JPS63317535A - Composite textile cloth reinforced with synthetic polymer - Google Patents

Abstract

PURPOSE:To obtain a composite textile cloth having high strength and elastic modulus, resistant to delamination and useful for helmet for rider, by impregnating and curing a synthetic polymer in a cloth produced by compounding polyethylene fibers having high strength and elastic modulus with wholly aromatic polyamide fibers. CONSTITUTION:A textile cloth which is a woven fabric or crossed nonwoven fabric is produced by compounding (A) 30-95wt.% of a high-tenacity and high- modulus polyethylene fiber having a tensile strength of >=20g/de and a tensile modulus of >=500g/de with (B) 70-5wt.% of wholly aromatic polyamide fiber and/or wholly aromatic polyester fiber having a tensile strength of >=15g/de and a tensile modulus of >=500g/de. The textile cloth is impregnated with a synthetic polymer (a thermosetting unsaturated polyester polymer or epoxy polymer) in an amount to attain a total fiber content of 30-90wt.% and the polymer is cured to obtain the objective reinforced cloth.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a synthetic resin-reinforced composite fiber cloth, and more specifically, it has high strength and high elasticity, and has high l, a fiber/ The present invention relates to a synthetic resin-reinforced composite fiber cloth that has good delamination resistance at the resin interface, is lightweight, and has excellent light resistance and abrasion resistance.

Furthermore, delamination resistance means that when a synthetic resin-reinforced composite fiber cloth is subjected to various external stresses such as shearing, bending, and fI 5 force, the fibers that make up the reinforced fiber cloth and the thermosetting matrix resin It refers to resistance to delamination phenomenon (usually observed as whitening phenomenon) that occurs at the interface of It is said to be an extremely important characteristic from the viewpoint of quality assurance, including initial and durability, in application fields such as helmets, bulletproof helmets, and various bulletproof plates.

[Conventional technology] Conventionally, impact-resistant materials used in the field of helmets such as rider helmets and bulletproof helmets, or as bulletproof panels for interior linings of automobiles, ships, aircraft, etc., have been designed to reduce weight and improve impact resistance. What about high strength and high modulus fibers, such as high strength and high modulus polyethylene? The use of A-fibers and aromatic polyamide fibers (for example, manufactured by DuPont, USA, trade name Kevlar, etc.) is being considered.

However, in both applications, known high-strength
The use of high modulus fibers alone cannot simultaneously satisfy the required properties in terms of strength and economic efficiency.

For example, fully aromatic polyamide fibers or fully aromatic polyester fibers are expensive, but they are not all-purpose in terms of physical properties, and have the drawbacks of extremely low light resistance and insufficient impact resistance. have.

On the other hand, high-strength, high-modulus polyethylene fibers are less expensive than fully aromatic polyamide fibers and fully aromatic polyester fibers, and in terms of physical properties, they are high strength, lightweight, and have high impact resistance. Although it has various advantages such as excellent light resistance, abrasion resistance, and chemical resistance, the city! - Low delamination resistance during shearing, bending, and breaking, and high shear resistance, bending, and city use, such as in the field of helmets and bulletproof plates! In fields where performance is required, it cannot be said that both physical properties and economic efficiency can be satisfied.

[Problems to be Solved by the Invention] The present invention addresses the excellent properties of high-strength, high-modulus polyethylene fibers, namely, high strength, high modulus of elasticity, lightness, light resistance, abrasion resistance, and chemical resistance. By combining this with other fibers without impairing its properties, we aim to improve its delamination resistance, which is considered its biggest drawback, and provide a synthetic resin-reinforced composite fiber cloth with excellent impact resistance. It is something.

[Means for Solving the Problems] The structure of the reinforced resin cloth of the present invention that can solve the above-mentioned problems is that the reinforced resin cloth of the present invention is composed of high-strength, high-modulus polyethylene fibers (A), wholly aromatic polyamide fibers (B), and The gist is that a fabric made by blending/or wholly aromatic polyester fiber (C) is impregnated with a synthetic resin to strengthen it.

[Function] The high strength and high elasticity polyethylene fiber used in the present invention (
^) means that the tensile strength is at least 20 g/denier or more, preferably 30 g/denier or more, and more preferably 4
0 g/denier or more and a tensile modulus of at least 5
00 g/denier or more, preferably 800 g/denier or more, more preferably 1000 g/denier or more, and has a tensile strength of less than 208 g/denier or a tensile modulus of less than 500 g/denier, such as a helmet. When used in the field of bulletproof boards, the impact resistance and bulletproof properties are insufficient, and the cost performance is inferior to conventional materials.

Fully aromatic polyamide fiber (B) used in the present invention
Typical examples include poly(P-phenylene terephthalamide) and polymers thereof. In addition, examples of wholly aromatic polyesters (C) include poly(P-)unine terephthalate).
Alternatively, typical examples include polymers thereof.

The fabric used in the present invention may be a knitted fabric, a woven fabric, or an orthogonal nonwoven fabric, but a woven fabric or an orthogonal nonwoven fabric is more preferable in terms of improving the physical properties of the resulting reinforced fabric.

The form of the 151 fibers used in the fabric may be long fibers, short fibers, or a mixture of long fibers and short 1a fibers, but
Long fibers are most preferred in order to provide the reinforcing fabric with a higher level of high strength and high elastic modulus.

A specific composite method for obtaining a fabric made of the above-mentioned high-strength/high-elasticity polyethylene fiber (A), wholly aromatic polyamide fiber (B), and/or wholly aromatic polyester fiber (C) is as follows: In fabrics using fibers (A), (B) and/or (C), 100% of the long fibers (A), (B) and/or (C) are used for each of the warp and weft yarns. If (A
)/(B), (A)/(C), (A)/(B)
/ (C) combination, or (A) / (B
) , (＾) / (C1゜(A) / (B) / (
A method in which one or several threads are alternately composited in each combination of C), or a method in which long fibers (A
), a method of using 100% of (B) and/or (C) and using the other one in the above arrangement or in combination at the ratio of one tree or several trees alternately, furthermore, the above (^) / (B),
(A) / (C) or (A) / (B) / (C
), it is possible to adopt a method of compounding as a filament mixed yarn.

The composite fiber fabric thus obtained is usually used by laminating two or more fabrics after applying a synthetic resin.

On the other hand, in the case of orthogonal nonwoven fabrics, 100% of each material (A), (B) and/or (C) made of long fibers with high strength and high elasticity is used to form a single layer, and then (A)/
(B), (A)/(C), (A)/(B)/(
A method of laminating multiple layers in a combination of C) and using it as an orthogonal nonwoven fabric, and a method of using a combination of long fibers (A) / (B), (A) / (
C) or each material of (A) / (B) / (C) is aligned, or one or several yarns are combined alternately, or mixed yarn is made into a single layer, then multi-layered is laminated, and then it is made into an orthogonal nonwoven fabric. The method used is exemplified.

The above-mentioned composite fiber material constituting the fabric may be mixed with other materials other than the above-mentioned fibers as the main component to the extent that the properties of the composite fiber resin-reinforced fabric, which is the final object of the present invention, are not impaired. This does not preclude configuring.

In the present invention, the excellent properties of high-strength, high-modulus polyethylene fibers, such as being lightweight and having excellent light resistance, abrasion resistance, and chemical resistance, can be improved without sacrificing the properties of high strength and high modulus polyethylene fibers. In order to provide synthetic resin-reinforced composite fiber cloth with sufficiently improved delamination properties, high strength and
Preferably 30 to 95% by weight of high modulus polyethylene fibers
, more preferably 40 to 80% by weight, fully aromatic polyamide fiber and/or wholly aromatic polyester fiber, preferably 70 to 5% by weight, more preferably 60 to 20% by weight.
It is desirable to combine them in proportions of % by weight.

When the content of high-strength, high-modulus polyethylene fibers is less than 30% by weight, delamination resistance tends to be further improved, but the amount of fully aromatic polyamide fibers and/or fully aromatic polyester fibers is relatively low. Negative factors due to an excessive increase in the number of materials, namely, the price becomes high, the weight reduction effect is diminished, and the impact resistance, light resistance, and abrasion resistance tend to decrease. Especially the latter two
As for the properties, care must be taken as they tend to become extremely poor when the content is less than 30% by weight.

On the other hand, when 95% by weight of high-strength, high-modulus polyethylene fibers are used as soil, the excellent properties of high-strength, high-modulus polyethylene fibers are not impaired, but the delamination resistance, which is the object of the present invention, is Regarding improvements, it is difficult to obtain the sufficient effects intended by the present invention.

The synthetic resins used in the present invention include thermosetting resins,
All examples include photocurable resins, thermoplastic resins, etc.
Most preferred are thermosetting resins, and particularly preferred among them are saturated polyester resins, unsaturated polyester resins, such as het acid polyesters, bisphenol A polyesters, vinyl polyester resins (
Examples include resins such as straight chain resins) or epoxy resins such as glycidyl ether, glycidyl ester, glycidyl amine, linear aliphatic epoxide, and alicyclic epoxide resins, and the final product is a synthetic resin reinforced composite. Particularly preferred are unsaturated polyester resins and epoxy resins from the viewpoint of delamination resistance, impact resistance, abrasion resistance, adhesion and reinforcing effects, etc. of the fiber cloth. When using epoxy resins, etc., the type and amount of curing agents and curing accelerators may vary depending on the molding method, structure of the laminate, curing temperature, etc. Group amines, tertiary amines, polyamides, etc. may be selected as appropriate, and the amount used may be selected each time. The preferred content of the fibers in the synthetic resin-reinforced composite fiber cloth according to the present invention is preferably in the range of 30 to 90% by weight, taking into consideration both adhesion/reinforcement effects and delamination resistance, and more preferably It ranges from 40 to 80% by weight. The curing method for synthetic resins varies depending on the type of matrix resin used, the molding method, etc., but usually a cold press method or a heat press method is used, and heat is applied in the range of room temperature (about 15℃) to 14.0℃. Let it harden.

When using the synthetic resin-reinforced composite fiber cloth of the present invention as various bulletproof materials, in order to obtain higher levels of light resistance and abrasion resistance, the composite fiber fabric that constitutes the surface layer of the synthetic resin-reinforced composite fiber cloth must be The content of high strength and high elasticity polyethylene fibers in the middle is 30 to 95% by weight, more preferably 40% by weight.
The content is preferably in the range of ~80% by weight, and this range is also preferred from the viewpoint of impact resistance and delamination resistance.

In addition, the composite fiber fabric used in the present invention, that is, the high strength
Of the various effects achieved by compositing high modulus polyethylene fiber (A) with wholly aromatic polyamide fiber (B) and/or wholly aromatic polyester 1ata (C), the cost and weight reduction are mainly due to the weight of the composite. It changes in proportion to the percentage.

Synthetic resin reinforced composite according to the present invention! Among the physical properties of Ii textiles, impact resistance is better as the content of high-strength, high-elasticity polyethylene fibers (A) in the composite fiber fabric is higher, and bending resistance, shear resistance, Regarding delamination resistance, there is a tendency that the lower the content of high-strength, high-elasticity polyethylene fiber (A), the better it is, but if the above three constituent fibers are used alone, the bulletproof material It is not possible to satisfy all of the above five characteristic values that influence the characteristics of. However, high strength and high elasticity polyethylene! The above-mentioned required characteristics can be achieved by using a composite fabric of a-fiber (A), wholly aromatic polyamide fiber (B) and/or wholly aromatic polyester fiber (C) in a preferred ratio, and curing this with a synthetic resin. It is possible to obtain synthetic resin-reinforced composite fiber cloth that satisfies all of the above requirements.

The present invention will be specifically explained below with reference to Examples.

[Example] The method of measuring physical properties used for evaluation of the present invention was as follows.

Measuring method of strength and elongation properties> According to JIS-L-1013 (1981). That is, using Tensilon manufactured by Toyo Baldwin Co., Ltd., the SS curve was measured under the conditions of a sample length (gauge length) of 200 mm and a crosshead speed of 100 mm for 7 minutes, and the tensile strength at break, tensile modulus, and elongation at break were calculated. The tensile modulus was calculated from the maximum slope near the origin of the SS curve.

Measuring method of shear center force (ILSS)〉Using a test piece with a thickness of 3 mm, width of 15 mm, and length of 18+++ m, distance between fulcrums of 12 + nmi/h = 4), and crosshead speed of 1 m.
After measuring the shear core force under the condition of m7 minutes, ILS was determined from the maximum shear core force P (in g) and the cross-sectional area A (mm2) of the specimen.
S value=3·P/4·A (in g/mm2) was calculated.

Bending property measurement method> Using a test piece with a thickness of 3 mm, a width of 15 mm, and a length of 60 mm, a 3-point bending tester was used to measure the presser bar R = 5 mm.
, fulcrum R = 2 mm, distance between fulcrums ll1li 48 m
ml/h=16) and a crosshead speed of 3 mm/min, and the maximum bending strength and bending elastic modulus were calculated from the following equations.

λ: Distance between fulcrums 1! ! (mm) W Test piece width (mm) h: Test piece thickness (mm) F/Y: Stress per 1 mm of displacement in the initial elastic region (g/mm2) Charpy impact strength measurement method> Thickness: 3 mm, A test piece with a width of 15 mm and a length of 42 mm was
Apply to Charpy impact tester and calculate Charpy impact strength using the following formula.

Charpy impact strength = -(Kg -cm/cm2)
ε: Charby impact energy (in g-cm) A: Test piece cross-sectional area (cm2) Delamination resistance measurement method The degree of delamination at the interface between the textile fabric and the resin was evaluated according to the following evaluation criteria from the width of the whitening phenomenon measured as a substitute measure.

Example 1 1200 denier, 720 filament high strength/high elasticity polyethylene fiber (HPE) and commercially available 1420 denier, 100G filament Kevlar 49 (fully aromatic polyamide fiber manufactured by DuPont) (KV) (both long fibers) After weaving a plain weave fabric at the composite ratio shown in Table 1 using g/Cm' and thermosetting at 120° C. for 45 minutes to obtain a synthetic resin-reinforced composite fiber cloth.

Resin liquid formulation> Rivolac 2508X (Showa Kobunshi Co., Ltd. unsaturated polyester resin) 100 parts by weight Benzoyl peroxide paste (50% liquid) 2 parts by weight Fiber content (% by weight) of the obtained synthetic resin reinforced composite fiber cloth, ILS
The S value, bending properties, Charpy impact properties, and delamination resistance are summarized in Table 1.

The direction of stress application when measuring the above characteristics is as follows:
The direction was perpendicular to the Kevlar fibers. Further, the physical properties of HPE and KV shown in Table 1 are as follows.

HPE: Takayumi Elastic polyethylene fiber Total denier 1200 (Denier) Number of filaments 72
0 (filament) tensile strength 32 (g
/denier) Breaking elongation 3.9 (%) Initial Young's modulus 1180 (g/denier) Kv:
Total aromatic polyamide fiber (trade name Kevlar 49, DuPont) Total denier 1420 (denier) Number of filaments tooo (filament) Tensile strength
lq, s (g/denier) elongation at break
2.2 (%) Initial modulus of elasticity 940 (g/denier) (hereinafter referred to as margin) , 3.4.5) are 100% high-strength, high-elasticity polyethylene fibers (Experiment No. 1) or 100% wholly aromatic polyamide fibers (trade name Kevlar 49).
It can be seen that the ILSS value, shear strength, bending strength, Charpy impact strength, and delamination resistance are all well-balanced and excellent compared to the sample (Experiment No. 6).

In addition, when the composite ratio of high-strength, high-elasticity polyethylene fibers is below the lower limit of the preferred range (Experiment No.

6.7) has good bending and delamination resistance, but the Charpy impact value is rather low, and - if it exceeds the sumo wrestler limit (experiment No. 1.2), although the Charpy impact value is good, , low delamination resistance and bending strength.

Example 2 300 denier, 208 filament high strength, high modulus polyethylene fiber (HPE) and commercially available 380 denier,
Using 262 filament Kevlar 49 (fully aromatic polyamide fiber manufactured by DuPont) (KV) (all long fibers), plain woven fabrics having the composite ratios shown in Table 2 were woven.

The woven fabric was coated with an epoxy resin liquid having the following component composition and dried at 100° C. for 30 minutes to produce a prepreg sheet. The fiber content of the obtained sheet was 52% by weight.

Resin liquid formulation> Araldite GY260 (low viscosity general-purpose epoxy manufactured by Ciba Geigy) 10-weight all Araldite HY97
4 (High viscosity general-purpose epoxy manufactured by Ciba Geigy)
40 parts by weight Epicote 154 (novolak epoxy manufactured by Shell Epoxy) 50 parts by weight dicyandiamide 4 Aromatic urea compound [3-(3,4-dichlorophenyl-1,1-dimethylurea)] 4 parts by weight methyl ethyl ketone/methanol゛・ (50150 weight ratio) 45 〃Total 153 parts by weight The number of prepreg sheets listed in Table 2 were laminated alternately with the fabric directions orthogonal, and then heated to a press pressure of 15 g/cm2 using a heat press method. It was thermally cured at 120° C. for 2 hours to obtain a thermosetting resin-reinforced composite fiber cloth with a thickness of 3 mm.

The lAl1 fiber content, ILSS value, bending properties, Charpy impact properties, and delamination resistance of the obtained thermosetting resin-reinforced composite fiber cloth are summarized in Table 2. The physical properties of HPE and KV used in this example are as follows.

HPE n high strength ・High elastic polyethylene 1#i fiber Total denier 300 (denier) Number of filaments 20
8 (Filament) Tensile strength 33 (g
/denier) Breaking elongation 3.6 (%) Initial Young's modulus 1250 (g/denier)K
v: Fully aromatic polyamide fiber (trade name: Kevlar 49, DuPont) Total denier: 380 (denier) Number of filaments: 262 (filament) Tensile strength: 19
．． 7 (g/denier) Breaking elongation 2.5 (%
) Initial modulus of elasticity aa2 (g/denier) 9.10) is slightly better in ILSS value, shear strength, and bending properties than the high-strength/high-elasticity polyethylene fiber 100% product (experiment No. 8), but Charpy impact strength and delamination resistance are slightly better. It can be seen that the performance has been significantly improved.

On the other hand, fully aromatic polyamide fiber (product name Kevlar 49
) Compared to the 100% product (Experiment No. 11), ILSS
It can be seen that although the shear strength and bending properties are inferior, the Charpy Street 5 strength is significantly improved.

From the above results, the synthetic resin-reinforced composite fiber cloth of the present invention (Experiment Nos.
It can be seen that this material exhibits very well-balanced characteristic values as a helmet material and bulletproof material compared to 8.11).

[Effects of the Invention] The present invention is configured as described above, and is said to have the excellent properties of high-strength, high-modulus polyethylene fibers, that is, it is lightweight and has excellent light resistance, abrasion resistance, chemical resistance, etc. Impact resistance is an important characteristic required when applied to the helmet field and bulletproof board field without compromising the characteristics! It is now possible to provide a synthetic resin-reinforced composite fiber cloth with greatly improved properties and delamination resistance. In particular, delamination resistance is important in ensuring a high level of impact 2 durability in fields that require high impact resistance, such as helmets and bulletproof plates. However, according to the present invention, both impact resistance and delamination resistance can be satisfied at a high level in a well-balanced manner.

Among the effects of improving the balance between impact resistance and delamination resistance, impact resistance is improved by the composite effect of high-strength, high-modulus polyethylene fibers and wholly aromatic polyamide fibers and/or wholly aromatic polyester fibers. They are mutually exerted.

As described above, the synthetic resin-reinforced composite fiber cloth of the present invention has all the required properties such as high impact resistance, high delamination resistance, high strength, high elastic modulus, and lightness improved in a well-balanced manner. Resin-reinforced composite fiber cloth can be widely used in the field of helmets such as rider helmets and bulletproof helmets, in the field of bulletproof panels for lining of automobiles, ships, aircraft, etc., and in other applications requiring impact resistance.

Also, when compared with conventional wholly aromatic polyamide fibers,
The light resistance and abrasion resistance, which are said to be disadvantageous, can be significantly improved by compositing with high-strength, high-modulus polyethylene fibers.

j, -) -4-

Claims (7)

[Claims] (1) Synthetic resin is impregnated and cured into a fabric made by blending high-strength, high-modulus polyethylene fiber (A) with wholly aromatic polyamide fiber (B) and/or wholly aromatic polyester fiber (C). A synthetic resin-reinforced composite fiber cloth characterized by being (2) The blending ratio of each fiber constituting the fabric is fiber (A)
: 30 to 95% by weight, fiber (B) and/or fiber (
C): 70 to 5% by weight of the synthetic resin reinforced composite fiber cloth according to claim 1. (3) The tensile strength of the fiber (A) is 20 g/denier or more,
The synthetic resin-reinforced conjugate fiber cloth according to claim 1 or 2, which has a tensile modulus of 500 g/denier or more. (4) Both fibers (B) and (C) have a tensile strength of 15 g/denier or more and a tensile modulus of 500 g.
The synthetic resin-reinforced conjugate fiber cloth according to any one of claims 1 to 3, wherein the synthetic resin-reinforced conjugate fiber cloth has a denier of at least 100%. (5) The synthetic resin reinforced composite fiber cloth according to any one of claims 1 to 4, wherein the cloth is a woven fabric or an orthogonal nonwoven fabric. (6) The synthetic resin reinforced composite fiber cloth according to any one of claims 1 to 5, wherein the synthetic resin is a thermosetting unsaturated polyester resin or an epoxy resin. (7) The synthetic resin-reinforced conjugate fiber cloth according to any one of claims 1 to 6, wherein the total content of fibers in the synthetic resin-reinforced conjugate fiber cloth is 30 to 90% by weight.