JPS6045632A - Composite fiber structure for thermal molding - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel composite fiber structure for thermoforming. More specifically, we will discuss how to combine thermoplastic wheels into thermoforming.
The present invention relates to a novel composite fiber structure for thermoforming, which can be made into a composite body using high-strength, high-modulus filaments as reinforcement materials.

Conventional technology For example, carbon fibers, poly(paraphenylene terephthalamide) fibers, or para-oriented fully aromatic polyamide fibers such as poly(paraphenylene terephthalamide) fibers are used as reinforcing materials with high strength and high modulus fibers that improve heat resistance, and epoxy resin is used as a reinforcing material. Composite materials having a matrix of thermosetting resins such as unsaturated polyester resins have been widely used.

Prepreg is used as an intermediate product for such composite materials, but conventional prepreg requires (1) storage and transportation of the prepreg at a low temperature of about -20°C.

(2) Since the prepreg changes over time, its storage period is at most 3 to 5 months, and it cannot withstand long-term storage.

(3) The time required for molding is long.

(/I) Prepreg is fragile and requires special care when handling.

There is a problem.

Purpose of the Invention As a result of research to solve the problems of conventional prepregs as described above, the present inventors have developed composite materials (composites 1 to 1) in which thermoplastic polymers have a
) was found to be useful. The present invention is based on this knowledge, and its main purpose is to provide a fiber structure that can be easily formed into a good composite material by thermoforming.

Structure of the Invention The fiber structure of the present invention, which achieves and fulfills the above-mentioned objects, is a high-strength, high-modulus filament (A>
The thermoplastic outer car combined filament 1-(B) with a low melting point that melts at the molding temperature was used as the warp yarn, and the weft yarns made of the thermoplastic filament (B) with a low melting point were inserted at coarse intervals to form a woven fabric. A composite fiber for thermoforming, which can be made into a composite material in which the reinforcements I of the high-strength, high-modulus filaments (A) are arranged in a matrix of thermoplastic polymer C by thermoforming. It is an H structure.

The invention w:! The "high-strength, high-modulus filament (A) made of heat-resistant material" that makes up the assembled structure is 250
It refers to a filament made of an inorganic material or a heat-resistant synthetic polymer that is stable even at temperatures of 0.degree. C., and has a strength of 20 g/de or more and an initial modulus of 300 g/de or more.

Examples of such filaments include (1) high-performance carbon fibers made from polyacrylonyl fibers or bidi fibers, (2) ceramic fibers such as alumina fibers and silicon carbide fibers, and (3) glass fibers.

(4) Boria relay 1 to fiber 2, e.g. poly(chloro-1
, 4-phenyleneethyldioxy-4,4'-dibenzony-1-/terephthalate) and polyarylates from bisphenol 8 and prephthalic acid and isophthalic acid.
li navy blue, (5) aramid fiber 1 e.g. poly(balaf J-
Aramid fibers made of dephthalamide of nylenterephthalamide) lit, 2,7-di)'minof], nanthridone, and 2-7-diamitfur A-renone are used.

On the other hand, the low melting point thermoplastic polymer filaments 1 to (B) may be any filament as long as it can be completely melted at the thermoforming temperature, but according to the research of the present inventors, nylon 6 is the main component. Undrawn yarn or partially oriented yarn (POY) of aliphatic polyamide and polybutylene terephthalate or poly(ethylene terephthalate/isophthalate 1~)
Undrawn yarn or partially oriented yarn (POY) of poly 1 stellate such as
However, it is preferable because the meltability and fluidity of the molten polymer in the ripening mold are good.

The above-mentioned filaments 1 to (A) and filament (B) may each be used one type at a time, but two or more types (Jl
may be used.

In the structure of the present invention, the filament (A
) and filaments 1 to (B) (for JI use), only the filaments 1 to (B) were used as wefts, and the wefts were inserted at coarse intervals to form a starry weave. be.

In the warp yarns, it is preferable to alternately arrange filaments (A) and filaments (B) so that the filaments (Δ) do not come into close contact with each other.

In particular, the filament (Δ) and the filament l-([3) are aligned, and the filament (13) is placed around this aligned thread.
I rolled it! 'C Provides convergence as red thread,
It is suitable for R that the filaments 1 to (A) are in close contact with each other and are 4f long.

Figure 1 shows the composite wire of the present invention woven in this way @t4
? This is an example of a 4-structured structure, and 1 in the figure is a high-strength, high-modulus filament made of heat-resistant moons! The yarns 2a, 2b and 2c made of (A) are each made of a low melting point thermoplastic polymer filament 1-(B). In the structure shown in the figure, there are J'3, and the warp threads are the filaments 1 to 1.
The yarn 1 made of (A>) and the yarn 2a made of the filament (B) are aligned, and the yarn 2b made of the filament (B) is wound in a helical shape. is composed of yarn 2C made of the filament 1-(B).

In the present invention, the filament 1 in the composite fiber structure
The interweaving ratio of ~(A> and filament (B) should be selected appropriately depending on the use of the composite material after molding, but in general, the weight ratio of filament hA/'B is 20/8.
A range of 0 to 80/20 is preferable. Generally 60/40~3
0/70 is preferred, especially 50/50 to 40/60
is optimal. Although the mesh size of the fabric also varies depending on the use of the composite material after molding, it is usually appropriate to range from 100 to 1009/min.

In addition, the preferred thickness and number of single yarns in the filament 1 to (△) vary depending on the material, but carbon fiber navy blue, carbon fiber navy blue,
1.In the case of lamic fiber, glass fiber, etc., the single yarn diameter is 5~
The yarn composition is preferably about 12μ and the number of yarns is preferably 1,000 to 10,000, and in the case of Aramid lIi navy blue and Aryle 1' fibers, the single yarn denier is 1 to 5 dc/fit and the yarn (total) annealing is 100 (preferably 1 to 5,000 dc).

On the other hand, considering the meltability of the filament (B) during aging, the smaller the yarn denier, the better.
It is preferable that it is about fil. In the case of Fig. 1, the number of filaments is 100 to 1000 for thread 2a, and 20 for thread 2b.
It is preferable that the number is 10 to 100.

In the example shown in Fig. 1, filaments (A
) and one yarn 2a consisting of filament 1-(B) are used. For example, two or three yarns 1 and one yarn 2a are used. It is also good to align the two pieces.

In addition, the filament h(B) may contain pigments,
111 fuel, filler, etc. may also be included.

Effects and Effects of the Invention The composite m-fiber structure of the present invention as described above is produced by hot press molding the filament 1-(B) in the structure at a temperature higher than the melting point of the filament 1-(B). is completely melted, and a composite material is formed in which filaments (A) serving as a reinforcing material are arranged in one direction in the thermoplastic polymer 71~lix. Therefore, when a plurality of composite fiber structures of the present invention are laminated one after another so that the warp directions are perpendicular to each other and hot press-molded, a strong reinforcing material (composite) in which reinforcing filaments are arranged in both the vertical and horizontal directions can be obtained.
It can be done.

The composite fiber structure of the present invention does not have the problems of conventional prepregs using thermosetting resins, and is extremely easy to mold. Therefore, it can be used as an intermediate product for Il fiber reinforced composite H in various ways. Can be used for a wide variety of purposes.

Example Next, the present invention will be explained in more detail with reference to examples.

Example 1 Multifilament yarn [■] made of commercially available carbon fiber made from polyacryloni 1-lyl (strength 199
/de, modulus 1400g/de, yarn fineness 1
800de/3000f i l) and undrawn polybutylene terephthalate 1 to 8#A spun by melting polybutylene terephthalate at a spinning take-off speed of 2500 m/min.
Mardifilamen 1~Yarn [■] (Yarn vA degree 300
The composite Ili dark blue structure of the present invention was manufactured using DSCT-i11 (de/60fil, melting point 225°C).

First, multifilament yarn [
112 yarns and two yarns [1['] made by twisting and twisting five multifilamen l-type yarns [11], and one helix of multifilamen 1-type yarns [II] around them. A composite yarn with bundled properties was formed by winding the yarn into a shape.

Next, this is used as a warp, and a multifilament yarn [II
] as weft threads at coarse intervals (20 threads/inch),
A mixed fiber of 1,500 g/rd was obtained.The weight ratio of multifilament yarn [I] to multifilament 1-line yarn [nl] in this mixed fiber was [I]/[
I ] -40760.

When four composite fiber structures of the present invention made of this mixed fiber were stacked in a direction perpendicular to each other and heated and pressurized with a heating press at 250°C, multificimen 1 to yarn Lit.
The polybutylene terephthalate completely melts and fills the gaps in the multifilament yarn [I], forming a -C plate shape, and the carbon M fibers are interlaced in the 71-ricks of polybutylene terephthalate -1. A composite plate (=J-posit l~) was obtained which was arranged perpendicularly to the difference.

This composite plate had extremely good tensile strength, l11g strength, and lli4 flexibility.

[Brief explanation of drawings]

FIG. 1 is a plan view showing an example of the composite fiber structure for thermoforming of the present invention. 1 in the figure is a yarn consisting of high-strength, high-modulus filaments 1 to (Δ) made of a heat-resistant material;
2a, 2b, and 2C each do not show a thread consisting of a thermoplastic polymer filament (B) that melts at the molding temperature. Figure 1? a Procedural Amendment (Import) August 78, 1981 1. Director General of the Agency 1. Indication of Case Patent Application No. 5'F3150344 No. 2, Title of Invention Composite Fiber Structure for Aging Type 3. Relationship with the case of the person making the amendment Patent applicant 1-11 Minamihonmachi, Higashi-ku, Osaka-shi, Osaka Prefecture (300>Representative of Teijin Ltd.: Sa Okamoto, Department 4, Agent: Chiyo-l, Tokyo) 2-1, Uchisaiwai-cho, Higashi-ku, Osaka Prefecture Number 1
No. (Iino Building) Teijin Limited Internal Statement 1, Name of Invention Composite Fiber Structure for Thermoforming 2, Claims (1) High strength, high modulus filament L (△ ) and low melting point thermoplastic synthetic polymer filaments M (B) that melt at the molding temperature are used as the warp yarns, and weft yarns made of the low melting point thermoplastic polymer filaments L (B) are inserted at coarse intervals and sagged with lυ. A composite fiber structure for thermoforming characterized by its woven structure. (2) The high-strength, high-modulus filament L (A) made of a heat-resistant material is carbon fiber or ceramic fiber. The composite fiber structure for thermoforming according to claim 1, which is a filament of at least 1 PJ selected from the group consisting of glass SiH, polyarylate m M , and aramid fiber. (3) The low melting point thermoplastic polymer filament 1j (B) is an undrawn filament yarn or partially oriented filament yarn of polyester or polyamide with a melting temperature of 270°C or less.
A composite fiber structure for aging type according to claim (1). (4) The warp threads align the high-strength, high-modulus filament 1 to yarn (A> made of a heat-resistant material) and the low-melting-point thermoplastic polymer filament L (B), and the Thermoplastic polymer filament L (B) of melting point is 1
A composite for aging molds according to claim (1), which is a spun composite yarn! lFL construct. (5) The proportion of high-strength, high-modulus fibers made of heat-resistant materials in the composite fiber structure is 20 to 80% by weight.
A composite fiber structure for thermoforming according to claim (1). 3. Detailed Description of the Invention Field of Industrial Application The present invention relates to a novel composite fiber structure for thermoforming. More specifically, the present invention relates to a novel composite fiber structure for maturing molds that can be thermoformed into a composite comprising a thermoplastic polymer as a matrix and a high-strength, high-modulus filament yarn covered with a reinforcing material. Prior art For example, carbon fiber, polyarylate fiber or poly(
High strength, high modulus fibers with heat resistance such as para-oriented fully aromatic polyamide fibers such as paraphenylene terephthalamide) fibers are used as reinforcement materials, and thermosetting resins such as earth poxy resins and unsaturated poly XL sprue resins are used as reinforcement materials. Composite materials containing a matrix (composites 1 to 1) have been widely used in the past. Prepreg is used as an intermediate product for such composite materials, but conventional prepreg requires (1) storage and transportation of the prepreg at a low temperature of about -20°C. (2) Since the prepreg changes over time, its storage period is at most 3 to 5 months, and it cannot withstand long-term storage. (3) The time required for molding is long. (4) Because prepreg is fragile, special care is required when handling it. There is a problem. Purpose of the Invention The present inventors have conducted research to solve the problems of conventional prepregs as described above, and have found that composite materials with a thermoplastic polymer as a matrix are sufficiently useful in certain fields. I found out that. The present invention is based on this knowledge, and its main purpose is to provide a fiber structure that can be easily made into a good composite material by thermoforming. Structure of the Invention The fiber structure of the present invention that can achieve the above-mentioned object is a high-strength, high-modulus filament yarn (Δ) made of a heat-resistant material.
A thermoplastic polymer filament yarn (B) with a low melting point that melts at the molding temperature was used as the warp, and weft yarns made of the thermoplastic filament yarn (B) with a low melting point were inserted at coarse intervals to form a woven fabric. A composite II fiber structure for aging molds, which can be made into a composite material in which the reinforcing material of the high-strength, high-modulus filament yarn (A) is arranged in a matrix of a thermoplastic polymer by thermoforming. There is a thing C. The "high-strength, high-modulus filament yarn (A) made of a heat-resistant material" that constitutes and covers the m-fiber structure of the present invention is heated to a temperature of 250°C.
Made of inorganic material or heat-resistant synthetic polymer that is stable even at temperatures of 20 g/de or more, initial modulus 3
00g/de or more multifilament yarn. Examples of such filament yarns include (1) high-performance carbon fibers made from polyacrylonitrile fibers or pitch fibers, (2) ceramic fibers such as alumina fibers and silicon carbide fibers, and (3) glass fibers. (4) Polyarylate fiber 9 such as poly(chloro-1,
(4-phenylene ethyl dioxy-4,41-dibenzoate/prephthalate) or bisphenol A and terephthalic acid and isophthalic acid, polyaryl 1 to fibers, (5) aramid fibers 2 such as poly(paraphenylene terephthalamide) Fiber, 2,7-Diamitsuphenanthridone, 2-7-Diamitsufluorenone of aramid consisting of terephthalamide! A filament yarn consisting of 1 tilt or the like is used. On the other hand, the thermoplastic polymer filament (B) with a low melting point may be any multifilament yarn that can be completely melted at the thermoforming temperature, but according to research by the present inventors, the melting point is 270°C. Hereinafter, undrawn yarn or partially oriented yarn (POY) of aliphatic polyamide mainly composed of nylon 6, preferably at a temperature of 250° C. or less, and polybutylene ethylene terephthalate.
Undrawn yarns or partially oriented yarns (POY
) is preferable because it has good meltability and fluidity of the polymer during thermoforming. The above filament yarn (A) and filament yarn (B)
Each of these may be used singly, or two or more may be used in combination. The structure of the present invention uses the filament yarn (
Both A) and filament yarn (B) are used in combination, and only the filament yarn (B) is used as the weft, and the weft is inserted at coarse intervals to form a sagging fiber. In the warp yarns, it is best to alternately arrange ficimen 1 to yarn (A) and filament yarns (B) so that ficimen 1 to yarn (A) do not come in close contact with each other as much as possible. > and the filament thread (B), and around this aligned thread, the filament thread (B)
It is optimal to wind the filament yarns (A) to provide convergence as warp yarns and to prevent the filament yarns (A) from coming into close contact with each other. FIG. 1 shows an example of the composite fiber structure of the present invention woven in this way, in which 1 is a yarn consisting of a high-strength, high-modulus filament yarn (△) made of a heat-resistant material;
2a, 2b and 2G are yarns each made of a low melting point thermoplastic polymer filament yarn (B). In the illustrated structure, the warp is formed by aligning the filament 1 with the thread 1 made of the thread (△) and the thread 2a made of the filament 1 to thread (B). It is composed of a composite yarn in which the yarn 21) is wound in a spiral shape, and the weft is constituted by the yarn 2C made of the filament yarn (B). In the present invention, the interweaving ratio of the filament yarn (A>) and the filament yarn (B) in the composite fiber structure should be selected as appropriate depending on the use of the composite material after molding.
Generally, the weight ratio of filaments A/B is 20/
A range of 80 to 80/20 is preferable. Generally 60/40 to 30/70 is preferred, especially 5
0150 to 40/60 is optimal. The texture of the fabric also varies depending on the use of the composite material after molding, but it is usually 100%.
~1000 (j/end is appropriate.Also, the preferred thickness of the filament yarn (A) and the number of constituent single fibers vary depending on the material, but carbon fiber,
In the case of ceramic fibers, glass fibers, etc., the single yarn diameter is 5~
It is preferably about 12μ and the number of constituent single fibers is 1000 to 10000. In the case of aramid fibers and arylate fibers, the single yarn denier is preferably 1 to 5 de/fil, and the yarn denier (total denier) is preferably 100 to 5000 de. On the other hand, the C1 single yarn denier of the filament yarn (B) should be smaller in consideration of meltability during thermoforming, and is 3 to 10 deniers.
/ f i l is preferable. The number of constituent single fibers is the first
In the case of the figure, yarn 2a has 100 to 1000 yarns, yarn 2b
For 2C and 2C, it is preferable to take 10 to 100 pieces. In the example shown in Fig. 1, filament yarn (
△) and one thread 2a consisting of filament yarn ([3)] are used. 1-2
You can also line it up with a tree. Further, the filament yarn (B) may contain a C1 pigment, a flame retardant, a filler, etc., if necessary. Functions and Effects of the Invention The composite fiber m-incorporated material of the present invention as described above is obtained by heat press molding the opening at a temperature higher than the melting point of the filament yarn (B), so that the filament yarn <8) in the structure is When completely melted, a composite material (composite) is formed in which filaments (~ yarns (A)) serving as reinforcing materials are arranged in one direction in the 71 ~ ricks of the thermoplastic polymer. When multiple pieces of the cylindrical structure are laminated one after another so that the warp directions are perpendicular to each other and hot press molded, it can be said to be a strong reinforcing material (comboji 1~) in which the filament yarns serving as the reinforcing material are arranged in both the vertical and horizontal directions. And C1: The composite fiber structure of the present invention does not have the problems of conventional prepregs using thermosetting resins, and is extremely easy to mold.
! It can be widely used as a product for a variety of purposes. EXAMPLES Next, the present invention will be roughly explained in detail using examples. Example 1 A multifilament yarn made of commercially available carbon fiber made from polyacrylic resin (Strength 19!?
Undrawn polybutylene terephthalate multi-filament 1~ yarn obtained by melt spinning polybutylene terephthalate 1- at a spinning take-off speed of 2500 m/min. ■1 <Fineness 300de/60fil
, melting point 225°C measured by DSC),
A composite fiber structure of the present invention was manufactured. First, use the warp screws to 1 multifilamen 1 to yarn [112
Yarn [I
I'] and put 1 multifilament around it.
A single thread [■] was wound in a helical shape to form a composite thread with convergence properties. Next, using this as the warp thread, the multifilament thread [n] is inserted into the weft thread at coarse intervals (20 threads/inch).
A mixed fiber of t 500q/rtl was obtained. The weight ratio of multifilament yarn [II] and multifilament yarn [1■] in this mixed fiber is [1]/[n] = 4
It was 0/60. When four composite fiber structures of the present invention made of this mixed fiber were stacked in mutually orthogonal directions and heated and pressed in a hot press at 250°C, Multificimen 1-based [II]
The polybutylene lenticule 1 is completely melted and fills the gap between the multifilament yarns [II], forming a plate shape.
A composite plate in which carbon mH is arranged perpendicularly to the difference η in the
Combinations 1 to 1) were obtained. This composite plate had extremely good tensile impact strength and bending resistance. 4. Brief Description of the Drawings FIG. 1 is a plan view showing an example of the composite fiber structure for thermoforming of the present invention. 1 in the figure is a yarn consisting of a high-strength, high-modulus filament yarn (A) made of a heat-resistant material;
2a, 2b, and 2c respectively indicate yarns consisting of ficimen 1 to yarn (B), which are thermoplastic polymers that melt at the molding temperature. Patent applicant Teijin Ltd.

Claims (5)

[Claims] (1) A high-strength, high-modulus filament (Δ) made of a heat-resistant material and a thermoplastic synthetic polymer filament (B) with a low melting point that melts at the molding temperature are used for the warp, and the thermoplastic polymer filament with the low melting point The weft yarns of (B) are inserted at coarse intervals to form a sudare woven fabric.
Composite fiber structure for thermoforming. (2) The high-strength, high-modulus filament h (A) made of a heat-resistant material is carbon fiber or ceramic fiber. The composite 11 fiber structure for aging molds according to claim 1, which is at least one type of filament 1 selected from the group consisting of glass fibers, polyarylate fibers, and aramid fibers. (3) The composite fiber for thermoforming according to claim (1), wherein the low melting point thermoplastic polymer filament (B) is an undrawn filament or partially oriented filament of polyester or polyamide with a melting point of 250° C. or less. Structure. (4) The warp threads align a high-strength, high-modulus filament (A) made of a heat-resistant material and a thermoplastic polymer filament (B) with a low melting point, and surround the aligned threads with a thermoplastic polymer with a low melting point. The composite fiber structure for thermoforming according to claim (1), which is a composite yarn in which hand-combined filaments (B) are wound. (5) The composite fiber structure for thermoforming according to claim (1), wherein the proportion of the high-strength, high-modicolus fibers made of a heat-resistant material in the composite fiber structure is 20 to 80% by weight. .