CN114561173B - Water-based pressure-sensitive adhesive for small-caliber labeling and preparation method thereof - Google Patents
Water-based pressure-sensitive adhesive for small-caliber labeling and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based pressure-sensitive adhesive for small-caliber labeling and a preparation method thereof, wherein the water-based pressure-sensitive adhesive consists of polymer particles with a hard core-soft shell structure, the hard core comprises an inorganic precursor and first polyacrylate formed on the surface of the inorganic precursor, and the first polyacrylate is formed by polymerizing acrylate hard monomers; the soft shell is formed on the surface of the hard core, the soft shell is composed of second polyacrylate, and the second polyacrylate is formed by polymerizing acrylate soft monomers. The aqueous pressure-sensitive adhesive has the advantages of high initial viscosity, long lasting time, high peel strength, no degumming and no residual adhesive at high temperature, obvious economic benefit, simple preparation process and easy realization of industrial process.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a water-based pressure-sensitive adhesive for small-caliber labeling and a preparation method of the water-based pressure-sensitive adhesive.
Background
Pressure sensitive adhesives (pressure sensitive adhesives, PSAs) are viscoelastic materials that adhere to an adherend under external pressure, wherein aqueous pressure sensitive adhesives have the characteristics of easy adhesion, easy removal, and no marking. Pressure-sensitive adhesives can be classified into acrylic esters, polyurethanes, rubbers, silicones, thermoplastic elastomers, and the like, depending on the type of matrix resin used. The acrylic pressure-sensitive adhesive is the pressure-sensitive adhesive which is most widely used at present, and has excellent pressure-sensitive property, adhesiveness, light resistance, aging resistance, oxidation resistance and the like and stable performance compared with the traditional rubber pressure-sensitive adhesive, so that the adhesive tape product is widely used in industries such as sealing tapes, labels, protective adhesive tapes, decorative plates and the like.
Acrylic pressure-sensitive adhesives are mainly divided into four categories according to the differences of the composition, the polymerization mode and the curing mode: solvent-based, emulsion-based, hot melt-based, and radiation-curable. The emulsion type acrylic ester pressure-sensitive adhesive has the advantages of no toxicity, no pollution, low price, safe production, short production time, wide viscosity change range, large polymer molecular weight, high solid content, long application period and the like, so that the emulsion type acrylic ester pressure-sensitive adhesive has more researches and is widely applied:
for example, chinese patent application publication No. CN112391134a discloses an acrylate pressure-sensitive adhesive and a preparation process thereof, which adopts the compounding of multiple monomers, introduces long-chain alkyl acrylate and fluorine-containing monomers, and carries out structural modification on a prepolymer by a step-by-step graft polymerization method, thus preparing the acrylate pressure-sensitive adhesive meeting the use requirements. However, the method uses an organic solvent as a reaction system and uses fluorine-containing acrylic ester, so that the environment is polluted, and the preparation method is complex, the reaction temperature is high, the production cost is increased undoubtedly, and the economic benefit is insufficient.
The Chinese patent application with publication number of CN111607340A discloses a water-based pressure-sensitive adhesive and a preparation method thereof, wherein ammonia water is added for treatment after emulsion is synthesized, so that a polymer can have more hydrogen bonds, and meanwhile, the pH of a reaction system is controlled, so that the peel strength of the finally prepared water-based pressure-sensitive adhesive is improved. But the pH control in the actual ammonia water treatment process is more complicated and the holding time is short.
In addition, chinese patent application publication No. CN107446530A discloses a water-based acrylate powder pressure-sensitive adhesive and a preparation method thereof, wherein the pre-emulsion composed of hard monomers and soft monomers is divided into two parts, an initiator is added into a first part for reflux reaction, and then another part of pre-emulsion is added dropwise for simultaneous initiation, so that the pressure-sensitive adhesive is obtained; hydrophobic SiO is then added to the pressure sensitive adhesive 2 Obtaining SiO as a product 2 Coated acrylate pressure sensitive adhesive microspheres. The method has the advantages of low cost, good adhesion performance and good water resistance. However, this scheme requires the adjustment of SiO throughout the reaction 2 The hydrophobic property of the polymer can regulate and control the static effective surface tension and the dynamic characteristic of the microsphere to obtain the acrylate powder pressure-sensitive adhesive which is not infiltrated with a common substrate, has poor wettability to the common substrate, complex operation of the reaction process, is mostly used for sealing precise equipment, has limited application in daily life and has insufficient economic benefit.
The Chinese patent application with publication number of CN111471145A discloses an emulsion type epoxy modified acrylic acid ester pressure-sensitive adhesive and a preparation method thereof, wherein an epoxy resin seed emulsion is prepared by a reverse rotation method, an epoxy modified acrylic acid ester pressure-sensitive adhesive emulsion is prepared by a core-shell polymerization method, and the epoxy groups are introduced to increase the corrosion resistance and high temperature resistance of the emulsion while the advantages of ageing resistance, light resistance, wide bonding surface, transparent pigment color and the like of the polyacrylate emulsion are maintained; the pressure-sensitive adhesive has higher initial adhesion, holding adhesion and peeling strength. However, in the scheme, the phase inversion is easy to fail when preparing seed emulsion, and the experimental operation is difficult and complicated.
The Chinese patent application with publication number of CN112724323A discloses a core-shell acrylate pressure-sensitive adhesive emulsion with core cross-linking, which is prepared by respectively obtaining a core pre-emulsion mainly composed of hard monomers and a shell emulsion mainly composed of soft monomers, and then reacting under the action of an initiator to prepare the core-shell acrylate pressure-sensitive adhesive, wherein the core cross-linking structure can provide excellent cohesive strength, the adhesive is not easy to be remained at high temperature, and the shell structure can provide excellent adhesive property for emulsion particles at normal temperature. However, in this scheme, only a hard monomer is used to form a core layer by nuclear crosslinking, which has insufficient supporting hardness for the pressure-sensitive adhesive, and may have a residual adhesive condition in a high-temperature environment for a long time.
Disclosure of Invention
In view of the foregoing, it is desirable to provide an aqueous pressure-sensitive adhesive for small-caliber labeling, which is composed of polymer particles having a hard core-soft shell structure, wherein the hard core provides the mechanical properties of the aqueous pressure-sensitive adhesive, and the soft shell provides the pressure-sensitive properties of the aqueous pressure-sensitive adhesive to a substrate, so that the aqueous pressure-sensitive adhesive has the advantages of high initial adhesion, long holding time, high peel strength and no residual adhesive.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a water-based pressure-sensitive adhesive for small-caliber labeling, which consists of polymer particles with a hard core-soft shell structure, wherein the hard core comprises an inorganic precursor and first polyacrylate formed on the surface of the inorganic precursor, and the first polyacrylate is formed by polymerizing acrylate hard monomers;
the soft shell is formed on the surface of the hard core, the soft shell is composed of second polyacrylate, and the second polyacrylate is formed by polymerizing acrylate soft monomers.
Further, the method comprisesThe inorganic precursor is selected from SiO 2 、TiO 2 One of ZnO.
Further, the acrylate hard monomer is selected from alkyl methacrylates or alkyl acrylates having an alkyl substituent with < 4 carbon atoms.
Further, the acrylic ester soft monomer is selected from methacrylic acid long-chain alkyl ester or acrylic acid long-chain alkyl ester with 4-18 carbon atoms of long-chain alkyl substituent.
The invention further discloses a preparation method of the water-based pressure-sensitive adhesive for labeling small caliber, which comprises the following steps:
preparing miniemulsion: uniformly mixing an acrylate hard monomer, an inorganic precursor, an initiator, a cross-linking agent and a co-stabilizer to form an oil phase; uniformly mixing an emulsifying agent and deionized water to form a water phase; adding the oil phase into the water phase, and uniformly stirring to obtain a pre-emulsion; adopting a homogenizing emulsification process to the pre-emulsion to form stable miniemulsion;
preparing aqueous pressure-sensitive adhesive emulsion: and heating the miniemulsion, initiating the acrylate hard monomer to polymerize to form seed particles, then dropwise adding the acrylate soft monomer into the seed particles, and after the initiation of polymerization is finished, preparing the water-based pressure-sensitive adhesive composed of polymer particles with a hard core-soft shell structure.
According to a further scheme, the preparation method comprises the following raw materials, by weight, 15-25 parts of acrylic ester soft monomers, 10-15 parts of acrylic ester hard monomers, 2-4 parts of inorganic precursors, 1 part of initiators, 2 parts of cross-linking agents, 2-3 parts of auxiliary stabilizers, 1-3 parts of emulsifying agents and 60-65 parts of deionized water.
Further, the acrylate hard monomer is selected from alkyl methacrylates or alkyl acrylates having less than 4 carbon atoms in the alkyl substituent.
Further, the acrylic ester soft monomer is selected from methacrylic acid long-chain alkyl ester or acrylic acid long-chain alkyl ester with 4-18 carbon atoms of long-chain alkyl substituent.
Further, the inorganic precursor is selected from SiO 2 、TiO 2 One of ZnO.
Further aspects, the initiator is selected from oil-soluble initiators;
the crosslinking agent is selected from oil-soluble compounds having more than two unsaturated bonds;
the auxiliary stabilizer is selected from long-chain aliphatic hydrocarbon with strong hydrophobicity and 15-18 alkyl substituent carbon atoms;
the emulsifier is selected from polyoxyethylene fatty alcohol ether or alkyl glycoside compound with HLB between 9-18.
Compared with the prior art, the invention has the following beneficial effects:
the water-based pressure-sensitive adhesive consists of polymer particles with a hard core-soft shell structure, wherein the hard core consists of an inorganic precursor and first polyacrylate polymerized by acrylate hard monomers on the surface of the inorganic precursor, the soft shell consists of second polyacrylate polymerized by acrylate soft monomers on the surface of the hard core, and the polymer particles with the hard core-soft shell structure have stable structure, wherein a core layer provides the mechanical property of the pressure-sensitive adhesive, and a soft shell layer provides the pressure-sensitive property of the pressure-sensitive adhesive to a substrate, so that the water-based pressure-sensitive adhesive can be well applied to small-caliber labeling.
The aqueous pressure-sensitive adhesive has the characteristics of high initial adhesion, long holding time, high peel strength and no residual adhesive.
The preparation of the aqueous pressure-sensitive adhesive adopts a seed miniemulsion polymerization method, belongs to a one-pot preparation process, has the advantages of easy operation, safety and environmental protection, adjustable core layer and shell layer polymer components, mild reaction conditions and easy control, and is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the structure of polymer particles of the aqueous pressure sensitive adhesive core-shell structure of the present invention;
FIG. 2 is a schematic diagram of the synthetic flow of the aqueous pressure sensitive adhesive of the present invention;
FIG. 3 is a graph showing the particle diameter distribution of polymer particles in the aqueous pressure-sensitive adhesive emulsion prepared in example 1.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and is provided merely to illustrate the invention and is not to be construed as limiting the invention.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In a first aspect, the present invention provides an aqueous pressure-sensitive adhesive for small-caliber labeling, which is composed of polymer particles having a hard core-soft shell structure, the structure of which is shown in fig. 1.
The hard core consists of two parts, namely an inorganic precursor and first polyacrylate formed on the surface of the inorganic precursor. The inorganic precursor is nano oxide particles with the particle size of 40-60nm, which is used for providing a template for polymerization of acrylic hard monomers to form a hard core layer structure on the surface, improving the cohesion of polymer particles, and the conventional nano oxide particles in the field can be used in the invention, and in some specific embodiments of the invention, the nano oxide particles are preferably selected from SiO (silicon dioxide) in view of the cost and availability of raw materials 2 、TiO 2 One of ZnO. Further, the first polyacrylate is formed by polymerizing an acrylate hard monomer on the surface of an inorganic precursor, it is understood that the acrylate hard monomer is defined conventionally in the art, preferably, the acrylate hard monomer is selected from alkyl methacrylate or alkyl acrylate with higher glass transition temperature and the alkyl carbon atoms in the acrylate hard monomer is less than 4, and this is mainly because the shorter the alkyl substituent is, the better the mechanical property is, and the better the core layer structure can be formed by polymerizing on the surface of the nano inorganic, so that the polymer cohesive force in the pressure-sensitive adhesive is better improved, the high temperature property is further improved, and the pressure-sensitive adhesive is less prone to degluing and adhesive residue at high temperature; examples which may be mentioned in particular include but are not limited toIs limited to one of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and vinyl acetate. In addition, the molecular weight of the first polyacrylate can be adjusted according to practical situations, and in some embodiments of the invention, the molecular weight is about 5-10 ten thousand.
Further, the soft shell is formed on the surface of the hard core, and is formed by polymerizing an acrylate soft monomer on the surface of the hard core, wherein the acrylate soft monomer is also defined as conventional in the art, preferably, the acrylate soft monomer is selected from methacrylic acid long chain alkyl ester or acrylic acid long chain alkyl ester with lower glass transition temperature, and specific examples include but are not limited to butyl methacrylate, isooctyl acrylate and 2-ethylhexyl acrylate. Similarly to the first polyacrylate, the molecular weight of the second polyacrylate may be adjusted according to the actual situation, and in some embodiments of the present invention, the molecular weight is about 5 to 15 ten thousand.
The water-based pressure-sensitive adhesive has a hard core-soft shell structure, so that the particle structure is stable, the core layer provides the mechanical property of the pressure-sensitive adhesive, and the soft shell layer provides the pressure-sensitive property of the pressure-sensitive adhesive to a substrate, so that various substrates can be wetted. The aqueous pressure-sensitive adhesive has the characteristics of high initial adhesion, long holding time, high peel strength and no residual adhesive.
The second aspect of the present invention provides a method for preparing an aqueous pressure-sensitive adhesive for labeling small caliber, wherein the flow is shown in fig. 2, and the main steps are as follows:
forming an oil phase
Specifically, acrylate hard monomer, inorganic precursor, initiator, cross-linking agent and auxiliary stabilizer are mixed uniformly to form oil phase.
Forming an aqueous phase
Specifically, the emulsifier and deionized water are uniformly mixed to form a water phase.
Forming a miniemulsion
Specifically, adding oil into an aqueous phase, and uniformly stirring to obtain a pre-emulsion; and then adopting a homogenizing emulsification process to the pre-emulsion to form stable miniemulsion. The parameters of the homogenizing and emulsifying process are not particularly limited as long as stable miniemulsion can be achieved, and those skilled in the art can adjust the parameters according to the actual situation, and in one or more embodiments of the present invention, the parameters of the homogenizing and emulsifying process are 15000rpm to 20000rpm,3 to 10min, preferably 18000rpm,5min.
Preparation of aqueous pressure sensitive adhesive emulsion
The fine emulsion is heated to initiate polymerization of the acrylate hard monomer on the inorganic precursor to form seed particles, and then the acrylate soft monomer is dripped into the seed particles, and after the initiation polymerization is finished, the aqueous pressure-sensitive adhesive of the polymer particles with the hard core-soft shell structure can be obtained.
The preparation method adopts a seed miniemulsion one-pot method, and the polymerization reaction on the nanoparticle precursor is initiated from the inside of the emulsion microsphere, so that the polymerization reaction is complete, the utilization rate of the monomer is high, the waste of raw materials is reduced, the production cost is reduced, and meanwhile, the particle size distribution of the formed particles is centralized, so that the primary viscosity of the aqueous pressure-sensitive adhesive is better, the holding time is longer, and the adhesive is not easy to deglue. The aqueous emulsion replaces organic solvent, has no volatilization of organic matters, and is environment-friendly and pollution-free.
Further, the amounts of the raw materials involved herein are not particularly limited, and may be adjusted according to the composition of the core layer and the shell layer in the desired product, and in one or more embodiments of the present invention, the raw materials are added in amounts of 15 to 25 parts by weight of the soft acrylate monomer, 10 to 15 parts by weight of the hard acrylate monomer, 2 to 4 parts by weight of the inorganic precursor, 1 part by weight of the initiator, 2 parts by weight of the crosslinking agent, 2 to 3 parts by weight of the auxiliary stabilizer, 1 to 3 parts by weight of the emulsifier, and 60 to 65 parts by weight of deionized water, respectively.
Further, the choice of mineral precursor, acrylate soft monomer and acrylate hard monomer is the same as described in the first aspect of the present invention, and will not be described in detail here. The initiator, crosslinker, co-stabilizer, and emulsifier herein may all be conventional choices in the art. It will be appreciated that the present invention employs an oil-in-water seed emulsion polymerization process, i.e., the core-shell polymer particles of the pressure-sensitive adhesive are formed in an oil phase, so that preferably, the initiator is an oil-soluble initiator, and specific examples include, but are not limited to, one of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile; the crosslinking agent is selected from oil-soluble compounds having two or more unsaturated bonds, and specific examples that may be mentioned include, but are not limited to, divinylbenzene. Further, in some embodiments of the present invention, to further enhance the stability of the miniemulsion so that it can be stably stored for several hours to several months, the co-stabilizer is preferably a long chain aliphatic hydrocarbon having strong hydrophobicity and alkyl substituent carbon atoms of 15 to 18, and specific examples that may be mentioned include, but are not limited to, hexadecane; the emulsifier is preferably a polyoxyethylene fatty alcohol ether or alkyl glycoside compound having an HLB between 9 and 18, including but not limited to one of polyoxyethylene sorbitan monolaurate Tween20, cetyl glucoside M68, sodium dodecyl benzene sulfonate SDS.
In summary, the nano inorganic particles are used as precursors, and the water-based pressure-sensitive adhesive with a certain size can be obtained by fully polymerizing the nano inorganic particles by adjusting the adding proportion of the soft and hard acrylic monomers, and the molecular weight of the core-shell layer can be regulated. In addition, the adopted nano inorganic particles have high hardness and low price, and the core layer formed by surface polymerization has high hardness, so that the cohesion of the polymer is improved, the pressure-sensitive adhesive can stably exist at high temperature for a long time, and the pressure-sensitive adhesive is not easy to deglue and remain adhesive even at high temperature.
The reaction process is simple, the specific composition structure of the polymer particles is not required to be considered, the method can be widely applied to daily small-caliber labeling, and obvious economic benefits are achieved.
The present invention will be illustrated by the following examples, which are given for illustrative purposes only and are not intended to limit the scope of the present invention in any way, and unless otherwise specified, the conditions or procedures not specifically described are conventional and the reagents and materials employed are commercially available. It is to be understood that the "parts", "parts" and the like mentioned in the following examples and comparative examples refer to parts by weight unless otherwise specified.
Example 1
Weighing the raw materials: respectively taking 22 parts of acrylic ester soft monomer butyl acrylate, 8 parts of acrylic ester hard monomer methyl acrylate and inorganic precursor SiO 2 2 parts of initiator azodiisobutyronitrile, 2 parts of cross-linking agent divinylbenzene, 3 parts of auxiliary stabilizer hexadecane, 20 parts of emulsifier polyoxyethylene sorbitan monolaurate Tween, and 60 parts of deionized water.
Preparing miniemulsion: methyl acrylate, siO 2 Mixing azobisisobutyronitrile, divinylbenzene and hexadecane uniformly to form an oil phase; uniformly mixing polyoxyethylene sorbitan monolaurate Tween20 and deionized water to form a water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; homogenizing and emulsifying the pre-emulsion (18000 rpm,5 min) to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 50 ℃ to initiate the methyl acrylate to be positioned on SiO 2 After the nano particles are polymerized to form seed particles, butyl acrylate is continuously dripped into the seed particles, and after the polymerization is initiated, the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure can be obtained.
Fig. 3 shows the particle size distribution of the aqueous pressure-sensitive adhesive emulsion of this example, which shows that the distribution is narrow, the average particle size is 80.2nm, and the pressure-sensitive adhesive has good performance.
Example 2
Weighing the raw materials: 20 parts of acrylic ester soft monomer isooctyl acrylate, 10 parts of acrylic ester hard monomer ethyl acrylate and inorganic precursor TiO 2 3 parts of initiator azo-bis-isoheptonitrile, 2 parts of cross-linking agent divinylbenzene, 2 parts of auxiliary stabilizer hexadecane, 68 parts of emulsifier cetyl glucoside M2 parts and 60 parts of deionized water.
Preparing miniemulsion: ethyl acrylate and TiO 2 Mixing azo diisoheptonitrile, divinylbenzene and hexadecane uniformly to form an oil phase; uniformly mixing cetyl glucoside M68 and deionized water to form a water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; homogenizing and emulsifying the pre-emulsion (18000 rpm,5 min) to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: the miniemulsion is heated to 65 ℃ to induce the ethyl acrylate to be in TiO 2 After the nano particles are polymerized to form seed particles, isooctyl acrylate is continuously dripped into the seed particles, and after the polymerization is initiated, the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure can be obtained.
Example 3
Weighing the raw materials: 15 parts of acrylic ester soft monomer acrylic acid-2-ethylhexyl ester, 15 parts of acrylic ester hard monomer vinyl acetate, 3 parts of inorganic precursor ZnO, 1 part of initiator benzoyl peroxide, 2 parts of cross-linking agent divinylbenzene, 2 parts of auxiliary stabilizer hexadecane, 2 parts of emulsifier sodium dodecyl benzene sulfonate SDS and 60 parts of deionized water.
Preparing miniemulsion: uniformly mixing vinyl acetate, znO, benzoyl peroxide, divinylbenzene and hexadecane to form an oil phase; uniformly mixing sodium dodecyl benzene sulfonate SDS and deionized water to form a water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; homogenizing and emulsifying the pre-emulsion (18000 rpm,5 min) to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 60 ℃, initiating the polymerization of vinyl acetate on ZnO nano particles to form seed particles, continuously dropwise adding 2-ethylhexyl acrylate into the seed particles, and obtaining the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure after the initiation of the polymerization.
Example 4
Weighing the raw materials: acrylic ester soft monomer acrylic acid-2-ethylhexyl ester 22 parts, acrylic ester hard monomer methyl methacrylate 8 parts, inorganic precursor TiO 2 2 parts of initiator azo diisoheptonitrile 1 part, cross-linking agent divinylbenzene 2 parts and auxiliary stabilizer ten parts3 parts of hexaane, 20 parts of polyoxyethylene sorbitan monolaurate Tween2 as an emulsifier and 60 parts of deionized water.
Preparing miniemulsion: methyl methacrylate, tiO 2 Uniformly mixing azodiisoheptonitrile, divinylbenzene and hexadecane to obtain an oil phase; uniformly mixing polyoxyethylene sorbitan monolaurate Tween20 and deionized water to obtain a water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; homogenizing and emulsifying the pre-emulsion (18000 rpm,5 min) to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 50 ℃ to initiate the methyl methacrylate to react with the TiO 2 And (3) after the seed particles are polymerized on the nano particles, continuously dripping 2-ethylhexyl acrylate into the nano particles, and after the polymerization is initiated, obtaining the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure.
Example 5
Weighing the raw materials: 20 parts of acrylic ester soft monomer acrylic acid isooctyl ester, 10 parts of acrylic ester hard monomer methyl acrylate, 3 parts of inorganic precursor ZnO, 1 part of initiator benzoyl peroxide, 2 parts of cross-linking agent divinylbenzene, 2 parts of auxiliary stabilizer hexadecane, 20 parts of emulsifier polyoxyethylene sorbitan monolaurate Tween, and 60 parts of deionized water.
Preparing miniemulsion: uniformly mixing methyl acrylate, znO, benzoyl peroxide, divinylbenzene and hexadecane to form an oil phase; uniformly mixing polyoxyethylene sorbitan monolaurate Tween20 and deionized water to form a water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; homogenizing and emulsifying the pre-emulsion (18000 rpm,5 min) to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 65 ℃, initiating the polymerization of methyl acrylate on ZnO nano particles to form seed particles, continuously dripping isooctyl acrylate into the seed particles, and after the initiation of the polymerization, obtaining the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure.
Comparative example (comparison with example 1)
Weighing the raw materials: 22 parts of acrylic ester soft monomer butyl acrylate, 10 parts of acrylic ester hard monomer methyl acrylate, 1 part of initiator azo-bis-isobutyronitrile, 2 parts of cross-linking agent divinylbenzene, 3 parts of auxiliary stabilizer hexadecane, 20 parts of emulsifier polyoxyethylene sorbitan monolaurate Tween2 and 60 parts of deionized water.
Preparing miniemulsion: uniformly mixing methyl acrylate, azodiisobutyronitrile, divinylbenzene and hexadecane to form an oil phase; uniformly mixing polyoxyethylene sorbitan monolaurate Tween20 and deionized water to form a water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; homogenizing and emulsifying the pre-emulsion (18000 rpm,5 min) to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: and heating the miniemulsion to 50 ℃, initiating the polymerization of methyl acrylate to form seed particles, continuously dropwise adding butyl acrylate into the seed particles, and obtaining the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure after the initiation of the polymerization is finished.
Test case
The five groups of pressure-sensitive adhesives prepared were subjected to the following performance tests, whereby the excellent characteristics of the present invention were verified. Performance test the results of the performance test are shown in table 1.
TABLE 1 pressure sensitive adhesive Performance test results
| Primary tack (ball number) | Room temperature holding adhesive (h) | 150 ℃ holding adhesive (min) | 180 ° peel strength | |
| Example 1 | 20 | 150 | 80 | 61N/2.5cm |
| Example 2 | 18 | 135 | 89 | 58N/2.5cm |
| Example 3 | 16 | 110 | 83 | 55N/2.5cm |
| Example 4 | 17 | 120 | 88 | 52N/2.5cm |
| Example 5 | 17 | 108 | 90 | 50N/2.5cm |
| Comparative example | 12 | 48 | 22 | 13.5N/2.5cm |
Note that: the test reference methods in table 1 are as follows:
initial tack test: according to the inclined plane ball method (J.Dow method) of GB/T4852-2002;
and (3) testing the holding power: the method for testing the holding viscosity of the pressure-sensitive adhesive tape is according to GB/T4851-2014;
180 ° peel force test: 180℃peel strength of the pressure-sensitive adhesive tape according to GB/T2792-2014.
As can be seen from the comparison, the aqueous pressure-sensitive adhesive has the advantages of high initial adhesion, long adhesion holding time, high peel strength, excellent adhesion holding even in a high-temperature environment, and no degumming and residual adhesive.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
1. The water-based pressure-sensitive adhesive for labeling small caliber is characterized by comprising polymer particles with a hard core-soft shell structure, wherein the hard core comprises an inorganic precursor and first polyacrylate formed on the surface of the inorganic precursor, and the first polyacrylate is formed by polymerizing acrylate hard monomers;
the soft shell is formed on the surface of the hard core, the soft shell consists of second polyacrylate, and the second polyacrylate is formed by polymerizing acrylate soft monomers;
the preparation method of the aqueous pressure-sensitive adhesive comprises the following steps:
preparing miniemulsion: uniformly mixing an acrylate hard monomer, an inorganic precursor, an initiator, a cross-linking agent and a co-stabilizer to form an oil phase; uniformly mixing an emulsifying agent and deionized water to form a water phase; adding the oil phase into the water phase, and uniformly stirring to obtain a pre-emulsion; adopting a homogenizing emulsification process to the pre-emulsion to form stable miniemulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion, initiating the acrylate hard monomer to polymerize to form seed particles, then dropwise adding the acrylate soft monomer into the seed particles, and after initiating polymerization, preparing the water-based pressure-sensitive adhesive composed of polymer particles with a hard core-soft shell structure;
the preparation method comprises the following steps of adding 15-25 parts of acrylic ester soft monomer, 10-15 parts of acrylic ester hard monomer, 2-4 parts of inorganic precursor, 1 part of initiator, 2 parts of cross-linking agent, 2-3 parts of auxiliary stabilizer, 1-3 parts of emulsifier and 60-65 parts of deionized water in parts by weight.
2. The aqueous pressure sensitive adhesive of claim 1, wherein the mineral precursor is selected from the group consisting of SiO 2 、TiO 2 One of ZnO.
3. The aqueous pressure sensitive adhesive of claim 1, wherein the acrylate hard monomer is selected from alkyl methacrylates or alkyl acrylates having < 4 carbon atoms in the alkyl substituent.
4. The aqueous pressure sensitive adhesive of claim 1, wherein the acrylate soft monomer is selected from the group consisting of long chain alkyl methacrylates or long chain alkyl acrylates having 4 to 18 carbon atoms in the long chain alkyl substituent.
5. The aqueous pressure sensitive adhesive of claim 1, wherein the initiator is selected from the group consisting of oil soluble initiators;
the crosslinking agent is selected from oil-soluble compounds having more than two unsaturated bonds;
the auxiliary stabilizer is selected from long-chain aliphatic hydrocarbon with strong hydrophobicity and 15-18 alkyl substituent carbon atoms;
the emulsifier is selected from polyoxyethylene fatty alcohol ether or alkyl glycoside compound with HLB between 9-18.
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| JP2000313867A (en) * | 1999-04-28 | 2000-11-14 | Kao Corp | Aqueous pressure-sensitive adhesive composition |
| CN1730592A (en) * | 2005-09-14 | 2006-02-08 | 北京高盟化工有限公司 | Composite adhesive for soft wrapper and its preparation method |
| CN101412783A (en) * | 2008-11-27 | 2009-04-22 | 河北工业大学 | Preparation of acrylic ester copolymer emulsion for pressure-sensitive adhesive |
| CN108816162A (en) * | 2018-05-22 | 2018-11-16 | 安徽大学 | A kind of preparation method of Yolk-Shell structural inorganic polymer hybrid microballoon |
| CN109880555A (en) * | 2019-01-31 | 2019-06-14 | 无锡海特信成高分子科技有限公司 | Pressure-sensitive polyacrylate emulsion glue, preparation method and its application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000313867A (en) * | 1999-04-28 | 2000-11-14 | Kao Corp | Aqueous pressure-sensitive adhesive composition |
| CN1730592A (en) * | 2005-09-14 | 2006-02-08 | 北京高盟化工有限公司 | Composite adhesive for soft wrapper and its preparation method |
| CN101412783A (en) * | 2008-11-27 | 2009-04-22 | 河北工业大学 | Preparation of acrylic ester copolymer emulsion for pressure-sensitive adhesive |
| CN108816162A (en) * | 2018-05-22 | 2018-11-16 | 安徽大学 | A kind of preparation method of Yolk-Shell structural inorganic polymer hybrid microballoon |
| CN109880555A (en) * | 2019-01-31 | 2019-06-14 | 无锡海特信成高分子科技有限公司 | Pressure-sensitive polyacrylate emulsion glue, preparation method and its application |
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