CN107722882B - Acrylate emulsion pressure-sensitive adhesive and preparation method thereof - Google Patents
Acrylate emulsion pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN107722882B CN107722882B CN201710993144.5A CN201710993144A CN107722882B CN 107722882 B CN107722882 B CN 107722882B CN 201710993144 A CN201710993144 A CN 201710993144A CN 107722882 B CN107722882 B CN 107722882B
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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Abstract
The invention provides an acrylate emulsion pressure-sensitive adhesive and a preparation method thereof, wherein the pressure-sensitive adhesive is prepared from the following components: 100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer comprises glycidyl methacrylate; 1-4 parts of an emulsifier; 0.07-0.93 part of thermal initiator; 0.03-0.07 part of a reducing agent; 0-3 parts of a silane coupling agent; 140-160 parts of water; 0.5-3 parts of a pH value regulator; 2-4 parts of cationic photoinitiator. The pressure-sensitive adhesive is mutually matched under the components with the content, and has excellent water resistance, alkali resistance and pressure sensitivity; the 180-degree peel strength is 0.38-1.03N/25 mm; no or slight whitening after water resistance; 4-12 min is required for the phenolphthalein to turn red.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to an acrylate emulsion pressure-sensitive adhesive and a preparation method thereof.
Background
The emulsion type acrylate pressure-sensitive adhesive is the most commonly used adhesive in aqueous adhesives and is characterized in that: the dispersing medium is water instead of an organic solvent, and no VOC is discharged; secondly, the light resistance and the weather resistance are good, and the oxidation is not easy to occur; high bonding strength, excellent 180-degree peel strength, initial adhesion and permanent adhesion; the monomers used for preparation are diversified, various products can be designed according to different requirements, and the application is wide. Due to the environmental protection characteristic and excellent performance, the emulsion type acrylate pressure-sensitive adhesive is the key point of development nowadays.
The ultraviolet curing technology utilizes the principle that a photoinitiator is decomposed into free radicals or cations under the irradiation of ultraviolet light to further enable unsaturated double bonds or epoxy groups in a system to perform chemical reaction, thereby achieving the purpose of rapid curing. In addition, the reticular cross-linked structure formed in the photocuring process enables the adhesive to have better water resistance, heat resistance, corrosion resistance and other properties. Therefore, the application of photo-curing technology in the field of pressure-sensitive adhesive is becoming more and more common.
The traditional emulsion type acrylate pressure-sensitive adhesive has poor compactness of an adhesive film, so that water vapor is easy to invade to cause the performance reduction of the pressure-sensitive adhesive. In addition, a large number of ester groups exist on the molecular chain of the polymer, and hydrolysis is easily caused under alkaline conditions to break the molecular chain, so that the continuity of the pressure-sensitive adhesive structure is damaged. Therefore, the acrylate emulsion pressure-sensitive adhesive with excellent alkali resistance and water resistance is developed, and has important application significance.
Disclosure of Invention
In view of the above, the present invention aims to provide an acrylate emulsion pressure sensitive adhesive and a preparation method thereof, wherein the acrylate emulsion pressure sensitive adhesive has excellent alkali resistance and water resistance.
The invention provides an acrylate emulsion pressure-sensitive adhesive which is prepared from the following raw materials in parts by weight:
100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer is glycidyl methacrylate;
1-4 parts of an emulsifier;
0.07-0.93 part of thermal initiator;
0.03-0.07 part of a reducing agent;
0-3 parts of a silane coupling agent;
140-160 parts of water;
0.5-3 parts of a pH value regulator;
2-4 parts of cationic photoinitiator.
Preferably, the soft monomer is selected from butyl acrylate and/or isooctyl acrylate;
the hard monomer is selected from one or more of methyl methacrylate, vinyl acetate, vinyl versatate and styrene.
Preferably, the thermal initiator is selected from potassium persulfate and/or ammonium persulfate;
the reducing agent is selected from sodium bisulfite.
Preferably, the emulsifier is selected from one or more of a DNS-86 reactive emulsifier, an FS-40 anionic emulsifier and a DP-100 nonionic emulsifier.
Preferably, the cationic photoinitiator is selected from cationic photoinitiators of the sulfonium salt type and/or cationic photoinitiators of the iodonium salt type.
Preferably, the silane coupling agent is selected from a type KH550 silane coupling agent and/or a type KH560 silane coupling agent.
Preferably, the pH regulator is selected from one or more of ammonia, N-dimethyl isopropanolamine and triethanolamine.
The invention provides a preparation method of the acrylate emulsion pressure-sensitive adhesive, which comprises the following steps:
a) mixing part of emulsifier and water, adding monomer, and stirring to obtain pre-emulsion;
b) mixing the rest part of emulsifier with water, mixing with part of the pre-emulsion, dropwise adding part of thermal initiator and part of reducing agent, and reacting to obtain seed emulsion;
c) and dropwise adding the rest of thermal initiator, the rest of reducing agent and the rest of pre-emulsion into the seed emulsion, then preserving heat and curing, adjusting the pH value by adopting a pH value regulator, then adding a silane coupling agent, stirring, adding a cationic photoinitiator, and stirring and dispersing to obtain the acrylate emulsion.
Preferably, the temperature of the reaction in the step b) is 45-55 ℃; the reaction time is 25-35 min.
Preferably, the temperature for heat preservation curing in the step c) is 85-90 ℃, and the time for heat preservation curing is 1.5-2.5 h;
the dripping time is 3-4 h.
The invention provides an acrylate emulsion pressure-sensitive adhesive which is prepared from the following raw materials in parts by weight: 100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer comprises glycidyl methacrylate; 1-4 parts of an emulsifier; 0.07-0.93 part of thermal initiator; 0.03-0.07 part of a reducing agent; 0-3 parts of a silane coupling agent; 140-160 parts of water; 0.5-3 parts of a pH value regulator; 2-4 parts of cationic photoinitiator. The acrylate emulsion pressure-sensitive adhesive adopts a functional monomer glycidyl methacrylate as a copolymer, is compatible with other components, and is cured by cationic light, so that latex particles in the emulsion pressure-sensitive adhesive are crosslinked with the latex particles through the reaction of epoxy groups, the compactness of an adhesive film is enhanced, and the water resistance and the alkali resistance of the pressure-sensitive adhesive are further improved. Also has excellent pressure-sensitive properties; the emulsion pressure-sensitive colloidal particle has narrow size distribution, stable storage performance, simple preparation process and easy application. The experimental results show that: the appearance of the acrylate emulsion pressure-sensitive adhesive is milky blue, and the standing stability time is more than 3 months; the 180-degree peel strength is 0.38-1.03N/25 mm; the hair does not turn white after 24 hours at 25 ℃; no or slight whitening after 10min at 90 ℃; the time required for phenolphthalein to turn red is 4-12 min.
Drawings
FIG. 1 is a DLS spectrum of an acrylate emulsion pressure sensitive adhesive prepared in example 1 of the present invention.
Detailed Description
The invention provides an acrylate emulsion pressure-sensitive adhesive which is prepared from the following raw materials in parts by weight:
100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer comprises glycidyl methacrylate;
1-4 parts of an emulsifier;
0.07-0.93 part of thermal initiator;
0.03-0.07 part of a reducing agent;
0-3 parts of a silane coupling agent;
140-160 parts of water;
0.5-3 parts of a pH value regulator;
2-4 parts of cationic photoinitiator.
The preparation raw material of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprises 100 parts of monomer. In the invention, the monomers comprise a soft monomer, a hard monomer and a functional monomer with the mass ratio of 40-80: 10-50: 5-15. The glass transition temperature of the soft monomer is 180-220K; the soft monomer is preferably selected from one or more of butyl acrylate, isooctyl acrylate, ethyl acrylate and isooctyl methacrylate, more preferably from butyl acrylate and/or isooctyl acrylate.
The glass transition temperature of the hard monomer is 300-400K; the hard monomer is preferably selected from one or more of methyl methacrylate, vinyl acetate, vinyl versatate and styrene.
The functional monomer is glycidyl methacrylate; the functional monomers preferably further include a crosslinking monomer; the crosslinking monomer is preferably hydroxyethyl methacrylate.
The preparation raw materials of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprise 1-4 parts of emulsifier, preferably 1.5-3.7 parts. The emulsifier is preferably one or more selected from DNS-86 reactive emulsifier, FS-40 anionic emulsifier and DP-100 nonionic emulsifier.
The preparation raw materials of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprise 0.07-0.93 part of thermal initiator and 0.03-0.07 part of reducing agent. The thermal initiator and the reducing agent form an oxidation-reduction system, the oxidation-reduction system can reduce the temperature of the emulsion polymerization process, the ring-opening reaction of epoxy groups in latex particles caused by overhigh temperature in the polymerization process is avoided, the epoxy groups are reserved, the reaction is carried out again in the cationic ultraviolet curing process, the crosslinking degree among the latex particles is enhanced, and the compactness of the adhesive film is improved.
The preparation raw materials of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprise 0-3 parts of silane coupling agent, preferably 0.2-2.6 parts. In the present invention, the silane coupling agent is preferably selected from the type KH550 silane coupling agents and/or the type KH560 silane coupling agents.
The preparation raw material of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprises 140-160 parts of water, and preferably 150-155 parts of water. The water is preferably selected from deionized water.
The preparation raw materials of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprise 0.5-3 parts of pH value regulator; preferably 0.7 to 2.8 parts. In the present invention, the pH adjuster is preferably one or more selected from the group consisting of ammonia, N-dimethylisopropanolamine, and triethanolamine.
The preparation raw materials of the acrylate emulsion pressure-sensitive adhesive provided by the invention comprise 2-4 parts of cationic photoinitiator, preferably 2.3-3.6 parts. In the present invention, the cationic photoinitiator is preferably selected from cationic photoinitiators of the sulfonium salts and/or cationic photoinitiators of the iodonium salts; more preferably selected from the group consisting of Gencure 842 cationic photoinitiators and Gencure 831 cationic photoinitiators from Shanghai Baolu chemical Co., Ltd.
The invention provides a preparation method of the acrylate emulsion pressure-sensitive adhesive, which comprises the following steps:
a) mixing part of emulsifier and water, adding monomer, and stirring to obtain pre-emulsion;
b) mixing the rest part of emulsifier with water, mixing with part of the pre-emulsion, dropwise adding part of thermal initiator and part of reducing agent, and reacting to obtain seed emulsion;
c) and dropwise adding the rest thermal initiator, the rest reducing agent and the rest pre-emulsion into the seed emulsion, preserving heat and curing, adjusting the pH value by adopting a pH value regulator, then adding a silane coupling agent, stirring, then adding a cationic photoinitiator, stirring and dispersing to obtain the acrylate emulsion pressure-sensitive adhesive.
The invention mixes partial emulsifier and water, adds monomer, and stirs to obtain pre-emulsion. The types of the emulsifier, the water and the monomer are consistent with those of the emulsifier, the monomer and the water in the technical scheme, and are not described again. The amount of the partial emulsifier is preferably 50% of the total amount of the emulsifier.
The present invention preferably mixes a portion of the emulsifier and water in a beaker; mixing preferably under stirring; the stirring speed is preferably 480-520 rpm, and more preferably 500 rpm. The stirring speed after the monomers are added is preferably 950-1050 rpm, and more preferably 1000 rpm; the time for stirring after adding the monomer is preferably 25-35 min, and more preferably 30 min.
After the pre-emulsion is obtained, the invention mixes the rest part of emulsifier with water, then mixes with part of the pre-emulsion, adds part of thermal initiator aqueous solution and part of reducing agent aqueous solution dropwise, and reacts to obtain the seed emulsion.
The remaining part of the emulsifier and water is preferably mixed in the present invention in a reaction vessel well known to the person skilled in the art. The remaining part of the emulsifier and water are preferably mixed under stirring; the stirring speed is preferably 330-360 rpm, and more preferably 350 rpm. Mixing the rest part of emulsifier and water under the heating condition; preferably, the pre-emulsion is heated to 45-55 ℃ and then mixed with part of the pre-emulsion. The mass of part of the pre-emulsion accounts for 5% of the mass of all the pre-emulsion.
In the present invention, it is preferable that the thermal initiator and the reducing agent are dissolved in water, respectively, to obtain an aqueous thermal initiator solution and an aqueous reducing agent solution. In practice, it is preferred to drop a part of the aqueous solution of the thermal initiator and a part of the aqueous solution of the reducing agent rapidly into the reaction vessel. The reaction temperature is preferably 45-55 ℃; the reaction time is 25-35 min, and more preferably 30 min.
After the seed emulsion is obtained, the remaining part of the thermal initiator aqueous solution, the remaining part of the reducing agent aqueous solution and the remaining part of the pre-emulsion are dripped into the seed emulsion, the seed emulsion is cured by heat preservation, the pH value is adjusted by adopting a pH value adjusting agent, then a silane coupling agent is added, the cationic photoinitiator is added after stirring, and the acrylic emulsion pressure sensitive adhesive is obtained after stirring and dispersing.
After the temperature of a seed emulsion system is preferably raised to 50-60 ℃, the rest of the thermal initiator aqueous solution, the rest of the reducing agent aqueous solution and the rest of the pre-emulsion are respectively dripped into the seed emulsion by adopting a first constant pressure funnel, a second constant pressure funnel and a third constant pressure funnel; the dripping time of the rest of the thermal initiator aqueous solution and the rest of the reducing agent aqueous solution is preferably 3-4 h, and more preferably 3.5 h; the time for dripping the residual part of the pre-emulsion is preferably 2.8-3.2 h, and more preferably 3 h. In the invention, the temperature of the heat preservation curing is preferably 85-90 ℃, and more preferably 88 ℃; the time for heat preservation and curing is preferably 1.5-2.5 h, and more preferably 2 h. And air cooling after heat preservation and curing.
The pH value is preferably adjusted to 7-8, and more preferably 7 by adopting a pH value regulator. The types and the use amounts of the pH value regulator, the silane coupling agent and the cationic photoinitiator are consistent with those of the pH value regulator, the silane coupling agent and the cationic photoinitiator in the technical scheme, and are not repeated herein.
According to the invention, the acrylate emulsion pressure-sensitive adhesive prepared by the technical scheme or the acrylate emulsion pressure-sensitive adhesive prepared by the preparation method of the technical scheme is preferably subjected to coating, drying and ultraviolet irradiation curing in sequence to prepare the pressure-sensitive adhesive tape.
In the present invention, the photo-curing (UV-curing) process of the pressure sensitive adhesive is: and (3) drying the emulsion pressure-sensitive adhesive, and carrying out ultraviolet curing by an LT-UV102 type ultraviolet crawler-type light curing machine.
The invention carries out related performance tests on the emulsion:
(1) emulsion morphology and stability: the state and color of the emulsion were observed, and the emulsion was filled in a transparent 10ml centrifuge tube and the stability in the state of standing was observed.
(2)180 ° peel strength test: according to the test of GB/T2792-;
(3) testing water-white resistance: referring to GB/T1733-;
(4) and (3) testing alkali resistance: coating the prepared emulsion on the smooth surface of 10cm x 10cm release paper by a wire bar coater with the thickness of 100 mu m, drying the release paper in an oven for 20min at 90 ℃, folding the release paper into a small box shape, wherein the smooth surface coated with the adhesive film faces outwards, placing a small amount of phenolphthalein powder on the paper box, soaking the paper box in a 2.5% sodium hydroxide aqueous solution, and observing the time for the phenolphthalein to turn red so as to represent the alkali corrosion resistance of the adhesive film.
(5) Testing the particle size of the emulsion: the mean particle size and polydispersity of the emulsion were characterized using a Zeta potential and particle size analyzer from Brookhaven.
The invention provides an acrylate emulsion pressure-sensitive adhesive which is prepared from the following raw materials in parts by weight: 100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer comprises glycidyl methacrylate; 1-4 parts of an emulsifier; 0.07-0.93 part of thermal initiator; 0.03-0.07 part of a reducing agent; 0-3 parts of a silane coupling agent; 140-160 parts of water; 0.5-3 parts of a pH value regulator; 2-4 parts of cationic photoinitiator. The acrylate emulsion pressure-sensitive adhesive adopts a functional monomer glycidyl methacrylate as a copolymer, is compatible with other components, and is cured by cationic light, so that latex particles in the emulsion pressure-sensitive adhesive are crosslinked with the latex particles through the reaction of epoxy groups, the compactness of an adhesive film is enhanced, and the water resistance and the alkali resistance of the pressure-sensitive adhesive are further improved. Also has excellent pressure-sensitive properties; the emulsion pressure-sensitive colloidal particle has narrow size distribution, stable storage performance, simple preparation process and easy application. The experimental results show that: the appearance of the acrylate emulsion pressure-sensitive adhesive is milky blue, and the standing stability time is more than 3 months; the 180-degree peel strength is 0.38-1.03N/25 mm; the hair does not turn white after 24 hours at 25 ℃; no or slight whitening after 10min at 90 ℃; the time required for phenolphthalein to turn red is 4-12 min.
In order to further illustrate the present invention, the following examples are provided to describe an acrylate pressure-sensitive adhesive and a method for preparing the same in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Pre-emulsification of monomers: mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 34.8 parts by mass of deionized water in a beaker, heating in a water bath to 50 ℃, stirring and dissolving by using a glass rod, then placing the mixture in an electric stirrer for stirring, wherein the rotating speed of the stirrer is 500rpm, sequentially adding 4 parts by mass of acrylic acid, 20 parts by mass of butyl acrylate, 53.5 parts by mass of isooctyl acrylate, 18 parts by mass of methyl methacrylate, 1.5 parts by mass of hydroxyethyl methacrylate and 3 parts by mass of glycidyl methacrylate, slowly increasing the stirring speed to 1000rpm after the monomer is added, and stirring at a constant speed for half an hour to prepare a pre-emulsion;
(2) preparing a seed emulsion: 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite were dissolved in 1 part by mass of deionized water, respectively. Mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 103.2 parts by mass of deionized water, fully stirring, heating for dissolving, placing in a reaction kettle, stirring at a constant speed, heating to 45-55 ℃, stirring at a speed of 350rpm, adding 6.8 parts by mass of pre-emulsion, after the temperature in the reaction kettle is constant, sequentially and rapidly dropping a potassium persulfate aqueous solution and a sodium bisulfite aqueous solution, keeping the temperature for half an hour, and allowing a system to generate blue light to prepare a seed emulsion;
(3) preparing an emulsion: heating the reaction kettle to 50-60 ℃, respectively dissolving 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite in 5 parts by mass of deionized water, and respectively dropwise adding the potassium persulfate and the sodium bisulfite into the reaction kettle at a constant speed by using a first constant pressure funnel and a second constant pressure funnel, wherein the dropwise adding time is 3.5 hours; dropwise adding the rest of the pre-emulsion into the reaction kettle by using a third constant-pressure funnel for 3 hours; and after the thermal initiator and the reducing agent are added dropwise, heating to 88 ℃, keeping the temperature and curing for two hours, air cooling, adding dropwise ammonia water to adjust the pH value of the system to 7.5, adding 3 parts by mass of a silane coupling agent KH-KH560, stirring for 10min, adding 4 parts by mass of Gencure 842, stirring and dispersing for 10min, and discharging to obtain the acrylate emulsion pressure-sensitive adhesive.
The invention carries out Dynamic Light Scattering (DLS) test on the acrylate emulsion pressure-sensitive adhesive prepared in the example 1, and the result is shown in figure 1, and figure 1 is a DLS spectrogram of the acrylate emulsion pressure-sensitive adhesive prepared in the example 1. Fig. 1 shows that: the average particle diameter of the acrylate emulsion pressure sensitive adhesive prepared in example 1 was 107.6nm, and the dispersion coefficient PI was 0.060.
The appearance and the standing stability of the acrylate emulsion pressure-sensitive adhesive prepared in example 1 are observed, and the result is shown in table 1, wherein table 1 shows the appearance and the standing stability result of the acrylate emulsion pressure-sensitive adhesive prepared in examples 1 to 4 of the invention:
TABLE 1 appearance and standing stability results for acrylate emulsion pressure sensitive adhesives prepared in inventive examples 1-4
The peel strength, water-white resistance and alkali resistance of the acrylate emulsion pressure-sensitive adhesive prepared in example 1 are tested, the test results are shown in table 2, and table 2 shows the peel strength, water-white resistance and alkali resistance test results of the acrylate emulsion pressure-sensitive adhesive prepared in examples 1 to 4 of the invention:
TABLE 2 Peel Strength, Water-whitening resistance and alkali resistance test results for acrylate emulsion pressure-sensitive adhesives prepared in inventive examples 1-4
Example 2
(1) Pre-emulsification of monomers: mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 34.8 parts by mass of deionized water in a beaker, heating in a water bath to 50 ℃, stirring and dissolving by using a glass rod, then placing the mixture in an electric stirrer for stirring, wherein the rotating speed of the stirrer is 500rpm, sequentially adding 4 parts by mass of acrylic acid, 60 parts by mass of butyl acrylate, 10 parts by mass of isooctyl acrylate, 13 parts by mass of vinyl versatate, 3 parts by mass of hydroxyethyl methacrylate and 10 parts by mass of glycidyl methacrylate, slowly increasing the stirring speed to 1000rpm after the monomer is added, and stirring at a constant speed for half an hour to obtain a pre-emulsion;
(2) preparing a seed emulsion: 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite were dissolved in 1 part by mass of deionized water, respectively. Mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 103.2 parts by mass of deionized water, fully stirring, heating for dissolving, placing in a reaction kettle, stirring at a constant speed, heating to 45-55 ℃, stirring at a speed of 350rpm, adding 6.8 parts by mass of pre-emulsion, after the temperature in the reaction kettle is constant, sequentially and rapidly dropping a potassium persulfate aqueous solution and a sodium bisulfite aqueous solution, keeping the temperature for half an hour, and allowing a system to generate blue light to prepare a seed emulsion;
(3) preparing an emulsion: heating the reaction kettle to 50-60 ℃, respectively dissolving 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite in 5 parts by mass of deionized water, and respectively dropwise adding the potassium persulfate and the sodium bisulfite into the reaction kettle at a constant speed by using a first constant pressure funnel and a second constant pressure funnel, wherein the dropwise adding time is 3.5 hours; dropwise adding the rest of the pre-emulsion into the reaction kettle by using a third constant-pressure funnel for 3 hours; and after the thermal initiator and the reducing agent are added dropwise, heating to 88 ℃, preserving heat and curing for two hours, air cooling, adding dropwise ammonia water to adjust the pH value of the system to 7.5, adding 4 parts by mass of Gencure 842, stirring and dispersing for 10min, and discharging to obtain the acrylate emulsion pressure-sensitive adhesive.
The appearance and the standing stability of the acrylate emulsion pressure-sensitive adhesive prepared in example 2 were observed, and the results are shown in table 1. The peel strength, water-white resistance and alkali resistance of the acrylate emulsion pressure-sensitive adhesive prepared in example 2 were tested according to the present invention, and the test results are shown in table 2.
Example 3
(1) Pre-emulsification of monomers: mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 34.8 parts by mass of deionized water in a beaker, heating in a water bath to 50 ℃, stirring and dissolving by using a glass rod, then placing the mixture in an electric stirrer for stirring, wherein the rotating speed of the stirrer is 500rpm, sequentially adding 4 parts by mass of acrylic acid, 20 parts by mass of butyl acrylate, 32.5 parts by mass of isooctyl acrylate, 37 parts by mass of methyl methacrylate, 1.5 parts by mass of hydroxyethyl methacrylate and 5 parts by mass of glycidyl methacrylate, slowly increasing the stirring speed to 1000rpm after the monomer is added, and stirring at a constant speed for half an hour to obtain a pre-emulsion;
(2) preparing a seed emulsion: 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite were dissolved in 1 part by mass of deionized water, respectively. Mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 103.2 parts by mass of deionized water, fully stirring, heating for dissolving, placing in a reaction kettle, stirring at a constant speed, heating to 45-55 ℃, stirring at a speed of 350rpm, adding 6.8 parts by mass of pre-emulsion, after the temperature in the reaction kettle is constant, sequentially and rapidly dropping a potassium persulfate aqueous solution and a sodium bisulfite aqueous solution, keeping the temperature for half an hour, and allowing a system to generate blue light to prepare a seed emulsion;
(3) preparing an emulsion: heating the reaction kettle to 50-60 ℃, respectively dissolving 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite in 5 parts by mass of deionized water, and respectively dropwise adding the potassium persulfate and the sodium bisulfite into the reaction kettle at a constant speed by using a first constant pressure funnel and a second constant pressure funnel, wherein the dropwise adding time is 3.5 hours; dropwise adding the rest of the pre-emulsion into the reaction kettle by using a third constant-pressure funnel for 3 hours; and after the thermal initiator and the reducing agent are added dropwise, heating to 88 ℃, preserving heat and curing for two hours, air cooling, adding dropwise ammonia water to adjust the pH value of the system to 7.5, adding 4 parts by mass of Gencure 842, stirring and dispersing for 10min, and discharging to obtain the acrylate emulsion pressure-sensitive adhesive.
The appearance and the standing stability of the acrylate emulsion pressure-sensitive adhesive prepared in example 3 were observed, and the results are shown in table 1. The peel strength, water-white resistance and alkali resistance of the acrylate emulsion pressure-sensitive adhesive prepared in example 3 were tested according to the present invention, and the test results are shown in table 2.
Example 4
(1) Pre-emulsification of monomers: mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 34.8 parts by mass of deionized water in a beaker, heating in a water bath to 50 ℃, stirring and dissolving by using a glass rod, then placing the mixture in an electric stirrer for stirring, wherein the rotating speed of the stirrer is 500rpm, sequentially adding 4 parts by mass of acrylic acid, 20 parts by mass of butyl acrylate, 26 parts by mass of isooctyl acrylate, 43.5 parts by mass of methyl methacrylate, 1.5 parts by mass of hydroxyethyl methacrylate and 5 parts by mass of glycidyl methacrylate, slowly increasing the stirring speed to 1000rpm after the monomer is added, and stirring at a constant speed for half an hour to obtain a pre-emulsion;
(2) preparing a seed emulsion: 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite were dissolved in 1 part by mass of deionized water, respectively. Mixing 1.03 parts by mass of DNS-86, 0.12 part by mass of DP-100 and 103.2 parts by mass of deionized water, fully stirring, heating for dissolving, placing in a reaction kettle, stirring at a constant speed, heating to 45-55 ℃, stirring at a speed of 350rpm, adding 6.8 parts by mass of pre-emulsion, after the temperature in the reaction kettle is constant, sequentially and rapidly dropping a potassium persulfate aqueous solution and a sodium bisulfite aqueous solution, keeping the temperature for half an hour, and allowing a system to generate blue light to prepare a seed emulsion;
(3) preparing an emulsion: heating the reaction kettle to 50-60 ℃, respectively dissolving 0.248 parts by mass of potassium persulfate and 0.052 parts by mass of sodium bisulfite in 5 parts by mass of deionized water, and respectively dropwise adding the potassium persulfate and the sodium bisulfite into the reaction kettle at a constant speed by using a first constant pressure funnel and a second constant pressure funnel, wherein the dropwise adding time is 3.5 hours; dropwise adding the rest of the pre-emulsion into the reaction kettle by using a third constant-pressure funnel for 3 hours; and after the thermal initiator and the reducing agent are added dropwise, heating to 88 ℃, preserving heat and curing for two hours, air cooling, adding dropwise ammonia water to adjust the pH value of the system to 7.5, adding 4 parts by mass of Gencure 842, stirring and dispersing for 10min, and discharging to obtain the acrylate emulsion pressure-sensitive adhesive.
The appearance and the standing stability of the acrylate emulsion pressure-sensitive adhesive prepared in example 4 were observed, and the results are shown in table 1. The peel strength, water-white resistance and alkali resistance of the acrylate emulsion pressure-sensitive adhesive prepared in example 4 were tested according to the present invention, and the test results are shown in table 2.
The above embodiment shows that the invention provides an acrylate emulsion pressure-sensitive adhesive, which is prepared from the following raw materials in parts by weight: 100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer comprises glycidyl methacrylate; 1-4 parts of an emulsifier; 0.07-0.93 part of thermal initiator; 0.03-0.07 part of a reducing agent; 0-3 parts of a silane coupling agent; 140-160 parts of water; 0.5-3 parts of a pH value regulator; 2-4 parts of cationic photoinitiator. The acrylate emulsion pressure-sensitive adhesive adopts a functional monomer glycidyl methacrylate as a copolymer, is compatible with other components, and is cured by cationic light, so that latex particles in the emulsion pressure-sensitive adhesive are crosslinked with the latex particles through the reaction of epoxy groups, the compactness of an adhesive film is enhanced, and the water resistance and the alkali resistance of the pressure-sensitive adhesive are further improved. Also has excellent pressure-sensitive properties; the emulsion pressure-sensitive colloidal particle has narrow size distribution, stable storage performance, simple preparation process and easy application. The experimental results show that: the appearance of the acrylate emulsion pressure-sensitive adhesive is milky blue, and the standing stability time is more than 3 months; the 180-degree peel strength is 0.38-1.03N/25 mm; the hair does not turn white after 24 hours at 25 ℃; no or slight whitening after 10min at 90 ℃; the time required for phenolphthalein to turn red is 4-12 min.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. The acrylic ester emulsion pressure-sensitive adhesive is prepared from the following raw materials in parts by weight:
100 parts of monomers, wherein the monomers comprise a soft monomer, a hard monomer and a functional monomer in a mass ratio of 40-80: 10-50: 5-15, and the glass transition temperature of the soft monomer is 180-220K; the glass transition temperature of the hard monomer is 300-400K; the functional monomer comprises glycidyl methacrylate; the soft monomer is selected from butyl acrylate and/or isooctyl acrylate; the hard monomer is selected from one or more of methyl methacrylate, vinyl acetate, vinyl versatate and styrene;
1-4 parts of an emulsifier; the emulsifier is selected from one or more of DNS-86 reactive emulsifier, FS-40 anionic emulsifier and DP-100 nonionic emulsifier;
0.07-0.93 part of thermal initiator; the thermal initiator is selected from potassium persulfate;
0.03-0.07 part of a reducing agent; the reducing agent is selected from sodium bisulfite;
0-3 parts of a silane coupling agent; the silane coupling agent is selected from a KH550 silane coupling agent and/or a KH560 silane coupling agent;
140-160 parts of water;
0.5-3 parts of a pH value regulator; the pH value regulator is selected from one or more of ammonia water, N-dimethyl isopropanolamine and triethanolamine;
2-4 parts of a cationic photoinitiator; the cationic photoinitiator is selected from Gencure 842 cationic photoinitiators and/or Gencure 831 cationic photoinitiators;
the preparation method of the acrylate emulsion pressure-sensitive adhesive comprises the following steps:
a) mixing part of emulsifier and water, adding monomer, and stirring to obtain pre-emulsion;
b) mixing the rest part of emulsifier with water, mixing with part of the pre-emulsion, dropwise adding part of thermal initiator and part of reducing agent, and reacting to obtain seed emulsion;
c) and dropwise adding the rest of thermal initiator, the rest of reducing agent and the rest of pre-emulsion into the seed emulsion, then preserving heat and curing, adjusting the pH value by adopting a pH value regulator, then adding a silane coupling agent, stirring, adding a cationic photoinitiator, stirring and dispersing to obtain the acrylate emulsion pressure-sensitive adhesive.
2. The acrylate emulsion pressure-sensitive adhesive according to claim 1, wherein the reaction temperature in the step b) is 45-55 ℃; the reaction time is 25-35 min.
3. The acrylate emulsion pressure-sensitive adhesive according to claim 1, wherein the temperature for heat preservation curing in the step c) is 85-90 ℃, and the time for heat preservation curing is 1.5-2.5 h;
the dripping time is 3-4 h.
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| CN112500521B (en) * | 2020-11-20 | 2022-04-22 | 万华化学集团股份有限公司 | Plasticizer-resistant aqueous pressure-sensitive adhesive emulsion for adhesive tape and preparation method thereof |
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