CN114143671A - Edge material for vibrating piece for electroacoustic transducer, micro-speaker vibrating piece, and film - Google Patents
Edge material for vibrating piece for electroacoustic transducer, micro-speaker vibrating piece, and film Download PDFInfo
- Publication number
- CN114143671A CN114143671A CN202111281828.5A CN202111281828A CN114143671A CN 114143671 A CN114143671 A CN 114143671A CN 202111281828 A CN202111281828 A CN 202111281828A CN 114143671 A CN114143671 A CN 114143671A
- Authority
- CN
- China
- Prior art keywords
- film
- electroacoustic transducer
- polyimide resin
- edge material
- vibrating piece
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 99
- 229920001721 polyimide Polymers 0.000 claims abstract description 138
- 239000009719 polyimide resin Substances 0.000 claims abstract description 132
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- 239000004697 Polyetherimide Substances 0.000 claims abstract description 43
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 150000004985 diamines Chemical class 0.000 claims abstract description 23
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims description 28
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
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- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
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- FEUISMYEFPANSS-UHFFFAOYSA-N 2-methylcyclohexan-1-amine Chemical compound CC1CCCCC1N FEUISMYEFPANSS-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- BXWSFKFIZQTMIG-UHFFFAOYSA-N 3-[2,5-di(propan-2-yl)phenyl]aniline Chemical compound NC=1C=C(C=CC=1)C1=C(C=CC(=C1)C(C)C)C(C)C BXWSFKFIZQTMIG-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
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- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
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- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
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- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
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- YNVQYOQLKGNUBZ-UHFFFAOYSA-N octadecane-1,1-diamine Chemical compound CCCCCCCCCCCCCCCCCC(N)N YNVQYOQLKGNUBZ-UHFFFAOYSA-N 0.000 description 1
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- XHDCCRKCHZGNFM-UHFFFAOYSA-N pentadecane-1,1-diamine Chemical compound CCCCCCCCCCCCCCC(N)N XHDCCRKCHZGNFM-UHFFFAOYSA-N 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- XGSHEASGZHYHBU-UHFFFAOYSA-N tetradecane-1,1-diamine Chemical compound CCCCCCCCCCCCCC(N)N XGSHEASGZHYHBU-UHFFFAOYSA-N 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- OLTHARGIAFTREU-UHFFFAOYSA-N triacontane Natural products CCCCCCCCCCCCCCCCCCCCC(C)CCCCCCCC OLTHARGIAFTREU-UHFFFAOYSA-N 0.000 description 1
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- 150000003673 urethanes Chemical class 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R7/00—Diaphragms for electromechanical transducers; Cones
- H04R7/16—Mounting or tensioning of diaphragms or cones
- H04R7/18—Mounting or tensioning of diaphragms or cones at the periphery
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R7/00—Diaphragms for electromechanical transducers; Cones
- H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R7/00—Diaphragms for electromechanical transducers; Cones
- H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
- H04R7/12—Non-planar diaphragms or cones
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R7/00—Diaphragms for electromechanical transducers; Cones
- H04R7/16—Mounting or tensioning of diaphragms or cones
- H04R7/18—Mounting or tensioning of diaphragms or cones at the periphery
- H04R7/20—Securing diaphragm or cone resiliently to support by flexible material, springs, cords, or strands
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/023—Diaphragms comprising ceramic-like materials, e.g. pure ceramic, glass, boride, nitride, carbide, mica and carbon materials
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/025—Diaphragms comprising polymeric materials
Landscapes
- Engineering & Computer Science (AREA)
- Multimedia (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Signal Processing (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Audible-Bandwidth Dynamoelectric Transducers Other Than Pickups (AREA)
Abstract
The present invention provides a vibrating piece edge material for an electroacoustic transducer, which contains a crystalline polyimide resin (A) composed of a tetracarboxylic acid component (a-1) and a diamine component (a-2) containing an aliphatic diamine as a main component. The present invention also provides a polyimide resin composition comprising a polyetherimide resin (B) and a crystalline polyimide resin (A), wherein the crystalline polyimide resin (A) comprises a tetracarboxylic acid component (a-1) and an aliphatic diamine component (a-2), and the content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (A) is (B)/(A) 1/99 to 99/1 on a mass basis.
Description
The present application is a divisional application of the application having an application date of 2017, 8/31/2017, an application number of 201780054392.1, and an invention name of "a polyimide resin composition and a molded article".
Technical Field
The present invention relates to a material for a diaphragm edge of an electroacoustic transducer used in various acoustic apparatuses, and more particularly, to a diaphragm for an electroacoustic transducer which is suitable as a speaker diaphragm and has excellent heat resistance, durability at high output, low-to-high sound reproduction, and secondary workability. The present invention also relates to a film suitable for use in a vibrating piece for an electroacoustic transducer or the like. The present invention also relates to a polyimide resin composition having excellent heat resistance, rigidity, and impact resistance, and a molded article, particularly a film, obtained by molding the polyimide resin composition.
Background
Due to the spread of small electronic devices (e.g., mobile phones, PDAs, notebook computers, DVDs, liquid crystal televisions, digital cameras, portable music devices, etc.), there is an increasing demand for small speakers (generally referred to as micro speakers), small receivers, and small electroacoustic transducers such as microphones and earphones to be used in these electronic devices.
In general, a loudspeaker diaphragm is required to have a low density for maintaining an acoustic radiation sound pressure level, a high rigidity for suppressing deformation and maintaining a high allowable input power, a specific tensile elastic modulus for extending a reproduction frequency band, a high internal loss for suppressing divided vibration of the diaphragm and flattening frequency characteristics, and the like. In addition, when the diaphragm is used in the vicinity of a voice coil as a drive source of a speaker, a vehicle-mounted speaker, or the like, the diaphragm is exposed to a high temperature for a long time, and therefore, heat resistance sufficient to withstand such use conditions is required.
On the other hand, in recent years, various small electronic devices have been developed to have higher functions and higher performance in the background of mobile society, ubiquitous society (ubiquitous society), or digitalization of music sources. For example, the input/output power withstand level required for a speaker vibrating reed of a cellular phone is about 0.3W in the case of a general-purpose model, while it is increased to about 0.5 to 0.6W or more (the upper limit of the current situation is about 1.2W) in the case of a high-output model. However, in the present situation, there are many models of about 0.6 to 0.8W, and the ratio of models exceeding 1.0W is low.
In order to solve such a problem, patent document 1 discloses a vibrating reed obtained by molding a polyimide resin film, and describes that the member is excellent in properties such as toughness, dimensional stability, corrosion resistance, heat and cold resistance, weather resistance, and strength.
Polyetherimide resins are amorphous super engineering plastics having a glass transition temperature of more than 200 ℃, and are widely used for automobile members, aircraft members, electric/electronic members, and the like, by sufficiently utilizing their excellent heat resistance, flame retardancy, and moldability. However, polyetherimide resins are very brittle materials and have a problem that they are difficult to use for applications requiring impact resistance. Further, since the film has high rigidity and low flexibility, it is difficult to use the film for applications requiring the original flexibility (flexibility) of the plastic film.
In order to solve such problems, patent document 3 discloses a resin composition obtained by mixing a polyester resin and an epoxy compound with a polyetherimide resin, and describes that the composition is excellent in impact resistance, hydrolysis resistance, and label bending resistance (bending resistance).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 51-006014
Patent document 2: japanese laid-open patent publication No. 60-055797
Patent document 3: japanese Kohyo publication No. 2002-532599
Disclosure of Invention
Technical problem to be solved by the invention
However, the polyimide resin used for the member of the vibrating reed disclosed in patent document 1 is thermosetting, and has a disadvantage of poor film productivity. Further, since the thermosetting polyimide resin has an excessively high elastic modulus, it is not suitable for reproducing bass sounds.
On the other hand, the polyetherimide resin used in patent document 2 is thermoplastic, and therefore has the characteristics of excellent film productivity, high glass transition temperature, and excellent heat resistance, which are disadvantages of the above thermosetting polyimide resin, but still has too high an elastic modulus, and is not suitable for low-sound reproduction.
Further, since the polyetherimide resin has a high glass transition temperature and a high temperature at the time of molding, there is a concern that the polyester resin may be decomposed or deteriorated at the time of mixing as in patent document 3. Further, there are many combinations of non-compatible polyether imide resins and polyester resins, and the blend does not necessarily improve the impact resistance. For example, in the examples of patent document 3, there are examples in which impact resistance evaluated by tensile elongation at break and bending resistance is improved, and examples in which elastic modulus (rigidity) is reduced to fall within an appropriate range, but there are no examples in which all performances are satisfied in a good balance, and it is not considered that the problems of the polyetherimide resin have been satisfactorily solved.
On the other hand, a crystalline polyimide resin formed from a tetracarboxylic acid and an aliphatic diamine has an excellent balance between heat resistance and impact resistance. However, although excellent in impact resistance, it has a problem that handling properties when used as a film are poor depending on the application because of low rigidity. Further, since an expensive monomer such as an alicyclic diamine is used, there is also a problem that the unit price of the raw material is increased and the use is limited.
The present invention has been made in view of the above circumstances, and a first object thereof is to provide an edge material which is excellent in heat resistance, durability at high output, low-to-high sound reproduction, and secondary workability and which can be used for a vibrating piece for an electroacoustic transducer, a vibrating piece for an electroacoustic transducer using the edge material, and a film which can be suitably used for the edge material and the like.
Further, the 2 nd problem is to provide a polyimide resin composition which can solve the above problems of the polyetherimide resin and the crystalline polyimide resin.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above-mentioned 1 st object can be solved by using a crystalline polyimide resin having a specific structure, and have completed the following invention.
That is, the invention according to the 1 st aspect is a vibrating piece edge material for an electroacoustic transducer, comprising a crystalline polyimide resin (a) composed of a tetracarboxylic acid component (a-1) and a diamine component (a-2') having an aliphatic diamine (a-2) as a main component.
In the aspect 1 of the present invention, it is preferable that the diamine component (a-2') contains at least a linear aliphatic diamine having 4 to 12 carbon atoms.
In the 1 st aspect of the present invention, it is preferable that the diamine component (a-2') contains at least an alicyclic diamine.
Further, in the 1 st aspect of the present invention, it is preferable that the alicyclic diamine is 1, 3-bis (aminomethyl) cyclohexane.
The edge material for a vibrating piece of an electroacoustic transducer according to claim 1 of the present invention preferably contains a crystalline polyimide resin (a) as a main component.
The edge material of the vibrating plate for an electroacoustic transducer according to claim 1 of the present invention is preferably formed of a film having a tensile elastic modulus of 1000MPa or more and less than 2500MPa in accordance with JIS K7127.
The edge material of the vibrating plate for an electroacoustic transducer according to claim 1 is preferably formed of a film having a flexural strength of 1000 times or more in accordance with JIS P8115.
The edge material for a vibrating piece of an electroacoustic transducer according to claim 1 of the present invention is preferably formed of a film having a tensile elongation at break of 200% or more in accordance with JIS K7127.
The crystal melting enthalpy (Δ Hm) of the edge material of the vibrating plate for an electroacoustic transducer according to aspect 1 of the present invention is preferably 25J/g or more.
The edge material for a vibrating plate for an electroacoustic transducer according to claim 1 is preferably formed of a film having a thickness of 1 μm or more and 200 μm or less.
In the vibrating piece edge material for an electroacoustic transducer according to the 1 st aspect of the present invention, the vibrating piece edge material for an electroacoustic transducer may be disposed as a front-back surface layer, and at least 1 adhesive layer selected from an acrylic adhesive, a rubber adhesive, a silicone adhesive, and a urethane adhesive may be disposed as an intermediate layer.
The 2 nd aspect of the present invention is a film containing a crystalline polyimide resin (a) composed of a tetracarboxylic acid component (a-1) and a diamine component (a-2') containing an aliphatic diamine (a-2) as a main component, wherein the film has a tensile elastic modulus of 1000MPa to 3000MPa in JIS K7127.
The film of the invention according to claim 2 is preferably formed from a polyimide resin composition (X) containing the crystalline polyimide resin (a) and a polyetherimide resin (B). The content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (a) is preferably 40/60 or less on a mass basis.
The film of claim 2 of the present invention preferably has a breaking strength of 1000 or more times in accordance with JIS P8115.
The film of claim 2 preferably has a tensile elongation at break of 200% or more in accordance with JIS K7127.
The thickness of the film of claim 2 is preferably 1 μm or more and 200 μm or less.
The invention according to claim 3 is a diaphragm edge material for an electroacoustic transducer, which is formed of the film according to claim 2. In addition, the vibrating piece edge material for an electroacoustic transducer according to claim 3 of the present invention may be disposed as a front-back surface layer, and at least 1 pressure-sensitive adhesive layer selected from an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and a urethane pressure-sensitive adhesive may be disposed as an intermediate layer.
The invention according to claim 4 is a vibrating piece for an electroacoustic transducer using the edge material for the vibrating piece for an electroacoustic transducer according to the above-mentioned invention according to claim 1 or 3.
The 5 th aspect of the present invention is a micro-speaker diaphragm using the diaphragm edge material for an electroacoustic transducer according to the 1 st or 3 rd aspect of the present invention.
Further, the present inventors have conducted extensive studies and as a result, have found that a mixture of a crystalline polyimide resin having a specific structure and a polyetherimide resin can solve the above problem 2 because of high compatibility between them, and have completed the following invention.
That is, the 6 th aspect of the present invention is a polyimide resin composition comprising a polyetherimide resin (B) and a crystalline polyimide resin (a) containing a tetracarboxylic acid component (a-1) and an aliphatic diamine component (a-2), wherein the content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (a) is (B)/(a) 1/99 to 99/1 on a mass basis.
In the 6 th aspect of the present invention, it is preferable that the aliphatic diamine component (a-2) contains at least a linear aliphatic diamine having 4 to 12 carbon atoms.
In the 6 th aspect of the present invention, it is preferable that the aliphatic diamine component (a-2) contains at least an alicyclic diamine.
In the 6 th aspect of the present invention, it is preferable that the alicyclic diamine is 1, 3-bis (aminomethyl) cyclohexane.
In the aspect 6 of the present invention, it is preferable that a peak of the loss tangent (tan. delta.) is present when measured at a strain of 0.1%, a frequency of 10Hz, and a temperature rise rate of 3 ℃/min by the temperature dispersion measurement of dynamic viscoelasticity described in JIS K7244-4.
In the 6 th aspect of the present invention, the temperature (Tg) indicated by the peak of the loss tangent (tan δ) is preferably 150 ℃ or higher and 300 ℃ or lower.
In the 6 th aspect of the present invention, the tensile modulus of elasticity measured in accordance with JIS K7127 is preferably 2200MPa to 3100 MPa.
In the 6 th aspect of the present invention, the tensile elongation at break measured in accordance with JIS K7127 is preferably 130% or more.
The 7 th aspect of the present invention is a molded article obtained by molding the polyimide resin composition according to the 6 th aspect of the present invention.
In the 7 th aspect of the present invention, the molded body is preferably a film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an edge material for a vibrating piece for an electroacoustic transducer, which has excellent heat resistance, durability at high output, low-to-high sound reproduction, and secondary workability and can be preferably used for various acoustic apparatuses, a vibrating piece for an electroacoustic transducer using the edge material, and a film which can be preferably used for the edge material and the like.
Further, according to the 6 th to 7 th aspects of the present invention, there can be provided a polyimide resin composition excellent in heat resistance, rigidity and impact resistance, and a molded article and a film using the composition.
Drawings
Fig. 1 is a sectional view showing a structure of a micro-speaker vibrating reed 1 according to an embodiment of the present invention.
Fig. 2 is a plan view of a micro-speaker vibrating reed 1' according to another embodiment of the present invention.
Description of the symbols
1. 1' loudspeaker vibrating reed
1a, 1 a' dome (main body)
1b concave embedding part
1c edge part (edge)
1d external attachment part
1e, 1f tangential edge
1g, 1h tangential edge portion
2 Voice coil
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the embodiments described below. Unless otherwise specified, the numerical values a and B "a to B" mean "a to B inclusive". In the above description, when a unit is added to the numerical value B, the unit is also applied to the numerical value a.
The edge material of a diaphragm for an electroacoustic transducer of the present invention contains a crystalline polyimide resin (A). In the present invention, the edge material of the vibrating piece for an electroacoustic transducer preferably contains the crystalline polyimide resin (a) as a main component.
Here, "main component" means that the proportion of the crystalline polyimide resin (a) contained in the edge material of the vibrating piece for the electroacoustic transducer exceeds 50 mass%. It is important that the content of the crystalline polyimide resin (a) in the edge material for the vibrating piece for an electroacoustic transducer exceeds 50 mass%, and it is preferably 60 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, particularly preferably 90 mass% or more, and it is particularly preferable that the entire (100 mass%) component constituting the edge material for the vibrating piece for an electroacoustic transducer is the crystalline polyimide resin (a).
The edge material for a vibrating piece for an electroacoustic transducer according to the present invention is preferably formed of a polyimide resin composition (X) containing a crystalline polyimide resin (a) and a polyetherimide resin (B). The polyimide resin composition (X) used in the present invention is described in detail below.
[ crystalline polyimide resin (A) ]
The crystalline polyimide resin (A) used in the present invention is obtained by polymerizing a tetracarboxylic acid component (a-1) and a diamine component (a-2').
Examples of the tetracarboxylic acid component (a-1) constituting the crystalline polyimide resin (a) include: alicyclic tetracarboxylic acids such as cyclobutane-1, 2,3, 4-tetracarboxylic acid, cyclopentane-1, 2,3, 4-tetracarboxylic acid and cyclohexane-1, 2,4, 5-tetracarboxylic acid, 3 ', 4, 4' -diphenylsulfone tetracarboxylic acid, 3 ', 4, 4' -benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid and pyromellitic acid. In addition, alkyl ester compounds thereof may be used.
Among these, pyromellitic acid is preferably used as the component of the tetracarboxylic acid component (a-1) in an amount exceeding 50 mol%. The vibrating plate edge material for an electroacoustic transducer of the present invention, and the film and the polyimide resin composition (X) described later are excellent in heat resistance, secondary processability and low water absorption properties by using pyromellitic acid as a main component as the tetracarboxylic acid component (a-1). From the above-mentioned viewpoints, in the tetracarboxylic acid component (a-1), pyromellitic acid is more preferably 60 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, and it is particularly preferable that the total (100 mol%) of the tetracarboxylic acid component (a-1) is pyromellitic acid.
It is important that the diamine component (a-2') constituting the crystalline polyimide resin (A) mainly contains the aliphatic diamine (a-2). That is, it is important that more than 50 mol% of the diamine component (a-2 ') is the aliphatic diamine (a-2), and more preferably 60 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and particularly preferably the whole (100 mol%) of the diamine component (a-2') is the aliphatic diamine (a-2). Accordingly, the vibrating plate for an electroacoustic transducer of the present invention, and the film and the polyimide resin composition described later can be provided with heat resistance, low water absorption, moldability, and secondary processability. The aliphatic diamine of the present invention also includes an alicyclic diamine.
The aliphatic diamine (a-2) contained in the diamine component (a-2') is not particularly limited, and may be a diamine component having amino groups at both ends of a hydrocarbon group, and when importance is attached to heat resistance, for example, an alicyclic diamine having amino groups at both ends of a cyclic hydrocarbon is preferably contained. Specific examples of the alicyclic diamine contained in the aliphatic diamine (a-2) include: 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 4 '-diaminodicyclohexylmethane, 4' -methylenebis (2-methylcyclohexylamine), isophoronediamine, norbornanediamine, bis (aminomethyl) tricyclodecane and the like. Among them, 1, 3-bis (aminomethyl) cyclohexane is preferably used from the viewpoint of compatibility between heat resistance, moldability and secondary processability.
On the other hand, in the vibrating plate for an electroacoustic transducer, the film and the polyimide-based resin composition described later of the present invention, when importance is attached to moldability, secondary processability, or impact resistance, moldability and secondary processability, the aliphatic diamine (a-2) contained in the diamine component (a-2') preferably contains a linear aliphatic diamine having amino groups at both ends of a linear hydrocarbon. The linear aliphatic diamine is not particularly limited as long as it is a diamine component having amino groups at both ends of an alkyl group, and specific examples thereof include: ethylenediamine (carbon number 2), propylenediamine (carbon number 3), butylenediamine (carbon number 4), pentylenediamine (carbon number 5), hexylenediamine (carbon number 6), heptylenediamine (carbon number 7), octylenediamine (carbon number 8), nonylenediamine (carbon number 9), decylenediamine (carbon number 10), undecylenediamine (carbon number 11), dodecylenediamine (carbon number 12), tridecanediamine (carbon number 13), tetradecanediamine (carbon number 14), pentadecanediamine (carbon number 15), hexadecanediamine (carbon number 16), heptadecanediamine (carbon number 17), octadecanediamine (carbon number 18), nonadecanediamine (carbon number 19), eicosane (carbon number 20), triacontane (carbon number 30), forty alkane (carbon number 40), and fifty alkane (carbon number 50). Among them, from the viewpoint of excellent moldability, secondary processability and low hygroscopicity, linear aliphatic diamines having 4 to 12 carbon atoms are exemplified. The aliphatic diamine (a-2) may be a structural isomer of a branched structure having 1 to 10 carbon atoms of the above linear aliphatic diamine.
The diamine component (a-2') may contain other diamine components in addition to the aliphatic diamine (a-2). Specifically, there may be mentioned: 1, 4-phenylenediamine, 1, 3-phenylenediamine, 2, 4-toluenediamine, 4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, α' -bis (4-aminophenyl) 1,4 '-diisopropylbenzene, α' -bis (3-aminophenyl) -1, 4-diisopropylbenzene, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4 '-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2, 4' -diaminodiphenylsulfone, and the like, Aromatic diamine components such as bis [4- (3-aminophenoxy) phenyl ] sulfone, 2, 6-diaminonaphthalene, 1, 5-diaminonaphthalene, p-xylylenediamine and m-xylylenediamine, and siloxane diamines.
The diamine component (a-2') (i.e., the aliphatic diamine (a-2)) may contain either one or both of an alicyclic diamine and a linear aliphatic diamine, and preferably contains both of an alicyclic diamine and a linear aliphatic diamine in view of excellent balance between heat resistance and moldability. When both of the alicyclic diamine and the linear aliphatic diamine are contained, the content of each is preferably 99: 1 to 1: 99, more preferably 90: 10 to 10: 90, still more preferably 80: 20 to 20: 80, particularly preferably 70: 30 to 30: 70, and particularly preferably 60: 40 to 40: 60 on a molar basis. When the ratio of the alicyclic diamine and the linear aliphatic diamine contained in the diamine component (a-2') is in the above range, the balance between the heat resistance and moldability, and the balance between the heat resistance, impact resistance and moldability are excellent in the vibrating plate edge material for an electroacoustic transducer of the present invention, and the film and polyimide resin composition described later.
The crystalline polyimide resin (a) preferably has a crystal melting temperature of 260 ℃ to 350 ℃, more preferably 270 ℃ to 345 ℃, and still more preferably 280 ℃ to 340 ℃. When the crystalline polyimide resin (a) has a crystal melting temperature of 260 ℃ or higher, the heat resistance is sufficient. On the other hand, when the crystal melting temperature is 350 ℃ or lower, for example, in molding, molding or secondary processing can be performed at a relatively low temperature, which is preferable.
When the crystalline polyimide resin (a) is contained as a main component, the crystalline melting temperature of the crystalline polyimide resin (a) is preferably 260 ℃ to 340 ℃, more preferably 270 ℃ to 335 ℃, and still more preferably 280 ℃ to 330 ℃. When the crystalline polyimide resin (a) has a crystal melting temperature of 260 ℃ or higher, the heat resistance of the edge material of the vibrating piece for an electroacoustic transducer is sufficient. For example, heat resistance that can withstand a reflow process with a peak temperature of 260 ℃. On the other hand, when the crystal melting temperature is 340 ℃ or lower, for example, in the melt molding of the film used for the edge material of the vibrating piece for the electroacoustic transducer of the present invention, secondary processing at a relatively low temperature can be performed using a general-purpose apparatus, and therefore, this is preferable.
[ Material for edge of vibrating plate for electroacoustic transducer ]
The edge material of the vibrating piece for an electroacoustic transducer according to the present invention is applicable to all electroacoustic transducers as long as it is used for an electroacoustic transducer such as a speaker, a receiver, a microphone, and an earphone, and can be preferably used as a vibrating piece of a micro speaker for a cellular phone and the like.
The glass transition temperature (Tg) of the edge material of the vibrating plate for an electroacoustic transducer (i.e., a film described later) is preferably 150 ℃ or higher, more preferably 160 ℃ or higher, and still more preferably 170 ℃ or higher. When the glass transition temperature of the edge material of the vibrating plate for the electroacoustic transducer is more than 150 ℃, the sufficient heat resistance can be maintained.
The crystal melting enthalpy (Δ Hm) of the edge material of the vibrating piece for an electroacoustic transducer (i.e., a film described later) is preferably 25J/g or more, more preferably 30J/g or more, and still more preferably 35J/g or more. When the crystal melting enthalpy (Δ Hm) is 25J/g or more, a film or a molded article having high crystallinity can be obtained, and the vibrating piece for an electroacoustic transducer is preferably excellent in heat resistance and also has an elastic modulus which ensures the reproducibility in a high audio frequency band as much as possible.
The crystal melting temperature of the edge material of the vibrating piece for an electroacoustic transducer (i.e., a film described later) is preferably 260 ℃ to 340 ℃, more preferably 270 ℃ to 335 ℃, and still more preferably 280 ℃ to 330 ℃. When the crystal melting temperature of the edge material of the vibrating piece for the electroacoustic transducer is 260 ℃ or more, sufficient heat resistance can be provided. On the other hand, when the crystal melting temperature of the edge material of the vibrating piece for the electroacoustic transducer is 340 ℃ or lower, the formability in melt molding is excellent.
The edge material of the vibrating plate for an electroacoustic transducer according to the present invention can be obtained by, for example, performing secondary processing on a film of the present invention having the following characteristics by a method described later.
The film of the present invention is used for the edge material of the vibrating plate for an electroacoustic transducer, and has a tensile elastic modulus of 1000MPa or more and 3000MPa or less in accordance with JIS K7127.
The film has sufficient rigidity when the tensile elastic modulus is 1000MPa or more. Further, the material has rigidity (stiffness) sufficient for securing not only the playability in a high audio frequency band but also the ability to be used as a material for a diaphragm edge for an electroacoustic transducer. From the above viewpoint, the tensile elastic modulus is more preferably 1500MPa or more, and particularly preferably 1800MPa or more.
Further, the tensile elastic modulus is more preferably 2200MPa or more from the viewpoint of further improving the rigidity (stiffness) and ensuring sufficient workability even when the thickness is reduced.
On the other hand, if the tensile elastic modulus of the film is more than 3000MPa, the flexibility of the film is reduced, and when the film is used as a material for the edge of the diaphragm for an electroacoustic transducer, the low-sound reproduction performance and the like are deteriorated.
The tensile modulus of elasticity of the film is preferably less than 2500 MPa. If the tensile elastic modulus is less than 2500Mpa, the lowest resonance frequency (f0) is sufficiently low even when a membrane having a thickness of 20 to 40 μm, which is excellent in operability and durability at high output, is used in a diaphragm for an electroacoustic transducer, for example, a diaphragm for a micro-speaker, and the like, and the reproducibility in a low-frequency band can be secured, and the sound quality is good, so that it is preferable. From the above viewpoint, the tensile elastic modulus is more preferably 2400MPa or less, and particularly preferably 2300MPa or less.
In the film, the content of the crystalline polyimide resin (a) is increased, and the tensile elastic modulus is easily decreased. That is, in the case where the film of the present invention contains the crystalline polyimide resin (a) as a main component as described above, the tensile elastic modulus is easily adjusted to less than 2500MPa, preferably 2400MPa or less, and more preferably 2300MPa or less.
The film of the present invention is formed of, for example, a polyimide resin composition (X) described later and contains a polyether imide resin (B), whereby the tensile elastic modulus is suitably increased, and for example, the tensile elastic modulus can be set to 2200MPa or more.
The film preferably has a breaking strength of 1000 times or more, more preferably 1500 times or more, in accordance with JIS P8115. When the flexural strength is in the above range, the durability at high output is excellent, and the vibrating reed is less likely to crack or break.
The tensile elongation at break of the film is preferably 200% or more, more preferably 250% or more, in accordance with JIS K7127. When the tensile elongation at break is within the above range, defects such as breakage do not occur, and secondary working can be stably performed even in various shapes, for example, shapes requiring deep drawability.
In the present invention, by containing the crystalline polyimide resin (a) as a main component as described above, the breaking strength and the tensile elongation at break of the film can be easily adjusted to the above ranges.
In addition to the above components, other resins, fillers, various additives such as a heat stabilizer, an ultraviolet absorber, a light stabilizer, a nucleating agent, a colorant, a lubricant, a flame retardant, and the like may be appropriately blended in the film within a range not departing from the gist of the present invention.
The film forming method of the film may be a known method, for example, an extrusion casting method using a T die, a calendering method, a casting method, or the like, and is not particularly limited, and an extrusion casting method using a T die is preferably used in view of productivity of the film or the like.
The molding temperature in the extrusion casting method using a T-die can be appropriately adjusted depending on the flow characteristics, film forming properties, and the like of the composition to be used, and is about 280 ℃ to 350 ℃. In the melt kneading, a generally used single screw extruder, twin screw extruder, kneader, mixer, or the like can be used, and there is no particular limitation.
In the case of the extrusion casting method using a T-die, the obtained film may be quenched to be taken out in an amorphous state, may be crystallized by heating with a casting roll, or may be taken out in an amorphous state, followed by heating treatment to be taken out in a crystallized state. In general, a film in an amorphous state is excellent in durability and secondary processability, and a film after crystallization is excellent in heat resistance and rigidity (stiffness), and therefore it is important to use a film in an optimum crystallized state depending on the application.
When a crystallized film is used, it is preferably crystallized by heating with a casting roll from the viewpoint of productivity and cost. In general, when a thin film is crystallized and taken by a casting roll, the line speed needs to be increased, and since the time for which the film is in contact with the casting roll is short, crystallization is not sufficiently completed, and a film having desired crystallinity cannot be obtained in some cases. The crystalline polyimide resin (a) used in the present invention has a very high crystallization rate, and therefore, a film having sufficient crystallinity can be obtained by heat treatment with a casting roll.
As a standard for setting the crystallization rate to a preferred value, the crystalline polyimide resin (a) is heated to a temperature of not less than the crystal melting temperature at a heating rate of 10 ℃/min using a Differential Scanning Calorimeter (DSC) to completely melt the crystal, and then the temperature of the crystallization peak at the time of cooling at 10 ℃/min is set as the temperature-lowered crystallization temperature, and in this case, the difference between the crystal melting temperature and the temperature-lowered crystallization temperature is preferably 70 ℃ or less, preferably 60 ℃ or less, and more preferably 50 ℃ or less. When the crystallization peak in the temperature decreasing process is in the above-mentioned temperature range, the crystallization rate is sufficiently high, and a film having sufficient crystallinity can be obtained by heat treatment with a casting roll.
The thickness of the film is not particularly limited, and is usually 1 to 200 μm as a material for the edge of a vibrating plate for an electroacoustic transducer. In addition, it is also important to form a film so that anisotropy of physical properties of the film in the traveling direction (MD) and The Direction (TD) perpendicular thereto is reduced as much as possible.
The film thus obtained can be further subjected to secondary processing as a diaphragm edge material for an electroacoustic transducer. The secondary processing method is not particularly limited, and for example, in the case of a speaker diaphragm, the film is heated in consideration of its glass transition temperature and softening temperature, and is secondarily processed into a dome shape, a cone shape, or the like by press molding, vacuum molding, or the like.
The edge material of the vibrating plate for the electroacoustic transducer is used for the vibrating plate for the electroacoustic transducer. The edge material of the vibrating plate for the electroacoustic transducer is preferably used for the vibrating plate of the micro-speaker. The shape of the vibrating piece is not particularly limited, and is arbitrary, and a circle, an ellipse, an oval, or the like can be selected. In general, a vibrating reed for an electroacoustic transducer has a body that vibrates in response to an electric signal or the like, and a rim surrounding the vicinity of the body. The body of the membrane is usually supported by the rim. The shape of the body may be dome-shaped or tapered, or may be other shapes used for the vibrating piece.
The edge material of the vibrating plate for the electroacoustic transducer of the present invention is not particularly limited. Any member may be used as long as it constitutes at least the edge of the vibrating piece. Therefore, both the body and the edge of the vibrating piece may be integrally molded by the vibrating piece edge material for the electroacoustic transducer, or only the edge of the vibrating piece may be molded by the vibrating piece edge material for the electroacoustic transducer, and a portion (for example, the body) other than the edge of the vibrating piece may be molded by another member. In the present invention, even when the edge of the vibrating piece and the main body are integrally molded by the vibrating piece edge material or the film for an electroacoustic transducer according to the present invention, the vibrating piece for an electroacoustic transducer having excellent workability and excellent performance can be obtained.
Fig. 1 is a diagram showing a structure of a micro-speaker vibration reed 1 according to an embodiment of the present invention, and is a cross-sectional view obtained by cutting the micro-speaker vibration reed 1 having a circular shape in a plan view along a plane passing through a center line of the circle. As shown in fig. 1, the micro-speaker vibration reed 1 includes a concave fitting portion 1b attached to the voice coil 2 around a dome portion (main body) 1a, an edge portion (edge) 1c, and an external attachment portion 1d attached to a frame or the like on the outer periphery thereof.
The film of the present invention is preferably used for a vibrating piece edge material for an electroacoustic transducer, particularly a vibrating piece edge material for a small electroacoustic transducer, because the tensile elastic modulus is not too high, because the film can ensure the playability in a low-frequency band and can improve the sound quality. Here, as the size of the vibrating piece, a size having a maximum diameter of 25mm or less, preferably 20mm or less, and a lower limit of usually about 5mm is preferably used. The maximum diameter is a diameter when the shape of the vibrating piece is circular, and a major diameter when the shape of the vibrating piece is elliptical or oval.
A groove or the like having a V-shaped cross-sectional shape called a so-called tangential edge may be appropriately given to the vibrating piece surface. Fig. 2 shows a plan view of a micro-speaker vibrating reed 1' according to another embodiment of the present invention. The micro-speaker vibration reed 1 'has a tangential edge 1g provided with a plurality of tangential edges 1e and a tangential edge 1h provided with a plurality of tangential edges 1f at an outer edge of a circular dome (main body) 1 a'. In the form having the tangential edges, the average thickness of the film is preferably 3 to 40 μm, and more preferably 5 to 38 μm, and in this case, since the thickness is sufficiently secured, the workability is also good, and the secondary processability per unit time such as press molding and the secondary processing accuracy (shape reproducibility) are easily improved, which is preferable.
The vibrating reed 1 and the vibrating reed 1' may be formed of the above-described film, or may be formed of a composite material of the film and another member, for example, a laminate described later.
The vibrating piece edge material for an electroacoustic transducer according to the present invention may be a laminate having the vibrating piece edge material for an electroacoustic transducer on the front and back surfaces and an adhesive layer having a high damping effect (internal loss) on the intermediate layer. By forming such a laminated structure, not only heat resistance, rigidity, durability and moldability of the edge material of the vibrating plate for an electroacoustic transducer having the front and back surface layers can be imparted, but also excellent attenuation characteristics of the intermediate layer can be imparted. The method for producing the edge material of the vibrating plate for the electroacoustic transducer as the laminate is not particularly limited. Examples thereof include: a method of producing a diaphragm edge material for an electroacoustic transducer, which is a surface layer and a back layer, by performing secondary processing on a pair of films having the above characteristics, and bonding the diaphragm edge material and the back layer with an adhesive for an intermediate layer; or a method in which a pair of films having the above characteristics are bonded to each other with a pressure-sensitive adhesive for an intermediate layer to prepare a laminated film, and the laminated film is subjected to secondary processing by the above method. In this case, as the kind of the adhesive used for the intermediate layer, there can be mentioned: acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and the like, and acrylic or silicone pressure-sensitive adhesives are preferably used from the viewpoint of adhesiveness. In this case, the thicknesses of the surface layer and the back layer are preferably 1 μm or more and 30 μm or less, more preferably 2 μm or more and 25 μm or less, and still more preferably 3 μm or more and 20 μm or less, respectively. On the other hand, the thickness of the intermediate layer is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 40 μm or less, and still more preferably 10 μm or more and 30 μm or less. If the material type of the intermediate layer and the thickness of each layer are configured as described above, the vibrating piece having various mechanical properties and excellent damping properties can be obtained while being molded.
In addition, in order to improve the suitability for secondary processing of the vibrating piece, dust resistance, adjustment of acoustic characteristics, improvement of design properties, and the like, the surface of the vibrating piece after molding or the film used as the edge material for the vibrating piece for an electroacoustic transducer according to the present invention may be further appropriately subjected to treatment such as coating, lamination of an antistatic agent, various elastomers (for example, urethanes, silicones, hydrocarbons, fluorine-containing compounds, and the like), evaporation of metal, sputtering, or coloring (black, white, and the like). Further, lamination with a metal such as aluminum, another film, or lamination with a nonwoven fabric may be appropriately performed.
The edge material for a vibrating piece for an electroacoustic transducer of the present invention is excellent in durability at a high output when used for a vibrating piece of a speaker. For example, a mobile phone can cope with a withstand power level of about 0.6 to 1.0W, which can be applied to a high output model, with respect to about 0.3W of a general model. Further, the film containing the crystalline polyimide resin (a) as a main component is excellent not only in basic acoustic characteristics as a speaker vibrating piece, particularly as a vibrating piece of a micro-speaker, but also in heat resistance and moldability in secondary processing of the vibrating piece.
[ film ]
As described above, the tensile modulus of elasticity of the film of the present invention is 1000MPa or more and 3000MPa or less in JIS K7127.
As described above, the film of the present invention can be used as a material for a diaphragm edge for an electroacoustic transducer, but can be used in other materials than the material for the diaphragm edge for the electroacoustic transducer.
The membrane of the present invention is made of the same material as the edge material of the vibrating plate for the electroacoustic transducer. That is, the film of the present invention preferably contains a crystalline polyimide resin (a) composed of a tetracarboxylic acid component (a-1) and a diamine component (a-2') and contains the crystalline polyimide resin (a) as a main component.
Here, "main component" means that the proportion of the crystalline polyimide resin (a) contained in the film exceeds 50 mass%. The proportion of the crystalline polyimide resin (a) contained in the film is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and it is particularly preferable that all (100% by mass) components constituting the film are the crystalline polyimide resin (a).
As described above, the details of the film are as described in the film used for the edge material of the vibrating plate for the electroacoustic transducer, and therefore, the description thereof is omitted. The details of the crystalline polyimide resin (a) used in the film are the same as those described above, and therefore, the description thereof is omitted.
The film of the present invention is also preferably formed from a polyimide resin composition (X) containing a crystalline polyimide resin (a) and a polyetherimide resin (B). The polyimide resin composition (X) used in the present invention is described in detail below.
[ polyimide resin composition (X) ]
The present invention also provides a polyimide resin composition (X) containing a crystalline polyimide resin (a) and a polyetherimide resin (B). As described above, the film and the edge material of the vibrating plate for an electroacoustic transducer according to the present invention are also preferably formed of the polyimide resin composition (X).
The crystalline polyimide resin (a) used in the polyimide resin composition (X) contains the tetracarboxylic acid component (a-1) and the aliphatic diamine component (a-2), and the details thereof are as described above. Among them, the crystalline polyimide resin (a) used in the polyimide resin composition (X) preferably has a crystal melting temperature of 260 ℃ to 350 ℃, more preferably 270 ℃ to 345 ℃, and still more preferably 280 ℃ to 340 ℃. When the crystalline melting temperature of the crystalline polyimide resin (a) is 260 ℃ or higher, the polyimide resin composition (X) has sufficient heat resistance. On the other hand, when the crystal melting temperature is 350 ℃ or lower, for example, in the case of molding using the polyimide resin composition (X) of the present invention, molding or secondary processing can be performed at a relatively low temperature, which is preferable.
The glass transition temperature of the crystalline polyimide resin (a) used in the polyimide resin composition (X) is preferably 150 ℃ to 300 ℃, more preferably 160 ℃ to 290 ℃, and still more preferably 170 ℃ to 280 ℃. When the glass transition temperature of the crystalline polyimide resin (a) is 150 ℃ or higher, the polyimide resin composition (X) has sufficient heat resistance. On the other hand, when the glass transition temperature is 300 ℃ or lower, the molding can be carried out at a relatively low temperature when the polyimide resin composition (X) of the present invention is used for molding, and therefore, it is preferable. Further, the case where the obtained molded article is subjected to secondary processing is also preferable for the same reason.
The crystalline polyimide resin (a) used in the polyimide resin composition (X) is not described herein, except for the crystal melting temperature and the glass transition temperature, since the description is as described above.
< polyetherimide resin (B) >)
The polyetherimide resin (B) used in the polyimide resin composition (X) is not particularly limited, and known compounds can be used, and the production method and properties thereof are described in, for example, U.S. Pat. No. 3,803,085 and U.S. Pat. No. 3,905,942.
Specifically, the polyetherimide resin (B) used in the present invention preferably has a structure represented by the following [ chemical formula 1] from the viewpoint of excellent balance between heat resistance and moldability.
[ chemical formula 1]
In the formula [ chemical formula 1], n (the number of repetitions) is an integer generally in the range of 10 to 1,000, preferably 10 to 500. When n is within the above range, the balance between moldability and heat resistance is excellent.
The above formula [ chemical formula 1] can be classified into structures represented by the following [ chemical formula 2] and [ chemical formula 3] according to the bonding method, specifically, the difference between the meta-bonding and the para-bonding.
[ chemical formula 2]
[ chemical formula 3]
In the above [ chemical formula 2] and [ chemical formula 3], n (the number of repetitions) is an integer generally in the range of 10 to 1,000, preferably 10 to 500. When n is in the above range, the balance between moldability and heat resistance is excellent.
As a specific example of the polyetherimide resin (B) having such a structure, for example, it is sold under the trade name "ULTEM" series by SABIC INDOVATIVE PLASTICS.
The glass transition temperature of the polyetherimide resin (B) is preferably 160 ℃ or more and 300 ℃ or less, more preferably 170 ℃ or more and 290 ℃ or less, still more preferably 180 ℃ or more and 280 ℃ or less, particularly preferably 190 ℃ or more and 270 ℃ or less, and particularly preferably 200 ℃ or more and 260 ℃ or less. The glass transition temperature of the polyetherimide resin (B) is set to 160 ℃ or higher, whereby the polyimide resin composition (X) has sufficient heat resistance. On the other hand, when the glass transition temperature of the polyetherimide resin (B) is 300 ℃ or lower, molding or secondary processing can be performed at a relatively low temperature, and therefore, when the polyetherimide resin (B) is mixed with the crystalline polyimide resin (a), decomposition or deterioration of the crystalline polyimide resin (a) does not occur.
The polyimide resin composition (X) of the present invention is characterized in that the content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (A) is (B)/(A) 1/99 to 99/1 on a mass basis.
The content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (a) can be appropriately adjusted according to the intended use. In the polyimide resin composition (X) of the present invention, for example, when importance is attached to heat resistance and rigidity, the content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (a) is preferably 5/95 or more, more preferably 10/90 or more, and further preferably 15/85 or more on a mass basis. On the other hand, when importance is placed on impact resistance, the content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (a) is preferably 80/20 or less, more preferably 70/30 or less, and still more preferably 60/40 or less on a mass basis.
In the case where the polyimide resin composition (X) of the present invention is used for the above-mentioned edge material or film of the vibrating plate for an electroacoustic transducer, the content of the crystalline polyimide (a) is preferably higher than the content of the polyetherimide resin (B) on a mass basis from the viewpoint of improving durability. Specifically, the ratio (B)/(a) is particularly preferably 40/60 or less, and particularly preferably 30/70 or less.
When the polyimide resin composition (X) is used for a diaphragm edge material or a diaphragm for an electroacoustic transducer, it is preferable that the polyimide resin composition (X) contains the crystalline polyimide (a) as a main component as described above.
The polyimide resin composition (X) of the present invention is characterized by having a peak of loss tangent (tan. delta.) when measured at a strain of 0.1%, a frequency of 10Hz, and a temperature rise rate of 3 ℃/min, according to the temperature dispersion measurement of dynamic viscoelasticity described in JIS K7244-4.
In the present invention, the temperature indicated by the peak of the loss tangent (tan δ) is defined as the glass transition temperature (Tg). In other words, the fact that there is one peak of the loss tangent (tan δ) means that the glass transition temperature (Tg) is single. In addition, it is also considered that, when the glass transition temperature is measured at a heating rate of 10 ℃/min using a differential scanning calorimeter in accordance with JIS K7121 standard, only 1 inflection point indicating the glass transition temperature appears.
In general, if the glass transition temperature of the polymer blend composition is single, the blended resin is in a compatible state at a molecular level, and a compatible system can be confirmed. Although there are two peaks of the loss tangent (tan δ) after mixing, when the respective peaks are close to the center, specifically, when the peak on the high temperature side is shifted to a low temperature side and the peak on the low temperature side is shifted to a high temperature side, they are considered to be partially compatible systems. The case where two peaks of loss tangent (tan. delta.) were present after mixing was considered to be a non-compatible system. In the present invention, all the compatible systems are treated as a compatible system except for the case where two or more peaks are clearly observed, because one peak is unclear and it is sometimes difficult to clearly distinguish the compatible system from the partially compatible system.
In general, in the case of a non-compatible system, when external force such as stretching or bending is applied, peeling occurs at the interface, resulting in deterioration of mechanical properties and whitening. Since the polyetherimide resin (B) and the crystalline polyimide resin (a) constituting the polyimide resin composition (X) of the present invention exhibit compatible systems, modification of each resin can be performed without impairing impact resistance.
As described above, the polyimide resin composition (X) of the present invention is a composition having a single glass transition temperature (Tg). The glass transition temperature is preferably 150 ℃ to 300 ℃, more preferably 160 ℃ to 290 ℃, and still more preferably 170 ℃ to 280 ℃. When the glass transition temperature of the polyimide resin composition (X) is 150 ℃ or higher, the heat resistance of the polyimide resin composition (X) is sufficient. On the other hand, when the glass transition temperature is 300 ℃ or lower, molding at a relatively low temperature is possible when molding is performed using the polyimide resin composition (X), and therefore, it is preferable. In addition, when the obtained molded article is subjected to secondary processing, the same reason is preferable.
The polyimide resin composition (X) of the present invention preferably has a tensile elastic modulus of 2200MPa to 3100MPa in accordance with JIS K7127 in order to improve the handling properties when formed into a film and to be suitably used for various applications. When the tensile elastic modulus is 2200MPa or more, the film obtained by using the polyimide resin composition (X) has sufficient rigidity and excellent handling properties. From the above viewpoint, the tensile elastic modulus is more preferably 2250MPa or more, and particularly preferably 2300MPa or more. On the other hand, a tensile elastic modulus of 3100MPa or less is preferable because the film has sufficient flexibility. From the above viewpoint, the tensile elastic modulus is more preferably 3050MPa or less, and particularly preferably 3000MPa or less.
When the polyimide-based resin composition (X) of the present invention is used for the above-described edge material for a vibrating piece for an electroacoustic transducer and a film for the edge material for a vibrating piece for an electroacoustic transducer, the tensile elastic modulus is preferably low, preferably 3000MPa or less, more preferably lower than 2500MPa, even more preferably 2400MPa or less, and particularly preferably 2300MPa or less.
The polyimide resin composition (X) of the present invention preferably has a tensile elongation at break of 130% or more, more preferably 135% or more, as measured according to JIS K7127. When the tensile elongation at break is within the above range, the film made of the polyimide resin composition (X) of the present invention has excellent impact resistance. In addition, the product can be stably molded or secondarily processed into various shapes without causing troubles such as breakage.
When the polyimide-based resin composition (X) of the present invention is used for the above-described edge material for a vibrating piece for an electroacoustic transducer and a film for the edge material for a vibrating piece for an electroacoustic transducer, the tensile elongation at break is preferably higher, more preferably 200% or more, and still more preferably 250% or more, as described above.
The tensile modulus of elasticity and tensile elongation at break of the polyimide resin composition (X) are values obtained by kneading the resin composition at 340 ℃ using a Φ 40mm co-rotating twin-screw extruder, extruding the kneaded resin composition through a T-die, rapidly cooling the extruded resin composition with a casting roll at about 200 ℃ to produce a film having a thickness of 0.1mm, and measuring the film.
In addition to the above-mentioned components, other resins, fillers, various additives such as a heat stabilizer, an ultraviolet absorber, a light stabilizer, a nucleating agent, a colorant, a lubricant, a flame retardant and the like may be appropriately blended in the polyimide resin composition (X) of the present invention within a range not departing from the gist of the present invention.
< moldings of polyimide resin composition (X) >
The polyimide resin composition (X) of the present invention can be molded into a molded article. The polyimide resin composition (X) of the present invention can be molded into a molded article having excellent rigidity and impact resistance. The membrane is characterized as described above. Examples of the molded article include, in addition to a film, a molded article having a shape such as a plate, a tube, a rod, a cap, and a bottle.
Applications of the molded article and the film include applications requiring heat resistance, rigidity, and impact resistance, such as automobile members, airplane members, and electric/electronic members.
As described above, the polyimide resin composition (X) is preferably used as a material for a diaphragm edge of an electroacoustic transducer among these applications. As described above, the edge material of the vibrating plate for an electroacoustic transducer is obtained by, for example, performing secondary processing on a film. The characteristics of the vibrating plate edge material for an electroacoustic transducer are as described above.
< method for producing molded article >
The method for producing the molded article is not particularly limited, and known methods such as extrusion molding, injection molding, blow molding, vacuum molding, compressed air molding, and press molding can be used.
The method for forming (film forming) the film formed from the polyimide resin composition (X) is not particularly limited, and a known method such as an extrusion casting method using a T die, a calendering method, a casting method, or the like can be used. The details of the extrusion casting method using a T-die are as described above, and the description thereof is omitted.
The film formed of the polyimide resin composition (X) may be a uniaxially or biaxially stretched film stretched in one direction or two directions, and examples of the method for producing the stretched film include: a method of producing an unstretched film as a precursor by a T-die casting method, a pressing method, a rolling method, or the like, and then performing stretch molding by a roll stretching method, a tenter stretching method, or the like; or a method of integrally performing melt extrusion and stretch molding by an inflation method, a tube film method, or the like.
The thickness of the film obtained by molding the polyimide resin composition (X) of the present invention is not particularly limited, and is usually 1 to 200. mu.m. In addition, it is also important to form a film so that anisotropy of physical properties of the film in the traveling direction (MD) and The Direction (TD) perpendicular thereto is reduced as much as possible.
As described above, the present invention provides a method for using a crystalline polyimide resin (a) for a diaphragm edge material for an electroacoustic transducer. In the present invention, as described above, by using the crystalline polyimide resin (a), the edge material for the vibrating piece for an electroacoustic transducer can be made excellent in heat resistance, durability at high output, low-to-high sound reproduction, secondary processability, and the like.
The present invention also provides a method for using the polyimide resin composition (X) in a vibrating piece edge material for an electroacoustic transducer, or a molded body or film other than the edge material. In the present invention, by using the polyimide resin composition (X), the edge material of the vibrating piece for an electroacoustic transducer, the molded body, and the film can have excellent properties such as heat resistance, rigidity, and impact resistance.
In general, "film" refers to a thin and flat product having a very small thickness as compared with the length and width and having a maximum thickness that can be arbitrarily defined, and is usually supplied in the form of a roll (JIS K6900), and "sheet" refers to a flat product having a small thickness as defined in JIS relative to the length and width. However, there is no clear boundary between the sheet and the film, and it is not necessary to distinguish the two in the present invention in terms of letters, and therefore, in the present invention, the term "film" also includes the "sheet" and the term "sheet" also includes the "film".
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. Various measurements of the raw materials described in the present specification, the polyimide resin composition of the present invention, and the film used for the edge material of the vibrating plate for an electroacoustic transducer of the present invention were performed as follows.
(1) Glass transition temperature
The raw materials, raw material particles, and the obtained film were subjected to temperature dispersion measurement of dynamic viscoelasticity (dynamic viscoelasticity measurement according to JIS K7244-4) using a viscoelasticity measuring apparatus DVA-200 (manufactured by IT measurement control corporation) at a strain of 0.1%, a frequency of 10Hz, and a temperature rise rate of 3 ℃/min, and the temperature of the peak showing the main dispersion of the loss tangent (tan δ) was defined as the glass transition temperature.
(2) Crystal melting temperature, crystal melting enthalpy, and crystallization temperature at the time of temperature decrease
The various raw materials and the obtained films were measured at a heating rate of 10 ℃ per minute using a Differential Scanning Calorimeter (DSC) in accordance with JIS K7121, and the crystal melting temperature and the crystal melting enthalpy during the temperature rise were measured. Then, the temperature of the crystallization peak (temperature-lowered crystallization temperature) was measured when the temperature of the crystalline material was lowered at 10 ℃/min, and the crystallization rate was evaluated from the difference from the crystal melting temperature.
(3) Modulus of elasticity in tension
The obtained film was measured at a temperature of 23 ℃ in accordance with JIS K7127.
(4) Flexural strength
The obtained film was measured at a temperature of 23 ℃ in accordance with JIS P8115.
(5) Elongation at tensile break
The obtained film was measured at a temperature of 23 ℃ and a test speed of 200 mm/min in accordance with JIS K7127.
1. Crystalline polyimide resin (A)
(A) -1: crystalline polyimide resin (product name: SAPLIM (サープリム) TO65S, manufactured by Mitsubishi gas chemical Co., Ltd., tetracarboxylic acid component: 100 mol%, diamine component: 1, 3-bis (aminomethyl) cyclohexane/octamethylenediamine: 60/40 (molar basis), crystal melting temperature: 322 ℃, crystal melting enthalpy: 40J/g, glass transition temperature: 208 ℃ C.)
2. Polyetherimide resin (B)
(B) -1: polyether imide (manufactured by SABIC INVAVIONE PLASTICS Co., Ltd., ULTEM 1000, glass transition temperature: 232 ℃ C.)
(B) -2: polyether imide (manufactured by SABIC INVAVIONE PLASTICS Inc., ULTEM CRS5001, glass transition temperature: 240 ℃ C.)
(example 1)
The crystalline polyimide resin (A) -1 was melt-kneaded at 340 ℃ using a single-screw extruder having a diameter of 40mm, extruded through a T-die, and then heated and crystallized by a casting roll having a temperature of about 200 ℃ to prepare a crystallized film having a thickness of 25 μm. The obtained film was subjected to the measurements (1) to (5) described above. The results are shown in Table 1.
Comparative example 1
Using (B) -1: a film was produced and measured in the same manner as in example 1 except that polyetherimide 1000 (manufactured by SABIC INVAVATIVE PLASTICS Co., Ltd., ULTEM 1000, amorphous resin, glass transition temperature: 232 ℃ C.) was used in place of the crystalline polyimide resin (A) and the molding temperature was 380 ℃. The results are shown in Table 1.
Comparative example 2
Using (B) -2: a film was produced and measured in the same manner as in example 1 except that polyether imide 5000 (manufactured by SABIC INVAVATIVE PLASTICS Co., Ltd., ULTEM CRS5001, amorphous resin, glass transition temperature: 240 ℃ C.) was used in place of the crystalline polyimide resin (A) and the molding temperature was 380 ℃. The results are shown in Table 1.
TABLE 1
In example 1, a film containing the crystalline polyimide resin (a) of the present invention as a main component was used in a crystallized state. Since the tensile elastic modulus of the film is in an appropriate range, the film is excellent not only in rigidity (stiffness) and handling properties but also in playability in a low-pitched audio band. In addition, although the toughness of the film after crystallization is generally lowered, the values of the flexural strength and the tensile elongation at break tend to be lowered, the film exhibits sufficiently excellent values for these items even in a state where crystallization is performed, and is excellent in durability at high output. Further, the enthalpy of crystal melting, crystal melting temperature, flexural strength, and tensile elongation at break are in preferred ranges, and therefore, the heat resistance, durability at high output, and secondary processability are excellent. Further, since the difference between the crystal melting temperature and the crystallization temperature at the time of temperature reduction is small, the crystallization rate is sufficiently high, and a 25 μm film having sufficient crystallinity is obtained by heat treatment with a casting roll.
On the other hand, in comparative examples 1 and 2, films made of polyetherimide, which is a heat-resistant amorphous resin, were used. Since this film uses an amorphous resin, it has no melting point and is inferior in heat resistance. Further, since the tensile modulus is high, the low sound reproduction is poor, and the breaking strength and the tensile elongation at break are low, the durability and the secondary processability at high output are insufficient.
(example 2)
A film having a thickness of 0.1mm was produced by dry-mixing the (B) -1 and (A) -1 at a mixing mass ratio ((B)/(A)) of 80/20, kneading the mixture at 340 ℃ using a 40 mm-diameter co-rotating twin-screw extruder, extruding the kneaded mixture through a T-die, and then rapidly cooling the extruded mixture by a casting roll at about 200 ℃. The obtained film was evaluated for glass transition temperature, tensile elastic modulus, tensile elongation at break and flexural strength. The results are shown in Table 1.
(example 3)
A film was produced and evaluated in the same manner as in example 1, except that the mixing mass ratio of (B) -1 to (A) -1 ((B)/(A)) was changed to 60/40. The results are shown in Table 1.
(example 4)
A film was produced and evaluated in the same manner as in example 1, except that the mixing mass ratio of (B) -1 to (A) -1 ((B)/(A)) was changed to 40/60. The results are shown in Table 1.
(example 5)
A film was produced and evaluated in the same manner as in example 1, except that the mixing mass ratio of (B) -1 to (A) -1 ((B)/(A)) was changed to 30/70. The results are shown in Table 1.
(example 6)
A film was produced and evaluated in the same manner as in example 1, except that the mixing mass ratio of (B) -1 to (A) -1 ((B)/(A)) was changed to 20/80. The results are shown in Table 1.
(example 7)
A film was produced and evaluated in the same manner as in example 2, except that (B) -2 was used instead of (B) -1. The results are shown in Table 1.
(example 8)
A film was produced and evaluated in the same manner as in example 2, except that (B) -2 was used instead of (B) -1 and the mixing mass ratio ((B)/(A)) of (B) -2 to (A) -1 was changed to 60/40. The results are shown in Table 1.
(example 9)
A film was produced and evaluated in the same manner as in example 2, except that (B) -2 was used instead of (B) -1 and the mixing mass ratio ((B)/(A)) of (B) -2 to (A) -1 was changed to 40/60. The results are shown in Table 1.
(example 10)
A film was produced and evaluated in the same manner as in example 2, except that (B) -2 was used instead of (B) -1 and the mixing mass ratio ((B)/(A)) of (B) -2 to (A) -1 was changed to 30/70. The results are shown in Table 1.
(example 11)
A film was produced and evaluated in the same manner as in example 2, except that (B) -2 was used instead of (B) -1 and the mixing mass ratio ((B)/(A)) of (B) -2 to (A) -1 was changed to 20/80. The results are shown in Table 1.
(example 12)
Films were produced and evaluated in the same manner as in example 2, except that (a) -1 was used alone. The results are shown in Table 1.
Comparative example 3
A film was produced and evaluated in the same manner as in example 2, except that (B) -1 was used alone. The results are shown in Table 1.
Comparative example 4
Films were produced and evaluated in the same manner as in example 2, except that (B) -2 was used alone. The results are shown in Table 2.
The films formed from the compositions of examples 2 to 11 were mixtures of the polyetherimide resin (a) and the crystalline polyimide resin (B), but were confirmed to be compatible systems in which the glass transition temperatures indicated by the main dispersion peaks were all single. All physical properties of the film are included in an appropriate range. The film of example 12 basically contained all physical properties within an appropriate range, but had a low tensile modulus, and was considered to be inferior in handling to the films of other examples 2 to 11.
On the other hand, the films of comparative examples 3 and 4 had a high tensile modulus of elasticity, insufficient flexibility, a low tensile elongation at break, and insufficient impact resistance.
Claims (16)
1. A vibrating piece edge material for an electroacoustic transducer, comprising a crystalline polyimide resin (A) composed of a tetracarboxylic acid component (a-1) and a diamine component (a-2') containing an aliphatic diamine (a-2) as a main component.
2. The material for the edge of a vibrating piece for an electroacoustic transducer according to claim 1, wherein the diamine component (a-2') contains at least a linear aliphatic diamine having 4 to 12 carbon atoms.
3. The vibrating plate edge material for an electroacoustic transducer according to claim 1 or 2, wherein the diamine component (a-2') contains at least alicyclic diamine.
4. The vibrating plate edge material for electroacoustic transducers as claimed in claim 3, wherein the alicyclic diamine is 1, 3-bis (aminomethyl) cyclohexane.
5. The edge material of a diaphragm for an electroacoustic transducer as claimed in any one of claims 1 to 4, wherein the enthalpy of crystal fusion (Δ Hm) is 25J/g or more.
6. The material for the edge of the vibrating plate of an electroacoustic transducer according to any one of claims 1 to 5, which contains a crystalline polyimide resin (A) as a main component.
7. A film comprising a crystalline polyimide resin (A) composed of a tetracarboxylic acid component (a-1) and a diamine component (a-2') comprising an aliphatic diamine (a-2) as the main component, wherein the film has a tensile elastic modulus of 1000MPa or more and 3000MPa or less in accordance with JIS K7127.
8. The film according to claim 7, wherein the film is formed from a polyimide-based resin composition containing the crystalline polyimide resin (A) and a polyetherimide resin (B).
9. The film according to claim 8, wherein a content ratio of the polyetherimide resin (B) to the crystalline polyimide resin (A) is 40/60 or less on a mass basis.
10. The film according to any one of claims 7 to 9, which has a breaking strength of 1000 times or more in accordance with JIS P8115.
11. The film according to any one of claims 7 to 10, which has a tensile elongation at break of 200% or more in accordance with JIS K7127.
12. The film according to any one of claims 7 to 11, which has a thickness of 1 μm or more and 200 μm or less.
13. A vibrating plate edge material for an electroacoustic transducer, which is formed of the film as defined in any one of claims 7 to 12.
14. A vibrating piece edge material for an electroacoustic transducer, wherein the vibrating piece edge material for an electroacoustic transducer according to any one of claims 1 to6 and 13 is disposed as a front-back surface layer, and at least 1 adhesive layer selected from an acrylic adhesive, a rubber adhesive, a silicone adhesive and a urethane adhesive is disposed as an intermediate layer.
15. A vibrating plate for an electroacoustic transducer, using the vibrating plate edge material for an electroacoustic transducer according to any one of claims 1 to6, 13 and 14.
16. A diaphragm for a micro-speaker using the diaphragm edge material for an electroacoustic transducer according to any one of claims 1 to6 and 13 to 15.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111281828.5A CN114143671B (en) | 2016-09-06 | 2017-08-31 | Vibrator element edge material for electroacoustic transducer, vibrator element for electroacoustic transducer, micro-speaker vibrator element, and method for manufacturing vibrator element |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-173286 | 2016-09-06 | ||
| JP2016173286A JP6394662B2 (en) | 2016-09-06 | 2016-09-06 | Diaphragm edge material for electroacoustic transducer, diaphragm for electroacoustic transducer, and microspeaker diaphragm |
| JP2016209251A JP6780440B2 (en) | 2016-10-26 | 2016-10-26 | Polyimide resin composition |
| JP2016-209251 | 2016-10-26 | ||
| CN201780054392.1A CN109691132B (en) | 2016-09-06 | 2017-08-31 | Polyimide resin composition and molded body |
| PCT/JP2017/031386 WO2018047708A1 (en) | 2016-09-06 | 2017-08-31 | Edge material of vibration plate for electro-acoustic transducer, vibration plate for electro-acoustic transducer, vibration plate for microspeaker, film, and polyimide resin composition |
| CN202111281828.5A CN114143671B (en) | 2016-09-06 | 2017-08-31 | Vibrator element edge material for electroacoustic transducer, vibrator element for electroacoustic transducer, micro-speaker vibrator element, and method for manufacturing vibrator element |
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| CN202111281828.5A Active CN114143671B (en) | 2016-09-06 | 2017-08-31 | Vibrator element edge material for electroacoustic transducer, vibrator element for electroacoustic transducer, micro-speaker vibrator element, and method for manufacturing vibrator element |
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| CN110798779B (en) * | 2019-10-31 | 2021-03-09 | 歌尔股份有限公司 | Vibrating diaphragm for miniature sound generating device and miniature sound generating device |
| CN110784807B (en) * | 2019-10-31 | 2021-07-06 | 歌尔股份有限公司 | Sound generating device's vibrating diaphragm and sound generating device |
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Also Published As
| Publication number | Publication date |
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| CN109691132B (en) | 2021-11-16 |
| CN114143671B (en) | 2024-07-02 |
| TWI813545B (en) | 2023-09-01 |
| WO2018047708A1 (en) | 2018-03-15 |
| TW201825554A (en) | 2018-07-16 |
| TW202231730A (en) | 2022-08-16 |
| TWI817455B (en) | 2023-10-01 |
| CN109691132A (en) | 2019-04-26 |
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