JP2005282623A - Spherical zone seal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spherical zone seal, having heat resistance and oxidation wear resistance from room temperature to a high temperature range around 700°C, and having excellent seal performance to have similar performance to that of an existing spherical zone seal, in which, in its manufacturing method, defects of material yield of heat resistant sheet material are eliminated to reduce manufacturing cost. <P>SOLUTION: This spherical zone seal 58 is provided with a spherical zone base body 56, provided with a through hole 51 at a center, and defined by a cylindrical inner surface 52, a partially protruding spherical surface 53, and circular end faces 54 and 55 on the large diameter side and the small diameter side of the partially protruding spherical surface 53, and an outer layer integrally formed with the partially protruding spherical surface 53 of the spherical zone base body 56. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a ball-shaped seal body used for a spherical pipe joint of an automobile exhaust pipe.

JP 54-76759 A Japanese Patent No. 3139179 Japanese Patent Laid-Open No. 10-9396 JP-A-10-9397 Japanese Patent Laid-Open No. 10-220584 Japanese Patent Laid-Open No. 10-220585 Japanese Patent Laid-Open No. 10-231934

  The ball-shaped seal body used for spherical joints in conventional exhaust pipes for automobiles has heat resistance, excellent compatibility with the mating material, and significantly improved impact strength. The lower friction often has the disadvantage of generating abnormal frictional noise (as described in Patent Document 1). The disadvantage of this seal body is that the difference between the coefficient of static friction and the coefficient of dynamic friction of the heat-resistant material (expanded graphite, etc.) forming the seal body is large, and that the seal body made of this heat-resistant material has a negative resistance to the sliding speed. This is considered to be caused by the fact that

  Therefore, in order to eliminate the above-described drawbacks, the present applicant has proposed a sealing body that satisfies the performance required for a sealing body that is excellent in sealing performance without causing abnormal frictional noise when sliding with a counterpart material. (Patent Document 2).

  However, even with the above-described seal body, new problems have been raised due to the recent improvement in performance of automobile engines. That is, when a spherical pipe joint is arranged near the exhaust gas outlet (manifold) for the purpose of improving the NVH characteristic (vehicle acoustic vibration characteristic) of the automobile due to the increase in the exhaust gas temperature resulting from the performance improvement of the automobile engine Due to the rise in exhaust gas temperature caused by the closer fitting of the spherical pipe joint to the engine side, the conventional seal body cannot satisfy the use conditions in terms of heat resistance, and the heat resistance of the seal body itself is inevitably improved. ing.

  In response to the newly raised problems, the present applicant has proposed a ball-shaped seal body with improved heat resistance and a method for producing the same (Patent Document 3 to Patent Document 7).

  The above-mentioned spherical belt-shaped sealing body has little oxidation consumption even at a high temperature of 600 to 700 ° C., does not generate abnormal friction noise, has excellent sealing properties, and satisfies the function as a sealing body. Since the band-shaped sealing body uses a heat-resistant sheet material, for example, a heat-resistant sheet material provided with a heat-resistant film of a heat-resistant material on the surface of the expanded graphite sheet, the expanded graphite sheet sacrifices the flexibility inherent to the expanded graphite sheet. As a result, there is a risk that the heat-resistant coating will often be cracked or damaged in the bending process, etc., which occurs in the manufacturing process of the ball-shaped seal body, resulting in damage to the heat-resistant sheet material, etc. In this respect, there is still room for improvement, and by eliminating the disadvantages of material yield, the manufacturing process of the ball-shaped seal body is shortened, and thus the manufacturing cost is reduced. It was found to have advantages such as lead.

  The present invention has been made in view of the above-mentioned points, and the object of the present invention is that it has heat resistance and oxidation wear resistance and excellent sealing properties even in a high temperature region from room temperature to around 700 ° C. To provide a spherical belt-shaped sealing body having performance equivalent to that of a prior art spherical belt-shaped sealing body, which eliminates the defect of the material yield of the heat-resistant sheet material and can reduce the manufacturing cost. is there.

  A spherical belt-shaped sealing body according to a first aspect of the present invention includes a spherical belt-shaped substrate defined by a cylindrical inner surface, a partially convex spherical surface, and annular end surfaces on the large-diameter side and small-diameter side of the partially convex spherical surface, In particular, it is used for an exhaust pipe spherical joint, which is provided with an outer layer integrally formed on a partially convex spherical surface of a spherical base, wherein the spherical base is a reinforcement made of a compressed wire mesh. And a heat-resistant material containing expanded graphite, phosphorus pentoxide, and an organic phosphorus compound, filled with a wire mesh of the reinforcing material, mixed and integrated with the reinforcing material, and compressed. Has a heat-resistant material containing expanded graphite, phosphorus pentoxide and an organophosphorus compound, and a reinforcing material made of a wire mesh mixed and integrated with this heat-resistant material, and has a partially convex spherical shape exposed to the outside in the outer layer. The outer surface is a smooth and integrated heat-resistant material and reinforcing material. Characterized in that it has become.

  According to the spherical belt-shaped sealing body of the first aspect, the spherical belt-shaped substrate defined by the cylindrical inner surface, the partially convex spherical surface, and the annular end surfaces on the large diameter side and the small diameter side of the partial convex spherical surface is compressed. A reinforcing material made of a wire mesh, and a heat-resistant material containing expanded graphite, phosphorus pentoxide, and an organic phosphorus compound that are filled with the reinforcing material and meshed together and compressed. Therefore, the oxidative consumption of the expanded graphite, which is the main component of the heat-resistant material, is reduced even in the high temperature region around 700 ° C. due to the oxidation-inhibiting action of phosphorus pentoxide and organophosphorus compounds, resulting in improved heat resistance of the spherical seal To do.

  Further, the outer layer has a heat-resistant material containing expanded graphite, phosphorus pentoxide and an organic phosphorus compound, and a reinforcing material made of a wire mesh mixed and integrated with the heat-resistant material, and the outer layer is exposed to a partially convex spherical shape. Since the outer surface of the surface is formed as a smooth surface in which the heat-resistant material and the reinforcing material are mixed and integrated, the expanded graphite, which is the main component of the heat-resistant material, is 700 ° C. due to the oxidation-inhibiting action of phosphorus pentoxide and organic phosphorus compounds. Oxidation consumption is reduced even in the nearby high temperature region, and in sliding contact with the mating material, formation of an excessive coating of heat-resistant material that forms an outer surface layer on the mating material surface is suppressed, and smooth sliding with the mating material surface is achieved. Contact is made.

  A spherical belt-shaped sealing body according to a second aspect of the present invention includes a spherical belt-shaped substrate defined by a cylindrical inner surface, a partially convex spherical surface, and annular end surfaces on the large-diameter side and small-diameter side of the partially convex spherical surface, In particular, it is used for an exhaust pipe spherical joint, which is provided with an outer layer integrally formed on a partially convex spherical surface of a spherical base, wherein the spherical base is a reinforcement made of a compressed wire mesh. And a heat-resistant material containing expanded graphite, phosphorus pentoxide, and an organic phosphorus compound, filled with a wire mesh of the reinforcing material, mixed and integrated with the reinforcing material, and compressed. Has a lubricating composition comprising at least one of boron nitride and at least one of alumina and silica, and a reinforcing material comprising a wire mesh mixed and integrated with the lubricating composition, and is exposed to the outside in the outer layer. The partially convex spherical outer surface is Wherein the slip composition and the reinforcing material is in the mixed integrated smooth lubrication sliding surface.

  According to the spherical belt-shaped sealing body of the second aspect, the spherical belt-shaped substrate defined by the cylindrical inner surface, the partially convex spherical surface, and the annular end surfaces on the large diameter side and the small diameter side of the partial convex spherical surface is compressed. And a heat-resistant material containing expanded graphite, phosphorus pentoxide and an organophosphorus compound, filled with the mesh of the reinforcement mesh, and mixed and integrated with the reinforcement. Therefore, the oxidative consumption of the expanded graphite, which is the main component of the heat-resistant material, is reduced even in a high-temperature region near 700 ° C. due to the oxidation-inhibiting action of phosphorus pentoxide and organophosphorus compounds. Improves.

  The outer layer has a lubricating composition composed of at least boron nitride and at least one of alumina and silica, and a reinforcing material composed of a metal mesh mixed and integrated with the lubricating composition. The partially convex spherical outer surface exposed to the surface is a smooth lubricating sliding surface in which the lubricating composition and the reinforcing material are mixed and integrated, so that smooth sliding is performed in sliding contact with the counterpart material. .

  In the spherical band-shaped sealing body of the second aspect, the lubricating composition is 70 to 90% by weight of boron nitride and at least one of alumina and silica is 10 as in the spherical band-shaped sealing body of the third aspect of the present invention. -30 wt% may be included.

  According to the spherical band-shaped sealing body of the third aspect, the partially convex spherical shape of the outer layer of the lubricating composition containing 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica. The outer surface of the metal is formed on a smooth surface exposed by a reinforcing material made of a wire mesh mixed and integrated with the lubricating composition, so that smooth sliding is performed particularly in the initial sliding with the counterpart material. The occurrence of abnormal sliding friction noise often occurring in the early stage of sliding is prevented.

  In the spherical band-shaped sealing body of the second or third aspect, the lubricating composition may further contain a polytetrafluoroethylene resin like the spherical band-shaped sealing body of the fourth aspect of the present invention.

  In the spherical band-shaped sealing body according to any one of the second to fourth aspects, the lubricating composition contains 70 to 90% by weight of boron nitride, alumina, and silica as in the spherical band-shaped sealing body according to the fifth aspect of the present invention. Among them, a mixture containing at least one of 10 to 30% by weight and 200 parts by weight or less of polytetrafluoroethylene resin may be contained with respect to 100 parts by weight of the mixture.

  In the spherical band-shaped sealing body according to any one of the second to fourth aspects, the lubricating composition contains 70 to 90% by weight of boron nitride, alumina, and silica as in the spherical band-shaped sealing body according to the fifth aspect of the present invention. A mixture containing 10 to 30% by weight of at least one of them and 50 to 150 parts by weight of polytetrafluoroethylene resin with respect to 100 parts by weight of the mixture may be included.

  According to the fourth embodiment, the fifth embodiment, and the sixth embodiment of the ball-shaped seal body, the outer surface of the partially convex spherical surface of the outer layer of the lubricating composition further containing a polytetrafluoroethylene resin is mixed in the lubricating composition. Since the reinforcement made of an integrated wire mesh is formed on a smooth surface that is exposed, smoother sliding is performed especially in the initial sliding with the counterpart material, often in the early stage of sliding The occurrence of abnormal sliding friction noise is prevented.

  In the spherical band-shaped sealing body according to any one of the first to sixth aspects, the cylindrical inner surface has an expanded graphite, phosphorus pentoxide, and organic material on the spherical inner surface as in the spherical band-shaped sealing body according to the seventh aspect of the present invention. The heat-resistant material containing a phosphorus compound may be exposed.

  According to the spherical band-shaped sealing body of the seventh aspect, due to the oxidation inhibiting action of phosphorus pentoxide and the organic phosphorus compound, the oxidation consumption of the expanded graphite forming the main part of the heat resistant material on the cylinder inner surface is reduced, and as a result, the heat resistance of the cylinder inner surface is reduced. Is improved. Further, when the ball-shaped seal body is fitted and fixed to the outer surface of the exhaust pipe, the sealing property between the cylindrical inner surface of the ball-shaped seal body and the outer surface of the exhaust pipe is improved, so that the exhaust gas from the contact surface can be reduced. Leakage can be prevented as much as possible.

  In the spherical band-shaped sealing body according to any one of the first to seventh aspects, a reinforcing material made of a metal mesh of the spherical band-shaped substrate is exposed on the inner surface of the cylinder as in the spherical band-shaped sealing body according to the eighth aspect of the present invention. It may be.

  According to the ball-shaped seal body of the eighth aspect, when the ball-shaped seal body is fitted and fixed to the outer surface of the exhaust pipe, the friction between the cylindrical inner surface and the outer surface of the exhaust pipe is increased, and as a result, the ball-shaped seal The body is firmly fixed to the outer surface of the exhaust pipe.

  In the spherical belt-shaped sealing body according to any one of the first to eighth aspects, a spherical belt-shaped substrate is provided on at least one end surface of both annular end surfaces as in the spherical belt-shaped sealing body according to the ninth aspect of the present invention. A heat-resistant material containing expanded graphite, phosphorus pentoxide, and an organic phosphorus compound may be exposed.

  According to the spherical belt-shaped sealing body of the ninth aspect, the oxidation consumption of the expanded graphite forming the main body of the heat-resistant material on the annular end surface is reduced by the oxidation inhibiting action of phosphorus pentoxide and the organophosphorus compound. The heat resistance of the end face is improved.

In the spherical belt-shaped sealing body according to any one of the first to ninth aspects, the heat-resistant material is 0.05 to 5% by weight of phosphorus pentoxide, organic phosphorus, like the spherical belt-shaped sealing body according to the tenth aspect of the present invention. It may contain 0.1 to 10% by weight of the compound and 85 to 99.85% by weight of expanded graphite.

  According to the spherical band-shaped sealing body of the tenth aspect, the heat-resistant material contains 0.05 to 5% by weight of phosphorus pentoxide and 0% of the organophosphorus compound necessary for preferably exerting an oxidation inhibiting action on the main expanded graphite. 0.1 to 10% by weight, the oxidative consumption of the expanded graphite is preferably reduced, and the weight reduction of the ball-shaped seal body due to the oxidative consumption of the expanded graphite is preferably reduced.

  In expanded graphite, phosphorus pentoxide and an organophosphorus compound coexist in a dispersed manner and are given heat resistance, and the organophosphorus compound coexists with phosphorous pentoxide. In particular, it contributes to the improvement of heat resistance and oxidation resistance in a high temperature region around 700 ° C. If the content of phosphorus pentoxide is less than 0.05% by weight, the heat-resistant sheet material used for the production of the ball-shaped seal body cannot be sufficiently imparted with heat resistance and oxidation wear resistance, and it exceeds 5% by weight. However, further improvement in heat resistance and oxidation consumption resistance cannot be achieved. The organophosphorus compound can impart heat resistance and oxidation consumption resistance in a high temperature region by blending a small amount with phosphorus pentoxide. If the content of the organophosphorus compound is less than 0.1% by weight, the heat resistance cannot be sufficiently improved and the oxidation resistance in the high temperature region cannot be sufficiently imparted. Further improvement in oxidation resistance cannot be achieved.

  An organophosphorus compound that is blended simultaneously with phosphorous pentoxide and preferably reduces the oxidative consumption of expanded graphite particularly in a high temperature region, like the organic phosphonic acid and the ball-shaped seal body of the eleventh aspect of the present invention. It may be selected from its esters, organic phosphinic acids and their esters, phosphate esters, phosphites and hypophosphites.

  As the organic phosphonic acid and its ester, the organic phosphonic acid represented by the following general formula (1) and its ester are preferably used as in the ball-shaped seal body of the twelfth aspect of the present invention.

In formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group comprising an alkylene part having 1 to 10 carbon atoms and an aryl part having 6 to 18 carbon atoms. There, ^{R 2} and ^{R 3} are a hydrogen atom, consisting of an alkyl group having 1 to 10 carbon atoms, an alkylene unit and the aryl portion having 6 to 18 carbon atoms having 1 to 10 aryl group or a carbon of 6 to 18 carbon atoms aralkyl It is a group.

  As the organic phosphinic acid and its ester, the organic phosphinic acid and its ester represented by the following general formula (2) are suitably used as in the ball-shaped sealing body of the thirteenth aspect of the present invention.

In Formula (2), R ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group composed of an alkylene part having 1 to 10 carbon atoms and an aryl part having 6 to 18 carbon atoms. R ⁵ and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylene group having 1 to 10 carbon atoms and an aralkyl group having 6 to 18 carbon atoms. It is a group.

  As the phosphoric acid ester, a phosphoric acid ester represented by the following general formula (3) is preferably used like the ball-shaped seal body of the fourteenth aspect of the present invention.

In formula (3), R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylene part having 1 to 10 carbon atoms and 6 to 6 carbon atoms. An aralkyl group consisting of 18 aryl moieties. However, the case of all hydrogen atoms is excluded.

  The phosphorous acid ester is a phosphorous acid triester represented by the following general formula (4) as well as phosphorous acid represented by the following general formula (5), like the ball-shaped seal body of the fifteenth aspect of the present invention. It may be used selected from diesters and phosphorous acid monoesters.

In formulas (4) and (5), R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms or an alkylene part having 1 to 10 carbon atoms and 6 carbon atoms. an aralkyl group consisting of an ~ 18 aryl portion, R ^13, R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and the alkylene portion having from 1 to 10 aryl group or a carbon number of 6 to 18 carbon atoms An aralkyl group composed of an aryl part having 6 to 18 carbon atoms. However, the case where both R ¹³ and R ¹⁴ are hydrogen atoms is excluded.

  As the hypophosphite, a hypophosphite diester (phosphonite) represented by the following general formula (6) or the following general formula (7) as in the ball-shaped seal body of the sixteenth aspect of the present invention. The hypophosphorous acid monoester represented by these is used suitably.

In formulas (6) and (7), R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylene moiety having 1 to 10 carbon atoms and 6 to 18 carbon atoms. an aralkyl group composed of an aryl ^{portion, R 16, R 17, R} 18 is an alkyl group having 1 to 10 carbon atoms, an alkylene unit and a carbon number of 1 to 10 aryl group or a carbon of 6 to 18 carbon atoms 6 An aralkyl group consisting of ˜18 aryl moieties.

  In the spherical belt-shaped sealing body of the present invention, the spherical belt-shaped substrate is filled with a compressed wire mesh and a mesh of the reinforcing metal mesh, and is mixed and integrated with the reinforcing material and compressed. A heat-resistant material containing expanded graphite, phosphorus pentoxide and an organic phosphorus compound, and the heat resistance of the sealing body itself is enhanced. The weight reduction rate due to oxidative consumption of the expanded graphite constituting can be suppressed to a low level, and the function as a spherical belt-shaped sealing body can be sufficiently exhibited and the durability of the spherical belt-shaped sealing body can be improved. Further, since the heat-resistant sheet material used for manufacturing the spherical band-shaped sealing body and containing expanded graphite, phosphorus pentoxide and an organic phosphorus compound has the flexibility of a normal expanded graphite sheet, the spherical band shape There is no problem in the bending process of the heat-resistant sheet material that occurs in the manufacturing process of the sealing body. This not only eliminates the step of forming a heat-resistant material film on the surface of the expanded graphite sheet in the prior art, but also cracks in the heat-resistant film generated in the bending process of the expanded graphite sheet provided with the heat-resistant film, As a result, the heat-resistant sheet material is not damaged, and as a result, the material yield is improved.

  The best mode of the present invention will be described.

  The constituent material in the spherical belt-shaped sealing body of the present invention and the manufacturing method of the spherical belt-shaped sealing body will be described.

<About heat-resistant sheet material>
While stirring concentrated sulfuric acid having a concentration of 98%, a 60% aqueous solution of hydrogen peroxide as an oxidant is added to make a reaction solution. The reaction solution is cooled and kept at a temperature of 10 ° C., scale-like natural graphite powder having a particle size of 30 to 80 mesh is added, and the reaction is performed for a predetermined time. After the reaction, the acid-treated graphite is separated by suction filtration, and the washing operation of stirring the acid-treated graphite with water for a predetermined time and suction-filtering is repeated twice to sufficiently remove the sulfuric acid content from the acid-treated graphite. Next, the acid-treated graphite from which sulfuric acid has been sufficiently removed is dried for a predetermined time in a drying furnace maintained at a predetermined temperature, and this is used as the acid-treated graphite raw material.

  While stirring the acid-treated graphite raw material, a predetermined amount of phosphoric acid and an organic phosphorus compound are blended in the acid-treated graphite raw material, and stirred uniformly to obtain a mixture. This mixture is heated (expanded) at a temperature of 950 to 1200 ° C. for a predetermined time (usually 1 to 5 seconds) to generate decomposition gas, and the graphite layer is expanded by the gas pressure to expand expanded graphite particles (expansion magnification). 200 to 300 times). This expanded graphite particle is roll-molded by compression molding or a twin-roller apparatus to produce a heat-resistant sheet material having a desired thickness.

  The heat-resistant sheet material produced by the above production method contains phosphorus pentoxide, an organic phosphorus compound and expanded graphite produced by a dehydration reaction of phosphoric acid, and is a flexible sheet.

Phosphorus pentoxide dispersed and contained in the heat-resistant sheet material imparts heat resistance to the expanded graphite, which is the main component of the heat-resistant sheet material, and acts to improve the oxidation consumption rate of the expanded graphite. This phosphorus pentoxide is produced by a dehydration reaction of phosphoric acid in the production process of expanding the acid-treated graphite raw material in the above production method. As phosphoric acid used, orthophosphoric acid (H ₃ PO ₄ ), Metaphosphoric acid (HPO ₃ ), polyphosphoric acid, specifically chain condensed phosphoric acid such as pyrophosphoric acid (H ₄ P ₂ O), tripolyphosphoric acid (H ₅ P ₈ O ₁₀ ), polymetaphosphoric acid, specifically trimetalin It may be selected from cyclic condensed phosphoric acids such as acid and tetrametaphosphoric acid. The content of phosphorus pentoxide dispersedly contained in the heat-resistant sheet material is 0.05 to 5% by weight, preferably 0.1 to 5% by weight, and more preferably 0.5 to 3% by weight. If the phosphorus pentoxide content is less than 0.05% by weight, sufficient heat resistance cannot be imparted to the expanded graphite, which is the main component of the heat-resistant sheet material, and the oxidation consumption rate of the expanded graphite cannot be reduced. Further, if the content exceeds 5% by weight, not only the heat resistance and the effect of oxidation consumption are not exhibited, but also the flexibility of the heat-resistant sheet material may be impaired.

  An organophosphorus compound contributes to the improvement of heat resistance and oxidation wear resistance particularly in a high temperature region by containing it together with phosphorus pentoxide. The content of the organic phosphorus compound is 0.1 to 10% by weight, preferably 0.5 to 7.0% by weight, and more preferably 2.0 to 5.0% by weight. If the content of the organophosphorus compound is less than 0.1% by weight, the heat resistance cannot be sufficiently improved and the oxidation resistance in the high temperature region cannot be sufficiently imparted. Further improvement in oxidation resistance cannot be achieved. Further, if the dispersion graphite contains 5% by weight of phosphorus pentoxide and 10% by weight of the organophosphorus compound in the expanded graphite, the flexibility of the heat-resistant sheet material as a heat-resistant material may be impaired. The bending of the heat-resistant sheet material is often caused in the bending process in the process.

  Organophosphorus compounds that are blended simultaneously with phosphorus pentoxide and that preferably reduce the oxidative wear of expanded graphite, particularly in the high temperature range, are organic phosphonic acids and esters thereof, organic phosphinic acids and esters thereof, phosphate esters, phosphorous acid. It may be selected from esters as well as hypophosphites.

  As organic phosphonic acid and its ester, the organic phosphonic acid represented by the following general formula (1) and its ester are preferably used.

In formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group comprising an alkylene part having 1 to 10 carbon atoms and an aryl part having 6 to 18 carbon atoms. R ² and R ³ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having an alkylene part having 1 to 10 carbon atoms and an aryl part having 6 to 18 carbon atoms. It is a group.

  As the alkyl group, a linear or branched alkyl group having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group). The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms (for example, a phenyl group or a naphthyl group). , An ethylphenyl group, a tolyl group, a xylyl group, etc.), and as the aralkyl group, the alkylene part is a linear or branched alkylene, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. And the aryl moiety is preferably aryl having 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms (for example, benzyl group, naphthylmethyl). Etc.).

  Specific examples include methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, tolylphosphonic acid, benzylphosphonic acid, methylphosphonic acid methyl, methylphosphonic acid dimethyl, methylphosphonic acid diphenyl, and phenylphosphonic acid diethyl.

  As the organic phosphinic acid and its ester, an organic phosphinic acid represented by the following general formula (2) and its ester are preferably used.

In formula (2), R ⁴ is an alkyl group, an aryl group or an aralkyl group, and R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. The alkyl group, aryl group and aralkyl group are the same as described above. Specific examples include methylphosphinic acid, ethylphosphinic acid, diethylphosphinic acid, methylethylphosphinic acid, phenylphosphinic acid, methylphenylphosphinic acid, diphenylphosphinic acid, ethyl methylphosphinate, ethyl dimethylphosphinate, phenylmethylphosphinate, Mention may be made of ethyl phenylphosphinate and the like.

  As the phosphate ester, a phosphate ester represented by the following general formula (3) is preferably used.

In formula (3), R ⁷ , R ⁸ and R ⁹ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. However, the case of all hydrogen atoms is excluded.

  As the alkyl group, a linear or branched alkyl group having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group). The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms (for example, a phenyl group, a naphthyl group, and ethyl). A phenyl group, a tolyl group, a xylyl group, etc.), and the aralkyl group is an alkylene part that is linear or branched, preferably alkylene having 1 to 10 carbons, more preferably 1 to 6 carbons. The aryl moiety is preferably aryl having 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms (for example, benzyl group, naphthylmethyl group, etc.).

  Specific examples include methyl phosphate, butyl phosphate, phenyl phosphate, diethyl phosphate, diphenyl phosphate, dibenzyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, methyl diphenyl phosphate, and the like. May be mentioned.

  The phosphite may be selected from a phosphite triester represented by the following general formula (4) and a phosphite diester and phosphite monoester represented by the following general formula (5).

In the formulas (4) and (5), R ¹⁰ , R ¹¹ and R ¹² are an alkyl group, an aryl group or an aralkyl group, and R ¹³ and R ¹⁴ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. is there. However, the case where both R ¹³ and R ¹⁴ are hydrogen atoms is excluded.

  The alkyl group, aryl group and aralkyl group are the same as described above. Specific examples include trimethyl phosphite, triphenyl phosphite, diethyl phosphite, diphenyl phosphite, butyl phosphite, phenyl phosphite and the like.

  As the hypophosphite, a hypophosphite diester (phosphonite) represented by the following general formula (6) or a hypophosphite monoester represented by the following general formula (7) is preferably used.

In formulas (6) and (7), R ¹⁵ is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R ¹⁶ , R ¹⁷ and R ¹⁸ are an alkyl group, an aryl group or an aralkyl group.

  The alkyl group, aryl group and aralkyl group are the same as described above. Specific examples include dimethyl phosphonite, diphenyl phosphonite, dibenzyl phosphonite, diethyl phenyl phosphonite, dimethyl phenyl phosphonite, methyl hypophosphite, ethyl hypophosphite, phenyl hypophosphite and the like. .

<About reinforcing material>
Reinforcing materials include stainless steel wires such as austenitic SUS304, SUS316, and ferrite SUS430, iron wire (JIS-G-3532) or galvanized iron wire (JIS-G-3547), and copper as copper. -Wire mesh formed by weaving or knitting using one or more fine wires made of nickel alloy (white copper), copper-nickel-zinc alloy (white and white), brass, beryllium copper is used. obtain. The wire diameter of the fine metal wire forming the wire mesh is preferably about 0.10 to 0.32 mm, and the wire mesh of about 3 to 6 mm is preferably used.

  As the reinforcing material, in addition to the above-described wire mesh, a so-called expanded metal in which a notch is formed in a stainless steel thin plate or a phosphor bronze thin plate and at the same time the notch is expanded to form a regular mesh line can be used. A stainless steel sheet or phosphor bronze sheet having a thickness of about 0.3 to 0.5 mm and an expanded metal mesh of about 3 to 6 mm are preferably used.

<About lubricating composition>
An aqueous dispersion containing 20 to 50% by weight of a lubricating composition comprising 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica as a solid content is another lubricating composition. In a lubricating composition comprising 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica as a product, 200 parts by weight or less, preferably 100 parts by weight of the lubricating composition, An aqueous dispersion containing 20 to 50% by weight of a lubricating composition containing 50 to 150 parts by weight of polytetrafluoroethylene resin as a solid content may be used.

  The aqueous dispersion of the lubricating composition is applied to the surface of the heat-resistant sheet material by means of brushing, roller coating, spraying, or the like in the manufacturing method described later, and the surface of the heat-resistant sheet material is coated to form the heat-resistant sheet material. It is used to form a lubricating sliding layer on the surface of the substrate. The formed lubricating sliding layer is spread to a uniform and minute thickness (10 to 300 μm) in the final compression step to form an outer layer having a partially convex spherical outer surface of the ball-shaped seal body.

  Boron nitride in the lubricating composition exhibits excellent lubricity particularly at high temperatures. However, boron nitride alone adheres to the surface of the heat-resistant sheet, and as a result, a part of the spherical band-shaped substrate in the final compression step. Adhesiveness to convex spherical surfaces is inferior, and there is a drawback that they easily peel off from these surfaces, but by blending at least one of alumina and silica at a certain ratio to boron nitride , By avoiding the disadvantages of boron nitride, greatly improving the adherence to the surface of the heat-resistant sheet, and thus the adherence to the partially convex spherical surface of the spherical base in the final compression step, It is possible to enhance the retention of the partially convex spherical outer surface which is the lubricating slip surface made of the lubricating composition in the outer layer. The blending ratio of at least one of alumina and silica with respect to boron nitride is determined from the viewpoint of improving the adhesion without impairing the lubricity of boron nitride and in the range of 10 to 30% by weight. Is preferred.

  A lubricating composition comprising 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica is added to a polytetrafluoroethylene in a certain ratio with respect to 100 parts by weight of the lubricating composition. In a lubricating composition containing a fluoroethylene resin, the polytetrafluoroethylene resin itself has a low friction property, and is blended in a lubricating composition comprising boron nitride and at least one of alumina and silica. Thus, the low friction property of the lubricating composition is improved and the spreadability of the lubricating composition during compression molding is improved.

  The blending ratio of the polytetrafluoroethylene resin is 200 parts by weight or less, preferably 100 parts by weight of the lubricating composition comprising 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica. Is in the range of 50 to 150 parts by weight. When the blending ratio of the polytetrafluoroethylene resin exceeds 200 parts by weight, the ratio in the lubricating composition increases, resulting in a decrease in the heat resistance of the lubricating composition, and the blending ratio of the polytetrafluoroethylene resin is If it is the range of 50-150 weight part, low friction property can be exhibited without impairing the heat resistance of a lubricating composition. As this polytetrafluoroethylene resin, an aqueous dispersion containing 30 to 50% by weight of fine powder having an average particle diameter of 10 μm or less as a solid content can be used.

  Next, a method for manufacturing a spherical belt-shaped seal body made of the above-described constituent materials will be described with reference to the drawings.

<The manufacturing method of a 1st aspect>
(First Step) As shown in FIG. 2, a strip metal mesh 4 having a predetermined width D is produced by passing a cylindrical metal mesh 1 formed by knitting a thin metal wire into a cylindrical shape between rollers 2 and 3. A reinforcing material 5 is prepared by cutting a wire mesh 4 directly formed by weaving or knitting a thin metal wire with a predetermined width D and a length L into a predetermined length L. .

  (Second Step) As shown in FIG. 3, the width d of the reinforcing material 5 is 1.1 × D to 2.1 × D and the width L of the reinforcing material 5 is 1. A heat-resistant sheet material 6 containing phosphorus pentoxide, an organic phosphorus compound, and expanded graphite cut to have a length 1 of 30 × L to 2.70 × L is prepared.

  (Third step) As will be described later (see FIG. 1), the ball-shaped seal body 58 has a heat resistance as a whole on the large-diameter end surface 54 which is an annular end surface in the axial direction of the partially convex spherical surface 53 in the axial direction. In order to expose the material, as shown in FIG. 4, it is 0.1 at the maximum from at least one edge 7 in the width direction of the reinforcing material 5 which becomes the end surface 54 on the large diameter side of the partially convex spherical surface 53. The heat-resistant sheet material 6 protrudes in the width direction by 0.8 × D from × D, and the protrusion amount δ1 of the heat-resistant sheet material 6 in the width direction from the end edge 7 is an annular end surface 55 on the small diameter side of the partially convex spherical surface 53. The amount of protrusion δ2 from the other end edge 8 in the width direction of the reinforcing material 5 is increased from one end edge 9 in the length direction of the reinforcing material 5 to a maximum of 0.30 × L to 1 The heat-resistant sheet material 6 protrudes in the length direction by 70 × L and the length direction of the reinforcing material 5 The other edge 10 and the edge 11 in the length direction of the heat-resistant sheet material 6 corresponding to the edge 10 are substantially matched, and the width direction and the length direction of the reinforcing material 5 and the heat-resistant sheet material 6. To obtain a polymer 12 in which the reinforcing material 5 and the heat-resistant sheet material 6 are overlapped with each other.

  (Fourth Step) The polymer 12 is spirally wound with the heat-resistant sheet material 6 inside as shown in FIG. 5 and wound so that the heat-resistant sheet material 6 is increased once, and the inner and outer peripheral sides are wound. A cylindrical base material 13 with the heat-resistant sheet material 6 exposed on both sides is formed. As the heat-resistant sheet material 6, from 1.30 × L to the length L of the reinforcing material 5 so that the number of windings of the heat-resistant sheet material 6 in the cylindrical base material 13 is larger than the number of windings of the reinforcing material 5. Those having a length l of 2.70 × L are prepared in advance. In the cylindrical base material 13, as shown in FIG. 6, the heat-resistant sheet material 6 protrudes from the one edge 7 of the reinforcing material 5 by δ1 in the width direction on one edge side in the width direction, On the other edge side of the sheet material 6 in the width direction, δ2 protrudes from the other edge 8 of the reinforcing material 5 in the width direction.

  (Fifth Step) As shown in FIG. 7, which is the same as the heat-resistant sheet material 6 but has a width d smaller than the width D and a length l enough to wind the cylindrical base material 13 once. A heat-resistant sheet material 6 is prepared separately. On the other hand, as described in the first step, after forming the cylindrical wire mesh 1 by knitting a thin metal wire, a reinforcing material 5 made of the belt-like wire mesh 4 produced by passing the wire between the rollers 2 and 3 is prepared separately. As shown in FIG. 8, the heat-resistant sheet material 6 is inserted into the belt-like metal mesh 4, and these are integrated by passing between rollers 14 and 15 as shown in FIG. And

  (Sixth Step) The outer surface layer forming member 16 obtained in this way is wound around the outer peripheral surface of the cylindrical base material 13 to produce a preliminary cylindrical molded body 17 as shown in FIG.

  (Seventh step) A cylindrical wall surface 31, a partially concave spherical wall surface 32 continuous to the cylindrical wall surface 31, and a through hole 33 continuous to the partially concave spherical wall surface 32 are provided on the inner surface, and a stepped core 34 is fitted into the through hole 33. A mold 37 as shown in FIG. 11 having a hollow cylindrical portion 35 and a spherical belt-shaped hollow portion 36 continuous with the hollow cylindrical portion 35 is prepared, and preliminary cylindrical molding is performed on the stepped core 34 of the mold 37. Insert body 17.

The pre-cylindrical molded body 17 positioned in the hollow cylindrical portion 35 and the ball-shaped hollow portion 36 of the mold 37 is compression-molded at a pressure of 1 to 3 ton / cm ^{2 in} the core axial direction, as shown in FIG. A spherical base 56 having a through hole 51 in the center and defined by a cylindrical inner surface 52, a partially convex spherical surface 53, and annular end surfaces 54 and 55 on the large diameter side and small diameter side of the partial convex spherical surface 53; Then, a spherical belt-shaped sealing body 58 including an outer layer 57 integrally formed on the partially convex spherical surface 53 of the spherical belt-shaped substrate 56 is produced.

  By this compression molding, the spherical base 56 is formed by compressing the heat-resistant sheet material 6 and the reinforcing material 5 made of the wire mesh 4 so that they are intertwined with each other and have structural integrity, and are made of the compressed wire mesh 4. A reinforcing material 5 and a heat-resistant material filled with the mesh of the metal mesh 4 of the reinforcing material 5 and mixed and integrated with the reinforcing material 5 and compressed and containing phosphorus pentoxide, an organic phosphorus compound and expanded graphite. The outer layer 57 includes a heat-resistant material made of a compressed heat-resistant sheet material 6 and a reinforcing material 5 made of a wire mesh 4 mixed and integrated with the heat-resistant material. The outer layer 57 is exposed to the outside. The partially convex spherical outer surface 59 is a smooth surface, and a heat resistant material made of phosphorus pentoxide, an organic phosphorus compound, and expanded graphite is exposed on the cylindrical inner surface 52 of the through hole 51.

  In the ball-shaped seal body shown in FIG. 1 manufactured by the above-described method, the heat-resistant material made of the heat-resistant sheet material 6 is intertwined with the reinforcing material 5 made of the wire mesh 4 forming the internal structure, and is partly convex. The spherical outer surface 59 is a smooth surface in which the heat-resistant material made of phosphorus pentoxide, an organic phosphorus compound and expanded graphite, and the reinforcing material 5 made of the wire mesh 4 are mixed and integrated. In addition, the heat-resistant sheet material 6 that protrudes in the width direction of the reinforcing material 5 is bent and extended on the annular end surface 54 on the large diameter side and the end surface 55 on the small diameter side of the partially convex spherical surface 53. As a result, a heat-resistant material composed of phosphorus pentoxide, an organic phosphorus compound and expanded graphite is exposed.

  In the second step described above, the heat-resistant sheet material 6 cut so as to have substantially the same length l as the length L of the reinforcing material 5 is prepared, and these are combined with the third step described above. In the same manner, a polymer 12 is obtained, and the cylindrical base material 13 is formed in the same manner as in the above-mentioned fourth step by using the polymer 12 with the reinforcing material 5 inside, and the following steps 5 to 7 are performed. Thus, the spherical band-shaped seal body 58 is produced in which the reinforcing material 5 made of the wire mesh 4 of the spherical band-shaped substrate 56 is exposed on the cylindrical inner surface 52 in the through hole 51.

<The manufacturing method of a 2nd aspect>
The first process to the fourth process are the same as the first process to the fourth process.

  (Fifth step) The heat-resistant sheet material 6 is the same as the heat-resistant sheet material 6 but has a width d smaller than the width D and a length l enough to wind the cylindrical base material 13 once (see FIG. 7) is prepared separately, and an aqueous dispersion or boron nitride, alumina, and silica in which a lubricating composition composed of boron nitride and at least one of alumina and silica is dispersed on one surface of the heat-resistant sheet material 6 is prepared. An aqueous dispersion in which a lubricating composition containing a predetermined amount of a polytetrafluoroethylene resin is dispersed in the lubricating composition is brush-coated, roller-coated, sprayed The lubricating slip layer 18 made of a lubricating composition as shown in FIG.

  The reinforcing material 5 made of the belt-like wire mesh 4 described in the fifth step is separately prepared, and as shown in FIG. 13, the heat-resistant sheet material 6 provided with the lubricating slip layer 18 is inserted into the belt-like wire mesh 4, and these are As shown in FIG. 14, the rollers 19 and 20 are integrated to form an outer surface layer forming member 21.

  (Sixth Step) The outer surface layer forming member 21 obtained in this way is wound around the outer peripheral surface of the cylindrical base material 13 with the lubricating slip layer 18 facing outside, and a preliminary cylindrical molded body 22 as shown in FIG. Make it. This pre-cylindrical molded body 22 is compression-molded in the same manner as in the seventh step, and has a through hole 51 at the center as shown in FIGS. 16 and 17, and a cylindrical inner surface 52 and a partially convex spherical surface 53. The spherical base 56 defined by the annular end faces 54 and 55 on the large diameter side and the small diameter side of the partially convex spherical surface 53, and the outer layer formed integrally with the partial convex spherical surface 53 of the spherical base 56. The ball-shaped seal body 58 provided with 57 is prepared. By this compression molding, the spherical base 56 is formed by compressing the heat-resistant sheet material 6 and the reinforcing material 5 made of the wire mesh 4 so that they are intertwined with each other and have structural integrity, and are made of the compressed wire mesh 4. The reinforcing material 5 is filled with the mesh of the metal mesh 4 of the reinforcing material 5 and is mixed and integrated with the reinforcing material 5 and compressed, and has a heat-resistant material made of phosphorus pentoxide, an organic phosphorus compound and expanded graphite. The outer layer 57 is configured such that the lubricating slip layer 18 and the reinforcing material 5 made of the wire mesh 4 integrated with the lubricating slip layer 18 are compressed and entangled with each other to have structural integrity. A predetermined amount of a lubricating composition comprising boron nitride and at least one of alumina and silica or a lubricating composition comprising boron nitride and at least one of alumina and silica with respect to the lubricating composition It has a lubricating composition containing a polytetrafluoroethylene resin, and a reinforcing material made of a wire mesh mixed and integrated with the lubricating composition, and has a partially convex spherical outer surface 59 exposed to the outside in the outer layer 57. Is a smooth lubricated sliding surface in which the lubricating composition and the reinforcing material are mixed and integrated, and the cylindrical inner surface 52 defining the through hole 51 is a surface where the compressed heat-resistant sheet material 6 is exposed, A heat-resistant material made of phosphorus pentoxide, an organic phosphorus compound, and expanded graphite is exposed on the spherical base 56, and the annular end surface 54 on the large diameter side and the end surface 55 on the small diameter side of the partially convex spherical surface 53 are reinforced. The heat-resistant sheet material 6 protruding in the width direction of the material 5 is bent and spread to expose the heat-resistant material made of phosphorus pentoxide, an organic phosphorus compound and expanded graphite.

  Also in the second manufacturing method, the heat-resistant sheet material 6 having substantially the same length l with respect to the length L of the reinforcing material 5 is prepared in the second step, and these are stacked in the same manner as described above. In addition, a polymer 12 is obtained, and the cylindrical base material 13 is formed in the same manner as described above with the polymer 12 being the reinforcing material 5 inside, and the spherical band-shaped sealing body 58 is formed from the cylindrical base material 13. Thus, the spherical band-shaped sealing body 58 in which the reinforcing material 5 made of the wire mesh 4 of the spherical band-shaped base 56 is exposed on the cylindrical inner surface 52 in the through hole 51 is obtained.

  The spherical belt-like seal body 58 is used by being incorporated in, for example, an exhaust pipe spherical joint shown in FIG. That is, a flange 200 is erected on the outer peripheral surface of the upstream side exhaust pipe 100 connected to the engine side, leaving the pipe end portion 101, and a ball-shaped seal body 58 is formed in the pipe end portion 101 with a through hole. 51 is fitted on a cylindrical inner surface 52, and a spherical belt-shaped sealing body 58 is abutted against and seated on the flange 200 on the end surface 54 on the large diameter side. A diameter-enlarging portion 301 having a concave spherical portion 302 at the end and a flange portion 303 at the periphery of the opening of the concave spherical portion 302 is formed integrally with the upstream exhaust pipe 100 and connected to the muffler side. The downstream exhaust pipe 300 is disposed with the concave spherical surface portion 302 in sliding contact with the partially convex spherical outer surface 59 of the spherical belt-shaped seal body 58.

  In the exhaust pipe spherical joint shown in FIG. 18, one end is fixed to the flange 200 and the other end is inserted through the flange portion 303 of the enlarged diameter portion 301 and a pair of bolts 400 and the enormous head and flange portion of the bolt 400. A spring force is always applied to the downstream side exhaust pipe 300 in the direction of the upstream side exhaust pipe 100 by the pair of coil springs 500 arranged between 303. The exhaust pipe spherical joint has a partially convex spherical outer surface 59 of the ball-shaped seal body 58 and an end of the downstream exhaust pipe 300 with respect to relative angular displacement occurring in the upper and downstream exhaust pipes 100 and 300. It is configured to allow this by sliding contact with the concave spherical surface portion 302 of the formed enlarged diameter portion 301.

  Next, the present invention will be described in detail based on examples. In addition, this invention is not limited to these Examples at all.

Examples 1-7
While stirring 300 parts by weight of concentrated sulfuric acid having a concentration of 98%, 5 parts by weight of a 60% aqueous solution of hydrogen peroxide was added as an oxidizing agent, and this was used as a reaction solution. The reaction liquid was cooled and maintained at a temperature of 10 ° C., and 100 parts by weight of scaly natural graphite powder having a particle size of 30 to 80 mesh was added to the reaction liquid, and the reaction was performed for 30 minutes. After the reaction, the acid-treated graphite was separated by suction filtration, and the washing operation of stirring the acid-treated graphite with 300 parts by weight of water for 10 minutes and suction filtration was repeated twice to sufficiently remove the sulfuric acid content from the acid-treated graphite. . Subsequently, the acid-treated graphite from which the sulfuric acid content was sufficiently removed was dried in a drying furnace maintained at a temperature of 110 ° C. for 3 hours to obtain an acid-treated graphite raw material.

  While stirring 100 parts by weight of the acid-treated graphite raw material, 1.15 to 1.28 parts by weight of orthophosphoric acid having a concentration of 84% as phosphoric acid and 0.1 to 11 phenylphosphonic acid as the organic phosphorus compound were added to the acid-treated graphite raw material. 2 parts by weight were mixed and stirred uniformly to obtain a mixture. These mixtures were each heat-treated at a temperature of 1000 ° C. for 5 seconds to generate a decomposition gas, and the graphite layer was expanded by the gas pressure to obtain expanded graphite particles having an expansion ratio of 240 times. The expanded graphite particles were passed through a rolling roll and roll-formed to produce an expanded graphite sheet having a thickness of 0.4 mm, which was used as a heat-resistant sheet material. Orthophosphoric acid generates phosphorus pentoxide by a dehydration reaction in the heat treatment step. The component compositions of these heat-resistant sheet materials are shown in Tables 1 and 2.

  Thus, the heat-resistant sheet material which consists of seven types of component compositions produced in this way was cut | disconnected in width 55mm and length 550mm, respectively.

  A cylindrical braided wire mesh having a mesh size of 4.0 mm is produced using two austenitic stainless steel wires (SUS304) having a wire diameter of 0.28 mm as thin metal wires, and this is passed between rollers 2 and 3 to have a width of 36 mm, A belt-like wire mesh 4 having a length of 360 mm was used, and this was used as a reinforcing material 5.

  The heat-resistant sheet material 6 cut to a width of 55 mm and a length of 550 mm is spirally wound around the outer peripheral surface of a core having a diameter of 50.8 mm, and then the reinforcing material 5 is stacked inside the heat-resistant sheet material 6. In addition, a cylindrical base material 13 in which the heat-resistant sheet material 6 is positioned on the outermost periphery by winding in a spiral shape was produced. In the cylindrical base material 13, both end portions in the width direction of the heat-resistant sheet material 6 protrude in the width direction of the reinforcing material 5.

  The heat-resistant sheet material 6 composed of the above seven kinds of component compositions was separately prepared, and these were cut with a width of 48 mm and a length of 212 mm, respectively.

  Using one metal wire similar to the above, a cylindrical braided wire net having a mesh size of 4.0 mm is produced, and this is passed between the pair of rollers 2 and 3 to form a belt-like wire net having a width of 52.0 mm and a length of 212 mm. It was set to 4. The seven types of heat-resistant sheet materials 6 are inserted into the belt-shaped wire mesh 4 and are integrated by passing them between a pair of rollers 14 and 15, and phosphorus pentoxide filled with the reinforcing material 5 and the mesh of the reinforcing material 5. The outer surface layer forming member 16 in which the heat-resistant sheet material 6 containing phenylphosphonic acid and expanded graphite was mixed was produced.

  The outer surface layer forming member 16 was wound around the outer peripheral surface of the cylindrical base material 13 to prepare a preliminary cylindrical molded body 17. The preliminary cylindrical molded body 17 is inserted into the stepped core 34 of the mold 37, and the preliminary cylindrical molded body 17 is positioned in the spherical band-shaped hollow portion 36 of the mold 37 in which the radius of curvature of the partially concave spherical wall surface 32 is 25.2 mm. I let you.

The pre-cylindrical molded body 17 positioned in the spherical zone 36 of the mold 37 is compression-molded at a pressure of 2 ton / cm ^{2 in} the core axial direction, and has a through hole 51 at the center and a cylindrical inner surface 52 and a partially convex shape. The spherical base 56 defined by the spherical surface 53 and the annular end surfaces 54 and 55 on the large diameter side and the small diameter side of the partially convex spherical surface 53, and the partially convex spherical surface 53 of the spherical base 56 are integrated. A spherical belt-shaped seal body 58 having an outer layer 57 formed on the surface was prepared. By this compression molding, the heat-resistant sheet material 6 containing phosphorus pentoxide, phenylphosphonic acid and expanded graphite and the reinforcing material 5 made of the wire mesh 4 are compressed, and the spherical base 56 is intertwined with each other so as to have structural integrity. The reinforcing material 5 is composed of a compressed wire mesh 4 and the heat-resistant sheet material 6 filled with the mesh of the wire mesh 4 of the reinforcing material 5 and compressed by being mixed and integrated with the reinforcing material 5. The outer layer 57 includes a heat-resistant material made of a heat-resistant sheet material 6 containing phosphorus pentoxide, phenylphosphonic acid and expanded graphite, and a reinforcing material 5 made of a wire mesh 4 integrated with the heat-resistant material. Are compressed and entangled with each other to have structural integrity. The outer surface 59 of the partially convex spherical surface exposed to the outside in the outer layer 57 has a resistance to resistance including phosphorus pentoxide, phenylphosphonic acid and expanded graphite. As a result, the compressed heat-resistant sheet material 6 is exposed on the cylindrical inner surface 52 that defines the through hole 51, thereby forming a spherical base 56. The heat-resistant material to be exposed is exposed, and the end surfaces 54 and 55 of the annular shape are bent and extended in the heat-resistant sheet material 6 in the width direction from the reinforcing material 5. Covered with.

Examples 8-14
In the same manner as in the above example, an acid-treated graphite material was prepared. While stirring 100 parts by weight of the acid-treated graphite raw material, 3.4 parts by weight of an orthophosphoric acid aqueous solution having a concentration of 84% as a phosphate and phenylphosphonic acid, phenyl phenylphosphonate, diethylphosphinic acid, 2.1 parts by weight of an organophosphorus compound selected from phenylphosphinic acid, diphenyl phosphate, triphenyl phosphite, and dimethylphosphonite was blended and uniformly mixed to obtain a mixture. These mixtures were each heat-treated at a temperature of 1000 ° C. for 5 seconds to generate a decomposition gas, and the graphite layer was expanded by the gas pressure to obtain expanded graphite particles having an expansion ratio of 240 times. The expanded graphite particles were passed through a rolling roll and subjected to roll forming to produce an expanded graphite sheet having a thickness of 0.4 mm. Orthophosphoric acid generates phosphorus pentoxide by a dehydration reaction in the heat treatment step. The component compositions of these heat-resistant sheet materials 6 are shown in Tables 3 and 4. Hereinafter, in the same manner as in the above embodiment, a spherical base body defined by the cylindrical inner surface 52, the partially convex spherical surface 53, and the annular end surfaces 54 and 55 on the large diameter side and the small diameter side of the partial convex spherical surface 53. A spherical belt-shaped sealing body 58 including 56 and an outer layer 57 integrally formed on the partially convex spherical surface 53 of the spherical belt-shaped substrate 56 was produced.

  By this compression molding, the spherical base 56 is compressed into the heat-resistant sheet material 6 containing phosphorus pentoxide, the selected organic phosphorus compound and expanded graphite, and the reinforcing material 5 made of the wire mesh 4, and entangled with each other to form a structural integral. And a heat-resistant sheet that is compressed so as to be filled with the reinforcing material 5 composed of the compressed wire mesh 4 and the mesh of the wire mesh 4 of the reinforcing material 5. The outer layer 57 is integrated with the heat-resistant material made of the heat-resistant sheet material 6 containing phosphorus pentoxide, the selected organic phosphorus compound and expanded graphite, and the heat-resistant material. The reinforcing material 5 made of the wire mesh 4 is compressed and entangled with each other to have structural integrity, and the partially convex spherical outer surface 59 exposed to the outside in the outer layer 57 is selected from the above-mentioned phosphorus pentoxide. Organic As a result, the heat-resistant material containing the compound and the expanded graphite and the reinforcing material 5 are mixed and integrated, and the cylindrical inner surface 52 defining the through-hole 51 is the surface where the compressed heat-resistant sheet material 6 is exposed. The heat-resistant material forming the spherical belt-shaped substrate 56 is exposed, and the annular end surfaces 54 and 55 are bent and extended in the heat-resistant sheet material 6 at the portion protruding from the reinforcing material 5 in the width direction. The sheet material 6 is covered with a heat resistant material.

Examples 15-21
In the same manner as in the above example, an acid-treated graphite material was prepared. While stirring 100 parts by weight of the acid-treated graphite raw material, 3.5 parts by weight of an orthophosphoric acid aqueous solution having a concentration of 84% as phosphoric acid, phenylphosphonic acid, phenyl phenylphosphonate, diethylphosphinic acid, An organic phosphorus compound (4.2 parts by weight) selected from phenylphosphinic acid, diphenyl phosphate, triphenyl phosphite, and dimethylphosphonite was blended and stirred uniformly to obtain a mixture. These mixtures were heat-treated at a temperature of 1000 ° C. for 5 seconds to generate a decomposition gas, and the graphite layer was expanded by the gas pressure to obtain expanded graphite particles having an expansion ratio of 240 times. The expanded graphite particles were passed through a rolling roll and roll-formed to produce an expanded graphite sheet having a thickness of 0.4 mm, which was used as a heat-resistant sheet material. Orthophosphoric acid generates phosphorus pentoxide by a dehydration reaction in the heat treatment step. The component compositions of these heat-resistant sheet materials 6 are shown in Tables 5 and 6. Hereinafter, in the same manner as in the above embodiment, a spherical base body defined by the cylindrical inner surface 52, the partially convex spherical surface 53, and the annular end surfaces 54 and 55 on the large diameter side and the small diameter side of the partial convex spherical surface 53. A spherical belt-shaped sealing body 58 including 56 and an outer layer 57 integrally formed on the partially convex spherical surface 53 of the spherical belt-shaped substrate 56 was produced.

  By this compression molding, the spherical base 56 is compressed into the heat-resistant sheet material 6 containing phosphorus pentoxide, the selected organic phosphorus compound and expanded graphite, and the reinforcing material 5 made of the wire mesh 4, and entangled with each other to form a structural integral. And a heat-resistant sheet that is compressed so as to be filled with the reinforcing material 5 composed of the compressed wire mesh 4 and the mesh of the wire mesh 4 of the reinforcing material 5. The outer layer 57 is integrated with the heat-resistant material made of the heat-resistant sheet material 6 containing phosphorus pentoxide, the selected organic phosphorus compound and expanded graphite, and the heat-resistant material. The reinforcing material 5 made of the wire mesh 4 is compressed and entangled with each other to have structural integrity, and the partially convex spherical outer surface 59 exposed to the outside in the outer layer 57 is selected from the above-mentioned phosphorus pentoxide. Organic As a result, the heat-resistant material containing the compound and the expanded graphite and the reinforcing material 5 are mixed and integrated, and the cylindrical inner surface 52 defining the through-hole 51 is the surface where the compressed heat-resistant sheet material 6 is exposed. The heat-resistant material forming the spherical belt-shaped substrate 56 is exposed, and the annular end surfaces 54 and 55 are bent and extended in the heat-resistant sheet material 6 at the portion protruding from the reinforcing material 5 in the width direction. The sheet material 6 is covered with a heat resistant material.

Examples 22-24
The same heat-resistant sheet material 6 as in Example 2, Example 8 and Example 15 and the reinforcing material 5 made of the wire net 4 are prepared, and the heat-resistant sheet material 6 and the reinforcing material 5 are respectively cylindrical in the same manner as in the above-described example. A base material 13 was produced.

  A heat-resistant sheet material 6 similar to the heat-resistant sheet material 6 forming each of the cylindrical base materials 13 is separately prepared, and on one surface of the heat-resistant sheet material 6 cut with a width of 48 mm and a length of 212 mm, an average particle diameter of 7 μm is formed. 100 parts by weight of a lubricating composition comprising 85% by weight of boron nitride and 15% by weight of alumina powder having an average particle diameter of 0.6 μm was contained, and 50 parts by weight of polytetrafluoroethylene resin powder having an average particle diameter of 0.3 μm was contained therein. An aqueous dispersion (17% by weight boron nitride) containing 30% by weight as a solid content of a lubricating composition (56.7% by weight boron nitride, 10.0% by weight alumina and 33.3% by weight polytetrafluoroethylene resin) (3% alumina, 10% polytetrafluoroethylene resin and 70% moisture) were coated with a roller and dried three times. To form the lubricating sliding layer 18 of the lubricating composition.

  A belt-like metal mesh 4 similar to that of the above-described embodiment is prepared, and a heat-resistant sheet material 6 having a lubricating sliding layer 18 of a lubricating composition is inserted into the belt-like metal mesh 4 and passed between a pair of rollers 19 and 20. The outer layer forming member 21 in which the reinforcing material 5 and the lubricating composition of the lubricating sliding layer 18 filled with the mesh of the reinforcing material 5 were mixed on one surface was produced.

  The outer layer forming member 21 was wound around the outer peripheral surface of the cylindrical base material 13 with the surface of the lubricated sliding layer 18 facing outward, thereby preparing preliminary cylindrical molded bodies 22 respectively. Hereinafter, in the same manner as in the above embodiment, the cylindrical inner surface 52, the partially convex spherical surface 53, and the annular end surfaces 54 on the large diameter side and the small diameter side of the partial convex spherical surface 53 are provided. A spherical belt-like sealing body 58 including a spherical belt-like base body 56 defined by 55 and an outer layer 57 integrally formed on the partially convex spherical surface 53 of the spherical belt-like base body 56 was produced.

  By this compression molding, the heat-resistant sheet material 6 containing phosphorus pentoxide, phenylphosphonic acid and expanded graphite and the reinforcing material 5 made of the wire mesh 4 are compressed, and the spherical base 57 is entangled with each other so as to have structural integrity. The reinforcing material 5 is composed of a compressed wire mesh 4 and the heat-resistant sheet material 6 filled with the mesh of the wire mesh 4 of the reinforcing material 5 and compressed by being mixed and integrated with the reinforcing material 5. The outer layer 57 is compressed so that the lubrication slip layer 18 and the reinforcing material 5 made of the wire mesh 4 integrated with the lubrication slip layer 18 are entangled with each other and have structural integrity. And a lubricating composition comprising 56.7% by weight of boron nitride, 10.0% by weight of alumina, and 33.3% by weight of polytetrafluoroethylene resin, and mixed and integrated in the lubricating composition. 4 wire mesh The partially convex spherical outer surface 59 exposed to the outside in the outer layer 57 becomes a smooth lubricating sliding surface in which the lubricating composition and the reinforcing material 5 are mixed and integrated. As a result of the compressed heat resistant sheet material 6 being exposed, the heat resistant material forming the spherical base 56 is exposed, and the annular end surfaces 54 and 55 are formed of the heat resistant sheet material 6. In FIG. 5, the portion protruding in the width direction from the reinforcing material 5 is bent and spread, so that it is covered with a heat-resistant material made of the heat-resistant sheet material 6.

Comparative Example 1
As a heat-resistant sheet material, an expanded graphite sheet (“Nika Film (trade name)” manufactured by Nippon Carbon Co., Ltd.) having a width of 55 mm, a length of 550 mm, and a thickness of 0.4 mm was prepared. As a reinforcing material, a belt-like wire mesh (width 36 mm, length 360 mm) similar to that of the above example was prepared. After winding the heat-resistant sheet material in a spiral shape, a reinforcing material is superimposed on the inside of the heat-resistant sheet material and wound in a spiral shape to produce a cylindrical base material in which the heat-resistant sheet material is positioned on the outermost periphery. did. In this cylindrical base material, both end portions in the width direction of the heat-resistant sheet material protrude in the width direction of the reinforcing material.

  A heat-resistant sheet material similar to the heat-resistant sheet material was separately prepared, and cut with a width of 48 mm and a length of 212 mm. On one surface of this heat-resistant sheet material, the same lubricating composition as in the above example (boron nitride 56.7% by weight, alumina 10.0% by weight, polytetrafluoroethylene resin 33.3% by weight) was used as a solid content. An aqueous dispersion containing 17% by weight of dispersion (17% by weight of boron nitride, 3% by weight of alumina, 10% by weight of polytetrafluoroethylene resin and 70% by weight of water) was applied with a roller and dried three times. A lubricating slip layer of the lubricating composition was formed.

  A belt-like wire mesh having a width of 52 mm and a length of 212 mm as in the above example was prepared, and a heat-resistant sheet material provided with a lubricating slip layer of a lubricating composition was inserted into the belt-like wire mesh, and these were passed between a pair of rollers. An outer layer forming member was prepared in which a reinforcing material and a lubricating composition of a lubricating sliding layer filled with a mesh of the reinforcing material were mixed on one surface. On the outer peripheral surface of the cylindrical base material, this outer layer forming member is wound with the lubricating sliding layer of the lubricating composition facing outward to produce a pre-cylindrical molded body. Hereinafter, a spherical band shape is produced in the same manner as in the first embodiment. A seal body was produced.

  In the spherical belt-shaped sealing body thus manufactured, the spherical belt-shaped substrate is configured such that a heat-resistant material made of a compressed heat-resistant sheet material and a reinforcing material made of a wire mesh are compressed and intertwined to have structural integrity. And a reinforcing material made of a compressed wire mesh, and a heat-resistant material filled with the reinforcing material wire mesh and mixed and integrated with the reinforcing material, and the outer layer is lubricated. A reinforcing material made of a wire mesh integrated with a sliding layer and a lubricating sliding layer is compressed and entangled with each other so as to have structural integrity. 56.7% by weight of boron nitride and 10.0% by weight of alumina And a polytetrafluoroethylene resin 33.3% by weight, and a reinforcing material made of a wire mesh mixed and integrated with the lubricating composition, and exposed to the outside in the outer layer portion The spherical outer surface is a smooth lubricating sliding surface in which the lubricating composition and the reinforcing material are mixed and integrated, and the cylindrical inner surface defining the through hole is a surface where the compressed heat-resistant sheet material is exposed. The heat-resistant material forming the band-shaped substrate is exposed, and the annular end surfaces are covered with the heat-resistant material as a result of the portions of the heat-resistant sheet material protruding from the reinforcing material in the width direction being bent and extended.

Comparative Example 2
An expanded graphite sheet similar to that of Comparative Example 1 was prepared. First, an aqueous solution of primary aluminum phosphate having a concentration of 25% was prepared, and this aqueous solution was roller-coated on the entire surface of the expanded graphite sheet. Thereafter, the surface of the expanded graphite sheet was dried in a drying furnace at a temperature of 150 ° C. for 20 minutes. A uniform heat-resistant film of 0.07 g / 100 cm ² was formed on the whole, which was used as a heat-resistant sheet material, and this heat-resistant sheet material was cut into a width of 55 mm and a length of 550 mm.

  A belt-like wire mesh (width: 36 mm, length: 360 mm) similar to that of Example 1 was prepared as a reinforcing material. After winding the heat-resistant sheet material in a spiral manner for one round, this reinforcing material is superimposed on the inside of the heat-resistant sheet material, and a cylindrical base material in which the heat-resistant sheet material is positioned on the outermost circumference wound in a spiral manner Produced. In this cylindrical base material, both end portions in the width direction of the heat-resistant sheet material protrude in the width direction of the reinforcing material.

  A heat-resistant sheet material similar to the heat-resistant sheet material was separately prepared, and cut with a width of 48 mm and a length of 212 mm. On one surface of this heat-resistant sheet material, the same lubricating composition as in Example 25 (boron nitride 56.7% by weight, alumina 10.0% by weight, polytetrafluoroethylene resin 33.3% by weight) As an aqueous dispersion (17% by weight of boron nitride, 3% by weight of alumina, 10% by weight of polytetrafluoroethylene resin and 70% by weight of water) with a dispersion of 30% by weight, the coating operation was repeated three times. Thus, a lubricating slip layer of the lubricating composition was formed.

  A belt-like wire mesh having a width of 52 mm and a length of 212 mm similar to that in Example 1 was prepared, and a heat-resistant sheet material provided with a lubricating slip layer of a lubricating composition was inserted into the belt-like wire mesh, and these were passed between a pair of rollers. Thus, an outer layer forming member in which a reinforcing material and a lubricating composition of a lubricating slip layer filled with a mesh of the reinforcing material are mixed on one surface was produced. On the outer peripheral surface of the cylindrical base material, this outer layer forming member is wound with the lubricating sliding layer of the lubricating composition facing outward to produce a pre-cylindrical molded body. Hereinafter, a spherical band shape is produced in the same manner as in the first embodiment. A seal body was produced.

  In the spherical band-shaped sealing body thus manufactured, the spherical band-shaped substrate is formed by compressing a heat-resistant sheet material provided with a heat-resistant coating made of primary aluminum phosphate and a reinforcing material made of a wire mesh, and entangled with each other. And a heat-resistant sheet material comprising a compressed wire mesh, and a heat-resistant sheet material that is filled with the mesh of the wire mesh of the reinforcement material and is compressed in a mixed and integrated manner with the reinforcement material. The outer layer is configured such that a lubricating slip layer and a reinforcing material made of a wire mesh integrated with the lubricating slip layer are compressed and entangled with each other to have structural integrity. A lubricating composition comprising 56.7% by weight of boron nitride, 10.0% by weight of alumina, and 33.3% by weight of polytetrafluoroethylene resin, and a wire mesh mixed and integrated in the lubricating composition A partially convex spherical outer surface exposed to the outside in the outer layer is a smooth lubricating sliding surface in which the lubricating composition and the reinforcing material are mixed and integrated, and the cylindrical inner surface that defines the through hole As a result of the exposed surface of the compressed heat-resistant material, a heat-resistant film made of primary aluminum phosphate is exposed, and each annular end surface has a portion that protrudes in the width direction from the reinforcing material in the heat-resistant sheet material. As a result of being bent and spread, it is covered with a heat-resistant film made of primary aluminum phosphate.

Comparative Example 3
An expanded graphite sheet similar to that of Comparative Example 1 was prepared. A first aluminum phosphate aqueous solution having a concentration of 25% was prepared, and 5 g of calcium fluoride powder having an average particle size of 4 μm was blended with 30 g of this aqueous solution to obtain a mixture. This mixture is roller-coated on the entire surface of the expanded graphite sheet, and then dried at a temperature of 150 ° C. for 20 minutes in a drying furnace, so that the entire surface of the expanded graphite sheet has a uniform thickness of 0.3 g / 100 cm ^2. The heat-resistant film (weight ratio of calcium fluoride and primary aluminum phosphate is 1: 1.5) is formed into a heat-resistant sheet provided with the heat-resistant film, and the heat-resistant sheet material has a width of 55 mm and a length. Cut to 550 mm.

  A belt-like wire mesh (width: 36 mm, length: 360 mm) similar to that of Example 1 was prepared as a reinforcing material. After winding the heat-resistant sheet material in a spiral manner for one round, this reinforcing material is superimposed on the inside of the heat-resistant sheet material, and a cylindrical base material in which the heat-resistant sheet material is positioned on the outermost circumference wound in a spiral manner Produced. In this cylindrical base material, both end portions in the width direction of the heat-resistant sheet material protrude in the width direction of the reinforcing material.

  A heat-resistant sheet material similar to the heat-resistant sheet material was separately prepared, and cut with a width of 48 mm and a length of 212 mm. On one surface of this heat-resistant sheet material, the same lubricating composition as in Example 22 (boron nitride 56.7% by weight, alumina 10.0% by weight, polytetrafluoroethylene resin 33.3% by weight) As an aqueous dispersion (17% by weight of boron nitride, 3% by weight of alumina, 10% by weight of polytetrafluoroethylene resin and 70% by weight of water) with a dispersion of 30% by weight, the coating operation was repeated three times. Thus, a lubricating slip layer of the lubricating composition was formed.

  A belt-like wire mesh having a width of 52 mm and a length of 212 mm similar to that in Example 1 was prepared, and a heat-resistant sheet material provided with a lubricating slip layer of a lubricating composition was inserted into the belt-like wire mesh, and these were passed between a pair of rollers. Thus, an outer layer forming member in which a reinforcing material and a lubricating composition of a lubricating slip layer filled with a mesh of the reinforcing material are mixed on one surface was produced. On the outer peripheral surface of the cylindrical base material, this outer layer forming member is wound with the lubricating sliding layer of the lubricating composition facing outward to produce a pre-cylindrical molded body. Hereinafter, a spherical band shape is produced in the same manner as in the first embodiment. A seal body was produced.

  In the spherical belt-shaped sealing body produced in this way, the spherical belt-shaped substrate is formed by compressing a heat-resistant sheet material having a heat-resistant coating composed of primary aluminum phosphate and calcium fluoride and a reinforcing material composed of a wire mesh so that they are intertwined with each other. A reinforcing material composed of a compressed wire mesh, a mesh of the reinforcing material wire mesh, and a heat resistant coating that is mixed and integrated with the reinforcing material and compressed. The outer layer has a heat-resistant sheet material, and the outer layer is compressed with a lubrication slip layer and a reinforcing material made of a wire mesh integrated with the lubrication slip layer, and entangled with each other to have structural integrity And a lubricating composition comprising 56.7% by weight of boron nitride, 10.0% by weight of alumina, and 33.3% by weight of polytetrafluoroethylene resin, and mixed with the lubricating composition. The partially convex spherical outer surface exposed to the outside in the outer layer is a smooth lubricating sliding surface in which the lubricating composition and the reinforcing material are mixed and integrated. The inner surface of the cylinder defining the hole is a surface where the compressed heat-resistant material is exposed. As a result, a heat-resistant film composed of primary aluminum phosphate and calcium fluoride is exposed, and each annular end surface is a heat-resistant sheet material. As a result of bending and extending the portion protruding from the reinforcing material in the width direction, the portion is covered with a heat-resistant film made of primary aluminum phosphate and calcium fluoride.

  For the spherical belt-like seal bodies composed of the above-described examples and comparative examples, using the exhaust pipe joint device shown in FIG. 18, the friction torque (N · m) for each cycle, the presence or absence of abnormal friction noise, and the oxidation loss ( The result of the test for (weight reduction) will be described.

<Test conditions>
Pressing force by a coil spring (spring set force): 706N
Swing angle: ± 3 °
Oscillation frequency: 12 hertz (Hz)
Atmospheric temperature (outer surface temperature of concave spherical surface portion 302 shown in FIG. 18): 700 ° C.

<Test method>
After performing 45,000 cycles of ± 3 ° swing motion at a frequency of 12 Hz at room temperature, the ambient temperature was raised to 700 ° C. while continuing the swing motion When the atmospheric temperature reaches 700 ° C., 115,000 rocking motions are performed, and then the ambient temperature is lowered to room temperature while continuing the rocking motion ( The total number of oscillations of 250,000 times, that is, the number of oscillations of 45,000 times during temperature reduction) is 4 cycles.

The presence or absence of abnormal frictional noise was evaluated as follows.
Evaluation symbol A: No abnormal friction sound is generated.
Evaluation symbol B: An abnormal frictional sound can be heard with the ear close to the test piece.
Evaluation symbol C: At a fixed position (position 1.5 m away from the test piece)
In general, it is difficult to distinguish, but it can be identified as abnormal frictional noise by the person in charge of the test.
Evaluation symbol D: A sound that can be identified as an abnormal frictional sound (unpleasant sound) by anyone at a fixed position.

  Tables 1 and 2 show the test results of the ball-shaped seal bodies of Examples 1 to 7 obtained by the above test method, and Tables 3 and Table show the test results of the ball-shaped seal bodies of Examples 8 to 14 4, Table 5 and Table 6 show the test results of the ball-shaped seal bodies of Example 15 to Example 21, Table 7 shows the test results of the ball-shaped seal bodies of Example 22 to Example 24, and Comparative Example 1 Table 8 shows the test results of the ball-shaped seal body of Comparative Example 3.

  In Table 7, PTFE represents a polytetrafluoroethylene resin.

  From the pre-test weight (g) and post-test weight (g) of the test results, the spherical belt-shaped seal body of the example is subjected to oxidation consumption of expanded graphite constituting the seal body under a high temperature condition of 700 ° C. It can be seen that the rate of weight reduction due to is small, and it has excellent oxidation resistance in comparison with the comparative example. In addition, since the heat-resistant sheet material made of phosphorus pentoxide, an organic phosphorus compound and expanded graphite has the flexibility of a normal expanded graphite sheet, even in the bending step in the production of a ball-shaped seal body, It was possible to carry out without causing any trouble. This not only eliminates the step of forming a heat-resistant material film on the surface of the expanded graphite sheet in the prior art, but also cracks in the heat-resistant film generated in the bending process of the expanded graphite sheet provided with the heat-resistant film, As a result, the heat-resistant sheet material is not damaged, and as a result, the material yield is improved.

It is a longitudinal cross-sectional view which shows the spherical belt shaped sealing body of this invention. It is explanatory drawing of the formation method of the reinforcing material in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a perspective view of the heat-resistant sheet material in the manufacturing process of the spherical belt-shaped sealing body of the present invention. It is a perspective view of the polymer in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a top view of the cylindrical preform | base_material in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a longitudinal cross-sectional view of the cylindrical base material shown in FIG. It is a perspective view of the heat-resistant sheet material in the manufacturing process of the spherical belt-shaped sealing body of the present invention. It is explanatory drawing of the formation method of the outer surface layer formation member in the manufacturing process of the spherical belt shaped sealing body of this invention. It is explanatory drawing of the formation method of the outer surface layer formation member in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a top view of the preliminary | backup cylindrical molded object in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a longitudinal cross-sectional view which shows the state which inserted the preliminary | backup cylindrical molded object in the metal mold | die in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a longitudinal cross-sectional view of the heat-resistant sheet material which formed the lubrication slip layer in the manufacturing process of the spherical belt shaped sealing body of this invention. It is explanatory drawing of the formation method of the outer surface layer formation member in the manufacturing process of the spherical belt shaped sealing body of this invention. It is explanatory drawing of the formation method of the outer surface layer formation member in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a top view of the preliminary | backup cylindrical molded object in the manufacturing process of the spherical belt shaped sealing body of this invention. It is a longitudinal cross-sectional view which shows the spherical belt shaped sealing body of this invention. FIG. 17 is a partially enlarged cross-sectional view of a partially convex spherical outer surface of the spherical belt-shaped sealing body shown in FIG. 16. It is a longitudinal cross-sectional view of the exhaust pipe spherical joint incorporating the spherical belt shaped sealing body of the present invention.

Explanation of symbols

4 Wire mesh 5 Reinforcement material 18 Lubricating slip layer 51 Through hole 52 Cylindrical inner surface 54, 55 End surface 57 Outer layer 56 Spherical belt-shaped substrate 58 Spherical belt-shaped sealing body 59

Claims (16)

  A spherical base defined by a cylindrical inner surface, a partially convex spherical surface, and annular end surfaces on the large diameter side and the small diameter side of the partially convex spherical surface, and an integrally formed on the partially convex spherical surface of the spherical base A spherical band-shaped sealing body, particularly used for exhaust pipe spherical joints, in which a spherical band-shaped substrate is filled with a reinforcing metal mesh and a mesh of the reinforcing metal mesh. And a heat-resistant material containing expanded graphite, phosphorus pentoxide, and an organic phosphorus compound that is mixed and integrated with the reinforcing material and compressed, and the outer layer is expanded graphite, phosphorus pentoxide, and an organic phosphorus compound And a reinforcing material made of a wire mesh that is mixed and integrated with the heat-resistant material, and the outer surface of the partially convex spherical surface exposed to the outside in the outer layer is a mixture of the heat-resistant material and the reinforcing material. Sphere with a smooth and smooth surface The seal body.   A spherical base defined by a cylindrical inner surface, a partially convex spherical surface, and annular end surfaces on the large diameter side and the small diameter side of the partially convex spherical surface, and an integrally formed on the partially convex spherical surface of the spherical base A spherical band-shaped sealing body, particularly used for exhaust pipe spherical joints, in which a spherical band-shaped substrate is filled with a reinforcing metal mesh and a mesh of the reinforcing metal mesh. And a heat-resistant material containing expanded graphite, phosphorus pentoxide and an organophosphorus compound, mixed and integrated with this reinforcing material, and the outer layer is made of at least boron nitride, alumina and silica. A lubricating composition comprising at least one and a reinforcing material comprising a wire mesh mixed and integrated in the lubricating composition, and the outer surface of the partially convex spherical surface exposed to the outside in the outer layer is the lubricating composition And reinforcement are mixed and integrated Spherical annular seal member, characterized in that it has a smooth lubricating sliding surface.   The spherical band-shaped sealing body according to claim 2, wherein the lubricating composition contains 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica.   The spherical band-shaped sealing body according to claim 2 or 3, wherein the lubricating composition further contains a polytetrafluoroethylene resin.   The lubricating composition comprises a mixture containing 70 to 90% by weight of boron nitride and 10 to 30% by weight of at least one of alumina and silica, and a ratio of 200 parts by weight or less with respect to 100 parts by weight of the mixture. The spherical belt-shaped sealing body according to any one of claims 2 to 4, comprising a polytetrafluoroethylene resin.   The lubricating composition comprises a mixture containing 70 to 90% by weight boron nitride and 10 to 30% by weight of at least one of alumina and silica, and 50 to 150 parts by weight with respect to 100 parts by weight of the mixture. The spherical belt-shaped sealing body according to any one of claims 2 to 4, comprising a proportion of polytetrafluoroethylene resin.   The spherical belt-shaped sealing body according to any one of claims 1 to 6, wherein a heat resistant material including expanded graphite, phosphorus pentoxide, and an organic phosphorus compound of the spherical belt-shaped substrate is exposed on the inner surface of the cylinder.   The spherical band-shaped sealing body according to any one of claims 1 to 7, wherein a reinforcing material made of a metal net of a spherical band-shaped substrate is exposed on the inner surface of the cylinder.   9. The heat-resistant material containing expanded graphite, phosphorus pentoxide, and an organic phosphorus compound of a spherical base is exposed on at least one end face of both annular end faces. Sphere-shaped seal body.   The heat-resistant material contains 0.05 to 5% by weight of phosphorus pentoxide, 0.1 to 10% by weight of an organophosphorus compound, and 85 to 99.85% by weight of expanded graphite. A ball-shaped seal body as described.   11. The organic phosphorus compound according to any one of claims 1 to 10, wherein the organic phosphorus compound is selected from organic phosphonic acids and esters thereof, organic phosphinic acids and esters thereof, phosphate esters, phosphite esters and hypophosphite esters. Sphere-shaped seal body. The spherical belt-shaped sealing body according to claim 11, wherein the organic phosphonic acid and its ester are represented by the following general formula (1).

Wherein (1), ^{R 1} is an alkyl group having 1 to 10 carbon atoms, an aralkyl group consisting of an alkylene unit and the aryl portion having 6 to 18 carbon atoms having 1 to 10 aryl group or a carbon of 6 to 18 carbon atoms R ² and R ³ are each composed of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylene part having 1 to 10 carbon atoms and an aryl part having 6 to 18 carbon atoms. Aralkyl group. ] The ball-shaped seal body according to claim 11, wherein the organic phosphinic acid and its ester are represented by the following general formula (2).

Wherein (2), ^{R 4} is an alkyl group of 1-10 carbon atoms, an aralkyl group consisting of an alkylene unit and the aryl portion having 6 to 18 carbons 1-10 aryl group or a carbon C6-18 R ⁵ and R ⁶ are each composed of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms or an alkylene part having 1 to 10 carbon atoms and an aryl part having 6 to 18 carbon atoms. Aralkyl group. ] The spherical belt-shaped sealing body according to claim 11, wherein the phosphate ester is represented by the following general formula (3).

Wherein ^{(3), R 7, R} 8, R 9 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkylene unit and a carbon number of 1 to 10 aryl group or a carbon of 6 to 18 carbon atoms 6 An aralkyl group consisting of ˜18 aryl moieties. However, the case of all hydrogen atoms is excluded. ] The sphere according to claim 11, wherein the phosphite is selected from a phosphite triester represented by the following general formula (4) and a phosphite diester and a phosphite monoester represented by the following general formula (5). Strip seal body.

[In the formulas (4) and (5), R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylene part having 1 to 10 carbon atoms and the number of carbon atoms. An aralkyl group comprising 6 to 18 aryl moieties, wherein R ¹³ and R ¹⁴ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylene moiety having 1 to 10 carbon atoms. And an aralkyl group consisting of an aryl part having 6 to 18 carbon atoms. However, the case where both R ¹³ and R ¹⁴ are hydrogen atoms is excluded. ] The sphere according to claim 11, wherein the hypophosphite is a hypophosphite diester (phosphonite) represented by the following general formula (6) or a hypophosphite monoester represented by the following general formula (7). Strip seal body.

In [Equation (6), (7), R 15 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 18 alkylene part and a carbon number of 1 to 10 aryl group or a carbon of 6 to 18 carbon atoms the aralkyl group comprising an aryl ^{moiety, R 16, R 17, R} 18 is an alkyl group having 1 to 10 carbon atoms, an alkylene unit and the number of carbon atoms of 1-10 aryl group or a carbon of 6 to 18 carbon atoms It is an aralkyl group consisting of 6 to 18 aryl moieties. ]

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