CN115477723A - Hyperbranched acrylate composition, photocuring acrylate pressure-sensitive adhesive and preparation method - Google Patents
Hyperbranched acrylate composition, photocuring acrylate pressure-sensitive adhesive and preparation method Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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Abstract
The invention belongs to the field of adhesive materials, and particularly relates to a hyperbranched acrylate composition, a photocuring acrylate pressure-sensitive adhesive and a preparation method thereof, wherein the hyperbranched acrylate composition is synthesized by a two-step method, firstly, a linear acrylic resin is prepared by free radical polymerization, the resin contains two functional groups of hydroxyl and epoxy, then, an initiator and a catalyst are added, the temperature is raised, the hydroxyl and the epoxy are subjected to stepwise polymerization reaction to synthesize the hyperbranched structure acrylate composition, and the composition is used as a raw material to prepare the photocuring acrylate pressure-sensitive adhesive; the whole reaction process has no solvent and three wastes, accords with the concept of green environmental protection chemical industry, belongs to an environment-friendly new material, and the obtained novel acrylate pressure-sensitive adhesive with the hyperbranched structure has the performances of high peeling strength, high light transmission, high weather resistance and the like.
Description
Technical Field
The invention belongs to the field of adhesive materials, and particularly relates to a hyperbranched acrylate composition, a photocuring acrylate pressure-sensitive adhesive and a preparation method thereof.
Background
The acrylate pressure-sensitive adhesive is widely applied in the fields of machinery, automobiles, electronics, packaging, consumption and the like, and is an adhesive type with a large using amount. Most of the traditional acrylate pressure-sensitive adhesives are solvent-type or emulsion-type: the solvent type pollutes the environment and affects the health of production personnel, and the application of a large amount of solvents has flammable and explosive risks in the production and transportation processes; the emulsion type has the disadvantages of high energy consumption, poor water resistance and the like. The photocuring technology has the characteristics of high efficiency, energy conservation, environmental protection and the like, the photocuring acrylate pressure-sensitive adhesive not only keeps the advantages of weather resistance, high transparency, wide bonding and low cost of an acrylate adhesive system, but also realizes the solvent-free, 100 percent solid content and quick curing of the system, and achieves the idea of green, environmental protection, energy conservation and health of the whole life cycle of the adhesive. Many studies have been made on photo-curing acrylate pressure-sensitive adhesives, but most of them are acrylate pressure-sensitive adhesives prepared by thermally or photo-initiating acrylate monomers to form linear acrylate resins through free radical polymerization, or polyurethane acrylate prepolymers are synthesized and then compounded with photo-crosslinking agents, photoinitiators and the like. No matter the linear acrylate resin or the polyurethane acrylate prepolymer is adopted, when the molecular weight is low, the pressure-sensitive adhesive is easy to infiltrate the base material, the spreadability is good, but the peel strength is not high due to low cohesive energy; when the molecular weight is high, the bulk strength of the pressure-sensitive adhesive is obviously improved, but the viscosity is also obviously improved, the pressure-sensitive adhesive is not beneficial to infiltrating a substrate, the high-viscosity adhesive solution is not easy to coat into a film, and the initial viscosity of the pressure-sensitive adhesive is reduced. Generally, the viscosity of the pressure-sensitive adhesive is reduced in a small amount of solvent (high solid content), water-based or hot-melt type mode through different modes such as solvent, water or temperature, and the like, so that the coating and film forming of the pressure-sensitive adhesive are facilitated. But causes environmental pollution and high energy consumption, and weakens the original advantages of the photo-curing acrylate pressure-sensitive adhesive.
The hyperbranched structural material has a topological structure which is completely different from the traditional linear molecule, and has the characteristics of a highly branched structure, a plurality of terminal groups, weak intermolecular entanglement and the like. Therefore, the coating has very unique physical and chemical properties and already shows excellent performance advantages in the fields of coatings, adhesives and the like. Under the condition of the same molecular weight, the hyperbranched structure resin has obviously lower viscosity, and the branched structure has more active sites (groups) to interact with the base material, so that the light-cured acrylate pressure-sensitive adhesive with better performance can be obtained by utilizing the technology.
The prior literature has more reports about hyperbranched acrylate materials. The patent CN107652443A describes hyperbranched poly (ester-amine) prepared by michael addition reaction of acrylate group and amine group, the hyperbranched molecule has a large number of acrylate groups at the end, and contains hydroxyl group or coexistent hydroxyl group and alkenyl group inside. However, the preparation process is troublesome, a large amount of solvents (methanol, dimethyl sulfoxide, diethyl ether and petroleum ether) are required to be used, the ethylenediamine raw material is recovered by distillation, unreacted amine groups are easily oxidized in the rotary evaporation process, the product color is dark, and the energy consumption is large. The use of a large amount of organic solvent easily causes the volatilization of the solvent to pollute the environment and has the potential safety hazard problems of flammability and explosiveness. The hyperbranched acrylate resin prepared by CN112321842A is also a hyperbranched acrylate resin with an acrylate group end-capped by Michael addition reaction of an acrylate group and an amino group, but the molecular weight and the functionality of the hyperbranched structure mainly depend on the number of active hydrogen of polyamine, and the hyperbranched acrylate resin has the characteristics of low molecular weight, high functionality and high photocuring activity and is suitable for preparing high-hardness ultraviolet light curing products. The two acrylate-terminated hyperbranched materials have no pressure sensitivity after photocuring, and are not suitable for preparation of pressure-sensitive adhesives.
Therefore, whether the photo-curing acrylate pressure-sensitive adhesive with better performance can be obtained becomes one of the problems to be solved in the field.
Disclosure of Invention
Aiming at various defects in the prior art, the invention provides a hyperbranched acrylic ester composition, a photocuring acrylic ester pressure-sensitive adhesive and a preparation method thereof, wherein the hyperbranched acrylic ester composition is synthesized by a two-step method, linear acrylic resin is prepared by free radical polymerization, the resin contains 2 functional groups of hydroxyl and epoxy, then an initiator and a catalyst are added, and the temperature is raised to ensure that the hydroxyl and the epoxy are gradually polymerized to synthesize the hyperbranched structural acrylic ester composition; the composition is used as a raw material to prepare the photo-curing acrylate pressure-sensitive adhesive. The whole reaction process has no solvent and three wastes, accords with the concept of green environmental protection chemical industry, belongs to an environment-friendly new material, and the obtained novel acrylate pressure-sensitive adhesive with the hyperbranched structure has the performances of high peeling strength, high light transmission, high weather resistance and the like.
The invention firstly provides a hyperbranched acrylic ester composition, and particularly relates to a hyperbranched acrylic ester composition synthesized by a two-step method.
The preparation method comprises the following specific steps:
the first step is as follows: adding acrylate monomers, dibenzoyl peroxide and dodecyl mercaptan into a three-neck flask, introducing nitrogen for protection, starting stirring, slowly heating to 56-60 ℃, and reacting for 5 hours under heat preservation to obtain linear acrylic resin;
wherein the mass ratio of the acrylate monomer to the dibenzoyl peroxide to the dodecyl mercaptan is 99-99.5:0.1-0.3:0.4-0.6;
the preferred mass ratio of the acrylate monomer, the dibenzoyl peroxide and the dodecyl mercaptan is 99.4:0.1: 0.5;
the second step: adding a catalyst accounting for 0.8 percent of the total weight of the linear acrylic resin into the linear acrylic resin obtained in the first step, adding a secondary amine monomer as an initiator according to the proportion of 1/26 to 1/8 of the mole number of epoxy groups in a reaction system, adding a diluent according to the proportion of 60 percent of the total mass of the linear acrylic resin, adding a polymerization inhibitor according to the proportion of 0.05 to 0.8 percent of the total mass of the linear acrylic resin, heating to 100 to 110 ℃, and reacting for 3 hours to obtain the hyperbranched acrylic ester composition.
Wherein the catalyst is selected from one of p-toluenesulfonic acid, benzyltriethylammonium chloride or triphenylphosphine;
the acrylate monomer consists of glycidyl methacrylate, hydroxyl-containing monomer, soft monomer, hard monomer and polar monomer; and the using amount of the glycidyl methacrylate is not more than 2 percent of the total weight of the acrylate monomer; meanwhile, the molar ratio of the total hydroxyl groups to the epoxy groups in all the monomers is 2-4: 1.
Further, the hydroxyl-containing monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxyl-terminated caprolactone acrylate and hydroxyethyl acrylamide;
the soft monomer is 2-ethylhexyl acrylate or/and butyl acrylate;
the hard monomer is isobornyl acrylate or/and methyl methacrylate;
the polar monomer is one or more selected from acryloyl morpholine, acrylonitrile, N-dimethylacrylamide and N, N-diethylacrylamide.
Most preferably, the acrylate monomers comprise the following components in parts by weight: 2 to 4 parts of glycidyl methacrylate, 4 to 16 parts of hydroxyl-containing monomer, 8 to 16 parts of hard monomer, 2 to 8 parts of polar monomer and 56 to 84 parts of soft monomer. At this time, the use amount of the glycidyl methacrylate still needs to be controlled not to exceed 2 percent of the total weight of the acrylate monomer; meanwhile, the molar ratio of the total hydroxyl groups to the epoxy groups in all the monomers is 2-4: 1, otherwise, the second step reaction is easy to form gel.
The secondary amine monomer is selected from but not limited to polyaspartic acid ester, jefflink136 and Jefflink754 of Huntsman company, clearllink 1000 and Clearllink 3000 of Dorf Ketal company, and can be one of the monomers or a mixture of the monomers;
the polyaspartic acid ester is a steric type difunctional secondary amine monomer, is specifically purchased from Shenzhen Feiyang Jun research New Material Co., ltd, and can be selected from F520, F420, F2850, F2872, F221 and the like.
The diluent is selected from but not limited to 2-ethylhexyl acrylate; polymerization inhibitors include, but are not limited to, p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol.
In the reaction process, the linear acrylic resin obtained in the first step contains hydroxyl and epoxy functional groups, the molar ratio of the hydroxyl to the epoxy group is kept at 2-4: 1, a trace amount of secondary amine is used as an initiator to react with the epoxy group, and then the acrylic resin with the hyperbranched structure is obtained through iterative reaction of the hydroxyl and the epoxy group.
For better understanding, the inventors hypothesized that the total hydroxyl to epoxide molar ratio of all monomers was 3: 1, as represented by polyaspartate as the secondary amine, and the second reaction procedure was specifically illustrated by the following formula (1 iteration):
in the above examples, R may represent an alkyl moiety containing from 1 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, which may be linear or branched; or a cycloalkyl group having 6 to 15 carbon atoms;
preferred alkyl and cycloalkyl moieties include, for example, 1,4-butyl, 1,6-hexyl, 2,2,4-trimethylhexyl, 3,3,5-trimethylcyclohexane, dicyclohexylmethane;
r' may represent an alkyl group having 1 to 6 carbon atoms, preferably a methyl group and/or an ethyl group.
After 1 iteration, the tail end of the polymer has 6 branched chains, and the terminal hydroxyl groups have 18; if the reaction reaches the second iteration, the hyperbranched structure is more complex, the tail end of the polymer has 18 branched chains, and the terminal hydroxyl can reach 54. By analogy, the more the iteration is, the molecular weight of the polymer is obviously increased, the viscosity is also obviously increased, the reaction stability is not facilitated, side reaction of secondary hydroxyl and epoxy is easy to occur, and gel is caused, so that the iteration times are controlled by controlling the adding amount of a secondary amine monomer, and the viscosity of the polymer is further controlled.
The inventors thus determined the condition that the number of moles of the above secondary amine monomer is 1/26 to 1/8, more preferably 1/16 to 1/8, of the number of moles of the total epoxy groups, and the number of iterations is not more than 2; when the ratio is lower than 1/26, the final molecular weight is too high, the viscosity is increased, gelation is easy to occur due to side reaction in the reaction process, and the too high viscosity is not beneficial to the infiltration of the pressure-sensitive adhesive on a substrate and construction; when the ratio is more than 1/8, sufficient branched chains cannot be formed, the hyperbranched structure is incomplete, and the properties of the hyperbranched structure are not exhibited.
During copolymerization, a small amount of polar monomer is added to increase intramolecular or intermolecular hydrogen bonds, obviously improve the cohesive force of the pressure-sensitive adhesive and improve the bonding force and the peel strength to a polar substrate. The polar monomers selected in the invention all belong to alkaline substances, do not contain acidic components, do not corrode bonding base materials such as ITO (indium tin oxide) layers and metal layers, and can be applied to the high-end electronic field.
The hyperbranched acrylic ester composition obtained by the method has the following characteristics:
the hyperbranched acrylic ester composition is obtained by further reacting linear acrylic resin serving as a raw material, the branched chains of the hyperbranched acrylic ester composition are long molecular chains (linear acrylic resin), each branched chain has very good flexibility, the full infiltration on a base material is facilitated, the initial adhesion and the elongation are improved, and the hyperbranched acrylic ester composition is different from the conventional hyperbranched polymer with a short chain structure obtained by small-molecule reaction; the multifunctional terminal hydroxyl is easy to establish the functions of hydrogen bonds and the like with a polar substrate, and the peel strength is improved, so that the pressure-sensitive adhesive prepared by taking the hyperbranched acrylate composition synthesized by the invention as a raw material has high peel strength and high elongation, which is a key property which is very important in the pressure-sensitive adhesive for attaching a flexible electronic screen.
The photo-curing acrylate pressure-sensitive adhesive prepared by taking the synthesized hyperbranched acrylate composition as a raw material comprises the following components in percentage by mass: 35-68.8% of hyperbranched acrylate composition, 30-60% of acrylate monomer diluent, 0.2-1% of antioxidant and 1-4% of photoinitiator;
the acrylate monomer diluent consists of 2-ethylhexyl acrylate, hydroxyethyl acrylate and isobornyl acrylate, wherein the mass part ratio of each component is as follows: 1-4 parts of 2-ethylhexyl acrylate, 1-4 parts of hydroxyethyl acrylate and 2-6 parts of isobornyl acrylate;
the antioxidant is one or a plurality of compositions of an antioxidant 245 (triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), an antioxidant 1076 (beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and an antioxidant 1135 (3,5-di-tert-butyl-4-hydroxyphenyl iso-octyl phenylpropionate);
the photoinitiator is one or a composition of more of benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexyl phenyl ketone (short for 184 photoinitiator), 2-hydroxy-2-methyl-1-phenyl-1-acetone (short for 1173 photoinitiator), 2-methyl-1- (4-methylthio) phenyl-2-morpholinyl propyl-1-ketone (IRGACURE 907), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (short for TPO photoinitiator), 2,4,6-trimethylbenzoyl phosphonic acid ethyl ester phenyl (short for TPO-L photoinitiator), and bis (2,4,6-trimethylbenzoyl) phosphine oxide (IRGACURE 819);
the preparation method of the photocuring acrylate pressure-sensitive adhesive comprises the following steps:
adding an acrylate monomer diluent into the container according to the mass percentage at room temperature, then adding the photoinitiator and the antioxidant, stirring until the photoinitiator and the antioxidant are dissolved and uniformly mixed, then adding the hyperbranched acrylate composition, and uniformly stirring, wherein the whole preparation process is carried out in a dark place (or under yellow light), so that the phenomenon that the photoinitiator initiates polymerization to cause viscosity increase or gelation is avoided.
The photo-curing pressure-sensitive adhesive prepared from the hyperbranched acrylate composition can be applied to self-supporting OCA adhesive films (used for laminating 3C product electronic screens), high-peel-strength double-sided pressure-sensitive adhesive tapes, high-performance weather-resistant and heat-resistant pressure-sensitive adhesives (such as in the fields of automobiles, household appliances and the like).
The innovation of the invention is that a novel acrylate composition with a hyperbranched structure is synthesized by a two-step method, and the composition is used as a raw material to prepare the photocuring acrylate pressure-sensitive adhesive. The whole reaction process has no solvent and three wastes, accords with the concept of green environmental protection chemical industry, belongs to an environment-friendly new material, and the obtained novel acrylate pressure-sensitive adhesive with the hyperbranched structure has the performances of high peeling strength, high light transmission, high weather resistance and the like.
Detailed Description
The present invention is further illustrated below with reference to examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way;
example 1:
the preparation method of the acrylate composition with the hyperbranched structure comprises the following steps:
the first step is as follows: adding a plurality of acrylate monomers, dibenzoyl peroxide and dodecyl mercaptan into a three-neck flask, introducing nitrogen for protection, stirring for 100-300 r/min, slowly heating to 56-60 ℃, and reacting for 5 hours under heat preservation to obtain linear acrylic resin;
the mass percent ratio of each raw material component in the first-step reaction is as follows: 99.4 percent of various acrylate monomers, 0.1 percent of dibenzoyl peroxide and 0.5 percent of dodecyl mercaptan;
the acrylate monomers comprise the following components in parts by mass: 2 parts of glycidyl methacrylate, 3 parts of hydroxypropyl methacrylate, 3 parts of hydroxyethyl acrylate, 16 parts of isobornyl acrylate, 6 parts of acryloyl morpholine and 70 parts of acrylic acid-2-ethylhexyl ester; wherein the molar ratio of the total amount of hydroxyl groups of the hydroxyl-containing monomer to the total amount of epoxy groups of the glycidyl methacrylate is 3: 1;
the second step is that: adding a triphenylphosphine catalyst, a proper amount of F420 secondary amine monomer as an initiator, acrylic acid-2-ethylhexyl ester as a diluent and a proper amount of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor into the linear acrylic resin obtained in the first step, heating to 100-110 ℃, and reacting for 3 hours to obtain the hyperbranched structure acrylate composition;
the mass percent ratio of each raw material component in the second step reaction is as follows: 77% of linear acrylic resin, 21.2% of 2-ethylhexyl acrylate, 0.6% of triphenylphosphine, 0.8% of 2,6-di-tert-butyl-p-cresol and 0.4% of F420 secondary amine.
The technical scheme for preparing the photocuring acrylate pressure-sensitive adhesive by taking the synthesized hyperbranched structure acrylate composition as a raw material is as follows:
the photocuring acrylate pressure-sensitive adhesive comprises the following components in percentage by mass: 60% of hyperbranched structure acrylate composition, 38.5% of acrylate monomer diluent, 245% of antioxidant: 0.5%, photoinitiator TPO: 1 percent.
Further, the acrylate monomer diluent consists of the following components in parts by mass: 2 parts of 2-ethylhexyl acrylate, 1.5 parts of hydroxyethyl acrylate and 5 parts of isobornyl acrylate;
the preparation method of the photocuring acrylate pressure-sensitive adhesive comprises the following steps: adding an acrylate monomer diluent into a container, then adding a photoinitiator and an antioxidant, stirring until the photoinitiator and the antioxidant are dissolved and uniformly mixed, then adding a hyperbranched acrylate composition, uniformly stirring, and filtering to remove impurities to obtain the photocuring acrylate pressure-sensitive adhesive. All materials need to be used at room temperature or heated to be not higher than 60 ℃, and the whole preparation process is carried out in a dark place (or under yellow light), so that viscosity increase or gel caused by polymerization initiated by a photoinitiator is avoided.
Example 2
The main experimental procedures are the same as in example 1, wherein the change part is as follows:
the mass percentage ratio of each raw material component in the second step reaction is as follows: 77% of linear acrylic resin, 21.4% of 2-ethylhexyl acrylate, 0.6% of triphenylphosphine, 0.8% of 2,6-di-tert-butyl-p-cresol and 0.2% of F420 secondary amine.
Example 3
The main experimental procedures are the same as in example 1, wherein the change part is as follows:
the mass percentage ratio of each raw material component in the second step reaction is as follows: 77% of linear acrylic resin, 21.5% of 2-ethylhexyl acrylate, 0.6% of triphenylphosphine, 0.8% of 2,6-di-tert-butyl-p-cresol and 0.1% of F420 secondary amine.
Example 4
In the first step of synthesizing the hyperbranched structure acrylate composition, the adding proportion of the acryloyl morpholine is changed from 6 parts to 4 parts, and the rest is the same as that of the acrylic acid composition in the example 1.
Example 5
In the first step of synthesizing the hyperbranched structure acrylate composition, the adding proportion of the acryloyl morpholine is changed from 6 parts to 2 parts, and the rest is the same as that of the example 1.
Example 6
In the first step of synthesizing the hyperbranched structure acrylate composition, the adding proportion of the acryloyl morpholine is changed from 6 parts to 8 parts, and the rest is the same as that of the example 1.
Comparative example 1
With reference to patent CN109810648a, an ultraviolet light curing non-woven fabric tape and example 1 of the preparation method thereof, an ultraviolet light curing type acrylate coating liquid was prepared and tested.
Comparative example 2
The performance was tested by preparing an acrylate emulsion pressure sensitive adhesive according to patent CN104497201A, example 1.
Product performance testing
The adhesive products of each example were coated on a PET (75 μm thick) film with a plate coater to control the film thickness to 80 μm, and then covered with a PET release film, placed under a 150W UV-LED lamp for 1 minute (dominant wavelength is 395 nm), and the release film was peeled off to obtain pressure-sensitive adhesive tapes, which were tested in accordance with the respective standards. 180. The degree peel strength and the holding time are respectively determined according to GB/T2792-2014 standard and GB/T4851-2014 standard, and the viscosity and the light transmittance are respectively determined according to GB/T2794-2013 standard and GB/T2410-2008 standard. The failure type refers to the failure type of 180 ° peel strength, and can be classified as: interfacial failure and cohesive failure.
The adhesive products of examples 1-6 were tested for adhesive properties, and the results are shown in the following table:
compared with the test result, as can be seen from the examples 1, 2 and 3, the viscosity of the prepared photo-curing acrylate pressure-sensitive adhesive gradually increases along with the gradual decrease of the content of the secondary amine of the initiator, the 180-degree peel strength also tends to increase, the content of the secondary amine of the initiator decreases, so that the number of iterations of the hyperbranched structure increases, the molecular weight increases, the cohesion is enhanced, the bonding strength is favorably improved, and the infiltration effect of the adhesive solution on the substrate is influenced when the viscosity is too high, so that the bonding strength is unsatisfactory.
In comparative examples 5, 4, 1 and 6, the addition proportions of the polar monomer acryloyl morpholine are respectively increased by 2 parts, 4 parts, 6 parts and 8 parts, the 180-degree peeling strength is increased gradually, and is increased from 15N/25mm to 34N/25mm, so that the content of the polar monomer is increased in the synthesis of the hyperbranched structure acrylate composition to promote the obvious increase of the peeling strength of the pressure-sensitive adhesive. The performance is integrated, the glue solution of the product prepared in the embodiment 6 is low in viscosity, beneficial to construction coating, maximum in 180-degree peel strength and optimal in performance.
The failure types of the examples are interfacial failures, which shows that the cohesive strength of the pressure-sensitive adhesive is higher than the interfacial adhesion strength, and compared with the linear acrylic resin used in the traditional pressure-sensitive adhesive, the hyperbranched structural acrylate used in the embodiment of the invention has the characteristic of high cohesive strength, so the hyperbranched structural acrylate is shown as the interfacial failures. Meanwhile, the light transmittance of the photo-curing acrylate pressure-sensitive adhesive is larger than 90%, and the photo-curing acrylate pressure-sensitive adhesive is suitable for optical applications such as electronic screen lamination and the like.
In contrast, in comparative example 1, an acrylate adhesive solution is directly coated to a thickness of 80 μm, after ultraviolet curing, the 180-degree peel strength is only 18N/25mm, and the failure mode is interface + cohesive failure, because the molecular structure is a linear structure, the cohesive force of the adhesive layer is low, and a small-molecular-weight acrylate oligomer exists, the adhesive property is reduced, the small-molecular-weight acrylate oligomer is easy to remain on the adhesive base material, the viscosity of the small-molecular-weight acrylate oligomer is 5000mPa S, which is much higher than the viscosity range of the embodiment of the application, and the coating is not easy to occur.
Comparative example 2, the viscosity is low, but the adhesive is a water-based pressure-sensitive adhesive, a drying process is needed after coating, the energy consumption and the process are complex, and the 180-degree peel strength is only 9.1N/25mm, which is far lower than the 180-degree peel strength of the adhesive of 15-34N/25 mm.
It can be seen that the technical solution of the present application has a significant advance over the prior art.
In summary, in the technical scheme of the invention, in the preparation process of the photocuring acrylate pressure-sensitive adhesive, the bonding strength can be improved by reducing the content of the secondary amine as the initiator or increasing the proportion of the polar monomer in the hyperbranched structure acrylate composition within a certain range.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A hyperbranched acrylate composition characterized by: the preparation method comprises the following steps of firstly preparing linear acrylic resin through free radical polymerization, then adding an initiator and a catalyst, and heating to ensure that hydroxyl and epoxy are gradually polymerized and reacted to obtain the acrylic resin, wherein the specific preparation method comprises the following steps:
the first step is as follows: adding acrylate monomers, dibenzoyl peroxide and dodecyl mercaptan into a three-neck flask, introducing nitrogen for protection, starting stirring, slowly heating to 56-60 ℃, and reacting for 5 hours under heat preservation to obtain linear acrylic resin;
wherein the mass ratio of the acrylate monomer to the dibenzoyl peroxide to the dodecyl mercaptan is 99-99.5;
the second step is that: adding a catalyst which accounts for 0.8 percent of the total weight of the linear acrylic resin into the linear acrylic resin obtained in the first step, adding a secondary amine monomer as an initiator according to the proportion of 1/26 to 1/8 of the mole number of epoxy groups in a reaction system, adding a diluent according to the proportion of 60 percent of the total weight of the linear acrylic resin, adding a polymerization inhibitor according to the proportion of 0.05 to 0.8 percent of the total weight of the linear acrylic resin, heating to 100 to 110 ℃, and reacting for 3 hours to obtain a hyperbranched acrylic ester composition;
wherein the catalyst is selected from one of p-toluenesulfonic acid, benzyltriethylammonium chloride or triphenylphosphine.
2. A method for preparing the hyperbranched acrylic ester composition of claim 1, wherein: the preparation method comprises the following specific steps:
the first step is as follows: adding acrylate monomers, dibenzoyl peroxide and dodecyl mercaptan into a three-neck flask, introducing nitrogen for protection, starting stirring, slowly heating to 56-60 ℃, and reacting for 5 hours under heat preservation to obtain linear acrylic resin;
wherein the mass ratio of the acrylate monomer to the dibenzoyl peroxide to the dodecyl mercaptan is 99-99.5;
the second step is that: adding a catalyst which accounts for 0.8 percent of the total weight of the linear acrylic resin into the linear acrylic resin obtained in the first step, adding a secondary amine monomer as an initiator according to the proportion of 1/26 to 1/8 of the mole number of epoxy groups in a reaction system, adding a diluent according to the proportion of 60 percent of the total weight of the linear acrylic resin, adding a polymerization inhibitor according to the proportion of 0.05 to 0.8 percent of the total weight of the linear acrylic resin, heating to 100 to 110 ℃, and reacting for 3 hours to obtain a hyperbranched acrylic ester composition;
wherein the catalyst is selected from one of p-toluenesulfonic acid, benzyltriethylammonium chloride or triphenylphosphine.
3. The method of preparing the hyperbranched acrylate composition of claim 2, wherein: the acrylate monomer is composed of glycidyl methacrylate, a hydroxyl-containing monomer, a soft monomer, a hard monomer and a polar monomer, and the mass ratio of the acrylate monomer to the dibenzoyl peroxide to the dodecyl mercaptan is 99.4.
4. The method of preparing the hyperbranched acrylate composition of claim 3, wherein:
the hydroxyl-containing monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxyl-terminated caprolactone acrylate and hydroxyethyl acrylamide;
the soft monomer is 2-ethylhexyl acrylate or/and butyl acrylate;
the hard monomer is isobornyl acrylate or/and methyl methacrylate;
the polar monomer is one or more selected from acryloyl morpholine, acrylonitrile, N-dimethylacrylamide and N, N-diethylacrylamide.
5. The method of preparing the hyperbranched acrylate composition of claim 3, wherein:
the secondary amine monomer is selected from one or more of polyaspartic acid ester, jefflink136 and Jefflink754 from Huntsman company, clearllink 1000 and Clearllink 3000 from Dorf Ketal company; the diluent is selected from but not limited to 2-ethylhexyl acrylate; the polymerization inhibitor includes but is not limited to one of p-hydroxyanisole, hydroquinone and 2,6-di-tert-butyl-p-cresol.
6. The method of preparing the hyperbranched acrylate composition of claim 4, wherein: the acrylate monomer comprises the following components in parts by weight: 2-4 parts of glycidyl methacrylate, 4-16 parts of hydroxyl-containing monomer, 8-16 parts of hard monomer, 2-8 parts of polar monomer and 56-84 parts of soft monomer; and the amount of the glycidyl methacrylate is not more than 2 percent of the total weight of the acrylate monomers.
7. The method of preparing the hyperbranched acrylate composition of claim 6, wherein:
the molar ratio of the total hydroxyl of the hydroxyl-containing monomer to the total epoxy of the glycidyl methacrylate is 2-4: 1.
8. the photo-curing acrylate pressure-sensitive adhesive is characterized by comprising the following components in parts by weight: the mass percentage ratio of each component is as follows: 35-68.8% of hyperbranched acrylate composition, 30-60% of acrylate monomer diluent, 0.2-1% of antioxidant and 1-4% of photoinitiator.
9. The photocurable acrylate pressure sensitive adhesive of claim 8, wherein:
the acrylate monomer diluent consists of 2-ethylhexyl acrylate, hydroxyethyl acrylate and isobornyl acrylate, wherein the mass parts of the components are as follows: 1-4 parts of 2-ethylhexyl acrylate, 1-4 parts of hydroxyethyl acrylate and 2-6 parts of isobornyl acrylate;
the antioxidant is one or a plurality of compositions of an antioxidant 245, an antioxidant 1076 and an antioxidant 1135;
the photoinitiator is one or a composition of more of benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-methyl-1- (4-methylthio) phenyl-2-morpholinopropyl-1-ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phosphonic acid ethyl ester phenyl and bis (2,4,6-trimethylbenzoyl) phosphine oxide.
10. The method for preparing the photo-curing acrylate pressure-sensitive adhesive according to claim 8, wherein the method comprises the following steps: the method comprises the following specific steps:
adding an acrylate monomer diluent into the container according to the mass percentage, then adding a photoinitiator and an antioxidant, stirring until the photoinitiator and the antioxidant are dissolved and uniformly mixed, then adding a hyperbranched acrylate composition, uniformly stirring, and filtering to remove impurities to obtain the photocuring acrylate pressure-sensitive adhesive;
wherein all materials are used at room temperature or heated to 60 deg.C or below, and the whole preparation process is carried out in dark or yellow.
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| CN101724173A (en) * | 2008-10-22 | 2010-06-09 | 蒂萨公司 | Thermally interlinking polyacrylate and method for its manufacture |
| EP2210906A1 (en) * | 2009-01-27 | 2010-07-28 | tesa SE | Adhesive tapes for electronic applications |
| CN114891160A (en) * | 2022-04-28 | 2022-08-12 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified waterborne hydroxyl acrylic resin and preparation method and application thereof |
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|---|---|---|---|---|
| CN101724173A (en) * | 2008-10-22 | 2010-06-09 | 蒂萨公司 | Thermally interlinking polyacrylate and method for its manufacture |
| EP2210906A1 (en) * | 2009-01-27 | 2010-07-28 | tesa SE | Adhesive tapes for electronic applications |
| CN114891160A (en) * | 2022-04-28 | 2022-08-12 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified waterborne hydroxyl acrylic resin and preparation method and application thereof |
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