CN110746728A - OCA acoustic film and preparation method thereof - Google Patents
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Abstract
The invention provides an OCA acoustic film which is prepared from the following raw materials: modified OCA adhesive emulsion, polylactic acid, an antioxidant and a coupling agent A; the modified OCA adhesive emulsion is prepared from the following raw materials: acrylic acid, acrylate adhesive, polyurethane acrylate oligomer, bisphenol A dimethacrylate, a defoaming agent, a crosslinking curing agent, nano aluminum oxide, polyformaldehyde and a composite coupling agent B. The acoustic film prepared by the method has smooth and stable surface, large diameter value compared with the thickness value, good acoustic characteristics, good responsiveness in the acoustic frequency range of 0.025Hz-25000Hz, sensitivity of 55-110mv/pa and static pressure sensitivity of 7 um/pa.
Description
Technical Field
The invention relates to the technical field of acoustic thin films, in particular to an OCA acoustic thin film and a preparation method thereof.
Background
The sound wave is a mechanical wave generated by the vibration of a sound source, the space for sound wave propagation is a sound field, and sound is a longitudinal wave when propagating in gas and liquid media, but may be mixed with a transverse wave when propagating in a solid medium. The frequency of the sound waves audible to the human ear is typically between 20Hz and 20000 Hz. Below 20Hz is infrasonic and above 20kHz is ultrasonic. The sound waves of different frequency bands have different purposes in the practical application process, and infrasound has important purposes in the aspects of ground sound exploration and ultrasound in the aspects of nondestructive testing, ultrasonic imaging and the like. When the sound waves are transmitted by the air, the density of the air is changed, and the air pressure is changed periodically; the effective method for detecting the sound wave is to convert sound vibration into an electric signal or an optical signal by utilizing the periodic change of the air pressure through the transduction of a film, and achieve the purpose of detecting the sound signal by detecting the electric signal or the optical signal; the common sound wave frequency detection means in the prior art is to use a capacitance type or piezoelectric type film for transduction, the weak pressure difference at two sides of the film is sensed by the film, the deformation of the film causes the change of the capacitance and the voltage of the film, and the change of the electric signal is consistent with the change of the sound signal; the capacitive or voltage type thin film requires that the thin film material has capacitance or piezoelectricity, the selectivity to the material is high, and the material cannot be used in the high magnetic field and high electromagnetic field.
In recent years, optical fiber microphones are widely researched, and particularly, partial performances of an acoustic sensing technology based on FP interference are equivalent to those of piezoelectricity or capacitance, and the optical fiber microphone has the characteristics of small volume, wide dynamic range, electromagnetic interference resistance, severe environment resistance and the like. The FP microphone film does not require piezoelectricity or capacitance, and various materials can be used for preparing acoustic films, such as silver films, silicon films, graphene films, polymer films, glycosyl films and the like; the sensitivity of an acoustic membrane is inversely proportional to the third power of the membrane thickness and directly proportional to the fourth power of the membrane radius; considering the size of the sensor, the thickness of the acoustic film is often smaller, and at the level of micron or even nanometer, the radius of the film is difficult to increase, the preparation process of the film is also complex, the cost is high, the low-frequency response is low, and the preparation of the acoustic film is a difficult point for the development of the acoustic sensor.
OCA optical cement (optical Clear Adhesive) is a special Adhesive used for gluing transparent optical elements such as lenses. The transparent adhesive is required to be colorless and transparent, has the light transmittance of more than 90 percent, has good adhesive strength, can be cured under thermosetting or Ultraviolet (UV), and has the characteristics of small curing shrinkage and the like. The traditional OCA optical adhesive is mainly used as a raw material of an important touch screen, and is prepared by manufacturing an optical acrylic adhesive into a non-base material, and then respectively attaching a release film to an upper bottom layer and a lower bottom layer to form a double-sided adhesive tape without a base material. In addition, the traditional OCA optical cement is mainly used for a mobile phone touch screen.
Disclosure of Invention
In order to solve the technical problems, the invention provides an OCA acoustic thin film and a preparation method thereof, and aims to provide the OCA acoustic thin film, wherein the nanometer aluminum oxide is adopted to modify an OCA material, so that the toughness of the OCA material is further enhanced, and the OCA acoustic thin film still has excellent mechanical properties when the ultrathin acoustic thin film is prepared.
The invention provides an OCA acoustic film which is prepared from the following raw materials: modified OCA adhesive emulsion, polylactic acid, an antioxidant and a coupling agent A;
the modified OCA adhesive emulsion is prepared from the following raw materials: acrylic acid, acrylate adhesive, polyurethane acrylate oligomer, bisphenol A dimethacrylate, defoaming agent, crosslinking curing agent, nano aluminum oxide, polyformaldehyde and composite coupling agent B;
the crosslinking curing agent has a structure shown in formula I:
the sensitivity of the OCA acoustic membrane in the sound wave frequency range of 0.025Hz-25000Hz is 55-110mv/pa, and the static pressure sensitivity is less than or equal to 7 um/pa.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 150 parts of modified OCA adhesive emulsion, 12-17 parts of polylactic acid, 1-3 parts of antioxidant and 1-5 parts of coupling agent A;
the modified OCA adhesive emulsion is prepared from the following raw materials in parts by weight: 10-30 parts of acrylic acid, 120 parts of acrylate adhesive, 20-30 parts of polyurethane acrylate oligomer, 30-50 parts of bisphenol A dimethacrylate, 2-5 parts of defoaming agent, 0.01-0.03 part of crosslinking curing agent, 10-15 parts of nano aluminum oxide, 12-17 parts of polyformaldehyde and 20-20 parts of composite coupling agent B10.
As a further improvement of the invention, the defoaming agent is selected from silicone emulsion, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene polyoxyethylene glycerol ether or polydimethylsiloxane.
As a further improvement of the invention, the modified OCA adhesive emulsion is prepared by the following method:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 0.5-1% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving the nano aluminum oxide and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding a defoaming agent and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
As a further improvement of the invention, the crosslinking curing agent is prepared by the following method:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 2-3h after dropwise adding is finished, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
As a further improvement of the invention, the coupling agent A is selected from one of KH550, KH560, KH570, KH792, DL602 and DL 171.
As a further improvement of the invention, the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with an amino group, the mass ratio of the common silane coupling agent to the silane coupling agent with the amino group is 5:2, and the common silane coupling agent comprises one of KH550, KH560, KH570, KH792, DL602 and DL 171.
As a further improvement of the invention, the antioxidant is selected from antioxidants including hindered phenol type primary antioxidants and/or phosphite type secondary antioxidants.
As a further improvement of the invention, the diameter of the OCA acoustic film is 1.75mm-2.77mm, and the thickness is 2.7 μm-7.0 μm.
The invention further provides a preparation method of the OCA acoustic film, which comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.2-0.4% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and an antioxidant in an ethanol aqueous solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by using ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 300-500r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 3-7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out the hollow stainless steel tube until the hollow stainless steel tube is cured by adopting ultraviolet irradiation, and obtaining the acoustic film.
The invention has the following beneficial effects:
the crosslinking curing agent prepared by the invention is an imidazole curing agent, wherein original secondary amine is replaced by tertiary amine, and a new tertiary amine group is introduced, so that the modified imidazole curing agent is beneficial to normal-temperature curing, and can complete good curing performance even in a very small addition amount, the cost is reduced, and the product has good mechanical property and thermal property;
the acoustic film prepared by the modified OCA adhesive emulsion material has excellent mechanical properties, good toughness and elasticity on the premise of extremely thin film material, good acoustic characteristics and high sensitivity; the OCA material is modified by adopting the nano aluminum oxide, so that the toughness of the OCA material is further enhanced, and the OCA material still has excellent mechanical properties when an ultrathin acoustic film is prepared;
according to the invention, two different silane modifiers are compounded to modify different particles, wherein one common silane modifier helps inorganic particles with oxygen on the surface to be modified and linked with a modified OCA adhesive emulsion, a silane coupling agent with amino helps organic particles such as polyformaldehyde and the like to be modified and linked with the modified OCA adhesive emulsion, and the modified particles and the modified OCA adhesive emulsion material are chemically bonded through the compounded silane coupling agent to prepare the modified OCA adhesive emulsion with better toughness and mechanical property for later-stage preparation of an OCA acoustic membrane material;
the acoustic film prepared by the method has smooth and stable surface, the diameter is 1.75mm-2.77mm, and the thickness is 2.7 mu m-7.0 mu m; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 55-110mv/pa and static pressure sensitivity of 7 um/pa.
Drawings
FIG. 1 is a liquid chromatogram of a crosslinking curing agent in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
Example 1
The raw materials comprise the following components in parts by weight: 120 parts of modified OCA adhesive emulsion, 12 parts of polylactic acid, 0.8 part of hindered phenol main antioxidant, 0.2 part of phosphite ester auxiliary antioxidant and 1 parts of coupling agent A. The coupling agent A is KH 560.
Preparing a modified OCA adhesive emulsion:
the raw materials comprise the following components in parts by weight: 10 parts of acrylic acid, 100 parts of acrylate adhesive, 20 parts of urethane acrylate oligomer, 30 parts of bisphenol A dimethacrylate, 2 parts of emulsified silicone oil, 0.01 part of crosslinking curing agent, 10 parts of nano aluminum oxide, 12 parts of polyformaldehyde and 10 parts of composite coupling agent B; the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH560, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 0.5% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving the nano aluminum oxide and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding emulsified silicone oil and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
The crosslinking curing agent is prepared by the following method:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 2 hours after dropwise adding is finished, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
The reaction formula is as follows:
referring to fig. 1, a liquid chromatogram of the crosslinking curing agent prepared in the present invention (acetonitrile: water: 5:1) shows that the compound is pure and peaks at about 32 min.
A preparation method of an OCA acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.2% to obtain a coupling agent A solution;
s2, dissolving polylactic acid, hindered phenol main antioxidant and phosphite auxiliary antioxidant in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by ultraviolet light to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 300r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 3S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing by adopting ultraviolet irradiation to obtain the acoustic film.
Example 2
The raw materials comprise the following components in parts by weight: 150 parts of modified OCA adhesive emulsion, 17 parts of polylactic acid, 3 parts of hindered phenol main antioxidant and 5 parts of coupling agent A. The coupling agent A is DL 171.
Preparing a modified OCA adhesive emulsion:
the raw materials comprise the following components in parts by weight: 30 parts of acrylic acid, 120 parts of acrylate adhesive, 30 parts of urethane acrylate oligomer, 50 parts of bisphenol A dimethacrylate, 5 parts of high-carbon alcohol fatty acid ester compound, 0.03 part of crosslinking curing agent, 15 parts of nano aluminum oxide, 17 parts of polyformaldehyde and 20 parts of composite coupling agent B; the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH570, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 1% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving nano aluminum oxide and polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding a high-carbon alcohol fatty acid ester compound and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
The crosslinking curing agent is prepared by the following method:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 3 hours after dropwise adding is completed, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
A preparation method of an OCA acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.4% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and hindered phenol main antioxidant in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 500r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing by adopting ultraviolet irradiation to obtain the acoustic film.
Example 3
The raw materials comprise the following components in parts by weight: 130 parts of modified OCA adhesive emulsion, 13 parts of polylactic acid, 1 part of phosphite ester auxiliary antioxidant and 2 parts of coupling agent A. The coupling agent A is KH 792.
Preparing a modified OCA adhesive emulsion:
the raw materials comprise the following components in parts by weight: 15 parts of acrylic acid, 105 parts of acrylate adhesive, 22 parts of urethane acrylate oligomer, 35 parts of bisphenol A dimethacrylate, 2 parts of polyoxyethylene polyoxypropylene ether, 0.02 part of crosslinking curing agent, 12 parts of nano aluminum oxide, 13 parts of polyformaldehyde and 12 parts of composite coupling agent B; the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH570, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 0.7% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving nano aluminum oxide and polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding polyoxyethylene polyoxypropylene amine ether and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
The crosslinking curing agent is prepared by the following method:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 2.5 hours after dropwise adding is finished, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
A preparation method of an OCA acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.25% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and phosphite ester auxiliary antioxidant in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 350r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 4S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing by adopting ultraviolet irradiation to obtain the acoustic film.
Example 4
The raw materials comprise the following components in parts by weight: 140 parts of modified OCA adhesive emulsion, 16 parts of polylactic acid, 2 parts of phosphite ester auxiliary antioxidant and 4 parts of coupling agent A. The coupling agent A is DL 602.
Preparing a modified OCA adhesive emulsion:
the raw materials comprise the following components in parts by weight: 25 parts of acrylic acid, 115 parts of acrylate adhesive, 27 parts of urethane acrylate oligomer, 45 parts of bisphenol A dimethacrylate, 4 parts of polyoxypropylene polyoxyethylene glycerol ether, 0.03 part of crosslinking curing agent, 14 parts of nano aluminum oxide, 15 parts of polyformaldehyde and 17 parts of composite coupling agent B; the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is DL171, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 0.9% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving nano aluminum oxide and polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding polyoxypropylene polyoxyethylene glycerol ether and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
The crosslinking curing agent is prepared by the following method:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 2.5 hours after dropwise adding is finished, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
A preparation method of an OCA acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.35% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and phosphite ester auxiliary antioxidant in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 450r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 6S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing by adopting ultraviolet irradiation to obtain the acoustic film.
Example 5
The raw materials comprise the following components in parts by weight: 135 parts of modified OCA adhesive emulsion, 14 parts of polylactic acid, 1.5 parts of hindered phenol main antioxidant and 3 parts of coupling agent A. The coupling agent A is KH 560.
Preparing a modified OCA adhesive emulsion:
the raw materials comprise the following components in parts by weight: 20 parts of acrylic acid, 110 parts of acrylate adhesive, 25 parts of urethane acrylate oligomer, 40 parts of bisphenol A dimethacrylate, 3 parts of polydimethylsiloxane, 0.022 part of crosslinking curing agent, 13 parts of nano aluminum oxide, 14 parts of polyformaldehyde and 14 parts of composite coupling agent B; the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH570, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 0.7% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving the nano aluminum oxide and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding polydimethylsiloxane and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
The crosslinking curing agent is prepared by the following method:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 2.5 hours after dropwise adding is finished, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
A preparation method of an OCA acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.3% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and hindered phenol main antioxidant in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 400r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 3-7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is obtained, and curing the hollow stainless steel tube by adopting ultraviolet irradiation to obtain the acoustic film.
Comparative example 1
Compared to example 5, an unmodified conventional OCA adhesive emulsion was used.
Comparative example 2
Compared to example 5, no polylactic acid was added.
Comparative example 3
In comparison with example 5, the composite coupling agent was not used, and a single silane coupling agent a171 was used.
Test example 1
The performance test of the OCA acoustic films prepared in examples 1 to 5 of the present invention and comparative examples 1 to 3 was performed, and the results are shown in table 1.
Table 1 table of performance test results
As can be seen from the above table, the acoustic thin films prepared in examples 1 to 5 of the present invention have a diameter of 1.75mm to 2.77mm and a thickness of 2.7 μm to 7.0 μm; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 55-110mv/pa, static pressure sensitivity of 7um/pa and long service life of 15-20 years; the acoustic film prepared by the unmodified common OCA adhesive emulsion in the comparative example 2 has poor mechanical property, the value of the diameter size is smaller than that of the upper thickness size, and the acoustic property is poor; in the comparative example 3, the LCP material is modified, so that the mechanical property is poor, and the fracture growth rate is only 59%; comparative example 4 does not adopt a compound coupling agent for coupling modification, has poor modification effect, little improvement on mechanical properties, a fracture growth rate of only 75 percent and poor acoustic characteristics.
Compared with the prior art, the crosslinking curing agent prepared by the invention is an imidazole curing agent, wherein original secondary amine is replaced by tertiary amine, and new tertiary amine groups are introduced, so that the modified imidazole curing agent is beneficial to normal-temperature curing, and can complete good curing performance even in a very small addition amount, thereby reducing the cost and enabling the product to have good mechanical property and thermal property;
the acoustic film prepared by the modified OCA adhesive emulsion material has excellent mechanical properties, good toughness and elasticity on the premise of extremely thin film material, good acoustic characteristics and high sensitivity; the OCA material is modified by adopting the nano aluminum oxide, so that the toughness of the OCA material is further enhanced, and the OCA material still has excellent mechanical properties when an ultrathin acoustic film is prepared;
according to the invention, two different silane modifiers are compounded to modify different particles, wherein one common silane modifier helps inorganic particles with oxygen on the surface to be modified and linked with a modified OCA adhesive emulsion, a silane coupling agent with amino helps organic particles such as polyformaldehyde and the like to be modified and linked with the modified OCA adhesive emulsion, and the modified particles and the modified OCA adhesive emulsion material are chemically bonded through the compounded silane coupling agent to prepare the modified OCA adhesive emulsion with better toughness and mechanical property for later-stage preparation of an OCA acoustic membrane material;
the acoustic film prepared by the method has smooth and stable surface, the diameter is 1.75mm-2.77mm, and the thickness is 2.7 mu m-7.0 mu m; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 55-110mv/pa and static pressure sensitivity of 7 um/pa.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.
Claims (10)
1. An OCA acoustic film is characterized by being prepared from the following raw materials: modified OCA adhesive emulsion, polylactic acid, an antioxidant and a coupling agent A;
the modified OCA adhesive emulsion is prepared from the following raw materials: acrylic acid, acrylate adhesive, polyurethane acrylate oligomer, bisphenol A dimethacrylate, defoaming agent, crosslinking curing agent, nano aluminum oxide, polyformaldehyde and composite coupling agent B;
the crosslinking curing agent has a structure shown in formula I:
the sensitivity of the OCA acoustic membrane in the sound wave frequency range of 0.025Hz-25000Hz is 55-110mv/pa, and the static pressure sensitivity is less than or equal to 7 um/pa.
2. The OCA acoustic film of claim 1, which is prepared from the following raw materials in parts by weight: 150 parts of modified OCA adhesive emulsion, 12-17 parts of polylactic acid, 1-3 parts of antioxidant and 1-5 parts of coupling agent A;
the modified OCA adhesive emulsion is prepared from the following raw materials in parts by weight: 10-30 parts of acrylic acid, 120 parts of acrylate adhesive, 20-30 parts of polyurethane acrylate oligomer, 30-50 parts of bisphenol A dimethacrylate, 2-5 parts of defoaming agent, 0.01-0.03 part of crosslinking curing agent, 10-15 parts of nano aluminum oxide, 12-17 parts of polyformaldehyde and 20-20 parts of composite coupling agent B10.
3. The OCA acoustic membrane of claim 1, wherein the defoaming agent is selected from silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, and mixtures thereof.
4. The OCA acoustic film of claim 1, wherein the modified OCA adhesive emulsion is prepared by the following method:
s1, mixing acrylic acid, an acrylate adhesive, a polyurethane acrylate oligomer and bisphenol A dimethacrylate to obtain an acrylic acid mixed solution;
s2, preparing the composite coupling agent B into a dilute solution with the concentration of 0.5-1% to obtain a composite coupling agent B solution;
and S3, mixing and dissolving the nano aluminum oxide and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the acrylic acid mixed solution prepared in the step S1, uniformly mixing, and adding a defoaming agent and a crosslinking curing agent to obtain the modified OCA adhesive emulsion.
5. The OCA acoustic film according to claim 1 or 5, wherein the crosslinking curing agent is prepared by a method comprising:
s1, dissolving 2-methyl-3- (dimethyl) aminophenol in a solvent, mixing the solution with malic acid, dropwise adding concentrated sulfuric acid in an ice bath, stirring the solution at room temperature for 1h, heating to 70 ℃, reacting for 3h, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate A;
s2, dissolving the intermediate A in a solvent, slowly dropwise adding thionyl chloride under ice bath, stirring while dropwise adding, continuously stirring for reacting for 2-3h after dropwise adding is finished, stopping the reaction, removing the solvent by rotary evaporation, washing with methanol, and performing suction filtration to obtain an intermediate B;
s3, dissolving imidazole and sodium borohydride in a solvent, adding the intermediate B, heating to 70 ℃, reacting for 2 hours, cooling, pouring into water, extracting with ethyl acetate, washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, removing the solvent by rotary evaporation, and recrystallizing with methanol to obtain the crosslinking curing agent.
6. The OCA acoustic membrane of claim 1, wherein the coupling agent a is selected from one of KH550, KH560, KH570, KH792, DL602, and DL 171.
7. The OCA acoustic membrane of claim 1, wherein the composite coupling agent B comprises a composite of a common silane coupling agent and a silane coupling agent with an amino group, the mass ratio of the common silane coupling agent to the silane coupling agent with an amino group is 5:2, and the common silane coupling agent comprises one of KH550, KH560, KH570, KH792, DL602 and DL 171.
8. The OCA acoustic film of claim 1, wherein the antioxidant is selected from the group consisting of hindered phenolic primary antioxidants and/or phosphite secondary antioxidants.
9. The OCA acoustic membrane of claim 1, wherein the OCA acoustic membrane has a diameter of 1.75mm to 2.77mm and a thickness of 2.7 μ ι η to 7.0 μ ι η.
10. A method of making an OCA acoustic membrane according to any one of claims 1-9, comprising the steps of:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.2-0.4% to obtain a coupling agent A solution;
s2, dissolving styrene butadiene rubber, polylactic acid and an antioxidant in an ethanol aqueous solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by using ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified OCA adhesive emulsion in an N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 300-500r/min for 30min, then immersing the tail end of the hollow stainless steel tube in the mixed solution for 3-7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out the hollow stainless steel tube until the hollow stainless steel tube is cured by adopting ultraviolet irradiation, and obtaining the acoustic film.
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