WO2019237696A1 - Adhésif sensible à la pression d'organosilicium et procédé de préparation associé, structure de film composite, diaphragme et dispositif de production de son - Google Patents

Adhésif sensible à la pression d'organosilicium et procédé de préparation associé, structure de film composite, diaphragme et dispositif de production de son Download PDF

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Publication number
WO2019237696A1
WO2019237696A1 PCT/CN2018/121430 CN2018121430W WO2019237696A1 WO 2019237696 A1 WO2019237696 A1 WO 2019237696A1 CN 2018121430 W CN2018121430 W CN 2018121430W WO 2019237696 A1 WO2019237696 A1 WO 2019237696A1
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Prior art keywords
sensitive adhesive
silicone
parts
pressure
layer
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PCT/CN2018/121430
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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 WO2019237696A1 publication Critical patent/WO2019237696A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the technical field of sound generating devices, in particular to a silicone-based pressure-sensitive adhesive, a method for preparing the silicone-based pressure-sensitive adhesive, a composite film structure using the silicone-based pressure-sensitive adhesive, and a vibration application of the composite film structure.
  • a silicone-based pressure-sensitive adhesive a method for preparing the silicone-based pressure-sensitive adhesive, a composite film structure using the silicone-based pressure-sensitive adhesive, and a vibration application of the composite film structure.
  • the diaphragm is the core component of the sound generator.
  • Acrylic pressure-sensitive adhesive has better damping performance.
  • acrylic pressure-sensitive adhesive is usually used to make the damping layer of the diaphragm.
  • the acrylic pressure-sensitive adhesive contains polar groups such as ester groups, the high temperature resistance of the damping rubber layer is poor.
  • the rigidity and damping performance of the damping rubber layer are reduced, resulting in a diaphragm Polarization occurs during the vibration process, which leads to poor sound quality and listening stability of the sounding device.
  • the present invention provides a silicone-based pressure-sensitive adhesive, which aims to make the diaphragm applying the silicone-based pressure-sensitive adhesive have better high temperature resistance performance, so that the diaphragm does not appear polarized when vibrating. This phenomenon further improves the sound quality and listening stability of the sound generating device using the diaphragm.
  • the raw materials for manufacturing the silicone pressure-sensitive adhesive provided by the present invention include:
  • the silicone resin includes an M chain link and a Q chain link
  • the M chain link is The Q chain link is The number ratio of the M chain link to the Q chain link is 1: 0.6 to 0.9, wherein R 1 is a methyl group, a hydrogen group or a vinyl group, and the range of m is 15 to 20.
  • R 2 is a methyl group, a vinyl group, or a phenyl group, and the range of n is 5000 to 10,000.
  • the range of the mass ratio of the silicone resin and the silicone rubber is: 1: 1 to 15: 1.
  • the raw materials further include 0 to 5 parts by weight of a crosslinking agent, the crosslinking agent being a hydrogen-containing silicone oil, an organic peroxide, or an alkoxysilane; and / or,
  • the raw material further includes 0 to 5 parts of a reaction inhibitor, the reaction inhibitor being at least one of an alkynol compound, a nitrogen-containing compound, and a vinyl compound; and / or,
  • the organic solvent is at least one of benzene, toluene, ethyl acetate, xylene, N-methylpyrrolidone and methyl ethyl ketone; and / or,
  • the catalyst is an organic complex of platinum or an organic tin compound.
  • the invention also provides a method for preparing a silicone-based pressure-sensitive adhesive, including the following steps:
  • the colloid is dried to obtain a silicone-based pressure-sensitive adhesive.
  • the method further includes the following steps:
  • the crosslinker is added to the colloid.
  • the method further includes the following steps:
  • reaction inhibitor 0 to 5 parts by weight of reaction inhibitor.
  • the reaction inhibitor is added to the colloid.
  • the invention also provides a composite film structure, which comprises at least two first substrate layers and at least one laminated sensitive adhesive layer, and the pressure sensitive adhesive layer is provided between the two first substrate layers At least one of the first substrate layers is a thermoplastic elastomer layer, and the material of the pressure-sensitive adhesive layer is the pressure-sensitive adhesive described in the above embodiment.
  • thermoplastic elastomer layer is selected from 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 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 two first substrate layers and two laminated sensitive adhesive layers.
  • the composite film structure further includes a second substrate layer, and the second substrate layer includes the first oppositely disposed first layers. A surface and a second surface, one of which is sandwiched between the first surface of the second substrate layer and the first substrate, and the other of which is sandwiched between the first substrate and the second substrate Between the two surfaces and another first substrate layer.
  • 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 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 the production of the silicone-based pressure-sensitive adhesive according to the technical solution of the present invention include: 15 to 60 parts of silicone resin, 5 to 55 parts of silicone rubber, 30 to 60 parts of organic solvent, and 0.1 to 5 part of catalyst, organic A condensation reaction or addition reaction occurs between the silicone rubber and the silicone resin, and a cross-linking reaction occurs between the silicone rubber.
  • the catalyst accelerates the reaction speed, thereby generating a three-dimensional network-structured silicone pressure-sensitive adhesive.
  • the network structure can make the silicone pressure-sensitive adhesive have 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 pressure-sensitive adhesive It is set to 15-60 parts to make the silicone pressure-sensitive adhesive have better compactness and adhesion.
  • the silicone rubber is set to 5 to 55 parts to improve the film-forming property of the silicone pressure-sensitive adhesive. , Adhesiveness and resilience, so that the diaphragm using the silicone pressure-sensitive adhesive does not appear polarization phenomenon during vibration, so that the sound device using the diaphragm has better sound quality and listening stability.
  • 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.
  • the invention provides a raw material for manufacturing a silicone-based pressure-sensitive adhesive, including:
  • 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 speed and catalyze the condensation reaction between silicone rubber and silicone resin.
  • 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 raw materials for the production of the silicone-based pressure-sensitive adhesive according to the technical solution of the present invention include: 15 to 60 parts of silicone resin, 0.1 to 5 parts of catalyst, 30 to 90 parts of organic solvent, and 5 to 55 parts of silicone rubber, organic A condensation reaction or addition reaction occurs between the silicone rubber and the silicone resin, and a cross-linking reaction occurs between the silicone rubber.
  • the catalyst accelerates the reaction speed, thereby generating a three-dimensional network-structured silicone pressure-sensitive adhesive.
  • the network structure can make the silicone pressure-sensitive adhesive have 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 pressure-sensitive adhesive It is set to 15-60 parts to make the silicone pressure-sensitive adhesive have better compactness and adhesion.
  • the silicone rubber is set to 5 to 55 parts to improve the film-forming property of the silicone pressure-sensitive adhesive. , Adhesiveness and resilience, so that the diaphragm using the silicone pressure-sensitive adhesive does not appear polarization phenomenon during vibration, so that the sound device using the diaphragm has better sound quality and listening stability.
  • the silicone pressure-sensitive adhesive of the present invention has high damping property, and its loss factor is ⁇ 0.5.
  • the silicone-based pressure-sensitive adhesive of the present invention has better high temperature holding viscosity, and its peeling time is greater than 1 hour under a test environment at 150 ° C.
  • 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 of M chain links and 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 viscosity.
  • the Q chain link has a reinforcing effect and can improve the cohesive strength of the prepared silicone pressure-sensitive adhesive.
  • 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 makes the silicone resin and the silicone rubber have better compatibility, so that the prepared silicones
  • the pressure-sensitive adhesive has good comprehensive properties and high solid content, and can also make the prepared silicone pressure-sensitive adhesive have better elasticity and cohesive strength.
  • R 1 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-based 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, which makes the molecular weight of the silicone rubber moderate, and the prepared silicone pressure-sensitive adhesive 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 in the technical solution of the present invention is set to 1: 1 to 15: 1, so that the prepared silicone-based pressure-sensitive adhesive has better initial viscosity and holding viscosity.
  • the raw materials also include 0 to 5 parts by weight of the crosslinking agent.
  • the cross-linking agent is a hydrogen-containing silicone oil, an organic peroxide, or an alkoxysilane.
  • the role of the cross-linking agent is to increase the cohesion 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 also 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.
  • silicone resin for the above-mentioned silicone resin, catalyst, silicone rubber, organic solvent, cross-linking agent, and reaction inhibitor, other materials may be used, and the present invention does not limit this.
  • the invention also provides a method for preparing a silicone-based pressure-sensitive adhesive, including the following steps:
  • the colloid is dried to obtain a silicone pressure-sensitive adhesive.
  • the silicone rubber is at least one of methyl hydroxy silicone rubber, vinyl silicone rubber, and phenyl silicone rubber.
  • 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 catalyst is an organic complex of platinum or an organic tin compound.
  • the main role of the catalyst is to speed up the reaction speed and catalyze the condensation reaction between silicone rubber and silicone resin.
  • 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 temperature range of the heat treatment is 70 to 90 ° C. and the reaction time is 50 to 70 min, so that a condensation reaction or an addition reaction occurs between the silicone rubber and the silicone resin.
  • drying the colloid to obtain the silicone pressure-sensitive adhesive in the above steps includes: coating the colloid on a substrate, and then drying the colloid.
  • the substrate may be a thermoplastic elastomer, an engineering plastic layer, a non-woven fabric, or a release film.
  • 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 is selected from the group consisting of polyetheretherketone, polyarylate, and polyetherimide. At least one of polyimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate, and polybutylene terephthalate.
  • the process of drying the colloid includes the first drying process and the second drying process.
  • the drying process may be the first drying process of the colloid, and then the first drying process of the colloid. Secondary drying treatment.
  • the temperature range of the first drying process is 60 to 120 ° C, and the reaction time is 2 to 3 minutes to remove the organic solvent in the colloid.
  • the temperature range of the second drying process is 80 to 160 ° C, and the reaction The time is 2 to 3 minutes to cure the colloid and form a silicone pressure-sensitive adhesive.
  • a condensation reaction or an addition reaction occurs between the silicone rubber and the silicone resin, and a cross-linking reaction also occurs between the silicone rubbers during the second drying treatment.
  • the catalyst accelerates the reaction speed, thereby generating a three-dimensional network structure of the silicone-based pressure-sensitive adhesive.
  • the three-dimensional network structure can make the silicone-based pressure-sensitive adhesive have a dense structure, so that the silicone-based pressure-sensitive adhesive has better resistance.
  • High temperature performance, and the silicone resin has the advantages of large molecular weight and high modulus.
  • the silicone resin is set to 15 to 60 parts, so that the silicone pressure-sensitive adhesive also has better density and adhesion.
  • the rubber is set to 5 to 55 parts, in order to improve the film-forming property, adhesiveness and resilience of the silicone pressure-sensitive adhesive, so that the vibration film of the silicone pressure-sensitive adhesive will not have polarization phenomenon during the vibration process. Furthermore, the sound generating device using the diaphragm has better sound quality and listening stability.
  • the crosslinker is added to the colloid.
  • the cross-linking 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.
  • reaction inhibitor 0 to 5 parts by weight of reaction inhibitor.
  • the reaction inhibitor is added to the colloid.
  • 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 membrane structure 100.
  • the composite film structure 100 includes at least two first substrate layers 10 and at least one laminated adhesive layer 30.
  • the pressure-sensitive adhesive layer 30 is disposed between the two first substrate layers 10, and the first substrate layer 10 is in the first substrate layer 10.
  • At least one layer is a thermoplastic elastomer layer, and the material of the pressure-sensitive adhesive layer 30 is the silicone-based pressure-sensitive adhesive described in the above embodiment.
  • the composite film structure 100 includes two first substrate layers 10, and the pressure-sensitive adhesive layer 30 is sandwiched between the two first substrate layers 10.
  • 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 between the two first substrate layers 100 is a thermoplastic elastomer layer
  • the composite film structure includes a first thermoplastic elastomer layer, the first pressure-sensitive adhesive layer, and a second thermoplastic elastic layer which are sequentially stacked.
  • 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 silicone-based pressure-sensitive adhesive is the silicone-based pressure-sensitive adhesive described in the above embodiments.
  • the material of the first base material layer 10 is selected from 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. The rigidity and damping performance will not be significantly reduced.
  • the composite film structure 100 includes two laminated adhesive layers 30.
  • the composite film structure 100 further includes a second substrate layer 50.
  • the second substrate layer 50 includes a first surface 51 and a second surface 50 opposite to each other.
  • the 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 other pressure-sensitive adhesive layer 30 is sandwiched between the second surface 53 of the second substrate layer 50.
  • 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 polyethylene terephthalate At least one of butylene glycol formate.
  • 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 30, and a second substrate layer 50, wherein a pressure sensitive adhesive layer 30 is sandwiched between the second substrate layers. 50 is between the first surface 51 and a first substrate layer 10, and another pressure-sensitive adhesive layer 30 is sandwiched between the second surface 53 of the second substrate layer 50 and the other first substrate layer 10, In order to increase the stiffness and anti-polarization ability of the composite film structure 100.
  • the present invention further provides a diaphragm 200.
  • the diaphragm 200 has a composite film structure 100.
  • the total thickness of the diaphragm 200 is 7 ⁇ m to 150 ⁇ 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, which can improve the vibration balance under large amplitudes and suppress polarization, so that the diaphragm 200 has higher sound quality and listening stability under high and low temperature working environments. .
  • the diaphragm 200 includes at least one folded ring portion 21, and the folded ring portion 21 has a composite film structure 100.
  • 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 present invention provides a sound generating device (not shown).
  • the sound generating device includes a 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.
  • methyl hydroxy silicone rubber According to parts by weight, 5 parts of methyl hydroxy silicone rubber, 15 parts of silicone resin, and 30 parts of benzene were provided. The methyl hydroxy silicone rubber and the silicone resin were dissolved in benzene to obtain a mixture; The mass ratio of the silicone resin is 1: 4, the number ratio of the M chain links and the Q chain links in the silicone resin is 1: 0.7, R 1 is a methyl group, and the range of m is 15.
  • chloroplatinic acid diethyl phthalate complex Provide 2 parts of chloroplatinic acid diethyl phthalate complex, add chloroplatinic acid diethyl phthalate complex to the mixture, and add chloroplatinic acid diethyl phthalate complex
  • the mixture of the compounds is subjected to a heat treatment.
  • the temperature of the heat treatment is 80 ° C. and the time is 70 minutes.
  • the chloroplatinic acid diethyl phthalate complex is used as a catalyst to promote the relationship between methyl hydroxy silicone rubber and silicone resin A condensation reaction occurs to obtain a colloid;
  • the first drying treatment is performed on the colloid coated on the release film to remove benzene, and the temperature of the first drying treatment is 70 ° C. and the time is 2 minutes;
  • the colloid after the first drying treatment is subjected to a second drying treatment to obtain a silicone-based pressure-sensitive adhesive.
  • the temperature of the second drying treatment is 160 ° C. and the time is 3 minutes.
  • methyl hydroxy silicone rubber According to parts by weight, 15 parts of methyl hydroxy silicone rubber, 30 parts of silicone resin, and 54 parts of toluene were provided.
  • the methyl hydroxy silicone rubber and the silicone resin were dissolved in toluene to obtain a mixture;
  • the mass ratio of the silicone resin is 1: 2
  • the number ratio of the M chain links and the Q chain links in the silicone resin is 1: 0.75
  • R 1 is a hydrogen group
  • the range of m is 17.
  • dibutyltin dilaurate 0.5 parts of dibutyltin dilaurate, add dibutyltin dilaurate to the mixture, heat the mixture to which dibutyltin dilaurate is added, and use dibutyltin dilaurate as a catalyst. It can promote the condensation reaction between methyl hydroxy silicone rubber and silicone resin to obtain colloid.
  • the temperature of the heat treatment is 85 ° C and the time is 60 minutes;
  • the colloid added with benzoyl peroxide is coated on a polyurethane elastomer and subjected to a first drying treatment to remove toluene.
  • the temperature of the first drying treatment is 75 ° C. and the time is 2.5 min.
  • a second drying process is performed on the colloid after the first drying process to obtain a silicone-based pressure-sensitive adhesive.
  • the temperature of the second drying process is 160 ° C. and the time is 2 minutes.
  • benzoyl peroxide as a cross-linking agent can promote the cross-linking reaction between methyl hydroxy silicone rubber.
  • the vinyl silicone rubber According to parts by weight, 25 parts of vinyl silicone rubber, 40 parts of silicone resin, and 32.3 parts of toluene are provided.
  • the vinyl silicone rubber and the silicone resin are dissolved in toluene to obtain a mixture;
  • the mass ratio is 5: 8
  • the ratio of the number of M links and Q links in the silicone resin is 1: 0.7
  • R 1 is a hydrogen group
  • the range of m is 18.
  • stannous octoate Provide 1 part of stannous octoate, add stannous octoate to the mixture, heat the mixture containing stannous octoate, and stannous octoate as a catalyst to promote the addition reaction between vinyl silicone rubber and silicone resin
  • the temperature of the heat treatment is 80 ° C., and the time is 65 min;
  • a colloid containing a solution of ethynylcyclohexanol, hydrogen-containing silicone oil, and chloroplatinic acid polysiloxane was coated on a polyester elastomer substrate and subjected to a first drying treatment to remove toluene.
  • the temperature of the first drying treatment is 80 ° C, and the time is 2min;
  • the colloid after the first drying treatment is subjected to a second drying treatment to obtain a silicone-based pressure-sensitive adhesive.
  • the temperature of the second drying treatment is 155 ° C and the time is 2.5 minutes.
  • ethynyl cyclohexanol as a reaction inhibitor can slow down the reaction speed
  • hydrogen-containing silicone oil as a cross-linking agent can promote the crosslinking reaction between vinyl silicone rubbers.
  • the hydrogen-containing silicone oil can also occur with vinyl silicone rubbers.
  • a solution of chloroplatinic acid polysiloxane as a catalyst can accelerate the reaction speed.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • phenyl silicone rubber According to parts by weight, 30 parts of phenyl silicone rubber, 80 parts of silicone resin, and 39 parts of ethyl acetate were provided.
  • the phenyl silicone rubber and the silicone resin were dissolved in ethyl acetate to obtain a mixture;
  • the mass ratio of the silicone resin is 1: 1
  • the number ratio of the M chain links and the Q chain links in the silicone resin is 1: 0.8
  • R 1 is a hydrogen group
  • the range of m is 20.
  • dibutyltin dilaurate 0.5 parts of dibutyltin dilaurate, add dibutyltin dilaurate to the mixture, heat the mixture with dibutyltin dilaurate added, and dibutyltin dilaurate as a catalyst can promote A condensation reaction or addition reaction occurs between the phenyl silicone rubber and the silicone resin to obtain a colloid.
  • the temperature of the heat treatment is 70 ° C. and the time is 55 minutes;
  • the colloid added with benzoyl peroxide is coated on a silicone elastomer substrate, and the first drying treatment is performed to remove ethyl acetate.
  • the temperature of the first drying treatment is 70 ° C. Time is 2.6min;
  • a second drying process is performed on the colloid after the first drying process to obtain a silicone-based pressure-sensitive adhesive.
  • the temperature of the second drying process is 160 ° C. and the time is 2.6 min.
  • benzoyl peroxide as a crosslinking agent can promote the crosslinking reaction between phenyl silicone rubber.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un adhésif sensible à la pression d'organosilicium, un procédé de préparation associé, une structure de film composite utilisant l'adhésif sensible à la pression d'organosilicium, un diaphragme utilisant la structure de film composite, et un dispositif de production de son utilisant le diaphragme. Les matières premières pour préparer l'adhésif sensible à la pression d'organosilicium comprennent, en parties en poids : de 15 à 60 parties d'une résine d'organosilicium, de 5 à 55 parties d'un caoutchouc d'organosilicium, de 30 à 90 parties d'un solvant organique, et de 0,1 à 5 parties d'un catalyseur. Dans la présente invention, le diaphragme utilisant l'adhésif sensible à la pression d'organosilicium présente une résistance à haute température améliorée. Par conséquent, la polarisation ne se produit pas au niveau du diaphragme lorsqu'il vibre, ce qui permet au dispositif de production de son employant la membrane d'avoir une qualité sonore et une stabilité sonore améliorées.
PCT/CN2018/121430 2018-06-15 2018-12-17 Adhésif sensible à la pression d'organosilicium et procédé de préparation associé, structure de film composite, diaphragme et dispositif de production de son WO2019237696A1 (fr)

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CN108774488A (zh) * 2018-06-15 2018-11-09 歌尔股份有限公司 有机硅类压敏胶及其制备方法、复合膜结构、振膜、及发声装置
CN112126374A (zh) * 2020-09-30 2020-12-25 东莞市骏青电子科技有限公司 一种用于聚合物锂电池加工过程中表面保护的有机硅压敏胶保护膜及其制备方法

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CN101177595A (zh) * 2007-12-13 2008-05-14 同济大学 纳米mq硅树脂增强的湿固化有机硅压敏胶及其制备方法
CN101560372A (zh) * 2009-04-02 2009-10-21 佛山市华联有机硅有限公司 一次成型有机硅自粘性压敏胶的制备方法
CN102051154A (zh) * 2010-11-26 2011-05-11 株洲时代电气绝缘有限责任公司 有机硅压敏胶粘剂及其制备方法
CN102127389A (zh) * 2011-01-11 2011-07-20 广东达美新材料有限公司 一种高固含量耐高温有机硅压敏胶及其制备方法

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CN101560372A (zh) * 2009-04-02 2009-10-21 佛山市华联有机硅有限公司 一次成型有机硅自粘性压敏胶的制备方法
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