CN114561173A - 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, 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 an acrylate hard monomer; the soft shell is formed on the surface of the hard core, and consists of second polyacrylate which is formed by polymerizing acrylate soft monomers. The water-based pressure-sensitive adhesive has the advantages of high initial adhesion, long lasting adhesion 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 (PSAs) are viscoelastic materials that can bond adherends under external pressure, and aqueous pressure sensitive adhesives have the characteristics of easy adhesion, easy peeling and no trace. Pressure-sensitive adhesives can be classified into acrylates, polyurethanes, rubbers, silicones, thermoplastic elastomers, and the like, depending on the type of the base resin used. The acrylate pressure-sensitive adhesive is the most widely applied pressure-sensitive adhesive at present, and compared with the traditional rubber pressure-sensitive adhesive, the acrylate pressure-sensitive adhesive has the advantages of excellent pressure-sensitive property, adhesion property, light resistance, aging resistance, oxidation resistance and the like and stable performance, so that the adhesive tape product is widely applied to industries such as box sealing tapes, labels, protective adhesive tapes, decorative plates and the like.
The acrylate pressure-sensitive adhesives are mainly classified into four categories according to the differences of the compositions, polymerization modes and curing modes of the acrylate pressure-sensitive adhesives: solvent type, emulsion type, hot melt type, and radiation curing type. The emulsion type acrylate 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 applicable period and the like, so that more researches are carried out, and the application is wide:
for example, chinese patent application publication No. CN112391134A discloses an acrylate pressure-sensitive adhesive and a preparation process thereof, wherein multiple monomers are used in combination, a long-chain alkyl acrylate and a fluorine-containing monomer are introduced, and a prepolymer is subjected to step-by-step graft polymerization to perform structural modification, so as to prepare the acrylate pressure-sensitive adhesive meeting the use requirements. However, the method uses an organic solvent as a reaction system and uses fluorine-containing acrylate, which causes environmental pollution, and the preparation method is complex and has high reaction temperature, which undoubtedly increases the production cost and has insufficient economic benefit.
Chinese patent application publication No. CN111607340A discloses an aqueous pressure-sensitive adhesive and a preparation method thereof, wherein the aqueous pressure-sensitive adhesive is prepared by adding ammonia water after emulsion synthesis to treat, so that the polymer can have more hydrogen bonds, and simultaneously, the pH of the reaction system is controlled, thereby improving the peel strength of the finally prepared aqueous pressure-sensitive adhesive. However, the pH control in the actual ammonia treatment process is complicated, and the duration of the sticking is short.
In addition, chinese patent application publication No. CN107446530A discloses an aqueous acrylate powder pressure-sensitive adhesive and a method for preparing the same, wherein a pre-emulsion composed of a hard monomer and a soft monomer is divided into two parts, an initiator is added into the first part for reflux reaction, and then the other part of the pre-emulsion is added dropwise and initiated at the same time to obtain the pressure-sensitive adhesive; then adding hydrophobic SiO into the pressure sensitive adhesive2To obtain SiO2And (3) coated acrylate pressure-sensitive adhesive microspheres. The method has the advantages of low cost and good adhesive property and water resistance. However, the scheme needs to adjust SiO in the whole reaction process2The hydrophobicity 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 into a common substrate, the wettability of the acrylate powder pressure-sensitive adhesive on the common substrate is poor, the operation of the reaction process is complex, the acrylate powder pressure-sensitive adhesive is mainly used for sealing precision equipment, the application in daily life is limited, and the economic benefit is insufficient.
The Chinese patent application with the publication number of CN111471145A discloses an emulsion type epoxy modified acrylate pressure-sensitive adhesive and a preparation method thereof, wherein an epoxy resin seed emulsion is prepared by a phase inversion method, and an epoxy modified acrylate pressure-sensitive adhesive emulsion is prepared by a core-shell polymerization method, so that the corrosion resistance and the high temperature resistance of the emulsion are improved by introducing an epoxy group while the advantages of aging resistance, light resistance, wide bonding surface, plain color transparency and the like of the polyacrylate emulsion are kept; and the pressure-sensitive adhesive has higher initial adhesion, permanent adhesion and peeling strength. However, phase inversion during the preparation of the seed emulsion in the scheme is easy to cause failure, and the experimental operation is difficult and tedious.
The Chinese patent application with publication number CN112724323A discloses a core-shell acrylate pressure-sensitive adhesive emulsion with crosslinked core and shell and its preparation method, respectively obtaining core pre-emulsion mainly composed of hard monomers and shell emulsion mainly composed of soft monomers, then reacting under the action of initiator to obtain the core-shell acrylate pressure-sensitive adhesive, wherein the core crosslinked structure can provide excellent cohesive strength, the residual adhesive is not easy to be left at high temperature, the shell structure at normal temperature gives excellent adhesive property to the emulsion particles, and the pressure-sensitive adhesive has excellent initial adhesion and stripping force. However, in this scheme, only the hard monomer is used for core crosslinking to form the core layer, the supporting hardness of the pressure-sensitive adhesive is insufficient, and the residual adhesive condition may exist in a high-temperature environment for a long time.
Disclosure of Invention
In view of the above, the present invention needs 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 mechanical properties of the aqueous pressure-sensitive adhesive, and the soft shell provides 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 lasting adhesion time, high peel strength and no adhesive residue.
In order to achieve the purpose, the 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 an acrylate hard monomer;
the soft shell is formed on the surface of the hard core, and is composed of a second polyacrylate which is formed by polymerizing acrylate soft monomers.
In a further aspect, the inorganic precursor is selected from SiO2、TiO2And ZnO.
In a further embodiment, the acrylate hard monomer is selected from alkyl methacrylates or alkyl acrylates with alkyl substituents having < 4 carbon atoms.
In a further embodiment, the acrylate soft monomer is selected from long chain alkyl methacrylate or long chain alkyl acrylate with 4-18 carbon atoms of the long chain alkyl substituent.
The invention further discloses a preparation method of the aqueous pressure-sensitive adhesive for small-caliber labeling, which comprises the following steps:
preparing a 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 emulsifier 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 homogeneous emulsification process to the pre-emulsion to form a stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to initiate the polymerization of the acrylate hard monomer to form seed particles, then dropwise adding the acrylate soft monomer into the miniemulsion, and after the initiation polymerization is finished, preparing the water-based pressure-sensitive adhesive consisting of the polymer particles with the hard core-soft shell structure.
According to a further scheme, the raw materials adopted in the preparation method are 15-25 parts by weight of acrylate soft monomer, 10-15 parts by weight of acrylate hard monomer, 2-4 parts by weight of inorganic precursor, 1 part by weight of initiator, 2 parts by weight of cross-linking agent, 2-3 parts by weight of co-stabilizer, 1-3 parts by weight of emulsifier and 60-65 parts by weight of deionized water.
In a further aspect, the acrylate hard monomer is selected from alkyl methacrylates or alkyl acrylates having alkyl substituents with less than 4 carbon atoms.
In a further embodiment, the acrylate soft monomer is selected from long chain alkyl methacrylate or long chain alkyl acrylate with 4-18 carbon atoms of the long chain alkyl substituent.
In a further aspect, the inorganic precursor is selected from SiO2、TiO2And ZnO.
Further, the initiator is selected from oil soluble initiators;
the cross-linking agent is selected from oil-soluble compounds with more than two unsaturated bonds;
the co-stabilizer is selected from long-chain aliphatic hydrocarbon with strong hydrophobicity and 15-18 carbon atoms of alkyl substituent;
the emulsifier is selected from polyoxyethylene fatty alcohol ether or alkyl glycoside compound with HLB of 9-18.
Compared with the prior art, the invention has the following beneficial effects:
the water-based pressure-sensitive adhesive is composed of polymer particles with a hard core-soft shell structure, wherein the hard core is composed of an inorganic precursor and first polyacrylate polymerized by an acrylate hard monomer on the surface of the inorganic precursor, the soft shell is composed of second polyacrylate polymerized by an acrylate soft monomer on the surface of the hard core, and the polymer particles with the hard core-soft shell structure are stable in structure, wherein 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 base material, so that the water-based pressure-sensitive adhesive can be well applied to small-caliber labeling.
The water-based pressure-sensitive adhesive has the characteristics of high initial adhesion, long time for sticking, high peel strength and no adhesive residue.
The preparation of the aqueous pressure-sensitive adhesive adopts a seed miniemulsion polymerization method, belongs to a one-pot preparation process, is easy to operate, safe and environment-friendly in the whole process, and is suitable for industrial production, and polymer components of a nuclear layer and a shell layer are adjustable, and the reaction conditions are mild and easy to control.
Drawings
FIG. 1 is a schematic diagram of the structure of the polymer particles of the hard core-soft shell structure of the aqueous pressure-sensitive adhesive of the present invention;
FIG. 2 is a schematic diagram of the synthetic process of the aqueous pressure-sensitive adhesive of the present invention;
FIG. 3 is a graph showing a distribution of the particle size 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 intended to be illustrative, 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.
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 structure of the polymer particles is shown in figure 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, and the function of the inorganic precursor is to provide a template for polymerization of acrylic acid hard monomers, so that the acrylic acid hard monomers are polymerized on the surface to form a hard nuclear layer structure, the cohesive force of polymer particles is improved, and the conventional nano oxide particles in the field are all nano oxide particlesIn some embodiments of the present invention, it is preferable that the nano-oxide particles are selected from SiO in consideration of the cost and availability of raw materials2、TiO2And ZnO. Further, the first polyacrylate described herein is formed by polymerizing an acrylate hard monomer on the surface of an inorganic precursor, and it is understood that the acrylate hard monomer described herein is a conventional definition in the art, and preferably, the acrylate hard monomer is selected from alkyl methacrylate or alkyl acrylate with a higher glass transition temperature, and the number of alkyl carbon atoms in the acrylate hard monomer is less than 4, mainly because the shorter the alkyl substituent is, the better the mechanical property thereof is, and a more excellent core layer structure can be formed by polymerization on the surface of the nano inorganic substance, so as to better improve the polymer cohesion in the pressure-sensitive adhesive, further improve the high temperature performance thereof, and make the pressure-sensitive adhesive less prone to degumming and adhesive residue at high temperature; examples that may be specifically mentioned include, but are not limited to, one of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, vinyl acetate. In addition, the molecular weight of the first polyacrylate can be adjusted to suit the application, and in some embodiments of the invention, the molecular weight is about 5 to 10 ten thousand.
In a further embodiment, the soft shell is formed on the surface of the hard core, and is formed by polymerizing a soft acrylate monomer on the surface of the hard core, and the soft acrylate monomer is also defined conventionally in the art, and preferably, the soft acrylate monomer is selected from long-chain alkyl methacrylate or long-chain alkyl acrylate with a low glass transition temperature, and the number of long-chain alkyl carbon atoms in the soft acrylate monomer is 4-18, and specific examples include, but are not limited to, butyl methacrylate, isooctyl acrylate, and 2-ethylhexyl acrylate. Similarly, the molecular weight of the second polyacrylate can be adjusted to suit the application, and in some embodiments of the invention, the molecular weight is about 5 to 15 million.
The water-based pressure-sensitive adhesive has a hard core-soft shell structure, 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 base material, so that various base materials can be wetted. The water-based pressure-sensitive adhesive has the characteristics of high initial adhesion, long time for sticking, high peel strength and no adhesive residue.
The invention provides a preparation method of a water-based pressure-sensitive adhesive for small-caliber labeling, the flow of which is shown in figure 2, and the preparation method mainly comprises the following steps:
forming an oil phase
Specifically, acrylate hard monomer, inorganic precursor, initiator, cross-linking agent and co-stabilizer are mixed uniformly to form oil phase.
Forming an aqueous phase
Specifically, the emulsifier and deionized water are mixed uniformly to form an aqueous phase.
Forming a miniemulsion
Specifically, adding the oil phase into the water phase, and uniformly stirring to obtain a pre-emulsion; then, the pre-emulsion is subjected to a homogeneous emulsification process to form a stable fine emulsion. The parameters of the homogenizing emulsification process are not particularly limited, as long as stable fine emulsion can be achieved, and can be adjusted by those skilled in the art according to the actual situation, and in one or more embodiments of the present invention, the parameters of the homogenizing emulsification are 15000rpm to 20000rpm, 3 to 10min, and preferably 18000rpm, 5 min.
Preparation of aqueous pressure-sensitive adhesive emulsions
Heating the miniemulsion to initiate the polymerization of the acrylate hard monomer on the inorganic precursor to form seed particles, then dropwise adding the acrylate soft monomer into the miniemulsion, and obtaining the aqueous pressure-sensitive adhesive of the polymer particles with the hard core-soft shell structure after the initiation polymerization is finished.
The preparation method adopts a seed miniemulsion one-pot method, the polymerization reaction on the nano particle precursor is initiated from the inside of the emulsion microsphere, so that the polymerization reaction is more complete, the utilization rate of monomers is high, the waste of raw materials is reduced, the production cost is reduced, the particle size distribution of formed particles is more concentrated, the initial viscosity performance of the water-based pressure-sensitive adhesive is better, the sticking time is longer, and the degumming is not easy. The aqueous emulsion replaces an organic solvent, has no volatilization of organic substances, is environment-friendly and has no pollution.
In a further embodiment of the present invention, the amount of the raw materials is not particularly limited, and may be adjusted and controlled 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 amount of the raw materials added is, by weight, 15 to 25 parts of the acrylate soft monomer, 10 to 15 parts of the acrylate hard monomer, 2 to 4 parts of the inorganic precursor, 1 part of the initiator, 2 parts of the cross-linking agent, 2 to 3 parts of the co-stabilizer, 1 to 3 parts of the emulsifier, and 60 to 65 parts of the deionized water.
Further, the selection of the inorganic precursor, the soft acrylate monomer and the hard acrylate monomer is the same as that described in the first aspect of the present invention, and will not be described in detail herein. The initiators, crosslinkers, co-stabilizers, and emulsifiers herein are all conventional choices in the art. It is understood that the oil-in-water seed emulsion polymerization method is adopted in the present invention, i.e. the core-shell polymer particles of the pressure sensitive adhesive are formed in the oil phase, so it is preferable that the initiator is selected from oil-soluble initiators, and specific examples include, but are not limited to, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile; the cross-linking 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, in order to further improve the stability of the miniemulsion, such that it can be stably stored for several hours to several months, the co-stabilizer is preferably a long-chain aliphatic hydrocarbon which is strongly hydrophobic and has 15 to 18 carbon atoms in the alkyl substituent, 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 of 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 invention takes the nano inorganic particles as the precursor, and fully polymerizes to obtain the aqueous pressure-sensitive adhesive with a certain size by adjusting the addition ratio of the soft and hard acrylic monomers, and the molecular weight of the nuclear shell layer can be adjusted and controlled. In addition, the adopted nano inorganic particles have high hardness and low price, and the core layer formed by polymerization on the surface of the nano inorganic particles has higher hardness, so that the cohesive force of the polymer is improved, the pressure-sensitive adhesive can stably exist at high temperature for a long time, and the adhesive is not easy to degum and residual adhesive even at high temperature.
The reaction process is simple, the specific composition structure of the polymer particles does not need to be considered, the method can be widely applied to daily labeling with small caliber, and has obvious economic benefit.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described. It is to be understood that "parts", and the like, referred to in the following examples and comparative examples, refer to parts by weight unless otherwise specified.
Example 1
Weighing the following raw materials: respectively taking 22 parts of acrylate soft monomer butyl acrylate, 8 parts of acrylate hard monomer methyl acrylate and inorganic precursor SiO22 parts of initiator azodiisobutyronitrile 1 part, cross-linking agent divinylbenzene 2 parts, co-stabilizer hexadecane 3 parts, emulsifier polyoxyethylene sorbitan monolaurate Tween 202 parts, and deionized water 60 parts.
Preparing a miniemulsion: mixing methyl acrylate and SiO2Uniformly mixing 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; adopting a homogenizing emulsification process (18000rpm, 5min) for the pre-emulsion to form stable fine emulsion;
preparation of aqueous pressure-sensitive adhesiveGlue emulsion: heating the miniemulsion to 50 ℃ to initiate the reaction of methyl acrylate on SiO2After the nano particles are polymerized to form seed particles, butyl acrylate is continuously dripped into the seed particles, and after the initiation polymerization is finished, the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure can be obtained.
FIG. 3 is a distribution diagram of the particle size of the aqueous pressure-sensitive adhesive emulsion in this example, which shows that the distribution is narrow, the average particle size is 80.2nm, and the performance of the pressure-sensitive adhesive is better.
Example 2
Weighing the following raw materials: 20 parts of acrylate soft monomer isooctyl acrylate, 10 parts of acrylate hard monomer ethyl acrylate and inorganic precursor TiO23 parts of initiator azodiisoheptanonitrile 1 part, cross-linking agent divinylbenzene 2 parts, co-stabilizer hexadecane 2 parts, emulsifier cetyl glucoside M682 parts and deionized water 60 parts.
Preparing a miniemulsion: mixing ethyl acrylate and TiO2Uniformly mixing azodiisoheptanonitrile, divinylbenzene and hexadecane to form an oil phase; mixing cetyl glucoside M68 and deionized water uniformly to form water phase; adding the oil phase into the water phase, and mechanically stirring uniformly to obtain a pre-emulsion; adopting a homogenizing emulsification process (18000rpm, 5min) for the pre-emulsion to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 65 ℃ to initiate the reaction of ethyl acrylate on TiO2After 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 following raw materials: 15 parts of acrylate soft monomer acrylic acid-2-ethylhexyl ester, 15 parts of acrylate 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 a 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; adopting a homogenizing emulsification process (18000rpm, 5min) for the pre-emulsion to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 60 ℃, initiating vinyl acetate to polymerize on the ZnO nanoparticles to form seed particles, continuing to dropwise add 2-ethylhexyl acrylate, and obtaining the aqueous pressure-sensitive adhesive emulsion of the polymer particles with the hard core-soft shell structure after the initiation polymerization is finished.
Example 4
Weighing the following raw materials: 22 parts of acrylate soft monomer acrylic acid-2-ethylhexyl ester, 8 parts of acrylate hard monomer methyl methacrylate and inorganic precursor TiO22 parts of initiator azodiisoheptonitrile, 1 part of cross-linking agent divinylbenzene, 3 parts of auxiliary stabilizer hexadecane, 202 parts of emulsifier polyoxyethylene sorbitan monolaurate Tween and 60 parts of deionized water.
Preparing a miniemulsion: mixing methyl methacrylate and TiO2Uniformly 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; adopting a homogenizing emulsification process (18000rpm, 5min) for the pre-emulsion to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 50 ℃ to initiate the reaction of methyl methacrylate on TiO2After the nano particles are polymerized to form seed particles, 2-ethylhexyl 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 5
Weighing the following raw materials: 20 parts of acrylate soft monomer isooctyl acrylate, 10 parts of acrylate 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, 202 parts of emulsifier polyoxyethylene sorbitan monolaurate Tween and 60 parts of deionized water.
Preparing a 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; adopting a homogenizing emulsification process (18000rpm, 5min) for the pre-emulsion to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 65 ℃, initiating methyl acrylate to polymerize on the ZnO nanoparticles to form seed particles, continuing to dropwise add isooctyl 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 polymerization is finished.
Comparative example (comparison with example 1)
Weighing the following raw materials: 22 parts of acrylate soft monomer butyl acrylate, 10 parts of acrylate hard monomer methyl acrylate, 1 part of initiator azodiisobutyronitrile, 2 parts of cross-linking agent divinylbenzene, 3 parts of auxiliary stabilizer hexadecane, 202 parts of emulsifier polyoxyethylene sorbitan monolaurate Tween and 60 parts of deionized water.
Preparing a 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; adopting a homogenizing emulsification process (18000rpm, 5min) for the pre-emulsion to form stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to 50 ℃, initiating methyl acrylate to polymerize to form seed particles, continuing to dropwise add 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 polymerization is finished.
Test example
The five groups of pressure-sensitive adhesives prepared were subjected to the following performance tests to verify the excellent characteristics of the present invention. The performance test results are shown in table 1.
Table 1 pressure sensitive adhesive performance test results
| Initial viscosity (ball) | Room temperature permanent adhesion (h) | 150 ℃ hold viscosity (min) | 180 degree 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 |
| Practice ofExample 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: the test reference methods in table 1 are as follows:
and (3) testing initial adhesion: according to the inclined surface rolling ball method (J.Dow method) of GB/T4852-2002;
and (3) permanent adhesion testing: according to the method for testing the permanent viscosity of the pressure-sensitive adhesive tape in GB/T4851-2014;
180 ° peel force test: the 180-degree peel strength of the pressure-sensitive adhesive tape is obtained according to GB/T2792-2014.
The comparison shows that the aqueous pressure-sensitive adhesive has high initial viscosity, long lasting time and high peel strength, has excellent lasting viscosity even in a high-temperature environment, and does not have degumming and adhesive residue.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The aqueous pressure-sensitive adhesive for small-caliber labeling is characterized by consisting 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 an acrylate hard monomer;
the soft shell is formed on the surface of the hard core, and is composed of a second polyacrylate which is formed by polymerizing acrylate soft monomers.
2. The aqueous pressure-sensitive adhesive of claim 1, wherein the inorganic precursor is selected from SiO2、TiO2And ZnO.
3. The aqueous pressure sensitive adhesive of claim 1 wherein the acrylate hard monomer is selected from the group consisting of alkyl methacrylates or alkyl acrylates having alkyl substituents with < 4 carbon atoms.
4. The aqueous pressure sensitive adhesive of claim 1 wherein the soft acrylate monomer is selected from the group consisting of long chain alkyl methacrylates or long chain alkyl acrylates having a long chain alkyl substituent group with 4 to 18 carbon atoms.
5. The preparation method of the water-based pressure-sensitive adhesive for small-caliber labeling is characterized by comprising the following steps of:
preparing a miniemulsion: uniformly mixing an acrylate hard monomer, an inorganic precursor, an initiator, a cross-linking agent and an auxiliary stabilizer to form an oil phase; uniformly mixing an emulsifier 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 homogeneous emulsification process to the pre-emulsion to form a stable fine emulsion;
preparing aqueous pressure-sensitive adhesive emulsion: heating the miniemulsion to initiate the polymerization of the acrylate hard monomer to form seed particles, then dropwise adding the acrylate soft monomer into the miniemulsion, and after the initiation polymerization is finished, preparing the water-based pressure-sensitive adhesive consisting of the polymer particles with the hard core-soft shell structure.
6. The preparation method of claim 5, wherein the raw materials used in the preparation method are 15-25 parts by weight of acrylate soft monomer, 10-15 parts by weight of acrylate hard monomer, 2-4 parts by weight of inorganic precursor, 1 part by weight of initiator, 2 parts by weight of cross-linking agent, 2-3 parts by weight of co-stabilizer, 1-3 parts by weight of emulsifier and 60-65 parts by weight of deionized water.
7. The method of claim 5 or 6, wherein the acrylate hard monomer is selected from alkyl methacrylates or alkyl acrylates having alkyl substituents with less than 4 carbon atoms.
8. The method of claim 5 or 6, wherein the soft acrylate monomer is selected from long chain alkyl methacrylates or acrylates having a long chain alkyl substituent group with 4 to 18 carbon atoms.
9. The method according to claim 5 or 6, wherein the inorganic precursor is selected from SiO2、TiO2And ZnO.
10. A method of preparation according to claim 5 or 6, wherein the initiator is selected from oil-soluble initiators;
the cross-linking agent is selected from oil-soluble compounds with more than two unsaturated bonds;
the co-stabilizer is selected from long-chain aliphatic hydrocarbon with strong hydrophobicity and 15-18 carbon atoms of alkyl substituent;
the emulsifier is selected from polyoxyethylene fatty alcohol ether or alkyl glycoside compound with HLB of 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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