CN109897595B - Heat-peelable pressure-sensitive adhesive, method for producing the same, and adhesive tape - Google Patents
Heat-peelable pressure-sensitive adhesive, method for producing the same, and adhesive tape Download PDFInfo
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- CN109897595B CN109897595B CN201910288959.2A CN201910288959A CN109897595B CN 109897595 B CN109897595 B CN 109897595B CN 201910288959 A CN201910288959 A CN 201910288959A CN 109897595 B CN109897595 B CN 109897595B
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Abstract
A pressure-sensitive adhesive capable of being thermally stripped and a preparation method thereof, and an adhesive tape relate to the technical field of adhesives. The heat-peelable pressure-sensitive adhesive comprises the following raw materials in parts by weight: 10-30 parts of an organic polymer matrix, 10-30 parts of a semi-crystalline polymer, 20-50 parts of tackifying resin, 0.5-5 parts of a cross-linking agent and 80-180 parts of a solvent; the semi-crystalline polymer has a melting point of 50-180 ℃. The heat-peelable pressure-sensitive adhesive and the adhesive tape provided by the application can recover the peel strength before heating after cooling, and have small volume change after heating. The present application also provides an adhesive tape comprising the above heat-peelable pressure-sensitive adhesive.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a heat-peelable pressure-sensitive adhesive, a preparation method thereof and an adhesive tape.
Background
A heat-peelable pressure-sensitive adhesive is an adhesive that has tackiness and that significantly decreases in tackiness when heated to a certain temperature. Tapes made of heat-peelable pressure-sensitive adhesives are widely used in the fields of electronic component preparation, labels, and the like.
The existing heat-peelable pressure-sensitive adhesive generally realizes the heat peeling function by adding a heat foaming material (thermal expansion microspheres) into the pressure-sensitive adhesive, and the heat foaming material expands when being heated to realize the function of reducing the peeling strength, but the heat-peelable pressure-sensitive adhesive has certain defects: firstly, the peeling strength reduction caused by the thermal expansion of the thermal foaming material is irreversible, namely, the thermal foaming material after thermal expansion can not be recovered to the form before foaming after cooling, so that the peeling strength of the adhesive tape is difficult to return to the high peeling strength state before heating; secondly, the thermal foaming material needs to occupy a larger space when expanding, when the thermal foaming material cannot obtain a space with sufficient expansion, the peeling strength of the adhesive tape is not enough, so that the adhesive is easy to remain on the adherend when peeling, when the thermal foaming material is fully expanded, the space occupied by the expanded adhesive tape exceeds the space reserved for the adhesive tape to cause deformation of the adherend, and the development trend that the volume of the electronic element is smaller and smaller at present is difficult to meet.
Disclosure of Invention
The invention aims to provide a heat-peelable pressure-sensitive adhesive and a preparation method thereof, and an adhesive tape, so as to solve the problems that the existing heat-peelable pressure-sensitive adhesive occupies a large space when being expanded by heat and the peel strength is difficult to recover after cooling.
The embodiment of the application is realized as follows:
in a first aspect, embodiments of the present application provide a heat-peelable pressure-sensitive adhesive, which includes the following raw materials in parts by weight:
wherein the melting point of the semi-crystalline polymer is 50-180 ℃.
The heat-peelable pressure-sensitive adhesive provided by the embodiment of the application comprises an organic polymer matrix, a semi-crystalline polymer with a melting point of 50-180 ℃, tackifying resin, a cross-linking agent and a solvent in a specific ratio; wherein the organic polymer matrix as a continuous phase is capable of cooperating with the semi-crystalline polymer to provide strong adhesive properties; the semi-crystalline polymer with the melting point of 50-180 ℃ can be used as a disperse phase to reduce the peeling strength when being heated to the melting point and improve the peeling strength when being cooled, and the tackifying resin, the cross-linking agent and the solvent can be used as auxiliary agents to enable the organic polymer matrix and the semi-crystalline polymer to be fully and uniformly mixed and subjected to cross-linking reaction to form the pressure-sensitive adhesive with high peeling strength and the peeling strength capable of changing along with temperature change.
The inventors have found in the course of carrying out the present application that, at normal temperature, in a pressure-sensitive adhesive layer formed of the heat-peelable pressure-sensitive adhesive provided by the present application, a semi-crystalline polymer is dispersed as a dispersed phase in an organic polymer matrix as a continuous phase to provide strong adhesive properties, and when the temperature is raised above the melting point of the semi-crystalline polymer by heating using a heat source, the semi-crystalline polymer melts to become a liquid state and is compatible with the organic polymer matrix to form a single phase, so that the adhesive properties of the entire single phase are significantly reduced as compared with a two-phase system composed of the dispersed phase and the continuous phase, at which time the semi-crystalline polymer functions like a softener, and a user can easily separate two adherends to which the pressure-sensitive adhesive layer is adhered without leaving a residual adhesive on; after the heat source is removed and the temperature is reduced to be lower than the melting point of the semi-crystalline polymer, the semi-crystalline polymer starts to recrystallize, the single-phase pressure sensitive adhesive layer is restored to two phases, and particles formed by crystallization of the semi-crystalline polymer are continuously dispersed in the organic polymer matrix serving as a continuous phase, so that the adhesive property of the pressure sensitive adhesive layer is restored to the high peel strength of the original state.
The heat-peelable pressure-sensitive adhesive provided by the application can be repeatedly converted between two phases and a single phase along with the fluctuation of temperature, is convenient for a user to operate for a long time, and can avoid adhesive residue on an adherend. In addition, compared with the volume change generated by the foaming expansion of the traditional foaming material, the change of the state of the semi-crystalline polymer between a solid phase and a liquid phase is very little, and the change can better meet the requirement of reducing the occupied space of the current electronic component.
In some alternative embodiments, the organic polymer matrix comprises at least one of an acrylate polymer, silicone, natural rubber, and synthetic rubber.
In the technical scheme, the acrylate polymer, the organic silicon, the natural rubber and the synthetic rubber are selected as the continuous phase matrix to be matched with the semi-crystalline polymer as the dispersed phase, and can be effectively matched with the tackifying resin, the cross-linking agent and the solvent which are used as the auxiliary agents, so that the pressure-sensitive adhesive which has strong peel strength and can be converted between two phases along with the temperature change is obtained.
In some alternative embodiments, the semi-crystalline polymer is a supramolecular polymer having a melting point of from 60 to 150 ℃; optionally, the semi-crystalline polymer is a supramolecular polymer with a melting point of 70-90 ℃.
In the technical scheme, the supramolecular polymer with the melting point of 60-150 ℃ is selected as the semi-crystalline polymer, when a user heats the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive capable of being thermally stripped to 60-150 ℃, the semi-crystalline polymer in the pressure-sensitive adhesive layer can generate a melting phenomenon and perform two-phase conversion, so that the situation that the user heats the pressure-sensitive adhesive layer to 60-150 ℃ is ensured, the stripping strength of the pressure-sensitive adhesive layer can be effectively reduced, and the user can separate two adherends bonded by the pressure-sensitive adhesive layer conveniently; certainly, a user can also select a supramolecular polymer with the melting point of 70-90 ℃ as a semi-crystalline polymer, so that the peeling strength and the temperature reduction of the pressure-sensitive adhesive layer can be further adjusted, and the user can conveniently separate objects bonded by the pressure-sensitive adhesive layer.
In some alternative embodiments, the semi-crystalline polymer is polymerized from a fatty acid monomer or a fatty acid dimer with an imidazolidinone containing a primary amine group.
In the technical scheme, the semi-crystalline polymer obtained by polymerizing the fatty acid monomer or the fatty acid dimer and the imidazolidinone containing a primary amine group can be used as a dispersed phase to be matched with an organic polymer matrix used as a continuous phase, so that the pressure-sensitive adhesive main body capable of being converted between two phases and a single phase is prepared, and the effect of repeated conversion between the two phases and the single phase along with the fluctuation of temperature is realized.
In some optional embodiments, optionally, the tackifying resin has a softening point temperature of 110 to 130 ℃; the tackifying resin comprises at least one of petroleum resin, rosin resin and terpene resin.
In the technical scheme, the tackifying resin with the softening point temperature of 110-130 ℃ is selected, so that the peel strength of the pressure-sensitive adhesive consisting of the organic polymer matrix and the semi-crystalline polymer can be effectively improved, the peel strength increased by the tackifying resin can be reduced along with the temperature rise to the softening point of the tackifying resin, and a user can conveniently heat the tackifying resin to reduce the peel strength to separate an adherend; at least one of petroleum resin, rosin resin and terpene resin is selected as tackifying resin, and the tackifying resin can be well matched with an organic polymer matrix and a semi-crystalline polymer to prepare the pressure-sensitive adhesive with strong peel strength.
In some alternative embodiments, the crosslinking agent comprises at least one of a polyisocyanate, a fatty amine, an aromatic amine, and an amidoamine.
In the technical scheme, at least one of polyisocyanate, aliphatic amine, aromatic amine and amidoamine is selected as a cross-linking agent, so that the organic polymer matrix can be promoted to generate a cross-linking reaction to form a three-dimensional network structure, and the creep resistance, solvent resistance, moisture resistance and corrosion resistance of the pressure-sensitive adhesive are effectively improved.
In some alternative embodiments, the solvent comprises at least one of toluene, ethyl acetate, butanone.
In the technical scheme, at least one of toluene, ethyl acetate and butanone is selected as a solvent, so that the organic polymer matrix, the semi-crystalline polymer, the tackifying resin and the crosslinking agent are fully and uniformly mixed and dispersed, and the heat-peelable pressure-sensitive adhesive with excellent performance is prepared.
In a second aspect, embodiments of the present application provide a method of making the heat-peelable pressure-sensitive adhesive of the first aspect, comprising the steps of: according to parts by weight, 10-30 parts of organic polymer matrix, 10-30 parts of semi-crystalline polymer with the melting point of 50-180 ℃, 20-50 parts of tackifying resin, 0.5-5 parts of cross-linking agent and 80-180 parts of solvent are mixed and stirred uniformly.
The heat-peelable pressure-sensitive adhesive provided by the embodiment of the application is obtained by fully mixing and uniformly stirring an organic polymer matrix, a semi-crystalline polymer with a melting point of 50-180 ℃, tackifying resin, a cross-linking agent and a solvent according to a specific weight ratio.
In a third aspect, embodiments of the present application provide an adhesive tape, which includes a substrate, at least one side of the substrate has an adhesive layer formed by the heat-peelable pressure-sensitive adhesive in the first aspect, and a release layer is further provided on a side of the adhesive layer away from the substrate.
The adhesive tape provided by the embodiment of the application is obtained by respectively and sequentially covering the pressure-sensitive adhesive and the release layer which can be thermally peeled on one side or two sides of the base material, and the adhesive tape can recover the peeling strength before heating after cooling and has small volume change after heating.
In some optional embodiments, the adhesive layer has a thickness of 2 to 70 μm; optionally, the thickness of the bonding layer is 10-40 μm; and/or the thickness of the base material is 2-100 mu m; optionally, the thickness of the base material is 0.05-10 mm.
In the technical scheme, the thickness of the bonding layer formed by the heat-peelable pressure-sensitive adhesive is controlled to be 2-70 μm, so that strong peel strength can be guaranteed, the peel strength of the bonding layer is rapidly reduced during heating, the peeling of a user is facilitated, and meanwhile, the change of the thickness of the bonding layer formed by the heat-peelable pressure-sensitive adhesive is small during heating, so that the volume limitation of an electronic element can be adapted; in addition, when the film base material is selected, the thickness of the base material is 2-100 μm, and when the foaming base material is selected, the thickness of the base material is 0.05-10 mm, so that the base material can be guaranteed to have enough strength to bear the pressure-sensitive adhesive.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 shows the change of peel strength during heating and stopping of heating of the adhesive tape provided in example 1 of the present application, a commercially available ordinary pressure-sensitive adhesive tape, and a commercially available thermal expansion pressure-sensitive adhesive tape.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that "and/or" in the present application, such as "scheme a and/or scheme B" means that the three modes of scheme a alone, scheme B alone, scheme a plus scheme B may be used.
The heat-peelable pressure-sensitive adhesive of the examples of the present application, the process for producing the same, and the adhesive tape are specifically described below.
In a first aspect, embodiments of the present application provide a heat-peelable pressure-sensitive adhesive, which includes the following raw materials in parts by weight: 10-30 parts of an organic polymer matrix, 10-30 parts of a semi-crystalline polymer, 20-50 parts of tackifying resin, 0.5-5 parts of a cross-linking agent and 80-180 parts of a solvent; wherein the melting point of the semi-crystalline polymer is 50-180 ℃.
Semi-crystalline polymers in this application are polymers that can partly form a crystalline phase and partly form an amorphous phase, the molecules becoming disordered or random when heated above their melting temperature, the molecules crystallizing to form crystals when cooled; an organic polymer matrix is a macromolecular substance having a plurality of repeating monomer units covalently bound by one or more molecules or groups of molecules (groups).
In some alternative embodiments, the weight parts of the organic polymer matrix may also be 15 to 25 parts, such as but not limited to 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts.
In some alternative embodiments, the weight fraction of the semi-crystalline polymer may also be from 15 to 25 parts, such as, but not limited to, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts.
In some alternative embodiments, the part by weight of the tackifying resin may also be 30 to 40 parts, such as but not limited to 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts.
In some alternative embodiments, the weight fraction of the crosslinking agent may also be 1 to 4 parts, or 2 to 3 parts, such as but not limited to 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts.
In some alternative embodiments, the weight fraction of solvent may also be from 90 to 160, or from 100 to 150, or from 110 to 140, or from 120 to 130, such as, but not limited to, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180.
In some alternative embodiments, the organic polymer matrix comprises at least one of an acrylate polymer, silicone, natural rubber, and synthetic rubber. In some alternative embodiments, the acrylate-based polymer may be polymerized from at least one of a viscous monomer having a relatively low glass transition temperature (Tg), a cohesive monomer having a relatively high glass transition temperature, and a functional group-containing modifying monomer. The viscous monomer can be alkyl acrylate with 4-12 carbon atoms, the glass transition temperature of the viscous monomer is-20 to-70 ℃, and the viscous monomer can be selected from isooctyl acrylate (Tg ═ 70 ℃) and butyl acrylate (Tg ═ 55 ℃); the cohesive monomer may be vinyl acetate (Tg 22 ℃), acrylonitrile (Tg 97 ℃), acrylamide (Tg 165 ℃), styrene (Tg 80 ℃), methyl methacrylate (Tg 105 ℃) and methyl acrylate (Tg 8 ℃), which have a high glass transition temperature; the modified monomer can be methacrylic acid, acrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate and diamino ethyl methacrylate; in some exemplary embodiments, the silicone may be a methyl silicone oil. In some exemplary embodiments, the synthetic rubber may be styrene butadiene rubber, nitrile butadiene rubber, butyl rubber.
In some alternative embodiments, the semi-crystalline polymer is a supramolecular polymer having a melting point of 60-150 ℃; optionally, the semi-crystalline polymer is a supramolecular polymer with a melting point of 70-90 ℃. Alternatively, the semi-crystalline polymer is obtained by polymerizing a fatty acid monomer or a fatty acid dimer with imidazolidinone containing a primary amine group.
In some alternative embodiments, the softening point temperature of the tackifying resin is 110-130 ℃; optionally, the tackifying resin comprises at least one of a petroleum resin, a rosin resin, and a terpene resin. The specific tackifying resin with the softening point temperature of 110-130 ℃ is selected, so that the peel strength of the pressure-sensitive adhesive capable of being peeled off can be effectively improved, and the function of reducing the peel strength above a set temperature is realized by matching with a semi-crystalline polymer.
In some alternative embodiments, the crosslinking agent comprises at least one of a polyisocyanate, an aliphatic amine, an aromatic amine, and an amidoamine. Wherein the polyisocyanate can be selected from Bayer Germany
L75. The aliphatic amine may be selected from dodecylamine, octadecylamine, etc. The aromatic amine may be aniline, o-toluidine, or the like. The selected organic polymer matrix, semi-crystalline polymer and tackifying resin can be subjected to a crosslinking reaction by selecting a specific crosslinking agent to obtain a heat-peelable pressure-sensitive adhesive layer with a stable three-dimensional structure and mechanical strength.
In some alternative embodiments, the solvent comprises at least one of toluene, ethyl acetate, butanone. The specific solvent is selected to ensure that the organic polymer matrix, the semi-crystalline polymer, the tackifying resin and the cross-linking agent are fully and uniformly mixed and further subjected to cross-linking reaction to obtain the heat-peelable pressure-sensitive adhesive layer with excellent mechanical property.
In a first aspect, embodiments herein provide a method of making a heat-peelable pressure-sensitive adhesive, comprising the steps of: according to parts by weight, 10-30 parts of organic polymer matrix, 10-30 parts of semi-crystalline polymer with the melting point of 50-180 ℃, 20-50 parts of tackifying resin, 0.5-5 parts of cross-linking agent and 80-180 parts of solvent are mixed and stirred uniformly.
According to the preparation method of the pressure-sensitive adhesive capable of being thermally stripped, the pressure-sensitive adhesive with high stripping strength and changeable stripping strength along with temperature change can be prepared only by mixing and uniformly stirring the organic polymer matrix, the semi-crystalline polymer with the melting point of 50-180 ℃, the tackifying resin, the cross-linking agent and the solvent according to the proportion.
In a third aspect, embodiments provide an adhesive tape including a substrate, one or both sides of the substrate having an adhesive layer formed of a heat-peelable pressure-sensitive adhesive, and a release layer on a side of the adhesive layer formed of the heat-peelable pressure-sensitive adhesive away from the substrate.
The adhesive tape provided by the embodiment of the application is prepared by coating the pressure-sensitive adhesive and the release layer which can be thermally peeled on one side of the surface of the base material in sequence, or respectively coating the pressure-sensitive adhesive and the release layer which can be thermally peeled on two sides of the surface of the base material in sequence, so that the adhesive tape which is convenient to use, high in peel strength and variable in peel strength along with temperature change is provided.
In some alternative embodiments, the heat-peelable pressure sensitive adhesive layer has a thickness of 2 to 70 μm, or 5 to 60 μm, or 10 to 40 μm, or 20 to 30 μm, such as but not limited to 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm.
In some alternative embodiments, the substrate may be a film-type substrate, such as but not limited to a PET (polyethylene terephthalate) film, a PI (polyimide) film, a PP (polypropylene) film, a PE (polyethylene) film, a PVC (polyvinyl chloride) film, etc., in which case the substrate may have a thickness of 2 to 100 μm, or 5 to 90 μm, or 10 to 80 μm, or 20 to 60 μm, or 30 to 50 μm, such as but not limited to 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm; in some optional embodiments, the substrate may also be a foam substrate, such as but not limited to PE foam (polyethylene foam), EVA foam (ethylene-vinyl acetate copolymer foam), PU foam (polyurethane foam), acrylate foam, etc., where the substrate may have a thickness of 0.05 to 10mm, or 0.5 to 5mm, or 1 to 4mm, or 2 to 3mm, such as but not limited to 0.05mm, 0.1mm, 0.2mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, 6.5mm, 7mm, 7.5mm, 8mm, 8.5mm, 9mm, 9.5mm, 10 mm.
In some optional embodiments, the release layer may be a release film, and the thickness of the release film may be 25 to 100 μm, or 30 to 90 μm, or 40 to 80 μm, or 50 to 60 μm, such as but not limited to 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm; in some alternative embodiments, the release layer may be release paper, and the thickness of the release paper may be 50-200 μm, or 60-200 μm, or 40-80 μm, or 50-60 μm, such as but not limited to 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm.
The characteristics and properties of the pressure-sensitive adhesives and tapes provided in the examples of the present application are described in further detail below with reference to the examples.
The semi-crystalline polymers used in the examples of the present application are all cyclic C18The dimer fatty acid is obtained by polymerizing imidazolidone (UDETA) containing primary amine group, and the specific reaction formula is as follows:
example 1
The embodiment of the application provides an adhesive tape, which is prepared by the following steps:
according to the parts by weight, 20 parts of styrene-butadiene rubber, 20 parts of semi-crystalline polymer, 30 parts of rosin resin and 3 parts of polyisocyanate (Germany Bayer)
L75) and 120 parts of toluene are uniformly mixed and stirred to prepare the heat-peelable pressure-sensitive adhesive;
the prepared heat-peelable pressure-sensitive adhesive was coated to a thickness of 30 μm on one side surface of a 50 μm-thick PET film, followed by attaching a 75 μm-thick PET release film.
Example 2
The embodiment of the application provides an adhesive tape, which is prepared by the following steps:
according to the parts by weight, 30 parts of nitrile rubber, 30 parts of semi-crystalline polymer, 45 parts of petroleum resin, 5 parts of aniline and 160 parts of ethyl acetate are mixed and stirred uniformly to prepare the heat-peelable pressure-sensitive adhesive;
the prepared heat-peelable pressure-sensitive adhesive was coated in a thickness of 40 μm on one side surface of a PP film in a thickness of 40 μm, followed by attaching a PET release film in a thickness of 80 μm.
Example 3
The embodiment of the application provides an adhesive tape, which is prepared by the following steps:
according to the weight parts, 10-30 parts of methyl silicone oil, 10-30 parts of semi-crystalline polymer, 20-50 parts of tackifying resin, 0.5-5 parts of octadecylamine and 80-180 parts of butanone are mixed and stirred uniformly to prepare the heat-peelable pressure-sensitive adhesive;
the prepared heat-peelable pressure-sensitive adhesive layer having a thickness of 20 μm was coated on both side surfaces of a 30 μm-thick PI film, and then a PE release film having a thickness of 30 μm was attached to each of the surfaces of the two heat-peelable pressure-sensitive adhesive layers.
Example 4
The embodiment of the application provides an adhesive tape, which is prepared by the following steps:
according to the weight portion, 15 portions of polyethylene glycol diacrylate, 15 portions of semi-crystalline polymer, 25 portions of terpene resin, 1 portion of amidoamine and 90 portions of toluene are mixed and stirred evenly to prepare the pressure-sensitive adhesive which can be peeled off thermally;
the prepared heat-peelable pressure-sensitive adhesive was coated to a thickness of 50 μm on one surface of an 80 μm PVC film, followed by application of a release paper having a thickness of 100 μm.
Example 5
The embodiment of the application provides an adhesive tape, which is prepared by the following steps:
in parts by weight, 20 parts of butadiene rubber, 25 parts of semi-crystalline polymer, 20 parts of rosin resin and 20 parts of terpene resin, 3 parts of polyisocyanate (German Bayer)
L75) and 150 parts of butanone are uniformly mixed and stirred to prepare the pressure-sensitive adhesive which can be thermally stripped;
the prepared heat-peelable pressure-sensitive adhesive was coated to a thickness of 60 μm on one side surface of a 5 mm-thick PE foam, followed by application of a release paper to a thickness of 150 μm.
Comparative example 1
A commercially available general pressure-sensitive adhesive tape, which is prepared by coating a pressure-sensitive adhesive having a thickness of 30 μm on one surface of a PET film having a thickness of 50 μm, followed by attaching a release film having a thickness of 75 μm; wherein the pressure-sensitive adhesive takes 40 parts of acrylate polymer as a matrix and is provided with 30 parts of rosin resin and 3 parts of polyisocyanate (Germany Bayer)
L75) is stirred and mixed in 120 parts of toluene.
Comparative example 2
A commercially available thermal foaming expansion pressure sensitive adhesive tape, which is prepared by coating a pressure sensitive adhesive having a thickness of 30 μm on one surface of a PET film having a thickness of 50 μm, followed by attaching a release film having a thickness of 75 μm; wherein, pressThe pressure-sensitive adhesive is prepared by using 40 parts of acrylate polymer as a matrix and mixing 30 parts of rosin resin, 10 parts of thermally-expanded foamed microspheres and 3 parts of polyisocyanate (Germany Bayer)
L75) is stirred and mixed in 120 parts of toluene.
As shown in fig. 1, the adhesive tape provided in example 1 of the present application, the commercially available ordinary pressure-sensitive adhesive tape provided in comparative example 1, and the commercially available thermal expansion pressure-sensitive adhesive tape provided in comparative example 2 were taken, and the adhesive tape provided in example 1, the commercially available ordinary pressure-sensitive adhesive tape, and the commercially available thermal expansion pressure-sensitive adhesive tape were heated for 5 minutes, and then the simulation operation of stopping heating was performed, and the change in peel strength was detected.
(1) A heating phase within 0-5 minutes.
As can be seen from figure 1, before heating (namely at 0 minute), the three adhesive tapes have strong adhesive performance which can reach 8-9N/cm, and the requirements of high-strength permanent adhesive performance in general application are met. When the adhesive tape and the thermal foaming expansion adhesive tape are heated to 85 ℃, the peel strength of the three adhesive tapes is reduced, wherein the peel strength of the adhesive tape and the thermal foaming expansion adhesive tape provided in the application example 1 is rapidly reduced from 8-9N/cm to about 1.2N/cm, the adhesive tape can be well separated from two adherends, and no pressure-sensitive adhesive is found to remain between the two adherends, but the adhesive tape provided in the application example 1 is also found to have no significant change in volume, and the thermal foaming expansion adhesive tape has a significant increase in volume. In the heating stage, the peel strength of the ordinary pressure-sensitive adhesive is also reduced because the pressure-sensitive adhesive is changed from a nearly solid form to a nearly liquid form at a high temperature, the fluidity is enhanced, the viscosity is also reduced, and the peel strength is reduced, but the degree of reduction is not reduced to 3.5N/cm from 8-9N/cm as compared with the case of the adhesive tape and the thermal foaming expansion adhesive tape provided in example 1 of the present application, and the two adherends are not easily separated, and if the forced air is increased to separate the two adherends, the ordinary pressure-sensitive adhesive remains on the adherends, which adversely affects the subsequent adherends.
(2) A cooling stage within 5-60 minutes.
At the 5 th minute, the heat source was removed to separate the two adherends, and at this time, the bulk temperature of the pressure-sensitive adhesive tape after the heat source was removed started to decrease, and the peel strength of each of the three kinds of tapes was gradually increased as the bulk temperature of the tape decreased. The peel strength of both the common pressure-sensitive adhesive tape and the adhesive tape provided in embodiment 1 of the present application can be increased to 6-8N/cm within 60 minutes, the requirement for the adhesive property after the tape is reworked is met, and the adhesive property can be restored to the initial state, i.e., 8-9N/cm, within 3 days. However, in the 5-60 minute peeling strength recovery process, the increasing speed of the peeling strength of the adhesive tape provided in the embodiment 1 of the present application at the initial stage is much lower than that of the common adhesive tape, which leaves enough time for the adhesive tape provided in the embodiment 1 of the present application to work again, and the difference of the recovery rates is also caused by the difference of the mechanisms that the peeling strength of the two adhesive tapes is reduced along with the temperature reduction. The common pressure-sensitive adhesive is reduced along with the temperature of the body, the whole colloid is changed from a state close to liquid to a state close to solid, the viscosity of the body is increased, the fluidity is weakened, and the peel strength is increased. Example 1 of the present application provides an adhesive tape in which the peel strength decreases with temperature, particularly to the melting temperature of the semicrystalline, and the semicrystalline is transformed from the organic polymer dissolved in the continuous phase to the organic polymer dispersed in the continuous phase, thereby increasing the peel strength. The thermal expansion pressure-sensitive adhesive tape is heated, the thermal expansion microspheres expand in a foaming manner, but in a cooling stage, the expanded microspheres do not shrink back to the original state any more, so that in the cooling stage, the peel strength of the thermal expansion pressure-sensitive adhesive tape is only slightly increased due to the fact that the body temperature is increased and the fluidity is slightly reduced, and the purpose of reusing the pressure-sensitive adhesive tape cannot be met.
To sum up, the pressure-sensitive adhesive and the sticky tape that can heat-peelable that this application embodiment provided can be after cooling the slow peeling strength before the recovery heating, and convenient to use person carries out reprocessing and uses, and the volume change is little after being heated, can adapt to the demand that the electronic component is little to the volume change.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (12)
1. A heat-peelable pressure-sensitive adhesive characterized in that it comprises the following raw materials in parts by weight:
wherein the melting point of the semi-crystalline polymer is 50-180 ℃;
the semi-crystalline polymer is composed of a cyclic C18Polymerizing fatty acid dimer with UDETA;
the structural formula of UDETA is as follows:
2. the heat-peelable pressure-sensitive adhesive according to claim 1, wherein the organic polymer matrix comprises at least one of an acrylate-based polymer, silicone, natural rubber, and synthetic rubber.
3. The heat-peelable pressure-sensitive adhesive according to claim 1, wherein the softening point temperature of the tackifier resin is 110 to 130 ℃.
4. The heat-peelable pressure-sensitive adhesive according to claim 3, wherein the tackifying resin comprises at least one of a petroleum resin, a rosin resin and a terpene resin.
5. The heat-peelable pressure-sensitive adhesive according to claim 1, wherein the crosslinking agent comprises at least one of a polyisocyanate, an aliphatic amine, an aromatic amine and an amidoamine.
6. The heat-peelable pressure-sensitive adhesive according to claim 1, wherein the solvent comprises at least one of toluene, ethyl acetate, and methyl ethyl ketone.
7. A method of preparing a heat-peelable pressure-sensitive adhesive, comprising the steps of: mixing and stirring 10-30 parts by weight of an organic polymer matrix, 10-30 parts by weight of a semi-crystalline polymer with a melting point of 50-180 ℃, 20-50 parts by weight of tackifying resin, 0.5-5 parts by weight of a cross-linking agent and 80-180 parts by weight of a solvent uniformly;
the semi-crystalline polymer is composed of a cyclic C18Polymerizing fatty acid dimer with UDETA;
the structural formula of UDETA is as follows:
8. an adhesive tape comprising a substrate having on at least one side thereof an adhesive layer formed of the heat-peelable pressure-sensitive adhesive according to any one of claims 1 to 6, and further having a release layer on a side of the adhesive layer remote from the substrate.
9. The adhesive tape according to claim 8, wherein the thickness of the adhesive layer is 2 to 70 μm.
10. The adhesive tape according to claim 9, wherein the thickness of the adhesive layer is 10 to 40 μm.
11. The adhesive tape according to claim 9 or 10, wherein the thickness of the base material is 2 to 100 μm.
12. The adhesive tape according to claim 9 or 10, wherein the substrate has a thickness of 0.05 to 10 mm.
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| FR2905698B1 (en) * | 2006-09-08 | 2012-08-31 | Arkema France | SEMI-CRYSTALLINE SUPRAMOLECULAR POLYMERS |
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