JP2002273729A - REINFORCING MATERIAL FOR FORMING FIBER REINFORCED RESIN COMPOSITE, FIBER REINFORCED RESIN COMPOSITE, AND PROCESS FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber reinforced resin composite molding excellent in heat resistance, strength and noise reduction effect, and suitable for teeth of a synthetic resin gear used under high load and high temperature conditions. To provide a fiber-reinforced resin composite using the material and the reinforcing material, and a method for producing the same. SOLUTION: This fiber-reinforced resin composite is obtained by impregnating a reinforcing material with a resin, wherein the reinforcing material has a thermal decomposition starting temperature of 40.
A fiber having a tensile strength of 20 cN / dtex or more at 0 ° C or more and a tensile modulus in a range of 450 to 1100 cN / dtex is included.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reinforcing material for molding a fiber-reinforced resin composite, a fiber-reinforced resin composite using the reinforcing material, and a method for producing the same. Is 400 ° C. or more, the tensile strength is 20 cN / dtex or more, and the tensile modulus is 450 to
The present invention relates to a reinforcing material containing fibers in a range of 1100 cN / dtex, a fiber-reinforced resin composite using the reinforcing material, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a metal material such as steel has been generally used as a material of a gear, particularly in an application requiring a high load. However, it is intended to eliminate noise generated at the time of gear engagement and to reduce the weight. Recently, the use of a fiber-reinforced resin composite in the teeth has been studied.

The physical properties required as a reinforcing material for such a fiber-reinforced resin composite for forming a tooth portion are as follows: a molding temperature at the time of resin molding, or 100 to 130 ° C. as in a timing gear used for an automobile engine. It has heat resistance that can withstand immersion in lubricating oil for a long time, and in recent years, the load on the teeth of vehicle gears has become even higher,
High strength and high toughness are also required.

Further, in order to reduce noise generated when the gears mesh with each other, it is necessary to use a material having an appropriate elastic modulus and an appropriate elongation as a reinforcing material.

It has been known that a meta-type aromatic polyamide fiber is used as such a reinforcing material (JP-A-2-241729). However, the meta-type aromatic polyamide fiber has poor moldability. Although it is excellent, its strength is inferior, so there is a concern about reliability in applications where a high load is applied.

In order to solve such a problem, Japanese Patent Laid-Open No.
JP-A-240325 discloses a reinforcing material in which a meta-type aromatic polyamide fiber and a carbon fiber are combined, but the carbon fiber has a low impact resistance, and thus is broken at the time of gear cutting or use. In addition to the above-mentioned problems, there is a problem that the effect of reducing noise generated at the time of gear engagement is small because the elastic modulus is very high.

Further, Japanese Patent Application Laid-Open No. Hei 7-113458 discloses a reinforcing material in which a meta-type aromatic polyamide fiber excellent in moldability and a high-strength para-type aromatic polyamide fiber are composited. In view of the recent increase in load due to high-speed rotation of gears and long-term use in a higher-temperature atmosphere, it cannot be said that a sufficient reinforcing effect is necessarily exerted.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber reinforced resin which is excellent in heat resistance, strength and noise reduction effect, and which is suitable for teeth of a synthetic resin gear used under high load and high temperature conditions. It is an object of the present invention to provide a reinforcing material for forming a composite, a fiber-reinforced resin composite using the reinforcing material, and a method for producing the same.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, controlled the thermal decomposition onset temperature, tensile strength and tensile modulus of the fibers constituting the reinforcing material to specific ranges. Then, the present inventors have sought to obtain a desired fiber-reinforced resin composite, and have reached the present invention.

Thus, according to the present invention, there is provided (1) a reinforcing material for molding a fiber-reinforced resin composite obtained by impregnating a reinforcing material with a resin, wherein the reinforcing material has a thermal decomposition onset temperature of 400 ° C. or more; A reinforcing material for molding a fiber-reinforced resin composite, comprising a fiber having a tensile strength of 20 cN / dtex or more and a tensile modulus in a range of 450 to 1100 cN / dtex; An impregnated fiber reinforced resin composite, wherein the reinforcing material has a thermal decomposition onset temperature of 40
A fiber reinforced resin composite, comprising a fiber having a tensile strength of 20 cN / dtex or more and a tensile modulus in a range of 450 to 1100 cN / dtex,
(3) Thermal decomposition onset temperature is 400 ° C. or higher and tensile strength is 20
cN / dtex or more and tensile modulus of 450 to 11
A fiber-reinforced resin composite, characterized in that a reinforcing material containing fibers in the range of 00 cN / dtex is impregnated with a thermosetting resin, dried to a semi-cured state, placed in a mold and molded. And (4) a thermal decomposition onset temperature of 40
After arranging a reinforcing material containing fibers having a tensile strength of 20 cN / dtex or more and a tensile modulus in the range of 450 to 1100 cN / dtex in a mold, a liquid resin is injected into the mold. There is provided a method for producing a fiber-reinforced resin composite, characterized by impregnating the reinforcing material and then molding the reinforcing material.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The reinforcing material of the present invention has a thermal decomposition onset temperature of 400 ° C. or more, a tensile strength of 20 cN / dtex or more, and a tensile modulus of 45.
Includes fibers in the range of 0-1100 cN / dtex.

That is, the molding temperature of the fiber-reinforced resin composite,
Considering long-term use in a high-temperature atmosphere, the thermal decomposition temperature of the fiber must be 400 ° C. or higher.

Fibers having a large thermal dimensional change rate at high temperatures cause thermal shrinkage during molding and use of the fiber-reinforced resin composite, causing large strain at the interface between the resin and the fiber. It is possible to significantly reduce the strength of the entire body, so that a fiber having a dimensional change rate of 2% or less and a strength retention of 80% or more after heat treatment at 200 ° C. for 500 hours is used as a reinforcing material. More preferred.

The tensile strength of the fiber is 20 cN / d
If it is less than tex, it cannot withstand a high load during high-speed rotation, and the fiber reinforced resin composite may be damaged or sufficient durability may not be obtained.

Further, the elastic modulus of the fiber is 450 cN /
If it is less than dtex, it is not preferable because it is deformed when an instantaneous load is applied.
If it exceeds 0 cN / dtex, the effect of reducing noise is deteriorated.
It is important to be within the range of 1100 cN / dtex. By using fibers having such an elastic modulus, noise or vibration generated when the gears mesh with each other is significantly reduced.

That is, the reinforcing material for molding a fiber-reinforced resin composite obtained by impregnating the reinforcing material with a resin has a thermal decomposition onset temperature of 4 ° C.
When the fiber contains fibers having a temperature of at least 00 ° C., a tensile strength of at least 20 cN / dtex, and a tensile modulus in the range of 450 to 1100 cN / dtex, it can withstand high loads and high temperatures during high-speed rotation, and generate noise when gears mesh. Thus, a gear made of a fiber-reinforced resin composite that can reduce vibration can be obtained.

Here, "comprising" means that the fiber is a main component of the reinforcing material, and the weight ratio of the fiber to the total weight of the reinforcing material is 40% by weight or more, preferably 50% by weight or more. And more preferably 60% by weight. The fibers are not limited to one type, and two or more types may be mixed and combined for use.

Fibers satisfying the above characteristics include wholly aromatic polyester fibers (including high-strength polyarylate fibers), polyparaphenylene benzobisoxazole fibers (PBO fibers), and para-type aramid fibers. Also, ultra-high molecular weight polyethylene fibers can be a suitable reinforcing material under conditions where the molding temperature or the temperature during use is relatively low.

The reinforcing material can be used in any form such as a woven or nonwoven fabric. In this case, for example, after knitting into a tubular knitted fabric, if a donut-shaped material is used as a reinforcing material by winding it upside down, there is no seam where the mechanical strength is weakened, so the mechanical strength is reduced over the entire circumference of the gear. Strength can be made uniform.

Here, the donut shape refers to a state in which the tubular knitted fabric is wound upside down or turned upside down from one end, and may be formed into a double donut shape upside down or turned upside down from both ends. Alternatively, after folding upside down or upside down to make a double, it may be rolled upside down or rolled upside down.

The reinforcing material may be a seamless cylindrical non-woven fabric, and may be formed into a donut shape by winding upside down or upside down, or a plurality of cylindrical non-woven fabrics having different diameters may be stacked. Further, the ordinary nonwoven fabric may be cut into a slit shape and wound around a bush of the gear so as to draw a vortex.

The basis weight and thickness of the above-mentioned woven or nonwoven fabric may be appropriately set according to the diameter of the gear, the impregnating property of the resin into the reinforcing material, and the required mechanical strength.

The single fiber fineness of the fibers is not particularly limited, but is preferably 0.4 to 5.0 dtex. If the single fiber fineness is larger than 5.0 dtex, the rigidity of the fiber becomes high, and it becomes difficult not only to obtain a uniform basis weight in the process of producing the reinforcing material, but also the number of single fibers per the same weight decreases. As a result, the resin reinforcing effect may be reduced. Further, if the number of single fibers per unit weight decreases, the surface area of the fibers decreases, and the adhesion to the resin is impaired, so that the durability of the gear may decrease. On the other hand, when the single fiber fineness is less than 0.4 dtex, the strength of the single fiber is reduced, so that the strength of the nonwoven fabric itself is reduced and the durability of the fiber reinforced resin composite may be reduced. Further, it is not preferable because fibers are easily cut or entangled in the manufacturing process of the reinforcing material, and the productivity is reduced.

When short fibers are used as the fibers constituting the reinforcing material, the short fiber length is preferably in the range of 15 to 90 mm. When the short fiber length is less than 15 mm, not only the opening becomes difficult, but also the strength of the nonwoven fabric and the like is reduced due to the reduced entanglement of the fibers, and the durability and impact resistance of the fiber-reinforced resin composite are reduced. Sometimes. On the other hand, if the short fiber length is longer than 90 mm, the uniformity during fiber opening is impaired, and the variation in the strength of a nonwoven fabric or the like is undesirably increased. When a plurality of materials are mixed, the fibers can be spread by a known mixing spreader. Furthermore, after preparing a blended spun yarn, a reinforcing material may be formed by cutting the fiber into an arbitrary short fiber length, or a reinforcing material may be formed by uniformly mixing various materials with air or the like. Is also good.

Further, various surfactants may be attached to the fibers to improve the impregnating property between the reinforcing material and the resin, or an oil agent or a scouring agent (which may be originally attached to the fibers). And those containing a surfactant) can be left in a small amount without being completely washed, so that the impregnation with the resin can be improved.

The method for producing the fiber-reinforced resin composite of the present invention is not particularly limited, and any conventionally known method can be arbitrarily adopted. For example, the above-mentioned fiber is turned into a tubular knitted fabric or a cylindrical nonwoven fabric, and these are turned inside out. One or more donut-shaped ones are placed in a mold while a liquid resin is injected into the mold, and the reinforcing material is impregnated and molded. Here, the impregnating property of the resin into the reinforcing material is further improved by reducing the pressure of the mold or increasing the temperature in advance. Alternatively, the tubular knitted fabric or the cylindrical nonwoven fabric may be impregnated with a thermosetting resin and dried to be in a semi-cured state, and then placed in a mold and molded.

In particular, when a gear is formed, the teeth are generally formed by mechanical cutting, but may be formed by forming a gear die.

The resin to be impregnated into the nonwoven fabric is phenol resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, polyaminoamide resin, PE
Thermosetting resins or thermoplastic resins such as S (polyethersulfone) resin, PEEK (polyetheretherketone) resin, and CP resin (crosslinked polyesteramide, crosslinked polyaminoamide) are exemplified. It can be used as a mixture of more than one species.

[0029]

The present invention will be described in more detail with reference to the following examples. The test conditions and measurement methods used in the examples are as follows.

(1) Fiber decomposition initiation temperature Measured using a thermal analyzer (TAS-200, manufactured by Rigaku Corporation).

(2) Tensile strength of fiber Measured in accordance with JIS L-1013.

(3) Tensile modulus of fiber Measured in accordance with JIS L-1013.

(4) Dimensional change rate of fiber after heat treatment A fiber having a length of 50 cm, which was allowed to stand in a constant temperature and humidity (25 ° C., 60% RH) atmosphere, was subjected to a heat treatment at 200 ° C. for 500 hours. The length L was measured, and the thermal dimensional change (%) was calculated by the following equation.

[0034]

(Equation 1)

(5) Strength retention of fiber after heat treatment K1 is the strength of the fiber left standing in a constant temperature and humidity (25 ° C., 60% RH) atmosphere, and the strength of the fiber after heat treatment at 200 ° C. for 500 hours. Is K2, and the strength retention (%) was calculated by the following equation.

[0036]

(Equation 2)

(6) Mechanical Strength of Fiber-Reinforced Resin Composite A gear is formed, a test piece of a predetermined size is manufactured from the gear, and a 3.5 mm diameter pin gauge is set at 2.5 mm / min.
At a speed of between the teeth, and the indentation strength when the teeth were broken was measured. Tooth destruction was caused by cracks at the base of the tooth.

(7) Noise of fiber-reinforced resin composite A gear is formed and the gear is made of an iron gear (material: JIS S4).
5C) and rotated in lubricating oil at 130 ° C,
The noise generated when the gears mesh with each other was sensory evaluated.
も の indicates that the noise was small, and × indicates that the noise was large.

(8) Machinability of Fiber-Reinforced Resin Composite After the gear was formed, a cutting process was performed to form a tooth portion, and the cut portion was observed with a microscope to make a judgment. The criterion was that the cutting surface was uniform, and that the cutting surface was difficult to cut, or that the fibers on the cutting surface were not cut cleanly, and that the projecting surface protruded into the cutting surface in a multi-shape manner was marked x. .

Example 1 A wholly aromatic polyester fiber having a single fiber freshness of 5.5 dtex (Kuraray Co., Ltd .: Vectran) is formed into a tubular knitted fabric, and the tubular knitted fabric is turned upside down from one end and wound into a donut shape. Was placed in a mold heated to about 200 ° C., and a polyaminoamide resin was injected under reduced pressure to impregnate the reinforcing material, and the impregnated resin was cured to form a fiber-reinforced resin composite. The composite was machine-cut to form teeth, thereby producing a fiber-reinforced resin composite gear.

Table 1 shows the thermal decomposition initiation temperature, tensile strength, tensile elastic modulus, dimensional change after heat treatment, and strength retention of the fibers used, and the mechanical strength, noise and gear of the fiber-reinforced resin composite gear. Table 2 shows the machinability during molding.

Example 2 In Example 1, a wholly aromatic polyester staple fiber having a single fiber fineness of 5.5 dtex (Kuraray Co., Ltd .: Vectran) and a meta-type aramid staple fiber having a single fiber fineness of 2.2 dtex (Teijin Co., Ltd .: Conex) in a weight ratio of 50:50 to produce a fiber reinforced resin composite gear in the same manner as in Example 1 except that a spun yarn was used as a tubular knitted fabric.

Table 1 shows the thermal decomposition start temperature, tensile strength, tensile elastic modulus, dimensional change after heat treatment and strength retention of the fibers used, and the mechanical strength, noise and gear of the fiber reinforced resin composite gear. Table 2 shows the machinability during molding.

Example 3 In Example 1, a wholly aromatic polyester staple fiber having a single fiber fineness of 5.5 dtex (Kuraray Co., Ltd .: Vectran) and a para-type aramid staple fiber having a single fiber fineness of 1.7 dtex (Teijin) Co., Ltd .: Technora) in a weight ratio of 50:50 to obtain a fiber reinforced resin composite gear by performing the same procedure as in Example 1 except that a spun yarn was formed into a tubular knitted fabric.

Table 1 shows the thermal decomposition onset temperature, tensile strength, tensile elastic modulus, dimensional change after heat treatment, and strength retention of the used fibers, and the mechanical strength, noise, and gear strength of the fiber-reinforced resin composite gear. Table 2 shows the machinability during molding.

Example 4 Example 1 was the same as Example 1 except that a polyparaphenylene benzobisoxazole fiber having a single fiber fineness of 1.7 dtex (Toyobo Co., Ltd .: Zylon-AS) was used as a tubular knitted fabric. To produce a fiber reinforced resin composite gear.

Table 1 shows the thermal decomposition initiation temperature, tensile strength, tensile elastic modulus, dimensional change rate after heat treatment, and strength retention of the fibers used, and the mechanical strength, noise, and gear strength of the fiber-reinforced resin composite gear. Table 2 shows the machinability during molding.

Example 5 Whole aromatic polyester fiber having a single fiber freshness of 5.5 dtex (Kuraray Co., Ltd .: Vectran) and meta-type aramid staple fiber having a single fiber fineness of 2.2 dtex (Teijin Corp .: Conex) And the weight ratio of 50:50
After the non-woven fabric mixed in the ratio of is formed into a donut shape by spirally winding it, it is arranged in a mold heated to about 200 degrees,
A polyaminoamide resin was injected under reduced pressure to impregnate the reinforcing material, and the impregnated resin was cured to form a fiber-reinforced resin composite. The composite was machine-cut to form teeth, thereby producing a fiber-reinforced resin composite gear.

Table 1 shows the thermal decomposition onset temperature, tensile strength, tensile elastic modulus, dimensional change after heat treatment and strength retention of the used fibers, and the mechanical strength, noise and gear of the fiber reinforced resin composite gear. Table 2 shows the machinability during molding.

Comparative Example 1 The procedure of Example 1 was repeated, except that only the meta-type aramid staple fiber having a single fiber fineness of 2.2 dtex (Tenex Corporation: Conex) was used as the tubular knitted fabric. Thus, a gear made of a fiber-reinforced resin composite was produced.

Table 1 shows the thermal decomposition onset temperature, tensile strength, tensile elastic modulus, dimensional change after heat treatment and strength retention of the fibers used, and the mechanical strength, noise and gear strength of the fiber-reinforced resin composite gear. Table 2 shows the machinability during molding.

Comparative Example 2 In Example 4, polyparaphenylene benzobisoxazole fiber having a single fiber fineness of 1.7 dtex (Toyobo Co., Ltd .: Zylon-AS) was used instead of polyparaphenylene benzo having a high tensile modulus. A gear made of a fiber-reinforced resin composite was produced in the same manner as in Example 4 except that bisoxazole fiber (Toyobo Co., Ltd .: Zylon-HM) was used.

Table 1 shows the thermal decomposition start temperature, tensile strength, tensile elastic modulus, dimensional change after heat treatment and strength retention of the fibers used, and the mechanical strength, noise and gear of the fiber-reinforced resin composite gear. Table 2 shows the machinability during molding.

[0054]

[Table 1]

[0055]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F072 AA01 AA04 AA07 AB05 AB06 AB07 AB17 AB28 AB30 AC02 AC08 AD44 AF29 AG02 AG06 AH04 AH25 AL16 4F204 AA36 AD16 AH12 EA03 EA04 EB01 EB12 EF01 EF05

Claims (10)

[Claims] 1. A reinforcing material for molding a fiber reinforced resin composite obtained by impregnating a reinforcing material with a resin, wherein the reinforcing material has a thermal decomposition start temperature of 400 ° C. or more and a tensile strength of 20 cN / dte.
x or more, and the tensile modulus is 450 to 1100 cN / d
A reinforcing material for molding a fiber-reinforced resin composite, comprising a fiber in the range of tex. 2. The fiber contained in the reinforcing material is 5 ° C. at 200 ° C.
The reinforcing material for molding a fiber-reinforced resin composite according to claim 1, wherein the fiber has a dimensional change rate of 2% or less and a strength retention rate of 80% or more after heat treatment for 00 hours. 3. The reinforcing material for forming a fiber-reinforced resin composite according to claim 1, wherein the fiber contained in the reinforcing material is a wholly aromatic polyester fiber. 4. The reinforcing material for molding a fiber-reinforced resin composite according to claim 1, wherein the fiber contained in the reinforcing material is a polyparaphenylene benzobisoxazole fiber. 5. The reinforcing material for molding a fiber-reinforced resin composite according to claim 1, wherein the fiber contained in the reinforcing material is a para-type aramid fiber. 6. A fiber-reinforced resin composite obtained by impregnating a reinforcing material with a resin, wherein the reinforcing material has a thermal decomposition start temperature of 40.
A fiber-reinforced resin composite comprising fibers having a temperature of 0 ° C. or higher, a tensile strength of 20 cN / dtex or higher, and a tensile modulus in a range of 450 to 1100 cN / dtex. 7. The fiber contained in the reinforcing material has a temperature of 5 ° C. at 200 ° C.
The fiber-reinforced resin composite according to claim 6, wherein the fiber has a dimensional change rate of 2% or less and a strength retention of 80% or more after heat treatment for 00 hours. 8. The fiber contained in the reinforcing material is at least two kinds of fibers selected from the group consisting of wholly aromatic polyester fibers, polyparaphenylene benzobisoxazole fibers and para-type aramid fibers. The fiber-reinforced resin composite according to the above. 9. A pyrolysis initiation temperature of 400 ° C. or higher, a tensile strength of 20 cN / dtex or higher, and a tensile modulus of 45
A fiber-reinforced resin characterized in that a reinforcing material containing fibers in the range of 0 to 1100 cN / dtex is impregnated with a thermosetting resin, dried to a semi-cured state, placed in a mold, and molded. A method for producing a composite. 10. A thermal decomposition onset temperature of 400 ° C. or more, a tensile strength of 20 cN / dtex or more, and a tensile modulus of 4
After arranging a reinforcing material containing fibers in the range of 50 to 1100 cN / dtex in a mold, injecting a liquid resin into the mold to impregnate the reinforcing material, followed by molding. A method for producing a resin composite.