic nanoparticles.
  • Commonly used nanoparticles are TiO 2 , SiO 2 and ZnO.
  • the transparency performance of the film obtained by this method is greatly affected, and it is difficult to meet the aesthetic requirements of the above-mentioned beverage and food labels.
  • Another example is to increase the surface roughness of the substrate, and then chemically deposit low surface energy substances such as fluorine-containing, long carbon chain polymers on the surface.
  • the present disclosure aims to provide a method for preparing a transparent and degradable label base material with good water resistance that can be obtained through industrial production, a material prepared thereby, and a label including the material.
  • the present disclosure provides a method for preparing water-resistant degradable modified bio-based materials, which method includes the following steps:
  • UV irradiation is performed on the surface of the bio-based material coated with UV primer to solidify the UV primer to form a degradable polymer and at least part of the degradable polymer is modified with cellulose grafted on the surface of the bio-based material
  • the agents are covalently linked through a reaction to form a primer layer.
  • bio-based materials may include, but are not limited to, regenerated cellulose films, natural cellulose films, cellulose derivative films, other bio-based polymers (such as polylactic acid PLA, polyhydroxyalkanoate PHA, microfiber Films formed from degradable bio-based materials such as cellulose (MFC, etc.) or mixtures of two or more thereof, provided that these materials can undergo the grafting reaction of the above-mentioned modifiers.
  • bio-based polymers such as polylactic acid PLA, polyhydroxyalkanoate PHA, microfiber Films formed from degradable bio-based materials such as cellulose (MFC, etc.
  • the bio-based material is one or more of PLA, PHA and MFC.
  • the bio-based material is a film material with a thickness of about 10 to 130 ⁇ m, preferably 30 to 50 ⁇ m, and more preferably 35 to 45 ⁇ m.
  • the cellulose dissolving liquid is a pre-cooled -9-15°C aqueous solution containing 6-10 wt% alkali metal hydroxide and 8-16 wt% urea.
  • a hydrogen bond network structure is formed between alkali, urea and water, and the lower the temperature, the more stable the structure is. Lowering the temperature can promote the dissolution of cellulose.
  • the interaction time between the cellulose solution and cellulose is 30 to 180 seconds.
  • the cellulose solution can partially swell and dissolve the cellulose molecules on the surface of the bio-based material, thereby facilitating further grafting reaction at the solid-liquid interface.
  • the cellulose solution contains a certain amount of alkali, which can serve as a catalyst for the grafting reaction and facilitate the grafting reaction.
  • the alkali metal hydroxide can be sodium hydroxide, potassium hydroxide, etc.
  • the cellulose molecules on the surface of the bio-based material can be further dissolved, fully exposing the hydroxyl groups in the molecules, and at the same time, the cellulose modifier can react with the hydroxyl groups to complete the grafting .
  • the cellulose modifier includes at least two functional groups, wherein the first functional group reacts with at least part of the hydroxyl groups in the cellulose molecules on the surface of the bio-based material, and the second functional group The group reacts with at least part of what forms the base coating, such as a cross-linker or initiator to attach to the UV curable resin, thereby forming a covalent bond between the bio-based material surface and the base coating.
  • the first functional group reacts with at least part of the hydroxyl groups in the cellulose molecules on the surface of the bio-based material
  • the second functional group reacts with at least part of what forms the base coating, such as a cross-linker or initiator to attach to the UV curable resin, thereby forming a covalent bond between the bio-based material surface and the base coating.
  • the first functional group is an epoxy group or a halogen and the second functional group is an alkenyl group.
  • the epoxy group or halogen in the cellulose modifier reacts with at least part of the hydroxyl groups in the cellulose molecules on the surface of the bio-based material to form ether bonds, and the alkenyl group reacts with the moiety forming the base coating.
  • UV curable resin polymerizes and connects to each other.
  • the cellulose modifier containing an epoxy group may be selected from alkyl esters of acrylic acid containing a propylene oxide group, alkyl esters of methacrylic acid containing a propylene oxide group, and allyl alkyl esters containing a propylene oxide group.
  • At least one of alkyl ethers of C 0 -C 10 alkyl allyl chloride and C 0 -C 10 alkyl allyl bromide can be selected from one or more of allyl chloride, allyl bromide, methylallyl chloride and methylallyl bromide.
  • the cellulose modifier is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl methacrylate, allyl chloride, allyl bromide, At least one of methylallyl chloride and methylallyl bromide.
  • the coating amount of the cellulose modifier is 1 to 5g/m 2 , such as 2g/m 2 , 3g/m 2 or 4g/m 2 ; the specific coating amount can be selected according to The specific cellulose modifier to choose.
  • the epoxy group when the cellulose modifier contains an epoxy group, the epoxy group undergoes a ring-opening reaction and shrinks with the hydroxyl group in the cellulose molecule to form an ether bond.
  • This reaction can be carried out under mild conditions. Due to the high tension of the three-membered ring, the epoxy group can undergo a ring-opening reaction with nucleophiles such as hydroxyl groups under mild conditions to form an ether bond.
  • the cellulose modifier when the cellulose modifier contains a halogen, the halogen group shrinks with the hydroxyl group in the cellulose molecule to form an ether bond.
  • the reaction can also be carried out under mild conditions.
  • the UV curing resin contained in the UV base oil is selected from the group consisting of water-based UV curing resin and vegetable oil-based UV resin.
  • the water-based UV curable resin is selected from polyepoxy acrylic acid C 1 -C 30 alkyl ester, polyurethane acrylic acid C 1 -C 30 alkyl ester, polyacrylic acid C 1 -C 30 alkyl ester and polyester acrylic acid C 1 -C 30 alkyl esters. Preference is given to polyurethane C 1 -C 30 alkyl acrylates and polyacrylates C 1 -C 30 alkyl esters. Water-based UV curable resins are usually used in the form of mixtures, such as a mixture of polyurethane acrylates or a mixture of polyacrylates with an alkyl group length ranging from 1 to 30 carbon atoms.
  • the vegetable oil-based UV resin is selected from the group consisting of vegetable oil-based epoxy acrylic resin, vegetable oil-based polyacrylic resin and vegetable oil-based polyurethane acrylic resin, wherein the vegetable oil is selected from the group consisting of soybean oil, castor oil, linseed oil, linseed oil, corn oil, and olive. oil, sunflower seed oil, cottonseed oil, rapeseed oil, peanut oil, palm oil, palm kernel oil, tung oil and rosin oil.
  • the vegetable oil-based UV resin is castor oil-based polyacrylic resin, palm oil-based polyurethane acrylic resin, and/or soybean oil-based polyurethane acrylic resin, etc.
  • the above-mentioned UV curable resin is degradable and has good printability.
  • UV-curable resins are well known to those skilled in the art and refer to polymers or prepolymers in which the polymer or prepolymer can be further cross-linked and cured by UV irradiation with the aid of, for example, diluents, photoinitiators, catalysts and/or other required auxiliaries. of resin.
  • the present disclosure does not specifically limit the use of UV curable resin and the necessary curing assistants, as long as it can react with the cellulose modifier connected to the surface of the bio-based material under UV irradiation conditions.
  • Useful photoinitiators include, for example, benzoin and derivative photoinitiators, benzoyl photoinitiators, alkylphenone photoinitiators, and acyl phosphorus oxide photoinitiators.
  • the photoinitiator can be 2,4,6-trimethylbenzoyl-diphenylphosphorus oxide (TPO), 1173 (2-hydroxy-2-methyl-1-phenyl acetone) , 184 (1-hydroxycyclohexyl phenyl ketone), 2959 (2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone), etc., but are not limited to these.
  • Diluents are usually compounds having 2 to 6, preferably 2 to 4 alkenyl groups.
  • diluent can be added according to specific circumstances.
  • the diluent is an acryloxy group-containing polymerizable monomer, and more preferably at least part of the diluent can be used as a cross-linking agent at the same time.
  • Useful diluents are, for example, isobornyl acrylate, acryloylmorpholine, tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate , neopentyl glycol diacrylate, diethylene glycol phthalate diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc., but are not limited to these.
  • the base oil is formed by curing a UV curing resin mainly containing at least one of the above-mentioned water-based UV curing resin or vegetable oil-based UV resin under the irradiation of ultraviolet light to form a base coating.
  • the UV base oil also contains the necessary additives as described above necessary for curing the UV curable resin.
  • the base oil may include 35 to 50 wt% of degradable UV curable resin, 45 to 63 wt% of diluent, and 0.5 to 5 wt% of photoinitiator.
  • the primer may include about 40 wt% of degradable UV curable resin, about 57 to 59 wt% of diluent, and about 1 to 3 wt% of photoinitiator.
  • the coating amount of the UV curable resin is such that the thickness of the finally obtained primer layer is ⁇ 3 ⁇ m, preferably 1 to 3 ⁇ m.
  • the conditions for performing light curing to form a primer layer may vary according to the type of resin in the selected UV primer.
  • the UV primer is commercially available, and its usage method and specific process conditions are well known to those skilled in the art, and will not be described in detail here.
  • part of the UV primer can undergo free radical polymerization with the alkenyl group of the grafted cellulose modifier at the interface of the bio-based material through interfacial free radical polymerization, thereby making the cured primer
  • the layers can be covalently linked to bio-based materials. The material formed in this way further improves the water resistance and can reach the optimal level.
  • the base coating is formed on both sides of the bio-based material.
  • the present disclosure provides a modified bio-based material prepared according to the above method, especially a label material, more specifically water-resistant and degradable PLA.
  • the label material provided by the present disclosure has a covalently bonded degradable base coating on its surface.
  • the interlayer bonding is tight and firm, the water resistance is significantly improved, and the entire base material is degradable.
  • cellulose modifiers allows the base coating to be more easily and uniformly connected to bio-based materials through reaction, avoiding problems such as reduced initiation efficiency and incomplete combination caused by direct grafting of polymerization initiators.
  • the present disclosure provides a label, which includes the above-mentioned modified bio-based material, which is in the form of a film, especially one or more of water-resistant and degradable PLA, PHA and MFC, and is located on the An ink layer is printed on the first surface of the modified bio-based material.
  • the label further includes a varnish protective layer located on the printing ink layer.
  • the label further includes an adhesive layer, which may be located on the second surface of the modified bio-based material or on the printing ink layer. According to other embodiments, the adhesive layer may also be located on the varnish protective layer.
  • the adhesive layer may be formed of a pressure-sensitive adhesive.
  • the coating amount of the adhesive is 6 to 16 g/m 2 , for example, 10 to 16 g/m 2 .
  • the adhesive layer further has a composite release material layer, including release paper and release film.
  • the first surface of the modified bio-based material is a surface with a primer layer and the second surface is a surface without a primer layer.
  • both the first surface and the second surface of the modified bio-based material are surfaces with a primer layer.
  • both surfaces of the modified bio-based material have primer layers, the water resistance of the modified bio-based material is better.
  • the printing ink may be UV ink, solvent-based ink or water-based ink.
  • the printing method can be flexographic printing, gravure printing, offset printing or silk screen printing.
  • the present disclosure has no particular limitations on printing inks and printing methods.
  • the UV varnish cured layer plays a role in protecting the printing ink, and preferably has a thickness of ⁇ 3 ⁇ m, preferably 1 to 3 ⁇ m. More preferably, the UV varnish cured layer is degradable and can be formed of degradable UV curable resin.
  • the degradable UV curing resin used for the varnish cured layer can also be a vegetable oil-based UV resin; the vegetable oil-based UV resin is selected from soybean oil, castor oil, linseed oil, linseed oil, corn oil, olive oil, and sunflower seeds.
  • the present disclosure has no particular limitations on the degradable UV curable resin used for the varnish cured layer and the formation method of the UV varnish cured layer, and any suitable UV varnish products and methods can be used.
  • the thickness of the label is 20-150 ⁇ m, preferably 50-70 ⁇ m, and more preferably 55-65 ⁇ m.
  • the label has a 180° peel strength of 6 to 16 N/cm, and a holding tack of greater than or equal to 8.
  • the label may also have an aluminum-plated layer located between the printing ink layer and the varnish protective layer.
  • the thickness of the aluminum plating layer can be 0.03 ⁇ 0.05 ⁇ m.
  • the aluminum coating can be obtained using conventional vacuum aluminum plating methods.
  • the label provided by the present disclosure is a transparent label, especially a water-resistant and degradable transparent label used for beer, beverages and other food and beverages.
  • the label may be a single wet glue label without an adhesive layer, a pre-glued disc label with an adhesive layer, or a self-adhesive label with an adhesive layer and a composite release material layer.
  • the modified bio-based materials provided by the present disclosure contain epoxy alkyl groups while ensuring the tensile strength, gloss, printability, heat resistance and degradability of the material.
  • the vinyl monomer such as glycidyl methacrylate GMA, reacts with the hydroxyl groups on the surface of the bio-based material, reducing the hydrophilic hydroxyl groups and introducing double bonds on the surface of the bio-based material; then, the coated degradable UV primer Oil, through interfacial free radical polymerization, polymerizes on the surface of the bio-based material to form a primer that is covalently connected to the surface of the bio-based material, thereby providing a material with further improved transparency and water resistance.
  • GMA glycidyl methacrylate
  • the modified bio-based material prepared according to the method of the embodiment of the present disclosure will not peel off between its water-resistant base coating and the film of the material, which improves the tear strength of the material.
  • This method has simple and easy-to-control steps, low cost, high surface reactivity, uniform polymerization, and the final material obtained has high water resistance and durability.
  • the label prepared using the modified bio-based material provided by the present disclosure has excellent water resistance.
  • a large amount of water is dripped on the label and baked at 50°C.
  • the label does not deform within 90 minutes. It is soaked in ice water and placed in a 4°C refrigerator. The label did not deform after 7 days of treatment, which shows that the modified label has excellent water resistance.
  • the label's hundred-grid adhesion can reach the optimal level; Grade 5B (ASTM label); the degradability is good, and the weight loss half-life can be reached within 27 days; and the transparency can reach more than 80%.
  • Figure 1 is a schematic structural diagram of a label according to an embodiment of the present disclosure.
  • Figure 2 is a schematic structural diagram of a label according to another embodiment of the present disclosure.
  • Figure 3 is a schematic structural diagram of a label according to yet another embodiment of the present disclosure.
  • Figure 4 is the ATR-FTIR spectrum of grafted materials prepared according to Examples 1 to 6 and untreated materials.
  • the terms "comprises,” “comprises,” or any other variation thereof are intended to cover a non-exclusive inclusion, such that a process or product including a list of elements includes not only those elements expressly recited, but also elements not expressly listed. other elements, or elements inherent to the implementation of the method or product.
  • bio-based materials used in this article refers to a type of materials produced through biological, chemical, physical and other means using renewable biomass and/or raw materials obtained through biological manufacturing.
  • the bio-based materials mentioned in this disclosure are degradable, compostable materials, and when formed into film form, can achieve the same self-adhesive applications as plastic film substrates.
  • FIG 1 is a schematic structural diagram of a tag (10) according to an embodiment of the present disclosure.
  • a label (10) according to an embodiment of the present disclosure includes a water-resistant degradable material (1) prepared according to the method of the present disclosure and a printing ink layer (2) on one side surface of the material (1) .
  • the surface of the water-resistant degradable material (1) has a degradable water-resistant base coating that is covalently connected to the surface of the bio-based material, it has excellent water resistance and the entire label is degradable.
  • An example of a label (10) may be a single wet glue label to which an adhesive layer may be applied before use in order to be adhered to the surface of a commodity such as a beverage bottle, especially a beer bottle.
  • the adhesive layer can be applied to either surface of the label (10). That is, an adhesive layer may be applied on the surface of the printing ink layer (2), or an adhesive layer may be applied on the surface of the water-resistant degradable material (1).
  • the label (10) may also have an adhesive coating (not shown) disposed on either surface to facilitate application of an adhesive layer prior to use.
  • FIG. 2 is a schematic structural diagram of a tag (21, 22) according to another embodiment of the present disclosure.
  • a label (21, 22) according to another embodiment of the present disclosure includes a water-resistant degradable material (1) prepared according to the method of the present disclosure, and a printing ink layer on one side surface of the material (1) (2), the varnish protective layer (3) on the surface of the printing ink layer (2) and the adhesive layer (4) on the surface of the varnish protective layer (3) (A, label (21)) or on Adhesive layer (4) (B, label (22)) on the surface of the material (1).
  • the labels (21, 22) shown in Figure 2 also have a varnish protective layer (3) on the adhesive layer (2). On the one hand, it protects the ink of the printing ink layer, and on the other hand, it also improves the appearance of the label. Smoother and brighter.
  • Examples of the labels (21, 22) shown in Figure 2 may be pre-glued disk labels, wherein the labels shown in Figure 2 may be in the form of a continuous strip and rolled into a disk shape. In order to prevent adhesion between the rolled labels, one side of the label also has a composite release material layer (not shown). According to other examples, pre-coated disc labels can also be provided with a protective layer of varnish (3).
  • FIG 3 is a schematic structural diagram of a tag (31, 32) according to yet another embodiment of the present disclosure.
  • A shows a label (31) of one embodiment.
  • the label (31) includes a water-resistant degradable material (1) prepared according to the disclosed method, a printing ink layer (2) on one side of the material (1), and a varnish on the surface of the printing ink layer (2).
  • B in Figure 3 shows a label (32) in another embodiment.
  • the label (32) includes a water-resistant degradable material (1) prepared according to the disclosed method, a printing ink layer (2) on one side of the material (1), and a varnish on the surface of the printing ink layer (2).
  • Examples of labels (31, 32) shown in Figure 3 are self-adhesive labels. Before use of this label, the composite release material layer (5) is removed, and the adhesive layer (4) is pasted to the surface of the product (such as beverages, especially beer).
  • tag of the present disclosure is exemplarily described above, but the tag of the present disclosure is not limited to the above structure. Obviously, for those of ordinary skill in the art, other deformed structures of the label can be obtained based on these drawings without exerting creative efforts. Any label made of water-resistant and degradable materials prepared by the method of the present disclosure is within the scope of protection of the present disclosure.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
  • the base coating is made of 40wt% degradable polyurethane acrylic resin, 37wt% isobornyl acrylate, 20wt% pentaerythritol tetraacrylate and 3wt% 1173 base oil, and is irradiated with UV light of 260-400nm wavelength for 2 seconds.
  • the thickness of the base coating was obtained to be ⁇ 3 ⁇ m.
  • surface-modified bio-based materials are obtained.
  • Ink is printed on the modified surface of the obtained surface-modified material, and UV ink (Bauhinia Bauhinia Company) is selected, and the printing method is offset printing; the other surface is laminated with a pressure-sensitive adhesive (3M Company), thereby obtaining a water-resistant label.
  • UV ink Bahinia Bauhinia Company
  • 3M Company a pressure-sensitive adhesive
  • Degradable polyepoxy acrylic resin is used as the main resin of UV varnish, with a thickness of ⁇ 3 ⁇ m.
  • the base coating uses a base oil containing 40wt% degradable castor oil-based polyacrylic resin, 32wt% acryloyl morpholine, 25wt% diethylene glycol diacrylate phthalate and 3wt% 184, with a wavelength of 260 ⁇ 400nm.
  • the light is obtained by UV irradiation for 2 seconds.
  • the thickness of the primer layer is ⁇ 3 ⁇ m. Thus, surface-modified bio-based materials are obtained.
  • Ink is printed on one surface of the obtained surface-modified material, water-based ink (Bauhinia Bauhinia Company) is selected, and the printing method is offset printing; a pressure-sensitive adhesive (3M Company) is laminated on the other surface to obtain a water-resistant label.
  • Degradable polyurethane acrylic resin is used as the main resin of UV varnish, with a thickness of ⁇ 3 ⁇ m.
  • the base coating uses a base oil containing 40wt% degradable soybean oil-based polyurethane acrylic resin, 30wt% tripropylene glycol diacrylate, 25wt% neopentyl glycol diacrylate and 5wt% BP, using light with a wavelength of 260 to 400nm. Obtained by UV irradiation for 2 seconds.
  • the thickness of the primer layer is ⁇ 3 ⁇ m. Thus, surface-modified bio-based materials are obtained.
  • Ink is printed on one surface of the obtained surface-modified material, and UV ink (Bauhinia Bauhinia Company) is selected, and the printing method is offset printing; the other surface is laminated with a pressure-sensitive adhesive (3M Company), thereby obtaining a water-resistant label.
  • UV ink Bahinia Bauhinia Company
  • 3M Company a pressure-sensitive adhesive
  • Degradable polyepoxy acrylic resin is used as the main resin of UV varnish, with a thickness of ⁇ 3 ⁇ m.
  • the base coating uses a base oil containing 40wt% degradable polyacrylic resin, 30wt% polyethylene glycol diacrylate, 27wt% trimethylolpropane triacrylate and 3wt% 1173, and uses light with a wavelength of 260 to 400nm for 2 seconds. Obtained by UV irradiation.
  • the thickness of the primer layer is ⁇ 3 ⁇ m. Thus, surface-modified bio-based materials are obtained.
  • Ink is printed on one surface of the obtained surface-modified material, water-based ink (Bauhinia Bauhinia Company) is selected, and the printing method is offset printing; a pressure-sensitive adhesive (3M Company) is laminated on the other surface to obtain a water-resistant label.
  • Degradable tung oil-based polyurethane acrylic resin is used as the main resin of UV varnish, with a thickness of ⁇ 3 ⁇ m.
  • the base coating uses a base oil containing 40wt% degradable soybean oil-based polyacrylic resin, 35wt% isobornyl acrylate, 22wt% tripentaerythritol tetraacrylate and 3wt% 184, and uses light with a wavelength of 260 to 400nm for 2 seconds of UV After irradiation, the thickness of the base coating is ⁇ 3 ⁇ m. Thus, surface-modified bio-based materials are obtained.
  • Ink is printed on one surface of the obtained surface-modified material, and UV ink (Bauhinia Company) is selected, and the printing method is offset printing; the other surface is laminated with a pressure-sensitive adhesive (3M Company), thereby obtaining a water-resistant label.
  • UV ink Bahinia Company
  • 3M Company a pressure-sensitive adhesive
  • Degradable tung oil-based polyurethane acrylic resin is used as the main resin of UV varnish, with a thickness of ⁇ 3 ⁇ m.
  • the base coating uses a base oil containing 40wt% degradable polyester acrylic resin, 35wt% dipropylene glycol diacrylate, 20wt% 1,6-hexanediol diacrylate and 5wt% 2959, with a wavelength of 260 ⁇ 400nm.
  • the light is obtained by UV irradiation for 2 seconds.
  • the thickness of the primer layer is ⁇ 3 ⁇ m. Thus, surface-modified bio-based materials are obtained.
  • Print ink on the modified surface of the obtained surface-modified material select water-based ink (Bauhinia Bauhinia Company), and the printing method is gravure printing; the other surface is laminated with a pressure-sensitive adhesive (3M Company), thereby obtaining a water-resistant label .
  • Degradable soybean oil-based polyacrylic resin is used as the main resin of UV varnish, with a thickness of ⁇ 3 ⁇ m.
  • Water resistance test Set up six groups, in which samples 1, 2, 3, 4, 5, and 6 respectively correspond to the labels prepared in Examples 1 to 6. Take one piece of label from each group and stick it on the beer bottle, spray as much water as possible on the label and the bottle, and let it stand in a 50°C thermostat for 90 minutes; then take one piece of label from each group and stick it on the beer bottle. Then soak them together in a mixture of ice and water and place them in a 4°C refrigerator for 7 days. At the end of the experiment, the beer bottles were taken out, the water was absorbed, and the appearance and deformation of the labels were carefully observed with the naked eye. The results show that there is no obvious deformation or degumming of the labels in each group, and the appearance is basically the same as before treatment.
  • Degradability performance test Set up six groups, in which samples 1, 2, 3, 4, 5, and 6 respectively correspond to the labels prepared in Examples 1 to 6. Cut each set of labels into a number of 10cm 2 The humidity is 20%, the pH is 6.8, and the ambient temperature is 30°C. The soil burial times are 3 days, 9 days, 15 days and 27 days respectively. After each time reaches the specified time, take out a sample from each group, rinse the soil on the surface of the water-resistant degradable paper label with tap water, and then put it on Dry in a vacuum drying oven at 40°C, weigh and calculate the weight loss rate of the label, and take the average value. The results are shown in Table 1 below.
  • Transparency test Set up six groups, in which samples 1, 2, 3, 4, 5, and 6 respectively correspond to the surface-treated bio-based materials prepared in Examples 1 to 6.
  • the transmittance test instrument PerkinElmer Company, Lambda35
  • the transmittance test instrument was used for testing respectively, and the haze was measured using a photoelectric haze meter (Shanghai Precision Scientific Instrument Co., Ltd., WGW type). Three different areas on each group of test samples were averaged. The results are shown in Table 2 below.
  • Example Transparency (%) Haze(%) 1 89.8 ⁇ 0.2 1.5 ⁇ 0.1 2 89.3 ⁇ 0.2 1.4 ⁇ 0.2 3 86.7 ⁇ 0.4 1.9 ⁇ 0.2 4 85.2 ⁇ 0.3 2.4 ⁇ 0.1 5 85.9 ⁇ 0.2 2.5 ⁇ 0.2 6 86.4 ⁇ 0.2 2.2 ⁇ 0.2
  • 180° peel force test Set up six groups, in which samples 1, 2, 3, 4, 5, and 6 respectively correspond to the labels prepared in Examples 1 to 6. Conducted with reference to the GB/T2792-1998 standard, each group of test samples was tested on 3 different areas, and the average value was taken. The results are as follows.
  • the present disclosure provides a method for preparing a waterproof and degradable bio-based material, which includes: providing a bio-based material; coating a cellulose dissolving solution containing a cellulose modifier on at least one surface of the material; Hot pressing under conditions of 20MPa and 90-130°C to graft the cellulose modifier to the surface of the material; further apply UV primer on the surface of the base material grafted with the cellulose modifier; and The surface of the substrate coated with UV primer is subjected to UV irradiation to solidify the UV primer to form a degradable polymer and at least part of the degradable polymer reacts with the cellulose modifier grafted on the surface of the substrate Covalently bonded to form a base coat.
  • the cellulose solution is a pre-cooled -9 ⁇ -15°C aqueous solution containing 6 ⁇ 10wt% alkali metal hydroxide and 8 ⁇ 16wt% urea, and the cellulose solution is left to stand after application. 30 ⁇ 180 seconds.
  • the cellulose modifier is selected from the group consisting of alkyl esters of acrylic acid containing propylene oxide groups, alkyl esters of methacrylic acid containing propylene oxide groups, and allyl alkyl esters containing propylene oxide groups. At least one of ether, C 0 -C 10 alkyl allyl chloride, C 0 -C 10 alkyl allyl bromide.
  • the cellulose modifier is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl methacrylate, allyl chloride, allyl bromide, methyl At least one of methylallyl chloride and methylallyl bromide.
  • the amount of the cellulose modifier in the cellulose solution is such that the coating amount of the cellulose modifier is 1 to 5 g/m 2 .
  • the UV curing resin contained in the UV base oil is selected from the group consisting of water-based UV curing resin and vegetable oil-based UV resin.
  • the water-based UV curable resin is selected from the group consisting of polyepoxy acrylic acid C 1 -C 30 alkyl ester, polyurethane acrylic acid C 1 -C 30 alkyl ester, polyacrylic acid C 1 -C 30 alkyl ester and polyester acrylic acid.
  • C 1 -C 30 alkyl esters are selected from the group consisting of polyepoxy acrylic acid C 1 -C 30 alkyl ester, polyurethane acrylic acid C 1 -C 30 alkyl ester, polyacrylic acid C 1 -C 30 alkyl ester and polyester acrylic acid.
  • the vegetable oil-based UV resin is selected from the group consisting of vegetable oil-based epoxy acrylic resin, vegetable oil-based polyacrylic acid resin and vegetable oil-based polyurethane acrylic resin, wherein the vegetable oil is selected from the group consisting of soybean oil, castor oil, linseed oil, linseed oil, The group consisting of corn oil, olive oil, sunflower seed oil, cottonseed oil, rapeseed oil, peanut oil, palm oil, palm kernel oil, tung oil and rosin oil.
  • the thickness of the bio-based material is 10-130 ⁇ m, preferably 30-50 ⁇ m, and more preferably 35-45 ⁇ m.
  • the thickness of the primer layer is ⁇ 3 ⁇ m.
  • the present disclosure also provides a bio-based material prepared according to any of the above methods.
  • the present disclosure also provides a label, including: the above-mentioned cellophane; and a printed ink layer located on the first surface of the bio-based material.
  • the above-mentioned label also has a varnish protective layer located on the printing ink layer.
  • the above-mentioned label also has an adhesive layer and a composite release material layer optionally located on the adhesive layer, wherein the adhesive layer is located on the second surface of the cellophane, or is located on the printing ink. layer.
  • the above-mentioned label also has an adhesive layer and a composite release material layer optionally located on the adhesive layer, wherein the adhesive layer is located on the second surface of the base material, or is located on the light oil protective layer.
  • the amount of adhesive in the adhesive layer in the above label is 6 to 16 g/m 2 .
  • the 180° peel strength of any of the above labels is 6 to 16 N/cm, and the holding tack is greater than or equal to 8.
  • the above-mentioned label also has an aluminum-plated layer located between the printing ink layer and the varnish protective layer.
  • the thickness of the label in the above label is 20-150 ⁇ m, preferably 50-70 ⁇ m, and more preferably 55-65 ⁇ m.
  • the above-mentioned labels are transparent; in particular, they are labels for beverages, preferably beer.

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Abstract

本公开涉及一种可生物堆肥降解的透明改性生物基材料,在自粘应用领域实现与薄膜材料相同的性能。所述制备方法包括:提供生物基材料;在所述生物基材料的一个表面涂布含有纤维素改性剂的纤维素溶解液;在10~20MPa和90~130℃的条件下热压,使所述纤维素改性剂接枝到生物基材料表面;在接枝有纤维素改性剂的生物基材料的表面进一步涂布UV底油;以及对涂布有UV底油的生物基材料表面进行UV照射以使所述UV底油固化形成可降解聚合物且至少部分所述可降解聚合物与接枝在生物基材料表面的纤维素改性剂通过反应以共价键连接形成底涂层。该制备方法简单,适于工业化生产。由该方法制备的改性生物基材料耐水性能优异,透明且可完全降解,适于作为标签,特别是啤酒标签的基材。

Description

一种可生物堆肥降解的透明改性生物基材料,在自粘应用领域实现与薄膜材料相同的性能 技术领域
本公开涉及可降解、可堆肥的生物基材料领域,具体涉及用于具有可实现与塑料薄膜基材相同的性能的透明改性生物基材料,更具体地涉及标签印刷技术领域。
背景技术
目前很多适于冷藏的瓶装或罐装的食品和饮品,如啤酒、饮料等,由于防水和美观的需要,通常使用以透明塑料薄膜为基材的透明标签。然而由于塑料制品主要来源于日益枯竭的石油资源,废弃后不可生物降解,易造成严重白色污染。面对资源和环境的双重压力,包装行业一直在寻求可降解的透明标签,以替代不可降解的透明塑料材质标签。
生物基材料(biobased material),具有较好的拉伸强度、光泽性、透明度和印刷适性,还具有良好的耐热性,可于与食品一起进行高温消毒。以生物基材料制备的薄膜,易生物降解,对环境的影响小,但易撕裂且易吸水软化。由于大多数啤酒等饮料标签有非常高的耐水性要求,影响了此类可降解材料作为标签基材的广泛使用。
目前市场上流通的生物基材料通常有两类方法。一类方法是通过在纤维素上引入亲脂性基团或接枝亲脂性聚合物进行改性或与耐水性聚合物共混后再成膜。此类方法成本高,成膜性和薄膜的综合性较难调节达到要求。另一类方法是通过在生物基材料上涂覆疏水性聚合物形成复合膜。例如涂布聚乙稀等不可降解材料,但不满足环境友好的要求。为获得可降解性, 已尝试了大量研究。例如,基材浸渍无机纳米颗粒悬浮液或表面喷涂含无机纳米颗粒的超疏水涂料,常用的为纳米颗粒为TiO 2、SiO 2及ZnO等。该方法获得的薄膜透明性能受到较大影响,难以满足上述饮料、食品标签的美观度要求。再如,增加基材表面粗糙度,然后表面化学沉积诸如含氟、长碳链聚合物等低表面能物质。该方法中制备微观粗糙结构工艺复杂,材料质量控制难度高,导致较高的成本;此外氟化物的使用对环境的影响也不容忽视,难以满足环境友好的要求。还有报道,在基材表面固定大分子引发剂,形成活性位点,后通过自由基聚合将功能性单体接枝到基材表面。该方法直接对基材进行改性不仅反应过程活性可控,而且制备的材料性能优异。但该方法成本高,催化剂和引发剂效率不理想,使用过渡金属催化剂会残留在接枝共聚物中难以去除,不能进行大批量生产。
综上,亟需开发可工业化生产,且满足耐水性、透明性和可降解等综合要求的标签用基材的需要。
发明内容
本公开旨在提供一种可以通过工业化生产获得的具有很好的耐水性的透明且可降解的标签基材的制备方法,由此制备的材料以及包括该材料的标签。
本公开的上述目的是通过以下技术方案实现的。
第一方面,本公开提供一种耐水可降解改性生物基材料的制备方法,所述方法包括以下步骤:
提供生物基材料,
在所述生物基材料的至少一个表面涂布含有纤维素改性剂的纤维素溶解液;
在10~20MPa和90~130℃的条件下热压,使所述纤维素改性剂接枝到生物基材料的表面;
在接枝有纤维素改性剂的生物基材料的表面进一步涂布UV底油;以及
对涂布有UV底油的生物基材料表面进行UV照射以使所述UV底油固化形成可降解聚合物且至少部分所述可降解聚合物与接枝在生物基材料表面的纤维素改性剂通过反应以共价键连接形成底涂层。
所述生物基材料的实例可包括,但不限于,再生纤维素薄膜,天然纤维素薄膜,纤维素衍生物薄膜,其他生物基聚合物(如聚乳酸PLA、聚羟基脂肪酸酯PHA、微纤化纤维素MFC等)等可降解的生物基材料或它们的两种或更多种混合物形成的薄膜,前提是这些材料能够进行上述改性剂的接枝反应。
根据一种实施方式,所述生物基材料为PLA、PHA和MFC中的一种或多种。
根据本公开的实施方式,所述生物基材料为膜材,厚度为约10~130μm,优选为30~50μm,更优选为35~45μm。
根据本公开的实施方式,所述纤维素溶解液为预冷-9~-15℃的含6~10wt%碱金属氢氧化物和8~16wt%尿素水溶液。在碱、尿素和水之间会形成一个氢键网络结构,而且温度越低该结构稳定性越好。降低温度可以促进纤维素的溶解。在该实施方式中,所述纤维素溶解液与纤维素的作用时长为30~180秒。
采用上述预冷的纤维素溶解液能够使生物基材料表面的纤维素分子部分溶胀并溶液化,从而易于进行进一步的固液界面处的接枝反应。此外该纤维素溶解液中含有一定量的碱,可作为接枝反应的催化剂,使接枝反应易于进行。
所述碱金属氢氧化物可为氢氧化钠、氢氧化钾等。
通过进一步的热压,例如1~2分钟,可促进生物基材料表面的纤维素分子进一步溶解,充分暴露出分子中的羟基,同时使所述纤维素改性剂与 羟基发生反应,完成接枝。
根据本公开的实施方式,所述纤维素改性剂包括至少两种功能基团,其中第一功能基团与所述生物基材料表面的如纤维素分子中的至少部分羟基反应,第二功能基团与形成所述底涂层的至少部分例如交联剂或引发剂反应从而连接到UV固化树脂,从而在所述生物基材料表面与所述底涂层之间形成共价键连接。
根据本公开的实施方式,所述纤维素改性剂中,所述第一功能基团为环氧基或卤素且所述第二功能基团为烯基。
根据一些实施方式,所述纤维素改性剂中的环氧基或卤素与所述生物基材料表面的例如纤维素分子中的至少部分羟基反应形成醚键,烯基与形成底涂层的部分UV固化树脂发生聚合反应而相互连接。
具体地,含有环氧基的纤维素改性剂可选自由丙烯酸的含有环氧丙烷基的烷基酯、甲基丙烯酸的含有环氧丙烷基的烷基酯、烯丙基的含有环氧丙烷基的烷基醚、C 0-C 10烷基烯丙基氯、C 0-C 10烷基烯丙基溴中的至少一种。具体可选自烯丙基氯、烯丙基溴、甲基烯丙基氯和甲基烯丙基溴中的一种或多种。
根据具体的实例,所述纤维素改性剂选自由甲基丙烯酸缩水甘油醚、丙烯酸缩水甘油酯、烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、烯丙基氯、烯丙基溴、甲基烯丙基氯和甲基烯丙基溴中的至少一种。
根据本公开的实施方式,所述纤维素改性剂的涂布量为1~5g/m 2,例如2g/m 2、3g/m 2或4g/m 2;具体涂布量可根据所选择的具体纤维素改性剂来选择。
根据本公开的一些实施方式,所述纤维素改性剂包含环氧基时,环氧基进行开环反应与纤维素分子中的羟基缩水形成醚键。该反应可在温和条件下进行,由于三元环高度张力的存在,使得环氧基能在温和的条件下与羟基等亲核试剂发生开环反应,形成醚键。根据本公开的另外一些实施方 式,所述纤维素改性剂包含卤素时,卤代基与纤维素分子中的羟基缩水形成醚键。该反应同样可在温和条件下进行。
根据本公开的一些实施方式,所述UV底油含有的UV固化树脂选自水性UV固化树脂和植物油基UV树脂。
所述水性UV固化树脂选自聚环氧丙烯酸C 1-C 30烷基酯、聚氨酯丙烯酸C 1-C 30烷基酯、聚丙烯酸C 1-C 30烷基酯和聚酯丙烯酸C 1-C 30烷基酯。优选聚氨酯丙烯酸C 1-C 30烷基酯和聚丙烯酸C 1-C 30烷基酯。水性UV固化树脂通常以混合物形式使用,例如烷基长度在1~30个碳原子范围内的多种聚氨酯丙烯酸酯混合物或者多种聚丙烯酸酯混合物等。
所述植物油基UV树脂选自植物油基环氧丙烯酸树脂、植物油基聚丙烯酸树脂和植物油基聚氨酯丙烯酸树脂,其中所述植物油选自由大豆油、蓖麻油、亚麻油、亚麻仁油、玉米油、橄榄油、向日葵籽油、棉籽油、油菜籽油、花生油、棕榈油、棕榈仁油、桐树油和松香油组成的组。具体地,植物油基UV树脂为蓖麻油基聚丙烯酸树脂、棕榈油基聚氨酯丙烯酸树脂和/或大豆油基聚氨酯丙烯酸树脂等。
上述UV固化树脂可降解,且具有良好的适印性。
UV固化树脂为本领域技术人员所熟知,是指其中的聚合物或预聚物能够通过紫外光照射借助例如稀释剂、光引发剂、催化剂和/或其它所需助剂进一步发生交联从而固化的树脂。本公开对UV固化树脂的使用和固化必要助剂没有特别限定,只要能够在UV照射条件下与连接到生物基材料表面的纤维素改性剂发生反应即可。
可用的光引发剂,例如,可为苯偶姻及衍生物光引发剂、苯偶酰类光引发剂、烷基苯酮类光引发剂、酰基磷氧化物光引发剂。示例性地,所述光引发剂可以为2,4,6-三甲基苯甲酰基-二苯基氧化磷(TPO)、1173(2-羟基-2-甲基-1-苯基丙酮)、184(1-羟基环己基苯基甲酮)、2959(2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮)等,但不限于此。
稀释剂通常为具有2~6,优选2~4个烯基的化合物。
为使UV固化树脂易于涂布,可根据具体情况加入稀释剂。优选地,稀释剂为含丙烯酰氧基的可聚合单体,且更优选至少部分稀释剂可同时作为交联剂使用。可用的稀释剂示例性地为丙烯酸异冰片酯、丙烯酰吗啉、二缩三丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、邻苯二甲酸二乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯等,但不限于此。
所述底油通过主要含有至少一种上述水性UV固化树脂或植物油基UV树脂的UV固化树脂在紫外光的照射下固化形成底涂层。此外,UV底油中还含有固化所述UV固化树脂所必须的如上所述的必要助剂。
根据一些实施方式,底油可包括35~50wt%的可降解的UV固化树脂、45~63wt%的稀释剂以及0.5~5wt%的光引发剂。示例性地,底油可包括约40wt%的可降解的UV固化树脂、约57~59wt%的稀释剂以及约1~3wt%的光引发剂。
根据本公开的实施方式,所述UV固化树脂的涂覆量为使最终获得的底涂层的厚度≤3μm,优选为1~3μm。
根据本公开的实施方式,进行光照固化形成底涂层的条件可根据所选择的UV底油中的树脂种类不同而不同。所述UV底油可商购获得,其使用方法和具体工艺条件为本领域技术人员所熟知,在此不再赘述。
在进行UV固化时,可以通过界面自由基聚合反应,使部分UV底涂在生物基材料界面与接枝的纤维素改性剂的烯基发生自由基聚合反应,从而使所固化得到的底涂层能够与生物基材料通过共价键联系在一起。如此形成的材料,进一步提高了耐水性能,可达到最优级别。
根据优选的实施方式,在所述生物基材料的两侧均形成所述底涂层。
第二方面,本公开提供一种根据上述方法制备得到的改性生物基材料,特别是标签用材料,更具体地为耐水可降解PLA。
本公开所提供的标签用材料其表面具有共价键结合的可降解底涂层,层间结合紧密且牢固,耐水性能得到显著提升,而且基材整体可降解。
此外纤维素改性剂的引入使底涂层能够更容易地且均匀地与生物基材料通过反应连接,避免了直接接枝聚合引发剂导致引发效率降低,结合不完全等的问题。
第三方面,本公开提供一种标签,所述标签包括上述改性生物基材料,所述材料为膜状,尤其是耐水可降解PLA、PHA和MFC中的一种或多种,以及位于所述改性生物基材料第一表面上印刷油墨层。
根据一些实施方式,所述标签还包括位于所述印刷油墨层上的光油保护层。
根据一些实施方式,所述标签还包括粘合剂层,所述粘合剂层可位于所述改性生物基材料的第二表面上或者位于所述印刷油墨层上。根据另一些实施方式,所述粘合剂层也可位于所述光油保护层上。
根据本公开的实施方式,所述粘合剂层可由压敏粘合剂形成。粘合剂的涂布量为6~16g/m 2,例如10~16g/m 2。可选地,所述粘合剂层上进一步具有复合离型材料层,包括离型纸和离型膜。
根据一些实施方式,所述改性生物基材料的第一表面是具有底涂层的表面,第二表面是不具有底涂层的表面。
根据优选的实施方式,所述改性生物基材料的第一表面和第二表面均为具有底涂层的表面。改性生物基材料的两个表面均具有底涂层时,改性生物基材料的耐水性更优异。
根据本公开的实施方式,印刷油墨可选择UV油墨、溶剂型油墨或水性油墨。印刷方式可选择柔性印刷、凹印、胶印或者丝印等。本公开对印刷油墨和印刷方式没有特别限制。
根据本公开的实施方式,所述UV光油固化层起到保护印刷油墨的作用,优选具有厚度为≤3μm,优选1~3μm。更优选地,所述UV光油固化层 是可降解的,可由可降解的UV固化树脂形成。用于光油固化层的可降解的UV固化树脂也可为植物油基UV树脂;所述植物油基UV树脂选自大豆油、蓖麻油、亚麻油、亚麻仁油、玉米油、橄榄油、向日葵籽油、棉籽油、油菜籽油、花生油、棕榈油、棕榈仁油、桐树油、松香油等植物油基丙烯酸树脂、环氧丙烯酸树脂,植物油基聚氨酯丙烯酸树脂等,但不限于此。具体实例如亚麻仁基环氧丙烯酸树脂、大豆油基聚氨酯丙烯酸树脂、桐树油基聚氨酯丙烯酸树脂,但不限于此。
本公开对用于光油固化层的可降解的UV固化树脂和UV光油固化层的形成方法没有特别限制,任何适宜的UV光油产品和方法均可使用。
所述标签的厚度为20~150μm,优选为50~70μm,更优选为55~65μm。
所述标签的180°剥离强度为6~16N/cm,且持粘性大于等于8。
所述标签还可具有镀铝层,位于印刷油墨层与光油保护层之间。镀铝层的厚度可为0.03~0.05μm。可采用常规的真空镀铝法获得镀铝层。
本公开提供的标签是透明标签,特别是用于啤酒、饮料等饮食品的耐水、可降解的透明标签。
所述标签可以是不具有粘合剂层的单张湿胶标签、具有粘合剂层的预涂胶盘标或具有粘合剂层和复合离型材料层的不干胶标签。
本公开提供的改性生物基材料,特别是耐水可降解标签用材料在保证材料的拉伸强度、光泽性、印刷适性、耐热性和可降解性能的情况下,通过含有环氧烷基的烯类单体,如甲基丙烯酸缩水甘油醚GMA,与生物基材料表面的羟基反应,在减少亲水的羟基的同时在生物基材料表面引入双键;然后,涂布的可降解UV底油,通过界面自由基聚合反应,实现在生物基材料表面聚合形成的底涂层与生物基材料表面通过共价键连接,从而提供了透明且耐水性进一步改进的材料。根据本公开实施例的方法制备的改性生物基材料,其耐水的底涂层与材料的薄膜之间不会发生剥离,提高了材料的撕裂强度。该方法步骤简单易控,成本低,表面反应度高、聚合均匀, 最终获得的材料耐水性能高且持久。
此外利用本公开提供的改性生物基材料制备的标签,具有优秀的耐水性能,标签上面滴上大量的水,50℃温度烘烤,90min内标签没有变形,泡冰水后置于4℃冰箱中7天后标签不变形,可见改性的标签具有优秀的耐水性能。此外,所述标签的百格附着力可以达到最优级别;5B级(ASTM标签);可降解性能良好,27天内均能达到失重半衰期;透明度可达80%以上。
附图说明
图1是根据本公开一种实施方式的标签结构示意图。
图2是根据本公开另一种实施方式的标签结构示意图。
图3是根据本公开再一种实施方式的标签结构示意图。
图4是根据实施例1~6制备的接枝后的材料以及未经处理的材料的ATR-FTIR谱图。
附图标记列表:
1:耐水可降解材料;
2:印刷油墨层;
3:光油保护层;
4:粘合剂层;和
5复合离型材料层。
具体实施方式
下面将结合本发明具体实施方式和实施例,对本发明实施方式中的技术方案进行清楚、完整地描述,显然,所描述的具有实施方式仅仅是本发明的一部分实施方式,而不是全部的实施方式。基于本发明中的实施方式,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施 方式,都属于本发明保护的范围。
在整个说明书中,除非另有特别说明,本文使用的术语应理解为如本领域中通常所使用的含义。因此,除非另有定义,本文使用的所有技术和科学术语具有与本发明所属领域技术人员的一般理解相同的含义。若存在矛盾,本说明书优先。
本文中,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的方法或者产品不仅包括所明确记载的要素,而且还包括没有明确列出的其他要素,或者还包括为实施所述方法或者产品所固有的要素。
除非另有说明,否则如在本文所使用的单数形式“一个/种”和“该”包括所指名词的复数。
本文中使用的术语,“生物基材料”指指利用可再生生物质和/或经由生物制造得到的原料,通过生物、化学、物理等手段制造的一类材料。本公开中提及的所述生物基材料是可降解、可堆肥的材料,同时当形成为薄膜形式时,能够实现与塑料薄膜基材相同的自粘应用。
以下结合附图示例性地说明本公开的标签的不同实施方式。
图1是根据本公开一种实施方式的标签(10)结构示意图。如图1所示,根据本公开一种实施方式的标签(10)包括根据本公开方法制备的耐水可降解材料(1)和在该材料(1)一侧表面上的印刷油墨层(2)。
由于耐水可降解材料(1)的表面具有与生物基材料表面通过共价键连接的可降解的耐水底涂层,因而具有优异的耐水性,而且标签整体可降解。
标签(10)的实例可为单张湿胶标签,该标签可在使用前施加粘合剂层以便粘贴到商品如饮料瓶,特别是啤酒瓶的表面。粘合剂层可施加在标签(10)的任何一个表面。即,可在印刷油墨层(2)的表面上施加粘合剂层,或者在耐水可降解材料(1)的表面上施加粘合剂层。该标签(10)还可具有布置在任意一个表面上的可施胶涂层(未示出),以便于在使用前 施加粘合剂层。
图2是根据本公开另一种实施方式的标签(21、22)结构示意图。如图2所示,根据本公开另一种实施方式的标签(21、22)包括根据本公开方法制备的耐水可降解材料(1),在该材料(1)一侧表面上的印刷油墨层(2),在印刷油墨层(2)表面上的光油保护层(3)以及在光油保护层(3)表面上的粘合剂层(4)(A,标签(21))或在该材料(1)表面上的粘合剂层(4)(B,标签(22))。
图2所示标签(21、22)在粘合剂层(2)之上还具有光油保护层(3),一方面对印刷油墨层的油墨起到保护作用,另一方面也使标签外观更加平整、鲜亮。
图2所示标签(21、22)的实例可为预涂胶盘标,其中图2所示标签可为连续的带状,并卷成盘状。为防止卷起的各层标签之间发生粘接,标签的一侧还具有复合离型材料层(未示出)。根据其他实例,预涂胶盘标也可缺省光油保护层(3)。
图3是根据本公开再一种实施方式的标签(31、32)结构示意图。如图3所示,其中,A示出了其中一种实施方式的标签(31)。该标签(31)包括根据本公开方法制备的耐水可降解材料(1),在该材料(1)一侧表面上的印刷油墨层(2),在印刷油墨层(2)表面上的光油保护层(3),在光油保护层(3)表面上的粘合剂层(4)以及在粘合剂层(4)上的复合离型材料层(5)。图3中B示出了其中另一种实施方式的标签(32)。该标签(32)包括根据本公开方法制备的耐水可降解材料(1),在该材料(1)一侧表面上的印刷油墨层(2),在印刷油墨层(2)表面上的光油保护层(3),在该材料(1)另一侧表面上的粘合剂层(4)以及在粘合剂层(4)上的复合离型材料层(5)。
图3所示标签(31、32)的实例为不干胶标签。该标签在使用前移除复合离型材料层(5),将粘合剂层(4)粘贴到商品(如饮料,特别是啤 酒)的表面。
以上示例性地说明了本公开标签的结构,但本公开的标签不限于上述结构。显然,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得标签的其他变形结构。任何利用本公开方法制备的耐水可降解材料制成的标签均在本公开保护的范围内。
除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用生物基材料、试剂和材料均为市购。
实施例1
将预冷的含8wt%氢氧化钠和12wt%尿素与烯丙基缩水甘油醚(单体涂布量:3g/m 2)水溶液涂布到生物基材料的一个表面,作用60s。在15MPa的压力下进行热压,热压温度为110℃,获得厚度为40μm的改性基材。经红外检测(德国Bruker公司,VERTEX 70),参见图4,可看到相比于基材本身,在3600cm -1到3200cm -1,特别是3430cm -1处O-H醇羟基伸缩振动的强度减弱进一步说明了基材接枝成功。
底涂层采用含40wt%可降解聚氨酯丙烯酸树脂、37wt%丙烯酸异冰片酯、20wt%季戊四醇四丙烯酸酯和3wt%1173底油,用260~400nm波长的光进行2s的UV照射。获得底涂层的厚度为≤3μm。从而获得表面改性的生物基材料。
在所获得的表面改性的材料的改性表面印刷油墨,选择UV油墨(洋紫荆公司),印刷方式为胶印;另一个表面层压压敏粘合剂(3M公司),从而获得耐水标签。可降解的聚环氧丙烯酸树脂作为UV光油的主体树脂,厚度为≤3μm。
实施例2
将预冷的含8wt%氢氧化钠和12wt%尿素与烯丙基缩水甘油醚(单体涂 布量:3g/m 2)水溶液涂布到生物基材料的两个表面,作用60s。在15MPa的压力下进行热压,热压温度为110℃,获得厚度为40μm的改性材料。经红外检测(德国Bruker公司,VERTEX 70),参见图4,可看到相比于基材本身,在3600cm -1到3200cm -1,特别是3430cm -1处O-H醇羟基伸缩振动的强度减弱进一步说明了基材接枝成功。
底涂层采用含40wt%可降解蓖麻油基聚丙烯酸树脂、32wt%丙烯酰吗啉、25wt%邻苯二甲酸二乙二醇二丙烯酸酯和3wt%184的底油,用260~400nm波长的光进行2s的UV照射获得。底涂层的厚度为≤3μm。从而获得表面改性的生物基材料。
在所获得的表面改性的材料的一个表面印刷油墨,选择水性油墨(洋紫荆公司),印刷方式为胶印;另一个表面层压压敏粘合剂(3M公司),从而获得耐水标签。可降解的聚氨酯丙烯酸树脂作为UV光油的主体树脂,厚度为≤3μm。
实施例3
将预冷的含8wt%氢氧化钠和12wt%尿素与甲基丙烯酸缩水甘油醚(单体涂布量:3g/m 2)水溶液涂布到生物基材料的两个表面,作用60s。在15MPa的压力下进行热压,热压温度为110℃,获得厚度为40μm的改性材料。经红外检测(德国Bruker公司,VERTEX 70),参见图1,可看到相比于基材本身,在3600cm -1到3200cm -1,特别是3430cm -1处O-H醇羟基伸缩振动的强度减弱进一步说明了材料接枝成功。
底涂层采用含40wt%可降解大豆油基聚氨酯丙烯酸树脂、30wt%二缩三丙二醇二丙烯酸酯、25wt%新戊二醇二丙烯酸酯和5wt%BP的底油,用260~400nm波长的光进行2s的UV照射获得。底涂层的厚度为≤3μm。从而获得表面改性的生物基材料。
在所获得的表面改性的材料的一个表面印刷油墨,选择UV油墨(洋 紫荆公司),印刷方式为胶印;另一个表面层压压敏粘合剂(3M公司),从而获得耐水标签。可降解的聚环氧丙烯酸树脂作为UV光油的主体树脂,厚度为≤3μm。
实施例4
将预冷的含10wt%氢氧化钠和16wt%尿素与烯丙基溴(单体涂布量:3g/m 2)水溶液涂布到生物基材料的两个表面,作用30s。在10MPa的压力下进行热压,热压温度为90℃,获得厚度为40μm的改性材料。经红外检测(德国Bruker公司,VERTEX 70),参见图4,可看到相比于基材本身,在3600cm -1到3200cm -1,特别是3430cm -1处O-H醇羟基伸缩振动的强度减弱进一步说明了材料接枝成功。
底涂层采用含40wt%可降解聚丙烯酸树脂、30wt%聚乙二醇二丙烯酸酯、27wt%三羟甲基丙烷三丙烯酸酯和3wt%1173的底油,用260~400nm波长的光进行2s的UV照射获得。底涂层的厚度为≤3μm。从而获得表面改性的生物基材料。
在所获得的表面改性的材料的一个表面印刷油墨,选择水性油墨(洋紫荆公司),印刷方式为胶印;另一个表面层压压敏粘合剂(3M公司),从而获得耐水标签。可降解的桐树油基聚氨酯丙烯酸树脂作为UV光油的主体树脂,厚度为≤3μm。
实施例5
将预冷的含10wt%氢氧化钠和16wt%尿素与烯丙基缩水甘油醚(单体涂布量:3g/m 2)水溶液涂布到生物基材料的两个表面,作用30s。在15MPa的压力下进行热压,热压温度为110℃,获得厚度为40μm的改性材料。经红外检测(德国Bruker公司,VERTEX 70),参见图4,可看到相比于基材本身,在3600cm -1到3200cm -1,特别是3430cm -1处O-H醇羟基伸缩振动的强度减弱进一步说明了材料接枝成功。
底涂层采用含40wt%可降解大豆油基聚丙烯酸树脂、35wt%丙烯酸异冰片酯、22wt%三季戊四醇四丙烯酸酯和3wt%的184的底油,用260~400nm波长的光进行2s的UV照射,获得底涂层的厚度为≤3μm。从而获得表面改性的生物基材料。
在所获得的表面改性的材料的一个表面印刷油墨,选择UV油墨(洋紫荆公司),印刷方式为胶印;另一个表面层压压敏粘合剂(3M公司),从而获得耐水标签。可降解的桐树油基聚氨酯丙烯酸树脂作为UV光油的主体树脂,厚度为≤3μm。
实施例6
将预冷的含6wt%氢氧化钠和8wt%尿素与甲基丙烯酸缩水甘油酯(单体涂布量:3g/m 2)水溶液涂布到生物基材料的一个表面,作用180s。在20MPa的压力下进行热压,热压温度为130℃,获得厚度为40μm的改性材料。经红外检测(德国Bruker公司,VERTEX 70),参见图4,可看到相比于基材本身,在3600cm -1到3200cm -1,特别是3430cm -1处O-H醇羟基伸缩振动的强度减弱进一步说明了材料接枝成功。
底涂层采用含40wt%可降解聚酯丙烯酸树脂、35wt%二丙二醇二丙烯酸酯、20wt%的1,6-己二醇二丙烯酸酯和5wt%的2959的底油,用260~400nm波长的光进行2s的UV照射获得。底涂层的厚度为≤3μm。从而获得表面改性的生物基材料。
在所获得的表面改性的材料的改性表面印刷油墨,选择水性油墨(洋紫荆公司),印刷方式为凹印;另一个表面层压压敏粘合剂(3M公司),从而获得耐水标签。可降解的大豆油基聚丙烯酸树脂作为UV光油的主体树脂,厚度为≤3μm。
测试例
1、耐水性能测试:设置六组,其中样品1、2、3、4、5、6分别对应 实施例1~6中制备的标签。将各组标签中取一片分别贴在啤酒瓶上,并在标签和瓶身上喷尽量多的水,在50℃恒温箱中静置90min;各组中再各取一片标签贴在啤酒瓶上,然后一起浸泡冰水混合物中,放置4℃冰箱7天。实验结束分别取出啤酒瓶,吸干水分,肉眼仔细观察标签的外观与形变情况。结果表明各组标签均无明显形变或脱胶,外观与处理前基本一致。
2、百格法附着力测试:设置六组,其中样品1、2、3、4、5、6分别对应实施例1~6中制备的经表面处理的生物基材料和最终获得的标签。附着力测试按照百格法参照ASTMD 3002标准执行,划格后以600#3M不干胶粘贴撕脱经表面处理的标签各层材料,观察破坏情况。按优至劣划分为5B、4B、3B、2B、1B、0B等级,其中5B级为完全无撕脱,4B~1B级对应逐步加重的部分撕脱的情况,0B级对应完全撕脱。结果表明无论是基材还是标签各层的附着力为均5B级。
3、可降解性能测试:设置六组,其中样品1、2、3、4、5、6分别对应实施例1~6中制备的标签。将各组标签剪成若干10cm 2×10cm 2的正方形分为6份,每份三个样品,然后用具有孔洞2mm 2×2mm 2的尼龙网包裹埋在约10cm深的农田土壤中,土壤的湿度为20%,pH为6.8,环境温度为30℃。土埋时间分别为3天、9天、15天和27天,每次到达规定的时间后将各组的一份样品取出,用自来水将耐水可降解纸标签表面的土壤冲洗干净,然后放在40℃的真空干燥箱内干燥,称量并计算标签的失重率,取平均值,结果如下表1所示。
表1:耐水可降解的生物基不干胶标签可降解性能测试结果
Figure PCTCN2022114871-appb-000001
Figure PCTCN2022114871-appb-000002
4、透明度测试:设置六组,其中样品1、2、3、4、5、6分别对应实施例1~6中制备的经表面处理的生物基材料。分别使用透光度测试仪器(PerkinElmer公司,Lambda35)进行测试,雾度的测试使用光电雾度仪(上海精密科学仪器有限公司,WGW型)测定。每组测试样品上3个不同的区域,取平均值,结果如下表2所示。
表2:表面改性的生物基材料的透明度和雾度测试结果
实施例 透明率(%) 雾度(%)
1 89.8±0.2 1.5±0.1
2 89.3±0.2 1.4±0.2
3 86.7±0.4 1.9±0.2
4 85.2±0.3 2.4±0.1
5 85.9±0.2 2.5±0.2
6 86.4±0.2 2.2±0.2
5、180°剥离力测试:设置六组,其中样品1、2、3、4、5、6分别对应实施例1~6中制备的标签。参照GB/T2792-1998标准进行,每组测试样品上3个不同的区域,取平均值,结果如下所示。
表3:耐水可降解的生物基不干胶标签透明度测试结果
实施例 180°剥离力(N/cm)
1 11.8±0.9
2 12.6±1.2
3 11.5±0.8
4 13.1±1.7
5 11.3±1.4
6 12.1±0.7
6、持粘性测试:设置六组,其中样品1、2、3、4、5、6分别对应实施例1~6中制备的标签。参照GB/T4852-1998标准进行,结果如下所示。
表4:耐水可降解的生物基不干胶标签持粘性测试结果
试验样品 持粘性(钢球号)
样品1 12
样品2 11
样品3 11
样品4 11
样品5 12
样品6 11
以上所述仅为本发明的部分实施方式的实例,并非因此限制本发明的专利范围,凡是在本发明的发明构思下,利用本发明说明书及附图内容所作的等效结构变换,或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
由此,本公开提供一种防水可降解生物基材料的制备方法,包括:提供生物基材料;在所述材料的至少一个表面涂布含有纤维素改性剂的纤维素溶解液;在10~20MPa和90~130℃的条件下热压,使所述纤维素改性剂接枝到材料的表面;在接枝有纤维素改性剂的基材的表面进一步涂布UV底油;以及对涂布有UV底油的基材表面进行UV照射以使所述UV底油固化形成可降解聚合物且至少部分所述可降解聚合物与接枝在基材表面的纤维素改性剂通过反应以共价键连接形成底涂层。
上述方法中,所述纤维素溶解液为预冷-9~-15℃的含6~10wt%碱金属氢氧化物和8~16wt%尿素水溶液,且所述纤维素溶解液涂布后静置30~180秒。
上述方法中,所述纤维素改性剂选自由丙烯酸的含有环氧丙烷基的烷基酯、甲基丙烯酸的含有环氧丙烷基的烷基酯、烯丙基的含有环氧丙烷基的烷基醚、C 0-C 10烷基烯丙基氯、C 0-C 10烷基烯丙基溴中的至少一种。
上述方法中,所述纤维素改性剂选自由甲基丙烯酸缩水甘油醚、丙烯酸缩水甘油酯、烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、烯丙基氯、烯丙基溴、甲基烯丙基氯和甲基烯丙基溴中的至少一种。
上述方法中,所述纤维素溶解液中所述纤维素改性剂的量为使得所述纤维素改性剂的涂布量为1~5g/m 2
上述方法中,所述UV底油含有的UV固化树脂选自水性UV固化树脂和植物油基UV树脂。
上述方法中,所述水性UV固化树脂选自聚环氧丙烯酸C 1-C 30烷基酯、聚氨酯丙烯酸C 1-C 30烷基酯、聚丙烯酸C 1-C 30烷基酯和聚酯丙烯酸C 1-C 30烷基酯。
上述方法中,所述植物油基UV树脂选自植物油基环氧丙烯酸树脂、植物油基聚丙烯酸树脂和植物油基聚氨酯丙烯酸树脂,其中所述植物油选自由大豆油、蓖麻油、亚麻油、亚麻仁油、玉米油、橄榄油、向日葵籽油、棉籽油、油菜籽油、花生油、棕榈油、棕榈仁油、桐树油和松香油组成的组。
上述方法中,所述生物基材料的厚度为10~130μm,优选为30~50μm,更优选为35~45μm。
上述方法中,所述底涂层的厚度≤3μm。
本公开还提供一种根据上述任意一种方法制备的生物基材料。
本公开还提供一种标签,包括:上述的玻璃纸;位于所述生物基材料的第一表面上印刷油墨层。
上述标签还具有位于所述印刷油墨层上的光油保护层。
上述标签还具有粘合剂层和可选地位于所述粘合剂层上的复合离型材料层,其中所述粘合剂层位于所述玻璃纸的第二表面上,或者位于所述印刷油墨层上。
上述标签还具有粘合剂层和可选地位于所述粘合剂层上的复合离型材料层,其中所述粘合剂层位于所述基材的第二表面上,或者位于所述光油保护层上。
上述标签中所述粘合剂层的粘合剂的量为6~16g/m 2
上述任意一种标签中所述标签的180°剥离强度为6~16N/cm,且持粘性大于等于8。
上述标签中所述标签还具有位于所述印刷油墨层和光油保护层之间的镀铝层。
上述标签中所述标签的厚度为20~150μm,优选50~70μm,更优选为55~65μm。
上述标签中所述标签是透明的;特别地为饮料,优选啤酒的标签。

Claims (21)

  1. 一种耐水可降解改性生物基材料的制备方法,包括:
    提供生物基材料;
    在所述生物基材料的至少一个表面涂布含有纤维素改性剂的纤维素溶解液;
    在10~20MPa和90~130℃的条件下热压,使所述纤维素改性剂接枝到生物基材料的表面;
    在接枝有纤维素改性剂的生物基材料的表面进一步涂布UV底油;以及
    对涂布有UV底油的生物基材料表面进行UV照射以使所述UV底油固化形成可降解聚合物且至少部分所述可降解聚合物与接枝在生物基材料表面的纤维素改性剂通过反应以共价键连接形成底涂层。
  2. 根据权利要求书1所述的方法,其中,所述纤维素溶解液为预冷-9~-15℃的含6~10wt%碱金属氢氧化物和8~16wt%尿素水溶液,且所述纤维素溶解液涂布后静置30~180秒。
  3. 根据权利要求书1所述的方法,其中,所述纤维素改性剂选自由丙烯酸的含有环氧丙烷基的烷基酯、甲基丙烯酸的含有环氧丙烷基的烷基酯、烯丙基的含有环氧丙烷基的烷基醚、C 0-C 10烷基烯丙基氯、C 0-C 10烷基烯丙基溴中的至少一种。
  4. 根据权利要求书3所述的方法,其中,所述纤维素改性剂选自由甲基丙烯酸缩水甘油醚、丙烯酸缩水甘油酯、烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、烯丙基氯、烯丙基溴、甲基烯丙基氯和甲基烯丙基溴中的至少一种。
  5. 根据权利要求书3或4所述的方法,其中,所述纤维素溶解液中所述纤维素改性剂的量为使得所述纤维素改性剂的涂布量为1~5g/m 2
  6. 根据权利要求书1所述的方法,其中,所述UV底油含有的UV固化树脂选自水性UV固化树脂和植物油基UV树脂。
  7. 根据权利要求书6所述的方法,其中,所述水性UV固化树脂选自聚环氧丙烯酸C 1-C 30烷基酯、聚氨酯丙烯酸C 1-C 30烷基酯、聚丙烯酸C 1-C 30烷基酯和聚酯丙烯酸C 1-C 30烷基酯。
  8. 根据权利要求书6所述的方法,其中,所述植物油基UV树脂选自植物油基环氧丙烯酸树脂、植物油基聚丙烯酸树脂和植物油基聚氨酯丙烯酸树脂,其中所述植物油选自由大豆油、蓖麻油、亚麻油、亚麻仁油、玉米油、橄榄油、向日葵籽油、棉籽油、油菜籽油、花生油、棕榈油、棕榈仁油、桐树油和松香油组成的组。
  9. 根据权利要求书1所述的方法,其中,所述生物基材料的厚度为10~130μm,优选为30~50μm,更优选为35~45μm。
  10. 根据权利要求书1所述的方法,其中,所述底涂层的厚度≤3μm。
  11. 根据权利要求书1所述的方法,其中,所述生物基材料为聚乳酸、聚羟基脂肪酸酯和微米化纤维纤维素中的一种或多种。
  12. 一种根据权利要求1~11任一项所述方法制备的改性生物基材料。
  13. 一种标签,包括:
    根据权利要求12所述的材料,所述材料为膜状;
    位于所述改性生物基材料的第一表面上印刷油墨层。
  14. 根据权利要求书13所述的标签,还具有位于所述印刷油墨层上的光油保护层。
  15. 根据权利要求书13所述的标签,还具有粘合剂层和可选地位于所述粘合剂层上的复合离型材料层,其中所述粘合剂层位于所述改性生物基材料的第二表面上,或者位于所述印刷油墨层上。
  16. 根据权利要求书14所述的标签,还具有粘合剂层和可选地位于所述粘合剂层上的复合离型材料层,其中所述粘合剂层位于所述改性生物基 材料的第二表面上,或者位于所述光油保护层上。
  17. 根据权利要求书15或16所述的标签,其中所述粘合剂层的粘合剂的量为6~16g/m 2
  18. 根据权利要求书13~16中任一项所述的标签,其中所述标签的180°剥离强度为6~16N/cm,且持粘性大于等于8。
  19. 根据权利要求书14所述的标签,其中所述标签还具有位于所述印刷油墨层和光油保护层之间的镀铝层。
  20. 根据权利要求书13~16中任一项所述的标签,其中所述标签的厚度为20~150μm,优选50~70μm,更优选为55~65μm。
  21. 根据权利要求书13~16中任一项所述的标签,其中所述标签是透明的;特别地为饮料,优选啤酒的标签。
PCT/CN2022/114871 2022-03-15 2022-08-25 一种可生物堆肥降解的透明改性生物基材料,在自粘应用领域实现与薄膜材料相同的性能 WO2023173685A1 (zh)

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