JP2021190753A - Resin film for speaker diaphragm and manufacturing method thereof, and speaker diaphragm - Google Patents

Abstract

To provide a resin film for a speaker diaphragm and a manufacturing method thereof, and a speaker diaphragm which can obtain excellent heat resistance and sound quality characteristics and prevent a speaker manufacturing process from becoming complicated.SOLUTION: A pair of diaphragm resin films 2 sandwich an elastomer layer 31 to form a diaphragm 30 of a speaker. The diaphragm resin film 2 is molded from a molding material containing 100 parts by mass of a polyarylene ether ketone resin and 1 part by mass or more and 100 parts by mass or less of an adhesive fluororesin, and contains the polyarylene ether ketone resin, and thus has toughness, excellent heat resistance, solvent resistance, etc. Further, since the adhesive fluororesin having excellent compatibility with the polyarylene ether ketone resin is used, the diaphragm resin film 2 can be smoothly manufactured by a melt extrusion molding method. In addition, in addition to the bass characteristics, the loss tangent is increased, and excellent sound quality characteristics in which the occurrence of resonance is suppressed can be obtained.SELECTED DRAWING: Figure 3

Description

The present invention relates to a resin film for a diaphragm of a speaker having excellent bass reproduction characteristics, heat resistance, etc., a method for manufacturing the same, and a diaphragm of the speaker.

A mobile device consisting of a mobile phone, a mobile game device, a smartphone, or the like has a built-in small speaker called a micro speaker. The 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 fabric, and (3) synthetic resin film. It becomes an important part that affects the sound quality.

When the vibrating plate is a film made of the synthetic resin of (3) instead of (1) and (2), a polyolefin resin such as polyethylene (PE) resin and polypropylene (PP) resin, polyethylene terephthalate (PET) has been used so far. A film made of a resin, a polyester resin such as polyethylene naphthalate (PEN) resin, polyphenylene sulfide (PPS), polyetherimide (PEI) resin, or the like is used (see Patent Documents 1 and 2).

By the way, speakers in recent years have been improved in functionality and performance. Therefore, the required characteristics for the diaphragm of the speaker are becoming more and more strict. The required characteristics of this diaphragm are light weight (small density or specific gravity), moderate rigidity (Young's modulus, elastic modulus), excellent thickness accuracy, and large elongation at break. , Excellent durability. In addition to these characteristics, it is also excellent in heat resistance, moisture resistance, water resistance, and moldability (press molding, vacuum forming, compressed air forming, etc.).

However, when the diaphragm of the speaker is the metal leaf of (1), although it is excellent in heat resistance, moisture resistance, and water resistance, it has a high density and rigidity, so that the minimum resonance frequency (f ₀ ) is high and the bass reproduction characteristic is high. It will be insufficient. Further, when the diaphragm of the speaker is the paper, woven cloth, or non-woven fabric made of natural resin of (2), the density is small and the weight is light, but there are problems in heat resistance, moisture resistance, and water resistance, and the speaker manufacturing process. Also becomes complicated.

Further, when the diaphragm of the speaker is a film made of the synthetic resin of (3), specifically, when the film is made of a polyolefin resin, it is lightweight, has a large loss rigidity, and is excellent in moisture resistance, water resistance, and moldability. , Poor rigidity and problem with heat resistance. Further, when the diaphragm of the speaker is a film made of polyethylene terephthalate resin, the heat resistance is better than that of the film made of a polyolefin resin, but the loss tangent is small and the sound quality is insufficient. Further, since it is deformed at a temperature of about 70 ° C., it cannot be said that the heat resistance is sufficient.

In addition, when the diaphragm of the speaker is a film made of polyethylene naphthalate resin, the loss tangent and strength are large, the durability is excellent, and the sound quality characteristics are also excellent. , Need to be oriented. However, when the film is highly biaxially stretched and oriented, the rigidity (elastic modulus) of the film becomes high, so that the minimum resonance frequency (f ₀ ) becomes high and the bass reproduction characteristic becomes insufficient. In addition, formability such as press forming, vacuum forming, and compressed air forming may be deteriorated.

Further, when the diaphragm of the speaker is a film made of polyphenyl sulfide resin, excellent heat resistance can be obtained if the diaphragm is highly biaxially stretched and oriented. However, if the alignment is highly biaxially stretched, the minimum resonance frequency (f ₀ ) becomes high, the bass reproduction characteristics become insufficient, and the formability of press forming, vacuum forming, pressure forming, etc. may deteriorate. .. In addition, the loss tangent is small, which causes a problem in sound quality.

In view of the above, a film made of polyetherimide (PEI) resin or a film made of polyetheretherketone (PEEK) resin has been proposed and used as a film for a vibrating plate (see Patent Documents 2, 3 and 4). ..

The polyetherimide resin has a lower density and is lighter than the polyethylene terephthalate resin, the polyethylene naphthalate resin, and the polyphenylene sulfide resin. Further, since the polyetherimide resin is an amorphous resin, when molding the film, the vibration plate is molded as compared with a film made of a crystalline resin such as polyethylene terephthalate resin, polyethylene naphthalate resin, or polyphenylene sulfide resin. Excellent properties (vibration plate molding: press molding, pneumatic molding, vacuum molding, etc.). Furthermore, since the polyetherimide resin film has a high loss tangent and excellent sound quality characteristics, it can be used as a speaker for various small electronic devices such as mobile phones, smartphones, portable music devices, portable game machines, and tablet personal computers. It is used for the diaphragm of in-vehicle speakers.

Japanese Unexamined Patent Publication No. 62-263797 Japanese Unexamined Patent Publication No. 60-139098 Japanese Unexamined Patent Publication No. 58-22629 Japanese Unexamined Patent Publication No. 2007-43597

However, it has been reported that the heat resistant temperature of a diaphragm made of a film made of a polyetherimide resin is 150 ° C. or lower (Patent Document 3). Therefore, a film made of a polyetherimide resin cannot obtain sufficient heat resistance. Further, since the elongation at tensile break is small, there is a problem that the film is torn when the external output is increased.

On the other hand, it has been reported that the heat-resistant temperature of the vibrating plate obtained from the film made of polyetheretherketone resin is about 200 to about 300 ° C., and the mechanical properties and heat resistance are higher than those of the polyetherimide resin. Excellent in terms of points. However, the elastic modulus (tensile elastic modulus) of the polyetheretherketone resin film is very large and exceeds ^{2800 N / mm 2.} Therefore, the diaphragm obtained from this film _{has a high minimum resonance frequency (f 0} ), and bass reproduction is insufficient.

The present invention has been made in view of the above, and a resin film for a diaphragm of a speaker and a method for manufacturing the same, which can obtain excellent heat resistance and sound quality characteristics and can prevent the manufacturing process of the speaker from becoming complicated. It is also intended to provide a diaphragm for a speaker.

As a result of diligent research in order to solve the above problems, the present inventors have focused on the combination of the polyarylene ether ketone resin and the adhesive fluororesin, and completed the present invention.

That is, in order to solve the above problems, the present invention is characterized in that it is molded by a molding material containing 100 parts by mass of a polyarylene ether ketone resin and 1 part by mass or more and 100 parts by mass or less of an adhesive fluororesin. ..

The tensile elastic modulus at 23 ° C. is not more than 100 N / mm ² or more 2500N / mm ^2, preferably has an elongation at break Tensile at 23 ° C. is 50% or more.
Further, it is preferable that the loss tangent at 20 ° C. is 0.010 or more, and the first inflection temperature of the storage elastic modulus after cooling is 130 ° C. or higher.

Further, in the present invention, in order to solve the above problems, the method for manufacturing a resin film for a diaphragm of a speaker according to claim 1, 2 or 3.
A molding material is prepared by melt-kneading 100 parts by mass of a polyarylene ether ketone resin and 1 part by mass or more and 100 parts by mass or less of an adhesive fluororesin, and this molding material is put into an extrusion molding machine and used for a vibrating plate by a die. It is characterized in that it is extruded into a resin film and the resin film for a vibrating plate is brought into contact with a cooling roll to be cooled.

Further, in order to solve the above problems, the present invention is characterized in that the resin film for a diaphragm of a speaker according to claim 1, 2 or 3 and an elastomer layer having a thickness of 10 μm or more and 100 μm or less are laminated. It is supposed to be.

The elastomer layer is a silicone resin, and the durometer hardness of the silicone resin is preferably A10 or more and A90 or less when measured with a durometer type A in accordance with JIS K 6253.
Further, it is preferable that a primer layer is interposed between the silicone resin and the resin film for the diaphragm.

Here, the resin film for a vibrating plate within the scope of the patent claim is not particularly limited to transparent, opaque, translucent, non-stretched resin film, uniaxially stretched resin film, and biaxially stretched resin film. This resin film for a diaphragm can be laminated on one side or both sides of an elastomer layer. If necessary, any of the antistatic agent layer, the elastomer layer, and the metal layer can be laminated and provided on the resin film for the diaphragm. Further, 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 notebook computer, and the like.

According to the present invention, since the molding material contains a polyarylene ether ketone resin, a resin film for a diaphragm having excellent toughness, heat resistance, solvent resistance and the like can be obtained. Further, since the molding material is prepared from the polyarylene ether ketone resin and the adhesive fluororesin, in addition to the bass characteristics, the loss tangent is increased, the occurrence of resonance is suppressed, and excellent sound quality characteristics can be obtained.

According to the present invention, it is possible to obtain excellent heat resistance and sound quality characteristics, and it is possible to prevent the manufacturing process of the speaker from becoming complicated.

According to the second aspect of the present invention, since the tensile modulus at 23 ° C. of the resin film diaphragm is 100 N / mm ² or more 2500N / mm ^2, such hereinafter, handling property is lowered during processing of the speaker, the treble reproduction It is possible to prevent it from becoming insufficient, and moreover, it is possible to satisfy the bass reproduction. Further, since the elongation at the time of tensile break of the resin film for the diaphragm is 50% or more at 23 ° C., there is little possibility that troubles such as breakage and cracking occur during the processing of the resin film for the diaphragm, and the production becomes easy. In addition, it is possible to prevent the durability of the diaphragm of the resin film for the diaphragm from being lowered.

According to the third aspect of the present invention, since the loss tangent of the resin film for a diaphragm at 20 ° C. is 0.010 or more, it is possible to prevent poor sound quality due to the occurrence of resonance. Further, since the first turning point temperature of the storage elastic coefficient after cooling of the diaphragm resin film is 130 ° C. or higher, sufficient heat resistance can be obtained, and the diaphragm obtained from the diaphragm resin film can be used as a speaker. When used, it is possible to prevent deterioration of durability such as deformation, cracking, or breakage of the diaphragm obtained from the resin film for the diaphragm due to high heat caused by high vibration of the voice coil.

According to the fourth aspect of the present invention, since the melt extrusion molding method is adopted for producing the resin fill for the diaphragm, it is possible to improve the handling property of the resin film for the diaphragm and to simplify the equipment.

According to the invention of claim 5, since a resin film obtained by adding an adhesive fluororesin to a polyarylene ether ketone resin having an appropriate tensile elastic modulus is used, a diaphragm of a high-performance speaker excellent in bass reproduction and treble reproduction. Can be obtained. Further, the resin film for a diaphragm in which an adhesive fluororesin is added to a polyarylene ether ketone resin can realize a diaphragm for a speaker having a small specific gravity, a light weight, and excellent heat resistance. Further, it is possible to prevent the compression permanent strain characteristic of the elastomer layer from deteriorating and the vibration propagation speed of the diaphragm of the speaker from being lowered to cause a problem in sound quality.

According to the invention of claim 6, it is possible to suppress deterioration of the compression set of the silicone resin of the elastomer layer and the decrease of the vibration propagation speed of the diaphragm of the speaker. In addition, it is possible to prevent the loss tangent from becoming smaller and the performance of the diaphragm from deteriorating.
According to the invention of claim 7, the resin film for the vibrating plate and the silicone resin of the elastomer layer can be firmly adhered to each other, and the peeling of the resin film for the vibrating plate and the silicone resin can be prevented.

It is an overall explanatory drawing which shows typically the embodiment of the resin film for the diaphragm of the speaker which concerns on this invention, and the manufacturing method thereof. It is a graph which shows typically the relationship between the first inflection point temperature and the storage elastic modulus in the Example of the manufacturing method of the resin film for the diaphragm of the speaker which concerns on this invention. It is explanatory drawing which shows typically the 2nd Embodiment of the resin film for the diaphragm of the speaker and the diaphragm of a speaker which concerns on this invention.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, the resin film 2 for a speaker diaphragm in the present embodiment includes a polyarylene ether ketone resin and an adhesive fluororesin. It is a resin film molded by the molding material 1 containing the above, and a plurality of sheets are combined with an elastomer layer to form a speaker vibrating plate called a micro speaker of a portable device.

The molding material 1 is prepared by containing 100 parts by mass of a polyarylene ether ketone resin and 1 part by mass or more and 100 parts by mass or less of an adhesive fluororesin. The molding material 1 includes a polyarylene ether ketone resin, an adhesive fluororesin, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a flame retardant, and a charge, as long as the characteristics of the present invention are not impaired. Inhibitors, heat improvers, inorganic compounds, organic compounds, resin modifiers and the like are selectively added.

The polyarylene ether ketone resin of the molding material 1 is a crystalline resin composed of an arylene group, an ether group, and a carbonyl group. Examples include the resins described in Super Engineering Plastics / PEEK (above), which grow in advanced applications, and are excellent in mechanical properties, heat resistance, water resistance, and the like.

Specific examples of the polyarylene ether ketone resin include a polyether ether ketone (PEEK) resin having a chemical structural formula represented by the chemical formula (1) and a polyether ketone having a chemical structure represented by the chemical formula (2) (2). PEK) resin, polyether ketone ketone (PEKK) resin having a chemical structure represented by the chemical formula (3), polyether ether ketone ketone (PEEKK) resin having the chemical structure of the chemical formula (4), or the chemical formula (5). Examples thereof include polyether ketones having a chemical structure and ether ketone ketone (PEKEKK) resins.

Among these polyetheretherketone resins, the polyetheretherketone resin and the polyetherketoneketone resin are preferable from the viewpoints of availability, cost, and moldability of the resin film. Specific examples of the polyetheretherketone resin include Victrex Powder series, Victrex Granules series, Daicel Evonik product name: Vestakeep series, and Solvay Specialty Polymers product name: Ketaspire. The PEEK series can be mentioned. Further, as a specific example of the polyetherketoneketone resin, the product name: KEPSTAN series manufactured by Arkema Co., Ltd. corresponds.

The polyarylene ether ketone resin may be used alone or in combination of two or more. Further, the polyarylene ether ketone resin may be a copolymer having two or more chemical structures represented by the chemical formulas (1) to (5). The polyarylene ether ketone resin is usually used in a form suitable for molding such as powder, granule, and pellet. The method for producing the polyarylene ether ketone resin is not particularly limited, but for example, the production method described in the literature [Asahi Research Center Co., Ltd .: Super engineering plastic PEEK (above) that grows for advanced applications] is used. can give.

The adhesive fluororesin has a repeating unit (a) based on tetrafluoroethylene (hereinafter referred to as TFE) and / or chlorotrifluoroethylene (hereinafter referred to as CTFE), a dicarboxylic acid anhydride group, and has an inner ring. Repeating unit (b) based on a cyclic hydrocarbon monomer having a polymerizable unsaturated group, and repeating based on other monomers (however, if it overlaps with the repeating units (a) and (b), the monomer is excluded). Contains the unit (c).

In the adhesive fluororesin, the repeating unit (a) is 50 to 99.89 mol% and the repeating unit (b) is 50 to 99.89 mol% with respect to the total molar amount of the repeating unit (a), the repeating unit (b), and the repeating unit (c). ) Is 0.01 to 5 mol%, and the repeating unit (c) is 0.1 to 49.99 mol%. The repeating unit (a) is preferably 50 to 99.47 mol%, the repeating unit (b) is 0.03 to 3 mol%, and the repeating unit (c) is 0.5 to 49.97 mol%, more preferably. The repeating unit (a) is 50 to 98.95 mol%, the repeating unit (b) is 0.05 to 2 mol%, and the repeating unit (c) is 1 to 49.95 mol%.

This is because the heat resistance and chemical resistance of the adhesive fluororesin are improved if the molar% of the repeating unit (a), the repeating unit (b), and the repeating unit (c) is within the relevant range. Further, if the molar% of the repeating unit (b) is within the relevant range, the adhesive fluororesin is excellent in adhesiveness to the crystalline polyarylene ether ketone resin. Further, if the molar% of the repeating unit unit (c) is within the relevant range, the adhesive fluororesin is excellent in mechanical properties such as moldability and stress crack resistance.

The above-mentioned "cyclic hydrocarbon monomer having a dicarboxylic acid anhydride group and having a polymerizable unsaturated group in the ring" (hereinafter, simply abbreviated as cyclic hydrocarbon monomer) has one or more 5-membered rings or 6 A cyclic hydrocarbon composed of a member ring, and a polymerizable compound having a dicarboxylic acid anhydride group and an intracyclically polymerizable unsaturated group.

As the cyclic hydrocarbon, a cyclic hydrocarbon having one or more bridged polycyclic hydrocarbons is preferable. That is, a cyclic hydrocarbon composed of Aribashi polycyclic hydrocarbons, a cyclic hydrocarbon obtained by condensing two or more of Aribashi polycyclic hydrocarbons, or a cyclic hydrocarbon obtained by condensing Aribashi polycyclic hydrocarbons with other cyclic hydrocarbons. It is preferable to have. Further, the cyclic hydrocarbon monomer has one or more polymerizable unsaturated groups in the ring, that is, one or more polymerizable unsaturated groups existing between the carbon atoms constituting the hydrocarbon ring. This cyclic hydrocarbon monomer further has a dicarboxylic acid anhydride group (-CO-O-CO-), and the dicarboxylic acid anhydride group may be bonded to two carbon atoms constituting the hydrocarbon ring, and the ring may be bonded. It may be bonded to two outer carbon atoms.

Preferably, the dicarboxylic acid anhydride group is a carbon atom constituting the ring of the cyclic hydrocarbon and is bonded to two adjacent carbon atoms. Further, a halogen atom, an alkyl group, an alkyl halide group, or another substituent may be bonded to the carbon atom constituting the ring of the cyclic hydrocarbon instead of the hydrogen atom. Specific examples include those represented by the following equations (6) to (13). Here, R in the formulas (7) and (10) to (13) is a halogen atom selected from a lower alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated alkyl group in which the hydrogen atom in the lower alkyl group is substituted with a halogen atom is shown.

The cyclic hydrocarbon monomer is preferably represented by the formula (6), 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as NAH), the formulas (8) and (9). Cyclic hydrocarbon monomers which are acid anhydrides, and cyclic hydrocarbon monomers whose substituent R is a methyl group in the formulas (7) and (10) to (13) can be mentioned. More preferably, NAH is good.

Examples of other monomers include vinyl fluoride, vinylidene fluoride (hereinafter referred to as VdF), CTFE (excluding the case where it is used as a repeating unit (a)), trifluoroethylene, and hexafluoropropylene (hereinafter referred to as HFP). ), CF ₂ = CFOR ^{f 1} (where R ^{f 1} is a perfluoroalkyl group having 1 to 10 carbon atoms and may contain oxygen atoms between carbon atoms), CF ₂ = CFOR ^{f 2} SO ₂ X ¹ (R ^{f). 2} is a perfluoroalkylene group having 1 to 10 carbon atoms and may contain an oxygen atom between carbon atoms, X ¹ is a halogen atom or a hydroxyl group), CF ₂ = CFOR ^{f 2} CO ₂ X ² (where R ^{f 2} is the above. Same as, X ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (where p is 1 or 2), CH ₂ = CX ³ (CF) ₂ ) _q X ⁴ (where X ³ and X ⁴ are hydrogen atoms or fluorine atoms independently of each other, q is an integer of 2 to 10), perfluoro (2-methylene-4-methyl-1,3-dioxolane). ), An olefin having 2 to 4 carbon atoms such as ethylene, propylene and isobutene, a vinyl ester such as vinyl acetate, a vinyl ether such as ethyl vinyl ether and a cyclohexyl vinyl ether, and the like. The other monomers may be used alone or in combination of two or more.

Specific examples of the CF ₂ = CFOR ^{f 1,} for example, _{CF 2 = CFOCF 2 CF 3,} CF 2 = CFOCF 2 CF 2 CF 3, CF 2 = CFOCF 2 CF 2 CF 2 CF 3, CF 2 = CFO (CF 2 ) ₈ F etc. can be mentioned. Preferably, CF ₂ = CFOCF ₂ CF ₂ CF ₃ . Specific examples of CH ₂ = CX ₃ (CF ₂ ) _q X ⁴ _{include CH 2} = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, and CH ₂ = CH (CF _2). ) ₄ F, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H and the like. Preferably, CH ₂ = CH (CF ₂ ) ₄ F or CH ₂ = CH (CF ₂ ) ₂ F.

Other monomers are preferably VdF, HFP, CTFE (except when used as a repeating unit (a)), CF ₂ = CFOR ^{f 1} , CH ₂ = CX ₃ (CF ₂ ) _q X ⁴ , One or more selected from the group consisting of ethylene, propylene, and vinyl acetate, more preferably HFP, CTFE (except when used as the repeating unit (a)), CF ₂ = CFOR ^{f 1} , ,. Ethylene and CH ₂ = one or more selected from the group consisting of ^{CX 3} (CF ₂ ) _q X ^4. Most preferably, HFP or CF ₂ = CFOR ^{f 1} . Further, as CF ₂ = CFOR ^{f 1} , ^{a perfluoroalkyl group having R f 1} having 1 to 6 carbon atoms is preferable, a perfluoroalkyl group having 2 to 4 carbon atoms is more preferable, and a perfluoropropyl group is most suitable.

Specific examples of the adhesive fluororesin include, for example, TFE / CF ₂ = CFOCF ₂ CF ₂ CF ₃ / NAH copolymer, TFE / HFP / NAH copolymer, TFE / CF ₂ = CFOCF ₂ CF ₂ CF ₃ /. HFP / NAH copolymer, TFE / VdF / NAH copolymer, TFE / CH ₂ = CH (CF ₂ ) ₄ F / NAH / ethylene copolymer, TFE / CH ₂ = CH (CF ₂ ) ₂ F / NAH / Ethylene copolymer, CTFE / CH ₂ = CH (CF ₂ ) ₄ F / NAH / ethylene copolymer, CTFE / CH ₂ = CH (CF ₂ ) ₂ F / NAH / ethylene copolymer, CTFE / CH ₂ = CH (CF ₂ ) ₂ F / NAH / ethylene copolymer and the like can be mentioned.

The melting point of the adhesive fluororesin is preferably 150 ° C. or higher and 330 ° C. or lower, and more preferably 200 ° C. or higher and 320 ° C. or lower. This melting point can be adjusted by appropriately selecting the content ratio of the repeating unit (a), the repeating unit (b), and the repeating unit (c) within the above range.
If the polymer terminal group of the adhesive fluororesin has an adhesive functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonylfluoride group, or an acid anhydride residue, crystals other than the adhesive fluororesin It is preferable because it has excellent adhesion to a thermoplastic polyimide resin. Further, the polymer terminal group having an adhesive functional group can be introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, or the like at the time of producing the adhesive fluororesin.

The method for producing the adhesive fluororesin is not particularly limited, but a radical polymerization method using a radical polymerization initiator is used. As this polymerization method, bulk polymerization, solution polymerization using an organic solvent such as fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated hydrocarbon, alcohol, hydrocarbon, aqueous medium, and an appropriate organic solvent as necessary are used. Suspension polymerization used, aqueous medium, and emulsion polymerization using emulsifiers can be mentioned, with solution polymerization being particularly preferred.

The adhesive fluororesin is not particularly limited, but preferably the adhesive fluororesin described in Japanese Patent No. 4424246, Japanese Patent No. 5263269, Japanese Patent No. 5365939, or Japanese Patent Application Laid-Open No. 2019-43134. can give. Specific examples of this adhesive fluororesin include LH-8000 [AGC: product name], AH-5000 [AGC: product name], AH-2000 [AGC: product name] EA-2000, and the like. [Manufactured by AGC: product name] can be mentioned. Among these adhesive fluororesins, EA-2000, which has excellent heat resistance, is suitable.

The amount of the adhesive fluororesin added is 1 part by mass or more and 100 parts by mass or less, preferably 10 parts by mass or less and 90 parts by mass or less, and more preferably 15 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the polyarylene ether ketone resin. More preferably, it is 20 parts by mass or more and 60 parts by mass or less. This is because when the amount added is less than 1 part by mass, a decrease in the tensile elasticity of the resin film 2 for the diaphragm cannot be expected, and conversely, when the amount added exceeds 100 parts by mass, the polyarylene ether ketone Since the dispersibility between the resin and the adhesive fluororesin is lowered and the elongation at the time of tensile break of the resin film 2 for the diaphragm is lowered, the handleability during processing of the portable device speaker is lowered, or the resin film 2 for the diaphragm is lowered. This is based on the reason that the durability of the diaphragm is reduced and the diaphragm is torn or cracked when the external output is increased.

From the above, if the amount of the adhesive fluororesin added is within the range of 1 part by mass or more and 100 parts by mass or less, the minimum resonance frequency (f ₀ ) is lowered and the bass reproduction characteristics are excellent, and the handling property and durability are further improved. A resin film 2 for a diaphragm of a speaker capable of preventing deterioration can be obtained.

In addition to the above resins, the molding material 1 includes polyimide resins other than the above, such as polyimide (PI) resin, polyamideimide (PAI) resin, polyetherimide (PEI) resin, polyamide 4T (PA4T) resin, and polyamide 6T (PA6T). ) Resin, modified polyamide 6T (PA6T) resin, polyamide 9T (PA9T) resin, polyamide 10T (PA10T) resin, polyamide 11T (PA11T) resin, polyamide 6 (PA6) resin, polyamide 66 (PA66) resin, polyamide 46 (PA46) ) Polypolymer resin such as resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyester resin such as polyethylene naphthalate (PEN) resin, polysulfone (PSU) resin, polyether sulfone (PES) resin, poly Polysulfone resin such as phenylsulfone (PPSU) resin, polyphenylene sulfide (PPS) resin, polyphenylene sulfide ketone resin, polyphenylene sulfide sulfone resin, polyarylene sulfide resin such as polyphenylene sulfide ketone sulfone resin, liquid crystal polymer (LCP), polycarbonate (PC) ) Resin, polyarylate (PAR) resin and the like are added as needed.

In the above, when manufacturing the resin film 2 for the vibration plate of the speaker, for example, as shown in FIG. 1, first, the polyarylene ether ketone resin and the adhesive fluororesin are stirred and mixed at room temperature and melted for a predetermined time. After kneading to prepare the molding material 1, the resin film 2 for the vibration plate of the band-shaped speaker is continuously molded by the molding material 1.

The method for preparing the molding material 1 is as follows: (1) Polyarylene ether ketone resin and adhesive fluororesin are stirred and mixed at room temperature (0 ° C. or higher and 50 ° C. or lower), and then melt-kneaded to obtain a resin film 2 for a vibration plate. Method for adjusting molding material 1, (2) Adhesive fluororesin is added to the molten polyarylene ether ketone resin without stirring and mixing the polyarylene ether ketone resin and the adhesive fluororesin, and these are melt-kneaded. A method of preparing the molding material 1 can be mentioned.

Any of these methods can be adopted. First, the method (1) will be described. When the polyarylene ether ketone resin and the adhesive fluororesin are stirred and mixed, a tumbler mixer, a hensyl mixer, a V-type mixer, a nouter mixer, a ribbon blender, or A universal stirring mixer or the like is used.

Polyarylene ether ketone resin and adhesive fluororesin are mixed by mixing rolls, pressure kneaders, Banbury mixers, planetary mixers, twin-screw extruders, triaxial extruders, and four-screw extruders. , It is prepared as a molding material 1 by melt-kneading and dispersing in a multi-screw extruder such as an octa-screw extruder. When the molding material 1 is prepared, the temperature at the time of melt-kneading by the melt-kneader is preferably 300 ° C. or higher and 400 ° C. or lower, preferably 330 ° C. or higher and 380 ° C. or lower. This is based on the reason that when the temperature at the time of melt kneading of the melt extrusion molding machine 10 exceeds 400 ° C., the adhesive fluororesin is violently decomposed, which is not preferable.

Next, the method (2) will be described. In the case of this method, the polyarylene ether ketone resin is mixed with a mixing roll, a pressure kneader, a Banbury mixer, a planetary mixer, a twin-screw extruder, and a triaxial extruder. Polyarylene by adding an adhesive fluororesin to a polyarylene ether ketone resin that has been melted by a multi-screw extruder such as a 4-screw extruder or an octa-screw extruder and then melt-kneaded and dispersed. A molding material 1 of an ether ketone resin and an adhesive fluororesin is prepared. The temperature at the time of melt-kneading by the melt-kneader in the case of preparing the molding material 1 composed of the polyarylene ether ketone resin and the adhesive fluororesin is preferably 300 ° C. or higher and 400 ° C. or lower, preferably 330 ° C. or higher and 380 ° C. or lower. This is because when the temperature of the melt extrusion molding machine 10 exceeds 400 ° C., the adhesive fluororesin decomposes violently as described above.

The molding material 1 is usually extruded into a lump, a strand, a sheet, or a rod, and then used in a form suitable for molding such as a powder, a granule, or a pellet by a crusher or a cutting machine.

The resin film 2 for a diaphragm made of the molding material 1 can be manufactured by a known method such as a melt extrusion molding method, a force render molding method, or a casting molding method. Here, in the melt extrusion molding method, a melt extrusion molding machine 10 including a single-screw extrusion molding machine, a twin-screw extrusion molding machine, or the like is used to melt the molding material 1 of the polyarylene ether ketone resin and the adhesive fluororesin. This is a method of kneading and continuously extruding a strip-shaped resin film 2 for a vibrating plate from a T-die 13 at the tip of a melt extrusion molding machine 10. From the viewpoint of handleability and simplification of equipment, the melt extrusion molding method is the most suitable method for manufacturing the resin film 2 for a diaphragm.

The melt extrusion molding machine 10 comprises, for example, a single-screw extruder, a twin-screw extruder, or the like, and functions to melt-knead the charged molding material 1. A raw material input port 11 for the molding material 1 is installed behind the upper part of the melt extrusion molding machine 10, and the raw material input port 11 has helium gas, neon gas, argon gas, krypton gas, nitrogen gas, and carbon dioxide gas. An inert gas supply pipe 12 for supplying an inert gas such as the above is connected, and the inflow of the inert gas through the inert gas supply pipe 12 is effective for oxidative deterioration and oxygen cross-linking of the molding material 1. Is prevented.

As the melt extruder 10 such as a single-screw extruder or a twin-screw extruder, it is preferable to use a melt extruder 10 having a vent port. This is because by melting and kneading under reduced pressure using the vent port, it becomes easy to sufficiently degas the water contained in the molding material 1 and the sublimated organic matter. Further, it is not necessary to adjust the water content of the molding material 1 before melting and kneading.

The temperature at the time of melt kneading of the melt extrusion molding machine 10 is a temperature at which the molding material 1 can be melted, and is not particularly limited as long as the molding material 1 does not decompose, but the temperature is equal to or higher than the melting point of the molding material 1. The range below the decomposition temperature is good. Specifically, the temperature is adjusted to 300 ° C. or higher and 400 ° C. or lower, preferably 330 ° C. or higher and 380 ° C. or lower. This is because if the temperature is lower than 300 ° C, the molding material 1 containing the polyarylene ether ketone resin cannot be melt-extruded, and conversely, if the temperature exceeds 400 ° C, the adhesive fluororesin is severely decomposed. This is because there is a risk.

The molding material 1 melt-kneaded by the melt extrusion molding machine 10 is continuously extruded into a band-shaped resin film 2 for a vibrating plate by a T-die 13 at the tip of the melt extrusion molding machine 10, and the continuous vibrating plate is formed. The resin film 2 is manufactured by being sandwiched between a pair of lower pressure-bonding rolls 17 and a cooling roll 18 to be cooled, and then wound by a winder 19.

The T-die 13 is attached to the tip of the melt extruder 10 via a connecting pipe 14 and functions to continuously push the strip-shaped diaphragm resin film 2 downward. The temperature at the time of extrusion of the T-die 13 is in the range of the melting point of the molding material 1 or more and less than the thermal decomposition temperature. Specifically, the temperature is adjusted to 300 ° C. or higher and 400 ° C. or lower, preferably 330 ° C. or higher and 380 ° C. or lower. This is because if the temperature is lower than 300 ° C, the molding material 1 containing the polyarylene ether ketone resin cannot be melt-extruded, and if the temperature exceeds 400 ° C, the adhesive fluororesin may be severely decomposed. Because there is.

It is preferable that the gear pump 15 and the filter 16 are mounted on the connecting pipe 14 upstream of the T-die 13. The gear pump 15 transfers the molding material 1 melt-kneaded by the melt extrusion molding machine 10 to the T-die 13 at a constant flow rate and with high accuracy via the filter 16. The filter 16 separates the gel, foreign matter, and the like of the molten molding material 1, and transfers the molten molding material 1 to the T die 13.

The pair of crimping rolls 17 are rotatably supported below the T-die 13 and sandwich the cooling roll 18 so as to be slidable, and sandwich the resin film 2 for the diaphragm between the cooling roll 18 and the cooling roll 18. And cool. Of the pair of crimp rolls 17, a take-up pipe 20 of a winder 19 for winding the resin film 2 for a diaphragm is rotatably installed further downstream of the crimp roll 17 downstream, and is wound with the crimp roll 17. A slit blade 21 that forms a slit on the side of the resin film 2 for the diaphragm is arranged so as to be able to move up and down between the take-up pipe 20 of the taker 19 and the slit blade 21 and the take-up machine 19. A required number of rotatable tension rolls 22 are supported between the take-up tube 20 and the resin film 2 for the diaphragm to apply tension to the take-up tube 20 for smooth winding.

From the viewpoint of improving the adhesion between the resin film 2 for the vibrating plate and the cooling roll 18, at least rubber layers such as natural rubber, isoprene rubber, butadiene rubber, silicone rubber, and fluororubber are formed on the peripheral surface of each crimping roll 17. A film is formed as needed, and an inorganic compound such as silica or alumina is selectively added to the rubber layer. Among these, it is preferable to use silicone rubber or fluororubber, which has excellent heat resistance.

As the crimping roll 17, a metal elastic roll having a metal surface is used as needed, and when this metal elastic roll is used, it is possible to form a resin film 2 for a diaphragm having an excellent surface smoothness. Become. Specific examples of the metal elastic roll include, for example, a metal sleeve roll, an air roll [manufactured by Dimco: product name], and a UF roll [manufactured by Hitachi Zosen Corporation: product name].

Such a crimping roll 17 is adjusted to a temperature of 50 ° C. or higher and 260 ° C. or lower, preferably 100 ° C. or higher and 240 ° C. or lower, more preferably 130 ° C. or higher and 220 ° C. or lower, and further preferably 150 ° C. or higher and 200 ° C. or lower, and vibrates. It is in sliding contact with the resin film 2 for a plate and is pressed against a cooling roll 18. The temperature of the crimping roll 17 is within the range when the temperature of the crimping roll 17 exceeds 260 ° C., the resin film 2 for the diaphragm being manufactured sticks to the crimping roll 17, and the resin film 2 for the diaphragm breaks. Alternatively, the rubber layer coated on the crimping roll 17 may be thermally decomposed.

On the contrary, when the temperature of the crimping roll 17 is less than 50 ° C., dew condensation occurs on the crimping roll 17, which is not preferable. Examples of the temperature adjusting and cooling method of the crimping roll 17 include a method using a heat medium such as air, water, and oil, an electric heater, and dielectric heating.

The cooling roll 18 is made of, for example, a metal roll having a larger diameter than the crimping roll 17, and narrows the resin film 2 for a diaphragm rotatably supported and extruded below the T-die 13 between the crimping roll 17 and the cooling roll 18. While holding and cooling the diaphragm resin film 2 together with the crimping roll 17, the thickness thereof is controlled within a predetermined range. Like the crimping roll 17, the cooling roll 18 has a temperature of 50 ° C. or higher and 260 ° C. or lower, preferably 100 ° C. or higher and 240 ° C. or lower, more preferably 130 ° C. or higher and 220 ° C. or lower, and further preferably 150 ° C. or higher and 200 ° C. or lower. It is adjusted and slides into contact with the diaphragm resin film 2.

The reason why the cooling roll 18 is adjusted to a temperature of 50 ° C. or higher and 260 ° C. or lower is that when the temperature of the cooling roll 18 exceeds 260 ° C., the resin film 2 for the diaphragm being manufactured is in close contact with the cooling roll 18. This is because the resin film 2 for the diaphragm may be broken, or in the case of the crimping roll 17 coated with the rubber layer, the rubber layer of the crimping roll 17 may be thermally decomposed. On the other hand, if the temperature of the cooling roll 18 is less than 50 ° C., dew condensation is caused on the cooling roll 18, 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, induction heating, and the like.

In the above configuration, when the resin film 2 for a vibrating plate is more specifically and actually manufactured, as shown in FIG. 1, first, the molding material 1 is first inserted into the raw material input port 11 of the melt extrusion molding machine 10. While supplying the inert gas indicated by the arrow, the polyarylene ether ketone resin of the molding material 1 and the adhesive fluororesin are melt-kneaded by the melt extrusion molding machine 10, and the resin film 2 for the vibrating plate is melted and kneaded from the T die 13. Is continuously extruded into a band shape. At this time, the water content of the molding material 1 before melt extrusion is adjusted to 2000 ppm or less, preferably 1000 ppm or less, and more preferably 100 ppm or more and 500 ppm or less. This is because when the water content exceeds 2000 ppm, the molding material 1 may foam immediately after being extruded from the T die 13.

After extruding the resin film 2 for the diaphragm, the resin film 2 for the diaphragm is sequentially wound around the pair of crimping rolls 17, the cooling roll 18, the tension roll 22, and the take-up pipe 20 of the winder 19, and the resin film 2 for the diaphragm is rolled by the cooling roll 18. After cooling, both sides of the diaphragm resin film 2 are cut by the slit blades 21 and sequentially wound around the winding tube 20 of the winder 19 to manufacture the diaphragm resin film 2 for the portable device speaker. can do. During the production of the diaphragm resin film 2, fine irregularities are formed on the surface of the diaphragm resin film 2 within a range that does not lose the effect of the present invention, and the friction coefficient of the surface of the diaphragm resin film 2 is determined. Can be reduced.

The thickness of the resin film 2 for the diaphragm is not particularly limited as long as it is 2 μm or more and 1000 μm or less, but it is preferably 2.5 μm or more from the viewpoint of ensuring sufficient thickness, handleability and thinning. It is preferably 100 μm or less, more preferably 3 μm or more and 95 μm or less, and further preferably 8 μm or more and 75 μm or less.

This is because when the thickness of the diaphragm resin film 2 is less than 2 μm, the mechanical strength of the diaphragm resin film 2 is significantly reduced, which makes it difficult to mold the diaphragm resin film 2. be. On the contrary, when the thickness of the resin film 2 for the diaphragm exceeds 100 μm, the molding accuracy on the diaphragm is lowered. The thickness of the diaphragm resin film 2 can be measured by various micrometer. The thickness tolerance of the resin film 2 for the diaphragm is preferably within the range of an average value of ± 5%, preferably within the range of an average value of ± 3%. This is because if the thickness tolerance of the resin film 2 for the diaphragm is out of the range of the average value of ± 5%, the sound quality varies, which is not preferable. The thickness tolerance of the resin film 2 for the diaphragm can be calculated by the following formula.

Film thickness tolerance [%] = {(MAX or MIN)-(AVE)} / (AVE) x 100
Here, MAX: maximum value of film thickness
MIN: Minimum film thickness
AVE: Average film thickness

The mechanical properties of the resin film 2 for a diaphragm can be evaluated by the elongation at tensile break at 23 ° C. and the tensile elastic modulus. The elongation at tensile break is preferably 50% or more, preferably 100% or more, more preferably 150% or more, still more preferably 200% or more by a measuring method based on JIS K 6251 or 7127. The upper limit of the elongation at tensile break is not particularly limited, but is preferably 500% or less.

This is because when the elongation at break is less than 50%, the resin film 2 for the diaphragm does not have sufficient toughness, so that troubles such as breakage and cracking occur during the processing of the resin film 2 for the diaphragm. This is because there is a risk and manufacturing becomes difficult. Further, it is based on the reason that the durability of the diaphragm of the resin film 2 for the diaphragm is lowered, and the diaphragm is torn or cracked when the external output is increased.

Tensile modulus at 23 ° C. of the diaphragm resin film 2, JIS K 6251 and JIS 100 N / mm ² or more K 7127 measurement method conforming to 2500N / mm ² or less, preferably 300N / mm ² or more 2000N / mm ² Below, the optimum range is more preferably 500 N / mm ² or more and 1500 N / mm ² or less, and further preferably 500 N / mm ² or more and 1000 N / mm ^{2 or less.} This is because when the tensile elasticity of the ^{resin film 2 for the diaphragm is less than 100 N / mm 2} , the rigidity of the resin film 2 for the diaphragm is inferior, so that the handling property is deteriorated or the vibration occurs during the processing of the mobile phone speaker. high-frequency diaphragm plate resin film 2 resonant frequency (f _H) is low, because becomes insufficient treble reproduction. Further, when it exceeds 2500 N / mm ² _{, the minimum resonance frequency (f 0} ) of the diaphragm obtained from the resin film 2 for the diaphragm is high, and the bass reproduction becomes insufficient.

The heat resistance property of the resin film 2 for a diaphragm can be evaluated by the first inflection temperature of the storage elastic modulus (see FIG. 2). Here, the first inflection point temperature of the storage modulus, the storage modulus appearing at temperature 25 ° C. The above is the temperature of the inflection point appearing in more than 9.0 × 10 9 ^Pa.

The first inflection temperature of the storage elastic modulus appearing at the temperature of the diaphragm resin film 2 at 25 ° C. or higher is 130 ° C. or higher, preferably 140 ° C. or higher, and more preferably 145 ° C. or higher. This is because when the first turning point temperature of the storage elastic coefficient of the diaphragm resin film 2 is less than 130 ° C., the heat resistance of the diaphragm resin film 2 becomes insufficient, and the diaphragm resin film 2 starts from the diaphragm resin film 2. When the obtained diaphragm is used as a speaker, the high heat associated with the high vibration of the voice coil causes the diaphragm obtained from the diaphragm resin film 2 to be deformed, cracked, or damaged, resulting in a decrease in durability. Is. The upper limit of the first inflection temperature of the storage elastic modulus of the diaphragm film is not particularly limited, but is preferably 250 ° C. or lower.

The loss tangent of the resin film 2 for the diaphragm at 20 ° C. is 0.010 or more, preferably 0.013 or more, more preferably 0.015 or more, still more preferably 0.018, in order to prevent resonance and obtain good sound quality. The above is optimal. This is because when the loss tangent is less than 0.010, good sound quality cannot be obtained due to the occurrence of resonance. The upper limit of this loss tangent is not particularly limited, but is preferably 0.45 or less.

The optimum specific gravity of the resin film 2 for a diaphragm after cooling is 1.1 or more and 1.8 or less, preferably 1.3 or more and 1.6 or less, and more preferably 1.4 or more and 1.5 or less. This is because, within such a range, the density is small, so that the weight can be reduced and good sound quality characteristics can be obtained.

Fine irregularities can be formed on the front and back surfaces of the diaphragm resin film 2 to reduce the coefficient of friction. As a method for forming the fine irregularities, (1) the resin film 2 for the vibration plate is sandwiched between the crimping roll 17 having the fine irregularities and the cooling roll 18 having the fine irregularities to form the fine irregularities. Method, (2) A method of spraying fine zirconia, glass, an inorganic compound such as stainless steel, a polycarbonate resin, a polyamide resin, or an organic compound such as a plant seed onto the resin film 2 for a vibrating plate to form fine irregularities, (2). 3) A method of press-molding the resin film 2 for a vibrating plate with a mold having fine irregularities to form fine irregularities can be mentioned. Among these methods, the method (1) is most suitable from the viewpoints of simplification of equipment, accuracy of unevenness size, uniformity of unevenness formation, ease of unevenness formation, and continuous formation of unevenness. ..

The method of (1) will be described in more detail. A method of discharging the discharged material onto the cooling roll 18 provided in the above, sandwiching the discharged material between the cooling roll 18 and a crimping roll 17 having fine irregularities on the peripheral surface, and forming the resin film 2 for a vibrating plate at the same time as melt extrusion molding. (1-2) A method of forming the unevenness by sandwiching the molded resin film 2 for a vibrating plate between a crimping roll 17 having fine unevenness on the peripheral surface and a cooling roll 18 having fine unevenness can be mentioned. Among these, the method (1-1) is preferable from the viewpoint of simplification of equipment.

According to the above configuration, since the molding material 1 contains the polyarylene ether ketone resin, it is possible to obtain a resin film 2 for a diaphragm having excellent toughness, heat resistance, solvent resistance and the like. It is also possible to add an adhesive fluororesin having excellent dispersibility to the molding material 1 to improve the slipperiness of the front and back surfaces of the resin film 2 for a diaphragm. Specifically, the slipperiness of the surface of the resin film 2 for a diaphragm can be evaluated by the coefficient of static friction and the coefficient of dynamic friction. The coefficient of static friction can be reduced to 0.40 or less, preferably 0.38 or less, and the coefficient of dynamic friction can be reduced to 0.30 or less, preferably 0.25 or less. It can be obtained, and when the resin film 2 for a diaphragm is wound by the winder 19, no wrinkles occur. Therefore, it is possible to effectively solve the problem that the resin film 2 for the diaphragm is broken or damaged during manufacturing or secondary processing.

The coefficient of static friction and the lower limit of elongation at the time of the coefficient of dynamic friction are not particularly limited, but are preferably 0.10 or more.

Further, since an adhesive fluororesin having excellent compatibility with the polyarylene ether ketone resin is used instead of a fluororesin such as a tetrafluoroethylene / perfluoroalkoxyethylene copolymer, the resin film 2 for a vibration plate is melt-extruded. By law, it can be manufactured smoothly. Further, since the molding material 1 is prepared with a polyarylene ether ketone resin and an adhesive fluororesin, it is possible to obtain excellent sound quality characteristics in which loss tangent is increased and resonance is suppressed in addition to bass characteristics. Become. Therefore, it is possible to emphasize or reproduce important bass on the mobile device without relying on the software of the mobile device or connecting a dedicated external speaker to the mobile device.

In addition, since the bass characteristics can be expected to be improved without making the speaker large and heavy, it is possible to contribute to the demand for thinning, downsizing, and weight reduction of mobile devices. Further, since the resin film 2 for a diaphragm having excellent heat resistance is used for the speaker of a portable device, excellent heat resistance can be expected. Further, since the resin film 2 for a diaphragm containing a crystalline polyarylene ether ketone resin having excellent heat dissipation characteristics is used, loss is reduced and stable long-term use of the resin film 2 for a diaphragm can be expected.

Next, FIG. 3 shows a second embodiment of the present invention. In this case, a pair of diaphragm resin films 2 are prepared, and a thickness is provided between the pair of diaphragm resin films 2. The elastomer layer 31 having a thickness of 10 μm or more and 100 μm or less is sandwiched and adhered to form a diaphragm 30 of a speaker having a laminated structure.

Examples of the elastomer of the elastomer layer 31 include silicone resin, urethane resin, acrylic resin, fluororesin, polyester resin, polyamide resin, hydrocarbon resin, styrene resin, vinyl chloride resin, vinyl acetate resin and the like. Among these elastomers, silicone resins, particularly heat-curable silicone resins, are preferable in that they are excellent in heat resistance, weather resistance, flame retardancy, sound quality characteristics, compression characteristics and the like. Examples of the heat-curable silicone resin include an addition-curable mirrorable silicone resin and an addition-curable liquid silicone resin.

The addition-curable mirabable silicone resin is usually an organopolysiloxane, a silica-based filler, a curing agent (a curing agent combining a known platinum-based catalyst and an organohydrogenpolysiloxane, an organic oxide, or the like. ) And various additives such as fine silica powder are added to the composition.

On the other hand, the addition-curable liquid silicone resin contains at least two organopolysiloxanes 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 (crushed diatomaceous soil, pearlite, foamed pearlite) 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.} , Mica, calcium carbonate, glass flakes, hollow filler, etc.) and addition reaction catalysts (platinum black, secondary platinum chloride, platinum chloride acid, reaction products of platinum chloride acid and monovalent alcohol, platinum chloride acid and olefins) It is used in the state of a resin composition to which a complex with, platinum bisacetoacetate, palladium-based catalyst, rhodium-based catalyst, etc.) is added.

The durometer hardness of the silicone resin when the silicone resin is used for the elastomer layer 31 is A10 or more and A90 or less, preferably A20 or more and A70 or less, more preferably, when measured by the type A of the durometer in accordance with JIS K 6253. The optimum range is A20 or more and A50 or less. This is because when the durometer hardness is less than A10, the compression set characteristics of the silicone resin deteriorate and the vibration propagation speed of the diaphragm 30 decreases, causing a problem in sound quality. On the contrary, when the durometer hardness exceeds A90, the loss tangent becomes small and the performance of the diaphragm 30 deteriorates.

A primer layer 32 is selectively interposed between the pair of diaphragm resin films 2 and the elastomer layer 31 for the purpose of firmly adhering them. Each primer layer 32 is interposed between the facing surfaces of the diaphragm resin film 2 and the silicone resin of the elastomer layer 31, and functions to firmly bond them.

The primer layer 32 is not particularly limited as long as it can adhere the silicone resin of the elastomer layer 31 and the resin film 2 for the vibrating plate, but is not particularly limited, for example, alkyd resin, phenol-modified / silicone-modified, and the like. Examples thereof include alkyd resin modified products, oil-free alkyd resins, acrylic resins, silicone resins, epoxy resins, fluororesins, phenol resins, silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and mixtures thereof. Examples of the cross-linking agent for curing and / or cross-linking these resins include isocyanate compounds, melamine compounds, epoxy compounds, peroxides, phenol compounds, hydrogen siloxane compounds, and silane compounds.

Each primer layer 32 has a thickness of 0.1 μm or more and 5 μm or less, preferably 1 μm or more and 3 μm or less. This is because when the thickness of the primer layer 32 is less than 0.1 μm, the adhesion between the elastomer layer 31 and the resin film 2 for the diaphragm is insufficient, and the layer is peeled off during molding or use on the diaphragm 30. This is because there is a risk of doing so. On the other hand, if the thickness of the primer layer 32 exceeds 5 μm, the secondary moldability to the diaphragm 30 or the acoustic characteristics may be adversely affected.

In this embodiment as well, the same effects as those in the above embodiment can be expected, and since the diaphragm 30 of the speaker is not made of metal leaf, the minimum resonance frequency (f ₀ ) is lowered and sufficient bass reproduction characteristics are obtained. Can be done. Further, since the diaphragm 30 is not a paper, woven cloth, or non-woven fabric made of natural resin, excellent moisture resistance, water resistance, and heat resistance can be obtained, and the manufacturing process of the speaker can be simplified or simplified. Can be planned. Further, the resin film 2 for a diaphragm in which an adhesive fluororesin is added to a polyarylene ether ketone resin having an appropriate tensile elastic modulus is excellent in bass reproduction and treble reproduction, so that a high-performance speaker diaphragm 30 can be obtained. Can be done.

Further, the resin film 2 for a diaphragm in which an adhesive fluororesin is added to a polyarylene ether ketone resin can realize a diaphragm 30 for a speaker having a small specific gravity, a light weight, and excellent heat resistance. Further, it is clear that it is possible to effectively prevent the compression permanent strain characteristic of the elastomer layer 31 from deteriorating and the vibration propagation speed of the diaphragm 30 of the speaker from being lowered to cause a problem in sound quality.

The surface of the resin film 2 for a vibrating plate in the above embodiment is coated with various elastomers such as various antistatic agents, silicone resin, acrylic resin, and urethane resin, or aluminum, as long as the effect of the present invention is not lost. , Tin, nickel, copper and other various metals may be vapor-deposited. Further, the opening shape of the filter 16 is not particularly limited to a circular shape, an elliptical shape, a rectangular shape, a polygonal shape, or the like.

Hereinafter, examples of a resin film for a diaphragm of a speaker and a method for manufacturing the same according to the present invention will be described together with comparative examples.
[Example 1]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. As the polyetherketone resin, 100 parts by mass of a commercially available polyetheretherketone resin [manufactured by Solvay Specialty Polymers, product name: KETAPIRE KT-851 NL SP (hereinafter abbreviated as "KT-851 NL SP")) The prepared polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours or more. As the adhesive fluororesin, 5 parts by mass of a commercially available adhesive fluororesin EA-2000 [manufactured by AGC: product name, hereinafter abbreviated as "EA-2000"] was prepared.

After preparing these, a stirring mixture is prepared by putting two kinds of resins into a mixer and stirring and mixing, and the stirring mixture is melt-kneaded by a co-rotating twin-screw extruder or the like and extruded into a strand shape. This extruded product was air-cooled and solidified, and then cut into pellets to prepare a molding material. As the co-rotating twin-screw extruder, a φ42 mm, L / D = 38 type was used. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 370 ° C. and a die temperature of 370 ° C. to prepare a molding material. The temperature at the time of melt-kneading was determined to be the temperature of the molded material in the molten state immediately after being extruded from the die, and was measured to be 366 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 12 hours or more, and after confirming that the water content of the dried molding material was 300 ppm or less, the dried molding material was placed in a T-die having a width of 900 mm. The melt-kneaded molding material was continuously extruded from the T-die and the resin film for the diaphragm of the speaker was extruded into a strip shape. At this time, the water content of the polyether ketone ketone resin was measured by the Karl Fischer titration method using a trace water content measuring device (product name CA-100 type manufactured by Mitsubishi Chemical Corporation).

The single-screw extruder was of the type of φ40 mm, screw: full flight screw (L / D = 32, compression ratio: 2.5). The cylinder temperature of this single-screw extruder was adjusted to 250 to 390 ° C, the temperature of the T-die was adjusted to 390 ° C, and the temperatures of the connecting pipe connecting the single-screw extruder and the T-die, the gear pump, and the filter were adjusted to 390 ° C, respectively. Further, regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 393 ° C. Further, when the molding material was charged into the single-screw extruder, nitrogen gas 18 L / min was supplied through the inert gas supply pipe.

After the resin film for the speaker's vibrating plate is extruded, this resin film for the vibrating plate is used as a pair of crimping rolls made of silicone rubber, a metal roll which is a cooling roll at 150 ° C. with irregularities on the peripheral surface, and downstream thereof. The length is 100 m and the width is 650 mm by sequentially winding on the 6-inch take-up pipe of the take-up machine located in, sandwiching it between the crimping roll and the metal roll, and sequentially winding it on the take-up pipe of the take-up machine. A resin film for a speaker vibration plate was manufactured.

After manufacturing the resin film for the diaphragm of the speaker, the film thickness, mechanical characteristics, heat resistance characteristics, and acoustic characteristics of the resin film for the diaphragm were evaluated, and the results are summarized in Table 1. The mechanical properties of the resin film for vibrating plates are elongation at tensile break and tensile elastic modulus, the heat resistance characteristics are the first turning point temperature of the storage elastic modulus of the resin film for vibrating plates, and the acoustic characteristics are 20 ° C. of the resin film for vibrating plates. It was evaluated by the loss tangent in.

-Thickness of resin film for vibrating plate The film thickness of the resin film for vibrating plate was measured using a micrometer [Product name manufactured by Mitutoyo Co., Ltd .: Coolant proof micrometer code MDC-25PJ]. At the time of measurement, arbitrary 10 points in the width direction (direction perpendicular to the extrusion direction) of the resin film for the diaphragm were measured, and the average value thereof was taken as the film thickness.

-Mechanical properties of the resin film for the diaphragm The mechanical properties of the resin film for the diaphragm were evaluated by the elongation at tensile break and the tensile elastic modulus. The elongation at break and the tensile elastic modulus were measured in accordance with JIS K 7127 (test piece type 1B) under the conditions of a tensile speed of 50 mm / min and a temperature of 23 ° C. This tensile modulus was measured in the extrusion direction and the width direction (direction perpendicular to the extrusion direction) of the film.

-First turning point temperature of the storage elastic modulus of the resin film for the diaphragm The heat resistance characteristics of the resin film for the diaphragm were evaluated by the first turning point temperature of the storage elastic modulus. The first inflection temperature of this storage elastic modulus was measured in the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) of the resin film for the diaphragm. Specifically, when measuring the storage elastic modulus of the resin film for a diaphragm, the size is 60 mm in the extrusion direction × 6 mm in the width direction, and when measuring the storage elastic modulus in the width direction, the size is 6 mm in the extrusion direction × 60 mm in width. It was cut out and measured.

When measuring the storage elastic modulus, a tension mode using a viscoelastic spectrometer (product name: RSA-G2 manufactured by TS Instruments Japan) has a frequency of 1 Hz, a strain of 0.1%, and a temperature rise rate. The measurement was performed under the conditions of 3 ° C./min, a measurement temperature range of 0 ° C. to 360 ° C., and a check interval of 21 mm.

As shown in FIG. 2, the first inflection temperature was the temperature at the intersection of two straight lines with respect to the change curve of the storage elastic modulus. Specifically, first, the straight line portion before the first sharp decrease in the storage elastic modulus is extended to the high temperature side, and the first straight line (a) is drawn. Next, the straight line portion after the storage elastic modulus first suddenly drops is extended to the low temperature side to draw a second straight line (b). After that, a vertical line at the intersection of both lines (a) and (b) was drawn on the temperature axis of the horizontal axis, and the temperature was obtained as the first inflection temperature.

-Loss tangent of the resin film for the diaphragm The loss tangent of the resin film for the diaphragm was measured in the extrusion direction and the width direction (direction perpendicular to the extrusion direction). Specifically, when measuring the loss positive contact in the extrusion direction of the resin film for a vibrating plate, the extrusion direction is 60 mm × 6 mm in the width direction, and when measuring the loss positive contact in the width direction, the extrusion direction is 6 mm × 60 mm in the width direction. It was cut out to the size of and measured. When measuring the loss tangent, a tension mode using a viscoelastic spectrometer (product name: RSA-G2 manufactured by TS Instruments Japan) has a frequency of 1 Hz, a strain of 0.1%, and a temperature rise rate of 3. The measurement was performed under the conditions of ° C./min, measurement temperature range of 0 ° C. to 360 ° C., and check interval of 21 mm, and a loss tangent of 20 ° C. was determined.

[Example 2]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. In Example 1, KT-851 NL SP was used as the commercially available polyetheretherketone resin, but in Example 2, the product name manufactured by Daicel Evonix was used as the commercially available polyetheretherketone resin: Vestakeep-. It was changed to J ZV7403 (hereinafter abbreviated as "ZV7403"). As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours or more. As the adhesive fluororesin, 15 parts by mass of the adhesive fluororesin EA-2000 used in Example 1 was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The temperature at the time of melt-kneading was determined to measure the temperature of the molded material in the molten state immediately after being extruded from the die, and was measured to be 376 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 12 hours or more, the moisture content of the molding material dried by the same method as in Example 1 was measured, and the moisture content of the dried molding material was measured. After confirming that the water content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 393 ° C. The temperature of the cooling roll was changed to 210 ° C.

After manufacturing the resin film for the diaphragm of the speaker, the film thickness, mechanical properties, heat resistance characteristics, and acoustic characteristics of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are summarized in Table 1.

[Example 3]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. In Example 1, KT-851 NL SP was used as the commercially available polyetheretherketone resin, but in Example 3, the product name: Victrex Granules 381G manufactured by Victrex was used as the commercially available polyetheretherketone resin. (Hereinafter, abbreviated as "381G"). As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours or more. As the adhesive fluororesin, 30 parts by mass of the adhesive fluororesin EA-2000 used in Example 1 was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The temperature at the time of melt-kneading was determined to be the temperature of the molded material in the molten state immediately after being extruded from the die, and the measured temperature was 365 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 12 hours or more, the moisture content of the molding material dried by the same method as in Example 1 was measured, and the moisture content of the dried molding material was measured. After confirming that the water content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1.

Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 393 ° C. The temperature of the cooling roll was the same as in Example 1. After manufacturing the resin film for the diaphragm of the speaker, the film thickness, mechanical properties, heat resistance characteristics, and acoustic characteristics of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are summarized in Table 1.

[Example 4]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. In Example 1, KT-851 NL SP was used as the commercially available polyetheretherketone resin, but in Example 4, the product name: Victrex Granules 450G manufactured by Victrex was used as the commercially available polyetheretherketone resin. (Hereafter, abbreviated as "450G"). As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours or more. As the adhesive fluororesin, 50 parts by mass of the adhesive fluororesin EA-2000 used in Example 1 was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The temperature at the time of melt-kneading was determined to be the temperature of the molded material in the molten state immediately after being extruded from the die, and the measured temperature was 365 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 12 hours or more, the moisture content of the molding material dried by the same method as in Example 1 was measured, and the moisture content of the dried molding material was measured. After confirming that the water content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 390 ° C. The temperature of the cooling roll was the same as in Example 1.

After manufacturing the resin film for the diaphragm of the speaker, the film thickness, mechanical properties, heat resistance characteristics, and acoustic characteristics of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are summarized in Table 1.

[Example 5]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. In this Example 5, the polyetheretherketone resin used in Example 1 was used as a commercially available polyetheretherketone resin. As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours or more. As the adhesive fluororesin, 85 parts by mass of the adhesive fluororesin EA-2000 used in Example 1 was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The temperature at the time of melt-kneading was determined to be the temperature of the molded material in the molten state immediately after being extruded from the die, and the measured temperature was 365 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 12 hours or more, the moisture content of the molding material dried by the same method as in Example 1 was measured, and the moisture content of the dried molding material was measured. After confirming that the water content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 391 ° C. The temperature of the cooling roll was the same as in Example 1.

After manufacturing the resin film for the diaphragm of the speaker, the film thickness, mechanical properties, heat resistance characteristics, and acoustic characteristics of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are summarized in Table 2.

[Example 6]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. As the polyetherketone ether ketone, a commercially available polyetherketoneketone resin [product name manufactured by Arkema Co., Ltd .: KEPSTAN 6003 (hereinafter, “KEPSTAN 6003”]] was used. As a molding material, 100 resin parts of polyetherketoneketone resin were prepared. , This polyetherketoneketone resin was allowed to dry for 12 hours or more in a dehumidifying / drying machine heated to 160 ° C. As an adhesive fluororesin, a commercially available adhesive fluororesin EA-2000 [manufactured by AGC: product name] , (Hereinafter abbreviated as “EA-2000”]] were prepared in 30 parts by mass.

After preparing these, a stirring mixture is prepared by putting two kinds of resins into a mixer and stirring and mixing, and the stirring mixture is melt-kneaded by a co-rotating twin-screw extruder or the like and extruded into a strand shape. This extruded product was air-cooled and solidified, and then cut into pellets to prepare a molding material. As the co-rotating twin-screw extruder, a φ25 mm, L / D = 41 type was used. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 385 ° C. and a die temperature of 385 ° C. to prepare a molding material. The temperature at the time of melt-kneading was determined to measure the temperature of the molded material in the molten state immediately after being extruded from the die, and the measured temperature was 387 ° C.

Next, the molding material was put into a dehumidifying / drying machine heated to 160 ° C. and dried for 12 hours or more. After confirming that the water content of the dried molding material was 300 ppm or less, the dried molding material was placed in a T-die having a width of 150 mm. The melt-kneaded molding material was continuously extruded from the T-die and the resin film for the diaphragm of the speaker was extruded into a strip shape. At this time, the water content of the polyether ketone ketone resin was measured by the Karl Fischer titration method using a trace water content measuring device (product name CA-100 type manufactured by Mitsubishi Chemical Corporation).

The single-screw extruder was of the type of φ20 mm, screw: full flight screw (L / D = 25, compression ratio: 2.5). The cylinder temperature of the single-screw extruder was adjusted to 360 ° C to 380 ° 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 380 ° C. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 377 ° C.

After the resin film for the vibration plate of the speaker is extruded, this resin film for the vibration plate is used for a pair of crimping rolls made of silicone rubber, a metal roll which is a cooling roll at 160 ° C., and a winder located downstream of these. By sequentially winding it on a 3-inch take-up tube, sandwiching it between a crimping roll and a metal roll, cutting both sides of the continuous resin film for a vibrating plate with a slit blade, and sequentially winding it on the take-up tube. A resin film for a vibration plate of a speaker having a length of 10 m and a width of 130 mm was manufactured. When the molding material was charged into the single-screw extruder, nitrogen gas was supplied at 18 L / min through the inert gas supply pipe.

After producing the resin film for the diaphragm of the speaker, the film thickness, mechanical properties, heat resistance characteristics, and acoustic characteristics of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are shown in Table 2. The mechanical properties of the resin film for diaphragms were evaluated by the elongation at break and the tensile modulus, but the elongation at break and the modulus of tensile modulus conformed to JIS K 6251 (test piece type No. 2) and were tensile. The measurement was performed under the conditions of a speed of 50 mm / min and a temperature of 23 ° C. The elongation at break and the tensile elastic modulus were measured in the extrusion direction and the width direction (direction perpendicular to the extrusion direction) of the resin film for a diaphragm.

[Comparative Example 1]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. The same polyetheretherketone resin as in Example 1 was used as the polyarylene ether ketone resin. As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours. As the adhesive fluororesin, 0.5 parts by mass of the adhesive fluororesin EA-2000 used in Example 1 was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The temperature at the time of melt-kneading was determined to measure the temperature of the molded material in the molten state immediately after being extruded from the die, and the measured temperature was 369 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 24 hours, and the moisture content of the molding material dried by the same method as in Example 1 was measured, and the moisture content of the dried molding material was measured. After confirming that the content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 391 ° C. The temperature of the cooling roll was set in the same manner as in Example 1.

After producing the resin film for the diaphragm of the speaker, the film thickness, tensile elastic modulus, heat resistance property, and acoustic property of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are shown in Table 3.

[Comparative Example 2]
First, a molding material was prepared from a polyarylene ether ketone resin and an adhesive fluororesin. The same polyetheretherketone resin as in Example 3 was used as the polyarylene ether ketone resin. As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours. As the adhesive fluororesin, 130 parts by mass of the adhesive fluororesin EA-2000 used in Example 1 was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The temperature at the time of melt-kneading was determined to be the temperature of the molded material in the molten state immediately after being extruded from the die, and was measured to be 366 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 24 hours, and the moisture content of the molding material dried by the same method as in Example 1 was measured, and the moisture content of the dried molding material was measured. After confirming that the content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 390 ° C. The temperature of the cooling roll was set in the same manner as in Example 1.

After producing the resin film for the diaphragm of the speaker, the film thickness, tensile elastic modulus, heat resistance property, and acoustic property of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are shown in Table 3.

[Comparative Example 3]
First, a molding material was prepared with a polyarylene ether ketone resin and a fluororesin tetrafluoride / perfluoroalkoxyethylene copolymer (hereinafter abbreviated as “PFA resin”) which is a fluororesin having no adhesiveness. The same KT-851NL SP as in Example 4 was used as the polyarylene ether ketone resin. As a molding material, 100 parts by mass of a polyetheretherketone resin was prepared, and the polyetheretherketone resin was dried in a dehumidifying dryer heated to 160 ° C. for 12 hours. As the PFA resin, 15 parts by mass of commercially available NEOFLON AP-201 [manufactured by Daikin Industries, Ltd .: product name, (hereinafter abbreviated as "AP-201")] was prepared.

After preparing these, a molding material was prepared by the same method as in Example 1. The cylinder temperature of the co-rotating twin-screw extruder was changed to 380 ° C, and the die temperature was changed to 380 ° C. Further, the temperature at the time of melt-kneading was determined to measure the temperature of the molded material in the molten state immediately after being extruded from the die, and the measured temperature was 377 ° C.

Next, the molding material was put into a dehumidifying dryer heated to 160 ° C. and dried for 24 hours, the moisture content of the molding material dried by the same method as in Example 1 was measured, and then the moisture content of the dried molding material was measured. After confirming that the water content was 300 ppm or less, a resin film for a vibration plate of the speaker was manufactured by the same method as in Example 1. Regarding the temperature of the molten molding material, it was decided to measure the resin temperature at the inlet of the T die, and the measured temperature was 389 ° C. The temperature of the cooling roll was the same as in Example 1.

After producing the resin film for the diaphragm of the speaker, the film thickness, tensile elastic modulus, heat resistance property, and acoustic property of the resin film for the diaphragm were evaluated according to the method of Example 1, and the results are shown in Table 3.

[Result]
In the resin film for the vibrating plate of each example, the polyether ether ketone resin film of Comparative Example 1 and the PFA resin which is a fluororesin having no adhesiveness from the adhesive fluororesin of Comparative Example 3 are used as the polyether ether ketone resin. Compared with the resin film for a vibrating plate obtained by addition, the tensile elastic coefficient is 850 N / mm ² or more and 2260 N / mm ² or less, showing a low tensile elastic coefficient, and it is presumed that the bass reproduction characteristics are excellent. On the other hand, in the cases of Comparative Examples 1 and 3, since the tensile elastic modulus exceeds 2800 N / mm ² , it is presumed that the bass reproduction characteristics are insufficient.

The loss tangent at 20 ° C. of the resin film for the diaphragm obtained in each example increased to 0.014 or more, and the occurrence of resonance was suppressed and good sound quality characteristics could be obtained. Further, unlike Comparative Example 2, the elongation at break of the resin film for the diaphragm of each example was 86% or more, and it was confirmed that the durability was sufficient. The first inflection temperature of each embodiment is 140 ° C. or higher, and it is presumed that the temperature is sufficiently heat resistant to be used as a resin film for a diaphragm.

On the other hand, in the case of Comparative Example 1, since the adhesive fluororesin was not added, the tensile elastic modulus of the resin film for the diaphragm ^{showed a high tensile elastic modulus at 2800 N / mm 2} or more, and the bass reproduction characteristic. The loss tangent at 20 ° C was less than 0.010. As a result, the occurrence of resonance could not be suppressed, and good sound quality could not be obtained.

In the case of Comparative Example 2, since 150 mass of the adhesive fluororesin was added to 100 parts by mass of the crystalline thermoplastic polyimide resin, the elongation at tensile break of the resin film for the vibrating plate was less than 50%, and the resin film for the vibrating plate was used. When the resin film was used for the vibrating plate, there was a problem with durability. In addition, the handleability was poor, and there was a problem in the formability of the diaphragm of the speaker.

For Comparative Example 3, the resin film diaphragm addition of PFA resin is a fluororesin having no adhesion, tensile modulus of greater than 2800N / mm ^2, was also increased f ₀ value.
From the above results, the polyarylene ketone resin film to which the adhesive fluororesin is added has an appropriate tensile elastic modulus, so that when it is used as a resin film for a diaphragm of a speaker, it has bass reproduction characteristics and durability. In addition to heat resistance, it is presumed to have excellent sound quality characteristics.

The resin film for a diaphragm of a speaker and a method for manufacturing the same according to the present invention, and the diaphragm of a speaker are used in the manufacturing field of audio equipment, portable equipment and the like.

1 Molding material 2 Resin film for diaphragm 10 Melt extrusion molding machine 13 T die (die)
17 Crimping roll 18 Cooling roll 19 Winder 30 Diaphragm 31 Elastomer layer 32 Primer layer

Claims (7)

A resin film for a diaphragm of a speaker, which is molded from a molding material containing 100 parts by mass of a polyarylene ether ketone resin and 1 part by mass or more and 100 parts by mass or less of an adhesive fluororesin. Tensile and a modulus of 100 N / mm ² or more 2500N / mm ² or less, the vibration plate resin film speaker according to claim 1, wherein the elongation at break Tensile at 23 ° C. is 50% or more at 23 ° C.. The resin film for a diaphragm of a speaker according to claim 1 or 2, wherein the loss tangent at 20 ° C. is 0.010 or more, and the first inflection temperature of the stored elastic modulus after cooling is 130 ° C. or higher. The method for manufacturing a resin film for a diaphragm of a speaker according to claim 1, 2, or 3.
A molding material is prepared by melt-kneading 100 parts by mass of a polyarylene ether ketone resin and 1 part by mass or more and 100 parts by mass or less of an adhesive fluororesin, and this molding material is put into an extrusion molding machine and used for a vibrating plate by a die. A method for manufacturing a resin film for a diaphragm of a speaker, which comprises extruding the resin film into a resin film and bringing the resin film for the diaphragm into contact with a cooling roll to cool the resin film. A speaker diaphragm, wherein the resin film for a speaker diaphragm according to claim 1, 2 or 3 is laminated with an elastomer layer having a thickness of 10 μm or more and 100 μm or less. The diaphragm of the speaker according to claim 5, wherein the elastomer layer is a silicone resin, and the durometer hardness of the silicone resin is A10 or more and A90 or less when measured with a durometer type A in accordance with JIS K 6253. The speaker diaphragm according to claim 6, wherein a primer layer is interposed between the silicone resin and the diaphragm resin film.

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