JP2009161627A - Method for producing fiber reinforced resin member, and ripple spring - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fiber reinforced resin member which is of low cost, has excellent durability and is very excellent in practicality, and a ripple spring. <P>SOLUTION: The method for producing the fiber reinforced resin member includes impregnating a resin composition into a base material, wherein the resin composition is prepared by mixing p-aminobenzoic acid and 1,3-phenylbisoxazoline to form amide amine as a curing agent, and mixing the amide amine into bismaleimide resin, and the resin composition is impregnated into the base material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a fiber reinforced resin member and a ripple spring.

  For example, as disclosed in Patent Document 1, a slot 2 of a stator core 1 of a rotating electrical machine is used to form a corrugated spring (ripple springs 4a and 4b) between the slot wall surface 5 and the wedge member 6 and the stator coil 3. ) Is used to absorb the vibration of the stator coil 3 by the ripple springs 4a and 4b and allow the armature current to flow stably (see FIG. 1).

  As the ripple spring, a fiber reinforced resin made by impregnating a base material such as glass fiber with an epoxy resin having excellent moldability is generally employed.

  By the way, in recent years, since further increase in size and output of the generator has been demanded, the ripple spring is required to have further durability so that a larger armature current can flow stably. It has been.

  That is, when the armature current increases, the heat generation amount of the stator coil increases. However, the epoxy resin has low heat resistance and cannot cope with the increase in the heat generation amount. Specifically, the epoxy resin is cured with diaminodiphenyl sulfone to improve heat resistance. However, since the resin composition becomes hard and brittle as it is, the rubbery epoxy resin is further added to improve the toughness. When there are many rubber-like epoxy resins, toughness will improve, but heat resistance will fall. Moreover, when there are few rubber-like epoxy resins, heat resistance will improve, but toughness will fall. Therefore, it is difficult to achieve both at a high level.

  Therefore, for example, it is conceivable to adopt a polyimide resin excellent in heat resistance and toughness in place of the epoxy resin, but the polyimide resin is very expensive and further has poor moldability, so that the cost is high. Inevitable.

  In addition, bismaleimide resin, which is cheaper than polyimide resin, has excellent heat resistance like polyimide resin, but since it is inferior in toughness, when this polyimide resin is used, the ripple spring becomes hard and brittle. At the same time, it is not suitable for use in a ripple spring that requires high toughness.

JP-A-9-82136

  In view of the present situation as described above, the present invention has been repeatedly tested by the inventors, and as a result, by reacting the bismaleimide resin with amidoamine, the toughness that is a disadvantage of the bismaleimide resin is reduced without deteriorating the heat resistance. The present invention has been completed by finding out that it can be improved, and provides a manufacturing method and a ripple spring of a fiber reinforced resin member having excellent durability at low cost and excellent in practicality.

  The gist of the present invention will be described with reference to the accompanying drawings.

  A method for producing a fiber reinforced resin member comprising a base material impregnated with a resin composition, wherein P-aminobenzoic acid and 1,3-phenylbisoxazoline are mixed to produce an amidoamine as a curing agent, The present invention relates to a method for producing a fiber-reinforced resin member, characterized in that a resin composition is produced by mixing this amidoamine with a bismaleimide resin, and the base material is impregnated with the resin composition.

  The method for producing a fiber-reinforced resin member according to claim 1, wherein the amidoamine is mixed with the bismaleimide resin and an aromatic amine-based curing accelerator is mixed. It concerns the method.

  The method for producing a fiber-reinforced resin member according to claim 2, wherein polymethylene polyphenylamine is employed as the aromatic amine-based curing accelerator. Is.

  The fiber reinforced resin member manufacturing method according to claim 3, wherein the bismaleimide resin is mixed with 1600 to 2000 parts by weight with respect to 250 to 300 parts by weight of the P-aminobenzoic acid. The present invention relates to a method for manufacturing a resin member.

  Moreover, in the manufacturing method of the fiber reinforced resin member of any one of Claims 1-4, it concerns on the manufacturing method of the fiber reinforced resin member characterized by the glass fiber being employ | adopted as the said base material. is there.

  Moreover, in the manufacturing method of the fiber reinforced resin member of any one of Claims 1-5, after making the said resin composition impregnate the said base material, it shape | molds in a corrugated sheet shape and makes it a ripple spring. This relates to a method for producing a fiber-reinforced resin member.

  A ripple spring manufactured by the method for manufacturing a fiber-reinforced resin member according to claim 6, wherein the ripple springs 4 a and 4 b are disposed in the slot 2 of the stator core 1 of the rotating electric machine. The present invention relates to a ripple spring that suppresses vibration in the slot 2 of the stator coil 3 to be housed.

  Since this invention is as mentioned above, it becomes a manufacturing method and a ripple spring of the fiber reinforced resin member which was excellent in the practicality which was excellent in durability at low cost.

  An embodiment of the present invention which is considered to be suitable will be briefly described with reference to the drawings showing the operation of the present invention.

  By reacting the bismaleimide resin with amidoamine, the toughness can be improved without deteriorating the heat resistance. Therefore, both the heat resistance and the toughness are obtained by using a bismaleimide resin that is cheaper and easier to mold than the polyimide resin. An excellent fiber reinforced resin member such as a ripple spring can be manufactured.

  Further, when the bismaleimide resin and the amidoamine are reacted, when the bismaleimide resin and the P-aminobenzoic acid forming the amidoamine are mixed together with 1,3-phenylbisoxazoline, the bismaleimide resin and the P-aminobenzoic acid are mixed. And the reaction with 1,3-phenylbisoxazoline is given priority, and the reaction between P-aminobenzoic acid and 1,3-phenylbisoxazoline becomes insufficient, so that the effect of improving the toughness is not observed. It is confirmed by. In this regard, in the present invention, P-aminobenzoic acid and 1,3-phenylbisoxazoline are first mixed to form an amidoamine and then mixed with the bismaleimide resin. This reaction is reliably performed, and the effect of improving the toughness can be obtained with certainty.

  Specific embodiments of the present invention will be described with reference to the drawings.

  This example is a method for producing a fiber reinforced resin member obtained by impregnating a resin composition into a base material, which comprises mixing P-aminobenzoic acid and 1,3-phenylbisoxazoline to form an amidoamine as a curing agent. Then, this amidoamine is mixed with a bismaleimide resin to produce a resin composition, and the substrate is impregnated with the resin composition.

  Specifically, in this example, the resin composition is impregnated into a glass fiber fabric composed of warps and wefts as the base material, heated and cured, and then formed into a corrugated plate shape. In this method, the ripple springs 4a and 4b used for suppressing the vibration of the stator coil 3 housed in the slot 2 of the stator core 1 are manufactured. In addition, as a base material, you may employ | adopt what consists of carbon fiber and an aramid fiber not only in glass fiber. Moreover, you may employ | adopt not only a textile fabric but the alignment fiber body formed by aligning a fiber in one direction.

  By the way, as illustrated in FIG. 1, as a ripple spring for suppressing the vibration of the stator coil 3, so-called top ripple for suppressing the vibration of the stator coil 3 in the vertical direction (radial direction of the stator core 1). 4a and a so-called side ripple 4b that suppresses vibration of the stator coil 3 in the left-right direction (circumferential direction of the stator core 1). The characteristics required for the top ripple 4a and the side ripple 4b are different from each other as apparent from the use conditions shown in FIG. 2, but according to this embodiment, a high compressive strength particularly required for the top ripple 4a is obtained. A ripple spring that can be cleared can be manufactured at low cost.

  This will be described in more detail below.

  In this example, as a resin composition to be impregnated into a substrate (glass fiber fabric), P-aminobenzoic acid and 1,3-phenylbisoxazoline were mixed in advance to produce an amidoamine (curing agent). What mixed this amidoamine with the bismaleimide resin is employ | adopted.

  Furthermore, in this embodiment, when the above-mentioned amidoamine is mixed with the bismaleimide resin, an aromatic amine-based curing accelerator (polymethylene polyphenylamine) is mixed as a curing accelerator. In addition, you may employ | adopt the hardening accelerator different from polymethylene polyphenylamine.

  Specifically, 250 to 300 parts by weight of P-aminobenzoic acid is mixed with a theoretical amount of phenylbisoxazoline with respect to the carboxyl group of the P-aminobenzoic acid to form an amidoamine, and then the bismaleimide resin is added to the amidoamine. The resin composition is produced by mixing a theoretical amount of polymethylene polyphenylamine with 1600 to 2000 parts by weight and the bismaleimide group of the bismaleimide resin.

  In this example, 274 parts by weight of P-aminobenzoic acid was mixed with 216 parts by weight of phenylbisoxazoline to form an amide amine, and then 1660 parts by weight of bismaleimide resin and 297 parts by weight of polymethylene polyphenylamine were added to the amide amine. The resin composition is produced by mixing.

  If the amount of P-aminobenzoic acid added is less than 250 parts by weight, the oxazoline reacts with the amine, leaving excessive reactive groups of bismaleimide, resulting in reduced heat resistance. On the other hand, if the amount of P-aminobenzoic acid added exceeds 300 parts by weight, the carboxylic acid remains and the heat resistance is also lowered. Moreover, since the bismaleimide group does not fully react when the addition amount of the bismaleimide resin is less than 1600 parts by weight, the heat resistance (Tg) is lowered. Moreover, when the addition amount of the bismaleimide resin exceeds 2000 parts by weight, the heat resistance (Tg) increases, but the bismaleimide group becomes excessive and becomes brittle.

  Here, heat resistance (Tg) and elongation can be controlled by controlling the amount of amidoamine (curing agent) and polymethylene polyphenylamine (aromatic amine-based curing accelerator). Specifically, if there are many amidoamines, Tg will become low and elongation will become large, and if there are many polymethylene polyphenylamines, Tg will become high and elongation will become small. Accordingly, the blending amount is appropriately set within the numerical range according to the standard of the rotating electrical machine to be used.

  Subsequently, the resin composition produced as described above is coated and impregnated on a base material in accordance with a conventional method and heat-cured, and then molded into a corrugated sheet shape, or a plurality of these are laminated, or a plurality are laminated together. To make a ripple spring.

  Since the present embodiment is as described above, by reacting the bismaleimide resin with amidoamine, it is possible to improve the toughness without deteriorating the heat resistance. Therefore, it is cheaper and easier to mold than the polyimide resin. A ripple spring excellent in both heat resistance and toughness can be produced using a maleimide resin.

  Further, when the bismaleimide resin and the amidoamine are reacted, when the bismaleimide resin and the P-aminobenzoic acid forming the amidoamine are mixed together with 1,3-phenylbisoxazoline, the bismaleimide resin and the P-aminobenzoic acid are mixed. And the reaction with 1,3-phenylbisoxazoline is given priority, and the reaction between P-aminobenzoic acid and 1,3-phenylbisoxazoline becomes insufficient, so that the effect of improving the toughness is not observed. It is confirmed by. In this regard, in the present invention, P-aminobenzoic acid and 1,3-phenylbisoxazoline are first mixed to form an amidoamine and then mixed with the bismaleimide resin. This reaction is reliably performed, and the effect of improving the toughness can be obtained with certainty.

  Therefore, the present embodiment can manufacture a ripple spring having excellent durability at a low cost and having excellent durability.

  An experimental example supporting the effect of the present embodiment will be described below.

  As shown in FIG. 3, the experimental examples 1 to 4 were examined for changes in Tg and long-term deterioration by changing the blending ratios of the respective materials. The results shown in FIG. 4 were obtained. The ripple springs according to Experimental Examples 1 to 4 employ a glass fiber fabric having an aspect ratio of 6.4: 1. The glass fiber fabric is impregnated with the above resin composition and initially cured at 160 ° C. for 1 hour. After the caulking, eight substrates which were post-cured at 200 ° C. for 2 h + 230 ° C. for 4 h were stacked to produce.

  Further, long-term degradation was evaluated by squeezing the sample flat with a 5 mm thick iron plate, holding the sample at 155 ° C. for a certain period of time, and visually observing changes in appearance every other week.

  3 and 4, it was confirmed that long-term deterioration was significantly improved in Experimental Example 4 in which bismaleimide was reduced by 7% from the theoretical site. Therefore, it was confirmed that the addition amount of bismaleimide is particularly preferably about 1660 parts by weight.

  It has been confirmed by experiments that both heat resistance and toughness are greatly improved as compared with the conventional example using an epoxy resin.

It is a schematic explanatory sectional drawing of the stator core of a rotary electric machine. It is a table | surface which shows the use conditions of a top ripple and a side ripple. It is a table | surface which shows the compounding ratio of each material of Experimental example 1-4. It is a table | surface which shows an experimental result.

Explanation of symbols

1 Stator core 2 Slot 3 Stator coil 4a, 4b Ripple spring

Claims (7)

  A method for producing a fiber reinforced resin member comprising a base material impregnated with a resin composition, wherein P-aminobenzoic acid and 1,3-phenylbisoxazoline are mixed to produce an amidoamine as a curing agent, A method for producing a fiber-reinforced resin member, wherein the amidoamine is mixed with a bismaleimide resin to form a resin composition, and the base material is impregnated with the resin composition.   The method for producing a fiber reinforced resin member according to claim 1, wherein the amidoamine is mixed with the bismaleimide resin and an aromatic amine-based curing accelerator is mixed.   3. The method for producing a fiber reinforced resin member according to claim 2, wherein polymethylene polyphenylamine is employed as the aromatic amine-based curing accelerator.   4. The fiber-reinforced resin member according to claim 3, wherein the bismaleimide resin is mixed in an amount of 1600 to 2000 parts by weight with respect to 250 to 300 parts by weight of the P-aminobenzoic acid. Manufacturing method.   The manufacturing method of the fiber reinforced resin member of any one of Claims 1-4 WHEREIN: Glass fiber is employ | adopted as the said base material.   In the manufacturing method of the fiber reinforced resin member of any one of Claims 1-5, after making the said resin composition impregnate the said base material, it shape | molds in a corrugated sheet shape, It is set as a ripple spring, It is characterized by the above-mentioned. A method for producing a fiber-reinforced resin member.   A ripple spring manufactured by the method for manufacturing a fiber reinforced resin member according to claim 6, wherein the ripple spring is disposed in a slot of a stator core of a rotating electric machine, and the stator coil accommodated in the slot is accommodated in the slot. A ripple spring characterized by suppressing vibration in the slot.

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