WO2019237696A1 - Organosilicon pressure-sensitive adhesive and preparation method thereof, composite film structure, diaphragm, and sound generating device - Google Patents

Abstract

The present invention provides an organosilicon pressure-sensitive adhesive, a preparation method thereof, a composite film structure using the organosilicon pressure-sensitive adhesive, a diaphragm using the composite film structure, and a sound generating device using the diaphragm. The raw materials for preparing the organosilicon pressure-sensitive adhesive include, in parts by weight: 15-60 parts of an organosilicon resin, 5-55 parts of an organosilicon rubber, 30-90 parts of an organic solvent, and 0.1-5 parts of a catalyst. In the present invention, the diaphragm using the organosilicon pressure-sensitive adhesive has improved high-temperature resistance. As a result, polarization will not occur at the diaphragm when vibrating, thereby allowing the sound generating device using the diaphragm to have improved sound quality and audio stability.

Description

Organic silicon-based pressure-sensitive adhesive and preparation method thereof, composite film structure, vibrating film, and sounding device Technical field

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. Membrane, and sound generator using the same.

Background technique

The diaphragm is the core component of the sound generator. Acrylic pressure-sensitive adhesive has better damping performance. In order to make the diaphragm have better damping performance, acrylic pressure-sensitive adhesive is usually used to make the damping layer of the diaphragm. However, because the acrylic pressure-sensitive adhesive contains polar groups such as ester groups, the high temperature resistance of the damping rubber layer is poor. When the input voltage is increased, 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.

Summary of the Invention

In view of the above problems, 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.

In order to solve the above technical problems, according to parts by weight, the raw materials for manufacturing the silicone pressure-sensitive adhesive provided by the present invention include:

15 to 60 parts of silicone resin;

5 to 55 parts of silicone rubber;

0.1 to 5 parts of catalyst; and

30 to 90 parts of organic solvent.

Further, the silicone resin includes an M chain link and a Q chain link, and 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.

Further, the structural formula of the silicone rubber is

Here, R ₂ is a methyl group, a vinyl group, or a phenyl group, and the range of n is 5000 to 10,000.

Further, the range of the mass ratio of the silicone resin and the silicone rubber is: 1: 1 to 15: 1.

Further, 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,

According to parts by weight, 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:

By weight parts, 15 to 60 parts of a silicone resin, 5 to 55 parts of a silicone rubber, and 30 to 90 parts of an organic solvent are mixed to obtain a mixture;

0.1 to 5 parts of a catalyst is added to the mixture, and the mixture to which the catalyst is added is heat-treated to obtain a colloid; and

The colloid is dried to obtain a silicone-based pressure-sensitive adhesive.

Further, after obtaining the colloid and before drying the colloid, the method further includes the following steps:

0 to 5 parts of cross-linking agent by weight; and

The crosslinker is added to the colloid.

After the colloid is obtained, before the colloid is dried, the method further includes the following steps:

Provide 0 to 5 parts by weight of reaction inhibitor; and

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.

Further, the material of the 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 μm; and / or,

The thickness of the pressure-sensitive adhesive layer ranges from 2 to 40 μm.

Further, the two substrate layers are both thermoplastic elastomer layers, and 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.

Further, the materials of the first thermoplastic elastomer layer and the second thermoplastic elastomer layer are the same.

Further, 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.

Further, the material of the second substrate layer is a thermoplastic elastomer or an engineering plastic, and the thermoplastic elastomer is selected from the group consisting of thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, and silicone elastomer. At least one, 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 μm.

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.

In terms of parts by weight, 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. 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.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly explain the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are merely These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on the structure shown in the drawings without paying creative labor.

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.

3 is a cross-sectional view of an embodiment of a diaphragm according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

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 realization of the purpose, functional characteristics and advantages of the present invention will be further described with reference to the embodiments and the drawings.

detailed description

In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

It should be noted that all directional indicators (such as up, down, left, right, front, back, etc.) in the embodiments of the present invention are only used to explain the relationship between components in a specific posture (as shown in the drawings) The relative positional relationship, movement situation, etc., if the specific posture changes, the directional indication also changes accordingly.

It should also be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it may be directly on the other element or there may be a centered element at the same time. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may be present concurrently.

In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes, and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on those that can be realized by a person of ordinary skill in the art. When the combination of technical solutions conflicts or cannot be achieved, such a combination of technical solutions should be considered non-existent. , Is not within the scope of protection claimed by the present invention.

The invention provides a raw material for manufacturing a silicone-based pressure-sensitive adhesive, including:

15 to 60 parts of silicone resin;

5 to 55 parts of silicone rubber;

0.1 to 5 parts of catalyst; and

30 to 90 parts of organic solvent.

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.

In terms of parts by weight, 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. 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

Here, 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. When the number of M and Q links is relatively small, the compatibility of silicone resin and silicone rubber is poor, and when the number of M and Q links is relatively large, Cohesive strength is poor. The number ratio of the M chain link and the Q chain link in the technical solution of the present invention is set to 1: 0.6 to 0.9, which not only 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.

It can be understood that 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.

The structural formula of silicone rubber is

Here, 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. .

In one embodiment of the present invention, 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.

Understandably, 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 butoxysilane Kind 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.

It should be noted that, 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:

20 to 80 parts by weight of a silicone resin, 5 to 55 parts of a silicone rubber, and 30 to 60 parts of an organic solvent are mixed to obtain a mixture;

Adding 0.1 to 5 parts of the catalyst to the mixture, and heating the mixture to which the catalyst is added to obtain a colloid; and

The colloid is dried to obtain a silicone pressure-sensitive adhesive.

In one embodiment of the present invention, 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.

It can be understood that 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.

In an embodiment of the present invention, 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.

In an embodiment of the present invention, 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.

During the heat treatment of the technical solution of the present invention, 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.

After obtaining the colloid and before drying the colloid, the following steps are also included:

0 to 5 parts of cross-linking agent by weight; and

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 butoxysilane Kind and so on.

After obtaining the colloid and before drying the colloid, the following steps are also included:

Provide 0 to 5 parts by weight of reaction inhibitor; and

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.

Referring to FIGS. 1-2, 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.

In one embodiment of the present invention, 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.

Since 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.

Further, the material between the two first substrate layers 100 is a thermoplastic elastomer layer, and 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. A body layer; wherein the materials of the first thermoplastic elastomer layer and the second thermoplastic elastomer layer may be the same or different.

Optionally, the material between the first thermoplastic elastomer layer and the second thermoplastic elastomer layer is the same. For example, the materials of the first thermoplastic elastomer layer and the second thermoplastic elastomer layer are both thermoplastic polyester elastomers. At this time, 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 μm.

Optionally, the thickness of the first substrate layer 10 is 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm , 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, or 40 μm.

It can be understood that 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 μm, 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 μm.

Optionally, the thickness of the pressure-sensitive adhesive layer 30 is 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, or 40 μm.

The thickness of the pressure-sensitive adhesive layer 30 of the technical solution of the present invention ranges from 2 to 40 μm, 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. And another first substrate layer 10.

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 μm.

Optionally, the thickness of the second substrate layer 50 is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm , 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, or 30 μm.

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.

Referring to FIG. 3, the present invention further provides a diaphragm 200.

The diaphragm 200 has a composite film structure 100.

In an embodiment of the present invention, the total thickness of the diaphragm 200 is 7 μm to 150 μm.

Since 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.

In addition, 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. In addition, 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.

In an embodiment of the present invention, the diaphragm 200 includes two folded ring portions 21.

In one embodiment of the present invention, the ball top portion 23 and the folded ring portion 21 are integrally formed.

In one embodiment of the present invention, the ball top portion 23 and the folded ring portion 21 are made of different materials.

In an embodiment of the present invention, 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.

Since 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.

In an embodiment of the present invention, 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.

Embodiment one:

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.

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;

After the colloid is cooled, apply the colloid on a release film;

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.

Embodiment two:

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, and the range of m is 17.

Provide 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;

After the colloid is cooled, provide 0.5 parts of benzoyl peroxide, add benzoyl peroxide to the colloid, and stir well;

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.

Among them, benzoyl peroxide as a cross-linking agent can promote the cross-linking reaction between methyl hydroxy silicone rubber.

Example three:

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, and the range of m is 18.

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 To obtain a colloid, the temperature of the heat treatment is 80 ° C., and the time is 65 min;

After the colloid is cooled, provide 0.1 parts of ethynylcyclohexanol, 2 parts of hydrogen-containing silicone oil, 0.5 parts of chloroplatinic acid isopropanol complex, and acetylene cyclohexanol, hydrogen-containing silicone oil, and chloroplatinic acid polysiloxane Add the solution to the colloid and stir well;

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.

Among them, ethynyl cyclohexanol as a reaction inhibitor can slow down the reaction speed, and hydrogen-containing silicone oil as a cross-linking agent can promote the crosslinking reaction between vinyl silicone rubbers. At the same time, the hydrogen-containing silicone oil can also occur with vinyl silicone rubbers. Cross-linking reaction. A solution of chloroplatinic acid polysiloxane as a catalyst can accelerate the reaction speed.

Embodiment 4:

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, and the range of m is 20.

Provide 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;

After the colloid is cooled, provide 0.5 parts of benzoyl peroxide, add benzoyl peroxide to the colloid, and stir well;

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.

Among them, benzoyl peroxide as a crosslinking agent can promote the crosslinking reaction between phenyl silicone rubber.

The above are only preferred embodiments of the present invention, and thus do not limit the patent scope of the present invention. Under the inventive concept of the present invention, equivalent structural transformations made using the description and drawings of the present invention, or directly or indirectly used in other Relevant technical fields are included in the patent protection scope of the present invention.

Claims (16)

1. A silicone-based pressure-sensitive adhesive, characterized in that, according to parts by weight, the raw materials for making the silicone-based pressure-sensitive adhesive include:

   15 to 60 parts of silicone resin;

   5 to 55 parts of silicone rubber;

   0.1 to 5 parts of catalyst; and

   30 to 90 parts of organic solvent.
2. The silicone-based pressure-sensitive adhesive according to claim 1, wherein the silicone resin comprises an M chain link and a Q chain link, and 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.
3. The silicone pressure-sensitive adhesive according to claim 1, wherein the structural formula of the silicone rubber is

   

   Here, R ₂ is a methyl group, a vinyl group, or a phenyl group, and the range of n is 5000 to 10,000.
4. The silicone-based pressure-sensitive adhesive according to claim 1, wherein a mass ratio of the silicone resin and the silicone rubber ranges from 1: 1 to 15: 1.
5. The silicone-based pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the raw material further comprises 0 to 5 parts by weight of a crosslinking agent, the crosslinking agent being a hydrogen-containing silicone oil, organic Peroxide, or alkoxysilane; and / or,

   According to parts by weight, 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.
6. A method for preparing a silicone-based pressure-sensitive adhesive includes the following steps:

   By weight parts, 15 to 60 parts of a silicone resin, 5 to 55 parts of a silicone rubber, and 30 to 90 parts of an organic solvent are mixed to obtain a mixture;

   0.1 to 5 parts of a catalyst is added to the mixture, and the mixture to which the catalyst is added is heat-treated to obtain a colloid; and

   The colloid is dried to obtain a silicone-based pressure-sensitive adhesive.
7. The method for preparing a silicone-based pressure-sensitive adhesive according to claim 6, wherein after obtaining the colloid and before drying the colloid, the method further comprises the following steps:

   0 to 5 parts of cross-linking agent by weight; and

   The crosslinker is added to the colloid.
8. The method for preparing a silicone-based pressure-sensitive adhesive according to claim 6, wherein after obtaining the colloid and before drying the colloid, the method further comprises the following steps:

   Provide 0 to 5 parts by weight of reaction inhibitor; and

   The reaction inhibitor is added to the colloid.
9. A composite film structure, characterized in that the composite film structure includes 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 according to any one of claims 1-5.
10. The composite film structure of claim 9, wherein the material of the thermoplastic elastomer layer is at least one selected from the group consisting of thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, and silicone elastomer. Species; and / or,

    The thickness of the first substrate layer ranges from 5 to 40 μm; and / or,

    The thickness of the pressure-sensitive adhesive layer ranges from 2 to 40 μm.
11. The composite film structure according to claim 9 or 10, wherein the two substrate layers are both thermoplastic elastomer layers, and the composite film structure comprises: a first thermoplastic elastomer layer stacked in sequence, the The first pressure-sensitive adhesive layer and the second thermoplastic elastomer layer.
12. The composite film structure according to claim 11, wherein the materials of the first thermoplastic elastomer layer and the second thermoplastic elastomer layer are the same.
13. The composite film structure according to claim 9 or 10, wherein the composite film structure comprises two laminated sensitive adhesive layers, and the composite film structure further comprises a second substrate layer, the second substrate layer The first surface and the second surface are oppositely arranged, wherein one pressure-sensitive adhesive layer is sandwiched between the first surface of the second substrate layer and a first substrate layer, and the other pressure-sensitive adhesive layer is sandwiched between the first surface Between the second surface of the two substrate layers and another first substrate layer.
14. The composite film structure according to claim 13, wherein the material of the second substrate layer is a thermoplastic elastomer or an engineering plastic, and the thermoplastic elastomer is selected from the group consisting of a thermoplastic polyester elastomer, a thermoplastic polyurethane elastomer, At least one of a thermoplastic polyamide elastomer and a silicone elastomer, the engineering plastic is selected from the group consisting of polyetheretherketone, polyarylate, polyetherimide, polyimide, polyphenylene sulfide, and polynaphthalene At least one of polyethylene formate, polyethylene terephthalate, and polybutylene terephthalate; and / or,

    The thickness of the second substrate layer ranges from 1 to 30 μm.
15. A vibrating membrane, wherein the vibrating membrane has a composite membrane structure according to any one of claims 9 to 14.
16. A sound generating device, characterized in that the sound generating device comprises the diaphragm according to claim 15.

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