CN116218456A - Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof - Google Patents

Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof Download PDF

Info

Publication number
CN116218456A
CN116218456A CN202310000461.8A CN202310000461A CN116218456A CN 116218456 A CN116218456 A CN 116218456A CN 202310000461 A CN202310000461 A CN 202310000461A CN 116218456 A CN116218456 A CN 116218456A
Authority
CN
China
Prior art keywords
sensitive adhesive
silicone
vinyl
methyl
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310000461.8A
Other languages
Chinese (zh)
Inventor
衣彦林
李卫飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202310000461.8A priority Critical patent/CN116218456A/en
Publication of CN116218456A publication Critical patent/CN116218456A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an organic silicon pressure-sensitive adhesive with stable adhesive force in a medium-high adhesive force range, which comprises a hydroxyl and alkoxy cage Polysilsesquioxane (POSS) functional additive, vinyl silicone rubber with different vinyl contents, hydroxyl raw rubber, methyl MQ silicone resin, vinyl MQ silicone resin, an inhibitor and a solvent. The prepared organic silicon pressure-sensitive adhesive can meet the severe requirements of narrow fluctuation range under the high adhesive force range in the fields of high-end process protective films and the like.

Description

Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof
Technical Field
The invention relates to the technical field of organosilicon pressure-sensitive materials, in particular to an organosilicon pressure-sensitive adhesive with stable adhesive force in a medium-high adhesive force range and small fluctuation of adhesive force with time and a preparation method thereof.
Background
The organosilicon pressure-sensitive adhesive is an adhesive of a special organosilicon system, and can provide better adhesive force only by applying certain pressure when being adhered to the surface of an adherend. The pressure sensitive adhesive and the surface of the object to be adhered form good interface interaction, which is commonly contributed by Van der Waals force, hydrogen bond, acid-base proton pair effect, donor-acceptor effect and other acting forces. The organosilicon pressure-sensitive adhesive mainly comprises organosilicon elastomer rubber (providing mechanical strength), organosilicon tackifying resin (providing viscosity), catalyst, cross-linking agent, solvent and other additives. The silicone pressure sensitive adhesive comprises silicone rubber and MQ silicone resin, wherein the silicone rubber and the MQ silicone resin are mainly composed of silicone, and the silicone pressure sensitive adhesive has the most performances.
Along with the rapid development of electronic and information technologies, the protection requirements for circuit boards, display screens and other components are continuously increased, and the application requirements of the process protection film are also continuously improved. The medium-high tack silicone pressure sensitive adhesive generally refers to a pressure sensitive adhesive having a 180 ° peel force in the range of 100-400 gf. The conventional organic silicon pressure-sensitive adhesive is usually used by combining high-viscosity (about 1000gf adhesive force) with low-viscosity (about 1 gf) pressure-sensitive adhesive, so that the stability is difficult to achieve under the adhesive force range of 100-400gf, the adhesive force curve is uneven, and the adhesive force fluctuation range is large; a few suppliers on the market have medium and high viscosity products, and the adhesive force is difficult to stabilize, and the batch-to-batch stability is poor. When in use, the adhesive force is difficult to control, and the situation of too high or too low adhesive force is easy to occur, so that the protection requirement of a high-end process cannot be met.
Chinese patent CN112175576a discloses a method for preparing an organosilicon pressure-sensitive adhesive, which is synthesized by adopting silicone resin, silicone rubber, cross-linking agent, solvent, etc., but only can achieve a higher adhesive force range, and the middle adhesive force range is not studied;
chinese patent CN106753195B discloses a method for preparing an organosilicon pressure-sensitive adhesive and a pressure-sensitive adhesive tape or film, but the middle-high adhesive force range between 100 and 400gf is blank, and the stability control of the middle-high adhesive force range cannot be achieved;
chinese patent CN113956837a discloses a method for synthesizing high-temperature silicone pressure-sensitive adhesive, which uses vinyl modified POSS as a functional additive, and only meets the requirements of non-stop printing and high anchoring property of screen protective film, but does not benefit the protective film in the middle-high adhesion process.
Disclosure of Invention
In order to solve the common defects in the prior middle-high adhesive force range, the invention provides the organic silicon pressure-sensitive adhesive with stable adhesive force in the middle-high adhesive force range, which can realize stable middle adhesive force and is applied to the field of process protection; the formula process is relatively simple, and is beneficial to large-scale preparation.
The invention also aims to provide a preparation method of the organosilicon pressure-sensitive adhesive with stable medium-high adhesive force.
It is still another object of the present invention to provide the use of the medium to high adhesion stable silicone pressure sensitive adhesive.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the organic silicon pressure-sensitive adhesive with stable adhesive force in a medium-high adhesive force range comprises POSS, methyl vinyl silicone rubber raw rubber, hydroxyl raw rubber, methyl MQ silicone resin, vinyl MQ silicone resin, a silicone-hydrogen crosslinking agent, an inhibitor and a solvent.
Preferably, the formula comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber raw rubber, 10-70 parts of hydroxyl raw rubber, 100-300 parts of MQ resin, 100-300 parts of solvent, 0.5-1.5 parts of silicon-hydrogen cross-linking agent, 0.1-2.0 parts of inhibitor and 0.2-2.0 parts of POSS; wherein the mass ratio of the methyl MQ silicone resin to the vinyl MQ silicone resin in the MQ resin is 1:0.2-5.
In a specific embodiment, the POSS has the formula:
Figure BDA0004034248930000031
the R functional groups are independently selected from hydroxyl, methoxy and ethoxy, preferably the R functional groups are hydroxyl or methoxy;
the POSS additive is added to participate in hydrosilylation through alkoxy and hydroxy instead of vinyl, so that the crosslinking network is toughened, the adhesive force of the adhesive film is stable, the stripping force of the cured organosilicon pressure-sensitive adhesive in a medium-high adhesive force range is stable, and the problem of unstable adhesive force of the conventional high-low adhesive pressure-sensitive adhesive is solved.
The preparation step of the POSS comprises the following steps:
(1) A three-necked flask equipped with a reflux condenser and a magnetic stirrer was charged with sodium ethoxide, isopropanol, and deionized water in an amount.
(2) The flask was sealed with dry nitrogen, a quantity of orthosilicic acid, alkoxytrimethoxysilane was added dropwise to the reaction mixture, stirred at 85.+ -. 5 ℃ under reflux for 5-6h, then cooled to room temperature and stirred for a further 6-8h.
(3) Filtering, precipitating, washing, and drying in a vacuum oven at 65+ -5deg.C for 6-8h to obtain white powder as target product;
in the invention, the dosage of sodium ethoxide in the step (1) is 0.1-1% of the total amount of orthosilicic acid and alkoxy trimethoxy silane in the step (2), the dosage of isopropanol and deionized water is 100-300% of the total amount of orthosilicic acid and alkoxy trimethoxy silane, and the ratio of isopropanol to deionized water is (0.5-2): 1, a step of;
in the present invention, in the step (2), the content of hydroxyl groups and alkoxy groups on the final product can be controlled by controlling the addition ratio of the orthosilicic acid and the alkoxy trimethoxy silane, preferably, the usage ratio of the orthosilicic acid to the alkoxy trimethoxy silane is 1:2-4; the reaction process involved is as follows:
Figure BDA0004034248930000041
the organic silicon pressure-sensitive adhesive is preferably one or a mixture of two of dihydroxyl hexamethoxy cage polysilsesquioxane, hydroxyl heptamethoxy cage polysilsesquioxane and the like.
In some specific embodiments, the silicone pressure-sensitive adhesive of the present invention, the methyl vinyl silicone rubber raw rubber has a vinyl mass fraction of 0.03 to 1.5%, preferably 0.05 to 0.5%, and a molecular weight of 50 to 80 ten thousand, preferably 60 to 70 ten thousand.
In some embodiments of the silicone pressure sensitive adhesive of the present invention, the hydroxy-terminated raw rubber is selected from hydroxy-terminated polydimethylsiloxane (107 raw rubber) having a molecular weight of 50 to 80 ten thousand, preferably 60 to 70 ten thousand.
The raw rubber and the POSS additive form an effective crosslinking network during crosslinking, and the final pressure-sensitive adhesive film has stable adhesive force and is not easy to climb and descend.
In some specific embodiments, the M/Q ratio of the methyl MQ silicone resin is 0.5-1.0, and the molar mass is 2700-5000 g/mol. The methyl MQ resin has the structural formula (R) 3 SiO 1/2 ) m (SiO 4/2 ) n Wherein R is methyl or hydroxyl.
In some specific embodiments, the silicone pressure sensitive adhesive of the present invention, the vinyl MQ silicone resin has an M/Q ratio of 0.5 to 1.0, a vinyl mass fraction of 0.5 to 2%, and a molar mass of 4000 to 5000g/mol. Vinyl MQ resin has the structural formula (R) 3 SiO 1/2 ) m (SiO 4/2 ) n Wherein R is vinyl or hydroxyl.
In some specific embodiments, the silicone pressure sensitive adhesive of the present invention, the solvent is selected from any one or a combination of several of toluene, esters solvents, ketones solvents, alkanes solvents, such as ethyl acetate, but not limited to ethyl acetate, ketones solvents, such as acetone, and alkanes solvents, such as n-heptane.
In some specific embodiments, the viscosity of the silicone pressure-sensitive adhesive is 20-150 mpa.s, and the silicone hydrogen cross-linking agent is hydrogen-containing silicone oil (such as H510 and H512) containing terminal hydrogen groups, lateral hydrogen groups and total hydrogen groups in a mass fraction of 0.7-1.6%.
In some specific embodiments, the inhibitor is selected from any one or a combination of several of tetramethyl tetravinyl cyclotetrasiloxane, divinyl tetramethyl disiloxane, methyl ethynyl alcohol, ethynyl cyclohexanol, methyl butynyl alcohol, 3, 5-dimethyl-1-hexynyl-3-alcohol, 3-methyl-1-dodecyn-3-alcohol, preferably ethynyl cyclohexanol.
In another aspect, the present invention provides a method for preparing an organosilicon pressure-sensitive adhesive having stable adhesion in a medium-high adhesion range, comprising the steps of:
1) Adding methyl vinyl silicone rubber raw rubber, hydroxyl raw rubber, methyl MQ silicon resin, vinyl MQ silicon resin, inhibitor, solvent and POSS into a reaction kettle, and starting stirring to fully dissolve the raw rubber in the solvent;
2) Introducing nitrogen, stirring, slowly adding a catalyst accounting for 0.05-2% of the weight of the raw methyl vinyl silicone rubber after stirring uniformly, heating to 120-150 ℃, and carrying out reflux dehydration reaction for 3-5h until no water is generated;
preferably, the catalyst is selected from any one or more of acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluoro benzene sulfonic acid or acid diatomite.
3) Cooling to room temperature, adding a silicon-hydrogen crosslinking agent, stirring for 1-3 hours, and uniformly mixing to obtain the organosilicon pressure-sensitive adhesive with stable adhesive force in a medium-high adhesive force range.
And coating and curing the organic silicon pressure-sensitive adhesive to obtain the pressure-sensitive adhesive film.
In still another aspect, the present invention relates to the use of the aforementioned silicone pressure-sensitive adhesive with stable adhesion in the middle-to-high adhesion range or the silicone pressure-sensitive adhesive prepared by the aforementioned preparation method in the field of high-end process protective films.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with the traditional organosilicon pressure-sensitive adhesive formula, in the invention, the POSS additive with alkenyl functional groups is added into the pressure-sensitive adhesive through physical blending, and when the pressure-sensitive adhesive is cured to form a film under the action of a catalyst at high temperature, alkoxy and hydroxyl are helpful to be dealcoholized and dehydrogenated to crosslink and form a net with silicon hydrogen under the action of the silicon hydrogen. Different from the common vinyl raw materials, the alkoxy and the hydroxyl are jointly reacted, so that the cross-linking reaction is avoided being too fast when the vinyl raw materials are heated and solidified, a more uniform cross-linking structure is formed, the cohesive strength of the adhesive is improved, the hardness of the adhesive surface is controlled, and the phenomenon of unstable initial adhesive force in the use process is avoided.
2) The organic silicon pressure-sensitive adhesive prepared by the formula can be coated on common 50-mu m PET, 100-mu m PET, PI and other base materials, has relatively stable stripping force on steel plates and glass, and has relatively good anchoring property on adhesive surfaces.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
The raw material sources are as follows:
methyl vinyl silicone rubber is used in the chemical industry,
the chemical of hydroxyl raw rubber and vanning,
MQ resin Wanhua chemistry,
toluene was analyzed for pure enokay,
the silicon hydrogen cross-linking agent is in the chemical state of Wanhua,
the inhibitor is in the form of Wanhua chemistry,
POSS vanning chemistry;
the performance test method of the prepared organic silicon pressure-sensitive adhesive comprises the following steps:
1. the viscosity detection method refers to GB/T10247-2008;
2. the adhesive force detection method is described in GB/T2792-1998;
3. adhesive force stability tracking method: the prepared adhesive film is adhered with a protective film, and the adhesive film is stored in a constant temperature and humidity (23 ℃ and 50% RH) environment, and the adhesive force is tested once every 1 week, and the tracking is continued for 1 month. Adhesion testing is described in GB/T2792-1998.
Example 1
The preparation method of POSS dihydroxy hexamethoxy cage polysilsesquioxane comprises the following steps:
(1) 0.08g of sodium ethoxide, 120g of isopropanol and 120g of deionized water were charged into a three-necked flask equipped with a reflux condenser and a magnetic stirrer.
(2) The flask was sealed with dry nitrogen, 20g of orthosilicic acid, 60g of methoxytrimethoxysilane were added dropwise to the reaction mixture, stirred at 85 ℃ under reflux for 6h, then cooled to room temperature and stirred for a further 6h.
(3) Filtering, precipitating, washing, and drying in a vacuum oven at 65 ℃ for 8 hours to obtain white powder, namely the target product and the mixture;
methyl vinyl silicone rubber green: molecular weight 60 ten thousand, vinyl mass fraction 0.5%;
vinyl MQ silicone resin: the M/Q ratio is 0.7, the vinyl mass fraction is 1.5%, and the molar mass is 4400g/mol;
hydroxy raw rubber: molecular weight 60 ten thousand;
methyl MQ silicone resin: the M/Q ratio is 0.7, and the molar mass is 3000g/mol;
silicon hydrogen cross-linking agent: the viscosity was 100mPa.s and the mass fraction of terminal and pendant hydrogen groups was 1.6%.
1) 15g of methyl vinyl silicone rubber raw rubber, 5g of hydroxyl raw rubber, 15g of vinyl MQ silicone resin, 25g of methyl MQ silicone resin, 35g of toluene, 0.25g of POSS and 0.1g of ethynyl cyclohexanol inhibitor are added into a reaction kettle, and stirred for dissolution;
2) Introducing nitrogen, stirring, diluting 0.18g of acetic acid with 5g of toluene, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) And cooling to room temperature, adding 0.1g of a hydrosilylation cross-linking agent, and uniformly stirring to obtain the pressure-sensitive adhesive-1.
15g of toluene is added into 20g of base adhesive-1, after being stirred uniformly, 0.6g of platinum catalyst with platinum content of 5000ppm is added, after being stirred uniformly, the mixture is coated on a PET substrate with thickness of 50 mu m, and after being placed in an oven for curing for 2min at 150 ℃, a fluoroplastic protective film is attached. The test performance of the peeled fluoroplastic protective film was as shown in Table 1.
Example 2
POSS: hydroxy heptaethoxy cage polysilsesquioxane and ethoxy cage polysilsesquioxane;
(1) 0.08g of sodium ethoxide, 120g of isopropanol and 120g of deionized water were charged into a three-necked flask equipped with a reflux condenser and a magnetic stirrer.
(2) The flask was sealed with dry nitrogen, 10g of orthosilicic acid, 70g of ethoxytrimethoxysilane were added dropwise to the reaction mixture, stirred at 90℃under reflux for 6h, then cooled to room temperature and stirred for a further 6h.
(3) Filtering, precipitating, washing, and drying in a vacuum oven at 70deg.C for 6 hr to obtain white powder as target product and mixture;
methyl vinyl silicone rubber green: molecular weight 70 ten thousand, vinyl mass fraction 0.1%;
vinyl MQ silicone resin: the M/Q ratio is 0.7, the vinyl mass fraction is 0.5%, and the molar mass is 4800g/mol;
hydroxy raw rubber: molecular weight 70 ten thousand;
methyl MQ silicone resin: the M/Q ratio is 0.7, and the molar mass is 5000g/mol;
silicon hydrogen cross-linking agent: the viscosity was 100mPa.s and the mass fraction of terminal and pendant hydrogen groups was 1.0%.
1) 33g of methyl vinyl silicone rubber raw rubber, 4g of hydroxyl raw rubber, 15g of vinyl MQ silicone resin, 20g of methyl MQ silicone resin, 35g of ethyl acetate, 0.6g of POSS and 0.3g of divinyl tetramethyl disiloxane inhibitor are added into a reaction kettle, and stirred for dissolution;
2) Introducing nitrogen, stirring, diluting 0.15g of benzoic acid with 5g of ethyl acetate, slowly adding the diluted benzoic acid, and then carrying out reflux dehydration at 120 ℃ for 3 hours;
3) And cooling to room temperature, adding 0.2g of a hydrosilylation cross-linking agent, and uniformly stirring to obtain the pressure-sensitive adhesive-2.
15g of ethyl acetate is added into 20g of base adhesive-2, after being stirred uniformly, 0.6g of platinum catalyst with platinum content of 5000ppm is added, after being stirred uniformly, the mixture is coated on a PET substrate with thickness of 80 mu m, and after being placed in an oven for curing for 2min at 150 ℃, a PET protective film is attached. The PET protective film was peeled off to test the properties, and the results are shown in Table 1.
Example 3
POSS: dihydroxyhexaethoxy cage polysilsesquioxane;
(1) 0.08g of sodium ethoxide, 120g of isopropanol and 120g of deionized water were charged into a three-necked flask equipped with a reflux condenser and a magnetic stirrer.
(2) The flask was sealed with dry nitrogen, 20g of orthosilicic acid, 60g of ethoxytrimethoxysilane were added dropwise to the reaction mixture, stirred at 80℃under reflux for 6h, then cooled to room temperature and stirred for a further 7h.
(3) Filtering, precipitating, washing, and drying in a vacuum oven at 60 ℃ for 7 hours to obtain white powder, namely the target product;
methyl vinyl silicone rubber green: 50 ten thousand molecular weight, vinyl mass fraction 0.4%;
vinyl MQ silicone resin: the M/Q ratio is 0.7, the vinyl mass fraction is 1.8%, and the molar mass is 4000g/mol;
hydroxy raw rubber: molecular weight 50 ten thousand;
methyl MQ silicone resin: the M/Q ratio is 0.7, and the molar mass is 3000g/mol;
silicon hydrogen cross-linking agent: the viscosity was 80mPa.s and the mass fraction of terminal and pendant hydrogen groups was 0.8%.
1) Adding 20g of methyl vinyl silicone rubber raw rubber, 10g of hydroxyl raw rubber, 20g of methyl MQ silicone resin, 10g of vinyl MQ silicone resin, 35g of toluene, 0.3g of POSS and 0.1g of ethynyl cyclohexanol inhibitor into a reaction kettle, stirring and dissolving;
2) Introducing nitrogen, stirring, diluting 0.2g of propionic acid with 5g of toluene, slowly adding the diluted propionic acid, and then carrying out reflux dehydration at 150 ℃ for 5 hours;
3) And cooling to room temperature, adding 0.2g of a hydrosilylation cross-linking agent, and uniformly stirring to obtain the pressure-sensitive adhesive-3.
15g of toluene is added into 20g of base adhesive-3, after being stirred uniformly, 0.5g of platinum catalyst with platinum content of 5000ppm is added, after being stirred uniformly, the mixture is coated on a PET substrate with thickness of 50 mu m, and after being placed in an oven for curing for 2min at 150 ℃, a PET protective film is attached. The PET protective film was peeled off to test the properties, and the results are shown in Table 1.
Example 4
POSS: hydroxy heptamethoxy cage polysilsesquioxane;
(1) 0.08g of sodium ethoxide, 120g of isopropanol and 120g of deionized water were charged into a three-necked flask equipped with a reflux condenser and a magnetic stirrer.
(2) The flask was sealed with dry nitrogen, 10g of orthosilicic acid, 70g of methoxytrimethoxysilane were added dropwise to the reaction mixture, stirred at 85℃under reflux for 5h, then cooled to room temperature and stirred for a further 8h.
(3) Filtering, precipitating, washing, and drying in a vacuum oven at 65 ℃ for 8 hours to obtain white powder, namely the target product and the mixture;
methyl vinyl silicone rubber green: molecular weight 60 ten thousand, vinyl mass fraction 0.5%;
vinyl MQ silicone resin: the M/Q ratio is 0.7, the vinyl mass fraction is 1.5%, and the molar mass is 4400g/mol;
hydroxy raw rubber: molecular weight 60 ten thousand;
methyl MQ silicone resin: the M/Q ratio was 0.7 and the molar mass was 4500g/mol;
silicon hydrogen cross-linking agent: the viscosity was 80mPa.s and the mass fraction of terminal and pendant hydrogen groups was 0.8%.
1) Adding 20g of methyl vinyl silicone rubber raw rubber, 5g of hydroxyl raw rubber, 25g of methyl MQ silicone resin, 10g of vinyl MQ silicone resin, 35g of toluene, 0.1g of POSS and 0.4g of methyl acetylene alcohol inhibitor into a reaction kettle, stirring and dissolving;
2) Introducing nitrogen, stirring, diluting 0.18g of propionic acid with 20g of toluene, slowly adding the diluted propionic acid, and then carrying out reflux dehydration at 130 ℃ for 5h;
3) And cooling to room temperature, adding 0.3g of a hydrosilylation cross-linking agent, and uniformly stirring to obtain the pressure-sensitive adhesive-4.
15g of toluene is added into 20g of base gum-4, after being stirred uniformly, 0.5g of platinum catalyst with platinum content of 5000ppm is added, after being stirred uniformly, the mixture is coated on a PI substrate with thickness of 25 mu m, and after being placed in an oven for curing for 2min at 150 ℃, a fluorine protective film is attached. The test performance of the fluorine protective film was peeled off, and the results are shown in table 1.
Comparative example 1
POSS: vinyl cage polysilsesquioxane (available from hybrid plastics company);
methyl vinyl silicone rubber green: molecular weight 60 ten thousand, vinyl mass fraction 0.5%;
vinyl MQ silicone resin: the M/Q ratio is 0.7, the vinyl mass fraction is 1.5%, and the molar mass is 4400g/mol;
hydroxy raw rubber: molecular weight 60 ten thousand;
methyl MQ silicone resin: the M/Q ratio is 0.7, and the molar mass is 3000g/mol;
silicon hydrogen cross-linking agent: the viscosity was 100mPa.s and the mass fraction of terminal and pendant hydrogen groups was 1.6%.
1) 15g of methyl vinyl silicone rubber raw rubber, 5g of hydroxyl raw rubber, 15g of vinyl MQ silicone resin, 25g of methyl MQ silicone resin, 35g of toluene, 0.25g of POSS and 0.1g of ethynyl cyclohexanol inhibitor are added into a reaction kettle, and stirred for dissolution;
2) Introducing nitrogen, stirring, diluting 0.18g of acetic acid with 5g of toluene, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) And cooling to room temperature, adding 0.1g of a hydrosilylation cross-linking agent, and uniformly stirring to obtain the pressure-sensitive adhesive-1.
15g of toluene is added into 20g of base adhesive-1, after being stirred uniformly, 0.6g of platinum catalyst with platinum content of 5000ppm is added, after being stirred uniformly, the mixture is coated on a PET substrate with thickness of 50 mu m, and after being placed in an oven for curing for 2min at 150 ℃, a fluoroplastic protective film is attached. The test performance of the peeled fluoroplastic protective film was as shown in Table 1.
Comparative example 2 traditional pressure sensitive adhesive without additional auxiliary agent
Methyl vinyl silicone rubber green: molecular weight 70 ten thousand, vinyl mass fraction 0.1%;
vinyl MQ silicone resin: the M/Q ratio is 0.7, the vinyl mass fraction is 0.5%, and the molar mass is 4800g/mol;
hydroxy raw rubber: molecular weight 70 ten thousand;
methyl MQ silicone resin: the M/Q ratio is 0.7, and the molar mass is 5000g/mol;
silicon hydrogen cross-linking agent: the viscosity was 100mPa.s and the mass fraction of terminal and pendant hydrogen groups was 1.0%.
1) Adding 33g of methyl vinyl silicone rubber raw rubber, 24g of hydroxyl raw rubber, 515g of vinyl MQ silicone resin, 20g of methyl MQ silicone resin, 35g of ethyl toluate and 0.3g of divinyl tetramethyl disiloxane inhibitor into a reaction kettle, stirring and dissolving;
2) Introducing nitrogen, stirring, diluting 0.15g of benzoic acid with 5g of ethyl acetate, slowly adding the diluted benzoic acid, and then carrying out reflux dehydration at 120 ℃ for 3 hours;
3) And cooling to room temperature, adding 0.2g of a hydrosilylation cross-linking agent, and uniformly stirring to obtain the pressure-sensitive adhesive-2.
15g of ethyl acetate is added into 20g of base adhesive-2, after being stirred uniformly, 0.6g of platinum catalyst with platinum content of 5000ppm is added, after being stirred uniformly, the mixture is coated on a PET substrate with thickness of 80 mu m, and after being placed in an oven for curing for 2min at 150 ℃, a PET protective film is attached. The PET protective film was peeled off to test the properties, and the results are shown in Table 1.
Test performance data of the silicone pressure-sensitive adhesives prepared in the above examples and comparative examples are shown in table 1 below:
TABLE 1 Silicone pressure sensitive adhesive Properties of examples 1-4 and comparative examples
Figure BDA0004034248930000131
Figure BDA0004034248930000141
As can be seen from the table, in the invention, the POSS additive with hydroxyl or alkoxy functional groups is added into the pressure-sensitive adhesive through physical blending, and when the pressure-sensitive adhesive is cured to form a film under the action of a catalyst at high temperature, wherein the hydroxyl or alkoxy groups are helpful to form a stable crosslinked network structure under the action of silicon hydride, and the POSS structure is crosslinked to play roles of stabilizing the crosslinking density and toughening, so that the conventional organosilicon pressure-sensitive adhesive is difficult to stabilize in a medium-high adhesive force range and can achieve more stable adhesive force. The organic silicon pressure-sensitive adhesive prepared by the formula can be coated on common 50um PET, 100um PET, 25um PI and other base materials, and can obtain stable adhesive force.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (10)

1. An organic silicon pressure-sensitive adhesive comprises the following components in weight: 100 parts of methyl vinyl silicone rubber raw rubber, 10-70 parts of hydroxyl raw rubber, 100-300 parts of MQ resin, 100-300 parts of solvent, 0.5-1.5 parts of silicon-hydrogen cross-linking agent, 0.1-2.0 parts of inhibitor and 0.2-2.0 parts of POSS; wherein the mass ratio of the methyl MQ silicone resin to the vinyl MQ silicone resin in the MQ resin is 1:0.2-5.
2. The silicone pressure sensitive adhesive of claim 1 wherein the POSS has the structural formula:
Figure FDA0004034248920000011
the R functional groups are independently selected from hydroxyl, methoxy, ethoxy, preferably the R functional groups are hydroxyl or methoxy.
3. The silicone pressure sensitive adhesive of claim 1 or 2, wherein the POSS is one or more of dihydroxyhexamethoxy cage polysilsesquioxane, hydroxyheptamethoxy cage polysilsesquioxane, and dihydroxyhexamethoxy cage polysilsesquioxane.
4. A silicone pressure-sensitive adhesive as claimed in any one of claims 1 to 3, characterized in that the methyl vinyl silicone rubber raw rubber has a vinyl mass fraction of 0.03 to 1.5%, preferably 0.05 to 0.5%, and a molecular weight of 50 to 80 ten thousand, preferably 60 to 70 ten thousand.
5. The silicone pressure sensitive adhesive of any one of claims 1-4, wherein the methyl MQ silicone resin has an M/Q ratio of 0.5 to 1.0 and a molar mass of 2700 to 5000g/mol; and/or the M/Q ratio of the vinyl MQ silicon resin is 0.5-1.0, the mass fraction of vinyl is 0.5-2%, and the molar mass is 4000-5000 g/mol.
6. The silicone pressure sensitive adhesive of any one of claims 1-5, wherein the solvent is selected from at least one of toluene, ester solvents, ketone solvents, alkane solvents; preferably, the ester solvent comprises ethyl acetate, the ketone solvent comprises acetone, and the alkane solvent comprises heptane.
7. The silicone pressure-sensitive adhesive as claimed in any one of claims 1 to 6, wherein the silicone hydrogen crosslinking agent has a viscosity of 20 to 150mpa.s and is a hydrogen-containing silicone oil containing terminal hydrogen groups and side hydrogen groups, the mass fraction of total hydrogen groups being 0.7 to 1.6%.
8. The silicone pressure sensitive adhesive of any one of claims 1-7, wherein the inhibitor is selected from at least one of tetramethyl tetravinyl cyclotetrasiloxane, divinyl tetramethyl disiloxane, methyl acetylene alcohol, ethynyl cyclohexanol, methyl butynol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol.
9. The method for preparing the silicone pressure-sensitive adhesive according to any one of claims 1 to 8, comprising the steps of:
1) Adding methyl vinyl silicone rubber raw rubber, hydroxyl raw rubber, methyl MQ silicon resin, vinyl MQ silicon resin, inhibitor, solvent and POSS into a reaction kettle, and starting stirring to fully dissolve the raw rubber in the solvent;
2) Introducing nitrogen, stirring, slowly adding a catalyst accounting for 0.05-2% of the weight of the raw methyl vinyl silicone rubber after stirring uniformly, heating to 120-150 ℃, and carrying out reflux dehydration reaction for 3-5h until no water is generated;
3) Cooling to room temperature, adding a silicon-hydrogen crosslinking agent, stirring for 1-3 hours, and uniformly mixing to obtain the organosilicon pressure-sensitive adhesive with stable adhesive force in a medium-high adhesive force range.
10. The use of the silicone pressure-sensitive adhesive according to any one of claims 1 to 8 or the silicone pressure-sensitive adhesive prepared by the preparation method according to claim 9 in the field of high-end process protective films.
CN202310000461.8A 2023-01-03 2023-01-03 Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof Pending CN116218456A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310000461.8A CN116218456A (en) 2023-01-03 2023-01-03 Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310000461.8A CN116218456A (en) 2023-01-03 2023-01-03 Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116218456A true CN116218456A (en) 2023-06-06

Family

ID=86588437

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310000461.8A Pending CN116218456A (en) 2023-01-03 2023-01-03 Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116218456A (en)

Similar Documents

Publication Publication Date Title
CN110819261B (en) Organic silicon release agent with ultra-light release force and preparation method thereof
CN109880523B (en) High-temperature-resistant low-transfer organic silicon release agent and preparation method thereof
CN106753195B (en) Organic silicon pressure-sensitive adhesive and pressure-sensitive adhesive tape or film
CN107503231B (en) Application of vinyl silicone oil with hydroxyl at tail end as release force regulator in preparation of release agent, release agent and release film
CN103228751B (en) Contact panel adhesive composition, adhesive film and contact panel
CN113956837B (en) Non-stop printing and high-anchoring organic silicon pressure-sensitive adhesive, preparation method and application thereof
TW201546223A (en) Silicone pressure-sensitive adhesive composition having improved substrate adhesion and pressure-sensitive adhesive article
CN113956833B (en) Organosilicon pressure-sensitive adhesive for fingerprint-resistant glass, preparation method and application thereof
CN113549413A (en) Benzene-free solvent-type peelable pressure-sensitive adhesive and preparation method thereof
CN111423844A (en) Transferable pressure-sensitive adhesive, pressure-sensitive adhesive tape and application method of pressure-sensitive adhesive tape
JP2023512220A (en) Silicone coating composition and silicone release film containing the same
CN114854367A (en) Anti-fingerprint glass organic silicon pressure-sensitive adhesive and preparation method and application thereof
CN112940326A (en) Release film special for MLCC and preparation method thereof
CN114958295A (en) Ultralow-adhesive-force and low-climbing organic silicon pressure-sensitive adhesive as well as preparation method and application thereof
CN113845861A (en) Low-climbing organic silicon protective film and preparation method thereof
CN114058290A (en) Solvent-free organic silicon release agent with ultralow release force and preparation method thereof
CN109536085B (en) Preparation method of organic silicon modified polyacrylate pressure-sensitive adhesive and pressure-sensitive adhesive prepared by preparation method
CN116218456A (en) Organosilicon pressure-sensitive adhesive with stable adhesion in medium-high adhesion range, preparation method and application thereof
CN115181542B (en) Organic silicon pressure-sensitive adhesive, and product and preparation method thereof
WO2008062603A1 (en) Adhesive composition and adhesive film
CN115651602A (en) High-temperature-resistant addition type organic silicon pressure-sensitive adhesive composition and preparation method and application thereof
CN115785862A (en) Bio-based anti-warping acrylic pressure-sensitive adhesive and preparation method thereof
CN115637116A (en) High-temperature-resistant low-climbing protective film and preparation method thereof
JP2008063464A (en) Adhesive composition, adhesive film and method for producing the adhesive composition
KR101538447B1 (en) Release sheet

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination