JP2020065274A - Film for diaphragm of speaker - Google Patents

Abstract

To provide a film for a diaphragm of a speaker, capable of securing heat resistance of 150°C or higher, and of improving durability of a diaphragm, high sound reproduction and low sound reproduction.SOLUTION: A film 2 that is a polyetherketoneketone resin film is controlled to have a tensile elastic modulus at 23°C of 2,000 N/mmor more and 4,000 N/mmor less, and a tensile elastic modulus at 150°C of 2,000 N/mmor more and 4,000 N/mmor less. Heat resistance of 150°C or higher can be obtained by setting the tensile elastic modulus at 23°C of a film 2 made of a polyetherketoneketone resin having excellent heat resistance in a high-temperature range to 2,000 N/mmor more and 4,000 N/mmor less, and setting the tensile elastic modulus at 150°C of the film 2 to 2,000 N/mmor more and 4,000 N/mmor less.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a diaphragm film for a speaker, which has excellent sound quality characteristics and heat resistance.

  2. Description of the Related Art Mobile devices such as mobile phones, mobile game devices, and smartphones have a small speaker called a micro speaker built therein. A diaphragm for generating sound waves of a speaker called a micro speaker is generally formed of (1) metal foil, (2) natural resin paper, woven cloth, non-woven cloth, and (3) synthetic resin film. It is an important component that affects the sound quality.

  If the diaphragm is a film made of (3) synthetic resin, polyethylene (PE) resin, polyolefin resin such as polypropylene (PP) resin, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, etc. have been used so far. Films made of polyester resin, polyphenylene sulfide (PPS) resin, polyetherimide (PEI) resin, etc. are used (see Patent Documents 1 and 2).

  By the way, in recent years, the speaker has been improved in function and performance. Therefore, the required characteristics of the diaphragm of the speaker are becoming more and more severe. The required characteristics of this diaphragm are that it is lightweight (small in density or specific gravity), has appropriate rigidity (Young's modulus, elastic modulus), is excellent in thickness accuracy, and has a loss tangent (both internal loss and internal loss). , Tan δ) and excellent heat resistance. In addition, it is also excellent in moisture resistance, water resistance, and moldability (press molding, vacuum molding, pressure molding, etc.).

However, when the diaphragm of the speaker is the metal foil of (1), it has excellent heat resistance, water resistance, etc., but has high rigidity, so that the minimum resonance frequency (f ₀ ) is high and the bass reproduction characteristic is insufficient. . Also, since the significant loss tangent (also called internal loss or tan δ) is small for the diaphragm, the diaphragm resonates and the acoustic characteristics are disturbed, high performance cannot be expected, and problems occur in sound quality. . Further, since the density is high, the vibration propagation speed becomes slow, the reproduction frequency band becomes narrow, and problems occur in the acoustic characteristics.

  Further, in the case where the speaker diaphragm is the natural resin paper, woven cloth, or non-woven cloth of (2), the density is low and the weight is low, but the rigidity is low, which causes a problem in reproduction in a high frequency region, and is important. Since the loss tangent is also small, there is still a problem with the sound quality. Moreover, it becomes difficult to obtain sufficient moisture resistance, water resistance, and heat resistance, and the manufacturing process of the speaker becomes complicated.

  On the other hand, when the diaphragm of the speaker is the synthetic resin film of (3), the loss tangent can be selected by changing the material of the synthetic resin, so that there are few problems and the diaphragm is thin. It is suitable for small, lightweight portable devices, because it is suitable for small size, light weight, and mass production. In consideration of these points, a diaphragm made of a synthetic resin film is used for a speaker built in a recent portable device.

  By the way, recently, due to the change in lifestyle accompanying the higher functionality of mobile devices, there are many users who want to enjoy TV programs, music, games, etc. on their mobile devices regardless of time and place. Specifically, even when commuting to work on a public transportation vehicle, at beaches and ski resorts where the temperature changes drastically, at recreational facilities during noisy vacations, when running up and down, back and forth, and even when running, you can use a single portable device to ensure good quality. There are many users who want to enjoy TV programs, music, games, etc. and make good use of their time to enrich their lives.

  In order to meet the demands of the users concerned, the speaker performance is considered in consideration of the special situation that the speaker is not built in the stationary audio device used in a stable environment but built in the portable device. It is necessary to improve or increase the output. Specifically, assuming that the portable device is used for a long time in an unfavorable usage environment, or the external output is increased to be used at a high volume for a long time, the heat resistance of the speaker diaphragm is further improved, There is a need to improve the durability of speakers.

  Since the synthetic resin film has insufficient heat resistance, when used as a diaphragm for a speaker, if the external output is increased, the diaphragm is deformed or damaged due to the high heat generated by the high vibration of the voice coil. Causes a problem in durability. Therefore, in recent years, a film made of polyether ether ketone (PEEK) resin has been proposed and implemented as a film for a diaphragm of a speaker (see Patent Document 3).

JP, 60-139098, A JP-A-64-067099 JP-A-58-222699

The film made of polyetheretherketone resin has a glass transition point of 140 ° C. or higher and 150 ° C. or lower (measurement method: differential scanning calorimetry method) and a melting point of 330 ° C. or higher and 350 ° C. or lower (measurement method: differential scanning calorimetry method). ) And excellent heat resistance.
However, it is said that a speaker with high functionality and high output heats up due to the high vibration of the voice coil at the time of output, and the temperature of the diaphragm reaches around 150 ° C. Since the film made of polyetheretherketone resin has a glass transition point of 150 ° C. or lower, when it is used as a diaphragm, the diaphragm may be deformed or damaged due to the high heat accompanying the high vibration of the voice coil. .

  The present invention has been made in view of the above, and provides a film for a diaphragm of a speaker, which can ensure heat resistance of 150 ° C. or higher, and can improve the durability of the diaphragm and high-pitched sound reproduction and low-pitched sound reproduction. Is intended.

  To solve the above problems, the inventors of the present invention have made extensive studies and as a result, focused on a polyether ketone ketone resin having a very high glass transition point, and a molding material containing this polyether ketone ketone resin has excellent heat resistance. The present invention was completed by producing a film.

That is, in order to solve the above problems in the present invention, the tensile modulus at 23 ° C. of polyether ketone ketone resin film, when measured by the measuring method conforming to JIS K7127 2000N / mm ² or more 4000 N / mm ² or less with a, a tensile modulus at 0.99 ° C. polyether ketone ketone resin film is characterized in that the 2000N / mm ² or more 4000 N / mm ² or less when measured by the measuring method conforming to JIS K7127.

The specific gravity of the polyetherketoneketone resin film is 1.2 or more and 1.4 or less when measured by the measuring method according to JIS K7112, and the loss tangent at 20 ° C. of the polyetherketoneketone resin film is 0.010. The above is preferable.
Further, it can be laminated and adhered to an elastomer layer having a thickness of 10 μm or more and 100 μm or less.
Further, the durometer hardness when the elastomer layer is made of a silicone resin and measured by the durometer type A according to JIS K 6253 can be set to A10 or more and A90 or less.

  Here, the diaphragm film in the claims is exclusively for a speaker, but this speaker is mainly a direct radiating type that directly radiates sound into the atmosphere from a diaphragm having a size similar to the wavelength of sound. Is. However, in addition to the direct radiation type, a horn type may be used. The speaker is mainly built in a mobile device, and the mobile device includes at least a mobile phone, a portable music device, a mobile game device, a smartphone, a tablet PC, a laptop computer, and the like.

According to the present invention, together with a tensile modulus at 23 ° C. of polyether ketone ketone resin film having excellent heat resistance high-temperature range 2000N / mm ² or more 4000 N / mm ² or less, 0.99 ° C. polyether ketone ketone resin film tensile since the elastic modulus and 2000N / mm ² or more 4000 N / mm ² or less at, it is possible to obtain a 0.99 ° C. or higher heat resistance.

According to the present invention, heat resistance of 150 ° C. or higher can be ensured, and there is an effect that durability of the diaphragm and high-pitched sound reproduction and low-pitched sound reproduction can be improved. Further, since the range tensile modulus of 2000N / mm ² or more 4000 N / mm ² or less at 23 ° C. of polyether ketone ketone resin film, it is possible to obtain a sufficient treble reproduction and low sound reproduction. Further, since the tensile modulus at 0.99 ° C. polyether ketone ketone resin film 2000N / mm ² or more 4000 N / mm ^2, such hereinafter become heat resistance enough polyether ketone ketone resin film obtained from polyether ketone ketone resin film When the diaphragm is used for a speaker, the diaphragm is less likely to be deformed or damaged.

  According to the invention of claim 2, since the specific gravity of the polyether ether ketone resin film is in the range of 1.2 or more and 1.4 or less, weight reduction can be expected, and further, the vibration propagation speed is increased and the reproduction frequency band is increased. Since it spreads, good sound quality and acoustic characteristics can be expected. Further, since the loss tangent at 20 ° C. of the polyetherketoneketone resin film is 0.010 or more, it is possible to prevent the sound quality characteristics from varying due to the occurrence of resonance.

  According to the invention of claim 3, a polyetherketoneketone resin film is laminated on an elastomer layer having excellent sound quality characteristics and compression characteristics to manufacture a diaphragm having both of these characteristics. It is possible to improve the durability and sound quality characteristics of the diaphragm even if the voice coil or the like generates heat or vibrates due to the high power of the speaker or the like, which is used for a long time in a non-use environment. Further, since the thickness of the elastomer layer is in the range of 10 μm or more and 100 μm or less, it is possible to reduce the weight and improve the acoustic characteristics.

According to the invention of claim 4, since the silicone resin is used for the elastomer layer, it is possible to obtain a diaphragm having excellent heat resistance, weather resistance, flame retardancy, sound quality characteristics, and compression characteristics. Further, since the durometer hardness of the silicone resin is in the range of A10 or more and A90 or less, it is possible to prevent the compression set characteristic of the silicone resin from being deteriorated and the vibration propagation speed of the diaphragm from being lowered to adversely affect the sound quality. it can. Furthermore, it is possible to prevent the performance of the diaphragm from deteriorating as the loss tangent decreases or the f ₀ value increases.

FIG. 3 is an overall explanatory view schematically showing the manufacturing method in the embodiment of the diaphragm film for the speaker according to the present invention. It is a cross-sectional explanatory view which shows typically the diaphragm in embodiment of the film for diaphragms of the speaker which concerns on this invention.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, a method of manufacturing a film for a diaphragm of a speaker according to the present embodiment uses a molding material 1 containing a resin to form a diaphragm. Is a method for molding a film 2 which is a polyetherketoneketone resin film for use in a melt-kneading molding material 1 containing a polyetherketoneketone resin which is excellent in heat resistance in a high temperature range by a melt extrusion molding machine 10. 1, a thin film 2 was continuously extruded from a T-die 13, and the extruded film 2 was cooled by being sandwiched between a pair of pressure rolls 17 and a cooling roll 18 for cooling. The thickness of the film 2 is set to 2 μm or more and 110 μm or less.

  The polyetherketoneketone resin of the molding material 1 is not particularly limited, but is a resin having a repeating unit represented by the chemical formula [Chemical Formula 1].

  More specifically, it is a resin having a repeating unit represented by the chemical formula [Chemical formula 2] or the chemical formula [Chemical formula 3].

  The repeating unit of the chemical formula [Chemical Formula 2] and the chemical formula [Chemical Formula 3] may be any of random repeating, alternating repeating, and block repeating.

  Here, the unit ratio of the chemical formula [Chemical Formula 2] and the chemical formula [Chemical Formula 3] is preferably in the range of (Chemical Formula [Chemical Formula 2] / Chemical Formula [Chemical Formula 3]) = (50/50) to (90/10). (Chemical formula [Chemical formula 2] / Chemical formula [Chemical formula 3]) = (70/30) to (90/10) is more preferable, and more preferably (Chemical formula [Chemical formula 2] / Chemical formula [Chemical formula 3]) = (75 / The range of 25) to (85/15) is preferable. If this is within the range of (Chemical formula [Chemical formula 2] / Chemical formula [Chemical formula 3]) = (75/25) to (85/15), the crystallization rate is high, and mechanical properties, solvent resistance, and heat resistance are high. This is because it is possible to obtain a film 2 containing a polyetherketoneketone resin that is excellent in

  Further, when the unit ratio of the chemical formula [Chemical Formula 2] is less than 50, the crystallinity and the crystallization rate of the polyetherketoneketone resin decrease, so that the molding compound 1 containing this polyetherketoneketone resin is obtained. This is because the mechanical properties, solvent resistance, and heat resistance of the film 2 are reduced. On the other hand, in the case of a polyetherketoneketone resin having a unit ratio of more than 90, the melting point of the polyetherketoneketone resin and the decomposition temperature of the polyetherketoneketone resin are close to each other, so that the polyetherketoneketone resin containing This is because the polyetherketoneketone resin may be thermally decomposed during molding when the film 2 is molded by melt extrusion molding of the molding material 1.

  The melting point of the polyetherketoneketone resin is usually 300 ° C. or higher and 370 ° C. or lower, preferably 330 ° C. or higher and 365 ° C. or lower, and more preferably 350 ° C. or higher and 360 ° C. or lower. The glass transition point of the polyetherketoneketone resin is 150 ° C. or higher and 180 ° C. or lower, preferably 155 ° C. or higher and 175 ° C. or lower, and more preferably 160 ° C. or higher and 170 ° C. or lower. A specific example of this polyetherketoneketone resin is the product name: KEPSTAN series manufactured by Arkema.

  As a method for producing a polyether ketone ketone resin, for example, U.S. Pat. No. 3,516,966, U.S. Pat. No. 3,637,592, U.S. Pat. No. 3,441,538, Japanese Patent Publication No. 4-63900, The manufacturing method described in Japanese Patent Publication No. 6-10258 is used. As the polyetherketoneketone resin, a random copolymer, an alternating copolymer, a block copolymer, or a modified product with another copolymerizable monomer is also used as long as the effect of the present invention is not impaired. It is possible.

  The molding material 1 containing the polyetherketoneketone resin includes, in addition to the polyetherketoneketone resin, a polyimide resin such as a polyimide (PI) resin, a polyamideimide (PAI) resin and a polyetherimide (PEI) resin, a polyamide 4T (PA4T). ) Resin, polyamide 6T (PA6T) resin, modified polyamide 6T (modified PA6T) resin, polyamide 9T (PA9T) resin, polyamide 10T (PA10T) resin, polyamide 11T (PA11T) resin, polyamide 6 (PA6) resin, polyamide 66 ( PA66) resin, polyamide resin such as polyamide 46 (PA46) resin, polyethylene terephthalate (PET) resin, polyester resin such as polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polyether Ton (PEK) resin, polyetheretherketone (PEEK) resin, polyetheretherketoneketone (PEEKK) resin, polyetherketoneetherketoneketone (PEKEKK) resin and other polyaryletherketone resins, polysulfone (PSU) resins, poly Polysulfone resins such as ether sulfone (PES) resins and polyphenylsulfone (PPSU) resins, polyphenylene sulfide (PPS) resins, polyphenylene sulfide ketone resins, polyphenylene sulfide sulfone resins, polyphenylene sulfide ketone sulfone resins and other polyarylene sulfide resins, Liquid crystal polymer (LCP), polycarbonate (PC) resin, polyarylate (PAR) resin and the like can be added as necessary.

  The molding material 1 includes, in addition to the above resins, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a flame retardant, an antistatic agent, a heat resistance improver, an inorganic compound, in addition to the above-mentioned resins within the range not impairing the characteristics of the present invention. , Organic compounds and the like can be selectively added.

  When a film 2 for a diaphragm is manufactured using such a molding material 1 containing polyetherketoneketone resin, a known manufacturing method such as a melt extrusion molding method, a calender molding method, or a casting molding method is adopted. can do. However, from the viewpoint of improving the thickness accuracy of the film 2, the productivity, the handling property, and simplifying the equipment, it is preferable to continuously and thinly extrude the film by the melt extrusion method. Here, the melt extrusion molding method, as shown in FIG. 1, melt-kneads the molding material 1 by using the melt extrusion molding machine 10, and from the T die 13 at the tip of the melt extrusion molding machine 10 to a diaphragm. This is a molding method in which the film 2 is continuously extruded.

  The melt extrusion molding machine 10 is composed of, for example, a single-screw extrusion molding machine or a twin-screw extrusion molding machine, and functions to melt-knead the input molding material 1. A raw material inlet 11 for the molding material 1 is installed in the upper rear part of the melt extrusion molding machine 10, and the raw material inlet 11 has helium gas, neon gas, argon gas, krypton gas, nitrogen gas, carbon dioxide gas. An inert gas supply pipe 12 for supplying an inert gas (see the arrow in FIG. 1) as necessary is connected, and the flow of the inert gas through the inert gas supply pipe 12 causes Oxidative deterioration and oxygen crosslinking are effectively prevented.

  The temperature of the polyetherketoneketone resin at the time of melt-kneading in the melt extruder 10 is a temperature at which melt-kneading is possible and is not particularly limited as long as it is a temperature at which the polyetherketoneketone resin is not thermally decomposed. , Above the melting point of the polyetherketoneketone resin and below the thermal decomposition temperature. Specifically, the temperature is adjusted to 320 ° C or higher and 450 ° C or lower, preferably 360 ° C or higher and 420 ° C or lower, and more preferably 380 ° C or higher and 400 ° C or lower. This is because if the melting point of the polyetherketoneketone resin is lower than the melting point, the molding material 1 containing the polyetherketoneketone cannot be melt-extruded. This is because the ketone resin may be severely decomposed.

  The T-die 13 is attached to the front end of the melt extrusion molding machine 10 via a connecting pipe 14, and functions to continuously push the strip-shaped film 2 downward. The temperature of the T die 13 at the time of extrusion is in the range of the melting point of the polyetheretherketone resin or more and less than the thermal decomposition temperature. Specifically, the temperature is adjusted to 320 ° C or higher and 450 ° C or lower, preferably 360 ° C or higher and 420 ° C or lower, and more preferably 380 ° C or higher and 400 ° C or lower. This is because when the melting point of the polyetherketoneketone resin is lower than the melting extrusion molding of the molding material 1, it becomes difficult, and when the temperature exceeds the thermal decomposition temperature, the polyetherketoneketone resin may decompose. Based on the reason.

  A gear pump 15 and a filter 16 are preferably attached to the connecting pipe 14 upstream of the T-die 13. The gear pump 15 functions to transfer the molding material 1 melt-kneaded by the melt-extrusion extruder 10 to the T-die 13 via the filter 16 at a constant flow rate and with high accuracy. Further, the filter 16 separates the gel or the like of the molten molding material 1 and transfers the molten molding material 1 to the T die 13.

  The pair of pressure-bonding rolls 17 are rotatably supported below the T-die 13 and sandwich the cooling roll 18 in a slidable contact manner. A winding tube 20 of a winder 19 for winding the film 2 is rotatably installed downstream of the pressure-bonding roll 17 on the downstream side of the pair of pressure-bonding rolls 17. A slit blade 21 that forms a slit in a side portion of the film 2 is vertically movable between the take-up tube 20 and the take-up tube 20, and between the slit blade 21 and the take-up tube 20 of the winder 19. A necessary number of rotatable tension rolls 22 for applying a tension to the film 2 and smoothly winding the film 2 are axially supported.

  From the viewpoint of improving the adhesion between the film 2 and the cooling roll 18, at least the natural rubber, the isoprene rubber, the butadiene rubber, the norbornene rubber, the acrylonitrile butadiene rubber, the nitrile rubber, the urethane rubber, and the silicone are provided on the peripheral surface of each pressure-bonding roll 17. A rubber layer such as rubber or fluororubber is formed by coating as necessary, and an inorganic compound such as silica or alumina is selectively added to this rubber layer. Among these, it is preferable to use silicone rubber or fluororubber having excellent heat resistance.

  As the pressure bonding roll 17, a metal elastic roll having a metal surface is used as necessary. When this metal elastic roll is used, the film 2 having a smooth surface can be formed. Specific examples of the metal elastic roll include a metal sleeve roll, an air roll (product name manufactured by Dimco), and a UF roll (product name manufactured by Hitachi Zosen Co., Ltd.).

  The pressure-bonding roll 17 is adjusted to a temperature of 260 ° C. or lower, preferably 50 ° C. or higher and 260 ° C. or lower, more preferably 130 ° C. or higher and 240 ° C. or lower, and is brought into sliding contact with the film 2 to press it against the cooling roll 18. . The temperature of the pressure-bonding roll 17 is within the range because the film 2 being manufactured may stick to the pressure-bonding roll 17 and the film 2 may be broken when the temperature of the pressure-bonding roll 17 exceeds 260 ° C. On the contrary, if the temperature is lower than 50 ° C., the pressure-bonding roll 17 will be condensed, which is not preferable. Examples of the method for adjusting the temperature of the pressure-bonding roll 17 and the cooling method include a method using a heat medium such as air, water or oil, or an electric heater or a dielectric heating roll.

  The cooling roll 18 is composed of, for example, a metal roll having a diameter larger than that of the pressure bonding roll 17, and holds the film 2 rotatably supported below the T die 13 and pushed out between the pressure bonding roll 17 and the pressure bonding roll 17. It functions together with 17 to control the thickness of the film 2 within a predetermined range while cooling the film 2. The cooling roll 18 is adjusted to a temperature of 260 ° C. or less, preferably 50 ° C. or more and 260 ° C. or less, more preferably 130 ° C. or more and 240 ° C. or less, and slidably contacts the film 2, like the pressure bonding roll 17.

  The cooling roll 18 is adjusted to a temperature of 50 ° C. or more and 260 ° C. or less, because when the temperature of the cooling roll 18 exceeds 260 ° C., the film 2 being manufactured may stick to the cooling roll 18 and break. Based on the reason that there is. On the other hand, when the temperature is lower than 50 ° C., the cooling roll 18 is condensed, which is not preferable. Examples of the temperature adjustment and cooling method of the cooling roll 18 include a method using a heat medium such as air, water and oil, an electric heater, and dielectric heating.

  In the above, when the film 2 for the diaphragm is manufactured, as shown in FIG. 1, the molding material 1 containing polyetherketoneketone resin is indicated by an arrow in the same figure at the raw material inlet 11 of the melt extrusion molding machine 10. The inert gas shown below is supplied while being supplied, the molding material 1 is melted and kneaded in a heated and pressurized state by the melt extrusion molding machine 10, and the thin film 2 is continuously extruded from the T die 13 into a strip shape.

  At this time, the water content of the molding material 1 containing the polyetherketoneketone resin before melt-kneading is adjusted to 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or more and 1000 ppm or less. This is because when the water content of the polyetherketoneketone resin before melt-kneading exceeds 2000 ppm, the polyetherketoneketone resin may foam.

  After the strip-shaped film 2 is extruded, it is wound around a pair of pressure-bonding rolls 17, a cooling roll 18, a tension roll 22 and a winding pipe 20 of a winder 19 in order, and the film 2 is cooled by the cooling roll 18, The film 2 for the diaphragm made of polyetherketoneketone resin can be manufactured by cutting both sides of 2 with the slit blades 21 and winding them sequentially on the winding tube 20. During the production of this film, fine unevenness can be formed on the surface of the film 2 within the range where the effect of the present invention is not lost, and the friction coefficient of the surface of the film 2 can be reduced.

  As a method of forming fine irregularities, for example, (1) a molding material 1 containing a polyetherketoneketone resin is melt-kneaded by a melt extrusion molding machine 10, and the melt-kneaded molding material 1 is finely irregularized from a T die 13. A method of discharging fine particles on a cooling roll 18 provided on the peripheral surface and closely adhering them, and simultaneously forming fine concavities and convexities at the time of molding the film 2, (2) After manufacturing the film 2, the cooling roll 18 having fine concavities and convexities on the peripheral surface There is a method of forming a fine concavo-convex by closely contacting the top. Although either method can be adopted, the method (1) is optimal from the viewpoints of simplification of equipment, control of thickness accuracy of the film 2, and maintenance of the appearance of the film 2.

  The thickness of the film 2 made of polyetherketoneketone resin after cooling is preferably 2 μm or more and 110 μm or less, preferably 3 μm or more and 105 μm or less, and more preferably 5 μm or more and 100 μm or less. This is because when the thickness of the film 2 is less than 2 μm, the mechanical strength of the film 2 is significantly reduced, so that the molding of the film 2 becomes difficult. On the contrary, when the thickness of the film 2 exceeds 110 μm, the diaphragm becomes thick and large, and the size of the speaker also becomes large, which makes it unsuitable for a speaker for portable equipment. The thickness of the film 2 can be measured by various contact thickness gauges.

  The thickness tolerance of the film 2 is within the range of the average value ± 10%, preferably within the range of the average value ± 5%. This is because when the thickness tolerance of the film 2 deviates from the range of the average value ± 10%, the sound quality varies. The thickness tolerance of the film 2 can be obtained by a predetermined formula.

The mechanical properties of the polyetherketoneketone resin film 2 after cooling can be evaluated by the tensile elastic modulus at 23 ° C. Tensile modulus at 23 ° C. of polyether ketone ketone resin film 2 after cooling, 2000N / mm ² or more 4000 N / mm ² or less, preferably in the range of 2300N / mm ² or more 3950N / mm ² or less, more preferably The optimum range is 2400 N / mm ² or more and 3900 N / mm ² or less. This is because when the tensile elastic modulus of the film 2 is less than 2000 N / mm ² , the high-frequency resonance frequency (f _H ) of the diaphragm made of film is low, and high-pitched sound reproduction becomes insufficient. On the other hand, when it exceeds 4000 N / mm ² , the lowest resonance frequency (f ₀ ) of the diaphragm obtained from the film 2 is high, and the bass reproduction becomes insufficient.

  The heat resistance characteristics of the film 2 made of polyetheretherketone resin after cooling can be evaluated by the glass transition point and the tensile elastic modulus at 150 ° C. The glass transition point of the polyetherketoneketone resin film 2 after cooling is 150 ° C. or higher, preferably 155 ° C. or higher, and more preferably 161 ° C. or higher. This is because when the glass transition temperature of the film 2 is lower than 150 ° C., the heat resistance of the film 2 is insufficient, and therefore when the diaphragm obtained from the film 2 is used for a speaker, it is caused by high vibration of the voice coil. This is because the high heat generated causes a problem in durability such as deformation or breakage of the diaphragm obtained from the film 2.

Tensile modulus at 0.99 ° C. polyether ketone ketone resin film 2 after cooling, 2000N / mm ² or more 4000 N / mm ² or less, preferably in the range of 2100 N / mm ² or more 3700N / mm ² or less, more preferably 2200N / mm ² or more 3650N / mm ² or less in the range is optimal. This is because when the tensile modulus of elasticity of the film 2 at 150 ° C. is less than 2000 N / mm ² , the heat resistance of the film 2 is insufficient, so when the diaphragm obtained from the film 2 is used for a speaker, This is because the high heat accompanying the high vibration of the coil causes a problem in durability such as deformation or damage of the diaphragm obtained from the film 2. In addition, the high-frequency resonance frequency (f _H ) of the diaphragm made of film is low, and high-pitched sound reproduction becomes insufficient. On the other hand, when it exceeds 4000 N / mm ² , the minimum resonance frequency (f ₀ ) of the diaphragm obtained from the film 2 is high, and the bass reproduction becomes insufficient.

  The acoustic characteristics of the film 2 made of polyetherketoneketone resin after cooling can be evaluated by the specific gravity of the film 2 at 23 ° C. and the loss tangent of the film 2 at 20 ° C. The specific gravity of the polyether ether ketone resin film 2 after cooling is 1.2 or more and 1.4 or less, preferably 1.22 or more and 1.35 or less, more preferably 1.25 or more and 1.31 or less. is there. This is because in the range, the density is small and therefore the weight can be expected to be reduced, and the vibration propagation speed is increased and the reproduction frequency band is widened, so that good sound quality and acoustic characteristics can be obtained.

  The loss tangent at 20 ° C. of the cooled film 2 made of polyetherketoneketone resin is preferably 0.010 or more, preferably 0.011 or more, more preferably 0.013 or more. This is because when the loss tangent is less than 0.010, the sound quality characteristics vary due to the occurrence of resonance. The upper limit of the loss tangent is not particularly limited, but is preferably 0.4 or less.

  The produced film 2 can be used as a diaphragm as it is, but from the viewpoint of obtaining excellent sound quality characteristics, compression characteristics, and loss tangent, it is made a part of the laminated intermediate body 3 shown in FIG. Is preferably formed into a diaphragm. As shown in FIG. 2, the laminated intermediate body 3 comprises an elastomer layer 4 having a thickness of 10 μm or more and 100 μm or less, and a pair of upper and lower films 2 laminated and adhered to both front and back surfaces of the elastomer layer 4 via a primer 5. It has a multi-layer structure and is mainly used for built-in mobile devices.

  Examples of the elastomer used for the elastomer layer 4 include silicone resin, urethane resin, acrylic resin, fluororesin, polyester resin, polyamide resin, hydrocarbon resin and the like. Among these elastomers, silicone resins are preferable because they are excellent in heat resistance, weather resistance, flame retardancy, sound quality characteristics, compression characteristics, and the like.

  The silicone resin used in the elastomer layer 4 is composed of a silicone resin composition, and the silicone resin composition is preferably a heat-curable silicone resin from the viewpoints of production suitability of the intermediate and storage suitability after production. Examples of the heat-curable silicone resin include addition-curable millable silicone resin and addition-curable liquid silicone resin. The addition-curable millable silicone resin is usually an organopolysiloxane, a filler such as silica, and a curing agent (a curing agent in which a known platinum-based catalyst and an organohydrogenpolysiloxane are combined, an organized oxide, and the like). ) Or silica fine powder, etc. are used in the state of the composition which added various additives.

On the other hand, the addition-curable liquid silicone resin contains an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule and at least two hydrogen atoms bonded to silicon atoms in one molecule. Organohydrogenpolysiloxane and an inorganic filler having an average particle size of 1 μm or more and 30 μm or less and a bulk density of 0.1 g / cm ³ or more and 0.5 g / cm ³ or less (diatomaceous earth, perlite, foamed perlite ground product) , Mica, calcium carbonate, glass flakes, hollow fillers, etc., and addition reaction catalysts (platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, chloroplatinic acid and olefins) Complex, platinum bisacetoacetate, palladium-based catalyst, rhodium-based catalyst, etc.) It is.

  The silicone resin composition used as the silicone resin is prepared by using a calender roll such as a two-roller or a three-roller, a roll mill, a kneading machine such as a Banbury mixer, a dough mixer (kneader), and the like, and various additives as desired. Can be obtained by kneading at room temperature or under heating for several minutes to several hours, preferably 5 minutes to 1 hour, until they are uniformly mixed. The normal temperature here means a temperature range of about 0 to 50 ° C.

  The thickness of the elastomer layer 4 is optimally 10 μm or more and 100 μm or less, preferably 20 μm or more and 80 μm or less, and more preferably 50 μm or more and 75 μm or less from the viewpoint of obtaining excellent acoustic characteristics by weight reduction. The thickness referred to here means a thickness after curing when a silicone resin is used for the elastomer layer 4.

  The durometer hardness of the silicone resin when a silicone resin is used for the elastomer layer 4 is A10 or more and A90 or less, preferably A20 or more and A70 or less, and more preferably, when measured with a durometer type A in accordance with JIS K6253. The range of A20 or more and A50 or less is optimal. This is because when the durometer hardness is less than A10, the compression set characteristic of the silicone resin layer is deteriorated and the vibration propagation speed of the diaphragm is lowered, causing a problem in sound quality. On the other hand, when the durometer hardness exceeds A90, the loss tangent becomes small and the performance of the diaphragm deteriorates.

  The primer 5 is interposed between the elastomer layer 4 and the film 2 made of polyetherketoneketone resin and functions to firmly bond them. The primer 5 is not particularly limited as long as it can bond the silicone resin and the film 2 made of polyetherketoneketone resin, and for example, alkyd resin, alkyd such as phenol-modified or silicone-modified, etc. Examples thereof include resin-modified products, oil-free alkyd resins, acrylic resins, silicone resins, epoxy resins, fluororesins, phenol resins, silane coupling agents, titanate coupling agents, aluminum coupling agents, and mixtures thereof. In addition, examples of crosslinking agents that cure and / or crosslink these resins include isocyanate compounds, melamine compounds, epoxy compounds, peroxides, phenol compounds, hydrogen siloxane compounds, and silane compounds.

  The primer 5 is used in the state of a mixture of the above compound and an organic solvent. As the organic solvent, a solvent that easily volatilizes is preferable, for example, an alcohol solvent such as methanol, ethanol, or isopropanol, an aromatic hydrocarbon solvent such as xylene, or toluene, n-hexane, cyclohexane, methylcyclohexane, or dimethylcyclohexane. And the like, ketone-based solvents such as acetone and methyl ethyl ketone, ester-based solvents such as ethyl acetate and butyl acetate, and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent added is appropriately adjusted according to the coating method of the primer 5 so as to have an appropriate concentration.

  The primer 5 is, for example, a spray method, a brush coating method, a gravure coating method, a die coating method, a bar coater (Meyer bar) method, an impregnation coating on any of the facing surfaces of the silicone resin and the film 2 made of polyetherketoneketone resin. A thin film is formed by a known method such as a method, and after evaporation of the organic solvent, a thin film layer is formed.

  The primer 5 of the thin film layer has a thickness of 0.1 μm or more and 5 μm or less, preferably 1 μm or more and 2 μm or less. This is because when the thickness of the primer 5 is less than 0.1 μm, the adhesion between the elastomer layer 4 and the film 2 is insufficient, and there is a risk that the primer layer may peel off during molding on the diaphragm or during use. Because. On the other hand, when the thickness of the primer 5 exceeds 5 μm, the secondary formability of the diaphragm or the acoustic characteristics may be adversely affected.

  In order to improve the wettability of the primer 5 to the elastomer layer 4 and the film 2, the surface of the elastomer layer 4 and the film 2 is treated by various surface treatment methods within a range not impairing the characteristics of the present invention. Just do it. Examples of various surface treatment methods include known methods such as corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, flame treatment, flame treatment, and itro treatment.

  The thickness of the pair of films 2 may be different on both surfaces of the elastomer layer 4 or may be the same, but preferably the same. This is because when the thicknesses of the pair of films 2 are different, the heat shrinkage rates of the films 2 are different, so that the diaphragm may be curled after molding.

  As a method for producing such a laminated intermediate body 3, first, the elastomer used in the elastomer layer 4 is molded into a sheet shape, and the elastomer and the pair of films 2 which have already been molded are inserted via the primer 5. Laminate. As a method for molding the elastomer into a sheet shape, a known manufacturing method such as a room temperature extrusion molding method, a melt extrusion molding method, a calender molding method, or a casting molding method can be adopted. When the elastomer used in the elastomer layer 4 has a problem in handling such as low mechanical properties or severe stickiness, the elastomer is placed on a non-stretchable base sheet such as a polyethylene terephthalate (PET) resin sheet. It may be divided into a predetermined thickness. The normal temperature here refers to a temperature range of 0 to 50 ° C.

  When the elastomer of the elastomer layer 4 is, for example, a silicone resin, first, a silicone resin composition is prepared and kneaded with two or three calender rolls, and the kneaded silicone resin composition is used as a polyethylene terephthalate (PET) resin sheet or the like. A non-stretchable substrate sheet is calendered into a sheet having a predetermined thickness, and the exposed film of the silicone resin composition is coated with a film 2 made of polyetherketoneketone resin as a primer. Laminate through 5.

  Next, the substrate sheet is placed on the film 2 side, the substrate sheet is peeled off to expose the adhesive surface of the silicone resin composition, and another film made of polyetherketoneketone resin is exposed on the exposed surface of the silicone resin composition. By laminating 2 via the primer 5, the laminated intermediate 3 can be produced.

  After the laminated intermediate body 3 is manufactured, if the laminated intermediate body 3 is formed into a diaphragm by thermoforming such as press forming using a mold, vacuum forming, or pressure forming, vibration of a small speaker without wrinkles can be obtained. Plates can be manufactured. At this time, when a silicone resin is used for the elastomer layer 4, if the silicone resin is cured at the same time as the diaphragm is molded and the silicone resin is adjusted to a predetermined size and shape, a small speaker diaphragm without wrinkles is manufactured. can do.

  The thermoforming temperature of the laminated intermediate 3 is equal to or higher than the glass transition point and lower than the melting point of the film 2 made of polyetherketoneketone resin from the viewpoint of moldability to the vibration plate. Specifically, it is 160 ° C or higher and 300 ° C or lower, preferably 180 ° C or higher and 250 ° C or lower. This is because when the thermoforming temperature is lower than the glass transition temperature of the film 2, it is difficult to form the laminated intermediate body 3 into the diaphragm, and conversely, when the thermoforming temperature is equal to or higher than the melting point of the film 2, This is because the film 2 is melted to cause deterioration in shape, or the elastomer used in the elastomer layer 4 is thermally decomposed or transformed.

According to the above, melt extruded by polyether ketone ketone resin excellent in heat resistance of the film 2 of the high temperature region, and a tensile modulus at 23 ° C. After cooling of the film 2 2000N / mm ² or more 4000 N / mm ² or less as well as, a tensile modulus at 0.99 ° C. of the film 2 after cooled to 2000N / mm ² or more 4000 N / mm ² or less, the specific gravity of the film 2 after cooling is 1.2 to 1.4, the film after cooling Since the loss tangent at 20 ° C. of 2 is 0.010 or more, heat resistance of 150 ° C. or more can be obtained. Therefore, even if it is used for the diaphragm of the speaker, it is possible to effectively eliminate the possibility that the diaphragm is deformed or damaged due to the high heat accompanying the high vibration of the voice coil.

  Moreover, since a pair of films 2 made of polyetherketoneketone resin are laminated on the elastomer layer 4 having excellent sound quality characteristics and compression characteristics to manufacture a diaphragm having these characteristics, even in a use environment where a portable device is not preferable. Even if the speaker is used for a long time and the speaker has high functionality and high output, the external output is increased, and even if the voice coil generates heat or vibrates, the durability and acoustic characteristics of the diaphragm can be improved.

  In particular, a silicone resin having excellent heat resistance, weather resistance, flame retardancy, sound quality characteristics, compression characteristics, etc. is used for the elastomer layer 4, and a pair of polyetherketoneketone resin films 2 are laminated on the silicone resin. If a diaphragm with characteristics is manufactured, even if a portable device is used for a long time in an unfavorable environment, the external output will increase due to the high performance and high output of the speaker, and the voice coil will generate heat and vibrate. Even if it occurs, it is possible to significantly improve the heat resistance and acoustic characteristics of the diaphragm.

Further, the composite of the elastomer layer 4 having an excellent loss tangent and the film 2 made of polyetherketoneketone resin improves the loss tangent of the diaphragm, so that the acoustic characteristics can be improved. In particular, if a composite of a silicone resin and a film 2 made of polyetherketoneketone, which has a large loss tangent and an excellent effect of preventing an increase in the f ₀ value, is combined with the heat resistance of the diaphragm, the loss tangent, and the reproduction of low frequencies. Since the characteristics are significantly improved, it is possible to obtain extremely excellent durability and acoustic characteristics.

  In the above embodiment, the vibration plate has a multilayer structure including the elastomer layer 4 and the film 2 laminated and adhered on both surfaces of the elastomer layer 4 with the primer 5 interposed therebetween, but the invention is not limited thereto. Not a thing. For example, only the film 2 may be used and the elastomer layer 4 may be omitted. On the surface of the film 2, various antistatic agents, various elastomers such as silicone resin, acrylic resin and urethane resin are coated on the surface without losing the effect of the present invention, and aluminum, tin, nickel, copper, etc. Various metals may be vapor-deposited.

Examples of the diaphragm film for the speaker according to the present invention will be described below together with comparative examples.
[Example 1]
First, a commercially available polyetherketoneketone resin [Product name: KEPSTAN 8002 manufactured by Arkema Co., Ltd.] is prepared as a molding material, and this polyetherketoneketone resin is dried for 12 hours by a hot air dryer heated to 160 ° C., and dried and molded. After confirming that the water content of the material was 300 ppm or less, the dried polyether ether ketone resin was set in a φ40 mm single-screw extruder equipped with a T die having a width of 400 mm, melt-kneaded, and melt-kneaded. A polyetherketoneketone resin was continuously extruded from a T-die of a single-screw extruder to extrude a film made of a polyetherketoneketone resin, which is a diaphragm film, into a strip shape.

  At this time, the water content of the polyetherketoneketone resin was measured by the Karl Fischer titration method using a trace moisture analyzer (product name CA-100, manufactured by Mitsubishi Chemical Corporation). The single-screw extruder was L / D = 32, compression ratio: 2.5, screw: full flight screw type. The temperature of the single screw extruder was adjusted to 380 to 400 ° C., the temperature of the T die was adjusted to 400 ° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 400 ° C., respectively.

  When the polyetherketoneketone resin was charged into the single-screw extruder, nitrogen gas of 18 L / min was supplied. Regarding the temperature of the molten polyetherketoneketone resin, the resin temperature at the inlet of the T-die was measured, and it was 396 ° C. when measured.

  After extruding a film made of polyetherketoneketone resin, both sides of this continuous film made of polyetherketoneketone resin are cut with slit blades and sequentially wound on a winding tube of a winder, a length of 50 m, A film for a diaphragm made of polyetherketoneketone resin having a width of 300 mm was manufactured. At this time, the film was sequentially wound around a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 210 ° C. having irregularities on its peripheral surface, and a 3-inch winding tube located downstream thereof. , And sandwiched between the pressure roll and the metal roll.

  When a film made of polyetherketoneketone resin, which is a film for a diaphragm, was obtained, the film thickness, film thickness tolerance, mechanical properties, heat resistance properties, and acoustic properties of this film were evaluated, and the results are shown in Table 1. did. Mechanical properties are evaluated by the tensile modulus of the film at 23 ° C, heat resistance is evaluated by the glass transition point of the film and the tensile modulus at 150 ° C of the film, and acoustic properties are evaluated by the specific gravity of the film at 23 ° C and the loss tangent of the film at 20 ° C. did.

-Film film thickness For the film thickness of 2 μm or more and 10 μm or less, a contact type thickness meter [Product name of Marh Co .: Millimar 1240 compact amplifier with Millimal inductive probe 1301 attached] is used. Measured. On the other hand, the film thickness of more than 10 μm to 110 μm or less was measured by using a micrometer [Product name: coolant proof micrometer, MDC-25PJ manufactured by Mitutoyo Corporation].

  At the time of measurement, the thickness at a predetermined position where the extrusion direction of the film and the width direction (direction perpendicular to the extrusion direction) intersect was measured at 20 points, and the average value was taken as the film thickness. The measurement points in the extrusion direction were 100 mm, 200 mm, 300 mm, and 400 mm from the tip of the film. On the other hand, the measurement points in the width direction were 50 mm from the left end of the film, and were 100 mm, 150 mm, 200 mm, and 250 mm at 50 mm intervals.

・ Film thickness tolerance of film The film thickness tolerance was calculated from the following formula.
Film thickness tolerance [%] = {(MAX or MIN) − (AVE)} / (AVE) × 100
Where MAX: maximum film thickness
MIN: Minimum film thickness
AVE: Average value of film thickness The obtained film thickness tolerance was A within the range of ± 5%, B within ± 5-10%, and NG within the range of ± 10%.

-Tensile elastic modulus of the film at 23 ° C The tensile elastic modulus of the film at 23 ° C was measured in the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) of the film. JIS K7160 3 type was used for the test piece for measurement. The tensile elastic modulus was measured according to JIS K7127 under the conditions of a tensile speed of 50 mm / min and a temperature of 23 ° C.

-Glass transition point of the film The glass transition point of the film is determined by using a differential scanning calorimeter [manufactured by SII Nano Technology Co., Ltd .: product name High-sensitivity differential scanning calorimeter X-DSC7000] according to JIS K7121. It was determined from the differential scanning calorimetry curve when the temperature was raised at 10 ° C / min.

-Tensile elastic modulus of the film at 150 ° C The tensile elastic modulus of the film at 150 ° C was measured in the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) of the film. JIS K7160 3 type was used for the test piece for measurement. Specifically, a test piece was cut out from the film into JIS K7160 3 type, and the test piece was attached to a tensile tester equipped with a constant temperature bath heated at 150 ° C. in advance and measured at a pulling speed of 50 mm / min in accordance with JIS K7127. . The measurement was performed after the test piece was attached to the knob of the tensile tester in the thermostatic chamber, the door of the thermostatic chamber was closed, the temperature of the thermostatic chamber reached 150 ± 2 ° C., and then left for 3 minutes.

-Specific Density of Film Regarding the specific gravity of the film at 23 ° C, it was measured at a temperature of 23 ° C in accordance with the measuring method of JIS K7112 (method A).
-Film loss tangent The film loss tangent was measured in the film extrusion direction and the width direction (direction perpendicular to the extrusion direction). Specifically, when measuring the loss tangent in the extrusion direction of the film, it is cut into a size of 60 mm in the extrusion direction x 6 mm in the width direction, and in measuring 6 mm in the extrusion direction x 60 mm in the width when measuring the loss tangent in the width direction. Measured.

  When measuring the loss tangent, a tension mode using a viscoelasticity spectrometer (TS Instruments Japan Co., Ltd. product name: RSA-G2) was used to measure a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 3 C./min., Measurement temperature range −60 to 380.degree. C., and a check interval of 21 mm, and the loss tangent at 20.degree.

[Example 2]
In the case of Example 1, the molding material was continuously extruded from the T-die of a single-screw extruder to extrude a film made of a polyetherketoneketone resin having a thickness of 100 μm, but in the case of Example 2, A film having a thickness of 25.3 μm was extruded. Other parts were the same as in Example 1.
When a film was obtained, the film thickness, film thickness tolerance, mechanical properties, heat resistance properties, and acoustic properties of this film were evaluated by the same methods as in Example 1, and the results are shown in Table 1.

[Example 3]
In the case of Example 1, the molding material was continuously extruded from the T-die of a single-screw extruder to extrude a film having a thickness of 100 μm, but in the case of Example 3, a film having a thickness of 12.5 μm was extruded. The film was extruded. Other parts were the same as in Example 1.
When a film was obtained, the film thickness, film thickness tolerance, mechanical properties, heat resistance properties, and acoustic properties of this film were evaluated by the same methods as in Example 1, and the results are shown in Table 1.

[Example 4]
In the case of Example 1, the molding material was continuously extruded from the T-die of a single-screw extruder to extrude a film made of a polyetherketoneketone resin having a thickness of 100 μm, but in the case of Example 4, A film having a thickness of 5.8 μm was extruded. Other parts were the same as in Example 1.
When a film was obtained, the film thickness, film thickness tolerance, mechanical properties, heat resistance properties, and acoustic properties of this film were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Example 5]
First, a commercially available polyetherketoneketone resin [Product name: KEPSTAN 7002 manufactured by Arkema Ltd.] was dried at 150 ° C. for 12 hours by the same heating dryer as in Example 1, and the moisture content of the dried molding material was 300 ppm or less. After confirming the existence, a strip-shaped polyetherketoneketone resin film was extrusion-molded from this dried polyetherketoneketone resin by using the same single-screw extruder and T-die as in Example 1. .

  At this time, the water content of the polyetherketoneketone resin was measured by the same method as in Example 1. Further, when the polyetherketoneketone resin was charged into the single-screw extruder, nitrogen gas of 18 L / min was supplied. The temperature of the single screw extruder was adjusted to 360 to 380 ° C, the temperature of the T die was adjusted to 380 ° C, and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 380 ° C. Regarding the temperature of the melted polyetherketoneketone resin, the resin temperature at the inlet of the T-die was measured, and it was 377 ° C. when measured.

  After extrusion molding a film made of polyetherketoneketone resin, both sides of this film made of polyetherketoneketone resin are cut with slit blades and sequentially wound on a winding tube of a winder, length 50 m, width 300 mm A film for a diaphragm made of polyetherketoneketone resin was manufactured. At this time, the film made of polyetherketoneketone resin is composed of a pair of pressure-bonding rolls made of silicone rubber, a metal roll which is a cooling roll at 160 ° C. having unevenness on the peripheral surface, and a 3-inch winding located downstream thereof. It was sequentially wound around a pipe and held between a pressure roll and a metal roll.

  When a film was obtained, the film thickness, film thickness tolerance, mechanical properties, heat resistance properties, and acoustic properties of this film were evaluated by the same methods as in Example 1, and the results are shown in Table 2.

[Example 6]
First, a commercially available polyetherketoneketone resin [Product name: KEPSTAN 6002 manufactured by Arkema Co., Ltd.] was dried at 130 ° C. for 12 hours by the same heating dryer as in Example 1, and the moisture content of the dried molding material was 300 ppm or less. After confirming the existence, a strip-shaped polyetherketoneketone resin film was extruded from the dried polyetherketoneketone resin by using the same single-screw extruder and T-die as in Example 1. did.

  At this time, the water content of the polyetherketoneketone resin was measured by the same method as in Example 1. Further, when the polyetherketoneketone resin was charged into the single-screw extruder, nitrogen gas of 18 L / min was supplied. The temperature of the single-screw extruder was adjusted to 330 to 370 ° C., the temperature of the T-die was 370 ° C., and the temperature of the connecting pipe connecting the single-screw extruder and the T-die was adjusted to 370 ° C., respectively. Regarding the temperature of the molten polyetherketoneketone resin, the resin temperature at the inlet of the T-die was measured, and it was 367 ° C. when measured.

  After extrusion molding a film made of polyetherketoneketone resin, both sides of this film made of polyetherketoneketone resin are cut with slit blades and sequentially wound on a winding tube of a winder, length 50 m, width 300 mm A film for a diaphragm made of polyetherketoneketone resin was manufactured. At this time, the film made of polyetherketoneketone resin is composed of a pair of pressure-bonding rolls made of silicone rubber, a metal roll which is a cooling roll at 130 ° C. having unevenness on the peripheral surface, and a 3-inch winding located downstream thereof. It was sequentially wound around a pipe and held between a pressure roll and a metal roll.

  Once the film was obtained, the film thickness, film thickness tolerance, mechanical properties, heat resistance properties, and acoustic properties of this film were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Comparative Example 1]
First, a commercially available polyetheretherketone resin [Product name: KetaSpire PEEK KT-851NL SP (hereinafter abbreviated as "KT-851NL SP") manufactured by Solvay Specialty Polymers, Inc.) was dried by the same heat dryer as in Example 1. After drying at 160 ° C. for 12 hours and confirming that the moisture content of the dried molding material is 300 ppm or less, this dried polyether ether ketone resin was subjected to the same single-screw extruder and T-die as in Example 1. By using, a strip-shaped film made of polyetheretherketone resin was extruded.

  The single-screw extruder was L / D = 32, compression ratio: 2.5, screw: full flight screw type. The temperature of the single screw extruder was adjusted to 380 to 400 ° C., the temperature of the T die was adjusted to 400 ° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 400 ° C., respectively. The water content of the polyether ether ketone resin was measured by the same method as in Example 1. Regarding the temperature of the melted polyether ether ketone resin, the resin temperature at the inlet of the T die was measured, and it was 395 ° C. when measured.

  After extrusion molding a film of polyetheretherketone resin, cut both sides of the continuous film with slit blades and wind the film sequentially on the winding tube of the winder. Made of polyetheretherketone resin with a length of 50 m and a width of 300 mm. The film for diaphragm of was manufactured. At this time, the film was sequentially wound around a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 200 ° C. having irregularities on its peripheral surface, and a 3-inch winding tube located downstream thereof. , And sandwiched between the pressure roll and the metal roll.

  When a film made of a polyetheretherketone resin, which is a film for a diaphragm, is obtained, the film thickness, film thickness tolerance, heat resistance property, and acoustic property of the film made of this polyetheretherketone resin are measured in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 2]
By changing the polyetheretherketone resin used in Comparative Example 1 to Bestakeep 3300G (product name manufactured by Daicel-Evonik) and using the same single-screw extruder and T-die as in Example 1, a strip shape was obtained. A film made of polyetheretherketone resin was extruded.

The temperatures of the single-screw extruder, the T-die, and the connecting pipe connecting the single-screw extruder and the T-die were the same as in Comparative Example 1. Regarding the temperature of the melted polyether ether ketone resin, the resin temperature at the inlet of the T die was measured, and it was 397 ° C. when measured. The temperature of the metal roll, which is a cooling roll, was 200 ° C., which was the same as in Comparative Example 1.
When a film made of polyetheretherketone resin, which is a film for a diaphragm, was obtained, the film thickness, film thickness tolerance, heat resistance characteristics, and acoustic characteristics of this polyetheretherketone resin film were measured by the same method as in Example 1. Evaluation was made, and the results are shown in Table 3.

[Comparative Example 3]
By changing the polyetheretherketone resin used in Comparative Example 1 to Victrex Peak 381G (manufactured by Victrex, product name) and using the same single-screw extruder and T-die as in Example 1, A film of polyetheretherketone resin in the shape of was extruded.

The temperatures of the single-screw extruder, the T-die, and the connecting pipe connecting the single-screw extruder and the T-die were the same as in Comparative Example 1. Regarding the temperature of the melted polyether ether ketone resin, the resin temperature at the inlet of the T die was measured, and it was 396 ° C. when measured. The temperature of the metal roll, which is a cooling roll, was changed to 130 ° C.
When a film made of polyetheretherketone resin, which is a diaphragm film, was obtained, the film thickness, the film thickness tolerance, the heat resistance property, and the acoustic property of this film were evaluated in the same manner as in Example 1, and the results are shown in a table. It was described in 3.

[Evaluation]
Film made polyetherketoneketone resin in each example, the glass transition point of 160 ° C. or more, a tensile elastic modulus at 0.99 ° C. is 2000N / mm ² or more 4000 N / mm ² or less, a specific gravity of 1.2 or more 1. 3 below, the tensile modulus at 23 ° C. is 2000N / mm ² or more 4000 N / mm ² or less, a loss tangent at 20 ° C. was 0.010 or more. Therefore, the films made of the polyetherketoneketone resin in each of the examples had high heat resistance, and thus were excellent in durability and also had excellent acoustic characteristics. Further, the film thickness tolerance was within ± 10%, and no problem was found in film moldability.

In contrast, films made of polyether ether ketone resin in Comparative Example has a specific gravity of 1.2 to 1.3, a tensile modulus at 23 ° C. is 2000N / mm ² or more 4000 N / mm ² or less, loss at 20 ° C. The tangent was 0.010 or more and the film thickness tolerance was within ± 10%, and no problems were found in acoustic characteristics and film moldability.
However, since the glass transition point was less than 150 ° C. and the tensile elastic modulus at 150 ° C. was less than 2000 N / mm ² , the heat resistance was low, and there was a problem in durability when used for a diaphragm.

  The diaphragm film for a speaker according to the present invention is used in the field of manufacturing a speaker incorporated in a mobile device or the like.

1 Molding Material 2 Film 3 Laminated Intermediate 4 Elastomer Layer 5 Primer 10 Melt Extrusion Machine (Extrusion Machine)
12 Inert gas supply pipe 13 T die 17 Crimping roll 18 Cooling roll 19 Winding machine 20 Winding pipe

Claims (4)

The tensile elastic modulus at 23 ° C. of polyether ketone ketone resin film with a 2000N / mm ² or more 4000 N / mm ² or less, a tensile modulus at 0.99 ° C. polyether ketone ketone resin film 2000N / mm ² or more 4000 N / mm ^A film for a diaphragm of a speaker, which is characterized in that the number is ² or less.   2. The speaker diaphragm film according to claim 1, wherein the specific gravity of the polyetherketoneketone resin film is 1.2 or more and 1.4 or less, and the loss tangent at 20 ° C. of the polyetherketoneketone resin film is 0.010 or more.   The speaker diaphragm film according to claim 1, which is laminated and adhered to an elastomer layer having a thickness of 10 μm or more and 100 μm or less.   The film for a diaphragm of a speaker according to claim 3, wherein the elastomer layer is made of a silicone resin and has a durometer hardness of A10 or more and A90 or less when measured with a durometer type A according to JIS K 6253.

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