WO2019237601A1 - 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 - Google Patents

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 Download PDF

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WO2019237601A1
WO2019237601A1 PCT/CN2018/110159 CN2018110159W WO2019237601A1 WO 2019237601 A1 WO2019237601 A1 WO 2019237601A1 CN 2018110159 W CN2018110159 W CN 2018110159W WO 2019237601 A1 WO2019237601 A1 WO 2019237601A1
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Prior art keywords
sensitive adhesive
silicone
parts
pressure
colloid
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Ceased
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PCT/CN2018/110159
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English (en)
French (fr)
Inventor
王海峰
王婷
李春
刘春发
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Goertek Inc
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Goertek Inc
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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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; ELECTRIC HEARING AIDS; PUBLIC ADDRESS SYSTEMS
    • H04R9/00—Transducers of moving-coil, moving-strip, or moving-wire type
    • H04R9/02—Details
    • 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 present invention also provides a composite film structure.
  • the composite film structure includes two first substrate layers and at least one laminated sensitive adhesive layer.
  • the pressure sensitive adhesive layer is sandwiched between the two first substrate layers.
  • the material of the pressure-sensitive adhesive layer is the pressure-sensitive adhesive.
  • the material of the first substrate layer is polyetheretherketone, polyetherimide, polyphenylene ether, or polyethylene naphthalate; and / or,
  • the thickness of the first substrate layer ranges from 2 to 40 ⁇ m; and / or,
  • the thickness of the pressure-sensitive adhesive layer ranges from 2 to 40 ⁇ m.
  • 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 polyethylene terephthalate or non-woven fabric; and / or,
  • the thickness of the second substrate layer ranges from 1 to 30 ⁇ m.
  • the present invention also provides a vibrating membrane having the composite membrane structure.
  • the present invention also provides a sound generating device, and the sound generating device includes the diaphragm.
  • the raw materials for the production of the silicone-based pressure-sensitive adhesive according to the technical solution of the present invention include: 20 to 80 parts of a silicone resin, 30 to 90 parts of an organic solvent, 0.1 to 5 parts of a catalyst, and 5 to 55 parts of a silicone rubber, organic A condensation reaction occurs between the silicone rubber and 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 be
  • the silicone-based pressure-sensitive adhesive has a dense structure, so that the silicone-based 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, in order to make the silicone pressure-sensitive adhesive have better compactness and adhesiveness, the silicone rubber is set to 5 to 55 parts to improve the film-forming property and adhesion of the silicone pressure-sensitive adhesive 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.
  • Label name Label name 100 Composite membrane structure 53 Second surface 10 First substrate layer 200 Diaphragm 30 Pressure sensitive adhesive twenty one Folding ring 50 Second substrate layer twenty three Ball top 51 First surface Zh Zh
  • the present 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 organotin-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: 20 to 80 parts of a silicone resin, 30 to 90 parts of an organic solvent, 0.1 to 5 parts of a catalyst, and 5 to 55 parts of a silicone rubber, organic A condensation reaction occurs between the silicone rubber and 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 be
  • the silicone-based pressure-sensitive adhesive has a dense structure, so that the silicone-based 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, in order to make the silicone pressure-sensitive adhesive have better compactness and adhesiveness, the silicone rubber is set to 5 to 55 parts to improve the film-forming property and adhesion of the silicone pressure-sensitive adhesive 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 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. high.
  • the silicone rubber is methyl hydroxy silicone rubber, vinyl silicone rubber, or 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 crosslinking agent is a hydrogen-containing silicone oil, an organic peroxide, or an alkoxysilane.
  • the role of the crosslinking agent is to increase the cohesive force of the silicone-based 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, 3-propyl-1-butyne-3 -At least one of 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 methyl hydroxy silicone rubber, vinyl silicone rubber, or 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 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 drying the colloid.
  • the material of the substrate can be plastic, non-woven fabric or release film.
  • the plastic can be a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic polyamide elastomer, a silicone elastomer, a polyetheretherketone, a polyarylate, a polyetherimide, a polyimide, a polyphenylene sulfide At least one of polyethylene naphthalate, polyethylene terephthalate, and polybutylene terephthalate.
  • the colloid drying process includes a first drying process and a second drying process.
  • the temperature of the first drying process ranges from 60 to 120 ° C. and the reaction time ranges from 2 to 3 min.
  • the temperature range of the second drying treatment is 80-160 ° C., and the reaction time is 2 to 3 minutes to cure the colloid to form a silicone-based pressure-sensitive adhesive.
  • a condensation reaction occurs between the silicone rubber and the silicone resin, and during the second drying treatment, a cross-linking reaction also occurs between the silicone rubber, and the catalyst accelerates the reaction speed.
  • a cross-linking reaction also occurs between the silicone rubber, and the catalyst accelerates the reaction speed.
  • the three-dimensional network structure can make the silicon-based pressure-sensitive adhesive have a dense structure, so that the silicon-based pressure-sensitive adhesive has better high temperature resistance.
  • the silicone resin has the advantages of large molecular weight and large modulus.
  • the silicone resin is set to 20 to 80 parts, so that the silicone pressure-sensitive adhesive also has better density and adhesion.
  • the silicone 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, thereby making the application
  • the sound generating device of the diaphragm has better sound quality and listening stability.
  • the crosslinker is added to the colloid.
  • the crosslinking agent is a hydrogen-containing silicone oil, an organic peroxide, or an alkoxysilane.
  • the function of the cross-linking agent is to cause a cross-linking reaction between the silicone rubbers and increase the cohesive force of the silicone-based 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 two first substrate layers 10 and at least one laminated pressure-sensitive adhesive layer 30.
  • the pressure-sensitive adhesive layer 30 is sandwiched between the two first substrate layers 10.
  • At least one of 10 is a plastic substrate layer, and the pressure-sensitive adhesive layer 30 is the silicone-based pressure-sensitive adhesive described in the above embodiment.
  • 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 repeated one by one here.
  • the material of the plastic substrate layer is polyetheretherketone, polyetherimide, polyphenylene ether, or polyethylene naphthalate.
  • 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, and the material of the plastic substrate layer is polyetheretherketone, polyetherimide, polyphenylene ether, or polynaphthalene dicarboxylic acid.
  • Glycol ester makes the softening temperature of at least one of the first substrate layers 10 greater than 80 ° C, has good high temperature resistance, and the thickness of the first substrate layer 10 is 2-20 ⁇ m, so that the composite film
  • the structure 100 not only has better strength and resilience, but also has excellent structural stability and better 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, 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 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 material between 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 silicone-based pressure-sensitive adhesive is the silicone-based pressure-sensitive adhesive described in the foregoing embodiment.
  • the composite film structure 100 includes two laminated sensitive adhesive layers 30.
  • the composite film structure 100 further includes a second substrate layer 50, and the second substrate layer 50 includes a first surface 51 and a second surface 50 opposite to each other.
  • 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 another pressure-sensitive adhesive layer 30 is sandwiched between the second substrate layer 50 and the first substrate 51. Between the second surface 53 and another first substrate layer 10.
  • At least one of the two pressure-sensitive adhesive layers is the silicone-based pressure-sensitive adhesive layer described in the foregoing embodiment, and the other pressure-sensitive adhesive layer may also be the silicone-based pressure-sensitive adhesive described in the foregoing embodiment.
  • the adhesive layer may also be a pressure-sensitive adhesive layer made of other materials, such as an acrylic adhesive layer, which is not limited in the present invention.
  • the material of the second base material 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.
  • first base material layer 10 and the second base material layer 50 may be other materials, such as a non-woven fabric, which is not limited in the present invention.
  • the thickness of the second base material layer 50 ranges from 1 to 30 ⁇ m.
  • the thickness of the second substrate layer 50 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, 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.
  • the total thickness of the diaphragm 200 is 6 ⁇ m to 110 ⁇ 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.
  • the folded ring portion 21 has a composite film structure 100.
  • the diaphragm 200 further includes a ball top portion 23 connected to the folded 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 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 preparation method of the silicone-based pressure-sensitive adhesive of the present invention includes the following examples:
  • methyl hydroxy silicone rubber According to parts by weight, 5 parts of methyl hydroxy silicone rubber, 20 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. Among them, the mass ratio of methyl hydroxy silicone rubber to the silicone resin is 1: 4, the ratio of the number of M links and Q links in the silicone resin is 1: 0.7, R 1 is a methyl group, and the range of m is 15.
  • chloroplatinic acid isopropanol complex Provide 0.1 parts of a chloroplatinic acid isopropanol complex, add the chloroplatinic acid isopropanol complex to the mixture, and heat the mixture to which the chloroplatinic acid isopropanol complex is added to obtain a colloid.
  • the temperature of the heat treatment is 80 ° C. and the time is 70 minutes.
  • the chloroplatinic acid isopropanol complex as a catalyst can promote the condensation reaction between the methyl hydroxy silicone rubber and the silicone resin.
  • the colloid After the colloid is cooled, the colloid is coated on a release film.
  • the colloid coated on the release film was subjected to a first drying treatment to remove benzene.
  • the temperature of the first drying treatment was 85 ° C. and the time was 2.3 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 15 parts of methyl hydroxy silicone rubber, 30 parts of silicone resin, 54 parts of toluene were provided, and methyl hydroxy silicone rubber and the silicone resin were dissolved in toluene to obtain a mixture.
  • the mass ratio of methyl hydroxy silicone rubber to the silicone resin is 1: 2
  • the ratio of the number of M chain links and 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, and heat treat the dibutyltin dilaurate added to obtain a colloid.
  • the temperature of the heat treatment is 90 ° C. and the time is 50 minutes.
  • Dibutyltin dilaurate as a catalyst can promote the condensation reaction between the methyl hydroxy silicone rubber and the silicone resin.
  • benzoyl peroxide After the colloid is cooled, 0.5 part of benzoyl peroxide is provided. The benzoyl peroxide is added to the colloid and stirred well.
  • the colloid added with benzoyl peroxide was coated on a polyetheretherketone substrate and subjected to a first drying treatment to remove toluene.
  • the temperature of the first drying treatment was 90 ° C and the time was 2min.
  • a second drying treatment is performed on the colloid after the first drying treatment, and the colloid is cured to obtain a silicone pressure-sensitive adhesive.
  • the temperature of the second drying treatment is 155 ° 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.
  • stannous octoate Provide 1 part of stannous octoate, add stannous octoate to the mixture, and heat-process the mixture to which stannous octoate is added to obtain a colloid.
  • the temperature of the heat treatment is 80 ° C. and the time is 60 minutes.
  • stannous octoate can promote the condensation reaction between the vinyl silicone rubber and the silicone resin.
  • a solution of 0.1 parts of ethynylcyclohexanol, 2 parts of hydrogen-containing silicone oil, and 0.5 parts of chloroplatinic acid polysiloxane is provided.
  • the acetylene cyclohexanol, hydrogen-containing silicone oil, and chloroplatinic acid polysiloxane are provided. The solution was added to the colloid and stirred well.
  • the colloid after the first drying treatment is subjected to a second drying treatment, and the colloid is cured to obtain a silicone-based pressure-sensitive adhesive.
  • the temperature of the second drying treatment is 160 ° 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 By weight parts, 30 parts of phenyl silicone rubber, 30 parts of silicone resin, and 39 parts of ethyl acetate were provided, and the phenyl silicone rubber and the silicone resin were dissolved in ethyl acetate to obtain a mixture.
  • the mass ratio of the phenyl silicone rubber to the silicone resin is 1: 1
  • the ratio of the number of M links and Q links in the silicone resin is 1: 0.8
  • R1 is a hydrogen group
  • the range of m is 20.
  • dibutyltin dilaurate 0.5 parts was provided, dibutyltin dilaurate was added to the mixture, and the mixture to which dibutyltin dilaurate was added was subjected to heat treatment to obtain a colloid.
  • the temperature of the heat treatment is 70 ° C. and the time is 55 minutes.
  • Dibutyltin dilaurate as a catalyst can promote the condensation reaction between the phenyl silicone rubber and the silicone resin.
  • benzoyl peroxide After the colloid is cooled, 0.5 part of benzoyl peroxide is provided. The benzoyl peroxide is added to the colloid and stirred well.
  • the colloid added with benzoyl peroxide was coated on a polyphenylene ether substrate, and was subjected to a first drying treatment to remove ethyl acetate.
  • the temperature of the first drying treatment was 70 ° C. for a period of time. It was 2.7min.
  • a second drying treatment is performed on the colloid after the first drying treatment, and the colloid is cured to obtain a silicone pressure-sensitive adhesive.
  • the temperature of the second drying treatment is 160 ° C. and the time is 2.6 min.
  • benzoyl peroxide as a cross-linking agent can promote the cross-linking reaction between methyl hydroxy silicone rubber.

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Abstract

本发明提供一种有机硅类压敏胶及有机硅类压敏胶的制备方法、应用该有机硅类压敏胶的复合膜结构、应用该复合膜结构的振膜及应用该振膜的发声装置。按重量份，所述有机硅类压敏胶的制作原料包括：有机硅树脂20～80份、催化剂0.1～5份、有机溶剂30～90份及有机硅橡胶5～55份。本发明应用该有机硅类压敏胶的振膜具有较佳的耐高温性能，使得该振膜在振动时不会出现偏振现象，进而使得应用该振膜的发声装置具有较佳的音质和听音稳定性。

Description

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 技术领域
本发明涉及发声装置技术领域，尤其涉及一种有机硅类压敏胶、该有机硅类压敏胶的制备方法、应用该有机硅类压敏胶的复合膜结构、应用该复合膜结构的振膜、及应用该振膜的发声装置。
背景技术
振膜是发声装置的核心部件。丙烯酸脂类压敏胶具有较佳的阻尼性能，为了使振膜具有较佳的阻尼性能，通常采用丙烯酸脂类压敏胶来制作振膜的阻尼胶层。然而，由于丙烯酸脂类压敏胶含有酯基等极性基团，导致该阻尼胶层的耐高温性能较差，在输入电压增加时，该阻尼胶层的刚性和阻尼性能下降，导致振膜在振动过程中出现偏振，进而导致发声装置的音质和听音稳定性均较差。
发明内容
鉴于上述问题，本发明提供了一种有机硅类压敏胶，旨在使应用该有机硅类压敏胶的振膜具有较佳的耐高温性能，使得该振膜在振动时不会出现偏振现象，进而使得应用该振膜的发声装置具有较佳的音质和听音稳定性。
为解决上述技术问题，按重量份，本发明提供的有机硅类压敏胶的制作原料包括：
有机硅树脂20～80份；
催化剂0.1～5份；
有机硅橡胶5～55份；及
有机溶剂30～90份。
进一步地，所述有机硅树脂包括M链节和Q链节，该M链节为
Figure PCTCN2018110159-appb-000001
该Q链节为
Figure PCTCN2018110159-appb-000002
该M链节和Q链节的数量比为1:0.6～0.9，其中，R 1为甲基、氢基或乙烯基，m的范围为15～20。
进一步地，所述有机硅橡胶的结构式为
Figure PCTCN2018110159-appb-000003
其中，R 2为甲基、乙烯基、或苯基，n的范围为5000～10000。
进一步地，所述有机硅树脂和有机硅橡胶的质量比的范围为：1:1～15:1。
进一步地，按重量份，所述原料还包括交联剂0～5份，该交联剂为含氢硅油、有机过氧化物、或烷氧基硅烷；且/或，
按重量份，所述原料还包括反应抑制剂0～5份，该反应抑制剂为炔醇化合物、含氮的化合物及乙烯基化合物中的至少一种；且/或，
所述有机溶剂为苯、甲苯、乙酸乙酯、二甲苯、N-甲基吡咯烷酮及丁酮中的至少一种；且/或，
所述催化剂为铂的有机络合物、或有机锡化合物。
本发明还提供一种有机硅类压敏胶的制备方法，包括以下步骤：
按重量份，混合有机硅树脂20～80份、有机硅橡胶5～55份、及有机溶剂30～90份，获得混合物；
提供催化剂0.1～5份，将催化剂加入至混合物中，对加入有催化剂的混合物进行加热处理，获得胶体；及
烘干所述胶体，获得有机硅类压敏胶。
进一步地，所述获得胶体后，烘干所述胶体前，还包括以下步骤：
按重量份，提供0～5份交联剂；及
向该胶体中加入该交联剂。
所述获得胶体后，烘干所述胶体前，还包括以下步骤：
按重量份，提供0～5份反应抑制剂；及
向该胶体中加入该反应抑制剂。
本发明还提供一种复合膜结构，所述复合膜结构包括两层第一基材层、和至少一层压敏胶层，该压敏胶层夹设于两层第一基材层之间，该压敏胶层的材质为所述压敏胶。
进一步地，该第一基材层的材质为聚醚醚酮、聚醚酰亚胺、聚苯醚、或聚萘二甲酸乙二醇酯；且/或，
所述第一基材层的厚度的范围为2～40μm；且/或，
所述压敏胶层的厚度的范围为2～40μm。
进一步地，所述复合膜结构包括两层第一基材层和两层压敏胶层，所述复合膜结构还包括一第二基材层，该第二基材层包括相对设置的第一表面和第二表面，其中一压敏胶层夹设于第二基材层的第一表面和一第一基材层之间，另一压敏胶层夹设于第二基材层的第二表面和另一第一基材层之间。
进一步地，所述第二基材层的材质为聚对苯二甲酸乙二醇酯或无纺布；且/或，
所述第二基材层的厚度的范围为1～30μm。
本发明还提供一种振膜，所述振膜具有所述复合膜结构。
本发明还提供一种发声装置，所述发声装置包括所述振膜。
按重量份，本发明技术方案的有机硅类压敏胶的制作原料包括：有机硅树脂20～80份、有机溶剂30～90份、催化剂0.1～5份及有机硅橡胶5～55份，有 机硅橡胶和有机硅树脂之间会发生缩合反应，有机硅橡胶之间还会发生交联反应，催化剂加快反应速度，从而生成三维网状结构的有机硅类压敏胶，该三维网状结构可使该有机硅类压敏胶具有致密的结构，以使有机硅类压敏胶具有较佳的耐高温性能，而且有机硅树脂具有分子量大和模量大的优点，将有机硅树脂设置为20～80份，以使有机硅类压敏胶还具有较佳的致密性、粘结性，将有机硅橡胶设置为5～55份，以提高有机硅类压敏胶的成膜性、粘结性和回弹性，使得应用该有机硅类压敏胶的振膜在振动过程中不会出现偏振现象，进而使得应用该振膜的发声装置具有较佳的音质和听音稳定性。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图示出的结构获得其他的附图。
图1为本发明复合膜结构第一实施例的剖视图。
图2为本发明复合膜结构第二实施例的剖视图。
图3为本发明振膜一实施例的剖视图。
附图标号说明：
标号 名称 标号 名称
100 复合膜结构 53 第二表面
10 第一基材层 200 振膜
30 压敏胶层 21 折环部
50 第二基材层 23 球顶部
51 第一表面    
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清 楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明，本发明实施例中所有方向性指示(诸如上、下、左、右、前、后……)仅用于解释在某一特定姿态(如附图所示)下各部件之间的相对位置关系、运动情况等，如果该特定姿态发生改变时，则该方向性指示也相应地随之改变。
还需要说明的是，当元件被称为“固定于”或“设置于”另一个元件上时，它可以直接在另一个元件上或者可能同时存在居中元件。当一个元件被称为是“连接”另一个元件，它可以是直接连接另一个元件或者可能同时存在居中元件。
另外，在本发明中涉及“第一”、“第二”等的描述仅用于描述目的，而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
按重量份，本发明提供一种有机硅类压敏胶的制作原料包括：
有机硅树脂20～80份；
催化剂0.1～5份；
有机硅橡胶5～55份；及
有机溶剂30～90份。
催化剂为铂的有机络合物、或有机锡化合物。
催化剂的主要作用是加快反应速度，可催化有机硅橡胶与有机硅树脂之间的缩合反应。
铂的有机络合物的浓度为1～100ul/L。铂的有机络合物可为氯铂酸聚硅氧烷的溶液、氯铂酸异丙醇络合物、及氯铂酸邻苯二甲酸二乙酯络合物中的至少一种。
有机锡类化合物选自二丁基二月桂酸锡、二月桂酸二辛基锡、二醋酸二丁 基锡及辛酸亚锡中的至少一种。
有机溶剂为苯、甲苯、乙酸乙酯、二甲苯、N-甲基吡咯烷酮及丁酮中的至少一种。有机硅树脂和有机硅橡胶可溶解在该有机溶剂中，以均匀混合。
按重量份，本发明技术方案的有机硅类压敏胶的制作原料包括：有机硅树脂20～80份、有机溶剂30～90份、催化剂0.1～5份及有机硅橡胶5～55份，有机硅橡胶和有机硅树脂之间会发生缩合反应，有机硅橡胶之间还会发生交联反应，催化剂加快反应速度，从而生成三维网状结构的有机硅类压敏胶，该三维网状结构可使该有机硅类压敏胶具有致密的结构，以使有机硅类压敏胶具有较佳的耐高温性能，而且有机硅树脂具有分子量大和模量大的优点，将有机硅树脂设置为20～80份，以使有机硅类压敏胶还具有较佳的致密性、粘结性，将有机硅橡胶设置为5～55份，以提高有机硅类压敏胶的成膜性、粘结性和回弹性，使得应用该有机硅类压敏胶的振膜在振动过程中不会出现偏振现象，进而使得应用该振膜的发声装置具有较佳的音质和听音稳定性。
本发明的有机硅类压敏胶具有较高的阻尼性，其损耗因子≥0.5。
本发明的有机硅类压敏胶具有高温持粘性较佳，在150℃的测试环境下，其脱落时间大于1小时。
有机硅树脂包括M链节和Q链节，该M链节为
Figure PCTCN2018110159-appb-000004
该Q链节为
Figure PCTCN2018110159-appb-000005
其中，R 1为甲基、氢基或乙烯基，m的范围为15～20。
M链节和Q链节的数量比为1:0.6～0.9。
有机硅树脂的M链节可提高对有机硅橡胶的相容性，并起增粘作用，Q链节具有补强作用，可以提高制得的有机硅类压敏胶的内聚强度。M链节和Q链节的数量比较小时，有机硅树脂与有机硅橡胶的相容性较差，而M链节和Q链节的数量比较大时，制得的有机硅类压敏胶的内聚强度较差。本发明技术方案的M链节和Q链节的数量比设置为1:0.6～0.9，不仅可使该有机硅树脂与有机硅橡胶具有较佳的相容性，以使制得的有机硅类压敏胶具有良好的综合性 能和高固含量，还可使制得的有机硅类压敏胶具有较佳的弹性和内聚强度。
M链节中的R 1为甲基、氢基或乙烯基，氢基及乙烯基可用于与有机硅橡胶发生缩合反应。
可以理解的，Q链节中m可为15、16、17、18、19、或20。
Q链节中m的数值代表羟基的含量，羟基的含量会影响有机硅树脂与有机硅橡胶反应的程度，并影响有机硅类压敏胶性能，如粘附力和粘接强度等。本发明的Q链节中m的数值范围为15～20，使得制得有机硅类压敏胶具有较佳的粘附力和粘结强度。
有机硅橡胶的结构式为
Figure PCTCN2018110159-appb-000006
其中，R 2为甲基、乙烯基、或苯基，n的范围为5000～10000。苯基可增加有机硅类压敏胶的耐热性能，乙烯基可与其他基团发生交联反应。
本发明有机硅橡胶具有以羟基为端基的线形结构，羟基可与有机硅树脂发生缩合反应。
有机硅橡胶n的范围为5000～10000，使得该有机硅橡胶的分子量适中，使得制得的有机硅类压敏胶具有较佳的柔韧性、内聚强度、低迁移率、粘度佳、固含量高。
在本发明一实施例中，有机硅橡胶为甲基羟基硅橡胶、乙烯基硅橡胶、或苯基硅橡胶。
有机硅树脂和有机硅橡胶的质量比的范围为：1:1～15:1。
可以理解的，有机硅树脂和有机硅橡胶的质量比为：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、或15:1等。
本发明技术方案的有机硅树脂和有机硅橡胶的质量比的范围设置为1:1～15:1，使得制得的有机硅类压敏胶具有较佳的初粘性和持粘性。
按重量份，原料还包括交联剂0～5份。该交联剂为含氢硅油、有机过氧化物、或烷氧基硅烷。
该交联剂的作用是增加有机硅类压敏胶的内聚力。
含氢硅油是指含有S-H键的硅油。可以理解的，有机硅橡胶还会与含氢硅油发生交联反应。
有机过氧化物可为过氧化苯甲酰、叔丁基过氧化氢、过氧化二异丙苯、2,4-二氯苯甲酰、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、二-(叔丁基过氧化异丙基)苯等。
烷氧基硅烷可为环氧硅烷、四甲氧基硅烷、辛基三甲氧基硅烷、二叔丁氧基二乙酰氧基硅烷、甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、甲基三乙酰氧肟基硅烷、甲基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙氧基硅烷、丙氧基硅烷、及丁氧基硅烷中的至少一种等。
按重量份，原料还包括反应抑制剂0～5份。
该反应抑制剂为炔醇化合物、含氮的化合物及乙烯基化合物中的至少一种。
反应抑制剂可减缓反应速度，以使压敏胶的存储期延长。
炔醇化合物可为乙炔基环己醇、2-甲基-3-丁炔-2-醇、3-苯基-1-丁炔-3-醇、3-丙基-1-丁炔-3-醇中的至少一种。
含氮的化合物可为喹啉、甲肼及苯肼中的至少一种。
乙烯基化合物可为全氯乙烯和/或四乙烯基四甲基环四硅氧烷。
需要说明的是，针对上述有机硅树脂、催化剂、有机硅橡胶、有机溶剂、交联剂、及反应抑制剂，还可以为其他材料，本发明对此不做限制。
本发明还提供一种有机硅类压敏胶的制备方法，包括以下步骤：
按重量份，混合20～80份有机硅树脂、5～55份有机硅橡胶、及30～90份有机溶剂，获得混合物；
提供催化剂0.1～5份，将催化剂加入至混合物中，对加入有催化剂的混合物进行加热处理，获得胶体；及
烘干胶体，获得有机硅类压敏胶。
在本发明一实施例中，有机硅橡胶为甲基羟基硅橡胶、乙烯基硅橡胶、或 苯基硅橡胶。
有机溶剂为苯、甲苯、乙酸乙酯、二甲苯、N-甲基吡咯烷酮及丁酮中的至少一种。有机硅树脂和有机硅橡胶可溶解在该有机溶剂中，以均匀混合。
该催化剂为铂的有机络合物、或有机锡化合物。
催化剂的主要作用是加快反应速度，可催化有机硅橡胶与有机硅树脂之间的缩合反应。
铂的有机络合物的浓度为1～100ul/L。铂的有机络合物可为氯铂酸聚硅氧烷的溶液、氯铂酸异丙醇络合物、氯铂酸邻苯二甲酸二乙酯络合物中的至少一种。
有机锡类化合物选自二丁基二月桂酸锡、二月桂酸二辛基锡、二醋酸二丁基锡及辛酸亚锡中的至少一种。
可以理解的，在对加入有催化剂的混合物进行加热处理时，该加热处理的温度范围为70～90℃，反应时间为50～70min，以使有机硅橡胶与有机硅树脂之间发生缩合反应。
在本发明一实施例中，上述步骤烘干胶体，获得有机硅类压敏胶包括：可将该胶体涂布于一基材上，再对该胶体进行烘干处理。该基材的材质可为塑料、无纺布或离型膜。该塑料可为热塑性聚酯弹性体、热塑性聚氨酯弹性体、热塑性聚酰胺弹性体、有机硅弹性体、聚醚醚酮、聚芳酯、聚醚酰亚胺、聚酰亚胺、聚苯硫醚、聚萘二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯及聚对苯二甲酸丁二醇酯中的至少一种。
在本发明一实施例中，烘干胶体的处理包括第一次烘干处理和第二次烘干处理，该第一次烘干处理的温度范围为60～120℃，反应时间为2～3min，以除去胶体中的有机溶剂，该第二次烘干处理的温度范围为80～160℃，反应时间为2～3min，来固化该胶体，形成有机硅类压敏胶。
本发明技术方案的加热处理的过程中有机硅橡胶和有机硅树脂之间会发生缩合反应，在第二次烘干处理的过程中有机硅橡胶之间还会发生交联反应，催化剂加快反应速度，从而生成三维网状结构的有机硅类压敏胶，该三维网状结构可使该有机硅类压敏胶具有致密的结构，以使有机硅类压敏胶具有较佳的耐高温性能，而且有机硅树脂具有分子量大和模量大的优点，将有机硅树脂设置为20～80份，以使有机硅类压敏胶还具有较佳的致密性、粘结性，将有机硅 橡胶设置为5～55份，以提高有机硅类压敏胶的成膜性、粘结性和回弹性，使得应用该有机硅类压敏胶的振膜在振动过程中不会出现偏振现象，进而使得应用该振膜的发声装置具有较佳的音质和听音稳定性。
获得胶体后，烘干胶体前，还包括以下步骤：
按重量份，提供0～5份交联剂；及
向该胶体中加入该交联剂。
该交联剂为含氢硅油、有机过氧化物、或烷氧基硅烷。
该交联剂的作用是使有机硅橡胶之间发生交联反应，增加有机硅类压敏胶的内聚力。
含氢硅油是指含有S-H键的硅油。可以理解的，有机硅橡胶还会与含氢硅油发生交联反应。
有机过氧化物可为过氧化苯甲酰、叔丁基过氧化氢、过氧化二异丙苯、2,4-二氯苯甲酰、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、二-(叔丁基过氧化异丙基)苯等。
烷氧基硅烷可为环氧硅烷、四甲氧基硅烷、辛基三甲氧基硅烷、二叔丁氧基二乙酰氧基硅烷、甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、甲基三乙酰氧肟基硅烷、甲基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙氧基硅烷、丙氧基硅烷、及丁氧基硅烷中的至少一种等。
获得胶体后，烘干胶体前，还包括以下步骤：
按重量份，提供0～5份反应抑制剂；及
向该胶体中加入该反应抑制剂。
该反应抑制剂为炔醇化合物、含氮的化合物及乙烯基化合物中的至少一种。
反应抑制剂可减缓反应速度，以使压敏胶的存储期延长。
炔醇化合物可为乙炔基环己醇、2-甲基-3-丁炔-2-醇、3-苯基-1-丁炔-3-醇、及3-丙基-1-丁炔-3-醇中的至少一种。
含氮的化合物可为喹啉、甲肼及苯肼中的至少一种。
乙烯基化合物可为全氯乙烯和/或四乙烯基四甲基环四硅氧烷。
参图1-2，本发明还提供一种复合膜结构100。
复合膜结构100包括两层第一基材层10、和至少一层压敏胶层30，该压敏胶层30夹设于两层第一基材层10之间，上述第一基材层10的中的至少一层为塑料基材层，该压敏胶层30为上述实施例所述的有机硅类压敏胶。
由于该复合膜结构100采用了上述所有实施例的全部技术方案，因此至少具有上述实施例的技术方案所带来的所有有益效果，在此不再一一赘述。
该塑料基材层的材质为聚醚醚酮、聚醚酰亚胺、聚苯醚、或聚萘二甲酸乙二醇酯。
第一基材层10的厚度的范围为2～40μm。
可选地，第一基材层10的厚度为2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34μm、35μm、36μm、37μm、38μm、39μm、或40μm。
可以理解的，该两层第一基材层10可选用相同的材质，也可选用不同的材质。
本发明技术方案的第一基材层10中的至少一层为塑料基材层，且塑料基材层的材质为聚醚醚酮、聚醚酰亚胺、聚苯醚、或聚萘二甲酸乙二醇酯，使得该第一基材层10中的至少一层的软化温度大于80℃，具有良好的耐高温性，且第一基材层10的厚度为2～20μm，使得该复合膜结构100不仅具有较佳的强度和回弹性，还具有优良的结构稳定性、和较佳的耐高温性。
压敏胶层30的厚度的范围为2～40μm。
可选地，压敏胶层30的厚度为2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34μm、35μm、36μm、37μm、38μm、39μm、或40μm。
本发明技术方案的压敏胶层30的厚度的范围为2～40μm，使得应用压敏胶层30的复合膜结构100具有较佳的耐高温特性，即使在输入电压增加时，复合膜结构100的刚性和阻尼性能也不会明显下降。
进一步的，上述两层基材层10均为塑料基材层。此时，复合膜结构100为依次堆叠的第一塑料基材层、第一压敏胶层及第二塑料基材层。且第一热塑料基材层与第二塑料基材层间的材质可以相同也可以不相同。
可选地，第一塑料基材层与第二塑料基材层的材质相同，例如均为聚醚醚酮。此时，复合膜结构为依次堆叠的聚醚醚酮，丙烯酸类压敏胶及聚醚醚酮结构。其中，有机硅类压敏胶为上述实施例所述的有机硅类压敏胶。
进一步的，复合膜结构100包括两层压敏胶层30，复合膜结构100还包括一第二基材层50，该第二基材层50包括相对设置的第一表面51和第二表面50，其中一压敏胶层30夹设于第二基材层50的第一表面51和一第一基材层10之间，另一压敏胶层30夹设于第二基材层50的第二表面53和另一第一基材层10之间。上述两层压敏胶层中的至少一压敏胶层为上述实施例所述的有机硅类压敏胶层，另一压敏胶层也可以为上述实施例所述的有机硅类压敏胶层，还可以是其他材质的压敏胶层，例如，丙烯酸类胶层，本发明对此不做限制。
第二基材层50的材质为热塑性弹性体、或工程塑料。其中，热塑性弹性体选自热塑性聚酯弹性体、热塑性聚氨酯弹性体、热塑性聚酰胺弹性体、及有机硅弹性体的至少一种。工程塑料选自聚醚醚酮、聚芳酯、聚醚酰亚胺、聚酰亚胺、聚苯硫醚、聚萘二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯及聚对苯二甲酸丁二醇酯中的至少一种。
需要说明的是，针对上述第一基材层10和第二基材层50，还可以为其他材料，如，无纺布，本发明对此不做限制。
第二基材层50的厚度的范围为1～30μm。
可选地，第二基材层50的厚度为2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、或30μm。
本发明技术方案的复合膜结构100包括两层第一基材层10、两层压敏胶层30及一第二基材层50，其中一压敏胶层30夹设于第二基材层50的第一表面51和一第一基材层10之间，另一压敏胶层30夹设于第二基材层50的第二表面53和另一第一基材层10之间，以增加该复合膜结构100的挺度和抗偏振能力。
参图3，本发明还提供一种振膜200。
振膜200具有复合膜结构。
在本发明一实施例中，振膜200的总厚度为6μm～110μm。
由于该振膜200采用了上述所有实施例的全部技术方案，因此至少具有上述实施例的技术方案所带来的所有有益效果，在此不再一一赘述。
另外，第一基材层10为振膜200的振动提供所需的刚度，获得较高的瞬态响应。压敏胶层30具有较高的粘结力，使得振膜200的各层的振动可保持一致性。而且，压敏胶层30具有较佳的阻尼特性，可以提高大振幅下的振动平衡性，抑制偏振，以使振膜200在高低温工作环境下，均具有较高的音质和听音稳定性。
振膜200包括至少一折环部21，该折环部21具有复合膜结构100。
振膜200还包括球顶部23，该球顶部23与折环部21连接。
本发明一实施例中，振膜200包括两个折环部21。
本发明一实施例中，球顶部23与折环部21一体成型。
本发明一实施例中，球顶部23与折环部21采用不同材质。
本发明一实施例中，球顶部23位于振膜200的中心位置，折环部21位于振膜200中心位置的周侧，环绕振膜200的中心位置。
本发明是提供一种发声装置(未图示)。发声装置包括所述振膜200。
由于该发声装置采用了上述所有实施例的全部技术方案，因此至少具有上述实施例的技术方案所带来的所有有益效果，在此不再一一赘述。
本发明一实施例中，发声装置还包括音圈(未图示)，振膜200与音圈牢固粘接，以提升振膜200的性能。
本发明的有机硅类压敏胶的制备方法包括以下实施例：
实施例一：
按重量份，提供5份甲基羟基硅橡胶、20份有机硅树脂、30份苯，将甲基羟基硅橡胶和有机硅树脂溶解于苯中，获得混合物。其中，甲基羟基硅橡胶与有机硅树脂的质量比为1:4，有机硅树脂中M链节和Q链节的数量比为1:0.7，R 1为甲基，m的范围为15。
提供0.1份氯铂酸异丙醇络合物，将氯铂酸异丙醇络合物加入至混合物中，对加入有氯铂酸异丙醇络合物的混合物进行加热处理，获得胶体。其中该加热处理的温度为80℃，时间为70min，氯铂酸异丙醇络合物作为催化剂可促进甲基羟基硅橡胶和有机硅树脂之间发生缩合反应。
待胶体冷却后，将胶体涂布于离型膜上。
对涂布于离型膜上的胶体进行第一次烘干处理，以除去苯，该第一次烘干处理的温度为85℃，时间为2.3min。
对经第一次烘干处理后的胶体进行第二次烘干处理，获得有机硅类压敏胶，该第二次烘干处理的温度为160℃，时间为3min。
实施例二：
按重量份，提供15份甲基羟基硅橡胶、30份有机硅树脂、54份甲苯，将甲基羟基硅橡胶和有机硅树脂溶解于甲苯中，获得混合物。其中，甲基羟基硅橡胶与有机硅树脂的质量比为1:2，有机硅树脂中M链节和Q链节的数量比为1:0.75，R 1为氢基，m的范围为17。
提供0.5份二丁基二月桂酸锡，将二丁基二月桂酸锡加入至混合物中，对加入有二丁基二月桂酸锡的进行加热处理，获得胶体。其中，该加热处理的温度为90℃，时间为50min，二丁基二月桂酸锡作为催化剂可促进甲基羟基硅橡胶和有机硅树脂之间发生缩合反应。
待胶体冷却后，提供0.5份过氧化苯甲酰，将过氧化苯甲酰加入至胶体中，搅拌均匀。
将加有过氧化苯甲酰的胶体涂布于聚醚醚酮基材上，对其进行第一次烘干处理，以除去甲苯，该第一次烘干处理的温度为90℃，时间为2min。
对经第一次烘干处理后的胶体进行第二次烘干处理，胶体固化，获得有机硅类压敏胶，该第二次烘干处理的温度为155℃，时间为2min。
其中，过氧化苯甲酰作为交联剂可促进甲基羟基硅橡胶之间发生的交联反应。
实施例三：
按重量份，提供25份乙烯基硅橡胶、40份有机硅树脂、32.3份甲苯，将乙烯基硅橡胶和有机硅树脂溶解于甲苯中，获得混合物。其中，乙烯基硅橡胶与有机硅树脂的质量比为5:8，有机硅树脂中M链节和Q链节的数量比为1:0.7，R 1为氢基，m的范围为18。
提供1份辛酸亚锡，将辛酸亚锡加入至混合物，对加入有辛酸亚锡的混合物进行加热处理，获得胶体。其中，该加热处理的温度为80℃，时间为60min，辛酸亚锡作为催化剂可促进乙烯基硅橡胶和有机硅树脂之间发生缩合反应。
待胶体冷却后，提供0.1份乙炔基环己醇，2份含氢硅油，0.5份氯铂酸聚硅氧烷的溶液，将乙炔基环己醇，含氢硅油及氯铂酸聚硅氧烷的溶液加入至胶体中，搅拌均匀。
将加有乙炔基环己醇，含氢硅油及氯铂酸聚硅氧烷的溶液的胶体涂布于聚醚酰亚胺基材上，对其进行第一次烘干处理，以除去甲苯，该第一次烘干处理的温度为80℃，时间为2.5min。
对经第一次烘干处理后的胶体进行第二次烘干处理，胶体固化，获得有机硅类压敏胶，该第二次烘干处理的温度为160℃，时间为2.5min。
其中，乙炔基环己醇作为反应抑制剂可减缓反应速度，含氢硅油作为交联剂可促进乙烯基硅橡胶之间发生交联反应，同时，该含氢硅油还会与乙烯基硅橡胶发生交联反应。氯铂酸聚硅氧烷的溶液作为催化剂可加快反应速度。
实施例四：
按重量份，提供30份苯基硅橡胶、30份有机硅树脂、39份乙酸乙酯，将苯基硅橡胶和有机硅树脂溶解于乙酸乙酯中，获得混合物。其中，苯基硅橡胶与有机硅树脂的质量比为1:1，有机硅树脂中M链节和Q链节的数量比为1:0.8，R1为氢基，m的范围为20。
提供0.5份二丁基二月桂酸锡，将二丁基二月桂酸锡加入至混合物，对加入有二丁基二月桂酸锡的混合物进行加热处理，获得胶体。其中，该加热处理的温度为70℃，时间为55min，二丁基二月桂酸锡作为催化剂可促进苯基硅橡胶和有机硅树脂之间发生缩合反应。
待胶体冷却后，提供0.5份过氧化苯甲酰，将过氧化苯甲酰加入至胶体中，搅拌均匀。
将加有过氧化苯甲酰的胶体涂布于聚苯醚基材上，对其进行第一次烘干处理，以除去乙酸乙酯，该第一次烘干处理的温度为70℃，时间为2.7min。
对经第一次烘干处理后的胶体进行第二次烘干处理，胶体固化，获得有机硅类压敏胶，该第二次烘干处理的温度为160℃，时间为2.6min。
其中，过氧化苯甲酰作为交联剂可促进甲基羟基硅橡胶之间发生的交联反应。
以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是在本发明的发明构思下，利用本发明说明书及附图内容所作的等效结构变换，或直接或间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。

Claims (14)

  1. 一种有机硅类压敏胶，其特征在于，按重量份，所述有机硅类压敏胶的制作原料包括：
    有机硅树脂20～80份；
    催化剂0.1～5份；
    有机硅橡胶5～55份；及
    有机溶剂30～90份。
  2. 如权利要求1所述的有机硅类压敏胶，其特征在于，所述有机硅树脂包括M链节和Q链节，该M链节为
    Figure PCTCN2018110159-appb-100001
    该Q链节为
    Figure PCTCN2018110159-appb-100002
    该M链节和Q链节的数量比为1:0.6～0.9，其中，R 1为甲基、氢基或乙烯基，m的范围为15～20。
  3. 如权利要求1或2所述的有机硅类压敏胶，其特征在于，所述有机硅橡胶的结构式为
    Figure PCTCN2018110159-appb-100003
    其中，R 2为甲基、乙烯基、或苯基，n的范围为5000～10000。
  4. 如权利要求1-3任一项所述的有机硅类压敏胶，其特征在于，所述有机硅树脂和有机硅橡胶的质量比的范围为：1:1～15:1。
  5. 如权利要求1至4任一项所述的有机硅类压敏胶，其特征在于，按重量份，所述原料还包括交联剂0～5份，该交联剂为含氢硅油、有机过氧化物、或烷氧基硅烷；且/或，
    按重量份，所述原料还包括反应抑制剂0～5份，该反应抑制剂为炔醇化合物、含氮的化合物及乙烯基化合物中的至少一种；且/或，
    所述有机溶剂为苯、甲苯、乙酸乙酯、二甲苯、N-甲基吡咯烷酮及丁酮中的至少一种；且/或，
    所述催化剂为铂的有机络合物、或有机锡化合物。
  6. 一种有机硅类压敏胶的制备方法，包括以下步骤：
    按重量份，混合有机硅树脂20～80份、有机硅橡胶5～55份、及有机溶剂30～90份，获得混合物；
    提供催化剂0.1～5份，将催化剂加入至混合物中，对加入有催化剂的混合物进行加热处理，获得胶体；及
    烘干所述胶体，获得有机硅类压敏胶。
  7. 如权利要求6所述的有机硅类压敏胶的制备方法，其特征在于，所述获得胶体后，烘干所述胶体前，还包括以下步骤：
    按重量份，提供0～5份交联剂；及
    向该胶体中加入该交联剂。
  8. 如权利要求6所述的有机硅类压敏胶的制备方法，其特征在于，所述获得胶体后，烘干所述胶体前，还包括以下步骤：
    按重量份，提供0～5份反应抑制剂；及
    向该胶体中加入该反应抑制剂。
  9. 一种复合膜结构，其特征在于，所述复合膜结构包括两层第一基材层、和至少一层压敏胶层，该压敏胶层夹设于两层第一基材层之间，所述两层第一基材层的至少一层为塑料基材层，该压敏胶层的材质为权利要求1-5任一项所述的有机硅类压敏胶。
  10. 如权利要求9所述的复合膜结构，其特征在于，该塑料基材层的材质为聚醚醚酮、聚醚酰亚胺、聚苯醚、或聚萘二甲酸乙二醇酯；且/或，
    所述第一基材层的厚度的范围为2～40μm；且/或，
    所述压敏胶层的厚度的范围为2～40μm。
  11. 如权利要求9或10所述的复合膜结构，其特征在于，所述复合膜结构包括两层压敏胶层，所述复合膜结构还包括一第二基材层，该第二基材层包括相对设置的第一表面和第二表面，其中一压敏胶层夹设于第二基材层的第一表面和一第一基材层之间，另一压敏胶层夹设于第二基材层的第二表面和另一第一基材层之间。
  12. 如权利要求11所述的复合膜结构，其特征在于，所述第二基材层的材质为热塑性弹性体或工程塑料，所述热塑性弹性体选自热塑性聚酯弹性体、热塑性聚氨酯弹性体、热塑性聚酰胺弹性体、及有机硅弹性体的至少一种，所述工程塑料选自聚醚醚酮、聚芳酯、聚醚酰亚胺、聚酰亚胺、聚苯硫醚、聚萘二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯及聚对苯二甲酸丁二醇酯中的至少一种；且/或，
    所述第二基材层的厚度的范围为1～30μm。
  13. 一种振膜，其特征在于，所述振膜具有如权利要求9至12任一项所述的复合膜结构。
  14. 一种发声装置，其特征在于，所述发声装置包括如权利要求13所述的振膜。
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