JPH10146907A - Fiber reinforced layered material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To allow the panel-like application and provide the durability and the fashion by laminating a canvas and a rigid material while maintaining the feeling of the canvas. SOLUTION: At least one side of a canvas made of a synthetic fiber fabric is coated with a thermoplastic resin to an extent where the feeling of the fabric is not ruined. The canvas has a 10,000mgf or less impact repulsion measured by the JIS L-1096 6.20.1A method (Gurley method). The canvas is produced by a coating method with a thermoplastic resin. A rigid material to be laminated on the canvas has a larger repulsion with respect to the canvas, and a 50,000mkr or more repulsion measured by the JIS L-1096 6.20. 1A method (Gurler method). The fiber reinforced layered material of the fiber fabric and the rigid material, can be formed by lamination via an adhesive, by lamination by heat welder, or by a combination thereof. By applying an anti-fouling treatment on the surface of the fiber reinforced layered material, a durable beautiful appearance can be maintained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to fashionability,
It is a material with excellent workability and durability, and is related to fiber reinforced laminates that are useful as vehicle bodywork materials, civil engineering / architecture materials, and interior materials that are used when carrying luggage by truck etc. It is.

[0002]

2. Description of the Related Art In recent years, sheet-like materials made of synthetic fiber fabrics made of polyester resin, polyamide resin or the like, or natural fiber fabrics such as cotton, coated with a thermoplastic resin such as a polyvinyl chloride resin or a polyolefin resin are used in building structures. It is used for various applications such as roofing materials, flexible containers, and canvas. For example, canvas is used as one of truck body materials when transporting luggage to protect the luggage from damage and dirt caused by the weather and the like. The canvas is lightweight, easily repairable, inexpensive, and excellent in adaptability to irregular-shaped products, and the texture of the fabric is preferred. The method of use is to cover the baggage directly, or to frame the members on the carrier in a box shape and spread the canvas (hereinafter referred to as a hood-mounted vehicle), but the canvas flaps due to the wind pressure during traveling. There is a disadvantage that the reduction is accelerated and the appearance is poor. In addition, there are problems such as weakness to tearing and rain leakage from a damaged portion. As a means for solving such a problem, box-type aluminum framed vehicles made of a light metal plate such as aluminum have been increasing in recent years.

[0003] On the other hand, a generally used soft polyvinyl chloride resin contains a large amount of a plasticizer in order to improve flexibility, and the plasticizer migrates to the surface when used for a long time, There is a drawback that dirt substances are easily attached and the appearance is impaired.

[0004]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention is a material which can be constructed in a panel type while maintaining the texture of canvas, has excellent durability, and is fashionable. It is an object of the present invention to provide an aesthetically pleasing fiber reinforced material having excellent properties.

[0005]

The present invention employs the following means in order to eliminate such a drawback. That is,
The fiber reinforced laminate of the present invention is a laminate of a canvas and a rigid material.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been made in view of the fact that, for a conventional truck body mounting material, a truck body mounting material having excellent fashionability, durability, and easy workability has been desired.
As a result of intensive studies, the present inventors have found that when the canvas is directly laminated on a rigid board, for example, a plywood board, the above-mentioned problems can be solved at once.

[0007] The fiber cloth referred to in the present invention is not particularly limited.
Synthetic fibers such as polyamide fibers, polyacrylonitrile fibers, polyolefin fibers, and polyarylate fibers, as well as fluorine fibers, glass fibers, carbon fibers,
Further, a woven fabric, a knitted fabric or a nonwoven fabric composed of one or two or more kinds of natural fibers such as cotton can be used. Among these fibers, the single yarn strength is 4.
It is preferable to use a high-strength fiber of 5 g / d or more,
It is more preferable to use a high-strength yarn having a single yarn strength of 5 g / d or more from the viewpoint of durability. For example, as a vehicle frame material, a woven fabric made of polyester fibers is preferably used in terms of workability, cost, and the like. The yarn constituting the fiber fabric may be a filament yarn or a spun yarn. However, a spun yarn fabric is preferable because a beautiful and attractive fashionable canvas can be formed. The thermoplastic resin constituting the canvas of the present invention has a lower melting point than the fibers constituting the fiber cloth, and is flexible, and is particularly limited as long as it has good weather resistance and workability. Not something. For example, at least one selected from a polyvinyl chloride resin, a polyolefin resin, a polyurethane resin, a polyacrylonitrile resin, a fluorine resin, and a silicon resin can be used. Such a thermoplastic resin can be selected and used according to the melting point of the fibers constituting the fiber cloth. Further, in order to improve the performance of the canvas, it is preferable to use a resin composition containing at least one additive selected from a weathering agent, an antibacterial agent, a flame retardant, a filler, a plasticizer, and a pigment. Can be.

The canvas of the present invention can be used as a single layer, but it is also possible to laminate at least two layers of canvas and use each layer with a different function.
In this case, a pattern can be formed with such at least two layers of canvas, and a quaint and fashionable canvas with an aesthetic appearance can be formed.

[0009] Among such thermoplastic resins, a typical polyvinyl chloride resin will be described below as an example. Such polyvinyl chloride resins include a vinyl chloride polymer, a vinyl chloride / vinyl acetate copolymer, a vinyl chloride / acrylic copolymer, and the like, and a vinyl chloride polymer is generally used. Such a vinyl chloride polymer includes, as additives, a plasticizer for imparting flexibility, an antioxidant for preventing light resistance deterioration of the polyvinyl chloride resin, a flame retardant for imparting flameproofing properties, and a fiber. Various additives such as a weathering agent for imparting weather resistance to the fabric, pigments and dyes for coloring, and other stabilizers and fillers may be added.

The canvas referred to in the present invention is one in which at least one surface of a fiber cloth is covered with a thermoplastic resin to such an extent that the texture of the fiber cloth is not impaired, and is preferably JIS L
It is preferable that the flexural resilience measured based on the -1096 6.20.1 A method (Gurley method) be 10,000 mgf or less. Such a canvas can be produced by coating a thermoplastic resin by a coating method, a calendar laminating method, a film laminating method or a melt laminating method.

The rigid material referred to in the present invention is a material having greater bending resilience than the canvas, and is preferably JIS.
L-1096 6.20.1 It is preferable that the flexural resilience measured based on the A method (Gurley method) is 50,000 mgf or more. For example, woods, metals, ceramics, concretes, fiber-reinforced plastics And at least one kind of material selected from synthetic resins and synthetic resins, as long as it has the above-mentioned rigidity. In addition, among the synthetic resins mentioned here, a thermosetting resin is preferably used from the viewpoint of rigidity rather than a thermoplastic resin. As such a thermosetting resin, an unsaturated polyester resin or a melamine resin can be preferably used.

It is preferable to use such a synthetic resin, for example, a thermosetting resin alone or a fiber reinforced plastic reinforced with a fiber such as glass fiber or carbon fiber, because a stronger rigid material can be provided.

[0013] Among such rigid materials, woods, especially molded plates mainly made of veneer or plywood, are preferably used in that they are lightweight, excellent in cost and excellent in workability.

The laminate of the present invention is laminated through an adhesive, laminated by heat fusion, or laminated by a combination thereof. For example, as the adhesive, it is possible to use at least one selected from polyurethane resins, polyacrylonitrile resins, polyvinyl chloride resins, melamine resins, silicone resins, epoxy resins and olefin resins. it can. These adhesive resins may be used singly or as a mixture or copolymer of two or more. A curing agent such as an isocyanate-based resin, a crosslinking agent, and a reaction accelerator can be further added to the adhesive.

The fiber-reinforced laminate of the present invention is preferably subjected to an antifouling treatment with an antifouling agent from the viewpoint of maintaining a durable aesthetic appearance. Further, by providing an antifouling resin film on the surface of the fiber reinforced laminate, a fiber reinforced laminate in which migration of a plasticizer or the like is suppressed can be provided. These treatments and coatings are performed on the other surface that is not the adhesive surface, and are not particularly limited as long as the performance is satisfactory. However, acrylic fluoride, vinylidene fluoride / acrylic copolymer, vinylidene fluoride / Urethane copolymer, fluoro rubber, tetrafluoroethylene /
An antifouling agent having excellent stain resistance, such as a fluorine-based antifouling agent such as ethylene tetrafluoride-6-propylene / vinylidene fluoride copolymer and vinylidene fluoride, and a silicon-based antifouling agent can be used. Also, tetrafluoroethylene, ethylene /
A tetrafluoroethylene copolymer, a tetrafluoroethylene / 4-tetrafluoroethylene-6-propylene / polyvinylidene fluoride copolymer, a perfluoroalkylvinyl ether copolymer, a vinyl fluoride, a vinylidene fluoride, If it is a fluororesin film such as tetrafluoroethylene / tetrafluoroethylene-6-fluoropropylene copolymer and fluororubber, a silicone resin film, or a resin having a high surface hardness, for example, a polyvinyl chloride resin Those having a small amount of the plasticizer have a high surface hardness and can be used for the antifouling resin film. When the type of the plasticizer contained is a phthalate ester type, the addition amount may be 40% or less. Preferably, a polyvinyl chloride resin of 25% or less, more preferably 20% or less for further improving the antifouling property can be used as the antifouling resin film. As a method of coating such a solution such as an antifouling agent, coating such as a reverse roll coater, a forward rotation roll coater, a gravure coater, a kiss roll coater, a cast coater, a curtain coater, a blade coater, a rod coater, a knife coater, a squeeze roll coater, etc. Method or impregnation method can be selected and used according to the resin to be coated. Means for laminating an antifouling resin film with a film include a calendar roll.
Lamination can be performed by heat fusion such as a hot rolling method, a hot press rolling method, a double belt pressing method, a batch pressing method, or a melt laminating method, or via an adhesive. The fiber reinforced laminate of the present invention is extremely useful as a vehicle body material, a civil engineering / building material, or an interior material. For example, the vehicle body mounting material is used to prevent breakage and dirt of luggage on a bed portion of a vehicle such as a truck, and is used to prevent breakage and dirt. There is a shape, and the opening and closing mechanism includes a wing type and a rear opening and closing type, but is not particularly limited to these.

[0016]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, the performance in an Example and a comparative example was measured by the following method.

Bending resilience: JIS L-1096
Measured based on 6.20.1 A method.

Weight: JIS L-1096 6.
Measured according to 4.2.

Adhesive strength: JIS K-6328
The adhesive strength between the sheet and the rigid material was measured according to the peel test of 3.7.

Antifouling property: Based on the outdoor exposure test method for plastic materials described in JIS A-1410, 10
A 0-day exposure test was performed. The evaluation of the antifouling property is as follows.
Samples before and after the contamination test were visually compared and judged.

(Determination method) ◎: No adhesion of dirt substance is observed. ○: Little adhesion of dirt substance. △: Dirt substance is adhering. X: Dirt substance is adhered in large amount. Thickness: Measured based on the thickness of JIS L-1096 6.5.

Fabric 1: A polyester short fiber fabric (manufactured by Toray Industries, Inc., woven structure; plain weave, basis weight: 280 g / m ² , single yarn strength: 5.0 g / d) impregnated with a water repellent using a roll press. Then, after pre-drying at 130 ° C. for 2 minutes, 18
Heat treatment was performed at 0 ° C. for 1 minute.

Resin 1: Polyvinyl chloride resin solution Polyvinyl chloride resin powder: 100 parts (Kanebuchi Chemical Industry Co., Ltd .: Kanevinyl Paste PSM-30) Phthalate ester plasticizer: 50 parts (Shin Nippon Rika ( Stabilizer: 3 parts Blue pigment: 13 parts Weatherproofing agent (CINUVINP manufactured by Ciba Geigy Co., Ltd.): 0.5 parts Resin 2: polyvinyl chloride resin sheet polyvinyl chloride resin powder (Kanebuchi Chemical Co., Ltd.) Industrial Co., Ltd .: 13 parts of blue pigment in Kanevinyl Paste P SM-30)
Weathering agent (Ciba Geigy Corporation CINUVIN P)
Was added using a mixing roll.
The mixture was kneaded at 80 ° C. and formed into a thickness of 0.1 mm at a temperature of 180 ° C. using a batch-type press.

Rigid material 1: Veneer plywood (Lauan material) Thickness: 5 mm Rigid material 2: Aluminum plate Thickness: 8 mm Adhesive 1: Main agent Polyurethane-based adhesive (solid content: 55%) Curing agent Isocyanate-based curing agent Main agent / curing agent = 100/5 parts (parts) Antifouling agent 1: Fluorine antifouling agent Zeffle LC-950 (manufactured by Daikin Industries, Ltd.) Antifouling resin coating 1: Polyvinylidene fluoride film (50 μm thickness) Dirty resin film 2: Polyvinyl chloride resin film (50 μm thickness) Plasticizer: Phthalate ester plasticizer 25 parts Weathering agent: Ciba Geigy Co., Ltd. CINUVIN P 0.5 part Face material: Fine particle titanium oxide 1.0 part Comparative Example 1: Rigid material 1 Comparative example 2: Rigid material 2 Example 1: Resin 1 was applied to woven fabric 1 using a roll press
After lamination on both sides of 00 g / m ² , it was then dried at 160 ° C. for 2 minutes.

Example 2: Antifouling agent 1 was applied to one surface of Example 1 using a knife coater, preliminarily dried at 130 ° C. for 2 minutes, and heat-treated at 180 ° C. for 1 minute. Example 3 An antifouling resin film 1 was heat-pressed on one side of Example 1 at a temperature of 180 ° C. using a batch-type press.

Example 4 An antifouling resin film 2 was heat-pressed on one side of Example 1 at a temperature of 180 ° C. using a batch-type press.

Example 5: The resin 2 was heated and pressed on both surfaces of the fabric 1 at 180 ° C. for 1 minute using a batch-type press.

Embodiment 6: Adhesive 1 is added to rigid material 1 for 150
After applying g / m ² , Example 1 was pressed at room temperature for 3 hours, and the pressure was released to cure at room temperature for 7 days.

Embodiment 7: Adhesive 1 is added to rigid material 1 for 150
After the application of g / m ^2, the non-fouling-treated surface of Example 2 and the rigid material were pressed at room temperature for 3 hours, and the pressure was released to cure for 7 days.

Embodiment 8: The adhesive 1 is added to the rigid material 1 by 150.
After application of g / m ^2, the non-fouling-treated surface of Example 3 and the rigid material were pressed at room temperature for 3 hours, and the pressure was released to cure for 7 days.

Embodiment 9: The adhesive 1 is added to the rigid material 1 by 150.
After applying g / m ^2, the non-fouling-treated surface of Example 4 and the rigid material were pressed at room temperature for 3 hours, and the pressure was released to cure for 7 days.

Embodiment 10: Adhesive 1 is added to rigid material 1 for 15
After applying 0 g / m ² , Example 5 was pressure-bonded at room temperature for 3 hours,
It was released for 7 days.

[0033]

[Table 1] As can be seen from Table 1, it is superior in fashionability, durability, and ease of construction as compared to the aluminum plate alone, and the antifouling treated sample is extremely excellent in antifouling property even after long-term outdoor exposure. It can be seen that it is. In addition, by using a fiber reinforced laminate having low bending resilience, it is possible to provide a material excellent in handleability during processing without impairing the warm texture of the fabric.

[0034]

According to the present invention, it is possible to provide a fiber reinforced laminate which is excellent in fashionability and durability because it is of a panel type and has good workability in mounting and the like.

Claims (18)

[Claims] 1. A fiber-reinforced laminate, which is a laminate of a canvas and a rigid material. 2. The fiber reinforced laminate according to claim 1, wherein the canvas is formed by coating at least one surface of a fiber cloth with a thermoplastic resin composition. 3. The fabric according to JIS L 1096.
The fiber reinforced laminate according to any one of claims 1 to 2, wherein the flexural resilience measured based on the 20.1 A method (Gurley method) is 10,000 mgf or less. 4. The thermoplastic resin constituting the canvas is at least one selected from a polyvinyl chloride resin, a polyolefin resin, a polyacrylic resin, a polyurethane resin, a silicone resin and a fluorine resin. The fiber reinforced laminate according to claim 2. 5. The thermoplastic resin composition according to claim 2, wherein the composition contains at least one additive selected from a weathering agent, an antibacterial agent, a flame retardant, a filler, a plasticizer, and a pigment.
5. The fiber-reinforced laminate according to any one of 4. 6. The fiber reinforced laminate according to claim 2, wherein said fiber cloth is made of synthetic fiber. 7. The fiber reinforced laminate according to claim 6, wherein the synthetic fiber is a polyester fiber. 8. The fiber-reinforced laminate according to claim 6, wherein the synthetic fiber is a high-strength fiber having a single yarn strength of 4.5 g / d or more. 9. The fiber reinforced laminate according to claim 6, wherein said fiber cloth is formed of spun yarn. 10. The fiber reinforced laminate according to claim 1, wherein said canvas is obtained by laminating at least two layers of canvas. 11. The fiber reinforced laminate according to claim 10, wherein said at least two layers of canvas form a pattern. 12. The rigid material according to JIS L 1096.
The fiber reinforced laminate according to claim 1, wherein the fiber reinforced laminate has a flexural resilience measured based on the 6.20.1 A method (Gurley method) of 50,000 mgf or more. 13. The rigid material is made of at least one material selected from woods, metals, ceramics, concrete, fiber reinforced plastics and synthetic resins. The fiber-reinforced laminate according to the above. 14. The fiber-reinforced laminate according to claim 13, wherein said synthetic resin is a thermosetting resin. 15. The laminate according to claim 1, wherein the laminate is laminated via an adhesive, laminated by heat fusion, or laminated by a combination thereof. The fiber-reinforced laminate according to any one of the above. 16. The fiber reinforced laminate according to claim 1, wherein the fiber reinforced laminate has been subjected to a surface treatment with an antifouling agent. 17. The fiber reinforced laminate according to claim 1, wherein the fiber reinforced laminate has an antifouling resin coating. 18. The fiber reinforced laminate according to any one of claims 1 to 17, wherein the fiber reinforced laminate is for vehicle bodywork materials, civil engineering / building materials, or interior materials.