JPH06126908A - Composite material - Google Patents

Abstract

PURPOSE:To achieve both simplification and making a short time of a forming process while interlayer shear and peeling strength are being made strong by a method wherein a three.dimensional knitting fabric wherein a face texture and a lining texture are interconnected with a connecting thread is used as a base fabric, and the base fabric is coated or filled with thermosetting or thermoplastic resin. CONSTITUTION:A combination of a face and a lining textures 1, 2 is as follows; both face and lining textures 1, 2 are mesh like or flat texture; the face texture is of a mesh form and the back texture 2 is a flat texture; an omission part is provided to the face texture 1 and partially in a warp direction of the face and back textures 1, 2 to construct a groove like void. The face lining texture 1, 2 are interconnected with the connecting thread 3, for example, horizontally, in an obliquely crossing manner, and obliquely to construct a three-dimensional knitting. A surface of fiber materials of the three-dimensional knitting thus obtained is coated with a paste, an expanded foam, a liquid material, etc., which have thermosetting or thermoplastic resin 4 as a main component which is filled with blocking or the like, or filled with grains, powdery materials, chipped materials, etc., and treated by drying, vulcanizing, curing, etc.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The composite material of the present invention is robust in interlaminar shear strength and peel strength, excellent in workability, and capable of imparting designability and texture change. It is used in a wide variety of fields, and is approved for a wide range of applications such as lightweight boards, decorative boards for building materials, interior materials, floor materials, interior and exterior materials for vehicles, waterproofing materials, impact protection materials, and bag materials such as attache cases. To be

[0002]

2. Description of the Related Art Conventionally, as the above-mentioned materials, an organic material such as polyester resin, melamine resin, epoxy resin, polyolefin resin, asbestos or a metal material, or an inorganic material such as concrete is used alone or by mixing them. Was there.

However, in these cases, because of the isotropic material,
Since it is designed according to the direction in which the maximum strength is required, an extra thickness is left in the part where strength is not required. In order to solve such a defect, a laminated composite material has been used in which lamina in which fibers are one-dimensionally or two-dimensionally arranged is laminated in multiple layers.

In the laminated composite material as described above, the strength is excellent in the fiber orientation direction, but in the penetration layer direction, the nature of the interface between the fiber and the resin governs,
Generally low. In addition, there is a problem in that it takes a long time to compose a thick material or a deformed material because the process is complicated.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, is robust against interlaminar shearing and peeling, and has improved workability, texture change, designability, etc. The purpose is to provide the material.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and have reached the following inventions. The present invention is based on a three-dimensional knitted woven fabric in which a surface fabric and a lining fabric are connected by connecting yarns, and the base fabric is covered or filled with a thermosetting or thermoplastic resin. The main point is the material.

The present invention will be described in detail below with reference to the drawings. FIG. 1 shows a three-dimensional knitted fabric in which a surface fabric 1 and a lining fabric 2 are connected by connecting yarns 3 by thermosetting or thermoplastic resin 4
It is an example of a schematic cross-sectional view of a composite material coated with. Figure 2
Is an example of a composite material having a structure in which resin sheets or resin plates 5 and 6 are further adhered on both front and back surfaces for reinforcement of the composite material of FIG. 1, and FIG. 3 is a surface of the composite material of FIG. In this example, a resin plate 8 in which the woven fabric 7 is enclosed on the front side is used as the resin plate to be adhered to. In this case, knitted fabric, non-woven fabric, paper or the like can be used instead of the woven fabric, and the structure can be made in consideration of the design effect such as the color pattern effect. FIG. 4 is an example of a schematic cross-sectional view of a composite material in which voids of a three-dimensional knitted fabric in which a surface fabric 1 and a lining fabric 2 are connected by connecting yarns 3 are filled with a thermosetting or thermoplastic resin 4. FIG. 5 shows an example in which one side of the three-dimensional knitted fabric is covered with a thermosetting or thermoplastic resin 4, and a structure in which a resin sheet or a resin plate is adhered may be used. FIG. 6 is an example in which synthetic leather 9 is adhered to the surface of the resin 4 of the composite material of FIG. 5, and paper, woven fabric, knitted fabric, etc. can be used instead of synthetic leather, and design, texture changes, etc. are taken into consideration. It becomes a composite material that can be. FIG. 7 is an example of a perspective schematic view of a composite material obtained by filling a three-dimensional knit fabric with a thermosetting or thermoplastic resin 4 on a curved surface.

The three-dimensional knitted fabric used as the base fabric of the composite material of the present invention can be obtained by weaving and knitting with a double Russell knitting machine or a moquette loom. FIG. 8 shows a surface material structure 1.
FIG. 9 is an example of a perspective schematic view of a honeycomb-type three-dimensional knitted fabric in which the lining fabric 2 and the lining fabric 2 are formed in a mesh shape, and FIG. 9 is a double-face type three-dimensional structure in which the surface fabric 1 and the lining fabric 2 are flat It is an example of a perspective schematic view of a knitted fabric.

The fibers used for the front and back ground structures are synthetic fibers,
Regenerated fiber, natural fiber, inorganic fiber, etc. may be used, and may be a single or mixed yarn. Furthermore, there is no restriction on using these yarns in the same kind or different kinds on the front and back, or knitting or knitting.

Any structure can be adopted for the front and back ground structures, but as a characteristic combination of structures, both the front and back ground structures are mesh-like structures, and both the front and back ground structures are flat structures. , The front side ground structure is a mesh structure and the back side ground structure is a flat structure, and a groove-like void is formed by partially providing a missing portion in the longitudinal direction of the front side ground structure,
There is a method of forming a groove-like void by partially providing a missing portion in both the front and back ground structures in the longitudinal direction.

The above-mentioned ground texture may be mesh or flat on the front and back sides, or any one of them may be different. Of course, there is no limitation when the mesh-like and flat ground structures are mixed on one side or both sides. Materials used for connecting yarns that three-dimensionally connect the front side fabric and the back side fabric are not limited to synthetic fibers such as nylon 6, nylon 66, nylon 46, polyester, polyethylene, polypropylene and inorganic fibers. Absent. In addition, since it requires three-dimensional shape retention, an appropriate amount of voids, and compression elasticity, it has a diameter of 0.025-
A yarn having an appropriate rigidity such as 0.4 mm mono-multi or mono-filament is preferable.

The distance between the connecting yarns, the arrangement position, the arrangement direction, and the like are matters that can be arbitrarily determined in consideration of the front and back ground structures. For example, the ground textures on the front and back sides may be connected in the vertical direction, or any two of the side-by-side and diagonal directions, or even three may be combined and connected. Further, the connecting threads may be arranged in a partially missing (toothless) shape.

In order to maintain the three-dimensional shape of the woven and knitted three-dimensional knitted fabric stably and to easily and uniformly apply the resin or fill the resin, heat setting is performed by a tenter. preferable. Furthermore, there is a case in which an appropriate amount of a cured resin is impregnated and cured to further maintain the three-dimensional shape.

The surface of the fibrous material of the three-dimensional knitted fabric thus obtained is impregnated, coated, topped or sprayed with a paste, foamed foam, or liquid material containing a thermosetting resin or a thermoplastic resin as a main component. The composite material as shown in FIG. 1 can be obtained by coating with a method such as up and performing treatments such as drying, vulcanization and curing.

Further, a resin sheet or a resin plate prepared in advance may be bonded to both sides of the composite material as shown in FIG. 1 to obtain a composite material having a sandwich structure as shown in FIG. In this case, if it is desired to add design, at least one side of the three-dimensional knitted fabric is preliminarily printed, or a paper on which colors and patterns are expressed,
The method of adhering cloth etc. should just be given. If we talk about resin sheets and resin plates,
Colors and materials can be freely selected and may be selected according to the application.

Further, the voids formed in the three-dimensional knitted fabric obtained as described above are coated with a paste containing a thermosetting resin or a thermoplastic resin as a main component, a foamed foam, or a liquid material, and put in a mold. Alternatively, the composite material as shown in FIG. 4 can be obtained by filling or filling with granules, powder, chips or the like, and then performing treatments such as drying, vulcanization and curing.

Furthermore, a thermosetting resin or a thermoplastic resin is coated on a flat design side of a three-dimensional knitted fabric having a flat design on at least one side, or a resin sheet or a resin plate prepared in advance is bonded. The composite material shown in FIG. 5 can also be used. In this case, when the resin sheet or the resin plate is adhered to the side of the mesh-like structure or the structure having the missing portion, the adhesion area is smaller than that of the flat structure, so that the resin sheet or the resin plate may be peeled off. Therefore, it is preferable to determine that a flat structure is preferable. If the resin sheet and the resin plate are mentioned here, the thickness, color and material can be freely selected, and may be selected according to the application.

In addition, the composite material shown in FIG. 5 can be produced by a method of adhering paper, cloth, leather, etc. according to the purpose.
It is also possible to use a composite material that can take into account the design, texture changes, etc. as shown in.

Further, by taking advantage of the elasticity of the three-dimensional knitted fabric, thermosetting resin can be applied to the voids formed in the three-dimensional knitted fabric by the normal pressure method, spray-up method, injection molding method, compression molding method, etc. A hollow columnar composite material shown in FIG. 7 may be obtained by subjecting a paste containing a thermoplastic resin as a main component, a foam, a liquid material, granules, powder, a chip-shaped material, etc. to a curved surface filling process.

Next, referring to the resin composite form of the base material of the composite material of the present invention, the composite by impregnation and coating,
The basic composite forms are composite by filling, composite by adhesion of plates and films, and composite by placing a base cloth on the resin layer before curing. Of course, these composite forms may be arbitrarily selected, such as forming the composite form by a single method or a combination thereof. Further, there is no particular restriction on the resin arrangement of the composite form, and the arrangement is uniform or nearly uniform on the whole surface, geometrical patterns such as islands, straight lines, curves, and lattices, arranged in other patterns, and partially. The basic pattern is an arrangement with a missing part (non-composite part). Any of these arrangements may be selected alone or in combination.

The resin used for the composite material of the present invention is not particularly limited, and either a thermosetting resin or a thermoplastic resin can be used. Examples of the thermosetting resin include polyester resin, vinyl ester resin, epoxy resin, melamine resin, hard polyurethane resin, phenol resin, urea resin, vulcanized rubber (ebonite), etc., alone, mixed or modified. Used as a resin. Examples of the thermoplastic resin include, for example, polyolefin resin, polystyrene resin, polyimide resin, polyarylate resin, vinyl resin, acrylic resin, polyamide resin, polycarbonate resin, cellulose resin, etc., which may be used alone or as a mixture or as a mixture. Polymerize and use. In either case, a thermosetting resin or a thermoplastic resin may contain modifiers such as pigments, fillers, flexible agents, diluents, plasticizers, heat stabilizers, and additives.

[0022]

[Operation] As described above, the present invention is based on a three-dimensional knitted fabric in which the surface design and the lining design are connected by connecting yarns. Inter-layer shearing and peeling strength and robust. In addition, since it has an appropriate gap from the beginning, it is suitable for weight reduction. Further, it is not necessary to laminate any number of layers unlike the laminated composite material. Furthermore, since it has a suitable void, it is easy to fill the resin. In addition, the three-dimensional knitted fabric is highly stretchable and can follow curved surfaces, has excellent formability, good appearance, etc., and can reach areas that were difficult at the conventional level.

[0023]

EXAMPLES Examples of the present invention will be described below.

Example 1 First, the three-dimensional knitted fabric shown in FIG. 8 was produced by the following means. The front and back ground textures 1 and 2 are polyester 250d / 4
With 8f multifilament, each side has two reeds to form a mesh-like structure, and the connecting thread 3 is nylon 220d
/ 1f monofilament, made by KARL MAYER 14
G-double ratcell machine is used for knitting, and in order to provide three-dimensional shape retention and execution stability during composite material production, heat setting is performed at 150 ° C for 2 minutes with a pin tenter made by Ichikin Co., Ltd. To obtain a honeycomb-shaped three-dimensional knitted fabric. The thickness of this three-dimensional knit was 6.3 mm.

Next, the obtained honeycomb-type three-dimensional knitted fabric having a mesh-like ground structure on the front and back sides is blended at a ratio shown in the following prescription 1 using a resin processing machine having a dipping device provided with a drawing roll. Immerse in the compounded resin and squeeze, and heat treatment zone of 20m
The composite material having the same structure as that of FIG. 1 in which the three-dimensional knitted fabric was coated with 108 g / m ² of resin was obtained by passing the mixture through 0 ° C., 160 ° C. in the third to fifth chambers) at a speed of 4 m / min. The obtained composite material was optimal as a material for reducing the weight of building structural materials, structural materials for vehicles, and the like.

(Formulation 1) Aqueous polyurethane resin HW350 100 parts (Dainippon Ink and Chemicals, Inc., solid content 30%) Epoxy crosslinking agent CR-5L 3 parts (Dainippon Ink and Chemicals, Inc., 100% viscous) Liquid) Crosslinking accelerator PA-20 1.5 parts (manufactured by Dainippon Ink and Chemicals, Inc.) Water 100 parts

Example 2 First, the three-dimensional knitted fabric shown in FIG. 9 was produced by the following means.
Ground textures 1 and 9 are polyester 250d / 48f
With the multifilament, two reeds on each side were made into a flat ground structure with dimensional stability and moderate elasticity due to the chain structure and insertion structure. As the connecting thread 3, nylon 220 is used.
Using d / 1f monofilament, made by KARL MAYER 1
Knitting was carried out using a 4G double Russell machine, and heat setting was carried out under the same conditions as in Example 1 to obtain a double-face type three-dimensional knitted fabric having a flat texture on the front and back sides. The thickness of this three-dimensional knit was 6.8 mm.

Next, one side of the obtained three-dimensional knitted fabric was printed, dipped in the compounded resin shown in Formulation 2 under the same conditions as in Example 1, squeezed, heat-treated and coated with 144 g / m ² of resin. A composite material having a structure similar to that of FIG. 1 was obtained.

(Formulation 2) Aqueous polyurethane resin HW350 100 parts (Dainippon Ink and Chemicals, Inc., solid content 30%) Epoxy crosslinking agent CR-5L 3 parts (Dainippon Ink and Chemicals, Inc., 100% viscous) Liquid) Crosslinking accelerator PA-20 1.5 parts (manufactured by Dainippon Ink and Chemicals, Inc.)

The obtained composite material is excellent in light weight, heat resistance, chemical resistance, compression resistance and impact resistance, and when it is put to practical use as a furniture material, a wall material and an interior material for a kitchen, it has sufficient strength. Yes, it was comparable to a lightweight board material.

Example 3 A composite material having a sandwich structure shown in FIG. 3 in which the composite material obtained in Example 1 was used as a core material and resin layers were placed on the front and back surfaces thereof was produced by the following method. First, a method of manufacturing resin layers to be placed on the front and back of the composite material that is the core material will be described.

A pattern-printed polyester 100d / 48f plain weave woven fabric 7 is placed in a mold having a depth of 1 mm, the compounded resin shown in Formula 3 is poured into the mold, and the mixture is cured at room temperature for 24 hours, and the front side The resin plate 8 to be mounted on the back side was obtained, and the resin plate 6 to be mounted on the back side was obtained using only the above-mentioned compounded resin by using the mold.

(Formulation 3) Epoxy resin SA5770A 100 parts (manufactured by Sanyu Resin Co., Ltd.) Polyamine curing agent SA5768B 25 parts (manufactured by Sanyu Resin Co., Ltd.)

Next, the resin mixture shown in Formulation 4 was applied as an adhesive to the resin plates 8 and 6, placed on the front and back of the composite material obtained in Example 1, and subjected to a pressure of 10 kgf / m ² for 24 hours. Bonding was carried out at room temperature to obtain a composite material having a sandwich structure similar to that shown in FIG.

(Formulation 4) Epoxy resin A-542A 100 parts (manufactured by Sanyu Resin Co., Ltd.) Polyamine curing agent H-5781 18 parts (manufactured by Sanyu Resin Co., Ltd.)

The obtained composite material was excellent in light weight, heat resistance, chemical resistance, compression resistance, impact resistance and the like, and when used in the same applications as in Example 2, it was a board material excellent in designability. It was not there.

Example 4 The composite material of the sandwich structure obtained in Example 3 was put to practical use as a body of a canoe and a board for windsurfing, and it was lightweight and easy to carry, and shock resistance,
It was a board with excellent water resistance.

Example 5 A honeycomb-type three-dimensional knitted fabric having a mesh-like ground structure on the front and back shown in FIG. 8 prepared in Example 1 was placed in a mold, and the voids of the fabric were treated with a formulation 5 containing a white pigment. Chemical resistance, water resistance,
12% under pressure of 0.1 kgf / cm ² in order to inject the compound resin with excellent flexibility and mirror-form the surface of the composite material.
Thermosetting was performed at 0 ° C. for 6 minutes to obtain a composite material in which the voids of the three-dimensional knitted fabric having the same structure as in FIG. 4 were filled with the thermosetting resin or the thermoplastic resin 4.

(Formulation 5) Epoxy resin Epicron EA850 80 parts (manufactured by Dainippon Ink and Chemicals, Inc.) Curing agent Raccamide EA330 60 parts (manufactured by Dainippon Ink and Chemicals, Inc.) Flexibility imparting agent Epicron TSR930 20 parts (large) Made by Nippon Ink Chemical Co., Ltd.)

The obtained composite material has excellent interlaminar shear strength,
When it was put into practical use as a floorboard tile, it did not get dented or scratched even if a heavy leg such as a chair, table, or piano got on it, and when these were scratched, the tile deformed and cracked. No delamination of the tile itself occurred. In addition, it has good wear resistance and does not require oil wiping because it has an appropriate gloss.

Example 6 Using the double-face type three-dimensional knitted fabric shown in FIG. 9 produced in Example 2, one side of the three-dimensional knitted fabric was coated with the compounded resin shown in Formulation 6 in a thickness of 3 mm, and the temperature was kept at room temperature for 24 hours. The resin layer 4 is cured and placed on one side of the three-dimensional knitted fabric.
A composite material having the same structure as was obtained.

(Formulation 6) Epoxy resin A-542A 100 parts (manufactured by Sanyu Resin Co., Ltd.) Polyamine curing agent A-542B 50 parts (manufactured by Sanyu Resin Co., Ltd.)

An attache case was made with the three-dimensional knitted fabric of the obtained composite material inside. Due to the excellent cushioning properties of the three-dimensional knit, the inside was a good fit for the stored items, no impact noise was generated when the contents hit, and it was a lightweight and sound-absorbing attache case.

Example 7 To the composite material obtained in Example 6, synthetic resin 9 provided with an embossed pattern made of polyurethane was bonded to the resin layer 4 side of the composite material in order to further improve the design, and the composite material shown in FIG.
A composite material having the same structure as was obtained.

A suitcase was produced with the three-dimensional knitted fabric of the obtained composite material inside. The suitcase had the same excellent performance as the attache case according to Example 6 and excellent design.

Example 8 The composite material obtained in Example 6 was put to practical use as a floor and wall material for nursery schools, kindergartens, nursing homes, rehabilitation rooms, etc. with the three-dimensional knit side facing up. Due to the excellent cushioning properties of the base cloth, it was possible to reduce the injuries when the floor or wall is collided due to a fall or the like, and it was confirmed that the safety was improved.

Example 9 The honeycomb type three-dimensional knitted fabric shown in FIG. 8 produced in Example 1 was fixed to a cylindrical mold, but fixed so that the base fabrics were overlapped at the joint, and the compounded resin shown in Formula 4 was used as a tertiary The voids of the original knit were filled with a hand roll to produce an exhaust duct having the structure shown in FIG. It was confirmed that the effect of simplifying the process and shortening the time is sufficient as compared with the conventional laminated composite material by the in-situ normal pressure method.

[0048]

The composite material of the present invention uses a three-dimensional knitted fabric made of a fiber material as a base fabric, and the fiber material of this fabric is
By coating or filling a thermosetting resin or a thermoplastic resin, it is robust against interlayer shearing and peeling, which are lacking in conventional laminated composite materials, and can simplify the molding process and shorten the molding process. . It is possible to add weight reduction, designability, and texture change, and also to add various performances by selecting resin material. Therefore,
INDUSTRIAL APPLICABILITY The composite material according to the present invention is excellent in that it can be used in a wide range of fields from daily life to industrial materials and has an extremely large economic effect.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a composite material according to the present invention, in which a three-dimensional knitted fabric is coated with a thermosetting or thermoplastic resin.

FIG. 2 is a schematic cross-sectional view of a composite material having a sandwich structure in which resin sheets or resin plates are bonded to both surfaces of the composite material of FIG.

FIG. 3 is a schematic cross-sectional view of a composite material using a resin plate in which a woven fabric is enclosed on one surface of the composite material of FIG.

FIG. 4 is a schematic cross-sectional view of a composite material according to the present invention, in which voids of a three-dimensional knitted fabric are filled with a thermosetting or thermoplastic resin.

FIG. 5 is a schematic cross-sectional view of a composite material of the present invention, in which at least one side of a three-dimensional knitted fabric is coated with a thermosetting or thermoplastic resin, or a resin sheet or a resin plate is adhered.

6 is a schematic cross-sectional view of a composite material obtained by adhering paper, cloth, leather or the like to one side of the composite material of FIG.

FIG. 7 is a schematic perspective view of a composite material obtained by subjecting a thermosetting or thermoplastic resin to a curved surface filling process in the composite material according to the present invention.

FIG. 8 is a schematic perspective view of a honeycomb-type three-dimensional knitted fabric used in the composite material of the present invention.

FIG. 9 is a schematic perspective view of a double-face type three-dimensional knitted fabric used for the composite material of the present invention.

[Explanation of symbols]

 1 Front side ground structure 2 Back side ground structure 3 Connecting yarn 4 Coated resin 5 Resin layer 6 Resin layer 7 Woven fabric 8 Resin plate 9 Synthetic leather

Claims (1)

[Claims] 1. A three-dimensional knitted woven fabric in which a surface fabric and a lining fabric are connected by connecting yarns is used as a base fabric, and the base fabric is covered or filled with a thermosetting or thermoplastic resin. Composite material.