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CN109266233B - Adhesive tape base material, adhesive tape with same and preparation method - Google Patents

Adhesive tape base material, adhesive tape with same and preparation method Download PDF

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Publication number
CN109266233B
CN109266233B CN201810897412.8A CN201810897412A CN109266233B CN 109266233 B CN109266233 B CN 109266233B CN 201810897412 A CN201810897412 A CN 201810897412A CN 109266233 B CN109266233 B CN 109266233B
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China
Prior art keywords
parts
adhesive tape
weight
base material
polylactic acid
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Expired - Fee Related
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CN201810897412.8A
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Chinese (zh)
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CN109266233A (en
Inventor
李东立
李伯涵
陈素梅
朱磊
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Beijing Zhongbang Jianye Printing Co ltd
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Beijing Zhongbang Jianye Printing Co ltd
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Priority to CN201810897412.8A priority Critical patent/CN109266233B/en
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    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides an adhesive tape base material, an adhesive tape with the same and a preparation method. The adhesive tape base material comprises a continuous phase and a dispersed phase dispersed in the continuous phase, wherein the continuous phase is made of L-polylactic acid, and the dispersed phase is made of toughening filler and dispersant, wherein the L-polylactic acid accounts for 55-95 parts by weight, the toughening filler accounts for 0.25-2.5 parts by weight, and the dispersant accounts for 0.25-2.5 parts by weight. The raw materials such as L-polylactic acid and the like are all biodegradable, so that the pollution of the adhesive tape with the base material to the environment is reduced, and the adhesive tape base material can have medium oxygen transmission rate and high water vapor transmission rate by limiting the proportion of the components, and can be used for packaging agricultural products.

Description

Adhesive tape base material, adhesive tape with same and preparation method
Technical Field
The invention relates to the field of adhesive tape preparation, in particular to an adhesive tape base material, an adhesive tape with the same and a preparation method.
Background
With the development of commodity economy, the improvement of the living standard of people and the acceleration of the life rhythm, online shopping becomes a main way for people to purchase living necessities, and logistics also becomes a first choice for enterprises to purchase raw materials and push products to users. With the increasing amount of commodity packaging, the demand for sealing adhesive tapes is also increasing.
In the domestic market at present, the base material of the sealing adhesive tape is mainly polyvinyl chloride, polypropylene and other materials, the degradation process of the base material needs hundreds of years, and the degradation process of the adhesive layer is long, so that the non-degradable sealing adhesive tape brings great pollution to the environment. In order to solve the problem of contamination of the adhesive tape, degradable substrates such as polylactic acid films, starch-modified films, polycaprolactone films, and the like, or blends thereof have been used. However, the degradation problem of the pressure-sensitive adhesive is not well solved all the time, the degradation time of the common polyacrylate pressure-sensitive adhesive is long, the carton can be polluted, and the recycling of the carton is influenced.
If the adhesive tape is used for packaging fresh agricultural products, the adhesive tape is required to have high moisture permeability and oxygen permeability, while the common polypropylene-based adhesive tape in the market has low moisture permeability and almost no moisture permeability, so that the adhesive tape can bring negative effects when packaging the fresh agricultural products, and fruits and vegetables are easy to rot.
Another problem still exists at present in the joint sealing sticky tape is that the glue film of sticky tape generally uses polyacrylic ester, and its biodegradability is not good, destroys the environment after abandoning, also can cause the influence to waste paper recovery rate.
Disclosure of Invention
The invention mainly aims to provide an adhesive tape base material, an adhesive tape with the same and a preparation method, and aims to solve the problems that the adhesive tape is not degradable and has poor moisture permeability in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided an adhesive tape base material, including a continuous phase and a dispersed phase dispersed in the continuous phase, the material of the continuous phase is L-polylactic acid, and the material of the dispersed phase is a toughening filler and a dispersant, wherein the L-polylactic acid is 55 to 95 parts by weight, the toughening filler is 0.25 to 2.5 parts by weight, and the dispersant is 0.25 to 2.5 parts by weight.
Furthermore, the toughening filler is nano silicon dioxide, and the dispersant is polyoxyethylene.
Furthermore, in the adhesive tape base material, the surface of the toughening filler is coated with the dispersing agent, and the toughening filler coated with the dispersing agent is dispersed in the L-polylactic acid.
Further, the adhesive tape base material also comprises microcrystalline cellulose, and the microcrystalline cellulose accounts for 5-25 parts by weight; the tape base material preferably further comprises microcrystalline cellulose grafted poly-L-lactic acid polymer, and the raw materials for forming the tape base material comprise, by weight, 55-95 parts of L-polylactic acid, 0.25-2.5 parts of nano silicon dioxide, 0.25-2.5 parts of polyethylene oxide, 2-25 parts of microcrystalline cellulose and 2.5-15 parts of microcrystalline cellulose grafted poly-L-lactic acid polymer, and more preferably 85-90 parts of L-polylactic acid.
Further, the oxygen transmission rate of the adhesive tape base material is 1000-5000 ml/m2At day.atm, a water vapor transmission rate of 100 to 400g/m2Day, longitudinal tensile strength 31-52N/cm, nominal strain at break 80-131%.
According to another aspect of the invention, an adhesive tape is provided, which includes a substrate layer and an adhesive layer covering the surface of the substrate layer, wherein the substrate layer is the adhesive tape substrate.
Further, the glue layer comprises 25-55 parts of peach gum and 5-15 parts of poly N-vinyl pyrrolidone by weight.
Further, the rubber layer also comprises natural rubber, and the weight part of the natural rubber is 10-15.
Further, the glue layer also comprises polyethylene oxide, and the weight part of the polyethylene oxide is 10-15.
Furthermore, the adhesive layer also comprises 5-10 parts by weight of sodium alginate.
Furthermore, the raw materials for forming the glue layer comprise, by weight, 25-55 parts of peach gum, 5-15 parts of poly-N-vinyl pyrrolidone, 10-15 parts of natural rubber, 10-15 parts of polyethylene oxide, 5-10 parts of sodium alginate and 15-20 parts of a solvent.
Furthermore, the initial adhesion of the adhesive layer is 14-17 balls, the lasting adhesion is more than 24 hours, and the 180-degree peel strength is 4-6N/cm.
According to another aspect of the present invention, there is also provided a method for preparing the adhesive tape, comprising the steps of: s1, melting, blending and forming a film by using a first raw material comprising L-polylactic acid, a toughening filler and a dispersing agent to obtain a tape base material; and S2, coating a second raw material comprising peach gum and poly N-vinyl pyrrolidone on the surface of the base material layer and drying to obtain a glue layer covering the surface of the adhesive tape base material.
Further, the toughening filler is nano silicon dioxide, and the dispersant is polyoxyethylene; the preparation method further comprises the step of pretreating the dispersing agent and the toughening filler before the step of melt blending, wherein the pretreatment step comprises the following steps: taking water glass as a raw material, preparing a gel product containing nano silicon dioxide by adopting a sol-gel method, and adding polyoxyethylene into a reaction system of the sol-gel method; drying the gel product to obtain a composition containing nano silicon dioxide and polyoxyethylene; preferably the gel product is neutralized before drying; after the pretreatment step, the composition and the L-polylactic acid are melt blended.
The technical scheme of the invention is applied to provide the adhesive tape base material which comprises 55-95 parts by weight of L-polylactic acid, 0.25-2.5 parts by weight of toughening filler, 0.25-2.5 parts by weight of dispersing agent, and the raw materials such as the L-polylactic acid and the like have biodegradability, so that the pollution of the adhesive tape with the base material to the environment is reduced, and the adhesive tape base material can have medium oxygen transmission rate and high water vapor transmission rate by limiting the proportion of the components, and can be used for realizing the packaging of agricultural products.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of an adhesive tape production apparatus used in a method for manufacturing an adhesive tape according to the present invention.
Wherein the figures include the following reference numerals:
10. a tape base material; 20. back coating equipment; 30. blade coating equipment; 40. a drying tunnel; 50. slitting equipment; 60. and (7) winding equipment.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged under appropriate circumstances in order to facilitate the description of the embodiments of the invention herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
As described in the background art, the adhesive tape in the prior art is not degradable and has poor moisture permeability. In order to solve the technical problem, the invention provides an adhesive tape base material which comprises a continuous phase and a dispersed phase dispersed in the continuous phase, wherein the continuous phase is made of L-polylactic acid, and the dispersed phase is made of toughening filler and dispersant, wherein the L-polylactic acid accounts for 55-95 parts by weight, the toughening filler accounts for 0.25-2.5 parts by weight, and the dispersant accounts for 0.25-2.5 parts by weight.
In the tape base material of the present invention, since the L-polylactic acid (PLLA, molecular weight 20 to 60 ten thousand) has biodegradability, the environmental pollution of the tape having the base material is reduced, and the compounding ratio of the components is limited, so that the tape base material can have a medium oxygen transmission rate and a high water vapor transmission rate, and can be used for packaging agricultural products.
In the adhesive tape base material of the present invention, a person skilled in the art can reasonably select the types of the toughening filler and the dispersant according to the prior art, and preferably, the toughening filler is nano silicon dioxide (SiO)2Granule of Chinese medicineDegree of 10-20nm), and the dispersant is polyethylene oxide (PEO, molecular weight 10)5-106And the viscosity of 1% aqueous solution (-25 ℃) is 8000-10000 mpa.s), and the toughening filler coated with the dispersing agent is dispersed in the L-polylactic acid by coating the dispersing agent on the surface of the toughening filler. Under the action of the dispersant, the nanometer silicon dioxide particles are dispersed in the L-polylactic acid matrix, the polar oxygen atoms on the ester groups in the L-polylactic acid chain segments have good compatibility with the polar nano-silica, the nano-silica adsorbs the ester groups on the PLLA chain segments to induce the L-polylactic acid to be directionally arranged on nano-silica particles, the nano-silica particles play a role of heterogeneous nucleation, the number of L-polylactic acid crystal particles is small and the size is large when the nano-silica is not added, the size of the crystal particles formed by the L-polylactic acid is small and the number of the crystal particles is large after the nano-silica is added, the fracture nominal strain of the blended base material is greatly improved, the toughness of the base material is greatly improved, the problem that the L-polylactic acid is easy to generate brittle fracture is thoroughly solved, and the service performance at low temperature is improved.
In the above tape base material of the present invention, preferably, the tape base material further includes microcrystalline cellulose (CNC, 60-100 mesh, 100-200 degree of polymerization), and the inexpensive microcrystalline cellulose not only increases the tensile strength of the modified L-polylactic acid, but also reduces the price of the modified L-polylactic acid. More preferably, the weight parts of the L-polylactic acid and the microcrystalline cellulose are 55-95: 5 to 25.
Further preferably, the tape base material further comprises a microcrystalline cellulose-grafted poly-L-lactic acid polymer (CNC-g-PLLA). The microcrystalline cellulose grafted poly-L-lactic acid polymer molecule contains a cellulose chain segment and a L-lactic acid poly chain segment, so that the compatibility between an L-polylactic acid matrix and microcrystalline cellulose can be improved, and the phase separation can not occur.
In a preferred embodiment, the content of the L-polylactic acid is 55 to 95 parts, the content of the nano silicon dioxide is 0.25 to 2.5 parts, the content of the polyethylene oxide is 0.25 to 2.5 parts, the content of the microcrystalline cellulose is 2 to 25 parts, the content of the microcrystalline cellulose grafted poly L-lactic acid polymer is 2.5 to 15 parts, and the content of the L-polylactic acid is more preferably 85 to 90 parts. By limiting the proportion of the components, the toughness of the adhesive tape base material is greatly improved and the cost of the adhesive tape base material is reduced while the adhesive tape base material has medium oxygen transmission rate and high water vapor transmission rate.
In the adhesive tape base material with the component ratio, the oxygen transmission rate of the adhesive tape base material is 1000-5000 ml/m2At day.atm, a water vapor transmission rate of 100 to 400g/m2Day, longitudinal tensile strength 31-52N/cm, nominal strain at break 80-131%. The adhesive tape base material has medium oxygen transmission rate and high water vapor transmission rate, can be used for packaging agricultural products, and has better mechanical property than the common adhesive tape base material.
According to another aspect of the present application, a tape is provided, which includes the tape substrate and a glue layer covering the surface of the tape substrate. The L-polylactic acid has biodegradability, so that the pollution of the adhesive tape with the base material to the environment is reduced, and the adhesive tape with the base material can have medium oxygen transmission rate and high water vapor transmission rate by limiting the proportion of each component in the base material, and can be used for packaging agricultural products.
In the above adhesive tape of the invention, preferably, the adhesive layer comprises peach gum (molecular weight 10)4-105) And poly-N-vinylpyrrolidone (PVP, molecular weight 10)6-107). Peach gum is a natural material and is easy to degrade, and poly-N-vinyl pyrrolidone is easy to dissolve in water, namely easy to hydrolyze, so that a glue layer prepared from peach gum and poly-N-vinyl pyrrolidone can be completely degraded. At the moment, the adhesive tape base material and the adhesive layer are both made of degradable materials, so that the problem that the adhesive tape in the prior art is not degradable is solved.
More preferably, the adhesive layer further comprises natural rubber (poly cis 1, 4-isoprene, NR, number average molecular weight of 1.0 to 1.7 x 10)5Elastic modulus of 2-4 MPa, softening at 130-140 deg.C, and softening at 150-160 deg.C), polyethylene oxide (PEO, molecular weight 10)5-106) And sodium alginate (molecular weight 270000-25-55 parts of peach gum and 10-15 parts of natural rubber; 10-15 parts by weight of polyoxyethylene; the weight part of the sodium alginate is 5-10. At the moment, the adhesive layers are all made of degradable materials, and the oxygen transmission rate and the water vapor transmission rate of the adhesive tape are improved by adjusting the types and the contents of the materials of all the components, so that the problems of nondegradability and poor moisture permeability of the adhesive tape in the prior art are solved.
In a preferred embodiment, the raw materials for forming the adhesive layer comprise, by weight, 25-55 parts of peach gum, 5-15 parts of poly-N-vinyl pyrrolidone, 10-15 parts of natural rubber, 10-15 parts of polyethylene oxide, 5-10 parts of sodium alginate and 15-20 parts of solvent (water). The components of the adhesive layer are completely hydrolyzable or degradable substances, the problem of pollution of the adhesive tape is solved thoroughly by combining the degradable adhesive tape base material, the adhesive layer with the component proportion can enable the initial adhesion to reach 14-17 # balls, the holding adhesion is more than 24h, and the 180-degree peel strength is 4-6N/cm.
In a preferred embodiment, the adhesive tape may further include a release layer disposed on a side of the adhesive tape substrate away from the adhesive layer, forming a three-layer structure of release layer-substrate-adhesive layer. The release agent can be coated on one side surface of the tape base material by a back coating process, and the release agent can use OP series (polycondensate of alkylphenol and ethylene oxide, OP10, OP13, OP15, OP20, OP30, OP40, OP50), Span series (sorbitan fatty acid ester, S-20, S-40, S-60, S-80, S-85), Tween series (polyoxyethylene sorbitan fatty acid ester T-20, T-40, T-60, T-80) and other oligomer molecules, which have water solubility and biodegradability and have no pollution to the environment.
According to another aspect of the present application, there is also provided a method for preparing the above adhesive tape, comprising the steps of: s1, melting, blending and forming a film by using a first raw material comprising L-polylactic acid, a toughening filler and a dispersing agent to obtain a tape base material; and S2, coating a second raw material comprising peach gum and poly N-vinyl pyrrolidone on the surface of the base material layer and drying to obtain a glue layer covering the surface of the adhesive tape base material.
In a preferred embodiment, the step S1 includes the following steps: s11, melting and blending the first raw material by adopting a double-screw extruder to obtain a modified blend; and S12, adopting a casting process to extrude the modified blend into a film by casting, and then cooling to obtain the tape base material.
In the preferred embodiment, more preferably, the double-screw extruder has a screw length-diameter ratio of 26, a screw compression ratio of 2.0:1, four heating zones and a die temperature of 160, 180, 190, 200 and 200 ℃ respectively, and a screw rotation speed of 200 to 260 rpm. Under the condition of melt blending, the nano silicon dioxide adsorbs an L-polylactic acid chain segment in the matrix resin, so that the thermal stability of the L-polylactic acid is improved, and the thermal degradation temperature of the L-polylactic acid can be improved by 5-12 ℃ so as to prevent the L-polylactic acid resin from thermal degradation during melt blending processing.
In the above preferred embodiment, more preferably, the four heating zones and the die temperature in the casting equipment used in the casting process are adjusted to 165, 185, 195, 205 and 205 ℃, respectively, the blend is cooled by the cooling medium of 30 to 50 ℃ after being extruded and molded, and the cooled modified blend is uniaxially stretched to obtain the tape base material.
In the above step S1, the toughening filler may be nano silica, and the dispersant is polyethylene oxide; at this time, in a preferred embodiment, the preparation method further includes a step of pretreating the dispersant and the toughening filler, prior to the step of melt blending, the pretreatment step including: taking water glass as a raw material, preparing a gel product containing nano silicon dioxide by adopting a sol-gel method, and adding polyoxyethylene into a reaction system of the sol-gel method; drying the gel product to obtain a composition containing nano silicon dioxide and polyoxyethylene; after the pretreatment step, the composition and the L-polylactic acid are melt blended.
The dispersant polyethylene oxide is coated on the surface of the nano-silica through the pretreatment, so that the nano-silica coated with the dispersant is dispersed in the L-polylactic acid during melt blending. In order to obtain a good dispersion effect, it is preferable that the gel product is neutralized before drying, and the dry weight ratio of nano silica to polyethylene oxide in the composition is 1: 1.
In the step S1, the first raw material preferably further includes microcrystalline cellulose and a microcrystalline cellulose-grafted poly-L-lactic acid polymer, and in this case, the microcrystalline cellulose may be prepared by the following method: preparing microcrystalline cellulose aqueous suspension by using cotton fibers as raw materials and utilizing an acid method; adding toluene into the microcrystalline cellulose aqueous suspension, and carrying out ultrasonic treatment to obtain microcrystalline cellulose-containing toluene suspension and further obtain microcrystalline cellulose; the microcrystalline cellulose grafted poly-L-lactic acid polymer is prepared by the following method: and (2) carrying out ring-opening polymerization on the microcrystalline cellulose and the L-polylactic acid by taking stannous isooctanoate as an initiator to obtain the microcrystalline cellulose grafted poly-L-lactic acid polymer. The above ring-opening polymerization can be carried out by reacting in an 80 degree oil bath for 24 hours, terminating the reaction with hydrochloric acid, washing with methanol as a cleaning agent, and vacuum-drying with 60 ℃ for 96 hours.
Before the blending modification of the resins and before the blending is processed into films, the five components in the first raw material and the modified resins after the melting blending can be dried and dewatered until the water content of the raw material or the blended resins is lower than 0.025 percent, so as to prevent the PLLA resin from thermal degradation during processing. When drying, air with dew point lower than-40 ℃ can be adopted, and the air is heated to 80 ℃ and dried for at least 2h, so that the requirement that the moisture content is lower than 0.025% can be met. The dried hot air can be recycled, and a fluidized bed type drying tower is adopted for continuous dehumidification.
After the step S1, the method of manufacturing the invention may further include a step of forming a release layer, where the release layer covers a side of the tape substrate away from the adhesive layer, and the step of forming the release layer may be before the step of forming the adhesive layer or after the step of forming the adhesive layer. Specifically, the adhesive layer and the release layer respectively covering the two side surfaces of the adhesive tape substrate can be formed by using an adhesive tape production apparatus as shown in fig. 1, and the adhesive tape substrate 10 is disposed in the adhesive tape production apparatus, a release agent is coated on one side surface of the adhesive tape substrate 10 by a back coating device 20, a glue solution is coated on the other side surface of the adhesive tape substrate 10 by a blade coating device 30, then the adhesive tape substrate 10 coated with the release agent and the glue solution is dried by a drying tunnel 40 to obtain the release layer and the adhesive layer respectively disposed on the two side surfaces of the adhesive tape substrate 10, and finally, the adhesive tape can be cut into appropriate sizes and wound by a cutting device 50 and a winding device 60.
The present invention is described in further detail below with reference to specific examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1
The preparation method of the adhesive tape provided in the embodiment comprises the following steps:
(1) preparation of nanosilica/polyethylene oxide composition: mixing 100 parts of polyoxyethylene with the weight concentration of 5% and 24.6 parts of sodium silicate aqueous solution with the weight concentration of 30% in a three-necked bottle, heating to 40-45 ℃, dropwise adding a 10% sulfuric acid solution until the pH value is 6-6.5, then heating to 80-90 ℃, preserving heat for 30min, cooling, centrifuging, pouring out the supernatant, continuously washing the lower-layer suspension with distilled water until no sulfate ions exist, and drying the centrifuged lower layer at 80 ℃ in vacuum for 2h.
(2) After 60 parts of poly-L-lactic acid and 4 parts of nano-silica/polyethylene oxide composition (containing 2 parts of nano-silica and 2 parts of polyethylene oxide) are mechanically blended, the three raw materials are melted and blended by a double-screw extruder, the length-diameter ratio of a screw is 26, the compression ratio of the screw is 2.0:1, the temperatures of four heating sections and a die head are respectively set to be 160, 180, 190, 200 and 200 ℃, and the rotating speed of the screw is 200 rpm. Cutting and drying to obtain the modified L-polylactic acid ternary blend.
(3) The modified L-polylactic acid ternary blend is utilized, tape base materials are prepared by adopting a tape casting process, the temperatures of four heating sections and a T-shaped die head of tape casting equipment are respectively set to be 165, 185, 195, 205 and 205 ℃, a melt is extruded from the die head and then is cooled by a stainless steel cooling roller, and cooling water with the temperature of 30 ℃ is introduced into the cooling roller for quenching, so that a modified L-polylactic acid tape casting film is obtained.
(4) Mixing 100 parts of poly-N-vinyl pyrrolidone aqueous solution (10 parts of dry basis) and 100 parts of peach gum aqueous solution (40 parts of dry basis) in a reaction kettle, and decompressing and removing water until the total solid content is 40% to prepare the water-based pressure-sensitive adhesive.
(5) And (3) using the adhesive tape equipment shown in FIG. 1, coating the modified L-polylactic acid cast film prepared in the step (4) as a base material on the front surface, coating the aqueous adhesive prepared in the step (5) on the back surface, and coating an OP90 release layer on the back surface, wherein the drying tunnel temperature is 60 ℃, and the linear speed is 50m/min, so as to obtain the product.
Example 2
The difference between the preparation method of the adhesive tape provided in this example and example 1 is that:
in step (3), the melt-blended raw materials include 55 parts of poly L-lactic acid, 0.25 part of nano silica, 0.25 part of polyethylene oxide.
Example 3
The preparation method of the adhesive tape of the embodiment is different from that of the embodiment 1 in that:
in step (3), the melt-blended raw materials include 95 parts of poly L-lactic acid, 2.5 parts of nano silica, and 2.5 parts of polyethylene oxide.
Example 4
The preparation method of the adhesive tape provided in the embodiment comprises the following steps:
(1) preparation of nanosilica/polyethylene oxide composition: mixing 100 parts of polyoxyethylene with the weight concentration of 5% and 24.6 parts of sodium silicate aqueous solution with the weight concentration of 30% in a three-necked bottle, heating to 40-45 ℃, dropwise adding a 10% sulfuric acid solution until the pH value is 6-6.5, then heating to 80-90 ℃, preserving heat for 30min, cooling, centrifuging, pouring out the supernatant, continuously washing the lower-layer suspension with distilled water until no sulfate ions exist, and drying the centrifuged lower layer at 80 ℃ in vacuum for 2h.
(2) Preparation of microcrystalline cellulose grafted poly-L-lactic acid polymer: mixing 100 parts of cotton fiber and 500 parts of 60% sulfuric acid in a three-neck flask, treating in a water bath at 40-45 ℃ for 24-48h to obtain a microcrystalline cellulose suspension, centrifuging, pouring out the supernatant, washing the lower layer with distilled water, centrifuging, and repeating the steps until the pH value is 6.5. Then, the mixture was centrifuged, the upper aqueous layer was decanted, 500 parts of acetone was added, and ultrasonic dispersion was carried out for 2 hours to obtain an acetone dispersion. And centrifuging the acetone-microcrystalline cellulose dispersion liquid, pouring out 200 parts of supernatant, adding 200 parts of toluene, carrying out ultrasonic treatment for 2 hours, and repeating the operation for 5 times to obtain the microcrystalline cellulose toluene suspension. The microcrystalline cellulose grafted poly-L-lactic acid polymer is obtained by initiating and ring-opening polymerizing L-lactic acid on the surface of microcrystalline cellulose by adopting an initiator. 100 parts by weight on a dry basis of a microcrystalline cellulose suspension in toluene are introduced into a bag-stirred three-necked flask which is placed in an oil bath at a temperature of 81 to 85 ℃. L-lactic acid with dry content of 100 parts is dissolved in 500 parts of toluene and added into the three-neck flask, then 1 part of stannous isooctanoate (Sn (Oct)2) catalyst is added into the three-neck flask for reaction for 24 hours, and a few drops of dilute hydrochloric acid are added to stop the reaction. And pouring the reactant into excessive methanol at the temperature of 0 ℃, performing centrifugal separation to obtain a microcrystalline cellulose grafted poly-L-lactic acid polymer product, and performing vacuum drying on the product at the temperature of 60 ℃ for 7 hours.
(3) After 60 parts of poly-L-lactic acid, 2 parts of nano silicon dioxide, 2 parts of polyethylene oxide, 5 parts of microcrystalline cellulose grafted poly-L-lactic acid blend and 10 parts of microcrystalline cellulose are mechanically blended, a double-screw extruder is adopted to melt and blend the five raw materials, the length-diameter ratio of a screw is 26, the compression ratio of the screw is 2.0:1, the temperatures of four heating sections and a die head are respectively set to be 160, 180, 190, 200 and 200 ℃, and the rotating speed of the screw is 200 rpm. Cutting and drying to obtain the modified L-polylactic acid five-element blend.
(4) The modified L-polylactic acid five-membered blend is processed and prepared into the tape base material by adopting a tape casting process, the temperatures of four heating sections and a T-shaped die head of tape casting equipment are respectively set to be 165, 185, 195, 205 and 205 ℃, a melt is extruded from the die head and then is cooled by a stainless steel cooling roller, and cooling water with the temperature of 30 ℃ is introduced into the cooling roller for quenching, so that the modified L-polylactic acid tape casting film is obtained.
(5) Mixing 100 parts of poly-N-vinyl pyrrolidone aqueous solution (10 parts of dry basis) and 100 parts of peach gum aqueous solution (40 parts of dry basis) in a reaction kettle, and decompressing and removing water until the total solid content is 40% to prepare the water-based pressure-sensitive adhesive.
(6) And (3) using the adhesive tape equipment shown in FIG. 1, coating the modified L-polylactic acid cast film prepared in the step (4) as a base material on the front surface, coating the water-based adhesive prepared in the step (5) on the back surface, and coating a T-80 release layer on the back surface, wherein the drying tunnel temperature is 70 ℃, and the linear speed is 30m/min, so as to obtain the product.
Example 5
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in the step (3), the raw materials for melt blending are 91 parts of poly-L-lactic acid, 2.5 parts of nano-silica, 2.5 parts of polyethylene oxide, 2.5 parts of a blend of microcrystalline cellulose grafted poly-L-lactic acid, and 2 parts of microcrystalline cellulose.
Example 6
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in the step (3), the raw materials for melt blending are 59 parts of poly-L-lactic acid, 0.5 part of nano-silica, 0.5 part of polyethylene oxide, 15 parts of a blend of microcrystalline cellulose grafted poly-L-lactic acid, and 25 parts of microcrystalline cellulose.
Example 7
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in the step (3), the raw materials for melt blending are 85 parts of poly-L-lactic acid, 2 parts of nano-silicon dioxide, 2 parts of polyethylene oxide, 3 parts of a blend of microcrystalline cellulose grafted poly-L-lactic acid and 8 parts of microcrystalline cellulose.
Example 8
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in the step (3), the melt-blended raw materials comprise 90 parts of poly-L-lactic acid, 1 part of nano-silicon dioxide, 1 part of polyethylene oxide, 2 parts of a blend of microcrystalline cellulose grafted poly-L-lactic acid and 6 parts of microcrystalline cellulose.
Example 9
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 25 parts of peach gum dry base and 15 parts of poly-N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 10
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 55 parts of peach gum dry base and 5 parts of poly-N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 11
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 55 parts of peach gum dry base, 10 parts of natural rubber dry base and 10 parts of poly-N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 12
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 25 parts of peach gum dry base, 15 parts of natural rubber dry base and 10 parts of poly-N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 13
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 25 parts of peach gum dry base, 15 parts of polyethylene oxide dry base and 10 parts of poly N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 14
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 55 parts of peach gum dry base, 10 parts of polyethylene oxide dry base and 10 parts of poly N-vinyl pyrrolidone dry base are mixed in a reaction vessel.
Example 15
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 55 parts of peach gum dry base, 5 parts of sodium alginate dry base and 10 parts of poly-N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 16
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
in step (5), 25 parts of peach gum dry base, 10 parts of sodium alginate dry base and 10 parts of poly-N-vinyl pyrrolidone dry base are mixed in a reaction kettle.
Example 17
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
the raw materials for preparing the water-based pressure-sensitive adhesive comprise 100 parts of natural rubber water-based dispersion liquid (10 parts of dry base), 100 parts of poly-N-vinyl pyrrolidone aqueous solution (15 parts of dry base), 100 parts of peach gum aqueous solution (55 parts of dry base), 10 parts of polyoxyethylene dry base, 50 parts of sodium alginate aqueous solution (5 parts of dry base) and 10 parts of water.
Example 18
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
the raw materials for preparing the water-based pressure-sensitive adhesive comprise 100 parts of natural rubber water-based dispersion liquid (15 parts of dry base), 100 parts of poly-N-vinyl pyrrolidone aqueous solution (15 parts of dry base), 100 parts of peach gum aqueous solution (25 parts of dry base), 15 parts of polyoxyethylene dry base and 50 parts of sodium alginate aqueous solution (10 parts of dry base).
Example 19
The difference between the preparation method of the adhesive tape provided in this embodiment and embodiment 4 is that:
the raw materials for preparing the water-based pressure-sensitive adhesive comprise 100 parts of natural rubber water-based dispersion liquid (13 parts of dry base), 100 parts of poly-N-vinyl pyrrolidone aqueous solution (10 parts of dry base), 100 parts of peach gum aqueous solution (40 parts of dry base), 12 parts of polyoxyethylene dry base and 50 parts of sodium alginate aqueous solution (12 parts of dry base).
Comparative example 1
The preparation method of the adhesive tape provided in the comparative example comprises the following steps:
the tape base material is prepared by adopting a tape casting process by taking only poly-L-lactic acid as raw material resin without adding any modified resin, the temperatures of four heating sections and a T-shaped die head of tape casting equipment are respectively set to be 165, 185, 195, 205 and 205 ℃, a melt is extruded from the die head and then is cooled by a stainless steel cooling roller, and cooling water with the temperature of 40 ℃ is introduced into the cooling roller for quenching, so that an unmodified L-polylactic acid tape casting film is obtained.
Mixing 33.3 parts of natural rubber water-based dispersion liquid (10 parts of dry base), 40 parts of poly-N-vinyl pyrrolidone aqueous solution (5 parts of dry base), 140 parts of peach gum aqueous solution (35 parts of dry base), 15 parts of polyethylene oxide dry base and 75 parts of sodium alginate aqueous solution (15 parts of dry base) in a reaction kettle, and decompressing and removing water until the total solid content is 40% to prepare the water-based pressure-sensitive adhesive.
By using the tape equipment shown in FIG. 1, the unmodified L-polylactic acid cast film is used as a base material, the water-based pressure-sensitive adhesive is coated on the front surface, an OP40 release layer is coated on the back surface, the drying tunnel temperature is 80 ℃, and the linear speed is 40m/min, so that the product is obtained.
Comparative example 2
The preparation method of the adhesive tape provided in the comparative example comprises the following steps:
the tape base material is prepared by adopting a tape casting process by taking only poly-L-lactic acid as raw material resin without adding any modified resin, the temperatures of four heating sections and a T-shaped die head of tape casting equipment are respectively set to be 165, 185, 195, 205 and 205 ℃, a melt is extruded from the die head and then is cooled by a stainless steel cooling roller, and cooling water with the temperature of 40 ℃ is introduced into the cooling roller for quenching, so that an unmodified L-polylactic acid tape casting film is obtained.
By using the tape equipment shown in FIG. 1, the unmodified L-polylactic acid cast film is used as a base material, the front surface is coated with a commercially available acrylic ester aqueous adhesive, the back surface is coated with an OP40 release layer, the drying tunnel temperature is 80 ℃, and the linear speed is 40m/min, so that the product is obtained.
The performance test method of the degradable adhesive tape related by the invention is as follows:
normal 180 ° peel strength: the test is carried out according to the national standard GB/T2792.
Peel strength 180 ° after humid heat aging: the adhesive tape is placed in a constant temperature and humidity box with the temperature of (60 +/-2) DEG C and the relative humidity of (80 +/-5)% for 24 hours, and immediately tested according to the national standard GB/T2792 after being taken out, and the test is completed within 3 minutes.
180 ° peel strength after low temperature treatment: the adhesive tape is placed in a constant temperature box with the temperature of (-20 +/-2) DEG C for 4 hours, and immediately tested according to the national standard GB/T2792 after being taken out, and the test is completed within 3 minutes.
Initial adhesion: the test was carried out according to the test method specified in method A of International Standard GB/T4852-2002, with a bevel inclination of 30 °.
Permanent adhesion: the test is carried out according to the test method specified in the method A in the national standard GB/T4851-2014, the width of the adhesive tape is (24 +/-0.5) mm, the length of the adhesive surface of the adhesive tape on the steel plate of the test platform is (12 +/-0.5) mm, and the weight mass is (1000 +/-5) g.
Normal tensile strength: the test was carried out at 25 ℃ and room temperature according to the national standard GB/T30776-.
Tensile strength after humid heat aging: the adhesive tape is placed in a constant temperature and humidity box with the temperature of (60 +/-2) DEG C and the relative humidity of (80 +/-5)% for 24 hours, and immediately tested according to the method A of the national standard GB/T30776-.
Tensile strength after low-temperature treatment: the adhesive tape is placed in a constant temperature box with the temperature of (-20 +/-2) DEG C for 4 hours, and immediately after being taken out, the test is carried out according to the national standard GB/T30776-2014 method A, and the test is completed within 3 minutes.
Nominal strain at break: the test was carried out at 25 ℃ and room temperature according to the national standard GB/T30776-.
Low speed unwinding force: the test was carried out at 25 ℃ and room temperature according to the national standard GB/T4850.
Right angle tear load: a5 mm cut was cut from the edge of the tape perpendicular to the tape direction and to the inside of the tape at 25 ℃ at room temperature using a tape having a width of (24. + -. 0.5) mm, and then tested according to the national standard GB/T1040.1. The initial distance between the clamps is 50mm, the cut is arranged at the middle position of the vertical central line of the upper clamp and the lower clamp, the stretching speed of the clamps is (500 +/-50) mm/min, the clamps are stretched at a constant speed until the adhesive tape is broken along the cut, and the maximum stretching load is read.
Limiting the residual amount of the solvent: the test was carried out according to the method specified in the national standard GB 10004-2008 6.6.17.
Heavy metal and specific substance limits: digesting the adhesive tape sample by a high-pressure microwave system, and testing by an atomic absorption spectrometer according to a method specified by the national standard GB/T15337.
Biodegradability: the inorganic content (volatile solids content) was measured according to the provisions of the national standard GB/T9345.1 method A, at a measurement temperature of 650 ℃. The biological decomposition rate is tested according to the regulations of national standards GB/T19277.1, GB/T19277.2, GB/T19276.1 and GB/T19276.2. In arbitration, the biological decomposition rate was tested according to the national standard GB/T19277.1.
Testing of Water Vapor Transmission Rate (WVTR) of the film was cut to an area of 50cm according to GB/T1037-88 test method for Water vapor permeability of Plastic films and sheets2The round shape is tested by adopting a Model 3/33 water vapor transmission rate tester of Mocon company in America; the Oxygen Transmission Rate (OTR) and the carbon dioxide transmission rate of the film are tested according to GB/T1038-2000 plastic film and sheet gas permeability test method pressure differential method, and the test instrument is an oxygen transmission rate tester with model 8001 of Mocon corporation in America.
The product indexes of the adhesive tapes prepared in the above examples 1 to 19 and comparative examples 1 to 2 are shown in tables 1 to 2.
TABLE 1
Figure BDA0001758533140000121
Figure BDA0001758533140000131
TABLE 2
Figure BDA0001758533140000132
Figure BDA0001758533140000141
Figure BDA0001758533140000151
From the test results, when the content of CNC-g-PLLA as a compatilizer in the base material is increased, the CNC as a reinforcing agent has obvious effect, the longitudinal tensile strength is improved, the CNC is uniformly dispersed in the base material, and the strength and the toughness of the base material are also improved (the fracture nominal strain is increased); the nano silicon dioxide is used as a heterogeneous nucleating agent, and when the dosage of the nano silicon dioxide is increased, the particle size of PLA crystal is reduced, the PLA crystal is facilitated, and the longitudinal tensile strength and the toughness (fracture nominal strain) of the modified PLLA are improved. In the PEO/nano-silica composition, PEO is used as a separant of nano-silica, and ether oxygen atoms can form hydrogen bonds with hydroxyl groups on silica particles, so that the agglomeration of the silica nanoparticles is effectively prevented, the particle size of the nanoparticles is maintained at 10-20nm, and the heterogeneous nucleation effect is realized in a modified PLLA matrix; with the increasing content of CNC in the base material, the CNC has obvious effect as a reinforcing agent, the longitudinal tensile strength is improved, and under the increasing effect of CNC-g-PLLA, if the CNC is uniformly dispersed in the base material, the toughness of the base material is also improved (the fracture nominal strain is increased), but if the CNC is used in a too high amount, the toughness of the modified PLLA base material is reduced.
In the composition of the pressure-sensitive adhesive, the peach gum has good bonding performance, and has the defects of large brittleness of a glue film, poor water resistance, large brittleness at low temperature and reduced bonding strength; the poly N-vinyl pyrrolidone can improve the initial viscosity and the permanent viscosity of the pressure-sensitive adhesive layer and reduce the brittleness of the adhesive layer; the NR can obviously improve the water resistance and low-temperature resistance of the adhesive layer, and the adhesive strength of the adhesive tape added with the NR is obviously improved after the wet heat treatment or the low-temperature treatment; the PEO can reduce the glass transition temperature of the adhesive layer and increase the flexibility of the adhesive layer; sodium alginate is beneficial to the water retention of the glue layer, and the excessive loss of water in the glue layer is prevented.
As can be seen from comparison of the data in Table 1, the pressure-sensitive adhesive layer having a composition comprising 10 to 15 parts by weight of NR, 5 to 15 parts by weight of PVP, 25 to 55 parts by weight of peach gum, 10 to 15 parts by weight of PEO, 5 to 10 parts by weight of sodium alginate and 15 to 20 parts by weight of water was obtained after drying the pressure-sensitive adhesive layer. The initial adhesion of the pressure-sensitive adhesive layer is 15-17 (ball), the permanent adhesion is more than 24h, the 180-degree peel strength is 5.8-7.9N/cm, the 180-degree peel strength after the wet heat treatment is 5.5-7.7N/cm, the 180-degree peel strength after the low temperature treatment is 5.3-7.7N/cm, and the pressure-sensitive adhesive layer meets the relevant national standard.
From the comparison of the data in table 2, it can be found that the heavy metal content of the adhesive tape of the present invention meets the national standard. No peculiar smell exists, no organic volatile matter is left in the product, the organic matter content is more than 95 percent, and the relative biodegradation rate is more than 95 percent. With the increase of the content of PEO and CNC in the modified PLA, the Water Vapor Transmission Rate (WVTR) and the Oxygen Transmission Rate (OTR) tend to increase, which is because the crystallization capacity of PLA molecules is reduced by PEO and CNC, so that the crystallinity of the modified PLA is reduced, the crystallization particles are reduced, the free volume is increased, and the barrier property to gas is reduced.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the technical scheme of the invention is applied to provide an adhesive tape base material which comprises 55-95 parts by weight of L-polylactic acid, 0.25-2.5 parts by weight of toughening filler, 0.25-2.5 parts by weight of dispersing agent, wherein the L-polylactic acid has biodegradability, so that the pollution of the adhesive tape with the base material to the environment is reduced, and the adhesive tape base material can have medium oxygen transmission rate and high water vapor transmission rate by limiting the proportion of the components, and can be used for realizing the packaging of agricultural products.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. The adhesive tape base material is characterized by comprising a continuous phase and a dispersion phase dispersed in the continuous phase, wherein the continuous phase is made of L-polylactic acid, the dispersion phase is made of toughening filler and a dispersing agent, the L-polylactic acid accounts for 55-95 parts by weight, the toughening filler accounts for 0.25-2.5 parts by weight, and the dispersing agent accounts for 0.25-2.5 parts by weight,
the toughening filler is nano silicon dioxide, and the dispersant is polyoxyethylene; the dispersant and the toughening filler having a step of pre-treating, the pre-treating step comprising:
taking water glass as a raw material, preparing a gel product containing the nano silicon dioxide by adopting a sol-gel method, and adding the polyoxyethylene into a reaction system of the sol-gel method;
and drying the gel product to obtain the composition containing the nano silicon dioxide and the polyethylene oxide.
2. The tape base according to claim 1, wherein the dispersant is coated on the surface of the toughening filler, and the toughening filler coated with the dispersant is dispersed in the L-polylactic acid.
3. The tape base according to claim 1, further comprising 5 to 25 parts by weight of microcrystalline cellulose.
4. The tape base according to claim 3, further comprising a microcrystalline cellulose-grafted poly (L-lactic acid) polymer, wherein the raw material for forming the tape base comprises, by weight, 55 to 95 parts of the L-polylactic acid, 0.25 to 2.5 parts of the nano-silica, 0.25 to 2.5 parts of the polyethylene oxide, 2 to 25 parts of the microcrystalline cellulose, and 2.5 to 15 parts of the microcrystalline cellulose-grafted poly (L-lactic acid) polymer.
5. The tape base material according to claim 4, wherein the L-polylactic acid is 85 to 90 parts.
6. The tape base according to any one of claims 3 to 5, wherein the tape base has an oxygen transmission rate of 1000 to 5000ml/m2At day.atm, a water vapor transmission rate of 100 to 400g/m2Day, longitudinal tensile strength 31-52N/cm, nominal strain at break 80-131%.
7. An adhesive tape, comprising a substrate layer and an adhesive layer covering the surface of the substrate layer, wherein the substrate layer is the adhesive tape substrate of any one of claims 1 to 5.
8. The adhesive tape according to claim 7, wherein the adhesive layer comprises 25 to 55 parts by weight of peach gum and 5 to 15 parts by weight of poly-N-vinylpyrrolidone.
9. The adhesive tape according to claim 8, wherein the adhesive layer further comprises natural rubber in an amount of 10 to 15 parts by weight.
10. The adhesive tape according to claim 8, wherein the adhesive layer further comprises polyethylene oxide, and the weight part of the polyethylene oxide is 10-15.
11. The adhesive tape according to claim 8, wherein the adhesive layer further comprises 5-10 parts by weight of sodium alginate.
12. The adhesive tape according to claim 7, wherein the raw materials for forming the adhesive layer comprise, by weight, 25 to 55 parts of peach gum, 5 to 15 parts of poly-N-vinyl pyrrolidone, 10 to 15 parts of natural rubber, 10 to 15 parts of polyethylene oxide, 5 to 10 parts of sodium alginate, and 15 to 20 parts of solvent.
13. The adhesive tape according to claim 12, wherein the initial adhesion of the adhesive layer is 14 to 17 balls, the tack strength is greater than 24 hours, and the 180 ° peel strength is 4 to 6N/cm.
14. A method of preparing the adhesive tape of any one of claims 7 to 13, comprising the steps of:
s1, melting, blending and forming a film by using a first raw material comprising L-polylactic acid, a toughening filler and a dispersing agent to obtain a tape base material;
s2, coating a second raw material comprising peach gum and poly N-vinyl pyrrolidone on the surface of the base material layer and drying to obtain a glue layer covering the surface of the adhesive tape base material,
the toughening filler is nano silicon dioxide, and the dispersant is polyoxyethylene; prior to the step of melt blending, the dispersant and the toughening filler have a step of pre-treating, the pre-treating step comprising:
taking water glass as a raw material, preparing a gel product containing the nano silicon dioxide by adopting a sol-gel method, and adding the polyoxyethylene into a reaction system of the sol-gel method;
drying the gel product to obtain a composition containing the nano silicon dioxide and the polyethylene oxide;
after the pre-treatment step, the composition and the L-polylactic acid are subjected to the melt blending.
15. The method of claim 14, wherein the gel product is neutralized before drying.
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