JP2536245B2 - Unidirectional reinforced composite fabric - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a unidirectionally reinforced composite material-forming woven fabric, and in particular, a reinforcing fiber yarn used as a warp is obtained by thermoforming the woven fabric. The present invention relates to a woven fabric for molding which can effectively exhibit its effect in a molded product.

(Prior Art) Recently, heat-resistant thermoplastic resins such as polyetheretherketone and polyetherimide have been industrially and constantly supplied, and continuous fiber reinforcement yarns have been blended with these resins for molding. A method of forming a thermoplastic resin reinforced with continuous fiber reinforcing yarns has been used. Various techniques relating to these molding methods are disclosed. For example, (1) a mixed woven fabric manufactured by using a reinforcing long fiber yarn and a matrix thermoplastic resin fiber yarn as warp and weft yarns respectively, (2) a reinforcing long fiber yarn and a matrix thermoplastic resin fiber yarn, A mixed woven fabric produced by making and twisting and with a single yarn, and using it for each of the warp and the weft, (3) Reinforcing long fiber yarns aligned in one direction as warp ,
A unidirectional reinforcing woven fabric produced by using a thermoplastic resin fiber yarn for matrix as a weft yarn, (4) Similarly, in a solution in which a thermoplastic resin for matrix is dissolved in a solvent in a unidirectional reinforcing filament yarn. There is a method of producing the prepreg by processing.

In the methods (1) and (2), the reinforcing long fiber yarns are dispersed in two directions, that is, the warp direction and the weft direction. Further, since the crossing points of the warp threads and the weft threads are formed, the reinforcing continuous fiber threads do not become straight in the molded body, and the strength considerably lower than the theoretical strength of the reinforcing continuous fiber threads is obtained.

In the method (3), since the reinforcing fiber yarns are aligned in one direction, the reinforcing effect of the reinforcing material in a specific direction is effectively exhibited. Further, since the reinforcing fiber yarn is not struck in the weft direction, the reinforcing fiber yarn used as the warp in the molded body exists in a straight line, and the reinforcing effect of the reinforcing fiber yarn is effectively exhibited. be able to. However, since there is no reinforcing effect in the weft direction, the reinforcing fiber yarn of the warp easily flows during press molding. In particular, the edges of the molded body are easy to flow, and also when the number of laminated layers is large or the pressing pressure is high, it is easy to flow. Therefore, in the case of the method (3), the pressing conditions are considerably limited. Further, in the case of the method (3), small cracks or cracks are likely to occur in the resin layer between the reinforcing fiber yarns of the warp yarns, and the strength of the molded body is likely to be lowered.

In the case of (4), it is easy to obtain strength characteristics close to the theoretical strength, but the sheet itself is very rigid, and it tends to be inferior in terms of handling and mold compatibility.

(Problems to be Solved by the Invention) The present invention relates to the method (3), which improves the flowability of the warp-reinforcing fiber yarn during press molding of the unidirectionally reinforced composite material forming fabric, and further forms The purpose is to prevent the resin layer between the warp-reinforcing fiber yarns from easily splitting and cracking. Another object is to obtain an entangled composite yarn of a glass fiber yarn and a thermoplastic resin fiber yarn used to solve these problems.

(Means for Solving the Problems) In order to solve these problems, the present inventors have developed a thermoplastic resin fiber thread, and a yarn count of 2Tex to 35Tex and cutting to a length of 10 mm to 30 mm. It is possible to solve the above-mentioned problems by producing an entangled composite yarn made of glass fiber yarns, and further weaving this entangled composite yarn as a weft yarn and a reinforcing fiber yarn as a warp yarn to form a woven fabric. I found it.

As the reinforcing long fiber yarn used as the warp in the woven fabric of the present invention, glass fiber yarn, carbon fiber yarn, alumina fiber yarn, aramid fiber yarn and the like can be used. Further, as the sizing agent for these reinforcing long-fiber yarns, it is necessary that the material has compatibility or affinity with the thermoplastic resin that is melted in the hot pressing step during molding and becomes the matrix, and the surface treatment Agents can be included. Further, as the thermoplastic resin fiber yarn used for the weft, as a resin, a fiber such as polyetheretherketone (PEEK), polyetherimide (PEI), polyethersulfone (PES), polycarbonate (PC), polyamide (PA) is formed. The resin is not particularly limited as long as it is a resin that can be melted by hot pressing to form a matrix. As the form of the yarn, a non-twisted yarn of a multifilament yarn or a single yarn of a sweet twist is desirable because it is entangled and compounded with a glass fiber yarn. The yarn count is preferably 20 Tex to 150 Tex. As the glass fiber yarn which is entangled with the thermoplastic resin fiber yarn to form the composite yarn, those having a yarn count of 2 Tex to 35 Tex are suitable, and those having a yarn count of 2.8 Tex to 11.2 Tex are particularly suitable. Further, the entangled composite yarn of the present invention has a glass fiber yarn of 10 mm to 30 mm.
It is characterized by being cut in the length range of.

As for the sizing agent for the glass fiber yarns and the thermoplastic resin fiber yarns used for the entangled composite yarns, a material having compatibility or affinity with the thermoplastic resin serving as the matrix, as in the case of the reinforcing fiber yarns for the warp yarns. It is necessary to be.

In order to produce the entangled composite yarn of the glass fiber yarn and the thermoplastic resin fiber yarn, both fibers are simultaneously supplied to the bulking process jet nozzle in the state of overfeed, and it is carried out by arbitrary air pressure. By passing through the air turbulent flow area in the nozzle, each yarn is opened in the nozzle, and the filaments are mixed and intertwined while being opened. As the air pressure is increased, the turbulence of the yarn in the nozzle increases. Glass fibers are more vulnerable to friction and bending than organic fibers. Therefore, when the air pressure increases, the glass fiber filament becomes more disturbed in the nozzle, and at the same time, the friction between the filaments and the friction between the filament and the inner wall surface of the nozzle increase, and the glass fiber filament is easily cut.
This cutting length is not cut into a substantially constant length, but varies in a certain range depending on the pressure, and the higher the pressure, the shorter the cutting length.
As the entangled composite yarn of the present invention, it is necessary that the cutting length of the glass fiber yarn is in the range of 10 mm to 30 mm, but the cutting length of this range is 1.5 kg / cm ^{2 to} 6.0 kg / pneumatic range. It is obtained by setting to cm ² . The specific pressure to be used is selected from the above pressure range depending on the type of glass fiber yarn or the type of thermoplastic resin fiber yarn to be used. The overfeed is selected from the range of 2% to 6%.

The entangled composite yarn thus obtained is used as a weft yarn, and the reinforcing long fiber yarn is used as a warp yarn to be woven by a usual method to obtain a woven fabric. The plain weave is most preferable as the weave structure of the woven fabric, but the effect of the present invention can be exhibited even with a weave structure other than the plain weave such as twill weave and satin weave. Further, the content of the reinforcing fiber yarn in the woven fabric in the present invention is preferably 40 to 65%
(Capacity).

(Operation) By laminating a required number of the thus obtained woven fabrics in the forming die with the warp directions aligned, and hot pressing,
The thermoplastic resin fiber yarn is melted and flows in the mold, impregnated with the reinforcing fiber yarn, and defoamed. Then, the molding die is cooled to obtain a unidirectionally reinforced composite molded body. In this case, at the stage of the woven fabric, since the reinforcing long fiber yarn of the warp intersects with the entangled composite yarn of the warp yarn, it exists in the woven fabric in a wavy form, but it should be laminated and hot pressed in the mold at the time of molding. As a result, the thermoplastic resin fiber yarn of the weft is melted and flows in the mold to impregnate the reinforcing fiber yarn of the warp, so that the reinforcing fiber yarn of the warp that is wavy in the woven state due to the pressure at the time of pressing is straightened. Try to extend to. The glass fiber yarn of the entangled composite yarn used for the weft of the present invention has a yarn count of 2 Tex to 35 Tex.
When the woven fabric of the present invention is used, the thermoplastic resin fiber yarn of the composite yarn of the weft is melted but the glass fiber yarn is in the weft direction in the range of 10 mm to 30 mm. Remain. However, as described above, these glass fiber yarns use a yarn having a smaller count than the reinforcing fiber yarn of the warp yarns, and the filaments constituting the yarns are cut, so that Does not impede the movement of the reinforcing fiber thread that tries to stretch straight under pressure. By being cut into short pieces, these glass fiber threads are formed in a state of being bent along the reinforcing fiber threads of the warp threads.

FIG. 1 is a schematic view of a cross section of a molded body produced by using the fabric of Examples 1 and 2 of the present invention, and FIG. 2 is a cross sectional view of a molded body produced by using the fabric of Comparative Example 1. A schematic diagram is shown. 1 and 2 are cross-sectional views taken along the warp direction of the molded product, 11 and 11 'are reinforcing fiber yarns of warp, 12 and 12' are thermoplastic resin matrix, and 13 and 14 are entangled composite. The glass fiber yarn used for the yarn is shown. In Fig. 1, the glass fiber thread remaining in the weft direction is thin and 10 mm to 30 mm.
Since it is cut in the range of mm, it does not hinder the movement of the reinforcing fiber yarn, which is the warp, to try to extend, and the reinforcing fiber yarn exists in a straight line. Therefore, the effect of the warp as a reinforcing material can be sufficiently exerted. In the case of FIG. 2, although the glass fiber yarn existing in the weft direction is cut because it is thick, it interferes with the movement of the warp yarn to try to extend straight, and the reinforcing yarn of the warp yarn is formed in a wavy state. It will exist inside. Therefore, the reinforcing effect as a reinforcing material cannot be fully exhibited.

FIG. 3 is a process drawing for producing the composite yarn of the present invention.
The yarns respectively drawn out from the package 1 in which the synthetic resin fiber yarn, for example, the PEI fiber yarn is wound, and the package 2 in which the glass fiber yarn is wound are supplied to the supply roller 4 through the guide 3. The two yarns leaving the supply roller pass through the guide 5 in a parallel state and are inserted into the jet nozzle 6 for bulking. The yarn inserted into the jet nozzle is opened by the action of the turbulent flow of compressed air, and the filaments of the two yarns are mixed and further entangled. At this time, when the pressure of the compressed air is higher than a certain pressure, the glass fiber filament is cut.
The entangled composite yarn exiting from the jet nozzle passes through the take-up roller 8 and is wound up by the take-up roller 9.
Will be 10. The yarn is in overfeed between the supply roller and the take-up roller.

Even when the count of the glass fiber yarn used for the entangled composite yarn of the weft yarn is thin, if the cutting length range is longer than the range of 10 mm to 30 mm, the reinforcing fiber yarn is prevented from extending straightly. As a result, they are present in the molded product in a wavy state as shown in FIG. Further, when the woven fabric of the present invention is used, since the glass fiber yarns cut at the time of press forming are present so as to be entangled with the warp yarns in the weft direction, the reinforcing fiber yarns of the warp yarns are produced by the flow of the molten thermoplastic resin. It becomes possible to suppress the tendency to flow. Therefore,
The selection range of pressing conditions is expanded, and it becomes possible to produce a molded product having better performance. Furthermore, the presence of the glass fiber yarn, which is one of the reinforcing fiber yarns, in the weft direction also suppresses the occurrence of tears and cracks that tend to enter the resin layer between the reinforcing fiber yarns of the warp. this is,
The occurrence of tears and cracks is presumed to be due to the internal stress generated inside the molded body during the process of expansion and contraction from heating press to cooling, but a reinforcing material also enters the weft direction. Is considered to act as a receptor for the stress.

When the cutting length of the glass fiber used for the entangled composite yarn of the present invention is shorter than 10 mm, the glass fiber is likely to fall off during weaving, so that the effect of suppressing the flow of the warp reinforcing fiber yarn during press molding becomes small.

Next, the present invention will be further described by showing Examples and Comparative Examples of the present invention.

Example 1 I. Glass fiber yarn Glass fiber yarn: (a) TCK-37 1/0 untwisted yarn (S glass fiber, count 135 Tex, filament diameter 13 μ) (b) ECD
-1800 1 / 01Z yarn (count 2.8Tex) Sizing agent component: (a) Film-forming component: Epoxy 828 with 1 mol of diethanolamine added (3% active ingredient).

(B) Coupling agent: γ-aminopropyltriethoxysilane 0.5%.

(C) Lubricant: Butyl stearate (0.5 in active ingredient)
%), Tetraethylenepentamine distearate (0.05% active ingredient).

(D) Water: Remaining sizing agent pH: adjusted to about 5 by adjusting with acetic acid.

Sizing agent attachment rate: 0.50% for the (a) yarn, 0.45% for the (b) yarn II. Thermoplastic resin fiber yarn for matrix Resin fiber yarn: PEI (polyetherimide) yarn [Product name:
Ultem # 1010 (Engineering Plastics Co., Ltd.) 90Tex sizing agent: Propylene oxide-ethylene oxide copolymer [Product name: WOPOL U (Matsumoto Oil & Fats Co., Ltd.) 3% active ingredient] Sizing agent adhesion rate: 1.5% III. Manufacture of composite yarn II. PEI (polyetherimide) yarn and I. glass fiber yarn ECD-1800 1/0 1Z yarn at the same jet nozzle (equipment is U-Tex TASLAN TEXTVRIZING MACHINE
The glass / PEI composite yarn having a glass fiber yarn content of 3.0% was produced by entanglement and mixing with an overfeed of 4% at an air pressure of 4.0 Kg / cm ² . In this case, the fiber length of the glass fiber was 10 mm to 30 mm.

IV. Weaving of unidirectionally reinforced fabric I. Glass fiber yarn TCK-37 1/0 untwisted yarn as warp,
Using the ECD1800 1/0 1Z yarn / PEI yarn composite yarn made in III. As the weft yarn, the following unidirectional reinforcing woven fabric was made.

Weaving structure: plain weave (a) Warp density 24.5 threads / 25 mm (b) Weft density 15.0 threads / 25 mm (c) Single weight 193 g / m ² Loom: MAV rapier room Example 2 I. Glass fiber thread Same as Example 1. However, the- (b) thread is ECD-9
001/0 1Z yarn (count 5.6Tex) was used, and the sizing agent attachment rate was 0.40%. II. Thermoplastic resin fiber yarn for matrix Same as in Example 1.

III. Production of composite yarn Same as in Example 1. However, when the air pressure is 5.0 kg / cm ² , the glass fiber yarn content is 5.9% and the fiber length is 1
The range is 0 mm to 30 mm.

IV. Weaving of unidirectional reinforcing fabric Same as in Example 1.

Example 3 I. Glass fiber yarn Same as Example 1. However, the- (b) thread is ECE225
Using 1/0 1Z yarn (count 22.5Tex), the sizing agent adhesion rate was 0.40%.

II. Thermoplastic resin fiber yarn for matrix Same as in Example 1.

III. Production of composite yarn Same as in Example 1. However, glass fiber yarn content rate 20.0%
I made it.

IV. Weaving of unidirectional fabric Same as in Example 1.

Comparative Example 1 I. Glass fiber yarn Same as in Example 1. However, the- (b) thread is ECG-7
Using 5 1/0 1Z thread (68Tex, filament diameter 9μ),
The sizing agent deposition rate was 0.35%.

II. Thermoplastic resin fiber yarn for matrix Same as in Example 1.

III. Production of composite yarn Same as in Example 1. However, the air pressure is 3.0 Kg / cm ² ~
Within the range of 3.5 Kg / cm ² , the glass fiber thread content is 42.9.
The fiber length in% was in the range of 20 mm to 45 mm.

IV. Weaving of unidirectional reinforcing fabric Same as in Example 1.

Comparative Example 2 Same as Example 1. However, starch was used as the sizing agent.

Comparative Example 3 I. Glass fiber yarn Same as in Example 1. However, the-(b) yarn was not used.

II. Thermoplastic resin fiber yarn for matrix Same as in Example 1.

III. No composite yarn was produced.

IV. Weaving of unidirectional reinforcing fabric Same as in Example 1. However, I. glass yarn is used as warp,
The yarn of II. Was used as the weft.

The content% of the reinforcing fiber yarn in the woven fabrics in Examples 1 to 3 and Comparative Examples 1 to 3 is shown in Table 1 below.

Measurement of the length of the glass fiber yarns that make up the entangled composite yarn The PEI fiber yarn that makes up the entangled composite yarn is dissolved with methylene chloride, and after removal, the length of the remaining 20 glass fiber filaments is measured. It was measured.

Reference Example Eight sheets of the fabrics of Examples 1 to 3 and Comparative Examples 1 to 3 were laminated with the warps in the same direction, and hot pressed under the conditions of a molding temperature of 360 ° C. and a molding pressure of 15 Kg / cm ² , and a thickness of 0.5 mm. A flat plate molded body was manufactured. The bending strength and appearance of the obtained molded body were tested. The results are shown in Table 2.

The following judgments are made from the results shown in this Table 2: (1) Examples 1 to 3 are excellent in all of bending strength, appearance of molded articles, and effect of glass fiber yarn.

(2) In Comparative Example 1, the strength is not sufficiently exhibited because the glass fiber yarn for warp reinforcement is not linear in the molded body.

(3) In Comparative Example 2, since the sizing agent of the glass fiber yarn of the weft yarn is a starch type, the adhesion with the matrix resin in that portion is not sufficiently performed (whitening), and the desired strength is obtained. Absent.

(4) In Comparative Example 3, since the glass fiber yarn is not contained in the weft yarn, the reinforcing glass fiber yarn of the warp flows and the resin layer between the reinforcing glass fiber yarns is torn or cracked so that the strength is sufficient. Not demonstrated.

(Effect of the invention) A small amount of glass fiber yarn is put in a thermoplastic resin fiber, and further, a unidirectional reinforcing fabric using a composite yarn in which the glass fiber yarn is controlled to a fiber length in the range of 10 mm to 30 mm is used as a weft yarn. Molded products obtained by stacking and heating / pressurizing are
It is possible to manufacture an excellent unidirectional reinforcing composite material forming woven fabric which functions to prevent the end portion of the reinforcing material from flowing due to the press molding pressure without bending the reinforcing material entering the warp in one direction. .

[Brief description of drawings]

FIG. 1 is a schematic view of a cross section of a molded body produced using the woven fabric of the present invention (Examples 1 and 2). FIG. 2 is a schematic view of a cross section of a molded body produced using the woven fabric of Comparative Example 1. FIG. 3 is a process drawing for producing the composite yarn of the present invention. 1: PEI thread, 2: Glass thread, 3: Guide, 4: Supply roller, 5: Guide, 6: Jet nozzle, 7: Entangled composite thread, 8: Take-up roller, 9: Take-up roller, 10: Composite thread Package, 11: warp reinforcing yarn, 11 ': warp reinforcing yarn, 12: thermoplastic resin matrix, 12': thermoplastic resin matrix, 13: glass yarn used for entangled composite yarn, 14: entangled composite yarn Used glass thread

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D03D 15/00 D03D 15/00 C 15/12 A 15/12 7310-4F B29C 67/14 X

Claims (2)

(57) [Claims] 1. A warp yarn is a reinforcing long fiber yarn, a weft yarn is a thermoplastic resin fiber yarn and a yarn count of 2 Tex to 35 Tex, and a length of 10 mm to 3
A woven fabric for forming a unidirectionally reinforced composite material, which is an entangled composite yarn made of 0 mm glass fiber yarn. 2. An entangled composite yarn comprising a thermoplastic resin fiber yarn and a glass fiber yarn, wherein the glass fiber yarn is cut.