Patent Application
20070272781
The resin pulley of the present invention is characterized by being formed of a resin composition containing a novolac-type phenolic resin, a silica and an alumina having an average particle diameter of 5 μm or larger, and a content ratio of the alumina is from 5 to 20% by weight. The reason that the average particle diameter is limited to 5 μm or larger in the present invention is that a minute alumina having an average particle diameter less than the foregoing range easily drops off from the surface of the resin pulley when a cloud of dust collides with the pulley in a dusty atmosphere to lower an effect of preventing abrasion by the dropping off of the alumina. The other reasons are that the alumina that drops off acts as an abrasive to accelerate the abrasion of the surface of the resin pulley, and that in cooperation with the dropping off of alumina, the abrasion resistance of the resin pulley is reduced.
The average particle diameter of alumina is preferably 60 μm or smaller. A larger alumina having an average particle diameter exceeding the foregoing range lowers flow ability of the resin composition in molding, which may cause difficulties to produce excellent resin pulleys, in particular, by injection molding without filling failures of the resin composition and gas burns. Further, there is a possibility of developing abrasion of the contact surface of a mold used for injection molding with the resin composition. Additionally, a load to facilities may be increased and the abrasion of the mold and screws and cylinders of a molding machine may be increased.
On the contrary, the alumina having an average particle diameter within the foregoing range has difficulties in dropping off from the surface of the resin pulley. Besides a good effect to improve abrasion resistance of the resin pulley, the flowability of the resin composition in molding may not be reduced. Therefore, excellent resin pulleys can be produced without molding defects such as filling failures and gas burns. Furthermore, the abrasion of the contact surface of a mold used for injection molding with the resin composition may not be accelerated. Still furthermore, a load to facilities can be reduced and the abrasion of the mold, and screws and cylinders of a molding machine can be suppressed. The average particle diameter of the alumina is preferably 5 to 40 μm in view of the balance of each property described above.
The reason that the content ratio of the alumina is limited to 5 to 20% by weight relative to a total of the resin composition in the present invention is that when the content ratio is less than 5% by weight, the effect by adding the alumina to reinforce the resin exposed on the surface of the resin pulley to improve resistance to abrasion cannot be obtained. When the ratio exceeds 20% by weight, the ratio of the alumina dropping off from the surface of the resin pulley is increased when a cloud of dust collides the pulley in a dusty atmosphere. The alumina dropped off serves as an abrasive to accelerate further abrasion of the surface of the resin pulley. Accordingly, the resistance to abrasion of the resin pulley is rather reduced.
The alumina has a specific gravity that is about three times heavier than a novolac-type phenolic resin. When a large amount of the alumina exceeding the foregoing range is added, a problem is caused that an advantage of weight reduction by replacement with resin pulleys cannot be obtained. The content ratio of the alumina is preferably 7.5 to 10% by weight in view of the balance of each property described above.
The silica in various shapes such as a spherical shape and indefinite shape can be used, and in particular, a spherical silica is preferable. The average particle diameter of the spherical silica is preferably 10 to 30 μm, and more preferably 15 to 25 μm.
An oversized spherical silica having an average particle diameter exceeding the foregoing range and an indefinite shaped silica lower flowability of the resin composition in molding, which may cause difficulties to produce excellent resin pulleys, in particular, by injection molding without molding defects such as filling failures of the resin composition and gas burns. Further, the abrasion of contact surface of a mold used for injection molding with the resin composition may be accelerated. The silica having a large particle diameter, the indefinite shaped silica, or a minute spherical silica having an average particle diameter less than the foregoing range easily cause aggregation in the resin composition. When the silica is aggregated and is not dispersed uniformly, the effect to reinforce the resin and to improve abrasion resistance of the resin pulley may be insufficient.
On the other hand, the spherical silica having an average particle diameter within the foregoing range has a small particle diameter and its surface is smooth due to the spherical shape. Thus, the flowability of the resin composition in molding cannot be reduced. As a result, excellent resin pulleys can be produced without molding defects such as the filling failures and gas burns. Further, there is no possibility of accelerating abrasion of the contact surface of the mold for injection molding with the resin composition. Furthermore, since the spherical silica does not aggregate easily in the resin composition and is dispersed uniformly, the effect of improving abrasion resistance of the resin pulley is also excellent.
The content ratio of the silica is preferably set in consideration of the content ratio of the alumina such that the total content ratio of the silica and the alumina is 30 to 50% by weight, and particularly 35 to 45% by weight relative to the total of the resin composition. When the total content ratio of the silica and the alumina is less than the range, the effect by the silica and the alumina to reinforce the resin and to improve abrasion resistance of the resin pulley may not be sufficiently obtained.
On the other hand, when the total content ratio of the silica and the alumina exceeds the range, the content ratio of the novolac-type phenolic resin is relatively reduced, and the flowability of the resin composition in molding is reduced. It may be difficult to produce excellent resin pulleys, in particular, by injection molding without molding defects such as filling failures of the resin composition and gas burns.
Furthermore, since the amount of hardened products of the novolac-type phenolic resin serving as a binder is deficient in a resin pulley after molding, the ratio, in particular, of the alumina dropping off from the surface of the resin pulley is increased when a cloud of dust collides with the pulley in a dusty atmosphere. At the same time, the alumina dropping off acts as an abrasive and accelerates further abrasion of the surface of the resin pulley. As a result, the resistance of abrasion of the resin pulley may be reduced.
For the novolac-type phenolic resin, it is preferable to use in combination of a first novolac-type phenolic resin having a number average molecular weight Mn1 of 850 or less and a second novolac-type phenolic resin having a number average molecular weight Mn2 exceeding 850. Using the two kinds of novolac-type phenolic resins having different number average molecular weights together, the cross-linking density of the cross-linking structure formed by hardening reaction is adjusted and the flexibility is imparted to the hardened products, which enables to impart high thermal shock resistance to the resin pulleys as described above.
That is, the second novolac-type phenolic resin having a number average molecular weight Mn2 exceeding 850 has a longer chain length than the first novolac-type phenolic resin having a number average molecular weight Mn1 of 850 or less. When the number of cross-linking points is the same, the possibility is high to increase a distance between adjacent cross-linking points, which functions so as to lower the cross-linking density of the hardened products.
Accordingly, using the second novolac-type phenolic resin with the first novolac-type phenolic resin and adjusting the weight ratio of both of the novolac-type phenolic resins can adjust the cross-linking density of hardened products at any range, improve the flexibility of the hardened products, and impart high resistance of thermal shock to the resin pulleys.
The first novolac-type phenolic resin having a number average molecular weight Mn1 of 850 or less fuses and flows by the application of heat more easily than the second novolac-type phenolic resin having a number average molecular weight Mn2 exceeding 850. Using the first novolac-type phenolic resin with the second novolac-type phenolic resin enables improvement of flowability of the resin composition in molding. There is also an advantage that excellent resin pulleys can be produced without molding defects such as filling failures of the resin composition and gas burns.
In view of the adjustment of the cross-linking density of hardened products at any range, and the improvement in flexibility of the hardened product to improve the effect of providing high thermal shock resistance to the resin pulley using the second novolac-type phenolic resin in combination together, the first novolac-type phenolic resin preferably does not have an extremely short chain length and the number average molecular weight Mn1 is preferably 750 or more even within the range as clear from the mechanism of adjusting the cross-linking density of the hardened products described above. For the first novolac-type phenolic resin, two or more kinds of novolac-type phenolic resins having a number average molecular weight Mn1 of 850 or less may be combined.
In view of an improvement in flow ability of the resin composition in molding and production of excellent resin pulleys without molding defects such as filling failures of the resin composition and gas burns using the first novolac-type phenolic resin in combination together, the second novolac-type phenolic resin preferably does not have an extremely large molecular weight and the number average molecular weight Mn2 is preferably 1,150 or less, and more preferably 1,050 to 1,150 even within the range. For the second novolac-type phenolic resin, two or more kinds of novolac-type phenolic resins having a number average molecular weight Mn2 exceeding 850 may be combined.
The first and second novolac-type phenolic resins can be mixed at any ratio. When a resin whose number average molecular weight Mn2 is relatively small even in the foregoing range so that its chain length is short so that the effect of lowering cross-linking density is small is used as the second novolac-type phenolic resin, for example, the ratio is preferably set to be relatively large. On the contrary, when a resin whose number average molecular weight Mn2 is relatively large in the range so that the chain length is long and the effect of lowering cross-linking density is significant is used as the second novolac-type phenolic resin, the ratio is preferably set to be relatively small.
More specifically, when a first novolac-type phenolic resin P1 having a number average molecular weight Mn1 of 750 to 850 and a second novolac-type phenolic resin P2 having a number average molecular weight Mn2 of 950 or more but less than 1,050 are combined, for example, a weight ratio P1/P2 of both preferably ranges from 35/65 to 65/35, anymore preferably from 45/55 to 55/45.
When a first novolac-type phenolic resin P1 having a number average molecular weight Mn1 of 750 to 850 and a second novolac-type phenolic resin P2 having a number average molecular weight Mn2 of 1,050 to 1,150 are combined, a weight ratio P1/P2 of both preferably ranges from 40/60 to 70/30, and more preferably from 50/50 to 60/40.
By setting the weight ratio of the first and second novolac-type phenolic resins within the foregoing ranges, a cross-linking density of hardened products formed by hardening both of the novolac-type phenolic resins is preferably adjusted to 0.25 mol/cm3 or less if expressed in the number of moles at cross-linking points contained within the unit volume of only the resin content in the hardened products, thereby enabling to impart high thermal shock resistance to the resin pulley.
In the present specification, based on a result of measuring a glass transition temperature Tg (° C.) and a storage modulus E′ (MPa) of hardened products obtained by hardening a measuring sample composition containing a resin content of a novolac-type phenolic resin and a hardening agent but not containing other components such as silica, alumina and reinforcing fibers, the cross-linking density ρ′ (mol/cm3) is expressed by a value obtained by the equation (1):
ρ′=E′/3φRT′ (1)
where φ is a coefficient determined according to a formation state of the cross-linking structure formed by hardening reaction and is set to 1 herein, R represents a gas constant (=8.3143 J/Kmol) and T′ represents a reference temperature (=Tg+40° C.).
The content ratio of the novolac-type phenolic resin (the total content ratio when the foregoing first and second novolac-type phenolic resins are combined) is preferably 20 to 40% by weight, and more preferably 25 to 35% by weight relative to the total of the resin composition. When the content ratio of the novolac-type phenolic resin is less than the range, flowability of the resin composition in molding is reduced and thus it may be difficult to produce excellent resin pulleys, in particular, by injection molding without molding defects such as filling failures of the resin composition and gas burns.
In addition, the amount of hardened products of the novolac-type phenolic resin serving as a binder is deficient in a resin pulley after molding. When a cloud of dust collides with the pulley in a dusty atmosphere, the ratio, in particular, of the alumina dropping off from the surface of the resin pulley is increased. At the same time, the alumina dropped off acts as an abrasive may accelerate the abrasion of the surface of the resin pulley, which may possibly lower the abrasion resistance of the resin pulley.
On the other hand, when the content ratio of the novolac-type phenolic resin exceeds the foregoing range, the content ratio of the silica and the alumina is relatively reduced. As a result, the effect by the silica and the alumina of reinforcing the resin and improving abrasion resistance of the resin pulley may not sufficiently achieved.
Since the novolac-type phenolic resin is not self-reactive as described above, a hardening agent for hardening-reaction after injection molding is added into a resin composition. Various hardening agents capable of hardening-reaction to the novolac-type phenolic resin can be used, and in particular, hexamethylenetetramine is preferable. The ratio of the hardening agent is preferably 12 to 20 parts by weight relative to 100 parts by weight of the total of the novolac-type phenolic resin.
A reinforcing fiber, a lubricant, an elastomer, etc., can be included in the resin composition. Inorganic or organic various reinforcing fibers can be used, and particularly an inorganic fiber is preferable. The inorganic fiber includes a glass fiber, a boron fiber, a carbon fiber, a silicon carbide fiber, an alumina fiber, an inorganic whisker, etc. In particular, the glass fiber is preferable due to not only ease in production, availability, and cost effectiveness, but also a superior reinforcement effect. The glass fiber is preferably about 6 to 20 μm in its average fiber diameter and about 1 to 6 mm in its average fiber length. A chopped strand which is often used for reinforcement of the novolac-type phenolic resin is preferable.
The content ratio of the reinforcing fiber is preferably 20 to 40% by weight, and more preferably 20 to 30% by weight relative to the total of the resin composition. When the content ratio is less than the range, the reinforcement effect by containing the reinforcing fiber, or the effect of improving dimensional stability and strength of a resin pulley may not be obtained. When the content ratio exceeds the range, belt attacking property to damage a counterpart of the resin pulley such as a belt may become stronger.
As a lubricant, a fluororesin powder superior in lubricity such as, for example, a polytetrafluoroethylene (PTFE) powder is preferable. The fluororesin powder as a lubricant is preferably 10 μm or smaller in its average particle diameter. The fine fluororesin powder having an average particle diameter of 10 m or smaller can be dispersed uniformly on the surface of a resin pulley. As a result, only adding a slight amount of fluororesin powder can impart satisfactory slip property to the surface of the resin pulley. It is more preferable that the average particle diameter of the fluororesin powder is smaller. However, if it is extremely small, dispersibility is reduced on the contrary. Thus, aggregation is easily caused and the powder may not be dispersed uniformly on the surface of the resin pulley. Accordingly, an excellent slip property cannot be imparted on the surface of the resin pulley. Therefore, the average particle diameter of the fluororesin powder is preferably 1 μm or larger.
The content ratio of the lubricants such as the fluororesin powder is preferably 0.5 to 5% by weight, and more preferably 0.5 to 3% by weight relative to the total of the resin composition. When the content ratio of the lubricants is less than the range, the effect by containing the lubricants for imparting satisfactory slip property on the surface of a resin pulley may not be obtained. When the ratio exceeds the range, thermal resistance of the resin pulley may be reduced since most of the lubricants are fluororesin powder with lower thermal resistance than hardened products of the novolac-type phenolic resin.
The resin composition for forming the resin pulley of the -present invention may be added with various additives such as a coloring agent like pigment and a mold releasing agent for facilitating to release a resin pulley after molding from a mold within a well-known range of the content ratio, besides each component described above.
The resin pulley of the present invention can be produced by heating and melting a resin composition containing each of the aforesaid components within a cylinder of an injection molding machine, thereafter injecting the molted composition into a mold cavity of a mold corresponding to a shape of the pulley. The mold is preheated at not less than a hardening temperature of the novolac-type phenolic resin. Then the novolac-type phenolic resin is subjected to hardening-reaction to produce the pulley. When the resin pulley is provided with a metal insertion member (for example, a bearing) as described above, the resin pulley integrated with the insertion member can be produced in the same manner by injecting the resin composition into the mold cavity and subjecting the novolac-type phenolic resin to hardening-reaction, while the insertion member is held by a holding portion provided in the mold cavity of the mold.
For the mold used for injection molding, a gate for injecting the resin composition melted within the cylinder into the mold cavity is preferably a film gate (in particular, a film gate extending over the circumference of the pulley) or a ring gate. Employing the mold with the foregoing film gate and the like can produce excellent resin pulleys without molding defects such as filling failures and weld lines of the resin composition using a low flowability resin composition containing a large amount of a silica, an alumina, a reinforcing fiber, etc. as described above.
Each component shown in Table 1 was mixed by a Henschel mixer, kneaded by a thermal roll heated at 85° C., sheeted and thereafter ground to prepare a resin composition.
Five kinds of alumina having an average particle diameter of 1.5 μm, 4 μm, 5.9 μm, 35 μm and 60 μm were used individually. The average particle diameters of silica and alumina were measured by a laser diffraction method with the use of a laser diffraction/scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.)
Number average molecular weights of the first and second novolac-type phenolic resins were measured by a high-speed liquid chromatograph (HLC-802A, manufactured by Tosoh Corporation) loaded with TSK-Gel column G3000H8 (×1), G2000H8 (×2) and G1000H8 (×1), each manufactured by Tosoh Corporation.
The weight ratio P1/P2 of the first novolac-type phenolic resin P1 and the second novolac-type phenolic resin P2was 55/45. Based on the results of measuring glass transition temperature Tg (° C.) and storage modulus E′ (MPa) of hardened products formed by hardening a measuring sample composition containing resin contents of two kinds of the novolac-type phenolic resins and a hardening agent but not containing other components such as a silica, an alumina and a reinforcing fiber, the cross-linking density ρ′ obtained by the equation (1) described above was 0.24 mol/cm3.
Subsequently, a mold having a film gate continuting over the entire circumstance was prepared that has a cavity corresponding to the shape of the pulley body 11 of the resin pulley 1 shown in
The ball bearing 2 formed with the outer ring 21, a ball 22, an inner ring 23, a holder 24 and seals 25 and 26 was set to the holding portion of the mold and clamped. In this state, the resin composition softened in a cylinder was injected into the cavity to fill in the mold cavity and then hardened. The pulley body 11 with a groove 11a on the outer circumferential surface was molded to produce the resin pulley 1.
Abrasion resistance for the five kinds of resin pulleys with different average particle diameters of alumina produced in Example 1 were evaluated based on Taber abrasion loss (mm3) which was measured by Japanese Industrial Standards (JIS) K7204:1999 “Plastics—Determination of resistance to wear by abrasive wheels”.
To evaluate thermal shock resistance for the five kinds of resin pulleys with different average particle diameters of alumina produced in Example 1, the process of cooling the resin pulleys at −40° C. for 30 minutes and heating them at 120° C. for 30 minutes was regarded as one cycle, and the process was repeated for 2,000 cycles. After that, the pulley bodies were observed for whether cracks were generated. The pulley body without any cracks was evaluated as Excellent. The pulley body with a few cracks but practically permissive was evaluated as Good. The pulley body with many cracks was evaluated as Bad.
The five kinds of resin pulleys with different average particle diameters of alumina produced in Example 1 were observed whether molding defects such as filling failures and gas burns were caused in pulley bodies after molding. The pulley body without any molding defects was evaluated as Excellent. The pulley body in which a few molding defects were detected but practically permissive was evaluated as Good. The pulley body unusable due to molding defects was evaluated as Bad.
The results of the abrasion resistance test are shown in
From Table 2, the results confirm that the five kinds of resin pulleys 1 were superior in thermal shock resistance since the cross-linking density was set to 0.25 mol/cm3 or less by combining two kinds of novolac-type phenolic resins as a base resin.
From Table 2 and
In addition, the results from Table 2 confirm that the resin pulleys containing alumina having an average particle diameter of 60 μm or smaller were all superior in moldability. The result confirms that the average particle diameter of alumina is preferably 60 μm or smaller.
Six kinds of resin pulleys with different content ratios of alumina were produced in the same manner as Example 1 except that a content ratio of alumina with the average particular diameter of 5.9 μm was set to 0% by weight, 5% by weight, 7.5% by weight, 10% by weight, 20% by weight and 39% by weight, and that a content ratio of silica was adjusted such that a total content ratio of silica and alumina became 39% by weight. The abrasion resistance test and the thermal shock resistance test of the resin pulleys were carried out and their properties were evaluated.
The results of the abrasion resistance test are shown in
The results confirm from Table 3 that the six kinds of resin pulleys 1 were all superior in thermal shock resistance since cross-linking density was set to 0.25 mol/cm3 or less by combining two kinds of novolac-type phenolic resins as a base resin.
The results confirm from Table 3 and
The disclosure of Japanese Patent Application No. 2006-144475 filed on May 24, 2006 is incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP2006-144475 | May 2006 | JP | national |
