CN112341826A - High-refractive-index optical-grade silica gel film and preparation method thereof - Google Patents
High-refractive-index optical-grade silica gel film and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
The invention discloses a high-refractive-index optical-grade silica gel film and a preparation method thereof. A method for preparing a pre-cured silica gel composition, comprising the steps of: uniformly mixing phenyl vinyl silicone oil, phenyl hydrogen-containing silicone oil, end-capped phenyl MQ resin, an inhibitor and a curing agent in a solvent, and then removing the solvent to form a pre-cured silica gel composition; the refractive index of the phenyl vinyl silicone oil is 1.48-1.52, the refractive index of the end-capped phenyl hydrogen-containing silicone oil is 1.48-1.52, the refractive index of the phenyl MQ resin is 1.48-1.52, and the ratio of the amount of hydrogen radical substances of the phenyl hydrogen-containing silicone oil to the amount of vinyl substances in the phenyl vinyl silicone oil is 1.2-1.6: 1. The high-refractive-index optical silica gel film can be stored for a long time at the temperature of below 0 ℃, the film is only required to be pasted between a substrate and an element when in use, and the film is cured in vacuum at the temperature of 60-70 ℃, and the high-refractive-index optical silica gel film can be used in the fields of precise optical elements and the like which require high luminous efficiency and high weather resistance.
Description
Technical Field
The invention relates to the technical field of photoelectric device packaging materials, in particular to a high-refractive-index optical-grade silica gel film and a preparation method thereof.
Background
The addition type liquid silicone rubber generally takes methyl hydrogen silicone oil and methyl vinyl silicone oil as two components, the two components are mixed according to proportion when in use, and the addition type liquid silicone rubber is cured and formed at room temperature or by heating. For some optical elements, the improvement of luminous efficiency requires the increase of the refractive index of the packaging material, so as to reduce the loss caused by interface refraction, and at the moment, the traditional methyl silicone rubber cannot meet the requirement. Meanwhile, the methyl silicone rubber packaging material is easily penetrated by oxygen and hydrogen sulfide gas, and then permeates to the surface of the element, so that the silver plating layer and the gold wire are oxidized, and the service life of the element is shortened.
Therefore, there is a need to develop a packaging material with environmental friendliness, high refractive index, high weather resistance and convenient use, and the packaging material is applied to the high-end packaging field of precision optical elements and the like.
Disclosure of Invention
The invention provides a high-refractive-index optical silica gel film and a preparation method thereof, wherein the high-refractive-index optical silica gel film can be stored for a long time at the temperature of below 0 ℃, and only needs to be pasted between a substrate and an element and cured in vacuum at the temperature of 60-70 ℃ when in use.
The invention aims to provide a preparation method of a pre-cured silica gel composition, which comprises the following steps: uniformly mixing phenyl vinyl silicone oil, phenyl hydrogen-containing silicone oil, end-capped phenyl MQ resin, an inhibitor and a curing agent in a solvent, and then removing the solvent to form a pre-cured silica gel composition; the refractive index of the phenyl vinyl silicone oil is 1.48-1.52, the refractive index of the phenyl hydrogen-containing silicone oil is 1.48-1.52, the refractive index of the end-capped phenyl MQ resin is 1.48-1.52, and the ratio of the amount of hydrogen radical substances of the phenyl hydrogen-containing silicone oil to the amount of vinyl substances in the phenyl vinyl silicone oil is 1.2-1.6: 1.
Preferably, the phenyl vinyl silicone oil is prepared by the following method: placing 40-60 parts by mass of octaphenylcyclotetrasiloxane and 40-60 parts by mass of vinyl silicone oil (the vinyl content in the vinyl silicone oil is 2.0 wt% -3.0 wt%) in a reaction vessel, adding 0.5-1 part by mass of potassium hydroxide as a catalyst, stirring and heating, heating to 150-180 ℃, and preserving heat for 3-4 hours; cooling to 60-80 ℃, adding 100-200 parts by mass of methylcyclohexane for dilution, adding 1-2 parts by mass of glacial acetic acid for neutralization reaction for 0.5-1h, adding 2-10 parts by mass of carbon black and 1-2 parts by mass of anhydrous calcium chloride, stirring for 0.5-1h to obtain a mixture, carrying out suction filtration on the mixture, and carrying out vacuum distillation on the obtained filtrate at 150-180 ℃ to obtain the phenyl vinyl silicone oil.
More preferably, the vinyl content of the phenyl vinyl silicone oil is 1.2 wt% -1.8 wt%, the viscosity is 3000-50000 MPa.S, and the hydrogen content of the phenyl hydrogen-containing silicone oil is 0.3 wt% -0.6 wt%.
Preferably, the end-capped phenyl MQ resin is prepared by the following method: dissolving 0.5-2 parts by mass of HDI tripolymer in toluene, dripping a toluene solution in which 100 parts by mass of common phenyl MQ resin is dissolved, dripping 0.1-0.3 part by mass of dibutyltin dilaurate, reacting for 3-6 hours, and then carrying out reduced pressure distillation to obtain the end-capped phenyl MQ resin. The mass fraction of the phenyl MQ resin in the toluene solution of the phenyl MQ resin is 40-50%.
Preferably, the total mass of the raw materials of the phenyl vinyl silicone oil, the phenyl hydrogen-containing silicone oil, the end-capped phenyl MQ resin, the inhibitor and the curing agent is taken as the standard, the mass of the end-capped phenyl MQ resin accounts for 45-52 wt% of the total mass of the raw materials, the mass of the inhibitor accounts for 0.02-0.05 wt% of the total mass of the raw materials, and the mass of the curing agent accounts for 0.04-0.2 wt% of the total mass of the raw materials.
Preferably, the refractive index of the phenyl vinyl silicone oil, the refractive index of the phenyl hydrogen silicone oil and the refractive index of the phenyl MQ resin are the same.
Preferably, the inhibitor is ethynylcyclohexanol or methylbutynol, the curing agent is a mixture of a platinum-based catalyst and dibenzoyl peroxide (BPO), the platinum-based catalyst is 5000ppm of a vinyl siloxane solution of a platinum-vinyl siloxane complex, and the solvent is cyclohexane or petroleum ether. The mass ratio of the platinum catalyst to the dibenzoyl peroxide (BPO) is 0.2-0.4: 1.
The invention also protects the pre-cured silica gel composition prepared by the preparation method, and the pre-cured silica gel composition is applied to preparation of optical silica gel films with high refractive indexes.
The invention also provides a preparation method of the high-refractive-index optical silica gel film, which comprises the following steps: and (3) dispersing the pre-cured silica gel composition between a light release film and a heavy release film, and performing hot pressing at 60-70 ℃ to form a film by a flat hot press, wherein the pressure is 5-20MPa, and the heat is preserved for 60-120s to obtain the high-refractive-index optical silica gel film.
Preferably, the light release film is glassine type release paper or silicone oil type release film, and the heavy release film is glassine type release paper or silicone oil type release film.
The invention protects the optical silica gel film with high refractive index prepared by the preparation method. When the high-refractive-index optical-grade silica gel film is used, the light release film is torn off, the silica gel surface is pasted on a workpiece, the heavy release film is torn off, the silica gel surface is pasted on another workpiece, and then vacuum curing is carried out for 3-5min at the temperature of 60-70 ℃, so that packaging can be completed.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention firstly prepares a pre-cured silica gel composition, and then prepares the silica gel film by hot-pressing molding, the size of the silica gel film can be tailored according to the requirement, and the silica gel film can be stored for a long time at 0 ℃ and is convenient to transport; the packaging process is simple, organic solvent is not needed, and the environment is protected.
2. Due to the introduction of phenyl, the silica gel film has high refractive index and can be used in the field of optical elements with high luminous efficiency; meanwhile, the packaging element has high weather resistance, and compared with methyl silicone rubber, the packaging element can be remarkably prolonged in service life.
3. HDI tripolymer is used for carrying out end capping on the phenyl MQ resin, so that unstable terminal hydroxyl is eliminated, and bubbles generated by condensation dehydration of the terminal hydroxyl in the long-term use process of the cured silica gel film are avoided; and meanwhile, the HDI tripolymer is used as a rigid structure, so that the tensile strength of the silica gel membrane can be enhanced.
4. BPO is introduced as an initiator, is in a dormant state at a low temperature below 0 ℃, rapidly initiates a carbon-carbon double bond reaction at a temperature above 60 ℃, and can play a synergistic effect with a platinum catalyst, so that the crosslinking curing time is greatly reduced, and the pre-cured silica gel film is cured into a film at a temperature of 60-70 ℃ for 3-5 min.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1
The phenyl vinyl silicone oil with the refractive index of 1.48 is prepared by the following method: placing 40g of octaphenylcyclotetrasiloxane and 60g of vinyl silicone oil with the vinyl content of 2.0 wt% in a three-neck flask, adding 0.75g of potassium hydroxide serving as a catalyst, stirring and heating, raising the temperature to 165 ℃, and preserving the heat for 3.5 hours; cooling to 70 ℃, adding 150g of methylcyclohexane for dilution, adding 1.5g of glacial acetic acid for neutralization reaction for 0.75h, adding 6g of carbon black and 1.5g of anhydrous calcium chloride, stirring for 0.75h to obtain a mixture, carrying out suction filtration on the mixture, and carrying out vacuum distillation on the obtained filtrate at 165 ℃ to obtain the phenyl vinyl silicone oil.
The end-capped MQ resin was prepared by the following method: 0.5g of HDI trimer is dissolved in toluene, and 100g of a toluene solution in which ordinary phenyl MQ resin is dissolved is dropped, wherein the mass fraction of the phenyl MQ resin in the toluene solution of the phenyl MQ resin is 50%. 0.1g of dibutyltin dilaurate is dripped to react for 6 hours, and then the phenyl MQ resin subjected to end capping treatment is obtained by reduced pressure distillation.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps:
46.97g of end-capped phenyl MQ resin with the refractive index of 1.48 is dissolved in 28.2g of cyclohexane, after the end-capped phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with the refractive index of 1.48 and the vinyl content of 1.2 wt%, 7.41g of phenyl hydrogen silicone oil with the refractive index of 1.48 and the hydrogen content of 0.3 wt% and 0.02g of ethynl cyclohexanol are sequentially added, after uniform mixing, 0.04g of vinyl siloxane solution of platinum-vinyl siloxane complex with the weight of 5000ppm and 0.1g of BPO are added, and after uniform mixing, a small planetary power mixer is put in to remove a solvent and bubbles in vacuum, so that the uniform and transparent gel-like pre-cured silica gel composition is formed.
And dispersing the prepared gel-like pre-cured silica gel composition between glassine-type release paper and a silicone oil-type release film, carrying out hot pressing to form a film at 60 ℃ by a flat hot press, keeping the pressure at 5MPa for 60s, and carrying out moderate crosslinking to obtain the pre-cured high-refractive-index optical silica gel film for packaging.
Example 2
The phenyl vinyl silicone oil with the refractive index of 1.52 is prepared by the following method: placing 40g of octaphenylcyclotetrasiloxane and 60g of vinyl silicone oil with the vinyl content of 2.4% in a three-neck flask, adding 0.5g of potassium hydroxide serving as a catalyst, stirring and heating, heating to 150 ℃, and preserving heat for 4 hours; and (3) cooling to 60 ℃, adding 100g of methylcyclohexane for dilution, then adding 1g of glacial acetic acid for neutralization reaction for 0.5h, then adding 2g of carbon black and 1g of anhydrous calcium chloride, stirring for 0.5h to obtain a mixture, carrying out suction filtration on the mixture, and carrying out vacuum distillation on the obtained filtrate at 150 ℃ to obtain the phenyl vinyl silicone oil.
The end-capped MQ resin was prepared by the following method: dissolving 1.0g of HDI trimer in toluene, dripping toluene solution in which 100g of common phenyl MQ resin is dissolved, dripping 0.2g of dibutyltin dilaurate, reacting for 4 hours, and then carrying out reduced pressure distillation to obtain the end-capped phenyl MQ resin, wherein the mass fraction of the phenyl MQ resin in the toluene solution of the phenyl MQ resin is 40%.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps:
54.13g of end-capped phenyl MQ resin with refractive index of 1.48 is dissolved in 40g of cyclohexane, after the end-capped phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with refractive index of 1.48 and vinyl content of 1.44 wt%, 10.8g of phenyl hydrogen silicone oil with refractive index of 1.48 and hydrogen content of 0.36 wt% and 0.02g of ethyne cyclohexanol are sequentially added, after uniform mixing, 0.04g of vinyl siloxane solution of platinum-vinyl siloxane complex with 5000ppm and 0.2g of BPO are added, and after uniform mixing, a small planetary power mixer is put in to remove solvent and bubbles in vacuum, so that the uniform and transparent gel-like pre-cured silica gel composition is formed.
And dispersing the prepared gel-like pre-cured silica gel composition between glassine-type release paper and a silicone oil-type release film, carrying out hot pressing to form a film at 60 ℃ by a flat hot press, keeping the pressure at 5MPa for 60s, and carrying out moderate crosslinking to obtain the pre-cured high-refractive-index optical silica gel film for packaging.
Example 3
The phenyl vinyl silicone oil with the refractive index of 1.50 is prepared by the following method: placing 50g of octaphenylcyclotetrasiloxane and 50g of vinyl silicone oil with the vinyl content of 3.0% in a three-neck flask, adding 1g of potassium hydroxide serving as a catalyst, stirring and heating, heating to 180 ℃, and preserving heat for 3 hours; cooling to 80 ℃, adding 200g of methylcyclohexane for dilution, adding 2g of glacial acetic acid for neutralization reaction for 1h, adding 10g of carbon black and 2g of anhydrous calcium chloride, stirring for 1h to obtain a mixture, carrying out suction filtration on the mixture, and carrying out vacuum distillation on the obtained filtrate at 180 ℃ to obtain the phenyl vinyl silicone oil.
The end-capped MQ resin was prepared by the following method: dissolving 2.0g of HDI trimer in toluene, dripping toluene solution in which 100g of common phenyl MQ resin is dissolved, dripping 0.3g of dibutyltin dilaurate, reacting for 3 hours, and then carrying out reduced pressure distillation to obtain the end-capped phenyl MQ resin, wherein the mass fraction of the phenyl MQ resin in the toluene solution of the phenyl MQ resin is 50%.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps:
46.97g of end-capped phenyl MQ resin with the refractive index of 1.50 is dissolved in 28.2g of cyclohexane, after the end-capped phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with the refractive index of 1.50 and the vinyl content of 1.2 wt%, 7.41g of phenyl hydrogen silicone oil with the refractive index of 1.50 and the hydrogen content of 0.3 wt% and 0.02g of ethynl cyclohexanol are sequentially added, after uniform mixing, 0.04g of vinyl siloxane solution of platinum-vinyl siloxane complex with the weight of 5000ppm and 0.3g of BPO are added, and after uniform mixing, a small planetary power mixer is put in to remove a solvent and bubbles in vacuum, so that a uniform and transparent gel-like pre-cured silica gel composition is formed.
And dispersing the prepared gel-like pre-cured silica gel composition between glassine-type release paper and a silicone oil-type release film, performing hot pressing to form a film at 60 ℃ by a flat hot press, keeping the pressure at 5MPa for 60s, and performing moderate crosslinking to obtain the optical silica gel film with high refractive index for packaging.
Example 4
Preparation procedure of phenyl vinyl silicone oil and end-capped phenyl MQ resin reference is made to example 2.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps: 57.78g of end-capped phenyl MQ resin with the refractive index of 1.50 is dissolved in 46.24g of cyclohexane, after the end-capped phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with the refractive index of 1.50 and the vinyl content of 1.5 wt%, 7.78g of phenyl hydrogen silicone oil with the refractive index of 1.50 and the hydrogen content of 0.5 wt% and 0.035g of methyl butynol are added, after uniform mixing, 0.12g of vinyl siloxane solution of platinum-vinyl siloxane complex with the weight of 5000ppm and 0.30g of BPO are added, and after uniform mixing, a small planetary power mixer is put in to remove solvent and bubbles in vacuum, so as to form the uniform and transparent gel-like pre-cured silica gel composition. Dispersing the prepared pre-cured composition between glassine type release paper and silicone oil type release film, hot-pressing the mixture into a film at 65 ℃ by a flat hot press, keeping the pressure at 10MPa, and keeping the temperature for 90s to ensure that the film is properly crosslinked, thus obtaining the optical silica gel film with high refractive index for packaging.
Comparative example 1
Preparation procedure of phenyl vinyl silicone oil and end-capped phenyl MQ resin reference is made to example 2.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps: 57.78g of end-capped phenyl MQ resin with the refractive index of 1.50 is dissolved in 46.24g of cyclohexane, after the end-capped phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with the refractive index of 1.50 and the vinyl content of 1.5 wt%, 7.78g of phenyl hydrogen silicone oil with the refractive index of 1.50 and the hydrogen content of 0.5 wt% and 0.035g of methyl butinol are added, after uniform mixing, 0.42g of vinyl siloxane solution of platinum-vinyl siloxane complex with the ppm of 5000 is added, and after uniform mixing, a small planetary power mixer is put in to remove solvent and bubbles in vacuum, so that the uniform and transparent gel-like pre-cured silica gel composition is formed. Dispersing the prepared pre-cured composition between glassine type release paper and silicone oil type release film, hot-pressing the mixture into a film at 65 ℃ by a flat hot press, keeping the pressure at 10MPa, and keeping the temperature for 90s to ensure that the film is properly crosslinked, thus obtaining the optical silica gel film with high refractive index for packaging.
Comparative example 2
Preparation procedure of phenyl vinyl silicone oil and end-capped phenyl MQ resin reference is made to example 2.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps: 57.78g of end-capped phenyl MQ resin with refractive index of 1.50 is dissolved in 46.24g of cyclohexane, after the end-capped phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with refractive index of 1.50 and vinyl content of 1.5 wt%, 7.78g of phenyl hydrogen silicone oil with refractive index of 1.50 and hydrogen content of 0.5 wt% and 0.035g of methyl butynol are added, after uniform mixing, 0.42g of BPO is added, after uniform mixing, a small planetary power mixer is put in for vacuum removal of solvent and bubbles, and the uniform and transparent gel-like pre-cured silica gel composition is formed. Dispersing the prepared pre-cured composition between glassine type release paper and silicone oil type release film, hot-pressing the mixture into a film at the temperature of 75-80 ℃ by a flat hot press, keeping the pressure at 10MPa, and keeping the temperature for 90s to ensure that the film is properly crosslinked, thus obtaining the optical silica gel film with high refractive index for packaging.
Comparative example 3
Procedure for preparation of phenyl vinyl silicone oil reference is made to example 2.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps: 57.78g of phenyl MQ resin which has a refractive index of 1.50 and is not subjected to end capping treatment is dissolved in 46.24g of cyclohexane, after the phenyl MQ resin is fully dissolved, 50g of phenyl vinyl silicone oil with a refractive index of 1.50 and a vinyl content of 1.5 wt%, 7.78g of phenyl hydrogen silicone oil with a refractive index of 1.50 and a hydrogen content of 0.5 wt% and 0.035g of methyl butinol are added, after uniform mixing, 0.12g of vinyl siloxane solution of platinum-vinyl siloxane complex with 5000ppm and 0.30g of BPO are added, after uniform mixing, a small planetary power mixer is put in to remove solvent and bubbles in vacuum, and the uniform and transparent gel-like pre-cured silica gel composition is formed. Dispersing the prepared pre-cured composition between glassine type release paper and silicone oil type release film, hot-pressing the mixture into a film at the temperature of 75-80 ℃ by a flat hot press, keeping the pressure at 10MPa, and keeping the temperature for 90s to ensure that the film is properly crosslinked, thus obtaining the optical silica gel film with high refractive index for packaging.
Example 5
Preparation procedure of phenyl vinyl silicone oil and end-capped phenyl MQ resin reference is made to example 2.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps: 63.80g of end-capped phenyl MQ resin with refractive index of 1.52 is dissolved in 63.80g of petroleum ether, after the petroleum ether is fully dissolved, 50g of phenyl vinyl silicone oil with 1.52 of refractive index and 1.8 wt% of vinyl content, 8.89g of phenyl hydrogen silicone oil with 1.52 of refractive index and 0.6 wt% of hydrogen content and 0.061g of methyl butinol are added, after uniform mixing, 0.24g of vinyl siloxane solution of platinum-vinyl siloxane complex with 5000ppm and 0.48g of BPO are added, and after uniform mixing, a small planetary power mixer is put in to remove solvent and bubbles in vacuum, so that the uniform and transparent gel-like pre-cured silica gel composition is formed. And dispersing the prepared pre-cured composition between a light release film and a heavy release film, performing hot pressing at 70 ℃ by using a flat hot press to form a film, keeping the pressure at 20MPa, and performing heat preservation for 120s to ensure that the film is appropriately crosslinked, thereby obtaining the optical silica gel film with high refractive index for packaging.
Example 6
Preparation procedure of phenyl vinyl silicone oil and end-capped phenyl MQ resin reference is made to example 2.
A preparation method of a high-refractive-index optical-grade packaging silica gel film comprises the following steps: 58.33g of end-capped phenyl MQ resin with the refractive index of 1.52 is dissolved in 58.33g of petroleum ether, after the petroleum ether is fully dissolved, 50g of phenyl vinyl silicone oil with the refractive index of 1.52 and the vinyl content of 1.5 wt%, 8.33g of phenyl hydrogen silicone oil with the refractive index of 1.52 and the hydrogen content of 0.4 wt% and 0.04g of ethynl cyclohexanol are added, after uniform mixing, 0.15g of vinyl siloxane solution of platinum-vinyl siloxane complex with the concentration of 5000ppm and 0.30g of BPO are added, and after uniform mixing, a small planetary power mixer is put in to remove solvent and air bubbles in vacuum, so that the uniform and transparent gel-like pre-cured silica gel composition is formed. And dispersing the prepared pre-cured composition between a light release film and a heavy release film, performing hot pressing at 70 ℃ by using a flat hot press to form a film, keeping the pressure at 10MPa for 60s to ensure that the film is properly crosslinked, and thus obtaining the optical silica gel film with high refractive index for packaging.
The pre-cured silicone rubber compositions of examples 1 to 6, comparative example 1 and comparative example 2 were hot-pressed to prepare standard samples, which were cured at 70 ℃ for 5min and tested for tensile strength according to the method for testing tensile properties of plastic films of GB 13022-1991, and the tensile strength results of the pre-cured silicone rubber compositions of the respective examples are shown in Table 1.
TABLE 1
| Standard test specimen | Tensile Strength (MPa) |
| Example 1 | 15.6 |
| Example 2 | 16.3 |
| Example 3 | 16.2 |
| Example 4 | 16.8 |
| Comparative example 1 | 12.3 |
| Comparative example 2 | 12.5 |
| Comparative example 3 | 13.8 |
| Example 5 | 15.9 |
| Example 6 | 16.1 |
As can be seen from Table 1, the tensile strength of the silicone membranes after curing in examples 1-6 is much greater than that of the silicone membranes after curing in comparative examples 1 and 2, the platinum-based catalyst in comparative example 1 alone and the BPO in comparative example 2 alone cannot enable the pre-cured silicone membranes to be completely crosslinked within 5min, and the tensile strength of the silicone membranes obtained in comparative examples 1 and 2 is lower, so that the platinum-based catalyst and the BPO in the curing agent of the pre-cured silicone composition provided by the invention are proved to be synergistic, and the curing time of the silicone membranes is greatly shortened. The tensile strength of the silicone membranes after curing in examples 1-6 was higher than that of the silicone membrane in comparative example 3, which shows that the tensile strength of the silicone membranes can be improved to a certain extent by the rigid structure after the MQ resin is introduced into the isocyanate blocking.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A method for preparing a pre-cured silica gel composition, comprising the steps of: uniformly mixing phenyl vinyl silicone oil, phenyl hydrogen-containing silicone oil, end-capped phenyl MQ resin, an inhibitor and a curing agent in a solvent, and then removing the solvent to form a pre-cured silica gel composition; the refractive index of the phenyl vinyl silicone oil is 1.48-1.52, the refractive index of the phenyl hydrogen-containing silicone oil is 1.48-1.52, the refractive index of the end-capped phenyl MQ resin is 1.48-1.52, and the ratio of the amount of hydrogen radical substances of the phenyl hydrogen-containing silicone oil to the amount of vinyl substances in the phenyl vinyl silicone oil is 1.2-1.6: 1.
2. The method of preparing a pre-cured silicone composition according to claim 1, wherein the phenyl vinyl silicone oil is prepared by the following method: placing 40-60 parts by mass of octaphenylcyclotetrasiloxane and 40-60 parts by mass of vinyl silicone oil in a reaction vessel, adding 0.5-1 part by mass of potassium hydroxide as a catalyst, stirring and heating, heating to 150-180 ℃, and preserving heat for 3-4 hours; cooling to 60-80 ℃, adding 100-200 parts by mass of methylcyclohexane for dilution, adding 1-2 parts by mass of glacial acetic acid for neutralization reaction for 0.5-1h, adding 2-10 parts by mass of carbon black and 1-2 parts by mass of anhydrous calcium chloride, stirring for 0.5-1h to obtain a mixture, carrying out suction filtration on the mixture, and carrying out vacuum distillation on the obtained filtrate at 150-180 ℃ to obtain the phenyl vinyl silicone oil.
3. The method of claim 2, wherein the phenyl vinyl silicone oil has a vinyl content of 1.2 wt% to 1.8 wt%, a viscosity of 3000 to 50000 MPa-S, and a hydrogen content of 0.3 wt% to 0.6 wt%.
4. The method of preparing the pre-cured silica gel composition of claim 1 wherein the end-capped phenyl MQ resin is prepared by the following method: dissolving 0.5-2 parts by mass of HDI tripolymer in toluene, dripping toluene solution in which 100 parts by mass of phenyl MQ resin is dissolved, dripping 0.1-0.3 part by mass of dibutyltin dilaurate, reacting for 3-6 hours, and then carrying out reduced pressure distillation to obtain the end-capped phenyl MQ resin.
5. The method of claim 1, wherein the end-capped phenyl MQ resin accounts for 45 wt% -52 wt%, the inhibitor accounts for 0.02 wt% -0.05 wt%, and the curing agent accounts for 0.04 wt% -0.2 wt%, based on the total mass of the raw materials of the phenyl vinyl silicone oil, the phenyl hydrogen silicone oil, the end-capped phenyl MQ resin, the inhibitor and the curing agent.
6. The method of claim 1 or 5, wherein the refractive index of the phenyl vinyl silicone oil, the refractive index of the phenyl hydrogen silicone oil and the refractive index of the phenyl MQ resin are the same.
7. The method of claim 5 wherein the inhibitor is ethynylcyclohexanol or methylbutynol, the curing agent comprises a platinum-group catalyst and dibenzoyl peroxide, the platinum-group catalyst is 5000ppm of a vinyl siloxane solution of a platinum-vinyl siloxane complex, and the solvent is cyclohexane or petroleum ether.
8. The pre-cured silica gel composition prepared by the method of preparing a pre-cured silica gel composition of claim 1.
9. The preparation method of the high-refractive-index optical-grade silica gel film is characterized by comprising the following steps of: dispersing the pre-cured silica gel composition of claim 8 between a light release film and a heavy release film, hot-pressing the mixture into a film at 60-70 ℃ by a flat hot press, keeping the pressure at 5-20MPa, and keeping the temperature for 60-120s to obtain the optical silica gel film with high refractive index.
10. The method for preparing the high refractive index optical silicone film according to claim 9, wherein the light release film is a glassine release paper or a silicone oil release film, and the heavy release film is a glassine release paper or a silicone oil release film.
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