CN113956833A - Organic silicon pressure-sensitive adhesive for anti-fingerprint glass, preparation method and application thereof - Google Patents
Organic silicon pressure-sensitive adhesive for anti-fingerprint glass, preparation method and application thereof Download PDFInfo
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- CN113956833A CN113956833A CN202111110893.1A CN202111110893A CN113956833A CN 113956833 A CN113956833 A CN 113956833A CN 202111110893 A CN202111110893 A CN 202111110893A CN 113956833 A CN113956833 A CN 113956833A
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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
- C09J11/08—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
- C09J7/30—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
- 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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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The invention discloses an organic silicon pressure-sensitive adhesive for anti-fingerprint glass, a preparation method and application thereof, wherein the novel organic silicon pressure-sensitive adhesive for anti-fingerprint glass comprises the following components in parts by weight: 10-20 parts of branched vinyl silicone oil, 20-70 parts of hydroxyl raw rubber, 40-70 parts of MQ silicone resin, 0.5-1.5 parts of silicon-hydrogen cross-linking agent, 0.4-1.0 part of inhibitor and 80-120 parts of solvent; the MQ resin comprises hydroxyl MQ silicon resin and vinyl MQ silicon resin, and the mass ratio is (10-1): (1-5). The organic silicon pressure-sensitive adhesive has better stripping force on the anti-fingerprint glass, the stripping force does not change obviously along with the time extension, the function of quickly removing bubbles can be met while the anti-fingerprint glass is bonded, and the organic silicon pressure-sensitive adhesive can be widely applied to the related fields of protective films for protecting the anti-fingerprint glass, protective films for electronic products or waste discharge films and the like.
Description
Technical Field
The invention relates to the technical field of organic silicon pressure-sensitive materials, in particular to an organic silicon pressure-sensitive adhesive which can be bonded with anti-fingerprint glass and has good stripping force and air discharge performance, a preparation method and application thereof.
Background
The silicone pressure-sensitive adhesive is an adhesive containing silicon elements, and not only has the pressure-sensitive property required by the pressure-sensitive adhesive, but also has a plurality of special properties, such as: (1) good adhesion to low surface energy materials; 2) the adhesive has outstanding high and low temperature resistance, can be used for a long time at the temperature of-50-200 ℃, and still keeps the bonding strength and flexibility at high temperature and low temperature; (3) the material has good chemical inertness, and has outstanding moisture resistance and electrical property; (4) good chemical resistance and solvent resistance; (5) the dielectric property is good.
With the rapid development of handheld electronic devices, the touch glass screen is more and more updated day by day, and the demand for protecting the screen is also continuously increased. Present glass touch screen need carry out surface treatment, and especially anti fingerprint coating's processing makes the screen more resistant dirty, more smooth for the water droplet angle of screen is bigger and bigger, and surface energy is lower and lower, and traditional protection film not only is difficult to stick tightly, still has the problem that air bubble is difficult to get rid of moreover when bonding anti fingerprint glass screen.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the organic silicon pressure-sensitive adhesive applied to the anti-fingerprint glass, the branched vinyl silicone oil is added in the formula, the anti-fingerprint glass has good stripping force and air bubble discharging performance, the stripping force is good in stability and does not attenuate, the preparation process is relatively simple, and the large-scale production is convenient to realize.
The invention also aims to provide a preparation method of the novel organic silicon pressure-sensitive adhesive for the anti-fingerprint glass.
The invention further aims to provide application of the organic silicon pressure-sensitive adhesive for the anti-fingerprint glass.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an organic silicon pressure-sensitive adhesive for anti-fingerprint glass comprises branched vinyl silicone oil, vinyl MQ silicone resin, hydroxyl raw rubber, hydroxyl MQ silicone resin, a silicon-hydrogen cross-linking agent, an inhibitor and a solvent; the components are as follows by weight: 10-20 parts of branched vinyl silicone oil, 20-70 parts of hydroxyl raw rubber, 40-70 parts of MQ silicone resin, 0.5-1.5 parts of silicon-hydrogen cross-linking agent, 0.4-1.0 part of inhibitor and 80-120 parts of solvent; wherein the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5).
In a particular embodiment, the branched vinyl silicone oil has a viscosity of 200-3000 mPa.s, preferably 500-1500 mPa.s; preferably, the mass content of vinyl in the branched vinyl silicone oil is 0.5-2%.
In a specific embodiment, the hydroxyl raw rubber has a molecular weight of 50 to 70 ten thousand.
In a specific embodiment, the M/Q ratio of the hydroxyl MQ silicon resin is 0.5-0.8, and the molar mass is 2700-5000 g/mol.
In a specific embodiment, the M/Q ratio of the vinyl MQ silicon resin is 0.5-0.8, the vinyl mass fraction is 0.5-2%, and the molar mass is 4000-5000 g/mol.
In a specific embodiment, the solvent is selected from any one or a combination of several of toluene, xylene, ester solvents, ketone solvents and alkane solvents.
In a specific embodiment, the viscosity of the hydrosilation crosslinking agent is 20 to 50mpa.s, and the hydrosilation crosslinking agent is hydrogen-containing silicone oil containing terminal hydrogen groups and side hydrogen groups, and the mass percentage of the terminal hydrogen groups and the side hydrogen groups is 0.7 to 1.6 wt%.
In a specific embodiment, the inhibitor is selected from any one or combination of tetramethyltetravinylcyclotetrasiloxane, divinyltetramethyldisiloxane, methylacetylene alcohol, ethynylcyclohexanol, methylbutynol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecyn-3-ol.
On the other hand, the preparation method of the organic silicon pressure-sensitive adhesive for the anti-fingerprint glass comprises the following steps:
1) adding a certain weight part of branched vinyl silicone oil, hydroxyl crude rubber, hydroxyl MQ silicon resin, vinyl MQ silicon resin, an inhibitor and a solvent into a reaction kettle, and stirring to fully dissolve and disperse the crude rubber in the solvent;
2) introducing nitrogen gas for stirring, slowly adding a catalyst accounting for 0.05-1% of the weight of the hydroxyl crude rubber after uniformly stirring, and then performing dehydration reaction at the reflux temperature of 120-150 ℃ for 3-5h until no water is generated; preferably, the catalyst is selected from any one of acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluorobenzene sulfonic acid or acidic diatomite.
3) And cooling to room temperature, adding a silicon-hydrogen cross-linking agent, stirring for 1-3 hours, and uniformly mixing to obtain the organic silicon pressure-sensitive adhesive for the anti-fingerprint glass.
On the other hand, the organic silicon pressure-sensitive adhesive for the anti-fingerprint glass is applied to the fields of protective films of the anti-fingerprint glass, protective films of electronic products or waste discharge films.
Compared with the prior art, the invention has the following beneficial effects:
1) compared with the traditional simple blending process, in the invention, the pressure-sensitive adhesive obtained by adding the branched vinyl silicone oil has good adhesive force stability, is protected by sticking a fluoroplastic release film, has no obvious attenuation on the peeling force of the anti-fingerprint screen after aging, and has the peeling force of less than 1000g/inch on a steel plate. The MQ silicon resin and the hydroxyl raw rubber are subjected to high-temperature polycondensation reaction, so that the shelf life of a product can be prolonged, the cohesive strength of the pressure-sensitive adhesive is improved, the temperature resistance and the stripping force stability of the product are improved, the stripping force of the product is adjusted by controlling the content of the MQ silicon resin and the content of vinyl, and a silicon-hydrogen cross-linking agent reacts with the vinyl under the action of a catalyst when the product is cured into a rubber film, so that the obtained pressure-sensitive adhesive has good stripping force against fingerprint glass, and meanwhile, the stripping force of a steel plate is not too high, and the gas discharge performance of the pressure-sensitive adhesive film is good.
2) The organic silicon pressure-sensitive adhesive prepared by the formula can be coated on common base materials of 50-micron PET, 100-micron PET, 80-micron SRF, TPU and the like, has higher stripping force against fingerprint glass, can reach 50g/inch, and has the steel plate stripping force less than 1000 g/inch.
3) The fingerprint-resistant glass organic silicon pressure-sensitive adhesive prepared by the invention has high strength, good stability of fingerprint-resistant glass peeling force, no attenuation, good exhaust performance and high light transmittance.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
An organic silicon pressure-sensitive adhesive for anti-fingerprint glass comprises a base adhesive component formula and a preparation method;
the base rubber component comprises 10-20 parts of branched vinyl silicone oil, 20-70 parts of hydroxyl raw rubber, 40-70 parts of MQ silicone resin, 0.5-1.5 parts of a silicon-hydrogen cross-linking agent, 0.4-1.0 part of an inhibitor and 80-120 parts of a solvent in parts by weight; the MQ silicon resin comprises hydroxyl MQ silicon resin and vinyl MQ silicon resin, and the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5).
The branched vinyl silicone oil has the following structural formula; specifically, the branched vinyl silicone oil has a viscosity of 200-3000 mPas, including, but not limited to, 200 mPas, 300 mPas, 400 mPas, 500 mPas, 800 mPas, 1000 mPas, 1200 mPas, 1500 mPas, 2000 mPas, 2500 mPas, 3000 mPas, preferably a viscosity of 500-1500 mPas. The mass content of vinyl in the branched vinyl silicone oil is 0.5-2%. Wherein the mass content of the vinyl is obtained by testing the near infrared spectroscopy. The branched vinyl silicone oil reacts with the silicon-hydrogen cross-linking agent under the action of the platinum catalyst, and the cured organic silicon pressure-sensitive adhesive has good stability for resisting the peeling force of fingerprint glass and low peeling force for a steel plate.
The preparation method of the branched vinyl silicone oil comprises the steps of hydrolytic condensation of phenyltrimethoxysilane and methylphenyldimethoxysilane, hydrolytic reaction of the phenyltrimethoxysilane and the methylphenyldimethoxysilane under the catalysis of acid, further dehydration condensation to obtain a hydroxyl-terminated T-shaped polysiloxane chain segment, adding a vinyl double-end socket to perform end-capping reaction when the chain segments reach a certain amount, and finally separating and purifying to obtain the branched vinyl silicone oil with the T structure.
In the preparation process of the branched vinyl silicone oil, the acid catalyst is selected from any one of concentrated sulfuric acid, acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluoro benzene sulfonic acid, acidic diatomite and the like, and concentrated sulfuric acid is preferred.
The preparation steps of the branched vinyl silicone oil are as follows:
1) adding a certain amount of water and concentrated sulfuric acid into a reaction flask, and stirring for a period of time at 40 ℃;
2) slowly dripping a proper amount of phenyltrimethoxysilane and a proper amount of methylphenyldimethoxysilane, heating to 50 ℃, and then preserving heat for 1 h;
3) distilling out theoretical amount of methanol generated in the step 2) at 80 ℃, adding a certain amount of toluene and potassium hydroxide aqueous solution, and refluxing for 5h at 130 ℃;
4) evaporating the toluene solvent under low pressure, and cooling to 70 deg.C;
5) adding a certain amount of tetramethylammonium hydroxide methanol solution and divinyl dimethyl disiloxane for end capping, stirring for 30min, heating to 90 ℃, and reacting for 5 h;
6) heating to 150 ℃, and finishing the reaction after 30 min;
7) washing with water, filtering, and rotary steaming to obtain the target product.
The reaction process involved in the preparation steps of the branched vinyl silicone oil of the present invention is as follows.
In the composition of the organic silicon pressure-sensitive adhesive for anti-fingerprint glass, the molecular weight of the hydroxyl MQ silicon resin is 2700-5000, such as, but not limited to 2700, 3000, 3200, 3500, 3800, 4000, 4300, 4500, 4750 and 5000; the molecular weight of the vinyl MQ silicone resin is 4000-5000, such as, but not limited to 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, wherein the vinyl content is 0.5-2% by mass, such as, but not limited to, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%. 10-30 parts of two MQ silicon resins, namely hydroxyl MQ silicon resin and vinyl MQ silicon resin, in the formula of the organic silicon pressure-sensitive adhesive are controlled, wherein the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5), preferably 10: 1, the pressure-sensitive adhesive can obtain good stripping force on the fingerprint-resistant glass, the stability of the stripping force on the fingerprint-resistant glass is good, and the stripping force on a steel plate is low.
In the composition of the organic silicon pressure-sensitive adhesive for the anti-fingerprint glass, the solvent is any one or combination of toluene, xylene, an ester solvent, a ketone solvent and an alkane solvent; wherein the ester solvent includes, for example, but is not limited to, ethyl acetate, the ketone solvent includes, for example, but is not limited to, acetone, and the alkane solvent includes, for example, but is not limited to, heptane.
In the composition of the organic silicon pressure-sensitive adhesive for anti-fingerprint glass, a catalyst used in the high-temperature condensation reaction is selected from any one of acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluorobenzene sulfonic acid or acidic diatomite, and preferably acetic acid.
The inhibitor in the invention is any one or any combination of several of tetramethyl tetravinylcyclotetrasiloxane, divinyl tetramethyl disiloxane, methyl acetylene alcohol, ethynyl cyclohexanol, methyl butynol, 3, 5-dimethyl-1-hexynyl-3-alcohol and 3-methyl-1-dodecyn-3-alcohol, and preferably ethynyl cyclohexanol.
In the composition of the organic silicon pressure-sensitive adhesive for anti-fingerprint glass, the hydrosilation cross-linking agent is hydrogen-based polysiloxane with viscosity of 20-50 mPa & s and hydrogen content of 0.7-1.6%, for example, the hydrogen content includes but is not limited to 0.7%, 0.8%, 0.9%, 1.0% and 1.55%.
In the invention, the hydroxyl silicone rubber of hydroxyl MQ silicone resin and hydroxyl raw rubber is subjected to high-temperature condensation reaction in advance, the resin and the raw rubber form an interpenetrating structure, so that the shelf life of the product can be prolonged, the viscosity change is small, the cohesive strength of the cured pressure-sensitive adhesive is improved, the temperature resistance and the stripping force stability of the product are improved, the stripping force required by the product is adjusted by controlling the content of the vinyl MQ silicone resin and the vinyl content, and a silicon-hydrogen cross-linking agent reacts with the vinyl under the action of a platinum catalyst when the adhesive film is cured, so that the stripping force of fingerprint glass is improved, and the stripping force of a steel plate is not too high, thereby ensuring that the pressure-sensitive adhesive film has good air exhaust performance.
The organic silicon pressure-sensitive adhesive prepared by the formula can be coated on common base materials such as 50-micron PET, 100-micron PET, 80-micron SRF, TPU and the like, has higher stripping force against fingerprint glass, and can reach 50g/inch, and the stripping force of a steel plate is less than 1000 g/inch; the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass prepared by the invention has high strength, good stability of the peeling force of the fingerprint-resistant glass, no attenuation, good exhaust performance and high light transmittance.
On the other hand, the preparation method of the anti-fingerprint glass organic silicon pressure-sensitive adhesive comprises the following steps:
1) adding the branched vinyl silicone oil, the vinyl MQ silicon resin, the hydroxyl raw rubber, the hydroxyl MQ silicon resin, the inhibitor and the solvent which are used for the anti-fingerprint glass pressure-sensitive adhesive into a reaction kettle, and stirring to fully dissolve and disperse the hydroxyl raw rubber in the solvent.
2) Introducing nitrogen gas, stirring, slowly adding a platinum catalyst accounting for 0.05-1% of the total amount of the crude rubber after uniformly stirring, and then performing dehydration reaction at the reflux temperature of 120-;
3) and cooling to room temperature, adding 0.5-1.5 parts of hydrosilation cross-linking agent, stirring for 1-3 hours, and uniformly mixing to obtain the anti-fingerprint glass organic silicon pressure-sensitive adhesive.
Specifically, for example, the preparation method of the base rubber component comprises the following steps: adding branched vinyl silicone oil with the viscosity of 200-3000mPa & s, vinyl MQ silicone resin, hydroxyl crude rubber, hydroxyl MQ silicone resin and an inhibitor into a reaction kettle, adding a diluent into the reaction kettle, fully dissolving and dispersing the crude rubber, adding a catalyst accounting for 0.05-1% of the total weight of the crude rubber into the reaction kettle, and performing high-temperature dehydration reaction in the reaction kettle for 3-5 hours under the protection of nitrogen; and cooling to room temperature, adding 0.5-1.5 parts of silicon hydrogen cross-linking agent, stirring for 1-3 hours, and uniformly mixing to obtain the anti-fingerprint glass organic silicon pressure-sensitive adhesive.
Wherein, the components of the formula are added according to the following weight portions: 10-20 parts of vinyl chloride silicone oil, 20-70 parts of hydroxyl raw rubber, 40-70 parts of MQ silicone resin, 0.5-1.5 parts of silicon-hydrogen cross-linking agent, 0.4-1.0 part of inhibitor and 80-120 parts of solvent; the MQ silicon resin comprises hydroxyl MQ silicon resin and vinyl MQ silicon resin, and the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5).
The principles and features of the present invention are described below in conjunction with specific embodiments, which are intended to illustrate only some embodiments of the invention and are not intended to limit the scope of the invention.
The following examples and comparative examples used the following sources of primary raw materials:
MQ resin: morning fly photoelectricity CF 808;
raw rubber: mixing and containing organic silicon;
xylene: chemical purification of julong;
ethynylcyclohexanol: alatin, analytically pure;
straight-chain vinyl silicone oil: mixing and containing organic silicon;
silicon hydrogen cross-linking agent: kexin silicone;
pt catalyst: helley, platinum content 4000 ppm.
The performance test method of the prepared organic silicon pressure-sensitive adhesive comprises the following steps:
1. the viscosity detection method is referred to GB/T10247-2008;
2. the peeling force detection method is referred to GB/T2792-1998;
3. the boiling performance detection method comprises the following steps: and (3) putting the pressure-sensitive adhesive tape (the thickness of the dry pressure-sensitive adhesive is 30-40 mu m) which is coated on the SRF film and is completely cured into boiled distilled water, continuously boiling for 2 hours, and taking out the pressure-sensitive adhesive tape, wherein the edge of the adhesive layer is not degummed, and the powder is not dropped, so that the pressure-sensitive adhesive tape is qualified.
4. The test is placed for 3 days to test the stability of the peeling force of the fingerprint glass, and the peeling force test is referred to GB/T2792-1998.
Preparation example preparation of branched vinyl Silicone oil
1) Adding 900g of water and 100g of concentrated sulfuric acid into a reaction flask, and stirring for 1h at 40 ℃ until the temperature is constant;
2) slowly dropwise adding 100g of phenyltrimethoxysilane and 100g of methylphenyldimethoxysilane, heating to 50 ℃, and then preserving heat for 1 h;
3) distilling off theoretical amount of methanol generated in the step 2) at 80 ℃, adding 500g of toluene and 100g of potassium hydroxide aqueous solution, and refluxing for 5h at 130 ℃;
4) evaporating the toluene solvent under low pressure, and cooling to 70 deg.C;
5) adding 10g of tetramethylammonium hydroxide methanol solution and 10g of divinyl dimethyl disiloxane for end capping, stirring for 30min, heating to 90 ℃, and reacting for 5 h;
6) heating to 150 ℃, and finishing the reaction after 30 min;
7) washing with water, filtering, and rotary steaming to obtain the target product.
Example 1
1) Adding 20g of branched vinyl silicone oil, 10g of vinyl MQ silicon resin, 20g of hydroxyl crude rubber, 60g of hydroxyl MQ silicon resin, 80g of dimethylbenzene and 0.8g of ethynyl cyclohexanol into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 60 ten thousand; the viscosity of the branched vinyl silicone oil is 500 mPa.s, and the vinyl mass fraction is 1.5%; the ratio of the hydroxyl MQ silicon resin to the vinyl MQ is 6: 1;
2) introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene after stirring uniformly, slowly adding, and then reacting for 4 hours at 150 ℃ under reflux dehydration;
3) cooling to room temperature, adding 1.5g of silicon-hydrogen cross-linking agent, and uniformly stirring to obtain a pressure-sensitive adhesive base adhesive 1;
4) 0.5g of anchoring agent and 100g of toluene are added into 100g of base rubber 1, 1.5g of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns after uniform stirring, the SRF substrate is placed in an oven at 150 ℃ for 2min to be cured, a fluoroplastic release film is attached, and the performance is tested, wherein the results are shown in Table 1.
Example 2
1) Adding 15g of branched vinyl silicone oil, 10g of vinyl MQ silicon resin, 25g of hydroxyl crude rubber, 60g of hydroxyl MQ silicon resin, 80g of dimethylbenzene and 0.8g of ethynyl cyclohexanol into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 62 ten thousand; the viscosity of the branched vinyl silicone oil is 1000 mPa.s, the mass fraction of the vinyl is 1.5%, and the ratio of the hydroxyl MQ silicone resin to the vinyl MQ is 6: 1;
2) introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene after stirring uniformly, slowly adding, and then reacting for 4 hours at 150 ℃ under reflux dehydration;
3) cooling to room temperature, adding 1.5g of silicon-hydrogen cross-linking agent, and uniformly stirring to obtain a pressure-sensitive adhesive base adhesive 2;
4) 0.5g of anchoring agent and 100g of ethyl acetate are added into 100g of base rubber 2, 1.5g of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns after uniform stirring, the SRF substrate is placed in an oven at 150 ℃ for 2min to be cured, a fluoroplastic release film is attached, and the performance is tested, wherein the results are shown in Table 1.
Example 3
1) Adding 10g of branched vinyl silicone oil, 70g of hydroxyl crude rubber, 30g of hydroxyl MQ silicone resin, 10g of vinyl MQ silicone resin, 80g of xylene and 0.8g of divinyl tetramethyl disiloxane into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 70 ten thousand; the viscosity of the branched vinyl silicone oil is 1000 mPa.s, and the vinyl mass fraction is 0.8%; the ratio of the hydroxyl MQ silicon resin to the vinyl MQ is 3: 1;
2) introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene after stirring uniformly, slowly adding, and then reacting for 4 hours at 150 ℃ under reflux dehydration;
3) cooling to room temperature, adding 0.5g of silicon-hydrogen crosslinking agent, and uniformly stirring to obtain a pressure-sensitive adhesive base adhesive 3;
4) 0.5g of anchoring agent and 100g of toluene are added into 100g of base rubber 3, 1.5g of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns after uniform stirring, the SRF substrate is placed in an oven at 150 ℃ for 2min to be cured, a fluoroplastic release film is attached, and the performance is tested, wherein the results are shown in Table 1.
Example 4
1) Adding 10g of branched vinyl silicone oil, 70g of hydroxyl crude rubber, 35g of hydroxyl MQ silicon resin, 5g of vinyl MQ silicon resin, 80g of dimethylbenzene and 0.8g of ethynyl cyclohexanol into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 50w, the viscosity of the branched vinyl silicone oil is 1500mPa & s, and the mass fraction of vinyl is 1.5%; the ratio of hydroxyl MQ silicon resin to vinyl MQ is 7: 1;
2) introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene after stirring uniformly, slowly adding, and then reacting for 4 hours at 150 ℃ under reflux dehydration;
3) cooling to room temperature, adding 1.0g of silicon-hydrogen crosslinking agent, and uniformly stirring to obtain a pressure-sensitive adhesive base adhesive 4;
4) 0.5g of anchoring agent and 100g of toluene are added into 100g of base rubber 4, 1.5g of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns after uniform stirring, the SRF substrate is placed in an oven at 150 ℃ for 2min to be cured, a fluoroplastic release film is attached, and the performance is tested, wherein the results are shown in Table 1.
Example 5
1) Adding 10g of branched vinyl silicone oil, 70g of hydroxyl crude rubber, 8g of hydroxyl MQ silicon resin, 32g of vinyl MQ silicon resin, 80g of dimethylbenzene and 0.8g of ethynyl cyclohexanol into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 60w, the viscosity of the branched vinyl silicone oil is 1500mPa & s, and the mass fraction of vinyl is 1.5%; the ratio of the hydroxyl MQ silicon resin to the vinyl MQ is 1: 4;
2) introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene after stirring uniformly, slowly adding, and then reacting for 4 hours at 150 ℃ under reflux dehydration;
3) cooling to room temperature, adding 1.5g of silicon-hydrogen cross-linking agent, and uniformly stirring to obtain a pressure-sensitive adhesive base adhesive 5;
4) 0.5g of anchoring agent and 100g of toluene are added into 100g of base rubber 5, 1.5g of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns after uniform stirring, the SRF substrate is placed in an oven at 150 ℃ for 2min to be cured, a fluoroplastic release film is attached, and the performance is tested, wherein the results are shown in Table 1.
Example 6
1) Adding 20g of branched vinyl silicone oil, 20g of hydroxyl crude rubber, 30g of hydroxyl MQ silicon resin, 10g of vinyl MQ silicon resin, 80g of dimethylbenzene and 0.8g of ethynyl cyclohexanol into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 60w, the viscosity of the branched vinyl silicone oil is 500mPa & s, and the mass fraction of vinyl is 1.5%; the ratio of the hydroxyl MQ silicon resin to the vinyl MQ is 3: 1;
2) introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene after stirring uniformly, slowly adding, and then reacting for 4 hours at 150 ℃ under reflux dehydration;
3) cooling to room temperature, adding 1.5g of silicon-hydrogen cross-linking agent, and uniformly stirring to obtain a pressure-sensitive adhesive base adhesive 6;
4) 0.5g of anchoring agent and 100g of toluene are added into 100g of base rubber 6, 1.5g of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns after uniform stirring, the SRF substrate is placed in an oven at 150 ℃ for 2min to be cured, a fluoroplastic release film is attached, and the performance is tested, wherein the results are shown in Table 1.
Comparative example 1 conventional pressure sensitive adhesive
Adding 100g of vinyl silicone rubber crude rubber, 140g of methyl MQ silicone resin, 20g of vinyl MQ silicone resin, 150g of dimethylbenzene, 0.8g of ethynylcyclohexanol and 1.5g of silicon-hydrogen cross-linking agent into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the raw vinyl silicone rubber is 60 ten thousand, the mass fraction of the vinyl is 0.05 percent, and the ratio of the methyl MQ silicone resin to the vinyl MQ is 7: 1; stirring for 4h to obtain the pressure-sensitive adhesive base adhesive 7.
0.5 part of anchoring agent and 100 parts of toluene are added into 100g of pressure-sensitive adhesive base adhesive 7, after uniform stirring, 1.5 parts of platinum catalyst with the platinum content of 4000ppm are added, the mixture is coated on an SRF substrate with the thickness of 80 microns, the SRF substrate is placed in an oven at 150 ℃ for 2min for curing, the adhesive surface is covered with a fluoroplastic release film, and the performance is tested, wherein the results are shown in Table 1.
Comparative example 2 conventional pressure sensitive adhesive with addition of straight-chain vinyl silicone oil
Adding 20g of straight-chain vinyl silicone oil, 10g of vinyl MQ silicon resin, 20g of hydroxyl crude rubber, 60g of hydroxyl MQ silicon resin, 80g of dimethylbenzene, 0.8g of ethynylcyclohexanol and 1.5g of silicon-hydrogen cross-linking agent into a reaction kettle, and stirring for dissolving; wherein the molecular weight of the hydroxyl raw rubber is 60 ten thousand; the viscosity of the straight-chain vinyl silicone oil is 500 mPa.s, and the mass fraction of vinyl is 1.5%; the ratio of the hydroxyl MQ silicon resin to the vinyl MQ is 6: 1; stirring for 4h to obtain the pressure-sensitive adhesive base adhesive 8.
0.5 part of anchoring agent and 100 parts of toluene are added into 100g of pressure-sensitive adhesive base adhesive 8, 1.5 parts of platinum catalyst with the platinum content of 4000ppm is added after uniform stirring, the mixture is coated on an SRF substrate with the thickness of 80 microns, the SRF substrate is placed in an oven at 150 ℃ for 2min for curing, the adhesive surface is covered with a fluoroplastic release film, and the performance is tested, wherein the results are shown in Table 1.
The test performance data of the silicone pressure-sensitive adhesive 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 1-2
As can be seen from the table, the pressure-sensitive adhesive obtained by adding the branched vinyl silicone oil has good adhesive force stability, is protected by a fluorine plastic film, has no obvious attenuation on the peeling force of resisting a fingerprint screen after aging, and has the peeling force of less than 1000g/inch on a steel plate. Compared with the traditional simple blending process, in the invention, the MQ silicon resin and the hydroxyl raw rubber are subjected to high-temperature polycondensation reaction, so that the quality guarantee period of the product can be prolonged, the cohesive strength of the pressure-sensitive adhesive is improved, the temperature resistance and the stripping force stability of the product are improved, the stripping force of the product is adjusted by controlling the content of the MQ silicon resin and the content of vinyl, and the silicon-hydrogen cross-linking agent reacts with the vinyl under the action of a platinum catalyst when the pressure-sensitive adhesive is solidified into an adhesive film, so that the obtained pressure-sensitive adhesive has good stripping force for resisting fingerprint glass, and meanwhile, the stripping force for a steel plate is not too high, and the air exhaust property of the pressure-sensitive adhesive film is good.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. An organic silicon pressure-sensitive adhesive for anti-fingerprint glass is characterized by comprising branched vinyl silicone oil, vinyl MQ silicone resin, hydroxyl raw rubber, hydroxyl MQ silicone resin, a silicon-hydrogen cross-linking agent, an inhibitor and a solvent; the components are as follows by weight: 10-20 parts of branched vinyl silicone oil, 20-70 parts of hydroxyl raw rubber, 40-70 parts of MQ silicone resin, 0.5-1.5 parts of silicon-hydrogen cross-linking agent, 0.4-1.0 part of inhibitor and 80-120 parts of solvent; wherein the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5).
2. The organic silicon pressure-sensitive adhesive for the anti-fingerprint glass as claimed in claim 1, wherein the viscosity of the branched vinyl silicone oil is 200-3000 mPa-s, preferably 500-1500 mPa-s; preferably, the mass content of vinyl in the branched vinyl silicone oil is 0.5-2%.
3. The organic silicon pressure-sensitive adhesive for the anti-fingerprint glass as claimed in claim 1, wherein the molecular weight of the hydroxyl raw rubber is 50-70 ten thousand.
4. The organic silicon pressure-sensitive adhesive for the fingerprint resistant glass as claimed in claim 1, wherein the M/Q ratio of the hydroxyl MQ silicon resin is 0.5-0.8, and the molar mass is 2700-5000 g/mol.
5. The organic silicon pressure-sensitive adhesive for the anti-fingerprint glass as claimed in claim 1, wherein the M/Q ratio of the vinyl MQ silicon resin is 0.5-0.8, the vinyl mass fraction is 0.5-2%, and the molar mass is 4000-5000 g/mol.
6. The organic silicon pressure-sensitive adhesive for the anti-fingerprint glass according to claim 1, wherein the solvent is selected from any one or a combination of several of toluene, xylene, ester solvents, ketone solvents and alkane solvents.
7. The organic silicon pressure-sensitive adhesive for the anti-fingerprint glass according to claim 1, wherein the viscosity of the silicon hydrogen cross-linking agent is 20-50 mPa.s, and the silicon hydrogen cross-linking agent is hydrogen-containing silicone oil containing terminal hydrogen groups and side hydrogen groups, and the mass percentage content of the terminal hydrogen groups and the side hydrogen groups is 0.7-1.6 wt%.
8. The silicone pressure-sensitive adhesive for fingerprint resistant glass according to claim 1, wherein the inhibitor is selected from any one or a combination of tetramethyltetravinylcyclotetrasiloxane, divinyltetramethyldisiloxane, methylacetylene alcohol, ethynylcyclohexanol, methylbutynol, 3, 5-dimethyl-1-hexyn-3-ol, and 3-methyl-1-dodecyn-3-ol.
9. The preparation method of the organic silicon pressure-sensitive adhesive for the fingerprint resistant glass as described in any one of claims 1 to 8, characterized by comprising the following steps:
1) adding a certain weight part of branched vinyl silicone oil, hydroxyl crude rubber, hydroxyl MQ silicon resin, vinyl MQ silicon resin, an inhibitor and a solvent into a reaction kettle, and stirring to fully dissolve and disperse the crude rubber in the solvent;
2) introducing nitrogen gas for stirring, slowly adding a catalyst accounting for 0.05-1% of the weight of the hydroxyl crude rubber after uniformly stirring, and then performing dehydration reaction at the reflux temperature of 120-150 ℃ for 3-5h until no water is generated; preferably, the catalyst is selected from any one of acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluorobenzene sulfonic acid or acidic diatomite.
3) And cooling to room temperature, adding a silicon-hydrogen cross-linking agent, stirring for 1-3 hours, and uniformly mixing to obtain the organic silicon pressure-sensitive adhesive for the anti-fingerprint glass.
10. Use of the silicone pressure-sensitive adhesive for anti-fingerprint glass 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 protective films for anti-fingerprint glass, protective films for electronic products or waste films.
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