WO2019237600A1 - Adhésif acrylique sensible à la pression et son procédé de préparation, structure de film composite, diaphragme et dispositif de production de son - Google Patents

Adhésif acrylique sensible à la pression et son procédé de préparation, structure de film composite, diaphragme et dispositif de production de son Download PDF

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Publication number
WO2019237600A1
WO2019237600A1 PCT/CN2018/110158 CN2018110158W WO2019237600A1 WO 2019237600 A1 WO2019237600 A1 WO 2019237600A1 CN 2018110158 W CN2018110158 W CN 2018110158W WO 2019237600 A1 WO2019237600 A1 WO 2019237600A1
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Prior art keywords
sensitive adhesive
pressure
adhesive layer
layer
composite film
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PCT/CN2018/110158
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English (en)
Chinese (zh)
Inventor
王海峰
王婷
李春
刘春发
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歌尔股份有限公司
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Publication of WO2019237600A1 publication Critical patent/WO2019237600A1/fr

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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension

Definitions

  • the present invention relates to the technical field of sound generating devices, and in particular, to an acrylic pressure-sensitive adhesive, a method for preparing the acrylic pressure-sensitive adhesive, a composite film structure using the acrylic pressure-sensitive adhesive, a diaphragm using the composite film structure, and A sound generating device using the diaphragm.
  • the present invention provides an acrylic pressure-sensitive adhesive, which aims to make the diaphragm applied with the acrylic pressure-sensitive adhesive have better damping performance without increasing the thickness of the pressure-sensitive adhesive to solve the problem. Low-frequency distortion of the sound generator.
  • the raw materials for making the acrylic pressure-sensitive adhesive include:
  • the soft monomer is n-butyl acrylate and / or 2-ethylhexyl acrylate; and / or,
  • the hard monomer is at least one of methyl methacrylate, styrene, and acrylic acid; and / or,
  • the functional monomer is at least one of methacrylic acid, acrylamide, and acrylic acid; and / or,
  • the initiator is benzoyl peroxide and / or azobisisobutyronitrile; and / or,
  • the cross-linking agent is ethyl isocyanate methacrylate and / or aluminum acetate; and / or,
  • the damping modifier is at least one of nitrile rubber, neoprene, chlorinated polyethylene rubber, and butyl rubber; and / or,
  • the organic solvent is at least one of benzene, toluene, ethyl acetate, xylene, N-methylpyrrolidone and methyl ethyl ketone.
  • the invention also provides a method for preparing an acrylic pressure-sensitive adhesive, including the following steps:
  • the colloid added with a crosslinking agent is dried to obtain a pressure-sensitive adhesive.
  • the step of drying the colloid added with a cross-linking agent includes sequentially performing a first drying treatment and a second drying treatment on the colloid added with a cross-linking agent, and the first drying
  • the drying temperature of the treatment is 70 to 100 ° C
  • the drying time is 2 to 3 minutes
  • the drying temperature of the second drying treatment is 130 to 150 ° C
  • the drying time is 2 to 3 minutes; and / or,
  • the heating temperature of the heat treatment is 75 to 85 ° C, and the heating time is 6 to 8 hours.
  • the present invention also provides a composite film structure, which includes two first substrate layers and at least one first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer is sandwiched between the two first substrates. Between the material layers, at least one of the two first substrate layers is a plastic substrate layer, and the material of the first pressure-sensitive adhesive layer is the acrylic pressure-sensitive adhesive described in the above embodiment.
  • the material of the plastic substrate layer is polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, and polyterephthalic acid. At least one of glycol esters; and / or,
  • the thickness of the first substrate layer ranges from 2 to 40 ⁇ m; and / or,
  • the thickness of the first pressure-sensitive adhesive layer ranges from 2 to 40 ⁇ m.
  • the composite film structure includes a second pressure-sensitive adhesive layer and a second substrate layer.
  • the second substrate layer includes a first surface and a second surface opposite to each other.
  • the first pressure-sensitive adhesive layer is sandwiched between the first pressure-sensitive adhesive layer and the second surface.
  • the second pressure-sensitive adhesive layer is sandwiched between the second surface of the second substrate layer and another first substrate layer, and the second
  • the material of the pressure-sensitive adhesive layer is the same as that of the first pressure-sensitive adhesive layer, or the material of the second pressure-sensitive adhesive layer is a silicone-based pressure-sensitive adhesive.
  • the second substrate layer is a thermoplastic elastomer layer or an engineering plastic layer
  • the thermoplastic elastomer layer is selected from a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer
  • At least one of the engineering plastic layer is selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyterephthalate At least one of ethylene glycol formate and polybutylene terephthalate; and / or,
  • the thickness of the second pressure-sensitive adhesive layer ranges from 2 to 40 ⁇ m; and / or,
  • the thickness of the second substrate layer ranges from 1 to 30 ⁇ m.
  • the present invention also provides a composite film structure, which includes two first substrate layers and at least one first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer is sandwiched between the two first substrates.
  • Between the material layers, at least one of the two first substrate layers is a thermoplastic elastomer layer, and the material of the first pressure-sensitive adhesive layer is the acrylic pressure-sensitive adhesive described in the above embodiment.
  • the material of the thermoplastic elastomer layer includes at least one of a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer; and / or,
  • the thickness of the first substrate layer ranges from 5 to 40 ⁇ m; and / or,
  • the thickness of the first pressure-sensitive adhesive layer ranges from 2 to 40 ⁇ m.
  • the two substrate layers are both thermoplastic elastomer layers
  • the composite film structure includes a first thermoplastic elastomer layer, the first pressure-sensitive adhesive layer, and a second thermoplastic elastomer layer that are sequentially stacked.
  • thermoplastic elastomer layer the materials of the first thermoplastic elastomer layer and the second thermoplastic elastomer layer are the same.
  • the composite film structure includes a second pressure-sensitive adhesive layer and a second substrate layer.
  • the second substrate layer includes a first surface and a second surface opposite to each other.
  • the first pressure-sensitive adhesive layer is sandwiched between the first pressure-sensitive adhesive layer and the second surface.
  • the second pressure-sensitive adhesive layer is sandwiched between the second surface of the second substrate layer and another first substrate layer, and the second
  • the material of the pressure-sensitive adhesive layer is the same as that of the first pressure-sensitive adhesive layer, or the material of the second pressure-sensitive adhesive layer is a silicone-based pressure-sensitive adhesive.
  • the material of the second substrate layer is a thermoplastic elastomer or an engineering plastic
  • the thermoplastic elastomer is selected from the group consisting of thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, and silicone elastomer.
  • the engineering plastic is selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, and polyethylene terephthalate At least one of a glycol ester and polybutylene terephthalate; and / or,
  • the thickness of the second pressure-sensitive adhesive layer ranges from 2 to 40 ⁇ m; and / or,
  • the thickness of the second substrate layer ranges from 1 to 30 ⁇ m.
  • the invention also provides a diaphragm, which has the composite film structure described in the above embodiment.
  • the invention also provides a sound generating device, which comprises the diaphragm described in the above embodiment.
  • the raw materials for making the acrylic pressure-sensitive adhesive according to the technical solution of the present invention include: 30 to 45 parts of soft monomers, 5 to 20 parts of hard monomers, 1 to 10 parts of functional monomers, 0.01 to 1 part of initiator, 0.01 to 1 part of cross-linking agent, 30 to 45 parts of organic solvent and 5 to 10 parts of damping modifier.
  • the soft monomer, hard monomer and functional monomer will undergo polymerization reaction under the action of the initiator, and cross-link A cross-linking reaction further occurs under the action of a cross-linking agent, thereby generating an acrylic pressure-sensitive adhesive having a three-dimensional network structure.
  • the three-dimensional network structure can make the acrylic pressure-sensitive adhesive have a dense structure to make the acrylic pressure-sensitive adhesive.
  • the diaphragm can ensure better damping performance without increasing the thickness of the acrylic pressure-sensitive adhesive, thereby solving the problem of low-frequency distortion of the sound device.
  • FIG. 1 is a cross-sectional view of a first embodiment of a composite membrane structure of the present invention.
  • FIG. 2 is a cross-sectional view of a second embodiment of the composite membrane structure of the present invention.
  • FIG 3 is a cross-sectional view of an embodiment of a diaphragm according to the present invention.
  • Label name Label name 100 Composite membrane structure 51 First surface 10 First substrate layer 53 Second surface 30 First pressure-sensitive adhesive layer 200 Diaphragm 30 ’ Second pressure-sensitive adhesive layer twenty one Folding ring 50 Second substrate layer twenty three Ball top
  • the invention provides an acrylic pressure-sensitive adhesive.
  • the raw materials for making acrylic pressure-sensitive adhesives include:
  • the raw materials for making the acrylic pressure-sensitive adhesive according to the technical solution of the present invention include: 30 to 45 parts of soft monomers, 5 to 20 parts of hard monomers, 1 to 10 parts of functional monomers, 0.01 to 1 part of initiator, 0.01 to 1 part of cross-linking agent, 30 to 45 parts of organic solvent and 5 to 10 parts of damping modifier.
  • the soft monomer, hard monomer and functional monomer will undergo polymerization reaction under the action of the initiator, and cross-link A cross-linking reaction further occurs under the action of a cross-linking agent, thereby generating an acrylic pressure-sensitive adhesive having a three-dimensional network structure.
  • the three-dimensional network structure can make the acrylic pressure-sensitive adhesive have a dense structure to make the acrylic pressure-sensitive adhesive.
  • the diaphragm can still ensure better damping performance without increasing the thickness of the acrylic pressure-sensitive adhesive, thereby solving the problem of low-frequency distortion of the sound device.
  • the soft monomer is n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • Soft monomers provide initial tack and peel strength for acrylic pressure-sensitive adhesives. If the amount of soft monomer is too small, the wettability and initial tack of acrylic pressure-sensitive adhesive are too poor; if too much is used, the acrylic pressure-sensitive adhesive's holding power is too poor.
  • the hard monomer is at least one of methyl methacrylate, styrene, and acrylic acid. If the amount of the hard monomer is too small, the cohesive force of the acrylic pressure-sensitive adhesive is insufficient; if it is too large, the initial viscosity of the acrylic pressure-sensitive adhesive is poor.
  • the functional monomer is at least one of methacrylic acid, acrylamide, and acrylic acid.
  • Functional monomers can be used to adjust the adhesion of acrylic pressure-sensitive adhesives to substrates.
  • the initiator is benzoyl peroxide and / or azobisisobutyronitrile.
  • the role of the initiator is to provide free radicals for the polymerization of acrylic monomers. If the amount is too small, the conversion rate of the acrylic pressure-sensitive adhesive will be reduced, and the polymerization reaction will not be complete. As a result, the cohesive force of the acrylic pressure-sensitive adhesive is reduced.
  • the cross-linking agent is ethyl isocyanate methacrylate and / or aluminum acetate.
  • the role of the cross-linking monomer causes a cross-linking reaction between the soft monomer, the hard monomer and the functional monomer, and increases the cohesive force of the acrylic pressure-sensitive adhesive. If the amount is too small, the degree of crosslinking of the acrylic pressure-sensitive adhesive is insufficient, which will lead to degumming; if the amount is too large, the crosslinking will be excessive, which will cause the initial viscosity of the acrylic pressure-sensitive adhesive to be seriously reduced.
  • the damping modifier is at least one of a nitrile rubber, a neoprene rubber, a chlorinated polyethylene rubber, and a butyl rubber.
  • the damping modifier has better damping characteristics. After adding it to the acrylic pressure-sensitive adhesive, the damping characteristics of the acrylic pressure-sensitive adhesive can be greatly improved.
  • the organic solvent is at least one of benzene, toluene, ethyl acetate, xylene, N-methylpyrrolidone and methyl ethyl ketone.
  • the soft monomer, the hard monomer, the functional monomer, the initiator, the cross-linking agent, and the damping modifier are soluble in the organic solvent.
  • the invention also provides a method for preparing an acrylic pressure-sensitive adhesive, including the following steps:
  • damping modifier 5 to 10 parts of damping modifier and 30 to 45 parts of organic solvent are provided by weight part, and the damping modifier is added to the organic solvent to obtain a mixture;
  • the colloid containing the crosslinking agent is dried to obtain an acrylic pressure-sensitive adhesive.
  • the damping modifier can be plasticized on an open mill for 10 to 15 minutes before being put into an organic solvent.
  • the organic solvent is at least one of benzene, toluene, ethyl acetate, xylene, N-methylpyrrolidone and methyl ethyl ketone.
  • the colloid added with a crosslinking agent when the colloid added with a crosslinking agent is dried to obtain an acrylic pressure-sensitive adhesive, the colloid may be coated on a substrate, and then the colloid is dried.
  • the material of the substrate may be a thermoplastic elastomer layer, a release film or an engineering plastic layer.
  • the thermoplastic elastomer layer is selected from at least a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer.
  • the engineering plastic layer is selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate Ester and at least one of polybutylene terephthalate.
  • the soft monomer, the hard monomer and the functional monomer of the technical solution of the present invention undergo a polymerization reaction under the action of an initiator, and further undergo a cross-linking reaction under the action of a cross-linking agent, thereby generating acrylic acid having a three-dimensional network structure.
  • Pressure-sensitive adhesive, the three-dimensional network structure can make the acrylic pressure-sensitive adhesive have a dense structure, so that the acrylic pressure-sensitive adhesive has better damping performance, and the addition of a damping modifier can further improve the pressure-sensitive adhesive Damping performance of pressure-sensitive adhesive.
  • the diaphragm can ensure better damping performance without increasing the thickness of the acrylic pressure-sensitive adhesive, thereby solving the problem of low-frequency distortion of the sound device.
  • the step of drying the colloid added with the crosslinking agent includes sequentially performing the first drying treatment and the second drying treatment on the colloid added with the crosslinking agent, and the drying temperature of the first drying treatment is 70 to 100. °C, drying time is 2 ⁇ 3min, drying temperature of the second drying treatment is 130 ⁇ 150 ° C, drying time is 2 ⁇ 3min.
  • the first drying process removes organic solvents from the colloid.
  • the second drying treatment can further cause a crosslinking reaction between the soft monomer, the hard monomer and the functional monomer, so as to cure the colloid to obtain an acrylic pressure-sensitive adhesive.
  • the polymerization of the soft monomers, hard monomers, and functional monomers occurs under the action of the initiator.
  • the present invention also provides a composite film structure 100.
  • the composite film structure 100 includes two first substrate layers 10 and at least one first pressure-sensitive adhesive layer 30 sandwiched therebetween. Between the two first substrate layers 10, at least one of the two first substrate layers 10 is a plastic substrate layer, and the material of the first pressure-sensitive adhesive layer 10 is the acrylic pressure-sensitive adhesive described in the above embodiment. gum.
  • the composite membrane structure 100 adopts all the technical solutions of all the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, which will not be described in detail here.
  • the material of the plastic substrate layer includes polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate At least one of.
  • the material may include at least one of a polyester elastomer, a polyurethane elastomer, and a silicone elastomer. Of course, other materials may also be used. The invention does not limit this.
  • the thickness of the first base material layer 10 ranges from 2 to 40 ⁇ m.
  • the thickness of the first substrate layer 10 is 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m , 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, 30 ⁇ m, 31 ⁇ m, 32 ⁇ m, 33 ⁇ m, 34 ⁇ m, 35 ⁇ m, 36 ⁇ m, 37 ⁇ m, 38 ⁇ m, 39 ⁇ m, or 40 ⁇ m.
  • the two first substrate layers 10 can be made of the same material or different materials.
  • At least one of the first substrate layers 10 in the technical solution of the present invention is a plastic substrate layer
  • the material of the plastic substrate layer is selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, and polyimide
  • the thickness of the first pressure-sensitive adhesive layer 30 ranges from 2 to 40 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer 30 is 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, 30 ⁇ m, 31 ⁇ m, 32 ⁇ m, 33 ⁇ m, 34 ⁇ m, 35 ⁇ m, 36 ⁇ m, 37 ⁇ m, 38 ⁇ m, 39 ⁇ m, or 40 ⁇ m.
  • the thickness of the first pressure-sensitive adhesive layer 30 of the technical solution of the present invention ranges from 2 to 40 ⁇ m, so that the composite film structure 100 using the first pressure-sensitive adhesive layer 30 has better high temperature resistance characteristics, even when the input voltage increases, The rigidity and damping performance of the composite membrane structure 100 will not be significantly reduced.
  • the two base material layers 10 are both plastic base material layers.
  • the composite film structure 100 is a first plastic substrate layer, a first pressure-sensitive adhesive layer, and a second plastic substrate layer that are sequentially stacked.
  • the materials of the first thermoplastic substrate layer and the second plastic substrate layer may be the same or different.
  • the materials of the first plastic substrate layer and the second plastic substrate layer are the same, for example, both are polyetheretherketone.
  • the composite film structure is a polyetheretherketone, an acrylic pressure-sensitive adhesive, and a polyetheretherketone structure which are sequentially stacked.
  • the acrylic pressure-sensitive adhesive is the acrylic pressure-sensitive adhesive modified by the damping modifier in the above embodiment.
  • the composite film structure 100 further includes a second pressure-sensitive adhesive layer 30 ′ and a second substrate layer 50.
  • the second substrate layer 50 includes a first surface 51 and a second surface 53 opposite to each other.
  • the adhesive layer 30 is sandwiched between the first surface 51 of the second substrate layer 50 and a first substrate layer 10, and the second pressure-sensitive adhesive layer 30 ′ is sandwiched between the second surface 53 of the second substrate layer 50.
  • the material of the second pressure-sensitive adhesive layer 30 ′ is the same as that of the first pressure-sensitive adhesive layer 30, or the material of the second pressure-sensitive adhesive layer 30 ′ is silicone Class pressure-sensitive adhesive.
  • the material of the second pressure-sensitive adhesive layer 30 ' may also be an adhesive of other materials, which is not limited in the present invention.
  • the material of the second substrate layer 50 is a thermoplastic elastomer or an engineering plastic.
  • the thermoplastic elastomer is selected from at least one of a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer.
  • the engineering plastic Selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate, and polyterephthalate At least one of butylene glycol formate.
  • the thickness of the second pressure-sensitive adhesive layer 30 ' ranges from 2 to 40 m.
  • the thickness of the second base material layer 50 ranges from 1 to 30 ⁇ m.
  • the thickness of the second pressure-sensitive adhesive layer 30 ' is 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, 30 ⁇ m, 31 ⁇ m, 32 ⁇ m, 33 ⁇ m, 34 ⁇ m, 35 ⁇ m, 36 ⁇ m, 37 ⁇ m, 38 ⁇ m, 39 ⁇ m, or 40 ⁇ m.
  • the thickness of the second substrate layer 50 is 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m , 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, or 30 ⁇ m.
  • the composite film structure 100 of the technical solution of the present invention includes two layers of a first substrate layer 10, a first pressure-sensitive adhesive layer 30, a second pressure-sensitive adhesive 30 ', and a second substrate layer 50, one of which is a pressure-sensitive adhesive layer 30 It is sandwiched between the first surface 51 of the second substrate layer 50 and a first substrate layer 10, and the second pressure-sensitive adhesive layer 30 'is sandwiched between the second surface 53 of the second substrate layer 50 and another Between the first substrate layers 10 to increase the stiffness and anti-polarization capability of the composite film structure 100.
  • the material of the second pressure-sensitive adhesive layer 30 ' may be a silicone-based pressure-sensitive adhesive.
  • the raw materials of the silicone pressure-sensitive adhesive include:
  • the catalyst is an organic complex of platinum or an organic tin compound.
  • the main role of the catalyst is to speed up the reaction.
  • the concentration of the platinum organic complex is 1 to 100 ul / L.
  • the organic complex of platinum may be at least one of a solution of chloroplatinic acid polysiloxane, a chloroplatinic acid isopropanol complex, and a chloroplatinic acid diethyl phthalate complex.
  • the organic tin-based compound is at least one selected from the group consisting of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, and stannous octoate.
  • the organic solvent is at least one of benzene, toluene, ethyl acetate, xylene, N-methylpyrrolidone and methyl ethyl ketone.
  • the silicone resin and the silicone rubber can be dissolved in the organic solvent for uniform mixing.
  • the manufacturing materials of the second pressure-sensitive adhesive layer 30 'of the technical solution of the present invention include: 20 to 80 parts of silicone resin, 30 to 90 parts of organic solvent, 0.1 to 5 parts of catalyst, 5 to 55 parts of silicone rubber, and silicone rubber.
  • a condensation reaction occurs with the silicone resin, a cross-linking reaction occurs between the silicone rubber, and the catalyst accelerates the reaction speed, thereby generating a three-dimensional network-structured silicone pressure-sensitive adhesive.
  • the three-dimensional network structure can make the
  • the silicone pressure-sensitive adhesive has a dense structure, so that the silicone pressure-sensitive adhesive has better high temperature resistance, and the silicone resin has the advantages of large molecular weight and high modulus.
  • the silicone resin is set to 20 to 80 parts.
  • the silicone rubber is set to 5 to 55 parts to improve the film-forming property, adhesiveness and return of the silicone-based pressure-sensitive adhesive.
  • the elasticity makes the diaphragm using the silicone pressure-sensitive adhesive not to cause polarization phenomenon during the vibration process, so that the sound generating device using the diaphragm has better sound quality and listening stability.
  • the second pressure-sensitive adhesive layer 30 'of the present invention has high damping property, and its loss factor is ⁇ 0.5.
  • the second pressure-sensitive adhesive layer 30 'of the present invention has better high temperature holding viscosity. In a test environment at 150 ° C, its falling time is more than 1 hour.
  • the silicone resin includes an M chain link and a Q chain link.
  • the M chain link is
  • the Q chain link is
  • R 1 is a methyl group, a hydrogen group, or a vinyl group, and the range of m is 15-20.
  • the number ratio between the M chain links and the Q chain links is 1: 0.6 to 0.9.
  • the M chain link of the silicone resin can improve the compatibility with the silicone rubber and play a role of increasing the viscosity.
  • the Q chain link has a reinforcing effect and can improve the cohesive strength of the second pressure-sensitive adhesive layer 30 'produced.
  • the compatibility between the silicone resin and the silicone rubber is poor, and when the number of M chain links and Q chain links is relatively large, the second pressure-sensitive adhesive layer 30 is obtained. 'Cohesive strength is poor.
  • the number ratio of the M chain link and the Q chain link in the technical solution of the present invention is set to 1: 0.6 to 0.9, which not only can make the silicone resin and the silicone rubber have better compatibility, so that the second pressure
  • the sensitive adhesive layer 30 ' has good comprehensive performance and high solid content, and can also make the second pressure-sensitive adhesive layer 30' prepared with better elasticity and cohesive strength.
  • R1 in the M chain link is a methyl group, a hydrogen group or a vinyl group, and the hydrogen group and the vinyl group can be used for a condensation reaction or an addition reaction with a silicone rubber.
  • m in the Q link may be 15, 16, 17, 18, 19, or 20.
  • the value of m in the Q chain link represents the content of hydroxyl groups.
  • the content of hydroxyl groups will affect the degree of reaction between silicone resin and silicone rubber, and affect the properties of silicone pressure-sensitive adhesives, such as adhesion and bonding strength.
  • the value of m in the Q chain link of the present invention ranges from 15 to 20, so that the prepared silicone pressure-sensitive adhesive has better adhesion and bonding strength.
  • R 2 is a methyl group, a vinyl group, or a phenyl group, and the range of n is 5000 to 10,000. Phenyl can increase the heat resistance of silicone pressure-sensitive adhesives, and vinyl can crosslink with other groups.
  • the silicone rubber of the present invention has a linear structure with a hydroxyl group as an end group, and the hydroxyl group can undergo a condensation reaction with the silicone resin.
  • the range of the silicone rubber n is 5000 to 10,000, so that the molecular weight of the silicone rubber is moderate, so that the prepared second pressure-sensitive adhesive layer 30 'has better flexibility, cohesive strength, low mobility, good viscosity, And solid content.
  • the silicone rubber is at least one of methyl hydroxy silicone rubber, vinyl silicone rubber, and phenyl silicone rubber.
  • the mass ratio of silicone resin and silicone rubber ranges from 1: 1 to 15: 1.
  • the mass ratio of silicone resin and silicone rubber is: 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, 12: 1, 13: 1, 14: 1, or 15: 1, etc.
  • the range of the mass ratio of the silicone resin and the silicone rubber according to the technical solution of the present invention is set to 1: 1 to 15: 1, so that the prepared second pressure-sensitive adhesive layer 30 'has better initial tack and stickiness.
  • the raw material of the second pressure-sensitive adhesive layer 30 'further includes 0 to 5 parts by weight of a crosslinking agent.
  • the crosslinking agent is a hydrogen-containing silicone oil, an organic peroxide, or an alkoxysilane.
  • the role of the cross-linking agent is to cause the cross-linking reaction of the silicone rubber and increase the cohesive force of the silicone pressure-sensitive adhesive.
  • Hydrogen-containing silicone oil refers to a silicone oil containing an S-H bond. Understandably, the silicone rubber also undergoes a crosslinking reaction with the hydrogen-containing silicone oil.
  • Organic peroxides can be benzoyl peroxide, t-butyl hydroperoxide, dicumene peroxide, 2,4-dichlorobenzoyl, 2,5-dimethyl-2,5-di ( Tert-butylperoxy) hexane, di- (tert-butylisopropylperoxy) benzene, and the like.
  • the alkoxysilane may be epoxysilane, tetramethoxysilane, octyltrimethoxysilane, di-tert-butoxydiacetoxysilane, methoxysilane, 3- (2,3-glycidoxy) At least one of propyltrimethoxysilane, methyltriacetoxyoximylsilane, methyltrimethoxysilane, vinyltrimethoxysilane, ethoxysilane, propoxysilane, and butoxysilanekind and so on.
  • the raw materials of the second pressure-sensitive adhesive layer 30 'further include 0 to 5 parts by weight of the reaction inhibitor.
  • the reaction inhibitor is at least one of an alkynol compound, a nitrogen-containing compound, and a vinyl compound.
  • the reaction inhibitor can slow down the reaction speed, so that the storage period of the pressure-sensitive adhesive is prolonged.
  • the alkynol compound may be ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3-phenyl-1-butyn-3-ol, and 3-propyl-1-butyn- At least one of 3-alcohols.
  • the nitrogen-containing compound may be at least one of quinoline, methylhydrazine, and phenylhydrazine.
  • the vinyl compound may be perchloroethylene and / or tetravinyltetramethylcyclotetrasiloxane.
  • the present invention also provides a composite film structure 100.
  • the composite film structure 100 includes two first substrate layers 10 and at least one first pressure-sensitive adhesive layer 30 sandwiched therebetween. Between the two first substrate layers 10, at least one of the two first substrate layers 10 is a thermoplastic elastomer layer, and the material of the first pressure-sensitive adhesive layer 10 is the acrylic pressure-sensitive adhesive described in the above embodiment. gum.
  • the composite membrane structure 100 adopts all the technical solutions of all the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, which will not be described in detail here.
  • the material of the thermoplastic elastomer layer includes at least one of a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer.
  • the thickness of the first base material layer 10 ranges from 5 to 40 ⁇ m.
  • the thickness of the first substrate layer 10 is 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m , 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, 30 ⁇ m, 31 ⁇ m, 32 ⁇ m, 33 ⁇ m, 34 ⁇ m, 35 ⁇ m, 36 ⁇ m, 37 ⁇ m, 38 ⁇ m, 39 ⁇ m, or 40 ⁇ m.
  • the two first substrate layers 10 can be made of the same material or different materials.
  • the material of the first substrate layer 10 of the technical solution of the present invention is selected from at least one of a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer, so that the first substrate layer 10 At least one of the layers has a softening temperature greater than 80 ° C, has good high temperature resistance, and the thickness of the first substrate layer 10 is 5 to 40 ⁇ m, so that the composite film structure 100 not only has better strength and resilience, but also has excellent Structural stability, and high temperature resistance.
  • the thickness of the pressure-sensitive adhesive layer 30 ranges from 2 to 40 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer 30 is 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, 30 ⁇ m, 31 ⁇ m, 32 ⁇ m, 33 ⁇ m, 34 ⁇ m, 35 ⁇ m, 36 ⁇ m, 37 ⁇ m, 38 ⁇ m, 39 ⁇ m, or 40 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer 30 of the technical solution of the present invention ranges from 2 to 40 ⁇ m, so that the composite film structure 100 using the pressure-sensitive adhesive layer 30 has better high temperature resistance characteristics. Even when the input voltage increases, the composite film structure 100 The rigidity and damping performance will not be significantly reduced.
  • the two base material layers 10 are both thermoplastic elastomer layers.
  • the composite film structure 100 is a first thermoplastic elastomer layer, a first pressure-sensitive adhesive layer, and a second thermoplastic elastomer layer that are sequentially stacked.
  • the material between the first thermoplastic elastomer layer and the second thermoplastic elastomer layer may be the same. It can be different.
  • the material between the first thermoplastic elastomer layer and the second thermoplastic elastomer layer is the same.
  • the materials of the first thermoplastic elastomer layer and the second thermoplastic elastomer layer are both thermoplastic polyester elastomers.
  • the composite film structure is a thermoplastic polyester elastomer layer, an acrylic pressure-sensitive adhesive, and a thermoplastic polyester elastomer layer. Structures stacked one after another.
  • the acrylic pressure-sensitive adhesive is the acrylic pressure-sensitive adhesive modified by the damping modifier in the above embodiment.
  • the composite film structure 100 further includes a second pressure-sensitive adhesive layer 30 ′.
  • the composite film structure 100 further includes a second substrate layer 50, and the second substrate layer 50 includes a first surface 51 disposed oppositely. And a second surface 50, wherein a pressure-sensitive adhesive layer 30 is sandwiched between the first surface 51 of the second substrate layer 50 and a first substrate layer 10, and the second pressure-sensitive adhesive layer 30 'is sandwiched between Between the second surface 53 of the two base material layers 50 and another first base material layer 10.
  • the material of the second pressure-sensitive adhesive layer 30 ' is the same as that of the first pressure-sensitive adhesive layer 30, or the material of the second pressure-sensitive adhesive layer 30' is a silicone-based pressure-sensitive adhesive.
  • the material of the second pressure-sensitive adhesive layer 30 ' may also be an adhesive of other materials, which is not limited in the present invention.
  • the material of the second substrate layer 50 is a thermoplastic elastomer or an engineering plastic.
  • the thermoplastic elastomer is selected from at least one of a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, and a silicone elastomer.
  • Engineering plastics are selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate, and polyparaphenylene terephthalate. At least one of butylene phthalate.
  • the thickness of the second pressure-sensitive adhesive layer 30 ' ranges from 2 to 40 m.
  • the thickness of the second base material layer 50 ranges from 1 to 30 ⁇ m.
  • the thickness of the second substrate layer 50 is 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m , 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, or 30 ⁇ m.
  • the composite film structure 100 of the technical solution of the present invention includes two first substrate layers 10, two laminated sensitive adhesive layers, and a second substrate layer 50, wherein a pressure sensitive adhesive layer 30 is sandwiched between the second substrate layers 50 Between the first surface 51 and a first substrate layer 10, the second pressure-sensitive adhesive layer 30 ′ is sandwiched between the second surface 53 of the second substrate layer 50 and another first substrate layer 10, In order to increase the stiffness and anti-polarization ability of the composite film structure 100.
  • the material of the second pressure-sensitive adhesive is the same as the material of the second pressure-sensitive adhesive when at least one of the first substrate layers is a plastic substrate layer.
  • the material of the second pressure-sensitive adhesive is the same as the material of the second pressure-sensitive adhesive when at least one of the first substrate layers is a plastic substrate layer.
  • the present invention further provides a diaphragm 200.
  • the diaphragm 200 has this composite film structure.
  • the thickness of the diaphragm 200 may be 12 to 190 ⁇ m.
  • the diaphragm 200 adopts all the technical solutions of all the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, which will not be repeated one by one here.
  • the first substrate layer 10 provides a required rigidity for the vibration of the diaphragm 200 and obtains a high transient response.
  • the pressure-sensitive adhesive layer 30 has a high adhesive force, so that the vibration of each layer of the diaphragm 200 can be kept consistent.
  • the pressure-sensitive adhesive layer 30 has better damping characteristics, so that the diaphragm 200 has higher sound quality and listening stability, so that the sound generating device can be overcome.
  • the diaphragm 200 includes at least one folded ring portion 21, and the folded ring portion 21 has the composite film structure.
  • the diaphragm 200 further includes a dome portion 23, and the dome portion 23 is connected to the folding ring portion 21.
  • the diaphragm 200 includes two folded ring portions 21.
  • the ball top portion 23 and the folded ring portion 21 are integrally formed.
  • the ball top portion 23 and the folded ring portion 21 are made of different materials.
  • the ball top portion 23 is located at the center position of the diaphragm 200
  • the folded ring portion 21 is located on the peripheral side of the center position of the diaphragm 200, and surrounds the center position of the diaphragm 200.
  • the invention also provides a sound generating device (not shown).
  • the sound generating device includes the diaphragm 200.
  • the sound generating device adopts all the technical solutions of all the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, which will not be repeated one by one here.
  • the sound generating device further includes a voice coil (not shown), and the diaphragm 200 and the voice coil are firmly adhered to improve the performance of the diaphragm 200.
  • the method for preparing the acrylic pressure-sensitive adhesive of the present invention includes the following examples:
  • nitrile rubber 5 parts by weight of nitrile rubber and 44.3 parts of toluene are provided in parts by weight. After the nitrile rubber is plasticized on an open mill for 10 min, it is dissolved in toluene to obtain a mixture;
  • the colloid is coated on a release film, the colloid is dried for the first time to remove toluene, and then the colloid is subjected to a second drying treatment to obtain the acrylic pressure-sensitive adhesive of Example 1, wherein the first drying
  • the treatment temperature was 70 ° C and the time was 2 minutes.
  • the temperature of the second drying treatment was 140 ° C and the time was 3 minutes.
  • benzoyl peroxide as an initiator can provide free radicals for the polymerization of acrylic monomers.
  • ethyl isocyanate methacrylate can cause a cross-linking reaction between methacrylic acid, 2-ethylhexyl acrylate, and methyl methacrylate.
  • Nitrile rubber can improve the damping performance of acrylic pressure-sensitive adhesives.
  • n-butyl acrylate 15 parts of acrylic acid, 8 parts of acrylamide, and 0.4 parts of azobisisobutyronitrile.
  • n-butyl acrylate, acrylic acid, acrylamide, and azobisisobutyronitrile to the mixture, and Heating to obtain a colloid, wherein the temperature of the heat treatment is 80 ° C. and the time is 8 h;
  • the colloid was coated on a polyphenylene sulfide substrate, the colloid was dried for the first time to remove ethyl acetate, and the colloid was subjected to the second drying treatment to obtain the acrylic pressure-sensitive adhesive of Example 2.
  • the temperature of the first drying process was 80 ° C and the time was 3 minutes, and the temperature of the second drying process was 150 ° C and the time was 2 minutes.
  • azobisisobutyronitrile as an initiator can provide free radicals for the polymerization of acrylic monomers.
  • Aluminum acetate as a crosslinking agent can cause a crosslinking reaction between n-butyl acrylate, acrylic acid and acrylamide.
  • Neoprene can improve the damping performance of acrylic pressure-sensitive adhesives.
  • the loss factor of the acrylic pressure-sensitive adhesive prepared by the preparation methods of Example 1 and Example 2 was tested.
  • the loss factor of the acrylic pressure-sensitive adhesive of Example 1 was 0.42
  • the acrylic pressure-sensitive adhesive of Example 2 was The loss factor of the sensitive adhesive is 0.45.
  • the loss factor of the acrylic pressure-sensitive adhesive in the prior art is usually 0.2. It is shown that the acrylic pressure-sensitive adhesive produced by the preparation method of the present invention has a loss factor greater than 0.4 and has good damping properties.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Signal Processing (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne un adhésif sensible à la pression acrylique et son procédé de préparation, une structure de film composite utilisant l'adhésif acrylique sensible à la pression, un diaphragme utilisant la structure de film composite et un dispositif de production de son utilisant le diaphragme. Les matières premières pour la production de l'adhésif acrylique sensible à la pression en poids comprennent : 30 à 45 parties de monomère mou, 5 à 20 parties de monomère dur, 1 à 10 parties de monomère fonctionnel, 0,01 à 1 partie d'initiateur, 0,01 à 1 partie d'agent de réticulation, 30 à 45 parties de solvant organique, et 5 à 10 parties d'agent de mouillage. La membrane utilisant l'adhésif acrylique sensible à la pression a encore une meilleure performance d'amortissement sans augmenter l'épaisseur de l'adhésif sensible à la pression, afin de résoudre le problème de distorsion à basse fréquence du dispositif de production du son.
PCT/CN2018/110158 2018-06-15 2018-10-13 Adhésif acrylique sensible à la pression et son procédé de préparation, structure de film composite, diaphragme et dispositif de production de son WO2019237600A1 (fr)

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CN109660920B (zh) * 2019-01-23 2020-09-22 歌尔股份有限公司 用于发声装置的振膜以及发声装置
CN109905815A (zh) * 2019-03-26 2019-06-18 瑞声科技(新加坡)有限公司 振膜基材及其制备方法、振膜及扬声器
CN110708638B (zh) * 2019-10-31 2020-11-24 歌尔股份有限公司 一种用于微型发声装置的振膜及微型发声装置
CN113411737B (zh) * 2020-03-17 2023-03-10 3M创新有限公司 用于微型扬声器的音膜及其制备方法
CN111923529A (zh) * 2020-09-23 2020-11-13 歌尔股份有限公司 一种复合振膜及其制备方法、以及发声装置
CN116023879A (zh) * 2022-12-30 2023-04-28 芜湖徽氏新材料科技有限公司 一种声学胶带及其制备方法

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