CN111484827A - Preparation method of emulsion pressure-sensitive adhesive and emulsion pressure-sensitive adhesive - Google Patents
Preparation method of emulsion pressure-sensitive adhesive and emulsion pressure-sensitive adhesive Download PDFInfo
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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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene 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
- 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]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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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
- C09J2483/00—Presence of polysiloxane
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a preparation method of an emulsion pressure-sensitive adhesive, which comprises the following steps: preparing organic silicon resin; preparing oily organic silicon pressure-sensitive adhesive by using the organic silicon resin; and mixing the oily organic silicon pressure-sensitive adhesive with an emulsifier. The emulsion pressure-sensitive agent prepared by the method is different from the solution pressure-sensitive agent in the prior art, namely the oily organic silicon pressure-sensitive agent, and the preparation process is safe, healthy and free of environmental pollution; moreover, the operation is simple, and the pressure sensitive agent with good performance can be formed.
Description
Technical Field
The invention relates to the field of organic silicon pressure-sensitive adhesives, in particular to a preparation method of an emulsion pressure-sensitive adhesive and the emulsion pressure-sensitive adhesive.
Background
In recent years, with the expansion of the demand for packaging, decoration, office supplies and various labels, the demand for pressure-sensitive adhesives has increased. Silicone Pressure Sensitive Adhesives (PSAs) are special adhesives that are semi-dry, capable of long-term viscoelastic behavior, and capable of maintaining permanent, sustained bonding capability, and adhere strongly to substrate surfaces with only finger pressure. The organic silicon pressure-sensitive adhesive has excellent service performance especially at high temperature (260 ℃) and low temperature (-73 ℃), and in addition, has very good electrical property, no corrosion to metal and no irritation to skin; with the development of human science and technology, the requirements for high and low temperature resistance of materials are gradually developed, and particularly, the high requirements for the permanent viscosity of the pressure-sensitive adhesive under the conditions of high and low temperatures are provided. However, most of the existing organosilicon pressure-sensitive adhesives are solution type, but the organosilicon pressure-sensitive adhesives are poor in safety and environmental friendliness, and the application range is greatly limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an emulsion pressure-sensitive adhesive and the emulsion pressure-sensitive adhesive, which can realize safety and environmental friendliness and have strong binding power.
The embodiment of the invention provides a preparation method of an emulsion pressure-sensitive adhesive, which comprises the following steps:
preparing organic silicon resin;
preparing oily organic silicon pressure-sensitive adhesive by using the organic silicon resin;
and mixing the oily organic silicon pressure-sensitive adhesive with an emulsifier.
Further, the preparing the silicone resin includes: hydrolyzing an organic silicon compound under the action of a catalyst; refluxing to remove the by-product; neutralizing to neutrality and regulating solid content.
The organic silicon compound is selected from monohydroxy organic siloxane or organic silicon chloride which can be hydrolyzed to generate monohydroxy organic siloxane or one or more of not less than trihydroxy organic siloxane or organic polysiloxane T, Q, the catalyst is L ewis acid or L ewis alkali, the hydrolysis temperature is 5-40 ℃, the hydrolysis time is 0.5-5h, the reflux temperature is 70-90 ℃, the reflux time is 1-5h, and the solid content range is 40-80% (w/w).
Further, the preparation of the oily silicone pressure-sensitive adhesive by using the silicone resin comprises the following steps: adding the organic silicon resin, the silicon rubber, the silane coupling agent and the catalyst into a reaction kettle, and heating for polymerization; the solid content was adjusted.
Furthermore, the molecular weight of the silicone rubber is 5 × 104-5 × 106, the molar ratio of the silicone rubber to the silicone resin is 1: 0.5-1: 5, the ratio of the silane coupling agent to the total amount of the silicone resin and the silicone rubber is 0.01-0.02(w/w), the catalyst is L ewis alkali, the polymerization temperature is 100-160 ℃, and the solid content range is 50-90% (w/w).
Further, the step of adjusting the solid content comprises adding a solvent, wherein the solvent is aromatic hydrocarbon, ketone or ester.
Further, the mixing the oily silicone pressure-sensitive adhesive with an emulsifier comprises: mixing 1-5 parts of emulsifier, 15-30 parts of water, 50-80 parts of oily organic silicon pressure-sensitive adhesive and 0.1-5 parts of nano silicon dioxide for adjusting the viscosity of the emulsion; the solid content was adjusted.
In another aspect, the invention provides an emulsion pressure-sensitive adhesive, wherein the particle size of the emulsion pressure-sensitive adhesive is 0.1-1 μm.
Further, the peel force of the emulsion pressure sensitive adhesive is greater than 3.67N/cm.
The invention also provides a polyethylene protective film, and the gluing layer of the polyethylene protective film contains the emulsion pressure-sensitive adhesive.
The preparation method of the emulsion type pressure-sensitive adhesive and the emulsion type pressure-sensitive adhesive provided by the embodiment of the invention have the advantages of safe preparation process, no pollution and strong binding power.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
An embodiment of the present invention provides a method for preparing an emulsion pressure-sensitive adhesive, including: preparing organic silicon resin; preparing oily organic silicon pressure-sensitive adhesive by using the organic silicon resin; and mixing the oily organic silicon pressure-sensitive adhesive with an emulsifier.
The emulsion pressure-sensitive agent prepared by the method is different from the solution pressure-sensitive agent in the prior art, namely the oily organic silicon pressure-sensitive agent, and the preparation process is safe, healthy and free of environmental pollution; moreover, the operation is simple, and the pressure sensitive agent with good performance can be formed.
Further, the organic silicon resin is also prepared by adopting a special method of the invention, and specifically comprises the following steps: hydrolyzing an organic silicon compound under the action of a catalyst; refluxing to remove the by-product; neutralizing to neutrality and regulating solid content.
The organic silicon resin is prepared by hydrolysis, and the method is simple and convenient; the content, concentration and state of the organic resin are determined by adjusting the solid content.
Further, the organosilicon compounds are one or more monohydroxyorganosiloxanes M, or organosilicon chlorides which can be hydrolyzed to monohydroxyorganosiloxanes, and one or more not less than trihydroxyorganosiloxanes or organopolysiloxanes T, Q, or not less than trihydroxyorganosiloxanes or organopolysiloxanes, and of course mixtures of the above compounds.
Further, the molar ratio M of the mixture in the organosilicon compound: T/Q ═ 0.5 to 1.5, preferably 0.6 to 1.0; m is preferably one or a combination of more of hexamethylsiloxane, hexamethylsilane, trimethylchlorosilane and the like; T/Q is preferably one or a combination of more of tetraethoxysilane, water glass, poly ethyl silicate and the like.
Further, the catalyst is L ewis acid or L ewis base, preferably L ewis acid.
Further, the hydrolysis temperature is 5-40 ℃, preferably 10-25 ℃, and preferably the hydrolysis is heated in a water bath; the hydrolysis time is 0.5-5h, preferably 1-3 h.
Further, the reflux temperature is 70-90 ℃, preferably 75-85 ℃; specifically, after hydrolysis is finished, the temperature is raised to the reflux temperature, and then reflux is started; the refluxing time is 1-5h, preferably 2-4 h;
further, the adjustment of the solid content includes adding a solvent or evaporating moisture; the solvent is aromatic hydrocarbon, ketone or ester solvent, preferably aromatic hydrocarbon solvent such as toluene or xylene; the solids content is in the range from 40 to 80% (w/w), preferably from 55 to 70% (w/w).
Further, M and T/Q are respectively hydrolyzed under the action of a catalyst, then mixed and refluxed to remove byproducts. The method of separate hydrolysis can adjust the hydrolysis conditions more suitable for the compounds according to the properties of the different compounds, and has higher efficiency. The preparation rate of the separate hydrolysis may be increased by at least 10-40 minutes compared to the rate of the mixed hydrolysis together. Specifically, the hydrolysis temperature of M is 15-20 ℃, and the hydrolysis time is 10-70 minutes; the hydrolysis temperature of the T/Q is 25-30 ℃, and the hydrolysis time is 10-70 minutes.
Further, the preparation of the oily silicone pressure-sensitive adhesive by using the silicone resin comprises the following steps: adding the organic silicon resin, the silicon rubber, the silane coupling agent and the catalyst into a reaction kettle, and heating for polymerization; the solid content was adjusted.
The organic silicon resin, the silicon rubber and the like are used for reaction, and the hydrothermal reaction can be directly carried out in a reaction kettle, so that the method is safe and simple, and the environment cannot be damaged.
Specifically, adding synthetic silicone resin into a reaction kettle, and heating; adding silicon rubber into a reaction kettle; adding a silane coupling agent into a reaction kettle; adding a catalyst into a reaction kettle; heating for polymerization; the solids content is adjusted. Of course, if the synthesis of the silicone resin is itself in a reaction kettle, other reactants may be added directly to the reaction kettle.
Further, the first temperature rise temperature is 40-80 ℃, and is preferably 55-65 ℃;
further, the selected molecular weight of the silicone rubber is 5 × 104-5×106Preferably 1 × 105- 1×106Particularly preferably 5 × 105-8×105(ii) a The molar ratio of the silicone rubber to the silicone resin is between 1:0.5 and 1:5, preferably between 1:1 and 1: 3; silicone rubbers with double bonds are preferred, and silicone rubbers with a double bond content of 0.1 to 0.8% are particularly preferred.
Further, silane coupling agents having double bonds and/or amino groups such as KH550, KH570 and the like are preferable, and the amount of the double bond coupling agent is 0.01 to 2% (w/w), preferably 0.1 to 1% (w/w) of the total amount of the silicone resin and the silicone rubber.
Further, the catalyst is preferably L ewis base, such as organic amines;
further, the polymerization temperature is 100-160 ℃, preferably 100-130 ℃;
likewise, adjusting the solids content of the solvent includes adding the solvent or evaporating the water; the solvent is aromatic hydrocarbon, ketone or ester solvent, preferably aromatic hydrocarbon solvent such as toluene or xylene; the solids content is in the range from 50 to 90% (w/w), preferably from 60 to 80% (w/w).
In another embodiment, the mixing the oily silicone pressure sensitive adhesive with an emulsifier comprises: mixing 1-5 parts of emulsifier, 15-30 parts of water, 50-80 parts of oily organic silicon pressure-sensitive adhesive and 0.1-5 parts of nano silicon dioxide; the solid content was adjusted.
The oily organic silicon is pressure-sensitive and is converted into an emulsion pressure-sensitive agent, so that the application range is wider, the safety is higher, and the adhesive force is stronger. Compared with the oily organic silicon pressure-sensitive adhesive (less than 3N/cm), the emulsion type pressure-sensitive adhesive has stronger stripping force (more than 4N/cm).
In another embodiment, the emulsifier is used in an amount of 0.1-15% (w/w), preferably 0.1-10% (w/w), more preferably 0.1-5% (w/w), and particularly preferably 0.1-2.5% (w/w) of the silicone content.
Further, the emulsifier is alkyl carboxylate, alkyl sulfonate, fatty alcohol sulfate, fatty alcohol polyoxyethylene ether sulfate, fatty acid sulfate, alkyl sulfonate, alkyl phosphate ester salt, alkyl ammonium salt, alkyl quaternary ammonium salt, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, aliphatic polyoxyethylene ester, polyoxyethylene alkylamine, polyol fatty acid ester, polyoxyethylene polyol ether, polyether, ethylene oxide/propylene oxide block polyether, graft-type high molecular surfactant, polyvinyl alcohol, modified polyvinyl alcohol surfactant, fluorocarbon-type surfactant, silicon-containing surfactant (silicon-containing carboxylate, carbonate, amine/ammonium salt, polyoxyethylene group, polyoxyethylene/polyoxypropylene group, etc.), boron-containing surfactant, or the like, preferably polyvinyl alcohol, such as vinca chemical BP-20, and branched polyoxyethylene/polyoxypropylene modified polydimethyl siloxane.
In some embodiments, the solids content is adjusted by supplementing water, wherein the solids content is in the range of 50-80% (w/w), preferably 60-70% (w/w).
Specifically, the process of mixing the oily silicone pressure-sensitive adhesive with the emulsifier is as follows: adding 40-50% (w/w) of emulsifier and water into an emulsifying machine to form a first thick phase; mixing the rest emulsifier with the oily organic silicon pressure sensitive agent, shearing, and adding water to form a second thick phase; then mixing the first thick phase and the second thick phase, specifically adding the second thick phase into an emulsifying machine of the first thick phase; adding water, adding nano silicon dioxide, heating and distilling to remove the solvent, and adjusting the solid content. Wherein, 5 to 7 parts of water is added in the first thick phase forming process; 6-8 parts of water is added in the second thick phase forming process; and finally, supplementing 4-15 parts of water. The emulsion pressure-sensitive adhesive prepared by mixing the two thick phases has more uniform finished product, smaller history and better adhesive force. The particle diameter of the direct and complete mixing method is 0.5-1 micron, the peeling force is 4-5N/cm), the peeling force of the emulsion type pressure sensitive agent mixed by two thick phases is more than 6N/cm, and the particle diameter is 0.1-0.5 micron.
Furthermore, the nano silicon dioxide can be used as a thickening agent to adjust the viscosity to enable the viscosity of the emulsion to reach a proper range, and the adhesive force can be further improved, wherein the stripping force of the emulsion type pressure sensitive agent without the silicon dioxide is 3.5-4.5N/cm, and the stripping force of the emulsion type pressure sensitive agent with the silicon dioxide is more than 5N/cm.
The invention also provides the emulsion pressure-sensitive adhesive prepared by the method, wherein the particle size of the emulsion pressure-sensitive adhesive is 0.1-1 mu m. Wherein the particle size is measured in a Malvern 3000 emulsion particle size.
Further, the peeling force of the emulsion pressure-sensitive adhesive is more than 4N/cm.
Specifically, the peeling force refers to 180 degrees, the emulsion type silicone pressure-sensitive adhesive is flatly laid and dried, release paper is attached, the pressure-sensitive adhesive tape is cut into the shapes with the length and the width of 200mm × 25mm under the environment of (23 +/-2) DEG C and the relative humidity of (65 +/-5)% to clean the surface of a test steel plate (the length is × mm, the width is ×: 125mm, × 50mm, × 1.5.5 mm) and the test steel plate is rolled back and forth three times under the self weight at the speed of about 300mm/min by a compression roller (air bubbles are not allowed to exist at the bonding part of the test steel plate and the test plate), the test sample is placed for half an hour under the test environment after being prepared, the free end of the test sample is folded by 180 degrees and is peeled off from the steel plate by 25mm, the free end of the test sample and the end of the steel plate are clamped under an upper clamp and a lower clamp respectively, the peeling rate of 300mm/min +/-10 mm/min is.
In another embodiment of the present invention, there is provided a polyethylene protective film, wherein the adhesive layer comprises the emulsion pressure sensitive adhesive according to any one of claims 8 to 9.
The invention provides a preparation method of an emulsion type pressure-sensitive adhesive and the emulsion type pressure-sensitive adhesive.
(1) Preparation of Silicone resins
Adding 200kg of hexamethyldisiloxane, 500kg of ethyl silicate and 10kg of concentrated sulfuric acid into a reaction kettle, uniformly mixing in a water bath at 20 ℃, stirring at a high speed, dropwise adding deionized water at the speed of 2L/min, completing dropwise adding within 1 hour, stirring for half an hour after completing dropwise adding, heating to 80 ℃, performing reflux reaction for 4 hours, removing by-products by evaporation, adding ammonia water for neutralization to neutrality, adding about 500kg of toluene, and adjusting the solid content to 50%.
(2) Preparing oily organic silicon pressure-sensitive adhesive by using organic silicon resin
Cooling the reactants to 60 ℃, adding 250kg of 107 silicone rubber (with molecular weight of 80 ten thousand and vinyl content of 0.55%), 5kg of vinyl trimethoxy silane and 200g of triethanolamine, stirring and mixing uniformly, heating to 110 ℃ for reaction for 4 hours, evaporating part of solvent, adjusting solid content to 65%, cooling and discharging;
(3) mixing the oily organic silicon pressure-sensitive adhesive with an emulsifier
Adding 2.5kg of BP-20 and 70kg of deionized water into an emulsifying machine, and shearing to form a first thick phase; 2.5kg of BP-20 and 300kg of the oily organic silicon pressure sensitive adhesive obtained above are mixed and sheared, 78kg of water is added to form a second thick phase; mixing the two thick phases; then adding 1.5kg of meteorological silica and 52kg of deionized water, emulsifying to a uniform phase, transferring to a reduced pressure distillation kettle, heating, distilling under reduced pressure to remove toluene, cooling, supplementing water until the solid content is 60%, uniformly stirring, and discharging. The product is not deteriorated after being placed for 6 months.
The particle size of the emulsion pressure sensitive adhesive was tested to be 0.2 micron in Malvern 3000; the peel force was 6N/cm.
Testing the breakdown strength of the polyethylene protective film prepared from the emulsion pressure-sensitive adhesive to be 3 kV/layer; tensile strength 180N/cm.
Comparative example 1
The solid content is not adjusted in each step, and other steps are the same as those in the best embodiment. The stripping force of the emulsion pressure-sensitive adhesive prepared by the method is 2N/cm, the particle size of the pressure-sensitive adhesive is 5 microns, and the breakdown strength of a polyethylene protective film prepared from the emulsion pressure-sensitive adhesive is 1 kV/layer; tensile strength 100N/cm.
Comparative example 2
After the oily organic silicon pressure-sensitive adhesive is mixed with the emulsifier, the nano silicon dioxide is not added, and other steps are the same as those of the best embodiment. The stripping force of the emulsion pressure-sensitive adhesive prepared by the method is 2.6N/cm, the particle size of the pressure-sensitive adhesive is 4 microns, and the breakdown strength of a polyethylene protective film prepared from the emulsion pressure-sensitive adhesive is 1.6 kV/layer; tensile strength 126N/cm.
Comparative example 3
After the oily organic silicon pressure-sensitive adhesive is mixed with the emulsifier, the non-nano silicon dioxide is added, and other steps are the same as those in the best embodiment. The stripping force of the emulsion pressure-sensitive adhesive prepared by the method is 3N/cm, the particle size of the pressure-sensitive adhesive is 3.8 microns, and the breakdown strength of a polyethylene protective film prepared from the emulsion pressure-sensitive adhesive is 1.7 kV/layer; tensile strength 130N/cm.
Comparative example 4
The reaction parameters in all steps are set to be different from those in the preferred embodiment and are not within the scope of other embodiments of the present application, and other steps are the same as those in the preferred embodiment. The stripping force of the emulsion pressure-sensitive adhesive prepared by the method is 3.1N/cm, the particle size of the pressure-sensitive adhesive is 3.7 microns, and the breakdown strength of a polyethylene protective film prepared from the emulsion pressure-sensitive adhesive is 1.5 kV/layer; tensile strength 128N/cm.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the emulsion pressure-sensitive adhesive is characterized by comprising the following steps:
preparing organic silicon resin;
preparing oily organic silicon pressure-sensitive adhesive by using the organic silicon resin;
and mixing the oily organic silicon pressure-sensitive adhesive with an emulsifier.
2. The method of producing according to claim 1, characterized in that the producing a silicone resin includes:
hydrolyzing an organic silicon compound under the action of a catalyst;
refluxing to remove the by-product;
neutralizing to neutrality and regulating solid content.
3. The preparation method of claim 2, wherein the organosilicon compound is selected from one or more of monohydroxy organosiloxane, organosilicon chlorine capable of being hydrolyzed to form monohydroxy organosiloxane, not less than trihydroxy organosiloxane, organopolysiloxane T, Q, and not less than trihydroxy organosiloxane or organopolysiloxane, the catalyst is L ewis acid or L ewis base, the hydrolysis temperature is 5-40 ℃, the hydrolysis time is 0.5-5h, the reflux temperature is 70-90 ℃, the reflux time is 1-5h, and the solid content is 40-80% (w/w).
4. The preparation method according to claim 1, wherein the preparation of the oily silicone pressure-sensitive adhesive by using the silicone resin comprises:
adding the organic silicon resin, the silicon rubber, the silane coupling agent and the catalyst into a reaction kettle, and heating for polymerization;
the solid content was adjusted.
5. The production method according to claim 4, wherein the silicone rubber has a molecular weight of 5 × 104-5×106The molar ratio of the silicon rubber to the silicon resin is 1: 0.5-1: 5, the ratio of the silane coupling agent to the total amount of the silicon rubber and the silicon resin is 0.01-0.02(w/w), the catalyst is L ewis alkali, the polymerization temperature is 100-160 ℃, and the solid content range is 50-90% (w/w).
6. The preparation method according to claim 2 or 4, wherein the step of adjusting the solid content comprises adding a solvent, wherein the solvent is an aromatic hydrocarbon solvent, a ketone solvent or an ester solvent.
7. The method for preparing according to claim 1, wherein the mixing the oily silicone pressure-sensitive adhesive with an emulsifier comprises:
mixing 1-5 parts of emulsifier, 15-30 parts of water, 50-80 parts of oily organic silicon pressure-sensitive adhesive and 0.1-5 parts of nano silicon dioxide; the solid content was adjusted.
8. The emulsion pressure-sensitive adhesive prepared by the preparation method of any one of claims 1 to 7, wherein the particle size of the emulsion pressure-sensitive adhesive is 0.1 to 1 μm.
9. The emulsion pressure-sensitive adhesive of claim 8, wherein the release force of the emulsion pressure-sensitive adhesive is greater than 4N/cm.
10. A polyethylene protective film characterized in that: the adhesive coated layer comprises the emulsion pressure sensitive adhesive according to any one of claims 8 to 9.
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|---|---|---|---|---|
| CN112477366A (en) * | 2020-11-25 | 2021-03-12 | 湖北平安电工材料有限公司 | Super-thick mica plate and manufacturing method thereof |
| US11781050B2 (en) | 2021-07-21 | 2023-10-10 | Dow Global Technologies Llc | Aqueous dispersion of a silicone pressure sensitive adhesive base and methods for preparation and use of the dispersion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561379A (en) * | 2001-10-01 | 2005-01-05 | 陶氏康宁公司 | Silicone pressure sensitive adhesive compositions |
| CN101230138A (en) * | 2007-01-25 | 2008-07-30 | 汉高股份两合公司 | Aqueous siliconiting polymer emulsion as well as preparation method and use thereof |
| US20110236573A1 (en) * | 2010-03-29 | 2011-09-29 | Kenneth Lin | Ultra-high solids emulsion pressure sensitive adhesives and their applications |
| WO2013022511A1 (en) * | 2011-08-08 | 2013-02-14 | 3M Innovative Properties Company | Curable cyclic anhydride copolymer/silicone composition |
-
2020
- 2020-04-24 CN CN202010329624.3A patent/CN111484827B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561379A (en) * | 2001-10-01 | 2005-01-05 | 陶氏康宁公司 | Silicone pressure sensitive adhesive compositions |
| CN101230138A (en) * | 2007-01-25 | 2008-07-30 | 汉高股份两合公司 | Aqueous siliconiting polymer emulsion as well as preparation method and use thereof |
| US20110236573A1 (en) * | 2010-03-29 | 2011-09-29 | Kenneth Lin | Ultra-high solids emulsion pressure sensitive adhesives and their applications |
| WO2013022511A1 (en) * | 2011-08-08 | 2013-02-14 | 3M Innovative Properties Company | Curable cyclic anhydride copolymer/silicone composition |
Non-Patent Citations (2)
| Title |
|---|
| 唐磊 等: "《耐高温隔热材料技术》", 31 July 2013, 国防工业出版社 * |
| 张玉龙 等: "《纳米改性剂》", 31 January 2004, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112477366A (en) * | 2020-11-25 | 2021-03-12 | 湖北平安电工材料有限公司 | Super-thick mica plate and manufacturing method thereof |
| US11781050B2 (en) | 2021-07-21 | 2023-10-10 | Dow Global Technologies Llc | Aqueous dispersion of a silicone pressure sensitive adhesive base and methods for preparation and use of the dispersion |
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|---|---|
| CN111484827B (en) | 2022-02-25 |
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