US3907063A - Non-flammable paper for speaker cones - Google Patents

Non-flammable paper for speaker cones Download PDF

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Publication number
US3907063A
US3907063A US489156A US48915674A US3907063A US 3907063 A US3907063 A US 3907063A US 489156 A US489156 A US 489156A US 48915674 A US48915674 A US 48915674A US 3907063 A US3907063 A US 3907063A
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United States
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weight
parts
chlorinated
speaker
loudspeaker
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US489156A
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Masahiko Nakazawa
Shizuo Nakamura
Mutumi Nakayama
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Adeka Corp
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Asahi Denka Kogyo KK
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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction

Definitions

  • a non-flammable paper for speaker cones is prepared by adding (1) chlorinated polyolefin having a molecu- [3O] Forelgn Apphcaton Pnonty Data lar weight of from 500 to 40,000 and a chlorine con- July 19, 1973 Japan 48-81162 tent of from 40 to 75 weight percent, or (1) brominecontaining chlorinated polyolefin having a molecular US s 6 weight of from 500 to 40,000, a chlorine content of [51] Int. Cl.
  • EXAMPLE 1 COM PAPATIVE EXAMPLE 1 SOUND PPESSURE (ab) I00 Z00 500 I000 2000 500010000 FREQUENCY (CYCLES PER SECOND) i PEIOQ 1 NON-FLAMMABLE PAPER FOR SPEAKER CONES BACKGROUND OF THE INVENTION 1.
  • This invention relates to a loudspeaker having a diaphragm or speaker cone made of a special non-flammale paper. Particularly, this invention relates to a paper for speaker cones having a good non-flammable property and good sound-reproducing characteristics.
  • This invention also Description of the Prior Art speaker cones which is capable of maintaining its strength for a long period of time because it possesses extremely reduced hygroscopic and increased metal protecting properties.
  • paper made of cellulosic fibers has been used as the material for making speaker cones because of its advantages such as its relatively low density, high Youngs modulus, high propagation velocity of longitudinal waves, moderate vibration loss, etc.
  • fire-retardants such as the following organic phosphorous compounds, halogenated organic compounds and inorganic compounds have been used as additives for imparting to paper a non-flammable property.
  • Such organic phosphorous compounds include tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, trichloroethyl phosphate, tributyl phosphate, triphenyl phosphate, tris(dichloropropyl) phosphate, tris(dibromopropyl) phosphate, chlorophosphonate, bromophosphonate, phosphorus-containing polyols and phosphonitrile chloride.
  • Representative halogenated organic compounds are chlorendic acid, perbrominated polyols, tetrabrominated phthalic anhydride, tetrabrominated bisphenol A, tetrachlorinated phthalic anhydride, decachlorobiphenyl, chlorinated paraffin, polyvinyl chloride, polyvinylidene chloride, etc.
  • representative inorganic compounds are alkali metal or alkali earth metal salts of phosphoric acid and boric acid, etc.
  • fireretardants cannot impart a sufficient non-flammable property to paper.
  • these fire-retardants are hygroscopic and therefore cause variations of sound reproduction caused by the decrease in strength and the deformation of the speaker cones due to variations in ambient humidity. Similar phenomena are caused by heat applied during processing.
  • above-mentioned halogenated organic compounds are corrosive to metals and therefore cause the corrosion of the parts of speaker cones made from metals due to dehydrohalogenation.
  • FIG. 1 is a graph showing the relationship between the frequency and the sound intensity of speaker cones.
  • FIG. 2 is a sectional view of a typical conventional loudspeaker, the cone of which can be made of the special paper in accordance with this invention.
  • the speaker cone of this invention has a good nonflammable property; and it possesses good soundreproducing characteristics.
  • Another object of this invention is to provide a speaker cone capable of maintaining its strength for a long period of time because of its extremely reduced hygroscopicity and increased metal protecting properties.
  • the physical shape and size of the speaker cone is not critical, according to this invention.
  • the speaker cone can be of any suitable shape and size in accordance with conventional practices in the loudspeaker art for the use of paper speaker cones or diaphragms, and the invention does not pertain to any improvement in such physical features.
  • FIG. 2 a prior art loudspeaker construction (US. Pat. No. 3 436 494) and illustrating the shape of one representative speaker cone.
  • the loudspeaker comprises a housing 2 having a permanently magnetized pole piece 4 and a core 6 with a space for receiving a voice coil 8 of a cone-shaped diaphragm or speaker cone 10.
  • the voice coil 8 has electrically conductive wires 12 wound around the exterior surface thereof.
  • the pole piece 4 and the core 6 provide a magnetic flux in the voice coil aperture 14 and AC electric signals conducted through wires 12 generate a second magnetic flux.
  • the interaction of the two magnetic fluxes induces axial movement of the voice coil to which the speaker cone 10 is attached.
  • Speaker cone 10 is supported by a compliant annulus 13 at the top and bottom.
  • the speaker cone 10 can be made of the special paper in accordance with this invention.
  • the invention is not limited to the speaker cone of the shape illustrated in FIG. 2 and that the invention can be incorporated into speaker cones of various shapes and sizes in accordance with the conventional practice in the art of loudspeakers using paper speaker cones and diaphragms.
  • the speaker cone of this invention is made of cellulosic fiber paper.
  • the paper contains as essential additive constituents uniformly distributed in the cellulosic fibers, (1) chlorinated polyolefin powder or (1) bromine-containing chlorinated polyolefin powder and (2) antimony trioxide.
  • chlorinated polyolefins are chlorinated polyethylene, chlorinated polypropylene and chlorinated rubber, wherein rubber means natural or synthetic rubber.
  • rubber means natural or synthetic rubber.
  • Such synthetic rubber includes polyisoprene rubber, polyisobutene rubber, butyl rubber, SB rubber, polybutadiene rubber, neoprene rubber and nitrile rubber, and the most prefera ble is polyisoprene rubber.
  • These chlorinated polyolefin materials such as chlorinated polyethylene, chlorinated polypropylene and chlorinated rubber are conventionally produced as follows.
  • a starting material of polyethylene, polypropylene or natural or synthetic rubber is dissolved in one or a mix ture of two or more halogenated hydrocarbon solvents and then it it is chlorinated by introducing a gas containing at least 80volume percent of chlorine, and which can contain more than 0.1 volume percent of oxygen and/or ozone, at l7070 C, preferably 4060C, in the presence of mineral acids containing water and radical initiators, whereby to form a reaction mixture containing chlorinated polyolefin having a chlorine content of from 40 to 75 weight percent.
  • the chlorinated polyolefin powder having a molecular weight of 500 to 40,000 and preferably, a particle size of more than 300 mesh and less than 80 mesh, is obtained by steam distillation of the reaction mixture or precipitation in water. If the need arises, pulverization can be carried out after steam distillation or precipitation in order to adjust the particle size of the chlorinated polyolefin powder.
  • the halogenated hydrocarbon solvents used for dissolving said starting polyolefin must be inert during the chlorination step.
  • the preferred solvents are halogenated lower aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene and tetrachloroethylene, and halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene.
  • the most preferred and practical solvent is carbon tetrachloride because of the solubility of the polyolefins therein, the ease of solvent removal after chlorination, and the closeness of its boiling point to that of the reaction temperature.
  • the amount of polyolefin dissolved in the halogenated hydrocarbon solvent is in the range of l to 20, preferably 3 to 10, percent by weight.
  • the preferred mineral acids are phosphoric acid, sulfuric acid, hydrochloric acid, etc.
  • the concentration thereof in the aqueous acid solution is usually more than 0.1 N.
  • the amount of aqueous mineral acid solution added to the solution of polyolefin in the halogenated hydrocarbon solvent is from 0.5 to 3.1, preferably l to 2, parts by weight, per one part by weight of polyolefin.
  • the addition of mineral acid to the chlorination reaction system is not always essential during the initial stage of the chlorination reaction, because the hydrogen chloride gas by-produced during the chlorination becomes dissolved in the water added at the initial stage to form aqueous hydrochloric acid solution.
  • the concentration of the mineral acid aqueous solution must be more than 0.1 N during the final stage of the chlorination reaction.
  • radical initiators used in this reaction are nitrogen-containing compounds (azo compounds) having the following formula:
  • R I R" R C N N C R'" l X X wherein R, R, R" and R, which can be the same or different, are alkyls having one to four carbon atoms, and X is CN or C0 R, wherein R' is alkyl having one to four carbon atoms.
  • the amount of these azo compounds such as azobisisobutyronitrile, added to the reaction system is from 0.01 to 1.0, preferably 0.1 to 0.5, percent by weight, based on the weight of said polyolefin.
  • the chlorine gas used for chlorinating the polyolefins in the halogenated hydrocarbon solvents can be supplied in admixture together with oxygen and/or ozone. Howex er, the gas mixture must contain at least volume percent of chlorine.
  • the oxygen employed can be the oxygen gas industrially produced by air fractionation of gaseous mixtures of oxygen together with inert gases such as nitrogen and carbon dioxide, or air. Ozone, produced industrially for example by corona discharge, can also be used together with the chlorine gas.
  • the oxygen and/or ozone content of the chlorinecontaining gas is less than 0.1 volume percent, the stabilizing effect of oxygen on the chlorinated polyolefin cannot be observed.
  • the upper limit of the oxygen and/or ozone content of the chlorine-containing gas is 20 volume percent in order to maintain the chlorine content of the gas high enough to highly chlorinate polyolefins from the economical point of view.
  • the preferred range of oxygen and/or ozone content is 0.1 to 10 volume percent.
  • the oxygen can also be supplied in the form of air.
  • the reaction gas can contain nitrogen as a nonreactive diluent, provided that the chlorine content of the gas is at least 80 volume percent.
  • Bromine-containing chlorinated polyolefins are also effective for the purpose of this invention. These brominecontaining chlorinated polyolefins are produced in such a way as disclosed in the Japanese Patent Publication No. 49-8952. The water suspension of the polyolefins listed above is reacted with a brominating agent and chlorine gas to give a bromine-containing chlorinated polyolefins.
  • the preferred example is a bromine-containing polyolefin having a chlorine content of from 10 to 30 percent by weight and a bromine content of from 60 to 80 percentv
  • powders of chlorinated polymers have been obtained by either direct pulverization of the solid polymers or the removal of solvent from solvent solutions of the polymers by steam distilling, precipitating or spraying the reaction solution.
  • the powder of chlorinated polyolefins used in this invention is obtained most preferably by removing the solvent from the reac- 6
  • the amount of chlorinated polyolefins added to the pulp is from 10 to 50, preferably 20 to 40, parts by weight, per 100 parts by weight of fibers.
  • the preferred fixing agents are polyacryl amides, modified epoxy restion solution by means of steam distillation or precipi- 5 ins, starches, polyethylene imines, polyethylene oxides, tation into water.
  • pulverization can be carpolyvinyl alcohol, ethylene-vinyl acetate copolymer, ried out after said solvent removal to adjust the particle and carboxymethyl cellulose, the amount of antimony size.
  • Chlorinated polyolefins obtained by steam distillatrioxide added to the pulp is from 5 to 40, preferably 10 tion are macroscopically thin leaf or scale-like powders to 30 parts by weight, per 100 parts by weight of fibers. of low bulk density.
  • the amount of fixing agent added is from 1 to Chlorinated polyolefin powders obtained by precipi- 5, preferably 3 to 5, parts by weight, per 100 parts by tation in non-solvents, for example water, are macroweight of fibers.
  • scopically globular or ellipsoidal powders are macroweight of fibers.
  • the preferred coagulating agents are polyacrylpowders have more uniform particle sizes, compared amide, aluminum sulfate, polyaluminium chloride, with powders obtained by the other methods, and are, polyethylene imine, modified polyamide-epichlorohytherefore, more preferable for use in this invention.
  • the particle size of chlorinated polyolefins in this inpulp is from 0.01 to 0.1, preferably 0.05 to 0.08, parts vention is preferably more than 300 mesh size and less by weight, per 100 parts by weight of fibers. than 80 mesh size.
  • parts vention is preferably more than 300 mesh size and less by weight, per 100 parts by weight of fibers. than 80 mesh size.
  • This invention provides a non-flammable speaker Another essential constituent present in the paper of come capable of maintaining its strength for a long perthe speaker cone, namely, (2) antimony trioxide is also iod of time because of its extremely reduced hygroemployed in the form of a powder of preferably more scopicity and its improved metal protecting property. than 300 mesh size and less than 80 mesh size.
  • the speaker cone of this invention is prepared in the'followmolecular weight and the chlorine content of chlori ing way.
  • nated polyolefins must be from 500 to 40,000 and from The preparation of the paper pulp fibers can be car- 40 to 75 weight percent, respectively.
  • the beaten pulp is thoroughly mixed with dyes, lower molecular weights and chlorine contents than the pigments and paper strengthening agents, and with the above-mentioned ranges does not impart sufficient chlorinated polyolefins and antimony trioxide in a non-flammability to the speaker cones, it causes stickibeater, in the same manner as is conventional for sizing ness of the speaker cones and a decrease of the sizing paper.
  • These additives are precipitated on the fibers by degree. adding a precipitating and fixing agent such as alumi- A preferred example of the preparation of chlorinum sulfate, as is conventional.
  • nated polyolefins an essential constituent of this invenother additives such as coagulating agents is extremely tion, is as follows: effective.
  • a chlo- The pulp-water suspension is poured into a porous rine introducing tube, a thermometer and a condenser, mold to form a paper product in the form of a speaker are charged 60 parts (the term parts employed cone.
  • the speaker-cone-type paper product is therein refers to parts by weight) of polyethylene dried to give a speaker cone.
  • the speaker (Trademark Sumikathene G 801 melt index 20) and cone can be shaped by compression molding.
  • CPE-Z, CPP 1 CPP-2, paste, polyacrylamide, ureaformaldehyde resins, epoxy CR-l and CR-2 are produced in a similar way as in the resins, polyethylene imine, polyethylene oxide and mixproduction of CPE1. Their chlorine content, molecutures thereof.
  • the amount of paper strengthening agent lar weight and particle size are shown in Table 1. added to the pulp is from 0.1 to 5 parts by weight, per 100 parts by weight of fibers.
  • Table 2 shows the amount of each ingredient added and the non-flammability and sound-reproducing char- Speaker cones are produced in the following way. acteristics of the speaker cones produced.
  • FIG. 1 shows the relationship between the frequency and the sound pressure level of speaker Pans cones in this invention.
  • direct black dye 3 speaker cones of this invention have improved sound Paper Strengthcnmg characteristics in the high frequency region and give a (urea-formaldehyde resin) 3 chlorinated polymer", 30 substantially flat sound pressure level in the middle freantimony trioxide quency regi n aluminum sulfate 5 coagulating agent (Trademark Aquoflock) 008 TABLE 2
  • Addition amount (parts) fibers dye paper fire fixing agent coagulating strengthening retardant agent agent N.B.K direct urea- CPE-l/ aluminum Aquoflock (20SR) black fonnaldehyde pans sulfate 305
  • Example 2 31 250 Example 3 33 210 Example 4 3] 250 Example 5 32 200
  • Example 6 30 240 Addition amount (parts) fiber dye paper fire fixing coagulating strengthening retardant agent agent agent N.B.K,, direct ureaphosphoaluminum Aquoflock Comparative (20SR) black formaldehyde nitrile sulfate 305
  • Example 1 100 dye resin chloride 5 parts 0.08 parts parts 3 parts 3 parts parts Comparative polyvinyl
  • Example 2 chloride 50 parts Comparative none Example 3 fiber content weight/area oxygen index propagation frequency in water velocity character suspension istics Comparative 0.05% 30 g/m 23 900 m/sec dotted line Example 1 in FIG.
  • a loudspeaker of the type which comprises a speaker diaphragm or cone adapted to generate sonic and/or subsonic vibrations in response to an electrical signal
  • said diaphragm or speaker cone is made of cellulose fiber paper containing uniformly distributed therein l from 10 to 50 parts by weight of particles of chlorinated polyolefin having a molecular weight of from 500 to 40,000 and a chlorine content of from 40 to 75 percent by weight and (2) from 5 and 40 parts by weight of particles of antimony trioxide, the amounts of (l) and (2) each being based on 100 parts by weight of cellulosic fibers, whereby said diaphragm or speaker cone is non-flammable.
  • a loudspeaker according to claim 1 wherein said chlorinated polyolefin is chlorinated polypropylene.
  • a loudspeaker according to claim 1 wherein said chlorinated polyolefin is chlorinated polyethylene.
  • chlorinated polyolefin is a mixture comprising at least two components selected from the group consisting of chlorinated polyethylene, chlorinated polypropylene and chlorinated natural or synthetic rubber.
  • a loudspeaker of the type which comprises a speaker diaphragm or cone adapted to generate sonic and/or subsonic vibrations in response to an electrical signal
  • said diaphragm or speaker cone is made of cellulose fiber paper containing uniformly distributed therein 1) from 10 to 50 parts by weight of particles of bromine containing chlorinated polyolefin having a molecular weight of from 500 to 40,000, a chlorine content of from 10 to 30 percent by weight and a bromine content of from 60 to percent by weight, and (2) from 5 to 40 parts by weight of particles of antimony trioxide, the amounts of (l) and (2) each being based on parts by weight of cellulosic fibers, whereby said diaphragm or speaker cone is nonflammable.

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  • Engineering & Computer Science (AREA)
  • Multimedia (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Signal Processing (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
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US489156A 1973-07-19 1974-07-17 Non-flammable paper for speaker cones Expired - Lifetime US3907063A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2345048A1 (fr) * 1976-03-19 1977-10-14 Harwood Hugh Membrane de transducteur electro-acoustique
US4086449A (en) * 1974-05-14 1978-04-25 Matsushita Electric Industrial Co., Ltd. Loudspeaker with burning resistant diaphragm
US4291781A (en) * 1978-10-17 1981-09-29 Matsushita Electric Industrial Co., Ltd. Speaker diaphragm and method of preparation of the same
EP0034503B1 (en) * 1980-02-21 1984-05-16 Wharfedale Limited Improvements in moving coil loudspeakers
US4451609A (en) * 1981-06-26 1984-05-29 Pioneer Electronic Corporation Flame-retarded acoustic diaphragm
US4472543A (en) * 1981-06-01 1984-09-18 Pioneer Electronic Corporation Flame retardant diaphragm for acoustic transducers
US5920040A (en) * 1997-02-27 1999-07-06 Kenneth R. Lavacot Speaker diaphragm
US20050178516A1 (en) * 2004-02-13 2005-08-18 Pioneer Corporation Speaker component, method of manufacturing the same and speaker apparatus including the same
US20060062423A1 (en) * 2004-09-22 2006-03-23 Kazuharu Kawata Speaker diaphragm and method of forming the same
KR101464132B1 (ko) * 2013-12-09 2014-11-21 에스텍 주식회사 종이 진동판의 제조방법
US20160032583A1 (en) * 2014-08-01 2016-02-04 Usg Interiors, Llc Acoustic ceiling tiles with anti-sagging properties and methods of making same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1759387A (en) * 1928-10-16 1930-05-20 Specialty Insulation Mfg Compa Acoustic diaphragm and process for its manufacture
US2416447A (en) * 1943-07-27 1947-02-25 Du Pont Weather resistant flameproof paper
US3092537A (en) * 1959-06-05 1963-06-04 Cons Paper Corp Ltd Flameproofing of organic materials
US3436494A (en) * 1965-10-11 1969-04-01 R T Bozak Mfg Co The Compliant annulus for loudspeaker and related circuit
US3560441A (en) * 1968-12-16 1971-02-02 M & T Chemicals Inc Antimony trioxide inorganic compound glass flame retardant compositions and methods for their preparation
US3624028A (en) * 1970-05-12 1971-11-30 Phillips Petroleum Co Processing of flame-resistant polymers
US3738958A (en) * 1972-02-10 1973-06-12 Thiokol Chemical Corp Synergistic flame retarding composition for polypropylene of 1,2,3,4,5-pentabromo-6-chlorocyclohexane,tetrabromophthalic anhydride and antimony trioxide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1759387A (en) * 1928-10-16 1930-05-20 Specialty Insulation Mfg Compa Acoustic diaphragm and process for its manufacture
US2416447A (en) * 1943-07-27 1947-02-25 Du Pont Weather resistant flameproof paper
US3092537A (en) * 1959-06-05 1963-06-04 Cons Paper Corp Ltd Flameproofing of organic materials
US3436494A (en) * 1965-10-11 1969-04-01 R T Bozak Mfg Co The Compliant annulus for loudspeaker and related circuit
US3560441A (en) * 1968-12-16 1971-02-02 M & T Chemicals Inc Antimony trioxide inorganic compound glass flame retardant compositions and methods for their preparation
US3624028A (en) * 1970-05-12 1971-11-30 Phillips Petroleum Co Processing of flame-resistant polymers
US3738958A (en) * 1972-02-10 1973-06-12 Thiokol Chemical Corp Synergistic flame retarding composition for polypropylene of 1,2,3,4,5-pentabromo-6-chlorocyclohexane,tetrabromophthalic anhydride and antimony trioxide

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086449A (en) * 1974-05-14 1978-04-25 Matsushita Electric Industrial Co., Ltd. Loudspeaker with burning resistant diaphragm
FR2345048A1 (fr) * 1976-03-19 1977-10-14 Harwood Hugh Membrane de transducteur electro-acoustique
US4291781A (en) * 1978-10-17 1981-09-29 Matsushita Electric Industrial Co., Ltd. Speaker diaphragm and method of preparation of the same
EP0034503B1 (en) * 1980-02-21 1984-05-16 Wharfedale Limited Improvements in moving coil loudspeakers
US4472543A (en) * 1981-06-01 1984-09-18 Pioneer Electronic Corporation Flame retardant diaphragm for acoustic transducers
US4451609A (en) * 1981-06-26 1984-05-29 Pioneer Electronic Corporation Flame-retarded acoustic diaphragm
US5920040A (en) * 1997-02-27 1999-07-06 Kenneth R. Lavacot Speaker diaphragm
US20050178516A1 (en) * 2004-02-13 2005-08-18 Pioneer Corporation Speaker component, method of manufacturing the same and speaker apparatus including the same
US20060062423A1 (en) * 2004-09-22 2006-03-23 Kazuharu Kawata Speaker diaphragm and method of forming the same
KR101464132B1 (ko) * 2013-12-09 2014-11-21 에스텍 주식회사 종이 진동판의 제조방법
US20160032583A1 (en) * 2014-08-01 2016-02-04 Usg Interiors, Llc Acoustic ceiling tiles with anti-sagging properties and methods of making same
US9492961B2 (en) * 2014-08-01 2016-11-15 Usg Interiors, Llc Acoustic ceiling tiles with anti-sagging properties and methods of making same

Also Published As

Publication number Publication date
JPS5346087B2 (US08142518-20120327-C00011.png) 1978-12-11
JPS5029028A (US08142518-20120327-C00011.png) 1975-03-24

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