CN111732918A - Hot-melt pressure-sensitive adhesive for breathable film and preparation method thereof - Google Patents
Hot-melt pressure-sensitive adhesive for breathable film and preparation method thereof Download PDFInfo
- Publication number
- CN111732918A CN111732918A CN202010418590.5A CN202010418590A CN111732918A CN 111732918 A CN111732918 A CN 111732918A CN 202010418590 A CN202010418590 A CN 202010418590A CN 111732918 A CN111732918 A CN 111732918A
- Authority
- CN
- China
- Prior art keywords
- parts
- hot
- sensitive adhesive
- melt pressure
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
Abstract
The invention relates to a hot-melt pressure-sensitive adhesive for a breathable film and a preparation method thereof, wherein the hot-melt pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 20-45 parts of thermoplastic elastomer, 8-20 parts of toughened epoxy resin, 20-35 parts of tackifying resin, 0.5-5 parts of functionalized modified graphene, 0.1-1 part of antioxidant and 1-5 parts of cross-linking agent; the preparation process provided by the invention is simple in steps and good in controllability, and the prepared hot-melt pressure-sensitive adhesive is good in temperature resistance, stable in adhesion with polyethylene materials, high in initial adhesion, good in permanent adhesion and good in application prospect.
Description
Technical Field
The invention belongs to the technical field of high-molecular adhesives, and relates to a hot-melt pressure-sensitive adhesive for a breathable film and a preparation method thereof.
Background
As is well known, hot melt pressure sensitive adhesives are one type of pressure sensitive adhesives, and are mainly a new type of adhesive tape made of synthetic rubber, resin, rubber oil, etc. which are mixed and heated to a molten state and then applied to a base material such as tissue paper, cloth, or plastic film. In particular, hot melt pressure sensitive adhesives have both hot melt and pressure sensitive properties. The adhesive can be changed into liquid when heated to 130-200 ℃, can be used by spraying, rolling, blade coating and other methods, is solid when cooled to room temperature, and can generate good bonding effect by applying certain pressure. The greatest advantage of hot-melt pressure-sensitive adhesives is their low cost, but they have the disadvantage that the viscosity is influenced significantly by temperature. This also greatly limits the application of hot melt pressure sensitive adhesives.
For example, in the production process of the breathable film, the hot-melt pressure-sensitive adhesive needs to be sprayed or blade-coated, but because the hot-melt pressure-sensitive adhesive has poor heat resistance, for example, the hot-melt pressure-sensitive adhesive can only bear the temperature of 60 ℃, the double-sided adhesive tape has almost no viscosity in winter and can be layered, but the adhesive on the surface of the double-sided adhesive tape can be thermally adhered in summer, so that the popularization and application of the breathable film are greatly restricted.
Therefore, there is a need to develop a hot-melt pressure-sensitive adhesive for breathable films, which is suitable for breathable films, has outstanding heat-resistant stability, good low-temperature flexibility, high initial adhesion and good permanent adhesion.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the hot-melt pressure-sensitive adhesive for the breathable film, which has good temperature resistance, stable adhesion with polyethylene materials, high initial adhesion and good permanent adhesion.
The invention also aims to provide a preparation method of the hot melt pressure sensitive adhesive.
The purpose of the invention can be realized by the following technical scheme:
the hot-melt pressure-sensitive adhesive for the breathable film is prepared from the following raw materials in parts by weight: 20-45 parts of thermoplastic elastomer, 8-20 parts of toughened epoxy resin, 20-35 parts of tackifying resin, 0.5-5 parts of functionalized modified graphene, 0.1-1 part of antioxidant and 1-5 parts of cross-linking agent.
The preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 80-90 parts of epoxy resin, 20-40 parts of toughened elastomer, 10-30 parts of compatilizer, 0.3-1 part of coupling agent and 0.5-2 parts of processing aid;
step B): uniformly mixing the toughened elastomer, 50-60% of compatilizer, coupling agent and processing aid by weight in a hot melting way at the temperature of 120-150 ℃, preserving the heat for 15-45 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
The epoxy resin is selected from one or two of bisphenol A epoxy resin or novolac epoxy resin, the toughening elastomer is selected from one or two of styrene-butadiene-styrene block copolymer or styrene-isoprene-styrene block copolymer, the compatilizer is selected from coumarone resin, the coupling agent is selected from silane coupling agent KH560, and the processing aid is selected from any one of calcium stearate, sodium stearate or zinc stearate.
The functionalized modified graphene is obtained by modifying the surface of graphene by adopting a silane coupling agent.
The thermoplastic elastomer is formed by mixing a polyolefin thermoplastic elastomer and a fluorine-containing thermoplastic elastomer according to a mass ratio of 10: 1-5.
The polyolefin thermoplastic elastomer is one or two selected from styrene-ethylene-propylene-styrene block copolymer or ethylene-octene copolymer.
The tackifying resin is selected from one or more than two of petroleum resin, terpene phenolic resin, rosin ester or rosin.
The antioxidant is at least one of tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 2, 6-di-tert-butyl-p-cresol, tris [2, 4-di-tert-butylphenyl ] phosphite or dilauryl thiodipropionate.
The crosslinking agent is at least one selected from diethylenetriamine, tert-butylperoxyethane or hexamethylenetetramine.
A preparation method of a hot-melt pressure-sensitive adhesive for a breathable film comprises the following steps:
step 1): adding 40-50% of tackifying resin, toughening epoxy resin, functionalized modified graphene, antioxidant and cross-linking agent into a kneader according to parts by weight;
step 2): and heating the kneader to 150-180 ℃, preserving the heat for 15-60 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to the parts by weight, kneading the mixture at 150-180 ℃ for 30-60 minutes, melting and mixing the mixture uniformly, and cooling the mixture to room temperature.
Compared with the prior art, the invention has the following characteristics:
1) the thermoplastic elastomer is taken as a matrix, the introduction of the toughened epoxy resin is beneficial to improving the heat-resistant stability of a material system, and the toughened epoxy resin is toughened and modified by the toughened elastomer, so that the compatibility between the epoxy resin and the thermoplastic elastomer can be improved, and the toughened epoxy resin in the matrix can block and passivate the expansion of cracks, so that the low-temperature flexibility of the material system is improved;
2) the functionalized graphene is introduced into the thermoplastic elastomer matrix, and the surface of the graphene is modified by the silane coupling agent, so that the dispersibility of the graphene in the thermoplastic elastomer can be effectively improved, the phenomenon of graphene agglomeration can be effectively prevented, the thermal stability of the material system in a high-temperature environment can be further improved, the phenomenon of thermal adhesion can be effectively prevented, and the negative influence on the toughness of the material system due to the introduction of the graphene can be offset due to the introduction of the toughening epoxy resin;
3) the thermoplastic elastomer is an elastomer compounded by the polyolefin thermoplastic elastomer and the fluorine-containing thermoplastic elastomer, the polyolefin thermoplastic elastomer can ensure the cohesiveness of the matrix to polyethylene materials, and the fluorine-containing thermoplastic elastomer can improve the chemical resistance and the stain resistance of the matrix, thereby being beneficial to improving the service life of the colloid;
4) the preparation process has simple steps and good controllability, and the prepared hot-melt pressure-sensitive adhesive has good temperature resistance, stable adhesion with polyethylene materials, high initial adhesion, good permanent adhesion and good application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. For example, "a range of from 1 to 10" should be understood to mean every and every possible number in succession between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific points, it is to be understood that any and all data points within the range are to be considered explicitly stated.
In particular embodiments, unless specifically stated otherwise, all materials or processing techniques are conventional in the art, and are intended to be commercially available.
Example 1:
the hot-melt pressure-sensitive adhesive for the breathable film is prepared from the following raw materials in parts by weight: 40 parts of thermoplastic elastomer, 15 parts of toughened epoxy resin, 20 parts of tackifying resin, 1.6 parts of functionalized modified graphene, 0.6 part of antioxidant and 2 parts of crosslinking agent.
The preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 82 parts of epoxy resin, 32 parts of toughened elastomer, 16 parts of compatilizer, 0.5 part of coupling agent and 0.5 part of processing aid;
step B): uniformly mixing the toughened elastomer, 50% of compatilizer, coupling agent and processing aid by weight in a hot melting way at 130 ℃, preserving heat for 30 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare a premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
In the above steps, the epoxy resin is a commercially available bisphenol a epoxy resin, the toughening elastomer is a commercially available styrene-butadiene-styrene block copolymer, the compatibilizer is a commercially available coumarone resin, the coupling agent is a commercially available silane coupling agent KH560, and the processing aid is a commercially available calcium stearate.
In this embodiment, the adopted functionalized modified graphene is obtained by modifying the surface of graphene with a silane coupling agent, and the preparation method is as follows:
preparation of graphene oxide (Hummers method): 2 g of graphite and 1 g of NaNO346 ml of 98% concentrated sulfuric acid, the mixture was placed in an ice-water bath, stirred for 30 minutes to mix the mixture sufficiently, and 6 g of KMnO was weighed4Adding into the above mixed solution for several times, stirring for 2 hr, transferring into 35 deg.C warm water bath, and stirring for 30 min; slowly adding 92 ml of distilled water, controlling the temperature of the reaction liquid to be about 98 ℃ for 15 minutes, and adding a proper amount of 30% H2O2Removing excessThen adding 140 mL of distilled water to dilute the solution, filtering the solution while the solution is hot, and washing the solution by using 0.01 mol/L HCl, absolute ethyl alcohol and deionized water in sequence until no SO exists in the filtrate4 2-Until the graphite exists, preparing graphite oxide; then ultrasonically dispersing graphite oxide in water to prepare a dispersion liquid of graphene oxide; and (3) drying the dispersion liquid of the graphene oxide in a vacuum drying oven at 60 ℃ for 48 hours to obtain a graphene oxide sample, and storing for later use.
Preparing functionalized graphene oxide: weighing 100 mg of graphene oxide in 60 mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1 hour to form a uniform dispersion liquid; adding a certain amount of HCl, and adjusting the pH value of the dispersion liquid to 3-4; then, slowly adding 10 mL of 95% ethanol solution containing 0.3 g of KH-570 under stirring, continuously reacting for 24 hours at 60 ℃, centrifugally separating, washing with absolute ethanol and deionized water for multiple times to remove unreacted KH-570, and making the washing liquid to be neutral to obtain the functionalized graphene oxide.
Preparing functionalized graphene: dispersing washed and undried functionalized graphene oxide in 60 mL of absolute ethyl alcohol, performing ultrasonic dispersion for 1 hour to form uniform and stable functionalized graphene oxide dispersion liquid, then adding 1 g of hydrazine hydrate, and reducing for 24 hours at 60 ℃; and washing the obtained product with absolute ethyl alcohol and deionized water to neutrality, and drying the product in a vacuum drying oven at the temperature of 60 ℃ for 48 hours to obtain the functionalized graphene.
The thermoplastic elastomer used in this example was a mixture of a styrene-ethylene-propylene-styrene block copolymer and a fluorinated thermoplastic elastomer (for example, a commercially available fluorinated thermoplastic polyurethane) at a mass ratio of 10:4, the tackifier resin was a commercially available petroleum resin, the antioxidant was a commercially available tetrakis [ methyl-. beta. - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, and the crosslinking agent was a commercially available diethylenetriamine.
The preparation method of the hot-melt pressure-sensitive adhesive for the breathable film comprises the following steps:
step 1): adding 40% of tackifying resin, toughening epoxy resin, functionalized modified graphene, antioxidant and cross-linking agent into a kneader according to parts by weight;
step 2): and (3) heating the kneader to 165 ℃, preserving heat for 20 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to parts by weight, kneading at 175 ℃ for 40 minutes, melting and mixing uniformly, and cooling to room temperature.
Example 2:
the hot-melt pressure-sensitive adhesive for the breathable film is prepared from the following raw materials in parts by weight: 20 parts of thermoplastic elastomer, 8 parts of toughened epoxy resin, 25 parts of tackifying resin, 0.5 part of functionalized modified graphene, 0.1 part of antioxidant and 1 part of crosslinking agent.
The preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 80 parts of epoxy resin, 20 parts of toughened elastomer, 10 parts of compatilizer, 0.3 part of coupling agent and 0.6 part of processing aid;
step B): uniformly mixing the toughened elastomer, 50% of compatilizer, coupling agent and processing aid by weight in a hot melting way at 120 ℃, preserving the heat for 45 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
In the above steps, the epoxy resin is a commercially available bisphenol a epoxy resin, the toughening elastomer is a commercially available styrene-butadiene-styrene block copolymer, the compatibilizer is a commercially available coumarone resin, the coupling agent is a commercially available silane coupling agent KH560, and the processing aid is a commercially available calcium stearate.
The functionalized modified graphene used in this example is the same as in example 1.
The thermoplastic elastomer used in this example was a mixture of a styrene-ethylene-propylene-styrene block copolymer and a fluorinated thermoplastic elastomer (e.g., a commercially available T-550 fluorinated thermoplastic elastomer) at a mass ratio of 10:1, the tackifier resin was a commercially available terpene phenolic resin, the antioxidant was commercially available 2, 6-di-T-butyl-p-cresol, and the crosslinking agent was commercially available T-butylperoxyethane.
The preparation method of the hot-melt pressure-sensitive adhesive for the breathable film comprises the following steps:
step 1): adding 45% of tackifying resin, toughened epoxy resin, functionalized modified graphene, antioxidant and cross-linking agent into a kneading machine according to parts by weight;
step 2): and (3) heating the kneader to 150 ℃, preserving the heat for 60 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to the parts by weight, kneading the mixture at 150 ℃ for 60 minutes, melting and mixing the mixture uniformly, and cooling the mixture to room temperature.
Example 3:
the hot-melt pressure-sensitive adhesive for the breathable film is prepared from the following raw materials in parts by weight: 45 parts of thermoplastic elastomer, 20 parts of toughened epoxy resin, 35 parts of tackifying resin, 5 parts of functionalized modified graphene, 1 part of antioxidant and 5 parts of crosslinking agent.
The preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 90 parts of epoxy resin, 40 parts of toughened elastomer, 30 parts of compatilizer, 1 part of coupling agent and 2 parts of processing aid;
step B): uniformly mixing the toughened elastomer, 50% of compatilizer, coupling agent and processing aid by weight in a hot melting way at 120 ℃, preserving the heat for 45 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
In the above steps, the epoxy resin is a commercially available novolac epoxy resin, the toughening elastomer is a commercially available styrene-isoprene-styrene block copolymer, the compatibilizer is a commercially available coumarone resin, the coupling agent is a commercially available silane coupling agent KH560, and the processing aid is a commercially available sodium stearate.
The functionalized modified graphene used in this example is the same as in example 1.
The thermoplastic elastomer used in this example was an ethylene-octene copolymer mixed with a fluorothermoplastic elastomer (for example, a commercially available T-530 fluorothermoplastic elastomer) at a mass ratio of 10:5, while the tackifier resin was a commercially available rosin ester, the antioxidant was commercially available tris [2, 4-di-T-butylphenyl ] phosphite, and the crosslinking agent was commercially available hexamethylenetetramine.
The preparation method of the hot-melt pressure-sensitive adhesive for the breathable film comprises the following steps:
step 1): adding 48% of tackifying resin, toughened epoxy resin, functionalized modified graphene, antioxidant and crosslinking agent into a kneader according to parts by weight;
step 2): and (3) heating the kneader to 180 ℃, preserving the temperature for 15 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to the parts by weight, kneading the mixture at 180 ℃ for 30 minutes, melting and mixing the mixture uniformly, and cooling the mixture to room temperature.
Example 4:
the hot-melt pressure-sensitive adhesive for the breathable film is prepared from the following raw materials in parts by weight: 36 parts of thermoplastic elastomer, 12 parts of toughened epoxy resin, 28 parts of tackifying resin, 2.5 parts of functionalized modified graphene, 0.5 part of antioxidant and 4 parts of crosslinking agent.
The preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 85 parts of epoxy resin, 29 parts of toughened elastomer, 17 parts of compatilizer, 0.6 part of coupling agent and 1.4 parts of processing aid;
step B): uniformly mixing the toughened elastomer, 60% of compatilizer, coupling agent and processing aid by weight in a hot melting way at 145 ℃, preserving heat for 30 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
In the above step, the epoxy resin is a mixture of a commercially available bisphenol a epoxy resin and a novolac epoxy resin according to a mass ratio of 5:1, the toughening elastomer is a commercially available styrene-isoprene-styrene block copolymer, the compatilizer is a commercially available coumarone resin, the coupling agent is a commercially available silane coupling agent KH560, and the processing aid is a commercially available zinc stearate.
The functionalized modified graphene used in this example is the same as in example 1.
The thermoplastic elastomer used in this example was a mixture of a styrene-ethylene-propylene-styrene block copolymer and a fluorinated thermoplastic elastomer (for example, a commercially available T-630 fluorinated thermoplastic elastomer) at a mass ratio of 10:2, the tackifier resin was a mixture of a commercially available rosin and a petroleum resin at a mass ratio of 1:4, the antioxidant was a mixture of commercially available dilauryl thiodipropionate and tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester at a mass ratio of 1:1, and the crosslinking agent was a mixture of commercially available diethylenetriamine and hexamethylenetetramine at a mass ratio of 2: 3.
The preparation method of the hot-melt pressure-sensitive adhesive for the breathable film comprises the following steps:
step 1): adding 50% of tackifying resin, toughened epoxy resin, functionalized modified graphene, antioxidant and cross-linking agent into a kneader according to parts by weight;
step 2): and (3) heating the kneader to 160 ℃, preserving the heat for 40 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to the parts by weight, kneading for 45 minutes at 180 ℃, melting and mixing uniformly, and cooling to room temperature.
Example 5:
the hot-melt pressure-sensitive adhesive for the breathable film is prepared from the following raw materials in parts by weight: 28 parts of thermoplastic elastomer, 16 parts of toughened epoxy resin, 20 parts of tackifying resin, 1.8 parts of functionalized modified graphene, 0.4 part of antioxidant and 3.8 parts of crosslinking agent.
The preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 89 parts of epoxy resin, 34 parts of toughened elastomer, 26 parts of compatilizer, 1 part of coupling agent and 2 parts of processing aid;
step B): uniformly mixing the toughened elastomer, 55% of compatilizer, coupling agent and processing aid by weight in a hot melting way at 140 ℃, preserving heat for 25 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare a premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
In the above steps, the epoxy resin is a mixture of a commercially available bisphenol a epoxy resin and a novolac epoxy resin in a mass ratio of 1:1, the toughening elastomer is a mixture of a commercially available styrene-isoprene-styrene block copolymer and a styrene-butadiene-styrene block copolymer in a mass ratio of 3:7, the compatilizer is a commercially available coumarone resin, the coupling agent is a commercially available silane coupling agent KH560, and the processing aid is a commercially available calcium stearate.
The functionalized modified graphene used in this example is the same as in example 1.
The thermoplastic elastomer used in this example was a mixture of a styrene-ethylene-propylene-styrene block copolymer and a fluorinated thermoplastic elastomer (for example, a commercially available T-530 fluorinated thermoplastic elastomer) at a mass ratio of 10:3, and the tackifier resin was a commercially available terpene phenol resin, and the rosin and the petroleum resin were mixed at a mass ratio of 1: 1:3, the antioxidant is commercially available tris [2, 4-di-tert-butylphenyl ] phosphite, tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and 2, 6-di-tert-butyl-p-cresol in a mass ratio of 2:2:1, and the crosslinking agent is commercially available tert-butylperoxyethane.
The preparation method of the hot-melt pressure-sensitive adhesive for the breathable film comprises the following steps:
step 1): adding 46% of tackifying resin, toughening epoxy resin, functionalized modified graphene, antioxidant and crosslinking agent into a kneader according to parts by weight;
step 2): and (3) heating the kneader to 150 ℃, preserving heat for 50 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to parts by weight, kneading at 175 ℃ for 40 minutes, melting and mixing uniformly, and cooling to room temperature.
Comparative example 1:
the raw materials and the preparation method of the hot-melt pressure-sensitive adhesive in the comparative example are basically the same as those in example 1, except that the commercially available common epoxy resin is used for replacing the toughened epoxy resin, and the commercially available common graphene is used for replacing the functionalized modified graphene in the comparative example, which is otherwise the same as that in example 1.
Comparative example 2:
the raw materials and the preparation method of the hot-melt pressure-sensitive adhesive in the comparative example are basically the same as those in example 1, except that the raw material components in the comparative example do not contain the functionalized modified graphene, and the rest is the same as that in example 1.
Comparative example 3:
the raw materials and the preparation method of the hot-melt pressure-sensitive adhesive of the comparative example are basically the same as those of the example 1, except that the raw material components in the comparative example do not contain the toughening epoxy resin, and the rest is the same as that of the example 1.
Comparative example 4:
the raw materials and the preparation method of the hot-melt pressure-sensitive adhesive in the comparative example are basically the same as those in example 1, except that the raw material components in the comparative example do not contain toughened epoxy resin and functionalized modified graphene, and the rest is the same as that in example 1.
The results of the performance test of the hot melt pressure sensitive adhesives obtained in examples 1 to 5 and comparative examples 1 to 4 are shown in Table 1. Wherein, the initial adhesion peeling test is carried out by using a rolling ball plane stopping method (PSTC-6), and the 180-degree peeling strength test is carried out according to the GB2792-1998 standard.
TABLE 1 Hot-melt pressure-sensitive adhesive Performance test results
| Item | Initial viscosity/ball number # | Viscosity per hour | 180 degree peel strength (Kg/2.5 cm) | Heat resistance (70 ℃,5 h) | Low temperature flexible, glue line (-25 ℃ C.) |
| Example 1 | 20 | 57 | 2.8 | Is substantially unchanged | Without cracks |
| Example 2 | 19 | 55 | 2.6 | Is substantially unchanged | Without cracks |
| Example 3 | 22 | 52 | 2.9 | Is substantially unchanged | Without cracks |
| Example 4 | 25 | 69 | 3.1 | Is substantially unchanged | Without cracks |
| Example 5 | 23 | 63 | 3.4 | Is substantially unchanged | Without cracks |
| Comparative example 1 | 15 | 42 | 2.2 | Slight heat-sticking phenomenon | With obvious cracks |
| Comparative example 2 | 13 | 38 | 1.7 | Slight heat-sticking phenomenon | Without cracks |
| Comparative example 3 | 16 | 34 | 1.9 | Moderate heat-sticking phenomenon | With slight cracking |
| Comparative example 4 | 12 | 26 | 1.6 | Severe hot-tack and adhesive failure | Has severe cracks |
As can be seen from the analysis of Table 1, the hot melt pressure sensitive adhesive of the present invention uses the thermoplastic elastomer as the matrix, and the introduction of the toughened epoxy resin is not only beneficial to the improvement of the heat resistance stability of the material system, but also can improve the compatibility between the epoxy resin and the thermoplastic elastomer due to the adoption of the toughened elastomer for toughening and modifying the epoxy resin in the toughened epoxy resin, and can hinder and passivate the propagation of cracks due to the presence of the toughened epoxy resin in the matrix, which is beneficial to the improvement of the low temperature flexibility of the material system; in addition, due to the introduction of the functionalized graphene, the thermal stability of a material system in a high-temperature environment is further improved, and the thermal adhesion phenomenon can be effectively prevented. Meanwhile, the hot-melt pressure-sensitive adhesive has good initial adhesion and sustained adhesion.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The hot-melt pressure-sensitive adhesive for the breathable film is characterized by being prepared from the following raw materials in parts by weight: 20-45 parts of thermoplastic elastomer, 8-20 parts of toughened epoxy resin, 20-35 parts of tackifying resin, 0.5-5 parts of functionalized modified graphene, 0.1-1 part of antioxidant and 1-5 parts of cross-linking agent.
2. The hot-melt pressure-sensitive adhesive for breathable films according to claim 1, wherein the preparation method of the toughened epoxy resin comprises the following steps:
step A): preparing the following components in parts by weight: 80-90 parts of epoxy resin, 20-40 parts of toughened elastomer, 10-30 parts of compatilizer, 0.3-1 part of coupling agent and 0.5-2 parts of processing aid;
step B): uniformly mixing the toughened elastomer, 50-60% of compatilizer, coupling agent and processing aid by weight in a hot melting way at the temperature of 120-150 ℃, preserving the heat for 15-45 minutes, then adding epoxy resin while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step C): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step B).
3. The hot melt pressure sensitive adhesive for breathable films according to claim 2, wherein the epoxy resin is selected from one or two of bisphenol a epoxy resin and novolac epoxy resin, the toughening elastomer is selected from one or two of styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer, the compatibilizer is selected from coumarone resin, the coupling agent is selected from silane coupling agent KH560, and the processing aid is selected from any one of calcium stearate, sodium stearate or zinc stearate.
4. The hot-melt pressure-sensitive adhesive for breathable films according to claim 1, wherein the functionalized modified graphene is obtained by modifying the surface of graphene by using a silane coupling agent.
5. The hot-melt pressure-sensitive adhesive for the breathable film according to claim 1, wherein the thermoplastic elastomer is formed by mixing a polyolefin thermoplastic elastomer and a fluorine-containing thermoplastic elastomer according to a mass ratio of 10: 1-5.
6. The hot-melt pressure-sensitive adhesive for breathable films according to claim 5, wherein the polyolefin-based thermoplastic elastomer is one or two selected from styrene-ethylene-propylene-styrene block copolymers and ethylene-octene copolymers.
7. The hot-melt pressure-sensitive adhesive for breathable films according to claim 1, wherein the tackifying resin is one or more selected from petroleum resin, terpene phenolic resin, rosin ester and rosin.
8. The hot melt pressure sensitive adhesive for breathable films according to claim 1, wherein the antioxidant is at least one selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 2, 6-di-t-butyl-p-cresol, tris [2, 4-di-t-butylphenyl ] phosphite and dilaurylthiodipropionate.
9. The hot melt pressure sensitive adhesive for breathable films according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of diethylenetriamine, t-butylperoxyethane and hexamethylenetetramine.
10. A method for producing a hot-melt pressure-sensitive adhesive for breathable films according to any one of claims 1 to 9, comprising the steps of:
step 1): adding 40-50% of tackifying resin, toughening epoxy resin, functionalized modified graphene, antioxidant and cross-linking agent into a kneader according to parts by weight;
step 2): and heating the kneader to 150-180 ℃, preserving the heat for 15-60 minutes, adding the rest tackifying resin and the thermoplastic elastomer into the kneader according to the parts by weight, kneading the mixture at 150-180 ℃ for 30-60 minutes, melting and mixing the mixture uniformly, and cooling the mixture to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010418590.5A CN111732918A (en) | 2020-05-18 | 2020-05-18 | Hot-melt pressure-sensitive adhesive for breathable film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010418590.5A CN111732918A (en) | 2020-05-18 | 2020-05-18 | Hot-melt pressure-sensitive adhesive for breathable film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111732918A true CN111732918A (en) | 2020-10-02 |
Family
ID=72647453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010418590.5A Pending CN111732918A (en) | 2020-05-18 | 2020-05-18 | Hot-melt pressure-sensitive adhesive for breathable film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111732918A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480960A (en) * | 2021-07-30 | 2021-10-08 | 厦门祺星新材料有限公司 | Positioning adhesive for sanitary towel and preparation process thereof |
| CN113637437A (en) * | 2021-08-10 | 2021-11-12 | 佛山市本嘉新材料科技有限公司 | Epoxy resin modified hot-melt pressure-sensitive adhesive for disposable hygienic products and preparation method thereof |
| CN117363253A (en) * | 2023-10-20 | 2024-01-09 | 临沂勤正复合材料有限公司 | Preparation method of hot-melt pressure-sensitive adhesive with good stability |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382606A (en) * | 2011-09-19 | 2012-03-21 | 常州合润新材料科技有限公司 | Graphene filling isotropic high-performance conducting adhesive and preparation method thereof |
| CN102516717A (en) * | 2011-12-22 | 2012-06-27 | 云南云岭高速公路养护绿化工程有限公司 | Thermoplastic elastomer toughened epoxy resin, its preparation and its application |
| CN102925089A (en) * | 2012-11-21 | 2013-02-13 | 苏州赛伍应用技术有限公司 | Flexible heat-conducting resin, and prepreg and metal base copper clad laminate prepared from same |
| CN107338014A (en) * | 2017-06-16 | 2017-11-10 | 深圳博睿丰科技发展有限公司 | A kind of graphene composite material medical hot melt adhesive and preparation method thereof |
-
2020
- 2020-05-18 CN CN202010418590.5A patent/CN111732918A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382606A (en) * | 2011-09-19 | 2012-03-21 | 常州合润新材料科技有限公司 | Graphene filling isotropic high-performance conducting adhesive and preparation method thereof |
| CN102516717A (en) * | 2011-12-22 | 2012-06-27 | 云南云岭高速公路养护绿化工程有限公司 | Thermoplastic elastomer toughened epoxy resin, its preparation and its application |
| CN102925089A (en) * | 2012-11-21 | 2013-02-13 | 苏州赛伍应用技术有限公司 | Flexible heat-conducting resin, and prepreg and metal base copper clad laminate prepared from same |
| CN107338014A (en) * | 2017-06-16 | 2017-11-10 | 深圳博睿丰科技发展有限公司 | A kind of graphene composite material medical hot melt adhesive and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480960A (en) * | 2021-07-30 | 2021-10-08 | 厦门祺星新材料有限公司 | Positioning adhesive for sanitary towel and preparation process thereof |
| CN113637437A (en) * | 2021-08-10 | 2021-11-12 | 佛山市本嘉新材料科技有限公司 | Epoxy resin modified hot-melt pressure-sensitive adhesive for disposable hygienic products and preparation method thereof |
| CN113637437B (en) * | 2021-08-10 | 2023-03-14 | 佛山市本嘉新材料科技有限公司 | Epoxy resin modified hot-melt pressure-sensitive adhesive for disposable hygienic products and preparation method thereof |
| CN117363253A (en) * | 2023-10-20 | 2024-01-09 | 临沂勤正复合材料有限公司 | Preparation method of hot-melt pressure-sensitive adhesive with good stability |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111732918A (en) | Hot-melt pressure-sensitive adhesive for breathable film and preparation method thereof | |
| CN109054688B (en) | Heat aging non-sticking hot melt pressure-sensitive adhesive and preparation method thereof | |
| CN107057607B (en) | A kind of butyl rubber hot-fusible pressure-sensitive adhesive and preparation method thereof of cohesion enhancing | |
| CN104031596A (en) | Low-molding-temperature waterborne polyurethane adhesive and preparation method thereof | |
| CN107603537B (en) | Hot-melt pressure-sensitive adhesive and preparation method thereof | |
| CN111334103B (en) | Non-cured rubber asphalt waterproof coating capable of being sprayed at low temperature | |
| CN114479709B (en) | Polyolefin pre-laid waterproof coiled material and preparation method thereof | |
| CN110540818B (en) | Non-reactive polyolefin hot melt adhesive, preparation method and application thereof | |
| CN113249059A (en) | End sealing hot melt adhesive without surface viscosity at 40 ℃ for sanitary materials and preparation method thereof | |
| CN111995973A (en) | Low-peeling-force hot-melt pressure-sensitive adhesive special for white cotton cloth application and preparation method thereof | |
| CN111909380A (en) | Addition type liquid silicone rubber tackifier, and preparation method and application thereof | |
| CN114292622A (en) | Hot-melt pressure-sensitive adhesive for house interior decoration wall sticker and preparation method thereof | |
| CN110746704A (en) | Soft oil-resistant ultralow-temperature-resistant halogen-free flame-retardant cable material for wind energy cable and preparation method thereof | |
| CN111675973A (en) | Light-color hot-melt pressure-sensitive adhesive for glass cloth adhesive tape and preparation method thereof | |
| CN112680149A (en) | Hot melt adhesive and preparation method and application thereof | |
| CN113249068B (en) | Thermoplastic polyether-ether-ketone modified hot melt adhesive and preparation method thereof | |
| CN108865059B (en) | Ultraviolet aging non-sticking hot melt pressure-sensitive adhesive and preparation method thereof | |
| CN112745783A (en) | Weather-resistant adhesive tape and preparation method thereof | |
| CN111592844A (en) | Hot-melt pressure-sensitive adhesive for high-temperature adhesive tape and preparation method thereof | |
| CN113683986B (en) | Cross-linking reactive hot-melt pressure-sensitive adhesive and preparation method thereof | |
| CN115322708B (en) | Environment-friendly grafted moisture curing spray adhesive and preparation method thereof | |
| CN108774487A (en) | A kind of automotive wire bundle flame-retardant hot-melt adhesive and preparation method thereof | |
| CN116694261B (en) | High-heat-resistance anti-yellowing transparent adhesive film for bonding various base materials and preparation method thereof | |
| CN115595071B (en) | High-performance hot melt adhesive film for bonding ethylene propylene diene monomer rubber and preparation method thereof | |
| KR20200082720A (en) | Solvent type adhesive composition improved heat resistance, manufacturing method of the same and adhesive film including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201002 |
|
| WD01 | Invention patent application deemed withdrawn after publication |