CN110305266B - Acrylic emulsion with self-wetting effect and emulsion type pressure-sensitive adhesive containing same - Google Patents
Acrylic emulsion with self-wetting effect and emulsion type pressure-sensitive adhesive containing same Download PDFInfo
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- CN110305266B CN110305266B CN201910556937.XA CN201910556937A CN110305266B CN 110305266 B CN110305266 B CN 110305266B CN 201910556937 A CN201910556937 A CN 201910556937A CN 110305266 B CN110305266 B CN 110305266B
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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
- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- 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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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
- 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
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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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
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- 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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- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
The invention discloses an acrylic emulsion with a self-wetting effect and an emulsion type pressure-sensitive adhesive containing the same. The acrylic emulsion and the emulsion type pressure-sensitive adhesive containing the same have good self-wetting effect, no auxiliary agents such as wetting agent and flatting agent are added, the coating and leveling effect of the emulsion type pressure-sensitive adhesive is improved, and the pressure-sensitive adhesive tape prepared from the acrylic emulsion and the emulsion type pressure-sensitive adhesive has the advantages of large initial adhesion, large permanent adhesion, high 180-degree peel strength and good high-temperature resistance, and is suitable for large-scale production and application.
Description
Technical Field
The invention relates to an acrylic emulsion with a self-wetting effect and an emulsion type pressure-sensitive adhesive containing the same.
Background
Emulsifiers have a crucial role in the emulsion polymerization process and emulsion stability, but generally have adverse effects during the use of the emulsion, for example: in the process of drying the emulsion polymer into a film, the small molecular emulsifier gradually migrates to the interface between the polymer and air along with the sedimentation of the polymer, so that the adhesive property, the water resistance and the like of the polymer are reduced. Moreover, the different types and amounts of the emulsifiers affect the coating effect of the emulsion, causing problems such as coating shrinkage, striae, and foaming. In order to solve this problem, a common method is to add an auxiliary agent such as a wetting agent, a leveling agent, an antifoaming agent, etc., which can provide a good application effect, but may cause problems such as compatibility, dispersibility, cost, etc., and may even reduce other properties of the emulsion. Therefore, reactive emulsifiers have attracted a great deal of attention in emulsion polymerization. By bonding the emulsifier molecules to the latex particles, the adverse effects of conventional emulsifiers can be avoided or reduced, and even some of the properties of the emulsion can be improved. However, the use of the reactive emulsifier can only solve the problem of stable performance, and the dosage is large, the viscosity of the obtained emulsion is high, the generation of gum residue is easy, and the requirement cannot be met well.
Therefore, it is necessary to develop an acrylic emulsion having a self-wetting effect, which does not require a wetting agent and a leveling agent, and has stable properties.
Disclosure of Invention
The invention aims to provide an acrylic emulsion with a self-wetting effect and an emulsion pressure-sensitive adhesive containing the same.
The technical scheme adopted by the invention is as follows:
an acrylic emulsion with a self-moistening effect is prepared from the following raw materials in parts by mass:
soft monomer: 75-99 parts of a modifier;
hard monomer: 1-24 parts;
functional monomer: 0-6 parts;
internal crosslinking monomer: 0-5 parts;
external crosslinking monomer: 0-5 parts;
reactive emulsifiers: 0.3-5 parts;
non-reactive anionic emulsifiers: 0.05-1 part;
initiator: 0.1-2 parts;
pH buffer: 0.1-1 part;
water: 80-150 parts of a solvent;
the total amount of the soft monomer, the hard monomer, the functional monomer, the internal crosslinking monomer and the external crosslinking monomer is 100 parts.
Preferably, the soft monomer is at least one of ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate and octadecyl acrylate.
Preferably, the hard monomer is at least one of styrene, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, and acrylamide.
Preferably, the functional monomer is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and beta-hydroxyethyl methacrylate.
Preferably, the internal crosslinking monomer is at least one of N-methylol acrylamide, N- (methoxymethyl) methacrylamide, tetraethylene glycol dimethacrylate, ethylene glycol dimethacrylate, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triepoxy silane, vinyl tri-tert-butyl peroxy silane, vinyl triacetoxy silane, tetramethyl divinyl disiloxane, glycidyl methacrylate, diacetone acrylamide and divinyl benzene.
Preferably, the external crosslinking monomer is at least one of aziridine, adipic acid dihydrazide and isocyanate.
Preferably, the reactive emulsifier is at least one of acrylamide isopropyl sodium sulfonate, ammonium allylpolyoxyethylene phenyl ether sulfate, sodium allylether hydroxypropane sulfonate, ammonium allyloxy nonylphenol polyoxyethylene (10) ether sulfate, sodium allyloxy hydroxypropyl sulfonate, sodium dodecyl allyl succinate sulfonate, sodium vinyl sulfonate, sodium hydroxypropyl methacrylate sulfonate and sodium methallyl hydroxypropyl sulfonate.
Preferably, the non-reactive anionic emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium methallyl hydroxypropyl sulfonate and ammonium nonylphenol polyoxyethylene ether sulfate.
Preferably, the initiator is at least one of potassium persulfate and ammonium persulfate.
Preferably, the pH buffer is sodium bicarbonate.
The preparation method of the acrylic emulsion with the self-wetting effect comprises the following steps:
1) adding water into a reactive emulsifier and a part of initiator for dispersion, adding a part of soft monomer, hard monomer, functional monomer and internal crosslinking monomer, and fully and uniformly mixing to obtain a pre-emulsion;
2) adding water to the rest initiator for dispersion to obtain an initiator solution;
3) adding water into a pH buffering agent and a non-reactive anionic emulsifier for dispersing, adding the rest of soft monomers, hard monomers, functional monomers and internal crosslinking monomers, fully mixing, heating to 75-82 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 15-50 min after blue light appears to obtain a seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3-5 h, the temperature of a reaction system is kept at 75-85 ℃, after the dropwise adding, the temperature is increased to 85-90 ℃, the reaction is carried out for 0.5-3 h under the condition of heat preservation, then the temperature is reduced to 40-50 ℃, the pH value of the emulsion is adjusted to 6.8-7.6, then an external crosslinking monomer is added, the full reaction is carried out, and the filtration is carried out, so that the acrylic emulsion with the self-moistening effect is obtained.
Preferably, the addition amount of the initiator in the step 1) accounts for 65-75% of the total mass of the initiator.
Preferably, the addition amount of the soft monomer in the step 1) accounts for 90-97% of the total mass of the soft monomer.
Preferably, the addition amount of the hard monomer in the step 1) accounts for 90-97% of the total mass of the hard monomer.
Preferably, the addition amount of the functional monomer in the step 1) accounts for 90-97% of the total mass of the functional monomer.
Preferably, the addition amount of the internal crosslinking monomer in the step 1) accounts for 90-97% of the total mass of the internal crosslinking monomer.
An emulsion pressure-sensitive adhesive comprises the acrylic emulsion with self-wetting effect.
Preferably, the emulsion pressure-sensitive adhesive comprises the following components in parts by mass:
the acrylic emulsion with self-wetting effect comprises the following components: 94-100 parts of a binder;
filling: 0-5 parts;
auxiliary agent: 0 to 1 part.
Preferably, the filler is at least one of regenerated cellulose, synthetic resin microbeads, flax fibers, hemp fibers, persimmon fibers, asbestos fibers, glass fibers, carbon fibers, silica, zirconia, mica powder, montmorillonite, graphite, wollastonite and talcum powder.
Preferably, the auxiliary agent is at least one of a tackifier, a pigment, an inhibitor, an accelerator, a wetting agent, a defoaming agent and a preservative.
The adhesive on the surface of the base material is the emulsion type pressure-sensitive adhesive.
The invention has the beneficial effects that: the acrylic emulsion and the emulsion type pressure-sensitive adhesive containing the same have good self-wetting effect, no auxiliary agents such as wetting agent and flatting agent are added, the coating and leveling effect of the emulsion type pressure-sensitive adhesive is improved, and the pressure-sensitive adhesive tape prepared from the acrylic emulsion and the emulsion type pressure-sensitive adhesive has the advantages of large initial adhesion, large permanent adhesion, high 180-degree peel strength and good high-temperature resistance, and is suitable for large-scale production and application.
1) The acrylic emulsion and the emulsion type pressure-sensitive adhesive containing the acrylic emulsion have good wettability, do not need to be additionally added with a wetting agent and a flatting agent, and have good stability in the storage and use processes;
2) the invention adopts the reactive emulsifier in the pre-emulsification process and adopts the non-reactive anionic emulsifier in the seed preparation process, thereby solving the problem that the reactive emulsifier is easy to generate glue residue in the polymerization process and ensuring that the emulsion polymerization process is more stable;
3) the raw materials used in the invention are simple and easy to obtain, the preparation cost is low, and the method is suitable for industrial production;
4) the acrylic emulsion and the emulsion pressure-sensitive adhesive containing the acrylic emulsion are suitable for protective films, sealing and packaging tapes, double-sided tapes, foaming tapes, masking tapes, crepe paper tapes, various decorative cloth-based tapes and the like, and have wide application range.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
an acrylic emulsion with self-wetting effect is prepared by the following steps:
1) 1.5g of ammonium allyloxynonyl phenol polyoxyethylene (10) ether sulfate and 0.5g of ammonium persulfate are added with 50g of deionized water to be stirred and dispersed, then 80g of butyl acrylate, 10g of methyl methacrylate, 3g of acrylic acid, 5g of hydroxypropyl acrylate and 2g of divinylbenzene are added to be fully stirred and uniformly mixed, and a pre-emulsion is obtained;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 50g of deionized water into 0.3g of sodium bicarbonate and 0.5g of ammonium nonylphenol polyoxyethylene ether sulfate, stirring and dispersing, then adding 3.2g of butyl acrylate, 0.4g of methyl methacrylate, 0.12g of acrylic acid, 0.2g of hydroxypropyl acrylate and 0.08g of divinylbenzene, fully stirring and uniformly mixing, heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain seed emulsion;
4) and (2) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is lowered to 40 ℃, the pH value of the emulsion is adjusted to 6.8 by ammonia water, and then the emulsion is filtered by a 100-mesh filter cloth, so that the acrylic emulsion with the self-wetting effect is obtained.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion with self-moistening effect.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the thickness of the adhesive film is about 25 mu m, and the surface is smooth and flat).
Example 2:
an acrylic emulsion with self-wetting effect is prepared by the following steps:
1) adding 50g of deionized water into 2g of ammonium allyloxynonylphenol polyoxyethylene (10) ether sulfate and 0.5g of ammonium persulfate, stirring and dispersing, then adding 75g of isooctyl acrylate, 19g of butyl methacrylate, 3g of methacrylic acid, 3g of hydroxypropyl acrylate and 5g of divinylbenzene, and fully stirring and uniformly mixing to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 45g of deionized water into 0.23g of sodium bicarbonate and 0.5g of sodium dodecyl diphenyl ether disulfonate, stirring and dispersing, then adding 3.75g of isooctyl acrylate, 0.95g of butyl methacrylate, 0.15g of methacrylic acid, 0.15g of hydroxypropyl acrylate and 0.25g of divinylbenzene, fully stirring and uniformly mixing, then heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is reduced to 40 ℃, the pH value of the emulsion is adjusted to 7.2 by ammonia water, and then filtering is carried out by a 100-mesh filter cloth, so that the acrylic emulsion with the self-wetting effect is obtained.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion with self-moistening effect.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the adhesive film is 27 mu m thick, and the surface is smooth and flat).
Example 3:
an acrylic emulsion with self-wetting effect is prepared by the following steps:
1) adding 50g of deionized water into 2.5g of allyloxy nonyl phenol polyoxyethylene (10) ether ammonium sulfate and 0.4g of ammonium persulfate, stirring and dispersing, then adding 90g of isooctyl acrylate, 5g of styrene, 2g of acrylamide, 2g of hydroxyethyl methacrylate and 2g of diacetone acrylamide, and fully stirring and uniformly mixing to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 50g of deionized water into 0.23g of sodium bicarbonate and 0.5g of sodium dodecyl diphenyl ether disulfonate, stirring and dispersing, then adding 5.4g of isooctyl acrylate, 0.3g of styrene, 0.12g of acrylamide, 0.12g of hydroxyethyl methacrylate and 0.12g of diacetone acrylamide, fully stirring and uniformly mixing, then heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain a seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding is finished, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is lowered to 40 ℃, the pH value of the emulsion is adjusted to 7.6 by using ammonia water, then 2g of adipic acid dihydrazide (dissolved in 1g of deionized water in advance) is added, the mixture is fully stirred and uniformly mixed, and then the mixture is filtered by using 100-mesh filter cloth, so that the acrylic emulsion with the self-wetting effect is obtained.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion with self-moistening effect.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on the textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the adhesive film thickness is about 28 mu m, and the surface is smooth and flat).
Example 4:
an acrylic emulsion with self-wetting effect is prepared by the following steps:
1) adding 50g of deionized water into 1.5g of allyloxy hydroxypropyl sodium sulfonate and 0.4g of ammonium persulfate, stirring and dispersing, then adding 80g of n-butyl acrylate, 8g of methyl acrylate, 3g of acrylic acid, 3g of hydroxypropyl acrylate and 6g of glycidyl methacrylate, and fully stirring and uniformly mixing to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 50g of deionized water into 0.23g of sodium bicarbonate and 0.5g of methallyl hydroxypropyl sodium sulfonate, stirring and dispersing, then adding 5.6g of n-butyl acrylate, 0.56g of methyl acrylate, 0.21g of acrylic acid, 0.21g of hydroxypropyl acrylate and 0.42g of glycidyl methacrylate, fully stirring and uniformly mixing, heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain a seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is reduced to 40 ℃, the pH value of the emulsion is adjusted to 7.4 by ammonia water, and then filtering is carried out by a 100-mesh filter cloth, so that the acrylic emulsion with the self-wetting effect is obtained.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion with self-moistening effect.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the thickness of the adhesive film is about 25 mu m, and the surface is smooth and flat).
Example 5:
an acrylic emulsion with self-wetting effect is prepared by the following steps:
1) adding 50g of deionized water into 1.5g of allyloxy hydroxypropyl sodium sulfonate and 0.5g of ammonium persulfate, stirring and dispersing, then adding 80g of isooctyl acrylate, 10g of methyl methacrylate, 3g of acrylic acid, 5g of hydroxypropyl acrylate and 2g of divinylbenzene, and fully stirring and uniformly mixing to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 50g of deionized water into 0.3g of sodium bicarbonate and 0.5g of sodium dodecyl diphenyl ether disulfonate, stirring and dispersing, then adding 6.4g of isooctyl acrylate, 0.8g of methyl methacrylate, 0.24g of acrylic acid, 0.4g of hydroxypropyl acrylate and 0.16g of divinylbenzene, fully stirring and uniformly mixing, heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is reduced to 40 ℃, the pH value of the emulsion is adjusted to 7.5 by ammonia water, and then filtering is carried out by a 100-mesh filter cloth, so that the acrylic emulsion with the self-wetting effect is obtained.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion with self-moistening effect.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the thickness of the adhesive film is about 26 mu m, and the surface is smooth and flat).
Comparative example 1:
an acrylic emulsion, the preparation method comprises the following steps:
1) 1.5g of ammonium nonylphenol polyoxyethylene ether sulfate, 0.5g of ammonium persulfate and 50g of deionized water are added, stirred and dispersed, then 80g of butyl acrylate, 10g of methyl methacrylate, 3g of acrylic acid, 5g of hydroxypropyl acrylate and 2g of divinylbenzene are added, and fully stirred and uniformly mixed to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 50g of deionized water into 0.3g of sodium bicarbonate and 0.5g of ammonium nonylphenol polyoxyethylene ether sulfate, stirring and dispersing, then adding 3.2g of butyl acrylate, 0.4g of methyl methacrylate, 0.12g of acrylic acid, 0.2g of hydroxypropyl acrylate and 0.08g of divinylbenzene, fully stirring and uniformly mixing, heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is reduced to 40 ℃, the pH value of the emulsion is adjusted to 6.8 by ammonia water, and then filtering is carried out by a 100-mesh filter cloth, so as to obtain the acrylic emulsion.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the thickness of the adhesive film is about 25 mu m, and the surface is smooth and flat).
Comparative example 2:
an acrylic emulsion, the preparation method comprises the following steps:
1) adding 50g of deionized water into 2g of ammonium allyloxynonylphenol polyoxyethylene (10) ether sulfate and 0.5g of ammonium persulfate, stirring and dispersing, then adding 75g of isooctyl acrylate, 19g of butyl methacrylate, 3g of methacrylic acid, 3g of hydroxypropyl acrylate and 5g of divinylbenzene, and fully stirring and uniformly mixing to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 45g of deionized water into 0.23g of sodium bicarbonate and 0.5g of sodium dodecyl diphenyl ether disulfonate, stirring and dispersing, then adding 3.75g of isooctyl acrylate, 0.95g of butyl methacrylate, 0.15g of methacrylic acid, 0.15g of hydroxypropyl acrylate and 0.25g of divinylbenzene, fully stirring and uniformly mixing, then heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is raised to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is reduced to 40 ℃, the pH value of the emulsion is adjusted to 8 by ammonia water, and then filtering is carried out by a 100-mesh filter cloth, so as to obtain the acrylic emulsion.
An emulsion pressure-sensitive adhesive is composed of the acrylic emulsion.
A pressure-sensitive adhesive tape, which is prepared by a method comprising the steps of: and (3) coating the emulsion pressure-sensitive adhesive on textured paper by adopting a wire bar knife coating method, and drying at 105 ℃ for 5min to obtain the pressure-sensitive adhesive tape (the adhesive film is 27 mu m thick, and the surface is smooth and flat).
Comparative example 3:
an acrylic emulsion, the preparation method comprises the following steps:
1) adding 50g of deionized water into 2.5g of allyloxy nonyl phenol polyoxyethylene (10) ether ammonium sulfate and 0.4g of ammonium persulfate, stirring and dispersing, then adding 90g of isooctyl acrylate, 5g of styrene, 2g of acrylamide, 2g of hydroxyethyl methacrylate and 2g of diacetone acrylamide, and fully stirring and uniformly mixing to obtain a pre-emulsion;
2) adding 0.2g of ammonium persulfate into 2g of deionized water, stirring and dispersing to obtain an initiator solution;
3) adding 50g of deionized water into 0.23g of sodium bicarbonate and 0.5g of ammonium allyloxy nonyl phenol polyoxyethylene (10) ether sulfate, stirring and dispersing, then adding 5.4g of isooctyl acrylate, 0.3g of styrene, 0.12g of acrylamide, 0.12g of hydroxyethyl methacrylate and 0.12g of diacetone acrylamide, fully stirring and uniformly mixing, heating to 80 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 30min after blue light appears to obtain a seed emulsion;
4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3.5h, the temperature of a reaction system is kept at 80 ℃, after the dropwise adding, the temperature is increased to 85 ℃, the temperature is kept for reaction for 1h, then the temperature is reduced to 40 ℃, the pH value of the emulsion is adjusted to 7.6 by using ammonia water, then 2g of adipic dihydrazide (dissolved by 1g of deionized water in advance) is added, the mixture is fully stirred and uniformly mixed, and then a 100-mesh filter cloth is used for filtering, so that acrylic emulsion (emulsion polymerization residue discharge) is obtained.
Test example:
the pressure-sensitive adhesive tapes of examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in the following table:
TABLE 1 Performance test results of pressure-sensitive adhesive tapes of examples 1 to 5 and comparative examples 1 to 3
Note:
initial adhesion: testing according to the GB/T4852-2002 standard;
180 degree peel strength: testing is carried out according to GB/T2790-1998 standard;
permanent adhesion: testing was carried out according to GB/T4851-1998;
permanent adhesion property at 120 ℃: the temperature resistance is judged by a constant viscosity test at the high temperature of 120 ℃, and the test is carried out according to the GB/T4851-1998 standard;
pH value: testing according to GB/T14518-1993 standard;
wetting effect: no shrinkage, no line, rated as +++; no shrinkage, slight lines, rated as + +; fine shrinkage, slight line, rated +; obvious shrinkage, slight line, rated as-; obviously shrink the hole and obviously line, and rate as-.
As can be seen from Table 1: when a reactive emulsifier is adopted for pre-emulsification, a non-reactive anionic emulsifier is adopted for preparing seeds, and the pH value in the adjustment period is 6.8-7.6, the pressure-sensitive adhesive has excellent performance and excellent wetting and leveling effects; when the non-reactive anionic emulsifier is completely adopted, the performance of the pressure-sensitive adhesive is obviously reduced, and the wetting and leveling effect is poor; when the reactive emulsifier is completely used, the emulsion polymerization proceeds with slag discharge and the polymerization stability becomes poor.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. An acrylic emulsion having a self-wetting effect, characterized in that: the feed is prepared from the following raw materials in parts by mass:
soft monomer: 75-99 parts of a modifier;
hard monomer: 1-24 parts;
functional monomer: 0-6 parts;
internal crosslinking monomer: 0-5 parts;
external crosslinking monomer: 0-5 parts;
reactive emulsifiers: 0.3-5 parts;
non-reactive anionic emulsifiers: 0.05-1 part;
initiator: 0.1-2 parts;
pH buffer: 0.1-1 part;
water: 80-150 parts of a solvent;
the total amount of the soft monomer, the hard monomer, the functional monomer, the internal crosslinking monomer and the external crosslinking monomer is 100 parts;
the soft monomer is at least one of ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate and octadecyl acrylate;
the hard monomer is at least one of styrene, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile and acrylamide;
the functional monomer is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and beta-hydroxyethyl methacrylate;
the internal crosslinking monomer is at least one of N-hydroxymethyl acrylamide, N- (methoxymethyl) methacrylamide, tetraethylene glycol dimethacrylate, ethylene glycol dimethacrylate, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-tert-butyl oxy silane, vinyl tri-tert-butyl peroxy silane, vinyl triacetoxy silane, tetramethyl divinyl disiloxane, glycidyl methacrylate, diacetone acrylamide and divinylbenzene;
the external crosslinking monomer is at least one of aziridine, adipic acid dihydrazide and isocyanate;
the reactive emulsifier is at least one of acrylamide isopropyl sodium sulfonate, ammonium allyl polyoxyethylene phenyl ether sulfate, sodium allyl ether hydroxypropane sulfonate, ammonium allyloxy nonyl phenol polyoxyethylene (10) ether sulfate, sodium allyloxy hydroxypropyl sulfonate, sodium dodecyl allyl succinate sulfonate, sodium vinyl sulfonate, sodium hydroxypropyl methacrylate sulfonate and sodium methallyl hydroxypropyl sulfonate;
the non-reactive anionic emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium methallyl hydroxypropyl sulfonate and ammonium nonylphenol polyoxyethylene ether sulfate;
the preparation method of the acrylic emulsion with the self-wetting effect comprises the following steps: 1) adding water into a reactive emulsifier and a part of initiator for dispersion, adding a part of soft monomer, hard monomer, functional monomer and internal crosslinking monomer, and fully and uniformly mixing to obtain a pre-emulsion; 2) adding water to the rest initiator for dispersion to obtain an initiator solution; 3) adding water into a pH buffering agent and a non-reactive anionic emulsifier for dispersing, adding the rest of soft monomers, hard monomers, functional monomers and internal crosslinking monomers, fully mixing, heating to 75-82 ℃, adding the initiator solution obtained in the step 2), and carrying out heat preservation reaction for 15-50 min after blue light appears to obtain a seed emulsion; 4) dropwise adding the pre-emulsion obtained in the step 1) into the seed emulsion obtained in the step 3), wherein the dropwise adding time is 3-5 h, the temperature of a reaction system is kept at 75-85 ℃, after the dropwise adding, the temperature is increased to 85-90 ℃, the reaction is carried out for 0.5-3 h under the condition of heat preservation, then the temperature is reduced to 40-50 ℃, the pH value of the emulsion is adjusted to 6.8-7.6, then an external crosslinking monomer is added, the full reaction is carried out, and the filtration is carried out, so that the acrylic emulsion with the self-moistening effect is obtained.
2. The acrylic emulsion having self-wetting effect according to claim 1, wherein: the initiator is at least one of potassium persulfate and ammonium persulfate; the pH buffer is sodium bicarbonate.
3. An emulsion pressure-sensitive adhesive is characterized in that: comprising the acrylic emulsion having a self-wetting effect of claim 1 or 2.
4. A pressure-sensitive adhesive tape characterized in that: the adhesive on the surface of the substrate is the emulsion type pressure-sensitive adhesive disclosed in claim 3.
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