WO2012077710A1 - ブッシュ・ブラケット一体スタビライザーバー - Google Patents
ブッシュ・ブラケット一体スタビライザーバー Download PDFInfo
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- WO2012077710A1 WO2012077710A1 PCT/JP2011/078297 JP2011078297W WO2012077710A1 WO 2012077710 A1 WO2012077710 A1 WO 2012077710A1 JP 2011078297 W JP2011078297 W JP 2011078297W WO 2012077710 A1 WO2012077710 A1 WO 2012077710A1
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- WIPO (PCT)
- Prior art keywords
- stabilizer bar
- bush
- rubber
- amine
- bracket
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G21/00—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces
- B60G21/02—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces permanently interconnected
- B60G21/04—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces permanently interconnected mechanically
- B60G21/05—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces permanently interconnected mechanically between wheels on the same axle but on different sides of the vehicle, i.e. the left and right wheel suspensions being interconnected
- B60G21/055—Stabiliser bars
- B60G21/0551—Mounting means therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G21/00—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces
- B60G21/02—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces permanently interconnected
- B60G21/04—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces permanently interconnected mechanically
- B60G21/05—Interconnection systems for two or more resiliently-suspended wheels, e.g. for stabilising a vehicle body with respect to acceleration, deceleration or centrifugal forces permanently interconnected mechanically between wheels on the same axle but on different sides of the vehicle, i.e. the left and right wheel suspensions being interconnected
- B60G21/055—Stabiliser bars
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/02—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant
- F16F1/024—Covers or coatings therefor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/02—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant
- F16F1/14—Torsion springs consisting of bars or tubes
- F16F1/16—Attachments or mountings
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
- F16F1/38—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers with a sleeve of elastic material between a rigid outer sleeve and a rigid inner sleeve or pin, i.e. bushing-type
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
- F16F15/04—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means
- F16F15/08—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means with rubber springs ; with springs made of rubber and metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2204/00—Indexing codes related to suspensions per se or to auxiliary parts
- B60G2204/10—Mounting of suspension elements
- B60G2204/12—Mounting of springs or dampers
- B60G2204/122—Mounting of torsion springs
- B60G2204/1222—Middle mounts of stabiliser on vehicle body or chassis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2204/00—Indexing codes related to suspensions per se or to auxiliary parts
- B60G2204/40—Auxiliary suspension parts; Adjustment of suspensions
- B60G2204/41—Elastic mounts, e.g. bushings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2204/00—Indexing codes related to suspensions per se or to auxiliary parts
- B60G2204/40—Auxiliary suspension parts; Adjustment of suspensions
- B60G2204/43—Fittings, brackets or knuckles
- B60G2204/4307—Bracket or knuckle for torsional springs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2206/00—Indexing codes related to the manufacturing of suspensions: constructional features, the materials used, procedures or tools
- B60G2206/01—Constructional features of suspension elements, e.g. arms, dampers, springs
- B60G2206/40—Constructional features of dampers and/or springs
- B60G2206/42—Springs
- B60G2206/427—Stabiliser bars or tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2206/00—Indexing codes related to the manufacturing of suspensions: constructional features, the materials used, procedures or tools
- B60G2206/01—Constructional features of suspension elements, e.g. arms, dampers, springs
- B60G2206/70—Materials used in suspensions
- B60G2206/73—Rubber; Elastomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2206/00—Indexing codes related to the manufacturing of suspensions: constructional features, the materials used, procedures or tools
- B60G2206/01—Constructional features of suspension elements, e.g. arms, dampers, springs
- B60G2206/80—Manufacturing procedures
- B60G2206/81—Shaping
- B60G2206/8106—Shaping by thermal treatment, e.g. curing hardening, vulcanisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2206/00—Indexing codes related to the manufacturing of suspensions: constructional features, the materials used, procedures or tools
- B60G2206/01—Constructional features of suspension elements, e.g. arms, dampers, springs
- B60G2206/80—Manufacturing procedures
- B60G2206/82—Joining
- B60G2206/821—Joining by gluing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
Definitions
- the present invention relates to a bush / bracket integrated stabilizer bar in which a stabilizer bar, which is a part of a suspension device for a vehicle such as an automobile, and a rubber bush and a bracket for mounting the stabilizer bar are integrated.
- the stabilizer bar is a member that mainly suppresses the roll of the vehicle body (rotational motion about the vehicle body longitudinal direction).
- the rubber bushing is attached between the stabilizer bar and the vehicle body to attenuate the propagation of vibrations input to the stabilizer bar to the vehicle body due to road surface conditions, etc., and flexibly follow the behavior of the stabilizer bar to support the vehicle body. is there.
- the rubber bush attached to the stabilizer bar applies a force in the direction of rotation of the stabilizer bar according to the vertical movement of the wheels (vehicle body). At the same time, the rubber bushing receives a vertical force to support the car body and to vibrate.
- Fig. 6 shows the generated torque (output) with respect to displacement of the stabilizer bar (input such as twisting of the stabilizer bar) when stick slip occurs in the non-adhesive type stabilizer bar with rubber bush.
- the stabilizer bar and the rubber bush, and the rubber bush and the bracket are not integrated by bonding, a gap is generated between the stabilizer bar when a large force is applied.
- the stabilizer bar and the bracket may be damaged and abnormal noise may be generated.
- abnormalities such as wear and breakage may occur when hard foreign objects such as sand and stones remain invaded.
- Patent Document 1 discloses a technique in which a stabilizer bar and a bracket are installed in a mold, and adhesion is performed simultaneously with vulcanization molding of a rubber bush.
- a metal stabilizer bar and a bracket are installed in the mold, the mold is required to have strength and accuracy, and the durability of the mold is also reduced.
- a stabilizer bar is about 1 m in length normally, there exists a problem that the installation including a metal mold
- the stabilizer bar and the like are coated after vulcanization and adhesion, poor coating is likely to occur between the rubber bush and the stabilizer bar, leading to a decrease in reliability.
- powder coatings and cationic coatings usually used for stabilizer bar coating require high temperature and long-time treatment for drying (curing), which may cause thermal degradation of the vulcanized rubber bush. Is also a problem.
- Patent Document 2 after the rubber bushing is vulcanized and bonded to the bracket, the rubber bush is bonded to the painted stabilizer bar using a chlorinated rubber adhesive. By doing so, problems such as enlargement of equipment are avoided.
- heat treatment is required to bond the rubber bush to the stabilizer bar with the chlorinated rubber adhesive, and the rubber bush is thermally deteriorated and the strength is increased. It has been confirmed that it decreases by 40 to 50%. Also, this method requires two brackets with upper and lower rubber bushes for the stabilizer bar, so it is difficult to say that it is advantageous in terms of cost.
- Patent Document 3 discloses a method of performing vulcanization adhesion to vulcanized rubber as a measure for suppressing an increase in cost by the method (1).
- vulcanized rubber is used, and disadvantages such as cost increase due to the increase in size of the equipment mentioned in (1) are eliminated.
- a prototype was made under the same conditions (10% compression, 160 ° C., 60 minutes heating) based on the disclosed contents, a significant decrease in strength of the rubber bush due to thermal deterioration was confirmed, and the long-term reliability of the rubber bush was confirmed. There was a problem in terms.
- patent document 3 since the bush and the bracket are not bonded and fixed, it is impossible to solve the problem of wear and breakage caused by the noise generated in this portion and the entry of foreign matter.
- Patent Document 4 discloses a method using a thermosetting adhesive.
- the adhesive is cured using a high-temperature coating process (130 to 200 ° C., 20 minutes) in the coating process.
- a high-temperature coating process 130 to 200 ° C., 20 minutes
- thermal deterioration due to exposure of the vulcanized rubber bush to a high temperature for a long time cannot be avoided.
- the stabilizer bar and the bush are only bonded, and the bush and the bracket are not bonded. Therefore, it is impossible to prevent the generation of noise, wear, and damage due to the intrusion of foreign matter into this portion.
- Patent Document 5 and Patent Document 6 disclose a method of applying a thermosetting adhesive to a stabilizer bar subjected to electrodeposition coating or powder coating, and bonding a rubber bush.
- the adhesive strength between the adhesive and the stabilizer bar or the adhesive and the rubber bush is inferior, so that the rubber does not break. Yes.
- the bush and the bracket are only clamped and fixed, and the bonding is not performed, there is a problem of wear or breakage due to abnormal noise generated in this portion or intrusion of foreign matter.
- Patent Document 7 discloses a method of bonding a chlorinated rubber bush to a coated stabilizer bar with a thermosetting adhesive. This method is considered to improve the adhesive strength of the rubber bush by performing chlorination treatment. However, as a result of trial production based on the disclosed information, the rubber surface was roughened by chlorination treatment, and some improvement in adhesion was confirmed by the anchor effect. It is confirmed that the rubber does not break. Further, even in this method, the bush and the bracket are only fixed by the clamp, so that it is not possible to cope with the problem of wear and breakage due to the noise generated in this portion and the entry of foreign matter.
- the object of the present invention is to solve the problems such as the generation of abnormal noise due to stick-slip phenomenon, the generation of abnormal noise due to the entry of foreign matter into the gap and the damage due to wear, and the integrated bush and bracket having excellent steering stability.
- the purpose is to provide a stabilizer bar at a low cost.
- a stabilizer bar a rubber bush mounted on the outer periphery of the stabilizer bar, and an outer periphery of the rubber bush, the stabilizer bar is attached to the bottom of the vehicle body via the rubber bush.
- the stabilizer bar has an amine-based cured epoxy paint or an amine-containing cationic paint and a surface treatment layer containing a halogen donor-type surface treatment agent on the paint, and the rubber bush has a halogen on the inner surface.
- the bracket further includes an amine-based cured epoxy paint or an amine-containing cationic paint on the inner surface and a surface treatment layer containing a halogen donor-type surface treatment agent on the paint, and the rubber
- the bush has a surface treatment layer containing a halogen donor surface treatment agent on the outer surface, and an amine-based or organic hydrazide-based curing agent and an epoxy resin via each surface treatment layer between the bracket and the rubber bush. It is preferable that an adhesive layer is formed.
- the stabilizer bar and the rubber bush are firmly bonded and fixed, so that an abnormal noise due to a stick-slip phenomenon, an abnormal noise due to intrusion of foreign matter into a gap, and a damage due to wear, etc.
- a bush / bracket integrated stabilizer bar having excellent steering stability equivalent to a rubber bush-bonded stabilizer bar by vulcanization bonding can be provided at low cost.
- FIG. 1 is a perspective view of a bush / bracket integrated stabilizer bar according to an embodiment of the present invention.
- FIG. 2 is a perspective view and a cross-sectional view of a test piece manufactured in the example.
- FIG. 3 is an FT-IR chart before and after the reaction between the amine-based cured epoxy coating and trichloroisocyanuric acid.
- FIG. 4 is an FT-IR chart before and after the reaction between the amine-containing cationic paint and trichloroisocyanuric acid.
- FIG. 5 is an FT-IR chart before and after the reaction between the amine curing agent and trichloroisocyanuric acid.
- FIG. 6 is a graph showing the relationship between the displacement of the stabilizer bar and the torque.
- FIG. 1 is a perspective view of a bush / bracket integrated stabilizer bar 1 according to an embodiment of the present invention.
- Bush-bracket integrated stabilizer bar 1 includes a stabilizer bar 2, two rubber bushes 3 mounted on the outer periphery of the stabilizer bar 2, and an outer periphery of the rubber bush 3.
- the stabilizer bar 2 is mounted on the vehicle body via the rubber bush 3.
- a bracket 4 for attaching to the bottom of the frame.
- the stabilizer bar 2 has an amine-based cured epoxy paint or amine-containing cationic paint (not shown in FIG. 1) on the surface and a surface treatment layer (not shown in FIG. 1) containing a halogen donor-type surface treatment agent on the paint.
- the bracket 4 has a surface-treated layer (not shown in FIG. 1) containing an amine-based cured epoxy paint or amine-containing cationic paint (not shown in FIG. 1) and a halogen donor-type surface treatment agent on the paint. ).
- the rubber bush 3 also has a surface treatment layer containing a halogen donor surface treatment agent on at least the inner surface (stabilizer bar 2 side).
- the rubber bush 3 preferably has a surface treatment layer containing a halogen donor surface treatment agent on the outer surface (on the bracket 4 side).
- An adhesive layer (not shown in FIG. 1) containing an amine-based or organic hydrazide-based curing agent and an epoxy resin is formed between the stabilizer bar 2 and the rubber bush 3 via respective surface treatment layers. .
- amine-based cured epoxy paint or amine-containing cationic electrodeposition paint generally used for automobile coating is used for the coating of the stabilizer bar and the bracket.
- Examples of the amine-based cured epoxy paint include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak type epoxy resin, as described in JP-A-7-224234.
- Examples of the curing agent include solid amines or organic acid hydrazides.
- Examples of the solid amine include 1,12-dodecanamine, 4,4′-diaminodiphenylmethane, and 2,4-tolylenediamine.
- Examples of the organic acid hydrazide include succinic hydrazide, adipic hydrazide, and sebacic acid hydrazide. And isophthalic acid hydrazide.
- amine-containing cationic electrodeposition coating As the amine-containing cationic electrodeposition coating, as described in JP-A No. 2002-121491, for example, a reaction product of a polyepoxy resin and a cationizing agent, a polycondensation product of a polycarboxylic acid and a polyamine is used as an acid. And those obtained by protonating a polyisocyanate compound and a polyaddition product of a polyol and a mono- or polyamine with an acid.
- the cationizing agent include primary amines, secondary amines, tertiary amines, and polyamine amine compounds.
- the surface treatment agent used to form the surface treatment layer is a halogen donor such as a halogenated isocyanuric acid such as trichloroisocyanuric acid, dibromomethylhydantoin, or N-chloroparatoluenesulfonic acid amide. What was melt
- dissolved is mentioned.
- trichloroisocyanuric acid is preferable because it is highly available and easy to handle and has a large effect of improving adhesiveness.
- a solvent for trichloroisocyanuric acid ethyl acetate, methyl ethyl ketone, methyl acetate, or the like can be used.
- 5% trichloroisocyanuric acid ethyl acetate solution is used as the surface treating agent, but is not limited thereto.
- a bisphenol F epoxy resin and various curing agents for curing the same are used as a two-component mixed adhesive. Only when an amine-based curing agent or an organic hydrazide-based curing agent is used as the curing agent, a strong adhesive force with the surface treatment layer can be obtained.
- the mixing ratio between the epoxy resin and each curing agent is optimal as long as the number of reaction points of the epoxy group in the epoxy resin is equal to the number of reaction points of the curing agent, but is not limited thereto.
- abrasive paper having a particle size P150 in JIS R6010 was used.
- a particle size range of P80 to P1200 can be used, and P120 to P360 is particularly preferable. Any means can be used as long as the surface of the rubber can be physically roughened, and the means for performing the roughening treatment is not particularly limited to that using abrasive paper.
- test pieces shown in FIG. 2 were produced and evaluated.
- 2A is a perspective view of the test piece
- FIG. 2B is a cross-sectional view of the test piece.
- a first steel material 10 was prepared as a substitute for the stabilizer bar, and the surface thereof was coated with an amine-based cured epoxy paint 11.
- a second steel material 20 was prepared as a substitute for the bracket, and its surface was coated with an amine-containing cationic electrodeposition paint 21.
- a disk-shaped vulcanized natural rubber 30 having a diameter of 20 mm and a thickness of 5 mm was prepared.
- the surface of the amine-based cured epoxy paint 11 on the first steel material 10, the surface of the amine-containing cationic electrodeposition paint 21 on the second steel material 20, and the upper and lower surfaces of the natural rubber 30 are each made of 5% trichloroisocyanuric acid.
- the adhesive layer 40 was formed by bonding the first steel material 10 and the natural rubber 30 with an epoxy adhesive via the respective surface treatment layers 12 and 31. Similarly, the adhesive layer 40 was formed by bonding the second steel material 20 and the natural rubber 30 with epoxy adhesives through the respective surface treatment layers 22 and 31.
- test piece not including any of the components shown in FIG. 2B was prepared and evaluated.
- test piece was subjected to a tensile test in a direction perpendicular to the plane of the disk-shaped natural rubber until the test piece broke, and the strength and fracture site at the time of the fracture were investigated.
- Example 1 A first steel material was prepared, and its surface was painted with an amine-based cured epoxy paint.
- a second steel material was prepared, and its surface was painted with an amine-containing cationic electrodeposition paint.
- a disk-shaped natural rubber having a Shore hardness of Hs60 was prepared. The surface of these members was surface-treated with 5% trichloroisocyanuric acid in ethyl acetate to form a surface treatment layer.
- a thermosetting epoxy adhesive containing 100 parts of Epicron EXA835 (trade name, manufactured by DIC), which is a bisphenol F type epoxy resin, and 20 parts of Fuji Cure FXR1000 (trade name, manufactured by Fuji Chemical Industry Co., Ltd.) as a curing agent. To form an adhesive layer. In this way, the test piece shown in FIG. 2 was produced.
- Example 2 A disk-shaped natural rubber having a Shore hardness of Hs85 was used. Other conditions were the same as in Example 1, and a test piece was produced.
- Example 3 A disk-shaped natural rubber having a Shore hardness of Hs55 was used. Other conditions were the same as in Example 1, and a test piece was produced.
- Example 4 A test piece was produced under the same conditions as in Example 1 except that the curing agent for the epoxy adhesive was changed to Amicure PN23 (manufactured by Ajinomoto Co., Inc.), which is an organic hydrazide type. The mixing ratio was 100 parts of epoxy resin and 30 parts of curing agent.
- Amicure PN23 manufactured by Ajinomoto Co., Inc.
- Example 5 A test piece was prepared under the same conditions as in Example 1 except that the epoxy resin and the curing agent were replaced with a commercially available epoxy adhesive Fosur320 / 322 (manufactured by LORD).
- the curing agent is amine-based.
- the mixing ratio is 100 parts of epoxy resin and 100 parts of curing agent.
- Example 6 Before the surface treatment of the natural rubber, the surface of the bonded portion was subjected to a surface treatment using a polishing paper having a particle size P150 in JIS R6010 to roughen the surface. Other conditions were the same as in Example 1, and a test piece was produced.
- Test piece was prepared by applying the surface treatment to the surface of the steel material without applying the first steel material and the second steel material (amine-based cured epoxy paint and amine-containing cationic electrodeposition paint). was made.
- the test piece showed almost no adhesive force, and the adhesive peeled off from the steel surface.
- Example 2 The surface of the first steel material was painted with an amine-based cured epoxy paint, but the surface treatment was not performed.
- the surface of the second steel material was painted with an amine-containing cationic electrodeposition paint, but the surface treatment was not performed.
- Other conditions were the same as in Example 1, and a test piece was produced.
- test piece peeled off at the steel material surface, specifically at the interface between the steel material surface and the adhesive, with almost no adhesive force.
- Example 3 No surface treatment was applied to the disk-shaped natural rubber. Other conditions were the same as in Example 1, and a test piece was produced.
- test piece peeled off at the rubber surface, specifically at the interface between the rubber surface and the adhesive, with almost no adhesive force.
- Example 4 A test piece was prepared under the same conditions as in Example 1 except that epoxilone B570 (manufactured by Hitachi Chemical Co., Ltd.), which is an acid anhydride curing agent, was used as the curing agent for the epoxy adhesive, and dimethylbenzylamine was used as a curing accelerator. did.
- the mixing ratio was 100 parts epoxy resin, 80 parts curing agent, and 0.8 part curing accelerator.
- the rubber was broken and its strength was 24 MPa.
- the steel surface and the rubber surface were observed to be discontinuously mottled, and intermittent peeling occurred both at the interface between the steel material and the adhesive layer and at the interface between the rubber and the adhesive layer.
- Example 5 A test piece was produced under the same conditions as in Example 1 except that the epoxy adhesive curing agent was replaced with EH317 (manufactured by Adeka) which is a polymercaptan curing agent. The mixing ratio was 100 parts of epoxy resin and 60 parts of curing agent.
- Test piece was prepared by performing vulcanization adhesion on unpainted steel using unvulcanized natural rubber. 6 As a result of conducting a tensile test of the test piece, the rubber was broken and the strength was 65 MPa. A bushing / bracket integrated stabilizer bar was prototyped and subjected to a threading test.
- Table 1 below shows a list of conditions and results of Examples 1 to 6, and Table 2 below shows a list of conditions and results of Comparative Examples 1 to 7.
- Tables 1 and 2 the circles in the first half indicate which processing is being performed, and the arrows indicate the same values as those in the left column.
- the marks in the evaluation column represent the following meanings. ⁇ : good, ⁇ : acceptable, ⁇ : poor.
- the breaks at the breaking strength of about 60 MPa and the threading test strength of about 150 N ⁇ m in the test piece are both breaks of the rubber itself, indicating that the adhesive strength exceeds the strength of the rubber.
- a halogen donor as a surface treating agent for example, a halogenated isocyanuric acid
- a solvent into a material having a double bond in the main chain such as natural rubber, and approaches around the double bond in the main chain.
- the halogenated isocyanuric acid is hydrolyzed and releases a halogen.
- the halogen attacks the double bond of the nearby vulcanized rubber main chain, and the addition reaction proceeds.
- free isocyanuric acid is added to the main chain of the vulcanized rubber together with chlorine while maintaining the ring structure as shown below.
- halogen donors such as halogenated isocyanuric acid as a surface treatment agent are hydrolyzed and released by the influence of moisture near the surface of amine-based cured epoxy coatings and amine-containing cationic electrodeposition coatings. It is considered that this halogen, particularly chlorine, combines with the hydrogen of R—NH 2 contained in the paint, and the other reactions cause the following reactions.
- FIG. 3 is an FT-IR chart before and after the reaction between the amine-based cured epoxy coating and trichloroisocyanuric acid.
- FIG. 4 is an FT-IR chart before and after the reaction between the amine-containing cationic paint and trichloroisocyanuric acid. From these charts, it can be seen that a peak occurs in the vicinity of 1050 cm ⁇ 1 after the reaction.
- the halogen donor surface treatment agent In order to react with the halogen donor surface treatment agent, it preferably has an R—NH 2 structure like an amine-based cured epoxy coating or an amine-containing cationic electrodeposition coating. This is also clear from the results of Comparative Example 6.
- the halogen donor surface treatment agent does not react with materials having no R—NH 2 structure, such as bisphenol F epoxy resin and bisphenol A epoxy resin, which are the main components of the adhesive.
- materials having no R—NH 2 structure such as bisphenol F epoxy resin and bisphenol A epoxy resin, which are the main components of the adhesive.
- an amine curing agent or an organic hydrazide curing agent is used as the curing agent for the adhesive, since the curing agent has an R—NH 2 structure, the following reaction occurs between the curing agent and trichloroisocyanuric acid: It is conceivable that
- FIG. 5 is an FT-IR chart before and after the reaction between the amine curing agent and trichloroisocyanuric acid. This chart also shows that a peak occurs in the vicinity of 1050 cm ⁇ 1 after the reaction.
- acid anhydride-based curing agents and polymercaptan-based curing agents do not react with trichloroisocyanuric acid because they do not have an R—NH 2 structure.
- the surface of the natural rubber bush may be roughened after vulcanization molding. Since the adhesive exerts an anchor effect on the fine irregularities on the surface caused by the roughening, the adhesive force can be further improved. Therefore, the water resistance test can exhibit sufficient adhesive strength to completely break the rubber even if the adhesive slightly deteriorates.
- a general amine-based cured epoxy paint, an amine-containing cationic electrodeposition paint, and a vulcanized natural rubber bush can be used at low cost as a coating for automobiles.
- a surface treatment with a halogen donor such as trichloroisocyanuric acid an inexpensive and highly adhesive adhesive bar can be manufactured at low cost using an epoxy adhesive that can be bonded by low-temperature and short-time curing. It becomes possible.
- each member chemically reacts with each other and adheres firmly, it is possible to express an adhesive force equivalent to that of vulcanization adhesion, and it is possible to manufacture at a lower cost than vulcanization adhesion.
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Abstract
Description
特許文献1は、スタビライザーバーおよびブラケットを金型内に設置し、ゴムブッシュの加硫成型と同時に接着を行う技術を開示している。しかし、金型内に金属製のスタビライザーバーおよびブラケットを設置するため、金型には強度および精度が要求されるうえに、金型の耐久性も低下する。また、通常、スタビライザーバーは長さが1m程度あるため、金型などを含む設備が大型化し、多大なコストがかかるという問題がある。さらに、加硫接着後にスタビライザーバーなどに塗装を施すため、ゴムブッシュとスタビライザーバーとの間などに塗装不良を生じやすく、信頼性の低下を招く。しかも、通常、スタビライザーバーの塗装に用いられる粉体塗装、カチオン塗装は、乾燥(硬化)に高温、長時間の処理を必要とするため、加硫接着されたゴムブッシュの熱劣化を生じる可能性も問題になる。
特許文献3は、(1)の方法によるコスト上昇を抑える方策として、加硫済みのゴムに対し加硫接着を行う方法を開示している。この方法では、加硫済みゴムを用い、(1)に挙げた設備の大型化によるコスト増などのデメリットを解消している。しかし、開示された内容に基づき同一条件(10%圧縮、160℃、60分加熱)で試作を行ったところ、熱劣化によるゴムブッシュの大幅な強度低下が確認され、ゴムブッシュの長期信頼性の点で問題があった。また、特許文献3では、ブッシュとブラケットを接着・固着していないため、この部分で発生する異音や異物の侵入による磨耗、折損の問題を解決できない。
特許文献4は、熱硬化性接着剤を用いる方法を開示している。この方法は、塗装工程における高温塗装処理(130~200℃、20分)を利用して接着剤を硬化させている。しかし、この方法でも、加硫済みのゴムブッシュを高温に長時間さらすことによる熱劣化を避けられない。また、この方法もスタビライザーバーとブッシュとを接着しているだけであり、ブッシュとブラケットとを接着していないため、この部分への異物の侵入による異音の発生や磨耗、破損を防げない。さらに、未塗装のスタビライザーバーにゴムブッシュを接着してから塗装を行うため、スタビライザーバーとゴムブッシュとの境界において、未塗装部が残るなどの塗装不良が発生し、塗装不良部からの腐食が進行し、長期間使用の際、スタビライザーバーが折損するなどの問題があった。
特許文献7は、塗装済みスタビライザーバーに対し、塩素化処理を行ったゴムブッシュを、熱硬化性接着剤で接着する方法を開示している。この方法は、塩素化処理を行うことでゴムブッシュの接着力を向上させていると考えられる。しかし、開示されている情報を基に試作した結果、塩素化処理によりゴム表面が粗化され、アンカー効果によりいくらかの接着力の向上は確認されたが、接着剤だけでは加硫接着の接着強度には大きく劣り、ゴム破断には至らないことが確認できている。また、この方法でもブッシュとブラケットをクランプにより固定しているだけであるため、この部分で発生する異音や異物の侵入による磨耗、折損の問題には対応できない。
第1の鋼材を用意し、その表面をアミン系硬化エポキシ塗料で塗装した。第2の鋼材を用意し、その表面をアミン含有カチオン電着塗料で塗装した。また、ショア硬度Hs60のディスク状天然ゴムを用意した。これらの部材の表面を、5%トリクロロイソシアヌル酸の酢酸エチル溶液で表面処理して表面処理層を形成した。次に、これらをビスフェノールF型エポキシ樹脂であるエピクロンEXA835(DIC社製の商品名)100部および硬化剤としてフジキュアーFXR1000(冨士化成工業社製の商品名)20部を含む熱硬化性エポキシ接着剤により接着して接着剤層を形成した。こうして図2に示すテストピースを作製した。
ディスク状の天然ゴムとしてショア硬度Hs85のものを用いた。その他の条件は、実施例1と同一にしてテストピースを作製した。
ディスク状の天然ゴムとしてショア硬度Hs55のものを用いた。その他の条件は、実施例1と同一にしてテストピースを作製した。
エポキシ接着剤の硬化剤を有機ヒドラジド系であるアミキュアーPN23(味の素社製)に代えた以外は実施例1と同一の条件でテストピースを作製した。混合比は、エポキシ樹脂100部、硬化剤30部とした。
エポキシ樹脂および硬化剤を、市販のエポキシ系接着剤であるFosur320/322(LORD社製)に代えた以外は実施例1と同一の条件でテストピースを作製した。硬化剤はアミン系のものである。混合比は、エポキシ樹脂100部、硬化剤100部である。
天然ゴムを表面処理する前に、接着部をJIS R6010における粒度P150を有する研磨紙を用いて、表面を粗化した後、表面処理を行った。その他の条件は実施例1と同一にしてテストピースを作製した。
第1の鋼材および第2の鋼材の塗装(アミン系硬化エポキシ塗料およびアミン含有カチオン電着塗料)を行わず、鋼材表面に表面処理を施し、その他の条件は実施例1と同一にしてテストピースを作製した。
第1の鋼材の表面をアミン系硬化エポキシ塗料で塗装したが表面処理を施さなかった。第2の鋼材の表面をアミン含有カチオン電着塗料で塗装したが表面処理を施さなかった。その他の条件は実施例1と同一にしてテストピースを作製した。
ディスク状天然ゴムに表面処理を施さなかった。その他の条件は実施例1と同一にしてテストピースを作製した。
エポキシ接着剤の硬化剤を酸無水物系硬化剤であるエピクロンB570(日立化成社製)に代え、硬化促進剤としてジメチルベンジルアミンを用いた以外は実施例1と同一の条件でテストピースを作製した。混合比は、エポキシ樹脂100部、硬化剤80部、硬化促進剤0.8部とした。
エポキシ接着剤の硬化剤をポリメルカプタン系硬化剤であるEH317(アデカ社製)に代えた以外は実施例1と同一の条件でテストピースを作製した。混合比はエポキシ樹脂100部、硬化剤60部とした。
未塗装の鋼材に対し、未加硫の天然ゴムを用いて、加硫接着を行って、テストピースを作製した。6
テストピースの引っ張り試験を行った結果、ゴム破断し、強度は65MPaであった。ブッシュ・ブラケット一体スタビライザーバーを試作してねじ切り試験を行った結果、ゴム内部で破断し、強度は149N・mであった。
Claims (4)
- スタビライザーバーと、前記スタビライザーバーの外周に装着されたゴムブッシュと、前記ゴムブッシュの外周に設けられ、前記ゴムブッシュを介して前記スタビライザーバーを車体の底部に取付けるためのブラケットとを具備し、
前記スタビライザーバーはアミン系硬化エポキシ塗料またはアミン含有カチオン塗料および前記塗料上にハロゲンドナー系表面処理剤を含む表面処理層を有し、前記ゴムブッシュは内表面にハロゲンドナー系表面処理剤を含む表面処理層を有し、前記スタビライザーバーと前記ゴムブッシュとの間にそれぞれの表面処理層を介して、アミン系または有機ヒドラジド系硬化剤およびエポキシ樹脂を含む接着剤層が形成されていることを特徴とするブッシュ・ブラケット一体スタビライザーバー。 - 前記ブラケットは内表面にアミン系硬化エポキシ塗料またはアミン含有カチオン塗料および前記塗料上にハロゲンドナー系表面処理剤を含む表面処理層を有し、前記ゴムブッシュは外表面にハロゲンドナー系表面処理剤を含む表面処理層を有し、前記ブラケットと前記ゴムブッシュとの間にそれぞれの表面処理層を介して、アミン系または有機ヒドラジド系硬化剤およびエポキシ樹脂を含む接着剤層が形成されていることを特徴とする請求項1に記載のブッシュ・ブラケット一体スタビライザーバー。
- 前記ハロゲンドナー系表面処理剤はトリクロロイソシアヌル酸を含むことを特徴とする請求項1または2に記載のブッシュ・ブラケット一体スタビライザーバー。
- 前記接着剤層が形成されている前記ゴムブッシュの表面が粗面化されていることを特徴とする請求項1または2に記載のブッシュ・ブラケット一体スタビライザーバー。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP11846567.3A EP2650150B1 (en) | 2010-12-07 | 2011-12-07 | Bush- and bracket-integrated stabilizer bar |
CN201180058789.0A CN103249580B (zh) | 2010-12-07 | 2011-12-07 | 集成了衬套、支架的横向稳定杆 |
ES11846567.3T ES2552464T3 (es) | 2010-12-07 | 2011-12-07 | Barra estabilizadora con cojinete y soporte integrados |
MX2013006380A MX345273B (es) | 2010-12-07 | 2011-12-07 | Barra estabilizadora integrada con buje y ménsula. |
KR1020137014496A KR101423015B1 (ko) | 2010-12-07 | 2011-12-07 | 부시·브래킷 일체 스태빌라이저 바 |
US13/911,934 US8613460B2 (en) | 2010-12-07 | 2013-06-06 | Bush- and bracket-integrated stabilizer bar |
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JP2010272759A JP5478472B2 (ja) | 2010-12-07 | 2010-12-07 | ブッシュ・ブラケット一体スタビライザーバー |
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CN110395083A (zh) * | 2019-08-08 | 2019-11-01 | 浙江创城汽车零部件有限公司 | 稳定杆与耐磨损橡胶衬套硫化一体的环保化加工工艺 |
CN111674223A (zh) * | 2019-08-08 | 2020-09-18 | 浙江创城汽车零部件有限公司 | 一种稳定杆与耐热耐蚀型橡胶衬套硫化一体的环保化加工工艺 |
CN111674222A (zh) * | 2019-08-08 | 2020-09-18 | 浙江创城汽车零部件有限公司 | 一种稳定杆耐蚀耐磨损衬套、稳定杆及汽车 |
CN111674223B (zh) * | 2019-08-08 | 2021-05-18 | 浙江创城汽车零部件有限公司 | 一种稳定杆与耐热耐蚀型橡胶衬套硫化一体的环保化加工工艺 |
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Publication number | Publication date |
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EP2650150A1 (en) | 2013-10-16 |
MX2013006380A (es) | 2013-08-08 |
JP2012121414A (ja) | 2012-06-28 |
US20130270787A1 (en) | 2013-10-17 |
EP2650150B1 (en) | 2015-09-02 |
MX345273B (es) | 2017-01-24 |
CN103249580A (zh) | 2013-08-14 |
KR101423015B1 (ko) | 2014-07-23 |
JP5478472B2 (ja) | 2014-04-23 |
KR20130086626A (ko) | 2013-08-02 |
US8613460B2 (en) | 2013-12-24 |
EP2650150A4 (en) | 2014-07-09 |
CN103249580B (zh) | 2015-06-03 |
ES2552464T3 (es) | 2015-11-30 |
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