CN117264555A - Biodegradable adhesive tape, biodegradable adhesive composition and preparation method of biodegradable adhesive tape - Google Patents
Biodegradable adhesive tape, biodegradable adhesive composition and preparation method of biodegradable adhesive tape Download PDFInfo
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- CN117264555A CN117264555A CN202311127071.3A CN202311127071A CN117264555A CN 117264555 A CN117264555 A CN 117264555A CN 202311127071 A CN202311127071 A CN 202311127071A CN 117264555 A CN117264555 A CN 117264555A
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- biodegradable
- tape
- adhesive
- adhesive composition
- polyurethane dispersant
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 127
- 239000000853 adhesive Substances 0.000 title claims abstract description 121
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 claims abstract description 59
- 239000004814 polyurethane Substances 0.000 claims abstract description 59
- 239000003522 acrylic cement Substances 0.000 claims abstract description 32
- 230000015556 catabolic process Effects 0.000 claims abstract description 19
- 238000006731 degradation reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002318 adhesion promoter Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229920006381 polylactic acid film Polymers 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000298 Cellophane Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002655 kraft paper Substances 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 150000003505 terpenes Chemical class 0.000 claims description 4
- 235000007586 terpenes Nutrition 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006065 biodegradation reaction Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004831 Hot glue Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009264 composting Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a biodegradable adhesive tape, a biodegradable adhesive composition and a preparation method of the biodegradable adhesive tape. Specifically, the biodegradable adhesive tape comprises: a biodegradable adhesive composition comprising: an acrylic adhesive and a polyurethane dispersant, the polyurethane dispersant having a dry weight of at least 8% or more relative to the wet weight of the biodegradable adhesive composition, and the polyurethane dispersant having a dry weight of no more than 40% relative to the dry weight of the acrylic adhesive; a biodegradable back-base film; wherein the biodegradable adhesive tape has a compostable degradation rate of at least 90% or more in 180 days as measured by GB/T19277.1. The adhesive tape and adhesive combination provided by the application has the advantages of easiness in obtaining raw materials, simplicity and convenience in preparation and good adhesion effect and biodegradation effect.
Description
Technical Field
The invention relates to an adhesive tape, an adhesive composition applied to the adhesive tape and a manufacturing method of the adhesive tape, in particular to a biodegradable adhesive tape, an adhesive composition applied to the biodegradable adhesive tape and a manufacturing method of the biodegradable adhesive tape.
Background
Along with the enhancement of environmental awareness, recycling of materials and various resources is also receiving attention. Among them, the decomposition of resources or materials has been developed as an important research field, and the degradation of materials has been an important field in which the influence on the environment is reduced, and even the conversion into resources that can be reused is performed.
Adhesives or tapes are common items in everyday life, such as: in the process of transporting goods, proper packages are required, and in order to ensure that the packages can be tightly sealed to protect the goods, adhesives or adhesive tapes are often required, but most adhesives or adhesive tapes cannot be recycled; there are adhesive tapes made of degradable back base films, but the adhesive itself is not degradable, and even if there are biodegradable adhesive tapes, the degradation rate or the adhesive tape performance is not easily balanced, in other words, the biodegradable adhesive tapes are still limited.
CN106574036a discloses biodegradable pressure-sensitive adhesives, achieved by chemical crosslinking of polyurethane prepolymers and by formulating pressure-sensitive adhesives with one or more of these polyurethanes as a major component.
CN107523253a provides a biodegradable pressure sensitive adhesive, but its pressure sensitive adhesive is provided as a dispersion in at least one solvent to make a tape. It is generally known that the use of solvents is generally not environmentally friendly.
CN106459694a is mainly concerned with a biodegradable protective surface tape comprising at least 60% by weight of at least one polyurethane, which is capable of being easily and largely separated from the surface to be protected without residue, and the adhesive has sufficient cohesion.
CN109957372a provides a polyester hot melt pressure sensitive adhesive, but the preparation of hot melt adhesives generally requires special equipment.
Other techniques are to make pressure sensitive adhesives from naturally occurring materials, such as CN106978116a.
Disclosure of Invention
In view of the prior art, it may be necessary to manufacture the biodegradable tape or adhesive by using a solvent system, a hot melt adhesive system, or the like, or using natural materials, but the process is complicated. The acrylic adhesive is an adhesive system commonly applied to pressure-sensitive adhesives, and generally cannot achieve a biodegradable effect, but the invention provides a biodegradable adhesive, an adhesive tape and a manufacturing method thereof, wherein the aqueous acrylic adhesive is used as a main body, and a polyurethane dispersing agent is added, so that good adhesive tape performance is considered, and a good biodegradation rate is more unexpectedly found, namely, the adhesive tape and the adhesive combination which are easy to obtain raw materials, simple and convenient to prepare and good in adhesive effect and biodegradation effect are provided.
In order to achieve the above technical effects, the technical scheme of the invention is as follows: a biodegradable adhesive tape comprising a biodegradable adhesive composition and a biodegradable back base film, wherein the biodegradable adhesive composition comprises an acrylic adhesive and a polyurethane dispersant, the polyurethane dispersant having a dry weight of at least 8% or more relative to the wet weight of the biodegradable adhesive composition and a dry weight of not more than 40% relative to the dry weight of the acrylic adhesive; the biodegradable adhesive tape has a compostable degradation rate of at least 90% in 180 days as measured by GB/T19277.1.
In some embodiments, the biodegradable back-base film may be a multi-layer back-base selected from one or a combination of polylactic acid film, kraft paper, and cellophane.
In some embodiments, the biodegradable back-base film can be a biaxially oriented biodegradable back-base film.
In some embodiments, the acrylic adhesive comprises an aqueous random copolymer having monomer units selected from one or more of acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, and methacrylamide.
In some embodiments, the polyurethane dispersant is an aqueous dispersant, such as an anionically modified polyurethane dispersant.
In some embodiments, the biodegradable tape further comprises a tackifier, wherein the tackifier may be selected from one or more of rosin resin, hydrogenated rosin resin, and terpene phenolic resin.
In some embodiments, the biodegradable tape has a tack (Room Temperature Shear Force) of at least greater than 24 hours as tested by GBT 4851-2014A; 180 degree Peel strength (180 DEG Peel Adhesion) measured in GBT 2792-2014 of at least 2.5N/cm or more; the Initial adhesion (Initial Tack) of the ball is at least greater than or equal to ball number 12 as measured by GB/T4582-2002.
In some embodiments, the biodegradable adhesive composition has a thickness of 10 μm to 200 μm after drying.
In some embodiments, the biodegradable tape further comprises a release layer.
The present disclosure further provides a biodegradable adhesive composition comprising: an acrylic adhesive and a polyurethane dispersant, wherein the polyurethane dispersant dry weight is at least 8% or more relative to the biodegradable adhesive composition wet weight and the polyurethane dispersant dry weight is not more than 40% relative to the acrylic polymer dry weight, wherein the biodegradable adhesive composition has a compostable degradation of at least 90% or more as measured in GB/T19277.1 for 180 days.
The scheme also relates to a manufacturing method of the biodegradable adhesive tape, which comprises the following steps: providing a biodegradable backing film and a biodegradable adhesive composition; coating the biodegradable adhesive composition onto the biodegradable backing film, wherein the biodegradable adhesive composition comprises an acrylic adhesive and a polyurethane dispersant, the polyurethane dispersant having a dry weight of at least 8% or more relative to the wet weight of the biodegradable adhesive composition, and the polyurethane dispersant having a dry weight of no more than 40% relative to the dry weight of the acrylic polymer; and drying and dehydrating the biodegradable backing film coated with the biodegradable adhesive composition to obtain the biodegradable adhesive tape, wherein the biodegradable adhesive tape has a compostable degradation rate of at least 90% or more in 180 days as measured by GB/T19277.1.
Drawings
FIG. 1 is a schematic structural view of a biodegradable adhesive tape according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a biodegradable adhesive tape according to another embodiment of the present invention;
FIG. 3 is a flowchart of manufacturing a biodegradable adhesive tape according to an embodiment of the present invention; and
fig. 4 is a flowchart for manufacturing a biodegradable adhesive tape according to another embodiment of the present invention.
Detailed Description
Some embodiments according to the present invention will be described in more detail below with reference to the accompanying drawings. It is to be understood that other various embodiments can be devised and modifications to the embodiments by those skilled in the art based on the teachings herein without departing from the scope or spirit of this invention. The following detailed description is, therefore, merely illustrative and not restrictive.
All numbers expressing feature sizes, amounts, and physical properties used in the specification and claims are to be understood as being modified by the term "about" unless otherwise indicated. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that can be varied by one of ordinary skill in the art to obtain the desired properties according to the teachings of the present invention. The recitation of numerical ranges by endpoints includes all numbers subsumed within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like. In addition, the term "biodegradable" as used herein refers to a material tested by the test method specified in the national standard GB/T19277.1-2011 for its final aerobic biological decomposition capacity and disintegration degree of more than 90% in the prescribed test period.
Please refer to fig. 1, which is a schematic diagram of a biodegradable adhesive tape according to an embodiment of the invention. As shown in fig. 1, the biodegradable adhesive tape 1 may include a biodegradable back base film 11 and a biodegradable adhesive composition 13, wherein the biodegradable back base film 11 may be a film made of any biodegradable material, for example: polylactic acid (PLA) film, cellophane, kraft paper, or the like, but not limited thereto, and may be a multi-layer back base film of one or a combination of biodegradable materials. In some embodiments, to enhance the properties of the back base film 11, such as mechanical properties, the biodegradable back base film 11 may be structurally modified, for example: if a polylactic acid film is used, the film may be biaxially stretched to obtain a biaxially stretched polylactic acid film (Biaxially Oriented PLA, BOPLA). In some embodiments, the adhesion of the biodegradable adhesive composition 13 to the biodegradable backing film 11 may also be enhanced by surface treatment (e.g., corona treatment may be used).
Referring again to fig. 1, the biodegradable tape 1 further comprises a biodegradable adhesive composition 13 coated on the biodegradable backing film 11. In the present invention, the biodegradable adhesive composition 13 comprises an acrylic adhesive and a polyurethane dispersant, both in between and in a suitable proportion relative to the biodegradable adhesive composition, wherein the dry weight of the polyurethane dispersant relative to the total wet weight of the biodegradable adhesive composition is at least 8% or more, such as 8.0%, 8.1%, 8.5%, 10.0%, 12.5%, or any proportion within the present interval, but the proportion of polyurethane should not be too high, in which case the dry weight of the polyurethane dispersant relative to the dry weight of the acrylic adhesive is preferably not more than 40.0%, such as not more than 40.0%, not more than 30.0%, or not more than 20.0%, such as 39.2%, 29.4%, 19.2%, or any proportion within the present interval. The adhesive of the invention is an acrylic acid system, the acrylic acid adhesive used by the adhesive is an aqueous acrylic acid adhesive, the adhesive comprises an aqueous random copolymer, monomer units of the adhesive can be one or more selected from acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, acrylamide and methacrylamide, and the polyurethane dispersing agent can be an aqueous dispersing agent, wherein the anionic modified aqueous polyurethane dispersing agent is preferable, but the invention is not limited thereto.
In some embodiments, the biodegradable adhesive composition 13 in the biodegradable adhesive tape 1 may further comprise an adhesion promoter, which may be one or more selected from rosin, hydrogenated rosin resin, terpene phenolic resin, preferably, but not limited to, emulsion type adhesion promoter, and in some embodiments, the additives such as adhesion promoter are optionally added, which is not necessary, and preferably, when added, the additives do not exceed 12% of the total wet weight of the adhesive composition; furthermore, the biodegradable adhesive composition 13 may optionally further include other additives such as: colorants or other adjuvants, and the like.
In the present invention, the biodegradable adhesive tape 1 has a tack (Room Temperature Shear Force) of at least more than 24 hours, in some embodiments, more than 30 hours, 90 hours, or even 160 hours, as measured by the national standard of the people's republic of China GBT 4851-2014A; 180 degree Peel strength (180 DEG Peel Adhesion) measured by national standard GBT 2792-2014 of the people's republic of China is at least 2.5N/cm or more, in certain embodiments, the 180 degree Peel strength of the biodegradable tape is greater than 3N/cm, or even near 8N/cm; the Initial adhesive force (Initial Tack) tested by the national standard GB/T4582-2002 of the people's republic of China is at least greater than or equal to the number 12 ball, and in some embodiments, the Initial adhesive force of the biodegradable adhesive tape can reach the number 14 ball, the number 16 ball or even the number 17 ball; in addition, the biodegradable adhesive tape 1 has a compostable degradation rate of 90% or more over 180 days as measured by the national standard of the people's republic of China GB/T19277.1. Therefore, the biodegradable adhesive tape 1 provided by the invention has good adhesion, can be firmly adhered to the surface of an adhered object, has good initial adhesion, not only provides good adhesion capability, but also has excellent biodegradability, and combines the adhesion performance and biodegradability of the adhesive tape, so that the biodegradable adhesive tape can be applied to various occasions requiring packaging, box sealing, adhesion and coating, for example, but not limited to, the case sealing adhesive tape.
Fig. 2 is a schematic structural diagram of a biodegradable adhesive tape according to another embodiment of the invention. As shown in fig. 2, in addition to the biodegradable adhesive composition 13 coated on the biodegradable backing film 11, a release layer 15 may be optionally added, and the release layer 15 is disposed opposite to the biodegradable adhesive composition 13 on the biodegradable backing film 11, that is, the biodegradable adhesive composition 13 and the release layer 15 may be disposed opposite to the biodegradable backing film 11. The release layer 15 is not limited, and for example, a release layer containing a long-chain alkyl or silica gel type release agent commonly used in adhesive tapes can be selected, so that the rolled biodegradable adhesive tape can be conveniently unwound for convenient use. It should be appreciated that in some embodiments, release paper may be used to facilitate the unwinding, but the release paper is attached to the biodegradable adhesive composition.
The biodegradable adhesive tape 1 of the present invention also has the advantage of simple process, as shown in fig. 3, the manufacturing method comprises the following steps: providing a biodegradable backing film 11 and a biodegradable adhesive composition 13 in step 1; coating a biodegradable adhesive composition 13 on the biodegradable backing film in step 2; and step 3, drying and dehydrating the biodegradable back base film coated with the biodegradable adhesive composition to obtain the biodegradable adhesive tape. Since the acrylic adhesive is an adhesive commonly used for pressure sensitive adhesives, the method for coating the adhesive is not limited as compared with the prior art, and a doctor blade coating method, a roll coating method, a blade coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method and the like can be used, for example, the method of coating the adhesive on a back base film can be applied, and the coating thickness is preferably the coating thickness of a general adhesive tape, so that the thickness of the finally dried biodegradable adhesive composition is about 10-200 μm, preferably 10-100 μm, more preferably 20-25 μm; in addition, the biodegradable adhesive composition used in the present invention may be composed of an aqueous system, and the method for drying the adhesive composition is not limited, for example, oven heating may be used, but not limited thereto, so that the present invention has the characteristics of simple processing and environmental friendliness. Furthermore, the present disclosure improves the biodegradability of the aqueous acrylic adhesives compared to the aqueous acrylic adhesives known in the art, making the acrylic adhesives useful in the context of biodegradable tapes. If the biodegradable adhesive composition with good adhesion property is directly dried, the biodegradable adhesive can be obtained. Fig. 4 is a flowchart for manufacturing a biodegradable adhesive tape according to another embodiment of the present invention. Compared to fig. 3, the present embodiment adds the steps of providing a release layer and applying a release agent to form the release layer, wherein the release layer and the biodegradable adhesive composition are respectively applied to two opposite sides of the biodegradable back base film. In some embodiments, the release agent and the biodegradable adhesive composition may be applied simultaneously to opposite sides of the biodegradable backing film in the same step, however, it should be understood that in other embodiments, the biodegradable backing film may alternatively be applied sequentially, but the order of the two is not limited, so as to form the biodegradable adhesive tape with a release layer.
The following detailed description is intended to illustrate the invention by way of example and not by way of limitation.
Table 1 shows the raw materials and sources used in the present invention.
Table 1 list of raw materials
The adhesive combinations of each group were prepared in the proportions shown in Table 1 below, using the materials described in Table 2 below.
The raw materials of each group in Table 2 were mixed uniformly with a small Mixer (Thinky Mixer) and 20g was coated on 400mm x 800mm biaxially oriented polylactic acid film (BOPLA) with a laboratory coater (lab coater). The adhesive composition was dehydrated by drying at 100℃for 5 minutes to prepare each set of adhesive tape samples.
TABLE 2 proportions of the components of the adhesive compositions of the groups
The following is a method of the present invention for testing the properties of the tape, and the test results of the properties of each set of tape samples are shown in Table 3.
Adhesive thickness of adhesive tape sample
The thickness of the adhesive tape is tested by a testing method of the adhesive tape thickness of national standard GB/T7125-2014 of the people's republic of China, and the measured adhesive tape thickness is deducted from the adhesive tape back base film to obtain the adhesive tape thickness of the adhesive tape.
Hold adhesive (Room Temperature Shear Force)
The adhesive tape is tested for adhesion by using the national standard GBT 4851-2014A of the people's republic of China. The 12mm wide and 150mm long tape sample was uniformly adhered to the stainless steel plate with a press roller so that the free end of the tape sample was vertical and a weight was applied to the free end, and the time required for separating the tape sample from the stainless steel test plate was recorded.
180 degree peel strength (180 degree PeelAdhesion)
The peel strength of each set of tape samples was tested with the national standard GBT 2792-2014 of the people's republic of China. A24 mm wide and 300mm long tape sample was stuck to a stainless steel plate, the stainless steel plate was fixed to a clamp of a tensile tester, the other clamp of the tester clamped the free end of the tape sample, the tape sample was pulled away at a 180 degree angle from the stainless steel plate and at a prescribed speed, and the peeling force required to separate the tape sample from the stainless steel plate was measured.
Initial adhesion (Initial Tack)
The initial adhesion of the tape samples was tested by the national standard of the people's republic of China GB/T4582-2002. The rolling balls with different numbers are placed on the adhesive surface of the adhesive tape on the inclined plate, and the initial viscosity is evaluated according to the maximum steel ball size which can be stuck by the adhesive surface with a specified length.
Adhesive force (# 2 Bond) of adhesive and back base film
The five tape samples of examples 1-5 were visually inspected for release of the adhesive from the backing film after the hold adhesion test and after the 180 degree peel strength test, respectively.
Degradation rate
The invention adopts the national standard GB/T19277.1-2011 of the people's republic of China, the method of measuring the carbon dioxide which is put into test is adopted for measuring the final aerobic biological decomposition capacity of the material under the controlled composting condition, and the final aerobic biological decomposition capacity and the disintegration degree of each adhesive tape sample under the simulated strong aerobic composting condition are tested. Each tape sample was mixed with the inoculum and introduced into a static compost container. In this vessel, the mixture undergoes intensive aerobic composting at the specified temperature, oxygen concentration and humidity. The percent biodegradation was calculated using the formula given by the standard.
Table 3 properties of each set of tape samples
In general, whether the adhesive property of the adhesive tape meets the use requirement is mainly referred to by three indexes of holding viscosity, peeling strength and initial viscosity. When the holding viscosity of the adhesive tape is higher, the adhesive tape has better continuous viscosity after the adhesive tape completely sticks to an object. For example, the case sealing tape generally has a requirement of holding adhesion for at least 24 hours, and as shown in examples 1 to 5 of the present invention, when the wet weight ratio of the polyurethane dispersant (dry weight) to the whole adhesive composition is increased to about 8% or more, the holding adhesion can reach the requirement of holding adhesion for at least 24 hours, and even the holding adhesion of the tape sample can reach the requirement of holding adhesion for at least 30 hours, which indicates that the adhesive persistence capability of the tape sample provided by the present invention is good; in contrast, comparative examples 1, 3, and 4, when the proportion of the polyurethane dispersant (dry weight) is less than 8% of the wet weight of the whole adhesive composition, the adhesive tape sample cannot meet the adhesion holding requirement for 24 hours, wherein when the polyurethane dispersant (comparative example 1) is absent from the adhesive composition, the cohesion is poor and the adhesion holding effect is poor; if the adhesive composition has only the polyurethane dispersant but no acrylic adhesive at all, it cannot exert the adhesive effect of the tape (comparative example 2); in addition, when the proportion of the polyurethane dispersant is increased, the holding viscosity value of the adhesive tape (comparative example 5) can be increased, but when the proportion of the polyurethane dispersant is too high compared with that of the acrylic adhesive (comparative example 5), the initial adhesion effect (i.e., initial adhesive force) of the adhesive tape is affected.
The initial adhesion of the tape represents the ability of the tape to adhere to an adherend in a short contact time, and the larger the test ball number is in GB/T4582-2002, the better the initial adhesion of the tape is. As can be seen from Table 3, the initial adhesion of each of the test examples 1 to 5 was more than 12 balls, that is, each of the adhesive tape samples of the test examples 1 to 5 was adhered to the adherend rapidly and firmly when applied to the adherend, which is advantageous for the application fields such as packaging and sealing. In contrast to comparative example 5, when the proportion of polyurethane dispersant as compared to acrylic adhesive (dry/dry) exceeds 40%, the tape sample does not have good initial adhesion.
The 180 degree peel strength of the tape reflects the cohesive strength of the material. Referring to Table 3, it is understood from experimental examples 1-5 that when the wet weight ratio of the polyurethane dispersant (dry weight) to the whole adhesive composition is 8% or more and the wet weight ratio of the polyurethane dispersant to the acrylic adhesive (dry weight/dry weight) is controlled to be 40% or less, 180 degree peel strength of each set of adhesive tape samples is at least 2.5N/cm or more, which shows that each set of adhesive tape samples has a certain adhesive strength. While comparative example 1 had inherently good 180 degree peel strength, as described above, the holding effect was poor, and in the absence of polyurethane dispersant, the addition of adhesion promoter slightly improved the holding and 180 degree peel strength (comparative example 3 compared to comparative example 1), but as described above, both comparative example 3 and comparative example 1 still failed to meet the general shear performance requirements for holding adhesive tape; in contrast, when a polyurethane dispersant is further added, the adhesion may be improved, but 180-degree peel strength may be also affected in comparison with comparative examples 3 and 4. From this, it is found that the polyurethane dispersant is added in an appropriate ratio to the acrylic adhesive, and the wet weight ratio of the polyurethane dispersant (dry weight) to the whole adhesive composition is at least 8% or more, and the adhesive tape sample has good holding strength, peel strength and initial tackiness by controlling the ratio of the polyurethane dispersant to the acrylic adhesive (dry weight/dry weight) to not more than 40%. In addition, by visual observation, the adhesives of examples 1 to 5 did not separate from the back base film after the hold adhesion test and after the 180-degree peel strength test, indicating that there was also good bonding force between the adhesive and the back base of the tape.
Generally, the acrylic adhesive is a crosslinked structure, so most of the acrylic adhesive cannot be degraded, and the degradation rate is only 6.77% at 62 days as in comparative example 1, which is tested in the GB/T19277.1 mode. The polyurethane dispersant is generally used for improving cohesive force of the adhesive, and may be physically crosslinked with the adhesive to make the internal bonding attraction of the adhesive stronger and generate better holding viscosity, so that when the internal bonding attraction of the adhesive is stronger, the polyurethane dispersant is not beneficial to decomposition, in other words, substances which are helpful for improving cohesive force may resist decomposition of unfavorable polymers. However, in addition to the excellent biodegradability of the polyurethane dispersant used in the present invention itself, it was unexpectedly found that the adhesive tape prepared by adding a small amount of the acrylic adhesive of the degradable polyurethane dispersant also has a biodegradable effect (as shown in comparative example 4), if the amount of the polyurethane dispersant is increased, the decomposition of the adhesive is theoretically disadvantageous due to the increase of the cohesive force, however, when the wet weight ratio of the polyurethane dispersant (dry weight) to the whole adhesive composition is increased to 8% or more in the present case and the degradation effect of the polyurethane dispersant to the acrylic adhesive (dry weight/dry weight) is controlled to 40% or less at the same time, as shown in table 3, the adhesive tape samples of examples 1 to 5 of the present invention can reach 90% or more at 180 days, not only have excellent cohesive force, but also have excellent biodegradable effect. In other words, the prepared adhesive tape is biodegradable and has good adhesion performance. In addition, since the adhesion promoter generally has a low molecular weight and does not crosslink with the adhesive, the addition of the adhesion promoter does not affect the adhesive properties and degradation rate of the tape sample when the amount of the polyurethane dispersant added, and the ratio of the polyurethane dispersant to the acrylic adhesive are as described. The adhesive composition prepared by the formulation of example 3 was subjected to degradation experiments, and the 127-day degradation rate thereof was 90.0%, so that it can be understood that the aqueous acrylic adhesive and the polyurethane dispersant were disposed in the proportions disclosed in the present application, and an adhesive composition having good adhesive effect and degradation ability was obtained.
Table 4 shows the adhesive properties and degradation rates of the biodegradable tapes of example 2.
Table 4 properties of biodegradable tapes prepared by coating the adhesive composition formulation of example 2 onto different biodegradable back-base films
As shown in table 4, the adhesive composition prepared with the formulation of example 2 maintains good adhesive tape adhesion properties and also gives good degradation effect regardless of being coated on biaxially oriented polylactic acid film, kraft paper or cellophane.
In summary, the present invention provides a simple and biodegradable adhesive composition which is a non-solvent type adhesive composition and thus is relatively environmentally friendly and has the advantage of being simple to manufacture compared to hot melt adhesives or other adhesives extracted from biological components. When the adhesive composition is coated on a biodegradable back substrate, various biodegradable adhesive tapes can be prepared, good adhesive performance is provided, and the adhesive requirements of adhesive tape on holding viscosity, peeling strength, initial viscosity and the like are met, so that the adhesive composition can be used in various application fields such as packaging, box sealing, adhesion, sticking and the like.
It will be appreciated by those having ordinary skill in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. Further, it will be apparent to those skilled in the art that various improvements and modifications can be made to the present invention without departing from the spirit and scope of the invention.
Claims (20)
1. A biodegradable tape comprising:
a biodegradable adhesive composition comprising: an acrylic adhesive and a polyurethane dispersant, the polyurethane dispersant having a dry weight of at least 8% or more relative to the wet weight of the biodegradable adhesive composition, and the polyurethane dispersant having a dry weight of no more than 40% relative to the dry weight of the acrylic adhesive; and
a biodegradable backing film;
wherein the biodegradable adhesive tape has a compostable degradation rate of at least 90% or more in 180 days as measured by GB/T19277.1.
2. The biodegradable tape of claim 1, wherein the biodegradable back-base film is a multi-layer back-base selected from one or a combination of polylactic acid film, kraft paper, and cellophane.
3. The biodegradable tape of claim 2, wherein the biodegradable back-base film is a biaxially oriented biodegradable back-base film.
4. The biodegradable tape of claim 1 wherein the acrylic adhesive comprises an aqueous random copolymer having monomer units selected from one or more of acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, and methacrylamide.
5. The biodegradable tape of claim 1, wherein the polyurethane dispersant is an aqueous dispersant.
6. The biodegradable tape of claim 5, wherein the polyurethane dispersant is an anionically modified polyurethane dispersant.
7. The biodegradable tape of claim 1, further comprising a tackifier.
8. The biodegradable tape of claim 7 wherein the tackifier is selected from one or more of rosin resins, hydrogenated rosin resins, and terpene phenolic resins.
9. The biodegradable tape of claim 1 having a tack at GBT 4851-2014A of at least greater than 24 hours.
10. The biodegradable tape of claim 1 having a 180 degree peel strength of at least 2.5N/cm or greater as tested in GBT 2792-2014.
11. The biodegradable tape of claim 1 having an initial adhesion of at least No. 12 balls as tested in GB/T4582-2002.
12. The biodegradable tape of claim 1, wherein the biodegradable adhesive composition has a thickness of 10-200 μιη after drying.
13. The biodegradable tape of claim 1, further comprising a release layer.
14. A biodegradable adhesive composition comprising:
an acrylic adhesive; and
a polyurethane dispersant having a dry weight of at least 8% or more relative to the wet weight of the biodegradable adhesive composition and a dry weight of not more than 40% relative to the dry weight of the acrylic adhesive, wherein the biodegradable adhesive composition has a compostable degradation rate of at least 90% or more as measured by GB/T19277.1 for 180 days.
15. The biodegradable adhesive composition according to claim 14, wherein the acrylic adhesive comprises an aqueous random copolymer having monomer units selected from one or more of acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide and methacrylamide.
16. The biodegradable adhesive composition of claim 14, wherein the polyurethane dispersant is an aqueous dispersant.
17. The biodegradable adhesive composition of claim 16, wherein the polyurethane dispersant is an anionically modified polyurethane dispersant.
18. The biodegradable adhesive composition of claim 14, comprising an adhesion promoter.
19. The biodegradable adhesive composition of claim 18, wherein the tackifier is selected from one or more of rosin resins, hydrogenated rosin resins, and terpene phenolic resins.
20. A method for making biodegradable adhesive tape, comprising:
providing a biodegradable backing film and a biodegradable adhesive composition;
coating the biodegradable adhesive composition onto the biodegradable backing film, wherein the biodegradable adhesive composition comprises an acrylic adhesive and a polyurethane dispersant, the polyurethane dispersant having a dry weight of at least 8% or more relative to the wet weight of the biodegradable adhesive composition, and the polyurethane dispersant having a dry weight of no more than 40% relative to the dry weight of the acrylic adhesive; and
drying and dehydrating the biodegradable back base film coated with the biodegradable adhesive composition to obtain the biodegradable adhesive tape;
wherein the biodegradable adhesive tape has a compostable degradation rate of at least 90% or more in 180 days as measured by GB/T19277.1.
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