CN112625626A - Packaging roll film with locking structure and application thereof - Google Patents
Packaging roll film with locking structure and application thereof Download PDFInfo
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- CN112625626A CN112625626A CN202011407062.6A CN202011407062A CN112625626A CN 112625626 A CN112625626 A CN 112625626A CN 202011407062 A CN202011407062 A CN 202011407062A CN 112625626 A CN112625626 A CN 112625626A
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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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/02—Wrappers or flexible covers
- B65D65/14—Wrappers or flexible covers with areas coated with adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/02—Wrappers or flexible covers
- B65D65/22—Details
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of packaging materials, in particular to a packaging roll film with a locking structure and application thereof. A packaging roll film with a locking structure is formed by connecting a plurality of packaging sections end to end through the locking structure 3 to form a whole; the packaging section is fixedly connected with the locking structure 3; the locking structure is composed of a base material 31, an adhesive layer 32 and a release layer 33; the substrate 31 and the release layer 33 are bonded and connected through an adhesive layer 32. The invention provides a novel locking structure which is simple in structure, smooth in separation and low in cost; meanwhile, the heat seal welding technology is adopted to replace the traditional adhesive bonding technology, the use amount of the adhesive is reduced, the environmental pollution is reduced, the operation is more flexible, the problem that the adhesive bonding is influenced by the environment and the temperature is avoided, and the problem that the release part cannot be combined due to the adhesive bonding is also avoided.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a packaging roll film with a locking structure and application thereof.
Background
Conventional packaging operations package an article with a web of film from a roll, the end of which must be bonded to the underlying web layer in order to securely wrap the article. Each package section of the web film wound on the roll includes a non-adhesive web section and an adhesive web section. Winding a plurality of turns through the non-adhesive film rolling section during packaging; winding the adhesive film winding section for multiple circles, wherein the parts in contact with each other when the adhesive film winding section is wound have viscosity but can be separated; eventually causing the ends of the adhesive roll film segments to adhere to the underlying adhesive roll film segments. The winding packaging roll film is applied to the field of packaging of crop harvesting materials, automatic packaging can be achieved through an automatic packaging machine, manual operation is not needed in the using process, packaging efficiency is greatly improved, and economic benefits are improved. At present, the conventional packaging operation for packaging cotton, silage and the like is to package materials by using a roll film from a reel, and the tail end of the roll film must be adhered to a roll film layer below the roll film so as to firmly wrap the articles.
Due to the variety of configurations of the rolled film, the effectiveness of use and the manufacturing process, such as CN100457567C, a wrapping material with a Z-lock system and methods of making and using the same are disclosed, wherein a complete roll of wrapping material is disclosed comprising a plurality of wrapping portions held together and released at their lateral ends, the lateral ends of each wrapping portion being Z-shaped to form the Z-lock system. The adhesive is bonded by the adhesive in the technology, so that the demand for the adhesive is large in the preparation process, and the adhesive contains harmful components, which is not beneficial to environmental protection. On the other hand, the separable bonding strip structure is complex, so that the production process is complex, the efficiency is low and the cost is high.
Aiming at the problems, the invention provides a packaging roll film with a locking structure, which comprises a novel locking structure, has simple structure, smooth separation and low cost, adopts a heat seal welding technology to replace the traditional adhesive bonding technology, reduces the using amount of the adhesive, reduces the environmental pollution, has more flexible operation, avoids the problem that the adhesive bonding is influenced by the environment and the temperature, and also avoids the problem that the release part can not be combined due to the adhesive bonding.
Disclosure of Invention
In order to solve the technical problem, the first aspect of the invention provides a packaging roll film with a locking structure, wherein the packaging roll film is an integral body formed by connecting a plurality of packaging sections end to end through the locking structure 3; the packaging section is fixedly connected with the locking structure 3; the locking structure is composed of a base material 31, an adhesive layer 32 and a release layer 33; the substrate 31 and the release layer 33 are bonded and connected through an adhesive layer 32.
As a preferred technical solution of the present invention, in the locking structure 3, the lengths of the substrate 31 and the release layer 33 are not less than the length of the adhesive layer 32.
As a preferred solution of the invention, the wrapping section comprises a non-adhesive zone 1 and an adhesive zone 2; the non-adhesive area 1 and the adhesive area 2 are fixedly connected.
In a preferred embodiment of the present invention, the adhesive area 2 of the front wrapping section and the non-adhesive area 1 of the rear wrapping section are connected by a closure 3 between the adjacent wrapping sections.
As a preferred technical solution of the present invention, the substrate 31 of the locking structure is fixedly connected with the non-adhesive area 1 of the subsequent packaging section; the release layer 33 of the locking structure is fixedly connected with the adhesive area 2 of the previous packaging section.
As a preferable technical scheme of the invention, the fixed connection is heat seal welding.
As a preferable technical scheme of the invention, the raw materials for preparing the adhesive layer at least comprise the following components in parts by weight: 100 parts of styrene thermoplastic elastomer, 10-50 parts of organic silicon resin, 80-120 parts of tackifying resin, 30-50 parts of plasticizer and 0.5-5 parts of antioxidant.
As a preferable technical solution of the present invention, the silicone resin is an epoxy resin modified silicone resin.
As a preferred embodiment of the present invention, the tackifying resin is a combination of terpene resin and rosin ester in a weight ratio of 1: (0.8-2).
The second aspect of the invention provides application of the packaging roll film with the locking structure in the field of agricultural products.
Advantageous effects
The invention provides a packaging roll film with a locking structure, which comprises a novel locking structure, and is simple in structure, smooth in separation and low in cost; meanwhile, the heat seal welding technology is adopted to replace the traditional adhesive bonding technology, so that the use amount of the adhesive is reduced, the environmental pollution is reduced, the operation is more flexible, the problem that the adhesive bonding is influenced by the environment and the temperature is avoided, and the problem that the release part cannot be combined due to the adhesive bonding is also avoided; in addition, the invention also provides an adhesive for a locking structure, which solves the problem of the use of adhesives in the field of packaging rolled films in different types at present, has excellent high temperature resistance, low temperature resistance, good initial adhesion, excellent lasting adhesion and high peel strength, and is suitable for the adhesion of the tail end of the packaging rolled film.
Drawings
Fig. 1 is a schematic structural diagram of a packaging roll film provided in embodiment 1 of the present invention.
The meaning of the reference numerals shown in fig. 1 is explained in turn as follows:
1 is a non-bonded area; 2 is a bonding area; 3 is a locking structure; 31 is a base material; 32 is an adhesive layer; and 33 is a release layer.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In order to solve the technical problem, the first aspect of the invention provides a packaging roll film with a locking structure, wherein the packaging roll film is an integral body formed by connecting a plurality of packaging sections end to end through the locking structure 3; the packaging section is fixedly connected with the locking structure 3; the locking structure is composed of a base material 31, an adhesive layer 32 and a release layer 33; the substrate 31 and the release layer 33 are bonded and connected through an adhesive layer 32.
In a preferred embodiment, in the locking structure 3, the length of the substrate 31 and the release layer 33 is not less than the length of the adhesive layer 32.
In a preferred embodiment, the adhesive area 2 of the preceding wrapping section is connected to the non-adhesive area 1 of the following wrapping section by a closure 3 between said adjacent wrapping sections.
In a preferred embodiment, the substrate 31 of the closure is fixedly attached to the non-adhesive area 1 of the subsequent package section; the release layer 33 of the locking structure is fixedly connected with the adhesive area 2 of the previous packaging section.
In a preferred embodiment, the fixed connection is a heat seal.
The inventor thinks that the locking structure adopts the full-release layer, so that the number of layers of the locking structure is reduced, the locking structure is simpler, the problem caused by the adhesion of the traditional adhesive is well solved through a heat seal welding mode, the efficiency is further improved, the process is simplified, and the cost is reduced.
In the invention, the raw materials for preparing the adhesive layer at least comprise the following components in parts by weight: 100 parts of styrene thermoplastic elastomer, 10-50 parts of organic silicon resin, 80-120 parts of tackifying resin, 30-50 parts of plasticizer and 0.5-5 parts of antioxidant.
Styrene thermoplastic elastomer
Styrenic thermoplastic elastomers (styrenic TPES), the main category of thermoplastic elastomers, styrenic thermoplastic elastomers (or styrenic block copolymers) are the most widely used ones because they can be mixed with a wide variety of materials such as fillers, extenders, modifiers, and other resins. This mixing can be used to closely control and vary the various properties of the material such as viscosity, stiffness, softening temperature and cohesive bond strength, depending on the requirements of a particular application. Therefore, styrenic TPES has an extremely wide range of applications. In contrast, styrene block copolymers are rarely used in pure form.
In the present invention, the styrene-based thermoplastic elastomer is at least one selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer.
In a preferred embodiment, the styrenic thermoplastic elastomer is a styrene-isoprene-styrene block copolymer.
In a preferred embodiment, the styrene thermoplastic elastomer has a melt flow rate of 5 to 20 g/min.
In a preferred embodiment, the styrene-isoprene-styrene block copolymer has a block ratio of styrene to isoprene of from 15/85 to 20/80.
In the present invention, the source of the styrene-isoprene-styrene block copolymer is not particularly limited, and may be selected from dry synthetic materials technologies, ltd, model numbers 1105, 1106, 1126, 1188, etc. in guangzhou.
In the invention, the weight ratio of the styrene-isoprene-styrene block copolymer to the organic silicon resin is 1: (0.1-0.5).
The inventor finds that the styrene thermoplastic elastomer has low modulus, low solution viscosity, good melt viscosity, good processability (such as coating property) and excellent adhesive property, and particularly, the adhesive prepared by the styrene thermoplastic elastomer has better adhesive property with the increase of the content of the diblock polymer in the styrene thermoplastic elastomer, but the holding adhesive property and the peeling strength of the adhesive are reduced. The inventors believe that this is possible because the diblock, which is a rubbery phase, has a better flexibility, and an increase in its content improves the adhesive properties of the glue, but the strength of the glue is reduced. The main chain of the organic silicon resin is composed of silicon-oxygen bonds, the bonds are high in energy and not easy to break, the strength of the adhesive can be improved after the organic silicon resin is compounded with a styrene thermoplastic elastomer, and particularly when a styrene-isoprene segmented copolymer is selected, the organic silicon resin has better compatibility with the organic silicon resin after the organic silicon resin is compounded with the methyl side chain of a dilute structure, so that the prepared adhesive has excellent bonding performance and strength. In the experimental process, the inventor finds that after the organic silicon resin is compounded, the curing temperature of the adhesive is increased, the curing time is prolonged, the adhesive force to an adhered material is reduced, and only when the weight ratio of the styrene thermoplastic elastomer to the organic silicon resin is 1: (0.1-0.5), the strength, curing temperature and time of the prepared adhesive can reach a balance value.
Silicone resin
Silicone resins (also known as polysiloxanes) are a general term for a class of polymers consisting of a backbone of alternating silicon and oxygen atoms, with different organic groups bonded to the silicon atoms. The organic silicon resin structure contains both organic groups and inorganic structures, and the special composition and molecular structure make the organic silicon resin integrate the characteristics of organic matters and the functions of inorganic matters.
In the invention, the organic silicon resin is polymethyl silicon resin.
In a preferred embodiment, the silicone resin is an epoxy modified silicone resin; the organic silicon resin is epoxy resin modified polymethyl silicon resin.
In a preferred embodiment, the epoxy resin is a bisphenol a epoxy resin.
In a more preferred embodiment, the bisphenol A epoxy resin has an epoxy value of 0.2 to 0.5.
In the present invention, the source of the epoxy resin is not particularly limited, and there may be mentioned designations E-44, E-42, E-35, E-31 and the like.
In the present invention, the source of the polymethylsilicone resin is not particularly limited, and there may be mentioned New four Hai chemical Co., Ltd, model Nos. SH-9501, SH-9502, SH-9503 and the like.
In a preferred embodiment, the weight ratio of the epoxy resin to the silicone resin is 1: (10-20).
In a more preferred embodiment, the epoxy resin modified silicone resin is prepared by the following steps: adding organic silicon resin into a solvent with the temperature of 40-70 ℃, and stirring for 20-60 min; then adding epoxy resin and silane coupling agent, and continuing stirring for 20-60 min; and finally, heating to 75-90 ℃, carrying out reflux reaction for 1-3h, cooling to room temperature, and removing the solvent to obtain the product.
In a preferred embodiment, the weight ratio of the epoxy resin to the silane coupling agent is 1: (0.01-0.5).
In a preferred embodiment, the silane coupling agent, without particular limitation, may be mentioned KH550, KH560, KH570, KH792, DL602 and the like.
In a preferred embodiment, the solvent is an alcoholic organic solvent; isopropyl alcohol is preferred.
In the invention, the addition of the organic silicon resin causes the adhesive force of the adhesive to the bonded material to be reduced. The inventor believes that the epoxy resin has excellent bonding strength and bonding toughness, can generate copolymerization reaction with the silicone resin besides being uniformly blended, prolongs the chain segment length of a polymerization network, forms a two-phase crosslinking interpenetrating network structure, and reduces the curing temperature and the curing time of the silicone resin. In addition, the inventor also unexpectedly finds that the adhesive prepared from the epoxy resin modified organic silicon resin has more obvious reinforcing effect in a high-temperature section, can effectively relieve the problem of high-temperature fragile bonding of the organic silicon resin, and has certain bonding flexibility. However, the inventors found in the course of experiments that the amount of epoxy resin used cannot exceed 20% of the amount of organic resin, otherwise the strength of the adhesive decreases. The reason for this may be that the excess epoxy resin destroys the integrity of the silicone resin polymeric network structure itself, resulting in a decrease in the cohesion of the modified silicone resin; meanwhile, excessive epoxy resin and organic silicon resin are blended and copolymerized to generate a more complex polymerization network, so that the cohesive strength and the high-temperature resistance can be improved to a certain extent, and the problem of high-temperature fragility of the adhesive is more obvious. The inventor also unexpectedly finds that the epoxy resin modified organic silicon resin can improve the high-temperature stability of the adhesive, and particularly when the epoxy value of the used epoxy resin is 0.2-0.5, silanol groups in the organic silicon resin can react with hydroxyl, hydroxymethyl, phenolic hydroxyl and the like in the epoxy resin to form the epoxy modified organic silicon resin, so that the epoxy modified organic silicon resin can effectively improve the thermal stability of the adhesive and avoid the problem of peeling strength reduction caused by high-temperature softening of the adhesive.
Tackifying resins
Tackifying resins are small molecule compounds that increase the tack, especially surface tack, of rubber materials. Typically, these small molecule species have a relative molecular mass of between about a few hundred and ten thousand, and have relatively high glass transition temperatures. According to their source and synthetic route, they can be mainly divided into two categories of natural products and their derivatives and synthetic resins. Tackifying resins are mainly used for modifying polymers, and are widely used in adhesives, coatings, inks, and as rubber compounds, asphalt modifiers, and polyolefin modifiers.
In the invention, the tackifying resin is a combination of terpene resin and rosin ester, and the weight ratio is 1: (0.8-2).
The inventor believes that the tackifying resin is mainly used for improving the wettability, the cohesion, the peeling strength and the shearing degree of the adhesive, enhancing the initial cohesion and the long-term bonding strength, reducing the melt viscosity of the adhesive and improving the wettability of the bonded material, thereby effectively improving the operating performance of the adhesive. In the system, single terpene resin is used as tackifying resin, and although the prepared adhesive has good elasticity, the compatibility with other raw materials is poor, so that the comprehensive performances of the adhesive, such as peel strength and the like, are reduced. The inventor unexpectedly finds that the compatibility problem among systems can be improved and the comprehensive performance of the adhesive can be improved after the rosin ester and the terpene resin are compounded for use. The inventors considered that the possible reason is that the cyclic structure in the monocyclic linear polymer terpene resin reduces the compatibility with the styrene-based thermoplastic elastomer and the silicone resin, thereby affecting the viscoelasticity of the adhesive. For nonlinear rosin ester, particularly when the softening point is between 80 and 115 ℃, the ring structure of the polymerization product of the resin has higher viscosity, is very close to the polarity of a styrene thermoplastic elastomer in a rubber phase, shows good compatibility and excellent shear strength, can effectively improve the compatibility among systems, reduces the phase separation degree, and thus improves the overall performance of the adhesive.
In a preferred embodiment, as said rosin ester, mention may be made of rosin glycerol ester, rosin pentaerythritol ester and the like.
In the invention, the rosin ester is a long-chain alkyl acid modified rosin ester.
In a preferred embodiment, the long chain alkyl acid is a C10-C30 alkyl acid.
In a more preferred embodiment, the weight ratio of the long chain alkyl acid to the rosin ester is 1: (3-9).
In the invention, the preparation method of the long-chain alkyl acid modified rosin ester comprises the following steps: mixing the rosin ester and the long-chain alkyl acid, heating to 350 ℃ for reaction for 3-8h to obtain the rosin ester.
In the invention, after the main polymer styrene thermoplastic elastomer and the epoxy resin modified organic silicon resin are compounded for use, the organic silicon resin has large molecular weight, large crosslinking density and high melt viscosity, has larger cohesive force, and reduces the poor wettability and initial viscosity of the adhesive to an adherend; meanwhile, although the prepared adhesive has better high-temperature bonding performance, the problem of high brittleness exists, and the prepared adhesive is more remarkable particularly in a low-temperature environment. In order to improve the problems of poor wetting and initial tack of the host polymer, increase the adhesion of the adhesive, and improve handling properties, tackifiers have to be added to the polymer. However, the inventor finds in the process of research that the rosin ester is solid at normal temperature, and the rosin ester may be crystallized at low temperature to influence the performance of the adhesive, and has no improvement effect on the low-temperature resistance of the adhesive. The inventor unexpectedly found that the low temperature resistance of the adhesive can be remarkably improved by adopting the rosin ester modified by the long-chain alkyl acid. The inventors thought that the modified rosin ester could improve the interaction between styrene-isoprene block copolymers in the system, make the molecular chain arrangement more compact, lower the glass transition temperature and melting temperature of the whole system, and improve the processability. The reason is that the existence of long-chain alkyl acid hinders the crystallization of styrene segment, reduces crystallization micro-area, reduces crystallinity, disturbs the ordered arrangement between molecules, increases the free volume between molecules of polyurethane, reduces the stacking of chain, has plasticizing effect, thereby reduces the glass transition temperature of soft segment and the melting temperature of styrene segment, and improves the low temperature resistance.
In addition, the system improves the flexibility of the system due to the existence of the long-chain alkyl, and improves the wettability and initial viscosity of the adhesive to the base material, probably because the modified rosin grafted with the long-chain alkyl molecules has stronger activity and is beneficial to improving the elasticity and wettability of the adhesive, so the viscosity is gradually increased along with the increase of the amount of the modified rosin. However, the inventors found in the course of experiments that as the content of the long-chain alkyl group increases, a phase separation phenomenon easily occurs between the long-chain alkyl group and the styrenic thermoplastic elastomer, resulting in a decrease in the initial tack of the adhesive, and thus the amount of the modified rosin ester is not as large as possible.
Plasticizer
Plasticizers are additives for polymer materials, which are widely used in industrial production, and are also called plasticizers. Any substance added to a polymeric material that increases the plasticity of the polymer is called a plasticizer. The plasticizer can improve the performance of the high polymer material, reduce the production cost and improve the production benefit. The phthalate ester is an important chemical product additive, is generally applied to materials such as plastic products, concrete, mud ash, cement, gypsum, cosmetics, cleaning agents and the like as an auxiliary agent, particularly polyvinyl chloride plastic products, and is required to be added in order to increase the plasticity of the plastic and improve the strength of the plastic, and the content of the phthalate ester can sometimes reach 50 percent of the product. The plasticizer mainly has the effects of weakening the secondary valence bonds among resin molecules, increasing the mobility of the molecular bonds of the resin, reducing the crystallinity of the resin molecules, increasing the plasticity of the resin molecules, enhancing the flexibility of the resin molecules, being easy to process, being legally applicable to industrial application, and being widely existed in food packaging, cosmetics, medical devices and environmental water.
In the present invention, the plasticizer is not particularly limited, and mineral oil, liquid paraffin, naphthenic oil, phthalate, and the like can be mentioned.
In a preferred embodiment, the plasticizer is a combination of dibutyl phthalate and naphthenic oil in a weight ratio of 1: (3-7).
The inventor finds that the plasticizer system adopts dibutyl phthalate and naphthenic oil as the plasticizer, so that the wettability and the adhesiveness of the adhesive can be improved, the cost can be reduced, and the plasticizer is a low-viscosity liquid at normal temperature, so that the melt viscosity of the adhesive can be remarkably reduced, the coating is facilitated, and the adhesiveness is improved. Meanwhile, the plasticizer has good compatibility with a system, and the low-temperature resistance of the adhesive is improved.
Antioxidant agent
The antioxidant is a substance capable of delaying the chemical combination aging of high polymers. Most of them can inhibit the action of oxygen, and some can inhibit the action of heat or light, so that the service life of the product can be prolonged. Generally divided into natural antioxidants, physical antioxidants and chemical antioxidants. They can be classified into antioxidants, antiozonants and copper inhibitors according to their action, or antioxidants which are discolored and not discolored, stained and not stained, heat-resistant or flex-aging resistant, and age-resistant against cracks and the like. The rubber phase of the styrene thermoplastic elastomer contains unsaturated double bonds and is easy to be subjected to O in air2、O3And ultraviolet rays, and oxidative aging occurs.
In the present invention, the antioxidant is not particularly limited, and there may be mentioned a phenol type antioxidant, an amine type antioxidant, a heterocyclic type antioxidant and the like.
In the invention, the preparation method of the adhesive layer comprises the following steps: under the protection of inert gas, mixing tackifying resin and plasticizer, and heating while stirring until the tackifying resin and the plasticizer are fully melted; then continuously heating to the temperature of 180 ℃ and 240 ℃, adding the styrene thermoplastic elastomer, the organic silicon resin and the antioxidant, and continuously stirring for 2-5 h; stopping stirring, cooling to room temperature, coating, and curing.
The second aspect of the invention provides application of the packaging roll film with the locking structure, which is applied to the field of agricultural products.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a packaging roll film with a locking structure, wherein the packaging roll film is an integral formed by connecting a plurality of packaging sections end to end through the locking structure 3; the packaging section is fixedly connected with the locking structure 3; the locking structure is composed of a base material 31, an adhesive layer 32 and a release layer 33; the substrate 31 and the release layer 33 are bonded and connected through an adhesive layer 32; in the locking structure 3, the lengths of the substrate 31 and the release layer 33 are not less than the length of the adhesive layer 32; the package section comprises a non-adhesive area 1 and an adhesive area 2; the non-adhesive area 1 and the adhesive area 2 are fixedly connected; the adhesive area 2 of the front packaging section is connected with the non-adhesive area 1 of the rear packaging section through a locking structure 3; the substrate 31 of the locking structure is fixedly connected with the non-adhesive area 1 of the subsequent packaging section; the release layer 33 of the locking structure is fixedly connected with the adhesive area 2 of the previous packaging section; the fixed connection is heat seal welding.
The raw materials for preparing the adhesive layer at least comprise the following components in parts by weight: 100 parts of styrene thermoplastic elastomer, 20 parts of organic silicon resin, 100 parts of tackifying resin, 40 parts of plasticizer and 1 part of antioxidant.
The thermoplastic elastomer is a styrene-isoprene-styrene block copolymer, available from Dry-Virginia synthetic materials science and technology, Inc., model 1105, Guangzhou;
the organic silicon resin is bisphenol A modified polymethyl silicon resin; the bisphenol A epoxy resin is purchased from the Onson building materials Hebei Co., Ltd, and is of a brand E-44; the polymethyl silicone resin is purchased from chemical industry Co., Ltd of New four seas in Hubei, model SH-9501; the preparation method of the bisphenol A modified polymethyl silicone resin comprises the following steps: adding polymethyl silicon into isopropanol at 60 deg.C, and stirring for 40 min; then adding bisphenol A epoxy resin and a silane coupling agent KH550, and continuously stirring for 30 min; finally, heating to 80 ℃, carrying out reflux reaction for 2 hours, cooling to room temperature, and removing the solvent to obtain the product; the weight ratio of the bisphenol A epoxy resin to the polymethyl silicone resin to the silane coupling agent KH550 is 1: 18: 0.2.
the tackifying resin is a combination of terpene resin and rosin ester, and the weight ratio is 1: 1.2; the rosin ester is stearic acid modified rosin pentaerythritol ester; the weight ratio of the octadecanoic acid to the rosin pentaerythritol ester is 1: 8; the preparation method of the octadecanoic acid modified rosin pentaerythritol ester comprises the following steps: mixing rosin pentaerythritol and octadecanoic acid, heating to 300 ℃, and reacting for 6 hours to obtain the rosin intermediate.
The plasticizer is a combination of dibutyl phthalate and naphthenic oil, and the weight ratio is 1: 5.
the antioxidant is antioxidant 1010.
The preparation method of the adhesive layer comprises the following steps: under the protection of inert gas, mixing tackifying resin and plasticizer, and heating while stirring until the tackifying resin and the plasticizer are fully melted; then, continuously heating to 220 ℃, adding the styrene thermoplastic elastomer, the organic silicon resin and the antioxidant, and continuously stirring for 4 hours; stopping stirring, cooling to room temperature, coating, and curing.
Example 2
Example 2 differs from example 1 in the adhesive layer.
The raw materials for preparing the adhesive layer at least comprise the following components in parts by weight: 100 parts of styrene thermoplastic elastomer, 10 parts of organic silicon resin, 80 parts of tackifying resin, 30 parts of plasticizer and 0.5 part of antioxidant.
The thermoplastic elastomer is a styrene-isoprene-styrene block copolymer available from dry-Vietnam synthetic materials, science and technology, Inc., Guangzhou, model 1125;
the organic silicon resin is bisphenol A modified polymethyl silicon resin; the bisphenol A epoxy resin is purchased from the Onson building materials Hebei Co., Ltd, and is of a brand number E-35; the polymethyl silicone resin is purchased from chemical industry Co., Ltd of New four seas in Hubei, model SH-9503; the preparation method of the bisphenol A modified polymethyl silicone resin comprises the following steps: adding polymethyl silicon into isopropanol at 40 deg.C, and stirring for 20 min; then adding bisphenol A epoxy resin and a silane coupling agent KH570, and continuously stirring for 20 min; finally heating to 75 ℃, carrying out reflux reaction for 1h, cooling to room temperature, and removing the solvent to obtain the product; the weight ratio of the bisphenol A epoxy resin to the polymethyl silicone resin to the silane coupling agent KH550 is 1: 10: 0.01.
the tackifying resin is a combination of terpene resin and rosin ester, and the weight ratio is 1: 0.8; the rosin ester is stearic acid modified rosin pentaerythritol ester; the weight ratio of the octadecanoic acid to the rosin pentaerythritol ester is 1: 3; the preparation method of the octadecanoic acid modified rosin pentaerythritol ester comprises the following steps: mixing rosin pentaerythritol and octadecanoic acid, heating to 200 ℃, and reacting for 3 hours to obtain the rosin intermediate.
The plasticizer is a combination of dibutyl phthalate and naphthenic oil, and the weight ratio is 1: 3.
the antioxidant is antioxidant 1010.
The preparation method of the adhesive layer comprises the following steps: under the protection of inert gas, mixing tackifying resin and plasticizer, and heating while stirring until the tackifying resin and the plasticizer are fully melted; then continuously heating to 180 ℃, adding the styrene thermoplastic elastomer, the organic silicon resin and the antioxidant, and continuously stirring for 2 hours; stopping stirring, cooling to room temperature, coating, and curing.
Example 3
Example 3 differs from example 1 in the adhesive layer.
The raw materials for preparing the adhesive layer at least comprise the following components in parts by weight: 100 parts of styrene thermoplastic elastomer, 50 parts of organic silicon resin, 120 parts of tackifying resin, 50 parts of plasticizer and 5 parts of antioxidant.
The thermoplastic elastomer is a styrene-isoprene-styrene block copolymer, available from Dry-Virginia synthetic materials science and technology, Inc., Guangzhou, model 1188;
the organic silicon resin is bisphenol A modified polymethyl silicon resin; the bisphenol A epoxy resin is purchased from the Onson building materials Hebei Co., Ltd, and is of a brand number E-31; the polymethyl silicone resin is purchased from chemical industry Co., Ltd of New four seas in Hubei, model SH-9502; the preparation method of the bisphenol A modified polymethyl silicone resin comprises the following steps: adding polymethyl silicon into isopropanol at 70 deg.C, and stirring for 60 min; then adding bisphenol A epoxy resin and a silane coupling agent KH792, and continuing stirring for 60 min; finally heating to 90 ℃, carrying out reflux reaction for 3 hours, cooling to room temperature, and removing the solvent to obtain the product; the weight ratio of the bisphenol A epoxy resin to the polymethyl silicone resin to the silane coupling agent KH550 is 1: 20: 0.5.
the tackifying resin is a combination of terpene resin and rosin ester, and the weight ratio is 1: 2; the rosin ester is stearic acid modified rosin pentaerythritol ester; the weight ratio of the octadecanoic acid to the rosin pentaerythritol ester is 1: 9; the preparation method of the octadecanoic acid modified rosin pentaerythritol ester comprises the following steps: mixing rosin pentaerythritol and octadecanoic acid, heating to 350 ℃, and reacting for 8 hours to obtain the rosin pentaerythritol.
The plasticizer is a combination of dibutyl phthalate and naphthenic oil, and the weight ratio is 1: 7.
the antioxidant is antioxidant 1010.
The preparation method of the adhesive layer comprises the following steps: under the protection of inert gas, mixing tackifying resin and plasticizer, and heating while stirring until the tackifying resin and the plasticizer are fully melted; then continuously heating to 240 ℃, adding the styrene thermoplastic elastomer, the organic silicon resin and the antioxidant, and continuously stirring for 5 hours; stopping stirring, cooling to room temperature, coating, and curing.
Example 4
Example 4 differs from example 1 in that the styrene-isoprene-styrene block copolymer has a styrene to isoprene block ratio of 29/81, available from Dry-also-recycled synthetic materials science, Inc., Guangzhou, model 1209.
Example 5
Example 5 differs from example 1 in that the silicone resin is a polymethylsilicone resin, purchased from new four seas chemical company, ltd, Hubei, model SH-9501.
Example 6
Example 6 differs from example 1 in that the bisphenol a epoxy resin has a brand number of E-55 and an epoxy value of 0.55 to 0.56.
Example 7
Example 7 differs from example 1 in that the bisphenol a epoxy resin has a brand number of E-03 and an epoxy value of 0.01 to 0.03.
Example 8
Example 8 differs from example 1 in that the tackifying resin is a terpene resin.
Example 9
Example 9 differs from example 1 in that the rosin ester is a rosin pentaerythritol ester.
Example 10
Example 10 differs from example 1 in that the rosin ester is a valeric acid modified rosin pentaerythritol ester.
Example 11
Example 11 differs from example 1 in that the rosin pentaerythritol ester is a tetradecanoic acid modified rosin pentaerythritol ester.
Example 12
Example 12 differs from example 1 in that the plasticizer is dibutyl phthalate.
Performance testing
1. Initial adhesion: the test was carried out according to the GB/T4852-2002 standard.
Mixing the colloidal solution (gum amount: 25.0 g/m)2-35.0g/m2) The coating was applied hook-wise to a PET film (effective coating area 10.0 cm. times.2.5 cm), mounted on a dry flat adhesive device, the device was inclined at an angle of 30 °, a standard 14# steel ball was rolled off the inclined surface, and the rolling distance of the respective ball was recorded on the PET film.
2. Permanent adhesion: the test was carried out according to the GB/T4851-84 standard.
Mixing the colloidal solution (amount of colloid: 2.0 g/m)2-3.0g/m2) The coating is uniformly coated on a PET film (the effective area is 7.0cm multiplied by 2.5cm), then the sample is placed on an adhesive tape automatic roller pressing machine (a pressing roller is 1KG, the speed is 300mm/min), the rolling is carried out for 3 times (the rolling is carried out for 1 time), then the sample is hung on a holding adhesion tester to be hung (the sample is piled up by 1KG), and the time when the broken sample falls is recorded.
3.180 ° peel strength: the test was carried out according to the GB/T2792-81 standard. Uniformly coating glue: PET film (glue amount: 25 g/m)2-35g/m2) The steel plate sample is placed on an automatic adhesive tape pressing roller machine (a pressing roller is 1KG, the speed is 300mm/mm), the steel plate sample is rolled back and forth for 3 times (the rolling speed is 1 time), the steel plate sample is placed for 20min at 25 ℃, the steel plate sample is tested on a peel strength tester, the reading is recorded, the number of the parallel numerical values is 3, and the average value is calculated.
4. Testing temperature resistance: the test was carried out according to the GB/T2792-81 standard. Uniformly coating glue: PET film (glue amount: 25 g/m)2-35g/m2) The sample steel plate is placed on an automatic adhesive tape pressing roller machine (a pressing roller is 1KG, the speed is 300mm/mm), the sample steel plate is rolled back and forth for 3 times (the rolling time is 1 time), the sample steel plate is placed for 7 days at the temperature of 20 ℃ below zero/50 ℃ below zero, then the sample steel plate is tested on a peeling strength tester, the reading is recorded, 3 parallel numerical values are recorded, and the average value is calculated. And (4) testing standard: compared with the peel strength at normal temperature, the peel strength at high temperature/low temperature has a reduction rate within 10% (including 10%), namely, the peel strength is resistant toExcellent high/low temperature properties; the reduction rate is within 10-25% (including 25%), namely the high/low temperature resistance is good; the decrease rate exceeds 25%, i.e., the high/low temperature resistance is excellent and poor.
The results of the performance tests are shown in table 1.
TABLE 1 results of the Performance test of examples
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The packaging roll film with the locking structure is characterized in that the packaging roll film is a whole formed by connecting a plurality of packaging sections end to end through the locking structure (3); the packaging section is fixedly connected with the locking structure (3); the locking structure is composed of a base material (31), an adhesive layer (32) and a release layer (33); the base material (31) and the release layer (33) are bonded and connected through an adhesive layer (32).
2. The packaging roll film with a locking structure according to claim 2, wherein the length of the substrate (31) and the release layer (33) in the locking structure (3) is not less than the length of the adhesive layer (32).
3. The wrapping web with closure according to claim 1, wherein the wrapping section comprises a non-adhesive area (1) and an adhesive area (2); the non-adhesive area (1) and the adhesive area (2) are fixedly connected.
4. A wrapping film with closure according to claim 3, characterized in that between said adjacent wrapping sections, the adhesive area (2) of the previous wrapping section is connected with the non-adhesive area (1) of the subsequent wrapping section by the closure (3).
5. The wrapping film with closure according to claim 4, wherein the base material (31) of the closure is fixedly connected to the non-adhesive area (1) of the subsequent wrapping section; the release layer (33) of the locking structure is fixedly connected with the adhesive area (2) of the previous packaging section.
6. The packaging film with a locking structure of any one of claims 1 to 5, wherein the fixed connection is a heat seal welding.
7. The packaging roll film with the locking structure as claimed in claim 1, wherein the raw materials for preparing the adhesive layer at least comprise the following components in parts by weight: 100 parts of styrene thermoplastic elastomer, 10-50 parts of organic silicon resin, 80-120 parts of tackifying resin, 30-50 parts of plasticizer and 0.5-5 parts of antioxidant.
8. The packaging roll film with the locking structure as claimed in claim 7, wherein the silicone resin is an epoxy resin modified silicone resin.
9. The packaging roll film with locking structure as claimed in claim 7, wherein the tackifying resin is a combination of terpene resin and rosin ester in a weight ratio of 1: (0.8-2).
10. Use of a packaging film roll with a closure according to any of claims 1 to 9 in the field of packaging of agricultural products.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107142033A (en) * | 2017-05-04 | 2017-09-08 | 海安鑫福缘农业科技有限公司 | A kind of automatic packing wound membrane and preparation method thereof |
CN109694691A (en) * | 2018-12-28 | 2019-04-30 | 山东聚东新材料有限责任公司 | A kind of waterproof roll hot-fusible pressure-sensitive adhesive and preparation method |
CN111560227A (en) * | 2020-03-01 | 2020-08-21 | 江苏晶华新材料科技有限公司 | Adhesive product |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107142033A (en) * | 2017-05-04 | 2017-09-08 | 海安鑫福缘农业科技有限公司 | A kind of automatic packing wound membrane and preparation method thereof |
CN109694691A (en) * | 2018-12-28 | 2019-04-30 | 山东聚东新材料有限责任公司 | A kind of waterproof roll hot-fusible pressure-sensitive adhesive and preparation method |
CN111560227A (en) * | 2020-03-01 | 2020-08-21 | 江苏晶华新材料科技有限公司 | Adhesive product |
Non-Patent Citations (3)
Title |
---|
中国轻工总会编: "《轻工业技术装备手册 第4卷》", 31 March 1996 * |
国营长风机器厂: "《工艺手册 下册》", 31 December 1979 * |
贺曼罗编著: "《建筑胶粘剂》", 30 September 1999 * |
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