JPH11130952A - Resinous flexible boot - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a boot made proof against the production of abnormal sliding sound by using a thermoplastic polyester elastomer prepared by compounding a polyester block copolymer with a compound selected among a glycol, a lactone, an adipate and an unmodified polyolefin. SOLUTION: There is provided a flexible boot molded from a thermoplastic polyester elastomer prepared by compounding 100 pts.wt. polyester block copolymer comprising a high-melting point crystalline polyester polymer segment and a low-melting point polymer segment with 0.01-20 pts.wt. at least one compound selected among compounds of formula I [e.g. poly(tetramethylene oxide) glycol, formula II (e.g polycaprolactone) and formula III (e.g. polybutylene adipate) and an unmodified polyolefin having a number-average molecular weight of 10,000-500,000]. In the formulas, R1 , R3 , R6 and R7 are each a functional group derived by the removal of two hydrogen atoms from a 1-6C hydrocarbon compound; R2 , R4 , R5 and R8 are each a functional group derived by the removal of one hydrogen atom from a 1-20C hydrocarbon; and x, y and z are each an integer of 1-1,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible boot mounted on a universal joint for dust prevention and for holding grease for lubricating the universal joint, and more particularly to a flexible boot molded from a thermoplastic polyester elastomer.

[0002]

2. Description of the Related Art Hitherto, chloroprene rubber has been mainly used for flexible boots for dustproof and grease holding of a universal joint such as a constant velocity joint of an automobile. However, when it is used as a flexible boot for a constant velocity joint of an automobile, chloroprene rubber is insufficient in durability against repeated bending stress, and there is a problem that cracks occur due to long-term use, leading to breakage. . Moreover, since it is inferior in cold resistance, it may be hardened at the time of use in an extremely cold region and may be damaged. In addition, chloroprene rubber flexible boots with low mechanical strength can be damaged by stepping stones during running, or abnormally expanded during high-speed rotation such as high-speed running of automobiles, resulting in deformation or damage due to interference with other parts. Problems arise.

In order to solve such problems, bending fatigue resistance,
As a material having excellent cold resistance and mechanical strength, a flexible boot formed of a thermoplastic polyester elastomer has been proposed and put into practical use.

[0004] However, when the universal joint is bent or rotated at a high angle, the adjacent side surfaces of the peaks forming the bellows of the flexible boot made of the thermoplastic polyester elastomer come into strong contact, and abnormal sliding noise is generated. There is.

The cause of the occurrence of the sliding noise is considered as follows. When the universal joint is rotated while being bent, if the surface of the flexible boot bellows is not slippery, the contacted bellows surfaces rotate while being in close contact with each other, and the bellows surface is deformed so as to shift. As the rotation progresses, the displacement increases, but at a certain point, the adhered surface separates, and the displacement returns. By this repetition, the bellows surface is periodically deformed, and the periodic deformation of the bellows becomes vibration of the surrounding air, thereby generating abnormal sliding noise.

Considering the above-mentioned cause of the sliding noise, it is considered that the abnormal sliding noise can be prevented by improving the smoothness of the bellows surface of the flexible boot. As a method,
As proposed in Japanese Utility Model Laid-Open No. 2-34829,
Part of or the whole of the bellows surface may be roughened. Further, Japanese Patent Application Laid-Open No. HEI 6-117535 proposes a flexible boot using a thermoplastic polyester elastomer containing a silicone resin as a friction and wear property improving agent.

[0007]

However, when the surface of the flexible boot is roughened, the surface of the flexible boot is worn out over a long period of use and the roughened surface is lost, so that the effect of suppressing the sliding noise is not maintained. It is enough.

[0008] In the case of a flexible boot molded using a polyester elastomer containing a silicone resin, the silicone resin oozing on the surface of the flexible boot makes the bellows surface slippery, and abnormal sliding noise is less likely to be generated.

However, when the surface of the flexible boot is wet with water, the bellows do not directly contact each other in the portion where water is interposed, and the coefficient of friction is extremely small. In this state, if the universal joint shaft rotates while being bent, the water interposed on the bellows surface is eliminated by the contact surface pressure between the bellows surfaces, but the portion without water is compared with the portion with water. As a result, the frictional force is rapidly generated, and the bellows surface is rapidly deformed. When this deformation returns to its original state, sliding noise is generated as in the case where the bellows surface is not wet. When a sliding noise is generated due to a difference in sliding between a portion having water on the bellows surface and a portion having no water on the bellows surface, the thermoplastic polyester elastomer containing a silicone resin is not different from a normal thermoplastic polyester elastomer, and the silicone resin has no difference. The flexible boot made of resin using the thermoplastic polyester elastomer contained therein has an insufficient sliding noise suppressing effect.

In addition, when a large amount of silicone resin is blended in order to reduce the difference in slip between a portion where water is present on the bellows surface and a portion where water is not present, the compatibility between the polyester elastomer and the silicone resin is poor. There is also a problem that sometimes delamination occurs and the boot is damaged due to the delamination.

The present inventors have determined that a flexible boot molded using a thermoplastic polyester elastomer does not generate sliding noise under any conditions while maintaining its original excellent durability and mechanical strength. As a result of investigation as an object, the present inventors have found that the above-mentioned target is achieved in a flexible boot molded using a specific thermoplastic polyester elastomer, and have reached the present invention.

[0012]

That is, the present invention relates to a resin-made flexible boot having a shape in which a large-diameter portion and a small-diameter portion are connected by a bellows portion, wherein the resin forming the flexible boot is a polyester block copolymer. With respect to 100 parts by weight, the following general formulas (I), (II) and (II)
A compound represented by I) and a number average molecular weight of 10,000
A resin-made flexible boot characterized by being a thermoplastic polyester elastomer containing at least 0.01 to 20 parts by weight of one or more compounds selected from 500,000 or less unmodified polyolefins.

[0013]

Embedded image (In the above formulas (I), (II) and (III), R ₁ ,
R ₃ , R ₆ , and R ₇ are 2 from hydrocarbon compounds having 1 to 6 carbon atoms.
Functional group excluding hydrogen. R ₂ and R ₄ are hydrogen or a functional group obtained by removing one hydrogen from a hydrocarbon compound having 1 to 20 carbon atoms. R ₅ is a functional group excluding hydrogen, or one hydrogen from a hydrocarbon compound having 1-20 carbon atoms or the R _7, 1
A functional group with a hydroxyl group attached. R ₈ is hydrogen, a functional group obtained by removing one hydrogen from a hydrocarbon compound having 1 to 20 carbon atoms, or a functional group in which a monohydroxyl group is bonded to R ₆ .
x, y, and z represent an integer of 1 to 1000. )

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The thermoplastic polyester elastomer used in the resin-made flexible boot of the present invention is mainly composed of a polyester block copolymer composed of a high-melting crystalline polyester polymer segment (a) and a low-melting polymer segment (b). Things.

The high melting point crystalline polyester polymer segment (a) of the polyester block copolymer constituting the thermoplastic polyester elastomer used in the flexible boot made of resin of the present invention comprises an aromatic dicarboxylic acid or an ester-forming derivative thereof. Polyesters formed from aliphatic diols, preferably terephthalic acid and / or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol, but in addition to isophthalic acid, phthalic acid, naphthalene- A dicarboxylic acid component such as 2,6-dicarboxylic acid or an ester-forming derivative thereof;
The following diols, for example, aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, and fats such as 1,4-cyclohexanedimethanol, tricyclodecane dimethylol Cyclic diol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane,
4,4′-dihydroxy-p-tert-phenyl, 4,4 ′
Polyesters derived from aromatic diols such as -dihydroxy-p-quater-phenyl and the like, or copolymerized polyesters using two or more of these dicarboxylic acid components and diol components in combination may be used. Further, an aliphatic dicarboxylic acid such as adipic acid or sebacic acid may be copolymerized. Furthermore, it is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component and the like in a range of 5 mol% or less.

The low-melting-point polymer segment (b) of the polyester block copolymer constituting the thermoplastic polyester elastomer used in the resin flexible boot of the present invention is an aliphatic polyether and / or an aliphatic polyester. Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide)
Glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of poly (propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. In addition, examples of the aliphatic polyester include polycaprolactone, polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. Among these aliphatic polyethers and / or aliphatic polyesters, poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, polycaprolactone, Butylene adipate and polyethylene adipate are preferred.
Further, the number average molecular weight of these low melting point polymer segments is preferably about 300 to 6000 in a copolymerized state.

The copolymerization amount of the low-melting polymer segment (b) in the polyester block copolymer is preferably from 10 to 80% by weight, more preferably from 15 to 75% by weight.

The compounds constituting the thermoplastic polyester elastomer used in the resin-made flexible boot of the present invention include, in addition to the above-mentioned polyester block copolymer,
It is at least one compound selected from the compounds represented by the following formulas (I), (II) and (III) and unmodified polyolefin compounds having a number average molecular weight of 10,000 or more and 500,000 or less.

[0020]

Embedded image (R ₁ , R ₃ , R ₆ and R ₇ are functional groups obtained by removing 2 hydrogen atoms from a hydrocarbon compound having 1 to 6 carbon atoms. R ₂ and R ₄ are hydrogen or a hydrocarbon compound having 1 to 20 carbon atoms. R ₅ is hydrogen, a functional group obtained by removing 1 hydrogen from a hydrocarbon compound having 1 to 20 carbon atoms, or a functional group in which a monohydroxyl group is bonded to R ₇ , R ₈ is hydrogen Or a functional group obtained by removing one hydrogen from a hydrocarbon compound having 1 to 20 carbon atoms, or a functional group in which a monohydroxyl group is bonded to R ₆ .
x, y, and z represent an integer of 1 to 1000. The compounds represented by the above formula (I) include poly (ethylene oxide) glycol, poly (propylene oxide)
Specific examples include glycol, poly (tetramethylene oxide) glycol, poly (pentamethylene oxide) glycol, poly (hexamethylene oxide) glycol, and among them, poly (tetramethylene oxide) glycol is preferable.

Examples of the compound represented by the above formula (II) include polycaprolactone, polyenantholactone, polycaprylolactone, and a terminal-capping compound thereof. Among them, polycaprolactone is preferable. .

Further, examples of the compound represented by the above formula (III) include polyethylene adipate and polybutylene adipate, among which polybutylene adipate is preferable.

The numbers x, y and z of the repeating units in the above formulas (I) to (III) are integers of 1 to 1000, preferably 10 to 500 in view of the availability from the market. .

Examples of the unmodified polyolefin include polyethylene, polypropylene and ethylene-propylene copolymer having a number average molecular weight of 10,000 or more and 500,000 or less, and among them, low density polyethylene is preferable. On the other hand, modified polyolefins obtained by copolymerizing reactive α and β unsaturated compounds such as maleic anhydride and glycidyl methacrylate are easily incorporated into polyester block copolymers due to their excellent compatibility with polyester block copolymers. In addition, the effect of improving the friction and wear characteristics is extremely poor.

The compound of the above formulas (I) to (IV) is used in an amount of 0.01 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the polyester block copolymer.
Parts by weight. If the amount is less than this, the abnormal sliding noise of the resinous flexible boot molded using the thermoplastic polyester elastomer cannot be suppressed, and if the amount is greater than this, the strength of the thermoplastic polyester elastomer decreases, It is not preferable because the resin-made flexible boot is easily damaged.

The method for producing the thermoplastic polyester elastomer used for the resinous flexible boot of the present invention is not particularly limited. For example, a polyester block copolymer and the above-mentioned formulas (I) to (III) and Additives including one or more compounds selected from the compound group of unmodified polyolefins are preliminarily mixed and supplied to a screw type extruder and melt-kneaded, or each raw material is separately fed to a screw type extruder. Supply and melt kneading.

The thermoplastic polyester elastomer used in the resin-made flexible boot of the present invention includes:
Known antioxidants within a range not to impair the purpose of the present invention,
Light fastener, hydrolysis inhibitor, carbon black, pigment,
A coloring agent such as a dye, a flame retardant and the like can be optionally contained.

The method for producing the resinous flexible boot of the present invention is not particularly limited, and examples thereof include blow molding methods such as extrusion blow, injection blow, and press blow, and injection molding methods.

The resin-made flexible boot of the present invention uses a specific thermoplastic polyester elastomer having excellent friction and wear characteristics, so that a universal joint such as a constant velocity joint for automobiles to which the flexible boot is mounted can be made high in height. Does not generate abnormal sliding noise even when bent or rotated at an angle. Further, the thermoplastic polyester elastomer used for the resin-made flexible boot of the present invention has inherent durability and mechanical strength, and exhibits excellent durability as a resin-made flexible boot.

[0030]

The resin-made flexible boot of the present invention reduces the friction coefficient of the surface by exuding the compound blended in the thermoplastic polyester elastomer to the bellows surface, and the sliding noise in a state where there is no water on the bellows surface. Suppress.
Furthermore, the bellows surface covered with the exuded compound has a good affinity for water, and the water on the surface is not completely eliminated by the contact surface pressure between the bellows surfaces, and water always intervenes on the bellows surface. State. Therefore, even when the universal joint shaft is bent or rotated while the surface of the flexible boot is wet with water, the frictional resistance of the bellows surface does not suddenly change, and no sliding noise is generated.

[0031]

EXAMPLES The effects of the present invention will be described below with reference to examples. All percentages and parts in the examples are on a weight basis unless otherwise specified.

Examples 1 to 8, Comparative Examples 1 to 3 Thermoplastic polyester elastomers (A-1) to (A-
8), Production of (B-1) to (B-4) Polybutylene terephthalate is used as a hard segment,
Polyester block copolymer having polytetramethylene oxide glycol as a soft segment (weight ratio of hard segment / soft segment = 45/55) 100
Parts were mixed with 0.5 part of "Irganox" 1010 (a hindered phenolic antioxidant manufactured by Ciba Geigy), 0.3 part of diphenylmethane diisocyanate, and 1 part of carbon black in a Henschel mixer. L / D = 30 is supplied to the feed port of the twin screw extruder, and the set temperature of the cylinder and the die is set to 240.
Melt kneading was performed at 130 ° C. and a screw rotation speed of 130 rpm. The polymer was discharged from the die in water in a strand form, cut, and pelletized to obtain a thermoplastic polyester elastomer (B-1).

"Irganox" 1010 was added to 100 parts by weight of the same polyester block copolymer as above.
(Hindered phenolic antioxidant manufactured by Ciba-Geigy)
0.5 parts, diphenylmethane diisocyanate 0.3
Parts and 1 part of carbon black in a Henschel mixer, poly (tetramethylene oxide) glycol (PTMG), polycaprolactone (PCL), polybutylene adipate (PBA), several molecular weight 10,000
Polyethylene (PE) No. 0 was mixed in the amounts shown in Table 1 and supplied to the supply port of a twin screw extruder having an inner diameter of 40 mm and L / D = 30. Melt kneading was performed at a rotation speed of 130 rpm. The polymer is discharged from the dice into a strand in water, cut and pelletized, and the thermoplastic polyester elastomer (A-1)-
(A-8) was obtained.

Similarly, “Irganox” 1010 was added to 100 parts of the polyester block copolymer.
(Hindered phenolic antioxidant manufactured by Ciba-Geigy)
0.5 parts, diphenylmethane diisocyanate 0.3
Parts and 1 part of carbon black with a Henschel mixer, a silicone resin (silicone) having a viscosity of 10 ⁷ cs / 25 ° C. and an unvulcanized fluoro rubber (fluoro rubber) were mixed in the amounts shown in Table 1. And inner diameter 40mm, L
The mixture was fed to the feed port of a twin screw extruder with a / D = 30, and melt kneading was performed at a set temperature of the cylinder and the die of 240 ° C. and a screw rotation speed of 130 rpm. The polymer was discharged from the dice into a strand in water, cut, and pelletized to obtain thermoplastic polyester elastomers (B-2) to (B-4).

[0035]

[Table 1] The physical properties of the obtained thermoplastic polyester elastomer were evaluated as follows using injection molded pieces.

Surface hardness: based on JIS K7215,
Measured on durometer D scale.

Tensile properties: in accordance with JIS K7113,
Measured for No. 2 test piece.

Melt index: ASTM D123
Measured at a measurement temperature of 220 ° C. and a load of 2160 g according to 8.

The bending fatigue resistance of the thermoplastic polyester elastomer was determined by pressing a 2 mm thick sheet and a 20 mm thick sheet.
The test was performed on the test piece of
The crack length after 100,000 flex cycles was measured.

Test conditions: Tester: Dematcher bending fatigue tester Test temperature: 100 ° C. Distance between chucks: 25 mm --- 5.6 mm Flexion cycle: 300 times / min In this test, the smaller the crack generation, the more durable Excellent.

After the obtained thermoplastic polyester elastomer was dried with hot air at 80 ° C. for 5 hours, the cylinder temperature was 230 ° C., the nozzle temperature was 230 ° C., and the pressure was 90 ° C. using a press blow molding machine (SBE50 / 140 manufactured by Osberger). Under the molding conditions of a mold temperature of 30 ° C., a flexible boot for a constant velocity joint was molded.

After the flexible boot was allowed to stand for at least 24 hours after molding, the flexible boot was mounted on a constant velocity joint, and the operating noise at the time of driving the joint was measured using a noise meter. The measurement was performed in a state where there was no water on the surface of the flexible boot and in a state where water was present.

Operating noise test conditions: Test temperature: 23 ° C. Test rotation speed: 200 rpm Operating angle: 40 ° Distance to sound level meter: 20 cm If the bellows of the flexible boots do not contact each other at an operating angle of the joint of 0 °, the joint The operating noise during driving is about 60 dB.

Table 2 shows the physical properties of the obtained thermoplastic polyester elastomer and the results of an operation sound test of a flexible boot molded using the thermoplastic polyester elastomer.

[0045]

[Table 2] In the case of the flexible boot molded using the thermoplastic polyester elastomer B-1 of Comparative Example 1, when there was no water on the surface, abnormal sliding noise was generated. Furthermore, when water was present on the surface, abnormal sliding noise was further increased.

In any of the flexible boots of the present invention in the examples, no abnormal sliding noise was generated in the operation noise test. In addition, the thermoplastic polyester elastomers of the Examples were compared with those of Comparative Example 1 in tensile strength and bending fatigue tests.
And almost no decrease in mechanical strength and durability.

On the other hand, the flexible boot of Comparative Example B-2 does not generate an abnormal sliding noise, but the thermoplastic polyester elastomer B-2 has the mechanical strength and durability of the thermoplastic polyester of Example. It is lower than that of the elastomer or the thermoplastic polyester elastomer of Comparative Example 1. Further, as shown in Comparative Examples B-3 and B-4,
With a thermoplastic polyester elastomer to which a silicone resin or a fluorine rubber is added, generation of sliding noise cannot be suppressed.

[0048]

According to the present invention, a universal joint such as a constant velocity joint for an automobile to which a flexible boot is mounted can be formed by using a thermoplastic polyester elastomer in which a specific compound is blended with a polyester block copolymer. Thus, a resin flexible boot that does not generate abnormal sliding noise even when bent or rotated can be obtained.
Furthermore, the thermoplastic polyester elastomer used for the resin-made flexible boot of the present invention has the original durability,
It has mechanical strength and exhibits excellent durability as a flexible boot made of resin.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoko Furuta 194-1, Kita-ku, Hoshiboshizakicho, Minato-ku, Nagoya-shi, Aichi 19 Toray Dupont Co., Ltd.

Claims (4)

[Claims] 1. A resin flexible boot having a shape in which a large diameter portion and a small diameter portion are connected by a bellows portion, wherein the resin forming the flexible boot is represented by the following general formula based on 100 parts by weight of a polyester block copolymer. One or more compounds 0.0 selected from the compounds represented by (I), (II) and (III) and an unmodified polyolefin having a number average molecular weight of 10,000 or more and 500,000 or less.
A resin-made flexible boot, which is a thermoplastic polyester elastomer containing 1 to 20 parts by weight. Embedded image (In the above formulas (I), (II) and (III), R ₁ ,
R ₃ , R ₆ , and R ₇ are 2 from hydrocarbon compounds having 1 to 6 carbon atoms.
Functional group excluding hydrogen. R ₂ and R ₄ are hydrogen or a functional group obtained by removing one hydrogen from a hydrocarbon compound having 1 to 20 carbon atoms.
R ₅ is hydrogen, a functional group obtained by removing one hydrogen from a hydrocarbon compound having 1 to 20 carbon atoms, or a functional group in which a monohydroxyl group is bonded to R ₇ . R ₈ is hydrogen or carbon 1
20 functional groups from hydrocarbon compounds except for one hydrogen or functional group 1 hydroxyl group is bonded to the R _6,. x, y,
z represents an integer of 1 to 1000. ) 2. The compound represented by the general formula (I) is poly (tetramethylene oxide) glycol.
The resin-made flexible boot as described in the above. 3. The resin-made flexible boot according to claim 1, wherein the compound represented by the general formula (II) is polycaprolactone. 4. The resinous flexible boot according to claim 1, wherein the compound represented by the general formula (III) is polybutylene adipate.