CN113956833B - Organosilicon pressure-sensitive adhesive for fingerprint-resistant glass, preparation method and application thereof - Google Patents

Organosilicon pressure-sensitive adhesive for fingerprint-resistant glass, preparation method and application thereof Download PDF

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CN113956833B
CN113956833B CN202111110893.1A CN202111110893A CN113956833B CN 113956833 B CN113956833 B CN 113956833B CN 202111110893 A CN202111110893 A CN 202111110893A CN 113956833 B CN113956833 B CN 113956833B
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sensitive adhesive
fingerprint
pressure
vinyl
hydroxyl
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CN113956833A (en
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章琦
衣彦林
程继业
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Wanhua Chemical Group Co Ltd
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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
    • 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
    • C09J7/30—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
    • 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

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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 a silicon-hydrogen cross-linking agent, 0.4-1.0 parts of an inhibitor and 80-120 parts of a solvent; wherein 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 good stripping force on the anti-fingerprint glass, the stripping force does not obviously change along with the time extension, the effect of rapidly 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 protecting the anti-fingerprint glass, protecting films of electronic products, waste films and the like.

Description

Organosilicon pressure-sensitive adhesive for fingerprint-resistant glass, 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 which can be bonded with fingerprint-resistant glass and has good stripping force and exhaust property, a preparation method and application thereof.
Background
An organosilicon pressure-sensitive adhesive is an adhesive containing silicon elements, which not only has the pressure-sensitive properties necessary for pressure-sensitive adhesives, but also has a number of special properties, such as: (1) good adhesion to low surface energy materials; 2) The outstanding high and low temperature resistance can be used for a long time between 50 ℃ below zero and 200 ℃, and the bonding strength and flexibility of the adhesive can be still maintained at high temperature and low temperature; (3) The coating has good chemical inertness and outstanding moisture resistance and electrical property; (4) good chemical resistance and solvent resistance; (5) good dielectric properties.
With the rapid development of handheld electronic devices, touch glass screens are updated more and more day-to-day, and the protection requirements for the screens are also increased. The existing glass touch screen is required to be subjected to surface treatment, particularly the treatment of the anti-fingerprint coating enables the screen to be more resistant to dirt and smoother, the water drop angle of the screen is larger and larger, the surface energy is lower and lower, the traditional protective film is difficult to adhere tightly, and the problem that air bubbles are difficult to remove when the anti-fingerprint glass screen is adhered is also existed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the organic silicon pressure-sensitive adhesive applied to the fingerprint-resistant glass, wherein branched vinyl silicone oil is added in the formula, so that the fingerprint-resistant glass has good stripping force and bubble-discharging performance, the stripping force stability is good, the attenuation is avoided, and the preparation process is relatively simple, thereby being convenient for realizing large-scale production.
The invention also aims to provide a preparation method of the novel organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass.
It is a further object of the present invention to provide the use of such silicone pressure sensitive adhesives for fingerprint resistant glass.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
an organosilicon pressure-sensitive adhesive for fingerprint-resistant glass comprises branched vinyl silicone oil, vinyl MQ silicone resin, hydroxyl raw rubber, hydroxyl MQ silicone resin, a silicon-hydrogen crosslinking agent, an inhibitor and a solvent; the components in parts by weight are: 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 parts of an inhibitor and 80-120 parts of a solvent; wherein, the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5).
In a specific embodiment, the branched vinyl silicone oil has a viscosity of 200 to 3000 mPas, preferably 500 to 1500 mPas; preferably, the mass content of vinyl in the branched vinyl silicone oil is 0.5-2%.
In a specific embodiment, the molecular weight of the hydroxypivalent is 50 to 70 ten thousand.
In a specific embodiment, the hydroxyl MQ silicone resin has an M/Q ratio of 0.5 to 0.8 and a molar mass of 2700 to 5000g/mol.
In a specific embodiment, the vinyl MQ silicone resin has an M/Q ratio of 0.5 to 0.8, a vinyl mass fraction of 0.5 to 2, and a molar mass of 4000 to 5000g/mol.
In a specific embodiment, the solvent is selected from any one or a combination of several of toluene, xylene, ester solvents, ketone solvents, alkane solvents.
In a specific embodiment, 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 0.7-1.6wt%.
In a specific embodiment, the inhibitor is selected from any one or a combination of several of tetramethyl tetra-vinyl cyclotetrasiloxane, divinyl tetra-methyl disiloxane, methyl ethynyl alcohol, ethynyl cyclohexanol, methyl butynyl alcohol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol.
On the other hand, the preparation method of the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass comprises the following steps of:
1) Adding a certain weight part of branched vinyl silicone oil, hydroxyl raw 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 raw rubber in the solvent;
2) Introducing nitrogen, stirring, slowly adding a catalyst accounting for 0.05-1% of the weight of the hydroxyl crude rubber after stirring uniformly, and then dehydrating at a 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, trifluoro benzene sulfonic acid or acid diatomite.
3) And cooling to room temperature, adding a silicon-hydrogen crosslinking agent, stirring for 1-3 hours, and uniformly mixing to obtain the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass.
In yet another aspect, the application of the aforementioned silicone pressure-sensitive adhesive for anti-fingerprint glass in the fields of anti-fingerprint glass protective films, electronic product protective films or waste films.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with the traditional simple blending process, the pressure-sensitive adhesive obtained by adding the branched vinyl silicone oil has good adhesive force stability, is protected by the fluoroplastic release film, has no obvious attenuation on the peeling force of an anti-fingerprint screen after aging, and has the peeling force smaller than 1000g/inch on a steel plate. The MQ silicone 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 peeling force stability of the product are improved, the peeling force of the product is regulated by controlling the content of the MQ silicone resin and the vinyl content, and when the product is solidified into a glue film, under the action of a catalyst, the silicon-hydrogen cross-linking agent reacts with the vinyl, so that the obtained pressure-sensitive adhesive has good peeling force against fingerprint glass, and the peeling force against a steel plate is not too high, so that the pressure-sensitive adhesive film has good air exhaust property.
2) The organic silicon pressure-sensitive adhesive prepared by the formula can be coated on common 50-mu m PET, 100-mu m PET, 80-mu m SRF, TPU and other base materials, has higher stripping force against fingerprint glass, can reach 50g/inch, and has the steel plate stripping force smaller than 1000g/inch.
3) The anti-fingerprint glass organic silicon pressure-sensitive adhesive prepared by the invention has high strength, good stability against stripping force of the anti-fingerprint glass, no attenuation, good exhaust performance and high light transmittance.
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.
An organosilicon pressure-sensitive adhesive for fingerprint-resistant glass comprises a base adhesive component formula composition and a preparation method;
the base adhesive comprises, by weight, 10-20 parts of branched vinyl silicone oil, 20-70 parts of hydroxyl crude rubber, 40-70 parts of MQ silicone resin, 0.5-1.5 parts of a silicone-hydrogen cross-linking agent, 0.4-1.0 part of an inhibitor and 80-120 parts of a solvent; wherein 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).
Wherein, the structural formula of the branched vinyl silicone oil is as follows; in particular, the viscosity of the branched vinyl silicone oil is 200-3000 mPas, including for example 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 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 through a 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 against fingerprint glass stripping force and low stripping force on a steel plate.
Figure BDA0003273970830000051
The preparation method of the branched vinyl silicone oil comprises the steps of carrying out hydrolytic condensation on phenyl trimethoxy silane and methyl phenyl dimethoxy silane, carrying out hydrolytic reaction on the phenyl trimethoxy silane and the methyl phenyl dimethoxy silane under the catalysis of acid, further carrying out dehydration condensation to obtain a hydroxyl-terminated T-shaped polysiloxane chain segment, adding a vinyl double-end socket to carry out end-capping reaction when the chain segments reach a certain number, and finally separating and purifying to obtain the branched vinyl silicone oil with a 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-benzenesulfonic acid, acid diatomite and the like, and is preferably concentrated sulfuric acid.
The preparation steps of the branched vinyl silicone oil of the invention 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 phenyl trimethoxy silane and a proper amount of methyl phenyl dimethoxy silane, heating to 50 ℃, and preserving heat for 1h;
3) Steaming out a theoretical amount of methanol generated by hydrolysis in the step 2) at 80 ℃, adding a certain amount of toluene and potassium hydroxide aqueous solution, and refluxing for 5 hours at 130 ℃;
4) Evaporating toluene solvent under low pressure, and cooling to 70 ℃;
5) Adding a certain amount of tetramethyl ammonium hydroxide methanol solution and divinyl dimethyl disiloxane for end capping, stirring for 30min, heating to 90 ℃, and reacting for 5h;
6) Heating to 150 ℃, and ending 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 step of the branched vinyl silicone oil of the present invention is as follows.
Figure BDA0003273970830000061
In the composition of the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass, the molecular weight of the hydroxyl MQ silicone resin is 2700-5000, and the hydroxyl MQ silicone resin comprises 2700, 3000, 3200, 3500, 3800, 4000, 4300, 4500, 4750 and 5000; the vinyl MQ silicone resin has a molecular weight of 4000 to 5000, including for example but not limited to 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, wherein the vinyl mass content is 0.5 to 2%, including for example but not limited to 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%. 10-30 parts of hydroxyl MQ silicon resin and vinyl MQ silicon resin in the organic silicon pressure-sensitive adhesive formula 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 of the fingerprint-resistant glass is good, and the stripping force of the pressure-sensitive adhesive 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 a combination of a plurality of toluene, dimethylbenzene, ester solvents, ketone solvents and alkane solvents; wherein the ester solvents include, for example, but are not limited to, ethyl acetate, the ketone solvents include, for example, but are not limited to, acetone, and the alkane solvents include, for example, but are not limited to, heptane.
In the composition of the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass, the catalyst used in the high-temperature condensation reaction is any one selected from acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluoro benzene sulfonic acid or acid diatomite, and acetic acid is preferable.
The inhibitor used in the invention is any one or a combination of more than one of tetramethyl tetravinyl cyclotetrasiloxane, divinyl tetramethyl disiloxane, methyl ethynyl alcohol, ethynyl cyclohexanol, methyl butynyl alcohol, 3, 5-dimethyl-1-hexynyl-3-alcohol and 3-methyl-1-dodecyn-3-alcohol, and is preferably ethynyl cyclohexanol.
In the composition of the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass, the silicon hydrogen crosslinking agent is hydrogen polysiloxane with the viscosity of 20-50 mPa.s and the hydrogen content of 0.7-1.6%, for example, the hydrogen content comprises, but is not limited to, 0.7%, 0.8%, 0.9%, 1.0% and 1.55%.
In the invention, the hydroxyl silicone rubber, namely hydroxyl MQ silicone resin and hydroxyl raw rubber, is subjected to high-temperature condensation reaction in advance, the resin and raw rubber form an interpenetrating structure, so that the quality guarantee period 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 peeling force stability of the product are improved, the peeling force required by the product is regulated by controlling the content of the vinyl MQ silicone resin and the vinyl content, and when the product is cured into a glue film, under the action of a platinum catalyst, the silicon hydrogen cross-linking agent reacts with the vinyl, the peeling force of the anti-fingerprint glass is improved, and meanwhile, the peeling force of the steel plate is not too high, so that the pressure-sensitive adhesive glue film has good air exhaust property.
The organic silicon pressure-sensitive adhesive prepared by the formula can be coated on common 50-mu m PET, 100-mu m PET, 80-mu m SRF, TPU and other base materials, has high stripping force against fingerprint glass, can reach 50g/inch, and has the steel plate stripping force smaller than 1000g/inch; the organic silicon pressure-sensitive adhesive of the anti-fingerprint glass prepared by the invention has high strength, good stability of the anti-fingerprint glass stripping force, no attenuation, good exhaust performance and high light transmittance.
On the other hand, the preparation method of the fingerprint-resistant glass organic silicon pressure-sensitive adhesive comprises the following steps:
1) Adding the branched vinyl silicone oil, vinyl MQ silicone resin, hydroxyl raw rubber, hydroxyl MQ silicone resin, inhibitor and solvent for the fingerprint-resistant 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, stirring, slowly adding a platinum catalyst accounting for 0.05-1% of the total amount of raw rubber after stirring uniformly, and then dehydrating at the reflux temperature of 120-150 ℃ for 3-5h until no water is generated;
3) 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 organosilicon pressure-sensitive adhesive.
Specifically, for example, the preparation method of the base adhesive component comprises the following steps: adding branched vinyl silicone oil with the viscosity of 200-3000 mPas, vinyl MQ silicone resin, hydroxyl crude rubber, hydroxyl MQ silicone resin and inhibitor into a reaction kettle, adding a diluting solvent into the reaction kettle, fully dissolving and dispersing the crude rubber, adding a catalyst accounting for 0.05-1% of the total amount of the crude rubber into the reaction kettle, and carrying out high-temperature dehydration reaction in the reaction kettle for 3-5 hours under the condition of nitrogen protection; and (3) cooling the mixture to room temperature, adding 0.5 to 1.5 parts of a silicon-hydrogen crosslinking agent, stirring the mixture for 1 to 3 hours, and uniformly mixing the mixture to obtain the organic silicon pressure-sensitive adhesive of the anti-fingerprint glass.
Wherein, the components of the formula are added according to the following weight portions: 10-20 parts of 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 parts of an inhibitor and 80-120 parts of a solvent; wherein 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 connection with specific embodiments, which are provided for illustration of some embodiments of the invention and are not intended to limit the scope of the invention.
The main raw material sources used in the following examples and comparative examples are as follows:
MQ resin: morning fly CF808;
raw rubber: combining and containing organic silicon;
xylene: chemical, analytical grade;
ethynyl cyclohexanol: aladine, analytically pure;
linear vinyl silicone oil: combining and containing organic silicon;
silicon hydrogen cross-linking agent: a keunfortunately silicone;
pt catalyst: he Lishi the platinum content is 4000ppm.
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 peel force detection method is described in GB/T2792-1998;
3. the water boiling performance detection method comprises the following steps: and (3) putting the pressure-sensitive adhesive tape (the thickness of the 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 does not fall off powder, thus obtaining the qualified pressure-sensitive adhesive tape.
4. The stability against fingerprint glass peel force was tested by standing for 3 days, peel force test is referred to GB/T2792-1998.
Preparation example preparation of branched vinyl Silicone oil
1) 900g of water and 100g of concentrated sulfuric acid are added into a reaction flask, and stirred at 40 ℃ for 1h until the temperature is constant;
2) Slowly dropwise adding 100g of phenyl trimethoxy silane and 100g of methylphenyl dimethoxy silane, heating to 50 ℃, and preserving heat for 1h;
3) Steaming out the theoretical amount of methanol generated by the hydrolysis in the step 2) at 80 ℃, adding 500g of toluene and 100g of potassium hydroxide aqueous solution, and refluxing for 5 hours at 130 ℃;
4) Evaporating toluene solvent under low pressure, and cooling to 70 ℃;
5) Adding 10g of tetramethyl ammonium hydroxide methanol solution and 10g of divinyl dimethyl disiloxane for end capping, stirring for 30min, heating to 90 ℃, and reacting for 5h;
6) Heating to 150 ℃, and ending 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 silicone resin, 20g of hydroxyl raw rubber, 60g of hydroxyl MQ silicone resin and 80g of xylene, and adding 0.8g of ethynyl cyclohexanol into a reaction kettle, stirring and dissolving; wherein, the molecular weight of the hydroxyl raw rubber is 60 ten thousand; the viscosity of the branched vinyl silicone oil is 500 mPas, and the mass fraction of vinyl is 1.5%; 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, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) Cooling to room temperature, adding 1.5g of a silicon-hydrogen cross-linking agent, and uniformly stirring to obtain pressure-sensitive adhesive 1;
4) To 100g of base adhesive 1, 0.5g of anchoring agent and 100g of toluene were added, after stirring uniformly, 1.5g of platinum catalyst with 4000ppm of platinum content was added, after stirring uniformly, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, a fluoroplastic release film was attached, and the performance was tested, and the results are shown in Table 1.
Example 2
1) 15g of branched vinyl silicone oil, 10g of vinyl MQ silicone resin, 25g of hydroxyl crude rubber, 60g of hydroxyl MQ silicone resin and 80g of xylene, and 0.8g of ethynyl cyclohexanol are added into a reaction kettle, stirred and dissolved; wherein, the molecular weight of the hydroxyl raw rubber is 62 ten thousand; the viscosity of the branched vinyl silicone oil is 1000 mPas, the mass fraction of 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, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) Cooling to room temperature, adding 1.5g of a silicon-hydrogen cross-linking agent, and uniformly stirring to obtain pressure-sensitive adhesive base adhesive 2;
4) To 100g of base adhesive 2, 0.5g of anchoring agent and 100g of ethyl acetate were added, after stirring uniformly, 1.5g of platinum catalyst with 4000ppm of platinum content was added, after stirring uniformly, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, a fluoroplastic release film was attached, and the performance was tested, and the results are shown in Table 1.
Example 3
1) 10g of branched vinyl silicone oil, 70g of hydroxyl raw rubber, 30g of hydroxyl MQ silicone resin, 10g of vinyl MQ silicone resin and 80g of dimethylbenzene, and 0.8g of divinyl tetramethyl disiloxane are added into a reaction kettle and stirred for dissolution; wherein, the molecular weight of the hydroxyl raw rubber is 70 ten thousand; the viscosity of the branched vinyl silicone oil is 1000 mPas, and the mass fraction of vinyl is 0.8%; the ratio of the hydroxyl MQ silicone resin to the vinyl MQ is 3:1;
2) Introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) Cooling to room temperature, adding 0.5g of a silicon-hydrogen cross-linking agent, and uniformly stirring to obtain pressure-sensitive adhesive base adhesive 3;
4) To 100g of base adhesive 3, 0.5g of anchoring agent and 100g of toluene were added, after stirring uniformly, 1.5g of platinum catalyst with 4000ppm of platinum content was added, after stirring uniformly, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, a fluoroplastic release film was attached, and the performance was tested, and the results are shown in Table 1.
Example 4
1) 10g of branched vinyl silicone oil, 70g of hydroxyl raw rubber, 35g of hydroxyl MQ silicone resin, 5g of vinyl MQ silicone resin and 80g of xylene, and 0.8g of ethynyl cyclohexanol are added into a reaction kettle, stirred and dissolved; wherein the molecular weight of the hydroxyl raw rubber is 50w, the viscosity of the branched vinyl silicone oil is 1500 mPa.s, and the mass fraction of vinyl is 1.5%; the ratio of hydroxyl MQ silicone to vinyl MQ is 7:1, a step of;
2) Introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) Cooling to room temperature, adding 1.0g of a silicon-hydrogen cross-linking agent, and uniformly stirring to obtain pressure-sensitive adhesive base adhesive 4;
4) To 100g of base adhesive 4, 0.5g of anchoring agent and 100g of toluene were added, after stirring uniformly, 1.5g of platinum catalyst with 4000ppm of platinum content was added, after stirring uniformly, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, a fluoroplastic release film was attached, and the performance was tested, and the results are shown in Table 1.
Example 5
1) 10g of branched vinyl silicone oil, 70g of hydroxyl raw rubber, 8g of hydroxyl MQ silicone resin, 32g of vinyl MQ silicone resin and 80g of xylene, and 0.8g of ethynyl cyclohexanol are added into a reaction kettle, stirred and dissolved; wherein the molecular weight of the hydroxyl raw rubber is 60w, the viscosity of the branched vinyl silicone oil is 1500 mPa.s, and the mass fraction of vinyl is 1.5%; the ratio of hydroxyl MQ silicone to vinyl MQ is 1:4, a step of;
2) Introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) Cooling to room temperature, adding 1.5g of a silicon-hydrogen cross-linking agent, and uniformly stirring to obtain pressure-sensitive adhesive base 5;
4) To 100g of base adhesive 5, 0.5g of anchoring agent and 100g of toluene were added, after stirring uniformly, 1.5g of platinum catalyst with 4000ppm of platinum content was added, after stirring uniformly, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, a fluoroplastic release film was attached, and the performance was tested, and the results are shown in Table 1.
Example 6
1) Adding 20g of branched vinyl silicone oil, 20g of hydroxyl raw rubber, 30g of hydroxyl MQ silicon resin, 10g of vinyl MQ silicon resin and 80g of xylene, and adding 0.8g of ethynyl cyclohexanol into a reaction kettle, stirring and dissolving; wherein the molecular weight of the hydroxyl raw rubber is 60w, the viscosity of the branched vinyl silicone oil is 500 mPa.s, and the mass fraction of vinyl is 1.5%; the ratio of hydroxyl MQ silicone to vinyl MQ is 3:1, a step of;
2) Introducing nitrogen, stirring, diluting 0.8g of acetic acid with 20g of dimethylbenzene, slowly adding the diluted acetic acid, and then carrying out reflux dehydration at 150 ℃ for 4 hours;
3) Cooling to room temperature, adding 1.5g of a silicon-hydrogen cross-linking agent, and uniformly stirring to obtain pressure-sensitive adhesive base 6;
4) To 100g of base adhesive 6, 0.5g of anchoring agent and 100g of toluene were added, after stirring uniformly, 1.5g of platinum catalyst with 4000ppm of platinum content was added, after stirring uniformly, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, a fluoroplastic release film was attached, and the performance was tested, and the results are shown in Table 1.
Comparative example 1 traditional pressure sensitive adhesive
100g of raw vinyl silicone rubber, 140g of methyl MQ silicone resin, 20g of vinyl MQ silicone resin and 150g of xylene, 0.8g of ethynyl cyclohexanol and 1.5g of silicon-hydrogen crosslinking agent are added into a reaction kettle, and stirred for dissolution; wherein the molecular weight of the raw vinyl silicone rubber is 60 ten thousand, the mass fraction of vinyl is 0.05%, and the ratio of methyl MQ silicone resin to vinyl MQ is 7:1; after stirring for 4 hours, pressure-sensitive adhesive base 7 was obtained.
To 100g of pressure sensitive adhesive 7, 0.5 part of anchoring agent and 100 parts of toluene were added, after stirring uniformly, 1.5 parts of platinum catalyst with 4000ppm of platinum content was added, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, the adhesive surface was covered with a fluoroplastic release film, and the performance was tested, and the results are shown in table 1.
Comparative example 2 conventional pressure sensitive adhesive with straight chain vinyl silicone oil
Adding 20g of linear vinyl silicone oil, 10g of vinyl MQ silicone resin, 20g of hydroxyl raw rubber, 60g of hydroxyl MQ silicone resin, 80g of xylene, 0.8g of ethynyl cyclohexanol and 1.5g of silicon-hydrogen crosslinking agent into a reaction kettle, stirring and dissolving; wherein, the molecular weight of the hydroxyl raw rubber is 60 ten thousand; the viscosity of the linear vinyl silicone oil is 500 mPas, and the mass fraction of vinyl is 1.5%; the ratio of the hydroxyl MQ silicone resin to the vinyl MQ is 6:1; after stirring for 4 hours, pressure-sensitive adhesive base 8 was obtained.
To 100g of pressure sensitive adhesive 8, 0.5 part of anchoring agent and 100 parts of toluene were added, after stirring uniformly, 1.5 parts of platinum catalyst with 4000ppm of platinum content was added, the mixture was coated on an 80 μm thick SRF substrate, and after curing in an oven at 150 ℃ for 2min, the adhesive surface was covered with a fluoroplastic release film, and the performance was tested, 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 1-2
Figure BDA0003273970830000141
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 fluoroplastic film, has no obvious attenuation on the peeling force of an anti-fingerprint screen after aging, and has the peeling force smaller than 1000g/inch on a steel plate. Compared with the traditional simple blending process, in the invention, the MQ silicone 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 peeling force stability of the product are improved, the peeling force of the product is regulated by controlling the content of the MQ silicone resin and the vinyl content, and when the product is solidified into a glue film, under the action of a platinum catalyst, the silicon-hydrogen cross-linking agent reacts with the vinyl, so that the obtained pressure-sensitive adhesive has good peeling force against fingerprint glass, and the peeling force against a steel plate is not too high, so that the air exhaust property of the pressure-sensitive adhesive film is good.
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 (14)

1. An organosilicon pressure-sensitive adhesive for fingerprint-resistant glass, which is characterized by comprising branched vinyl silicone oil, vinyl MQ silicone resin, hydroxyl raw rubber, hydroxyl MQ silicone resin, a silicon-hydrogen crosslinking agent, an inhibitor and a solvent; the components in parts by weight are: 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 parts of an inhibitor and 80-120 parts of a solvent; wherein, the mass ratio of the hydroxyl MQ silicon resin to the vinyl MQ silicon resin is (10-1): (1-5);
the vinyl mass fraction of the vinyl MQ silicon resin is 0.5-2%;
the branched vinyl silicone oil is branched vinyl silicone oil with a T structure; the preparation method comprises the steps of carrying out hydrolysis reaction on phenyl trimethoxy silane and methyl phenyl dimethoxy silane under the catalysis of acid, further dehydrating and condensing to obtain a hydroxyl-terminated T-shaped polysiloxane chain segment, adding a vinyl double-end socket to carry out end capping reaction after the chain segment reaches a certain number, and finally separating and purifying to obtain the branched vinyl silicone oil with a T structure.
2. The silicone pressure-sensitive adhesive for fingerprint-resistant glass according to claim 1, wherein the branched vinyl silicone oil has a viscosity of 200 to 3000 mPa-s.
3. The silicone pressure-sensitive adhesive for fingerprint-resistant glass according to claim 2, wherein the branched vinyl silicone oil has a viscosity of 500 to 1500 mPa-s.
4. The organic silicon pressure-sensitive adhesive for fingerprint-resistant glass according to claim 2, wherein the mass content of vinyl in the branched vinyl silicone oil is 0.5-2%.
5. The organic silicon pressure-sensitive adhesive for fingerprint-resistant glass according to claim 1, wherein the molecular weight of the hydroxyraw rubber is 50-70 ten thousand.
6. The organic silicon pressure-sensitive adhesive for fingerprint-resistant glass according to claim 1, wherein the hydroxyl MQ silicone resin has an M/Q ratio of 0.5-0.8 and a molar mass of 2700-5000 g/mol.
7. The silicone pressure-sensitive adhesive for fingerprint-resistant glass according to claim 1, wherein the M/Q ratio of the vinyl MQ silicone resin is 0.5 to 0.8 and the molar mass is 4000 to 5000g/mol.
8. The silicone pressure-sensitive adhesive for 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, alkane solvents.
9. The organic silicon pressure-sensitive adhesive for fingerprint-resistant glass according to claim 1, wherein the viscosity of the silicon hydrogen cross-linking agent is 20-50 mpa.s, the silicon hydrogen cross-linking 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 0.7-1.6wt%.
10. The silicone pressure-sensitive adhesive for anti-fingerprint glass according to claim 1, wherein the inhibitor is selected from any one or a combination of several 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.
11. The method for preparing the organic silicon pressure-sensitive adhesive for fingerprint-resistant glass as claimed in any one of claims 1 to 10, comprising the steps of:
1) Adding branched vinyl silicone oil, hydroxyl raw rubber, hydroxyl MQ silicon resin, vinyl MQ silicon resin, inhibitor and solvent into a reaction kettle according to the proportion, and stirring to fully dissolve and disperse raw rubber in the solvent;
2) Introducing nitrogen, stirring, slowly adding a catalyst accounting for 0.05-1% of the weight of the hydroxyl crude rubber after stirring uniformly, and then dehydrating at a reflux temperature of 120-150 ℃ for 3-5h until no water is generated;
3) And cooling to room temperature, adding a silicon-hydrogen crosslinking agent, stirring for 1-3 hours, and uniformly mixing to obtain the organic silicon pressure-sensitive adhesive for the fingerprint-resistant glass.
12. The method for preparing an organic silicon pressure-sensitive adhesive for fingerprint-resistant glass according to claim 11, wherein the catalyst in the step 2) is selected from any one of acetic acid, propionic acid, benzoic acid, phenylacetic acid, trifluoro-benzenesulfonic acid or acidic diatomite.
13. Use of the organic silicon pressure-sensitive adhesive for fingerprint-resistant glass as claimed in any one of claims 1 to 10 or the organic silicon pressure-sensitive adhesive prepared by the preparation method as claimed in any one of claims 11 to 12 in the field of protective films for electronic products.
14. The use of an organosilicon pressure sensitive adhesive for anti-fingerprint glass according to claim 13, in a protective film or waste film of anti-fingerprint glass.
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