ES2348485T3 - REINFORCED BASE MATERIAL WITH CARBON FIBERS, PREFORM AND COMPOSITE MATERIAL UNDERSTANDING THE SAME. - Google Patents

Abstract

Carbon fiber reinforced substrate (21, 41, 81) comprising a fabric composed of carbon fiber bundles (22, 42, 52, 62, 82) and a first resin (24, 74, 84) that adheres to said fabric, in which said carbon fiber bundles respectively comprise numerous continuous carbon filaments, the tensile modulus of said carbon fiber bundles is 210 GPa or more, the fracture tension energy of said bundles of Carbon fibers is 40 MJ / m3 or more, and the amount of said first resin that adheres to said fabric whose value is in the range between 1 and 20 parts by weight per 100 parts by weight of said fabric, in which the amount of the second resin (75, 85) higher at the melting point or the flow initiation temperature than said first resin (84) and adhering to said tissue is in the range between 1 and 10 parts by weight per 100 parts by weight of said fabric.

Description

Base material reinforced with fibers carbon, preform and composite material comprising the same.

Technical field

The present invention relates to a carbon fiber reinforced substrate, a preform comprising  the substrate, and a compound comprising the preform.

The present invention relates to a carbon fiber reinforced substrate that has properties of excellent handling in the formation of a substrate preform reinforced with carbon fibers. Handling properties mean at least any selected property of stiffness, shape stability, ability to impregnate and stickiness in the lamination of the substrate reinforced with carbon fibers.

The invention also relates to a preform that has excellent resin permeability in the formation of a fiber reinforced substrate compound of carbon that has such excellent handling properties.

In addition, the invention relates to a compound that has excellent mechanical properties, which is formed of the preform that has the resin permeability Excellent. The mechanical properties mean at least one selected property of compression force after impact and compression force after conditioning hot-wet

Prior art

Carbon fiber reinforced compounds They have been used in airplane, space and sports applications, Due to its excellent mechanical properties and light weight.

As a typical method of producing such compound, autoclave molding is known. In the method, the pre-impregnated comprising a sheet composed of bundles of carbon fiber where each of which is formed with fibers continuous carbon arranged in one direction and a matrix of resin being impregnated with it. The prepregs are piled up in a mold and they are heated and pressurized in an autoclave, to make a compound

The prepreg used as a substrate for being molded into a compound has an advantage in the production of compound that has high reliability. However, this also has a disadvantage that it is too stiff to be adaptable. In addition, the production of a compound that uses prepreg has problems such as high cost and low productivity.

To mold a compound with high productivity, injection molding or molding of infusion. Injection or infusion molding includes, by example, resin transfer molding (RTM). At resin transfer molding (RTM), a substrate composed of carbon fiber bundles not prepreg of a matrix resin (dry carbon fiber bundles) is placed in a mold formed of complicated mode, and a matrix resin liquid (low viscosity) is injected or infused into the mold, to make carbon fiber beams are impregnated with resin Matrix

However, although injection or molding infusion be excellent in composite productivity, the substrate used (for example, a dry tissue) has problems in as for the handling properties since it is very likely that a low texture slip occurs (instability of form), that the substrate is so stiff to allow easy bending, and that the substrate layers do not adhere the to each other when they are laminated (no sticky feature). In addition, since the matrix resin must be low in viscosity, the compound has a problem being low in mechanical properties, compared to the compound formed with a matrix resin that It has a high viscosity as used in the prepreg above  mentioned. These problems present a problem that the compound obtained cannot sufficiently expose the properties particular of carbon fibers and does not have the properties expected mechanical properties of carbon fibers used

To solve this problem, the request for US 5,071,711 A proposes a technique, in which a resin thermoplastic-like is applied to a fabric composed of fibers reinforcement, to improve the handling properties of dry tissue used as a substrate, and stabilizing the shape of the preform used for infusion or injection molding.

In addition, the Journal of Advanced Materials, Volume 32, No. 3, July 2000, P27-34 or Composites Part A, Volume 32, 2001, P721-729 mentions that if a tissue is covered with a resin obtained mixing an epoxy resin and elastomeric or polyamide 6 particles, By injection molding or infusion, the mechanical properties (such as the hardness of interlaminar fracture of Mode II) of the obtained CFRP are improved.

However, the proposal cannot improve the mechanical properties, or you can improve them only insufficiently, although this proposal can improve the handling properties of the substratum. That is, for example, the very high levels of mechanical properties required for structure elements primary or main of an airplane cannot be reached even if a woven fabric or something similar is simply covered with a resin, and in the case where the same carbon fibers used do not have the necessary properties, the compound obtained using them can not present the mechanical properties necessary (especially the compression force after impact) neither.

In addition, in the methods of injection or Molding infusion described in the above mentioned proposals, since a sheet composed of carbon fiber beams simply arranged in one direction cannot be handled with fiber orientation maintained in a dry state, a bidirectional fabric.

However, for example, the elements of primary or main aircraft structure require very high mechanical properties, especially compression force after impact and compressive strength after conditioning hot wet. In a bidirectional tissue, bundles of carbon fiber from a fabric structure bidirectional Therefore, the amount of reinforcing fibers in Each address is considerably half. Also, since the warp and weft are almost equal in fineness or in measure of concentration large curls of carbon fiber beams are formed at warp and weft interlocking points. Due these problems, the mechanical properties of a prepreg composed of carbon fibers arranged in two directions they could be only the halves of those of a prepreg composed of carbon fibers arranged in one direction.

That is, although the required properties of the carbon fibers to be used and the shape of the fabric composed of carbon fibers are especially factors important for presenting high mechanical properties, the proposals mentioned above do not reveal any explanation about such factors at all.

The object of the invention is (to) solve the prior art problems. In particular, the object of the invention is (of) providing a fiber reinforced substrate carbon that has excellent handling properties such as stiffness, shape stability, ability to conform and stickiness, to provide a preform formed by the substrate and having a Good matrix resin permeability, and provide a compound formed by the preform that has excellent mechanical properties as compression force after impact or force of compression after conditioning hot-wet, and also having a good productivity. WO 98/50211 describes preforms for the process of molded, preforms comprising multiple layers of material fibrous further comprising a preform resin binder which contains a thermosetting resin and a resin thermoplastic

Invention Innovation

The object is solved by the features of the Claims 1, 20 or 21.

It is preferable that the amount of the first resin is in the range between 1 and 10 parts by weight per 100 parts by weight of the fabric.

It is preferable that the first resin to be adheres to the fabric adhere relatively more densely on a surface of the fabric that inside the fiber bundles of carbon.

It is preferable that the extensible module of the carbon fiber beams are greater than 280 and less than 500 GPa, and that the fracture tension energy of the fiber beams of carbon is 53 MJ / m 3 or more.

It is preferable that the fabric is a fabric Unidirectional, bidirectional tissue or unidirectional sheet than the Carbon fiber unit weight of the fiber reinforced substrate carbon is in the range between 50 and 500 g / m2, and that the thickness of the substrate reinforced with fibers of Carbon is in the range between 0.1 and 0.8 mm.

It is preferable that the fabric is a fabric unidirectional or unidirectional sheet, and that the permeability of the carbon fiber substrate air is comprised in the range between 10 and 200 cm3 / cm2 ·.

It is preferable that the first resin is cover on a surface of the fabric, and that the diameters of the covered parts are 1 mm or less.

It is preferable that the first resin adhere discontinuously on a fabric surface.

It is preferable that the first resin adhere on a surface of the fabric, and that the average thickness of the first resin that adheres to the surface is comprised in the range between 5 and 250 µm

It is preferable that the melting point or the flow initiation temperature of the first resin is in the range between 50 and 150 ° C.

It is preferable that the main component of the First resin is a thermosetting resin.

It is preferable that the main component of the First resin is a thermoplastic resin.

It is preferable that the amount of resin thermoplastic is in the range between 70 and 100% of weight based on the weight of the first resin.

It is preferable that the main component of the first resin is at least one selected from the group consisting in epoxy resins, polyamide resins, polyetherimide resins, polyphenylene ether resins, polyether sulfone resins and resins phenoxy

It is preferable that the amount of a second resin neither molten nor cautilized to flow at the melting point or the flow initiation temperature of the first resin and adhering to the fabric is in the range between 1 and 10 parts by weight per 100 parts by weight of the fabric.

It is preferable that the second resin adheres on a surface of the fabric by the first resin.

It is preferable that the second resin be particles having an average particle diameter of 1 to 500 \ mum ..

It is preferable that the main component of the Second resin is a thermoplastic resin.

It is preferable that the main component of the second resin is at least one thermoplastic resin having a glass transition temperature of 30 to 280 ° C selected from group consisting of polyamide resins, resins polyamide-imide, polyetherimide resins and resins of polyether sulfone.

The preform of the invention is a laminate that comprises at least two or more layers of the substrate reinforced with carbon fibers, in which the layers of the substrate reinforced with carbon fibers are fully linked to each other by the first resin or the second resin.

The compound of the invention comprises at least the preform and a third resin, in which the preform is impregnated with the third resin different from the first resin.

Brief description of the drawings

Fig. 1 is a typical plant showing a substrate mode reinforced with carbon fibers.

Fig. 2 is a typical plant showing another substrate mode reinforced with carbon fibers.

Fig. 3 is a typical vertical sectional view. which shows yet another mode of the fiber reinforced substrate carbon.

Fig. 4 is a typical vertical sectional view which shows a still remote mode of the substrate reinforced with carbon fibers

Fig. 5 is a perspective view that shows a mode (unidirectional fabric) of the fabric used in the carbon fiber reinforced substrate of the invention.

Fig. 6 is a perspective view that shows yet another mode (unidirectional fabric) of the fabric used in the carbon fiber reinforced substrate of the invention.

Fig. 7 is a typical vertical sectional view which shows a first mode of the fiber reinforced substrate carbon of the invention.

Fig. 8 is a typical vertical sectional view which shows yet another mode of the fiber reinforced substrate carbon of the invention.

Fig. 9 is a typical vertical sectional view. which shows a mode of the preform of the invention.

Fig. 10 is a typical sectional view vertical showing a mode of the compound of the invention.

Fig. 11 is a schematic view of the perspective that shows the primary structure elements of a airplane.

Fig. 12 is a schematic view of the perspective that shows an example of a structural element in which the compound of the invention is applied.

Fig. 13 is a schematic view of the perspective that shows another example of a structural element in which the compound of the invention is applied.

Meanings of the symbols in the drawings:

11, 21, 31, 41, 71, 81: a fiber structure carbon

12, 22, 32, 42, 52, 62, 72, 82: a thread of warp formed by carbon fibers 13, 33, 73: a weft thread formed by carbon fibers

14, 24, 34, 44, 74, 84, 93: a first resin

15, 25, 35, 45, 76, 86: a cloth

23, 43, 53, 63, 83: an auxiliary weft thread formed by auxiliary fibers

51, 61: a unidirectional fabric

64: an auxiliary warp thread formed by auxiliary fibers

75, 85, 94: a second resin

90: a carbon fiber substrate

91: a preform

92: a fabric composed of continuous fibers of carbon

101: a compound

102: a third resin

111: a plane

112: a main wing

113: a keel beam

114: a fuselage

115: a vertical fin

116: a horizontal stabilizer

121, 131: a structure element

122, 132: a coating

123, 133: a stringer

124, 134: a hardener

It is mentioned that Figures 1-4 They are not covered according to the present invention.

Continuous carbon filaments mean that carbon filaments are considerably continuous in the cloth. The expression of being considerably continuous is used whereas there is a case where a very small number of Carbon filaments breaks during the formation of a beam of carbon fibers or in the formation of a fabric.

The carbon fiber beam in the substrate of Carbon fiber of the invention has a tension module of 210 GPa or more and a fracture tension energy of 40 MJ / m 3 or more.

It is preferable that the voltage module is of more than 250 and less than 600 GPa, more preferably more than 280 and less than 500 GPa, and still more preferably more than 290 and less of 400 GPa.

If the voltage module is less than 210 GPa, the mechanical properties of the compound formed using the Carbon fiber substrate are not enough.

The voltage module is measured according to the method measurement specified in JIS-R-7601. The unit is GPa.

It is preferable that the voltage energy of fracture is 45 MJ / m 3 or more, more preferably 53 MJ / m 3 or more, and still more preferably 56 MJ / m 3 or plus. A higher fracture tension energy is desirable, without However, based on carbon fiber bundles usually currently available, usually the voltage energy of fracture is 80 MJ / m 3 or less.

If the fracture tension energy is less than 40 MJ / m 3, the mechanical properties of the compound formed by the carbon fiber substrate are not sufficient. That is, when the compound collides, there is a case in which fractures in the carbon fiber beams occur. The mechanical properties can be judged in reference to the compressive force at room temperature after impact (hereinafter abbreviated as
CAI).

Especially if the voltage energy of fracture is less than 40 MJ / m 3, the compound that has a quasiisotropic stack architecture formed by rolling fabrics unidirectional plurals respectively that have fiber bundles carbon arranged in one direction becomes very low in CAI.

The CAI of a compound is a characteristic highly respected mechanics when the compound is used as a structure element (especially as a structure element primary or main) of a transport machine (especially a plane). To use a compound as said element of structure, recently it is highly demanded that the compound have excellent CAI.

The fracture tension energy (W) is calculated from the equation W = \ sigma2 / 2 x E based on the limit of tensile strength resistance (sig) and the extensible module (E) measured according to the measurement methods specified in JIS-R-7601. The unit is MJ / m 3 (106xJ / m3).

The amount of the first resin that adheres to the fabric in the carbon fiber substrate of the invention is between 1 and 20 parts per 100 parts of weight on the fabric. It is preferable that the quantity is between 1 and 10 parts of weight.

The first resin may exist within the fabric, that is between the carbon fiber beams respectively adjacent or between carbon filaments respectively adjacent in each bundle of carbon fibers, or it can be bad distributed and adhere relatively more densely over a fabric surface more than inside the fabric.

Bad distribution means a state in which the first 70% resin in vol. or more, desirably 80% in vol. or more, more desirably 90% in vol. or more exists on a surface of the cloth.

The adhesion of the first resin to the fabric in an amount from 1 to 20 parts by weight per 100 parts of Fabric weight brings the sticky (adhesive) characteristic between substrates in the formation of a preform by rolling the substrates reinforced with carbon fibers to each other. In addition, a rigidity measure is imparted to the fabric, and stability is achieved of the fabric preventing texture slipping of the beams of carbon fiber in the fabric. Therefore, a carbon fiber reinforced substrate that has properties of excellent handling.

The first resin in the adhesive quantity works as a crack prevention in the compound obtained rolling the layers of the substrate reinforced with carbon fibers and It also works to relax residual thermal stress when mold the compound. Especially when the compound collides, the First resin works to prevent interlaminar damage from carbon fiber reinforced substrate, and has excellent mechanical properties (especially CAI, the limit of resistance to tensile strength and compression force), that is, an effect of hardening of the compound.

The carbon fiber reinforced substrate has been completed based on discovering that the hardening effect by the first resin can be obtained when the first resin it is used in combination with carbon fiber beams that have a fracture tension energy of 40 MJ / m 3 or more.

In the case where you make carbon fiber that have a fracture stress energy of 40 MJ / m 3 or more not The hardening effect of the first resin is used decreases to said low level not detectable. On the contrary, in the case where the deposited amount of the first resin to be adheres to the fabric is not in the above mentioned interval even if carbon fiber beams are used, the effect of hardening by the first resin cannot be exposed essentially.

In addition to the hardening effect, if the first resin adheres relatively more densely on a fabric surface, the first resin that adheres to the fabric surface works like a spacer in the case where the layers of the substrate reinforced with carbon fibers are laminated on each other, to form a space between the adjacent layers of the substrate reinforced with carbon fibers. TO This is called the spacer effect by the first resin.

The spacer effect plays the role of tracks of flow that are formed for a third resin which is a resin matrix explained below in the molding of a compound by injection or by infusion of the third resin in the substrates laminated carbon fiber. The spacer effect facilitates the infiltration of the third resin in the substrate, increases the impregnation speed, and improves the productivity of the compound.

The spacer effect also plays the role for work on the hardening effect of the first resin of intensive way in the interlaminar part between the layers of compound substrate. Therefore, another can be achieved hardening effect higher. This is called the effect of interlaminar hardening by the first resin. It was not expected This effect at the beginning.

The hardening effect, the effect spacer and interlaminar hardening effect by the first  resin are further promoted by poor distribution of the First resin on a fabric surface.

The first resin can adhere relatively more densely on a surface of a single layer of cloth or on both surfaces of the fabric. The first is preferable for produce a carbon fiber reinforced substrate where the first resin adheres relatively more densely to the fabric with a lower cost. If you don't want to distinguish surfaces front and reverse of the carbon fiber substrate, the latter It is desirable. In a multilayer fabric, the first resin can adhere to one surface of each or both surfaces of each of the outer layers, but it is preferable that the first resin adheres to the surfaces of the respective layers, and that higher effects can be achieved.

In JP 6-94515 B or JP 5-337936 A, an arrangement technique is described of a fine powder or tissue on a surface of a Prepreg used for autoclave molding. But nevertheless, for the present invention that is intended to provide a compound at high productivity, the molding of autoclave. The handling properties such as stiffness and capacity to adapt cannot be achieved in a prepreg conventional. Since conventional prepreg is impregnated with a sticky matrix resin (corresponding to the third resin described later), it is easy to arrange a powder or something similar about it for adhesion. However, a fairly new technical concept to arrange a powder or similar on a dry and non-sticky cloth.

The present invention is described later. more particularly in reference to drawings 5 to 13.

Fig. 1 is a typical plant showing a substrate mode reinforced with carbon fibers. In Fig. 1, a carbon fiber reinforced substrate 11 comprises a fabric 15 and a first resin 14 that adheres to fabric 15. Fabric 15 comprises warp threads 12 formed by fiber bundles of carbon and weft threads 13 formed by carbon fiber beams, and the warp threads 12 and the weft threads 13 form the 15 fabric in a taffeta ligament. Fabric 15 is a kind of fabric bidirectional Each of the carbon fiber beams used as the warp threads 12 and the weft threads 13 comprise respectively numerous continuous carbon filaments. The first resin 14 is covered on a fabric surface fifteen.

Fig. 2 is a typical plant showing another substrate mode reinforced with carbon fibers other than mode of Fig. 1. In Fig. 2, a substrate reinforced with fibers of Carbon 21 comprises a fabric 25 and a first resin 24 adhered to the fabric 25. The fabric 25 comprises warp threads 22 formed by carbon fiber beams and auxiliary weft wires 23 formed by thinner auxiliary threads than warp threads 22, and warp threads 22 and auxiliary weft threads 23 form the 25 cloth in a taffeta ligament. Since the fabric 25 is composed mainly of warp threads 22 formed by fiber bundles carbon, this is a kind of unidirectional tissue. Each of the carbon fiber beams used as the threads of Warp 22 comprises numerous continuous carbon filaments. The first resin 24 adheres to a surface of the fabric 25 discontinuously

Fig. 3 is a typical vertical sectional view. which shows yet another mode of the fiber reinforced substrate carbon. In Fig. 3, a substrate reinforced with carbon fibers 31 comprises a fabric 35 and a first resin 34 adhered to the fabric 35. The fabric 35 comprises warp threads 32 formed by bundles of carbon fiber and weft threads 33 formed by fiber bundles of carbon, and the warp threads 32 and the weft threads 33 form the fabric 35 in a taffeta ligament. This fabric 35 is a kind of bidirectional fabric. Each of the carbon fiber beams used as warp threads 32 and weft threads 33 It comprises respectively numerous continuous carbon filaments. The first resin 34 adheres relatively more densely on a surface of the fabric 35.

Fig. 4 is a typical vertical sectional view which shows yet another mode of the fiber reinforced substrate carbon different from the mode of Fig. 3. In Fig. 4, a substrate reinforced with carbon fibers 41 comprises a fabric 45 and a first resin 44 adhered to the fabric 45. The fabric 45 comprises threads of warp 42 formed by carbon fiber bundles and threads of weft 43 formed by auxiliary fiber beams. The threads of warp 42 and weft threads 43 form the fabric 45 in a fabric flat. Since the fabric 45 is mainly composed of the threads of warp 42 formed by carbon fiber beams, this is a kind of unidirectional woven fabric. Each of the beams of Carbon fiber used as warp threads 42 comprises numerous continuous carbon filaments. The first resin 44 is adheres relatively more densely to a fabric surface Four. Five.

The first resin can adhere as dots on a surface of the fabric 15 as shown as first resin 14 in Fig. 1, or it can adhere on a surface of the fabric 25 to cover the surface more extensively than in Fig. 1, but discontinuously, as shown as first resin 24 in Fig. 2.

The state in which the first resin 14 is adheres as points on a surface of the fabric 15 in Fig. 1 It is also explained like this. That is, in Fig. 1, if a surface of the fabric 15 is considered as the sea while the first resin 14 it is considered as islands, then the first resin 14 that exists on the surface of the fabric 15 shown in Fig. 1, it can be Say it is a group of numerous small islands. The width maximum of the small islands is smaller than the widths of the warp threads 12 and weft threads 13.

The state in which the first resin 24 is adheres on a surface of the fabric 25 discontinuously in the Fig. 2 is also explained like this. That is in Fig. 2, if a fabric surface 25 is considered as the sea while the first resin 24 is considered as islands in Fig. 2, then the first resin 24 that exists on the surface of the fabric 25 is shown in Fig. 2, it can be said that it is a group of many Large islands scattered in the sea. Some large islands contain 26 lakes in them. The minimum width of the large islands is more larger than the width of each warp thread 22, and smaller than the total width of four warp threads 22.

Although not illustrated, a figure of existence of the first resin can also be a mixed state of small islands shown in Fig. 1 and the large islands shown in Fig. 2.

It is not preferable that the first resin be adhere to the fabric in such a way that it completely covers the fabric like a movie, from permeability (especially the permeability in the direction perpendicular to the surface of laminate) of the third resin described later in the reinforced laminated carbon fiber substrates are inhibited notably. In addition, it is also not preferable that the first resin can easily absorb water and adhere to the fabric of such way to cover the fabric continuously not only as a movie, but also as filaments or a nonwoven fabric, since where a formed compound is treated in condition hot-wet, the effect of water absorption It extends over a wide range through the first resin.

Therefore, it is desirable that the first resin adheres as points or discontinuously. In the case where the first resin adheres on a surface of the fabric 15 as points as shown in Fig. 1, if the average diameter of the points (islands) (the minor middle axis if the points are oval) is more small, the points can be dispersed more evenly over the surface of the fabric 15. Thus, it is desirable that the average diameter be 1 mm. or less, more desirably 250 µm or less, and even more desirably 50 µm or less.

In the case where the plural layers of the substrate reinforced with carbon fibers that has the first resin with relatively denser adhesion to the surfaces of the layers of fabric are laminated, if the first resin with relatively denser Adhesion on the surfaces of the fabric layers is in excess strong in the direction perpendicular to the surfaces of the substrate, carbon fiber beams located in contact with the First resin are greatly diverted. In this case, the Compression properties of the compound as the strength of compression at room temperature (hereinafter abbreviated as CS) and the high temperature compression force after the wet hot conditioning (hereinafter abbreviated as CHW) can be harmed.

On the other hand, if the amount of the first resin is too small, the compound cannot have the desired properties

Given the above, it is preferable that the average thickness of the first resin on the surface of the fabric is in the range between 5 and 250 µm. It's more preferably it is in the range between 10 and 100 µm, and another more preferable range is between 15 and 60 µ.

The amount of the first resin deposited on the fabric is in the range between 1 and 20 parts of weight per 100 parts of weight of the fabric. A preferred amount deposited is in the range between 1 and 10 parts of weight, and another preferred range is between 3 and 7 parts of weight. Another more preferred range is between 4 and 6 parts of weight.

If the deposited amount of the first resin It is less than 1 part weight, the substrate handling properties reinforced with carbon fibers such as stiffness, stability of shape, the ability to conform and stickiness in lamination it becomes poor, and the effect of improving mechanical properties of the compound is also small.

If the deposited amount of the first resin is more than 20 parts by weight, the compound obtained cannot be excellent in mechanical properties, especially in CHW, and the Carbon fiber content of the compound becomes too low. In addition, it may be that the permeability of the third resin as the matrix resin described later in the substrate reinforced with carbon fibers or in the preform can be prevented  when the compound is produced. In the case where the amount deposited of the first resin is 10 parts weight or less, since that the preform in the compound can be made narrow in space Interlayer and smooth, compression properties such as CHW and CS They can be improved.

The fabric is made of fiber bundles of carbon. The fabric can be in any of several ways known as a tissue (unidirectional, bidirectional or 3D, etc.), knitting, beak, fabric with warp threads (carbon fiber bundles) arranged in parallel to each other in one direction (hereinafter called a unidirectional sheet), the multiaxial sheet obtained by superimposing two or more sheets unidirectional in different directions, etc. Fabric too it can be an integral product that includes united plural fabrics by any of several joining means such as knitting threads, threads of knot or resin (porous film, non-woven fabric, binder, etc.).

In the case where the compound is used as a structure element of a transport machine, it is preferable that the carbon fiber reinforced substrate fabric be a unidirectional tissue, bidirectional tissue, unidirectional sheet or multiaxial fabric (especially multiaxial fabric joined by threads of point).

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A structure element is required primary or main of an airplane have very high properties mechanical (especially CAI and CHW). In a bidirectional fabric, already that carbon fiber beams form a structure of bidirectional ligament, it may be that the curls of the beams carbon fiber get big at the points of interlacing between warp threads and weft threads. In this In this case, it may be that the first resin 34 does not exist in the interlocking points between warp threads 32 and threads  of frame 33, although this exists in Fig. 3. In this case, you can that the mechanical properties are not able to meet the requirement.

Therefore, to obtain mechanical properties more preferred, it is preferable that the fabric is a fabric unidirectional or a unidirectional sheet. In addition, considering the matrix resin permeability, it is especially preferable that it is a unidirectional tissue, in which small curls formed by auxiliary weft threads exist between warp threads (carbon fiber beams). Curly are useful for forming steps to allow the permeability of the matrix resin, to noticeably improve the matrix resin permeability of the preform

Fig. 5 is a perspective view that shows a first mode (unidirectional fabric) of the fabric used in the carbon fiber reinforced substrate of the invention. In Fig. 5, a unidirectional tissue 51 is a taffeta ligament, in whose warp threads 52 arranged in parallel to each other in an address and auxiliary weft threads 53 perpendicular to the 52 warp threads intertwine with each other. The threads of Warp 52 are made of carbon fiber bundles, and the threads weft auxiliaries 53 are formed by fiber beams auxiliary

Each of the carbon fiber beams that they form the warp threads 52 of the unidirectional fabric 51 It comprises 5,000 to 50,000 continuous carbon filaments. He most preferred number of carbon filaments in each fiber bundle Carbon is 10,000 to 25,000.

It is preferable that the fineness or measurement of concentration of warp threads 52 of unidirectional tissue 51 is in the range between 300 and 5,000 tex. If the fineness is less than 300 tex, the number of interwoven points between the warp threads 52 and the auxiliary weft threads 53 is Too big. Therefore, the curls at the points of entanglement become large, and the number of curls also It becomes big. In this case, it may turn out that the properties mechanics of the compound obtained are poor. If the fineness is more of 5,000 tex, the number of interlocking points is too small, and the shape stability of the fiber reinforced substrate Carbon can become low.

It is preferable that the auxiliary fiber beams which form the auxiliary weft threads 53 are selected for ensure that the curls of the warp threads 52 at the points interlacing between warp threads 52 and threads frame auxiliaries 53 become small. In this case, the properties of the carbon fiber beams used as the 52 warp threads can be exposed to the maximum extent possible.

It is preferable that the fineness of the beams of auxiliary fibers that form the weft auxiliary threads 53 are not more than 1/5 of the fineness of the carbon fiber beams that form the warp threads 52, more preferably 1/10 or less. The particular fineness depends on the kinds of fiber beams of carbon and the auxiliary fiber beams used and the weight per tissue unit. For example, in the case where you make fiber 800 tex carbon are used to form a fabric with a weight per unit of 200 g / m2, it is preferable that the fineness of the auxiliary fiber beams are in the range between 10 and 100 tex, more preferably between 20 and 50 tex.

It is preferable that the number of the ends of weft of auxiliary weft threads 23 (Fig. 2) or threads frame auxiliaries 53 (Fig. 5) are in the range between 0.3 and 6 ends / cm to stabilize the shape of the fabric and to minimize the influence of warp yarn curls, more preferably from 1 to 4 ends / cm.

For auxiliary fiber beams, it can be used any desired material. However, as for the stability of warp ends and weft ends, is preferably a material that is unlikely to shrink, for example, It is preferable for heating for molding. For example, Carbon fibers, glass fibers, fibers can be used organic as aramid fibers, polyamide fibers (especially POY), PBO fibers, PVA fibers or PE fibers, or a combination of same. Secondary fibers can also be used spun, for example, bent, twisted, treated with wool or curly

Warp threads, weft threads and threads weft auxiliaries can also be used in combination with an adhesive component to fix the weaving structure. The Examples of the adhesive component include thermoplastic resins such as nylon resins and polyester resins, resins thermosetting materials such as epoxy resins, polyester resins unsaturated and phenol resins, etc. The shape of the component. Adhesive can be fibers, particles, emulsion or dispersion, etc. The adhesive component in any of these forms may be combined with warp threads, weft threads or auxiliary threads of plot. Above all, if the adhesive component in the form of fibers it is twisted together with the auxiliary fiber beams or used as thread cover to cover auxiliary fiber beams, for the use as auxiliary weft threads, the effect of fixing the Weaving structure is tall.

The unidirectional tissue can be a tissue Taffeta ligament as shown in Fig. 5, or a ligament twill or a satin weave. In addition, a fabric with a non-curly structure as shown in Fig. 6.

Fig. 6 is a perspective view that shows yet another mode (a unidirectional fabric) of the fabric used in the carbon fiber reinforced substrate of the invention. In Fig. 6, a unidirectional fabric 61 comprises 62 warp threads formed by carbon fiber bundles, threads of auxiliary warp 64 formed by auxiliary fiber bundles arranged in parallel with the warp threads 62, and threads weft auxiliaries 63 formed by auxiliary fiber beams arranged in the direction perpendicular to wires 62 and 64. The auxiliary warp threads 64 and auxiliary weft threads 63 are intertwined with each other, to fully support the 62 warp threads formed by carbon fiber beams, for form the tissue (tissue that has a non-curly structure) 61.

The tissue (tissue that has a structure not curly) 61 also has smaller curls than tissue unidirectional 51 with a taffeta ligament shown in the Fig. 5. Thus, the compound produced by the tissue can expose more high properties of carbon fiber beams. Further, also in terms of matrix resin permeability, since auxiliary fiber beams provide permeability steps Resin, permeability is excellent.

In the case where the fabric is a fabric bidirectional, a unidirectional tissue or a unidirectional sheet, as for the permeability of the third resin described more forward on the substrate reinforced with carbon fibers or on the preform and the mechanical properties of the compound, it is preferable than the carbon fiber unit weight of the reinforced substrate with carbon fibers, that is, the fiber unit weight of fabric carbon is in the range between 50 and 500 g / m2, more preferably 100 to 350 g / m2, and still more preferably from 150 to 250 g / m2. It is preferable that the substrate thickness reinforced with carbon fibers in the range between 0.1 and 0.8 mm, more preferably from 0.15 to 0.7 mm, and still more preferably from 0.2 to 0.6 mm

In the case where the cloth is a cloth multiaxial, it is preferable that the weight per unit of carbon fiber  of the substrate reinforced with carbon fibers is included in the range between 150 and 1500 g / m2, more preferably 300 to 1000 g / m2, and still more preferably 400 to 800 g / m2. The reasons why the weight per fiber unit of carbon of a multiaxial fabric can be larger than that of fabric Unidirectional or similar are that especially in the case where stitch threads or similar are in the thickness direction, the tracks of resin in the thickness direction the resin steps in the Thickness address can be secured, to allow more Easily resin permeability, and what if the weight per unit It is small, it is not necessary to have a multilayer fabric.

As for resin permeability, it is preferable that the air permeability of the substrate reinforced with Carbon fibers are in the range between 10 and 200 cm 3 / cm 2 •, more preferably from 12 to 120 cm 3 / cm 2 •, and still more preferably from 15 to 100 cm3 / cm2 ·.

If the air permeability is less than 10 cm3 / cm2 \ cdotsec, resin permeability is too much low. Air permeability of more than 200 is not preferable cm3 / cm2 \ cdotsec, because the gaps in the fabric are they are too large although the resin permeability is excellent, and since the compound obtained has many parts formed rich in resin, decreased properties occur mechanical, thermal cracking and the like.

Air permeability is expressed as the amount of air that permeates the fabric measured according to method A described in JIS-L-1096 (type Frazier) The air permeability value in the specification is measured by AP-360 produced by K.K. Daiei Kagakuseiki Seisakusho.

To minimize the output of the first Resin of the fabric when the fabric is covered with the first resin and also to show the properties of fiber bundles of carbon itself to the maximum extent, it is preferable that the factor of Fabric cover is 90% or more. It is more preferable than fabric cover factor is 97% or more, and 99% or more even more preferable.

The coverage factor refers to the percentage of the closed parts (covers) where the carbon fibers (auxiliary threads, stitch threads, knot threads and the like according the case) exist in the fabric per unit area of 100 mm. x 100 mm when the planar fabric is observed in the direction perpendicular to the same. The cover factor (%) is calculated from the equation next: Cover factor (%) = Total area (mm2) of parts closed / 10,000. In the case where the fiber reinforced substrate Carbon is used to measure the cover factor, it is not include the parts closed by the first resin. That is, the fabric cover factor, can be considered to be the same of the substrate factor of the fiber reinforced substrate carbon.

This measurement is done at least five times in optional places of the web. The cover factor value is the average value of these measured values. The total area of the parts closed is calculated by means of image processing based on the image optically collected by a CCD camera or a scanner, etc.

A fabric that has a cover factor of 90% or more is, for example, a fabric made of fiber bundles of carbon respectively having a width of 4 mm or more and flat transversely (a fabric comprising fiber bundles of carbon planes). It is preferable that the width of each fiber bundle Carbon be 5 mm. or more, more preferably 6 mm. or plus.

It is preferable that the flat carbon fiber fabric is extended by compressed air, roller or indenter, etc. The reason is that the extension can reduce the thickness of the fabric and improve the content of carbon fiber in the compound. The flat carbon fiber fabric (fabric) itself is described in more detail in JP 2955145 and
JP 11-1840 A. It is preferable that the carbon fiber beams do not twist considerably in terms of matrix resin permeability and the sample of mechanical properties.

It is preferable that the first resin has a melting point or flow initiation temperature of 50 to 150 ° C as for the temperature used to obtain the viscosity necessary to laminate fiber reinforced substrate layers carbon It is more preferable than the melting point or the flow initiation temperature are included in the range between 70 and 140 ° C, still more preferably from 90 to 120 ° C.

For a resin showing a melting point, the melting point refers to the temperature measured using a differential scanner calorimeter ( DSC ), in which the resin is cast. For a resin that does not show a melting point, the flow initiation temperature refers to the temperature measured by means of viscoelasticity (Flow Tester CFT 500D produced by Shimadzu Corporation, heating index 1.5 ° C / min), at which The resin begins to flow.

It is preferable that the water coefficient of absorption (water absorption equilibrium coefficient) of the first resin is 23 ° C and 50% RH is 3% by weight or less. It is more preferable that the water absorption is 2.2% in weight or less, still more preferably 1.8% by weight or less, even more preferably 1.4% by weight or less.

If the absorption equilibrium coefficient of water is more than 3% by weight, a compound with excellent mechanical properties (especially CHW). The coefficient of Water absorption balance is measured according to the method described in ASTM-D-570.

The first resin is not especially limited, if this can improve the handling properties of the carbon fiber reinforced substrate and improve properties mechanics of the compound obtained using the reinforced substrate with carbon fibers. As the first resin, a resin thermosetting and / or a thermoplastic resin can be used with enough selective criteria.

Examples of thermosetting resin include epoxy resins, phenol resins, resins polybenzoimidazole, benzoxazine resins, cyanate resins ester, unsaturated polyester resins, vinyl ester resins,  urea resins, melamine resins, bismaleimide resins, resins of polyimide and polyamide-imide resins, their copolymers and modification products, resins obtained by mixing two or more of the above, and resins containing an elastomer, rubber component, hardening agent, curing accelerator, catalyst or similar.

Examples of the thermoplastic resin include polyester resins, polyolefin resins, resins based on styrene, polyoxymethylene resin, polyamide resins, resins polyurethane, polyurea resins, polydicyclopentadidena resin, polycarbonate resins, polymethylene methacrylate resin, resins of polyetherimide, polysulfone resins, polyallilata resins, polyether sulfone resins, polyketone resins, resins ketone polyether, ketone ether polyether resins, resins of ketone polyether ketone, polyarylate resins, resins polyether nitrile, polyimide resins, resins polyamide-imide, phenol resins, phenoxy resins, fluorine based resins such as polytetrafluoroethylene resin, elastomers (preferably acrylonitrile butadiene, its acid carboxylic or amine modification products, fluoroelastomers, polysiloxane elastomers), rubber (butadiene, styrene butadiene, styrene butadiene styrene, styrene isoprene styrene, rubber natural, etc.), resins for RIM (for example, those that contain a catalyst or the like capable of forming polyamide 6, polyamide 12, polyurethane, polyurea or polycyclopentadiene), cyclic oligomers (those that contain a catalyst or similar capable of forming a polycarbonate resin, resin polybutylene terephthalate, etc.), copolymers and products of modification thereof, resins obtained by mixing two or more of the previous ones, etc.

In the case where a resin is used thermosetting as the main component of the first resin, it prefer at least one resin selected from the group consisting of epoxy resins, unsaturated polyester resins and phenol resins. Above all, an epoxy resin is especially preferable. Whether uses an epoxy resin, the substrate handling properties They are excellent because the adhesion is high, and especially in the case  where an epoxy resin is used as the third resin described later, high properties can preferably be shown mechanical

In the case where an epoxy resin is used as the main component of the first resin, it can, without being required, contain a hardening agent, curing catalyst or Similary. As for the life of the first resin, the last one is preferable. Even in the previous case, they don't pose any great problem a very latent hardening agent or catalyst of cured.

In the case where a resin is used Thermoplastic as the main component of the first resin, is preferred at least one resin selected from the group consisting in polyamide resins, polysulfone resins, polyether resins sulfone, polyetherimide resins, polyphenylene ether resins, polyimide resins, polyamide-imide resins and phenoxy resins. Among them, especially resins of polyamide, polyetherimide resins, polyphenylene ether resins, polyether sulfone resins and phenoxy resins.

It is preferable that a thermoplastic resin is the main component of the first resin, and that its content is in the range between 70 and 100% by weight. A most preferred range is between 75 and 97% by weight, and Another more preferable range is 80 to 95% by weight. If he content is less than 70% by weight, it can be difficult to obtain a Composed with excellent mechanical properties. In the case where use a thermoplastic resin as the main component, you can it turns out that the adhesion of the first resin to the fabric or the possibility of making the first resin adhesion to the fabric is come back low. In this case, it is desirable to add a small amount of a tackifying agent, plasticizer or similar to the first resin.

In the carbon fiber reinforced substrate, the second resin higher than the first resin at the point of melting or flow initiation temperature adheres to the fabric, In addition to the first resin. The amount of the second resin that adheres to the fabric is in the range between 1 and 10 parts of weight per 100 parts of weight of the fabric. In this case, the mechanical properties (especially CAI and CHW) can also be highly displayed It is preferable that the second resin has a melting point or flow initiation temperature of 150 ° C or more tall. It is more preferable than the melting point or temperature of flow initiation is 180 ° C or higher, and even more preferably it is 210 ° C or higher.

All that is required is that the second resin is not molten or does not flow at the melting point or the flow initiation temperature of the first resin. A resin which has neither melting point nor an initiation temperature of flow, that is to say a resin capable of decomposing before being melted or before the beginning of flow can also be used As the second resin.

As the second resin adheres to the fabric in addition to the first resin, preferably if these resins are adhere relatively more densely on a surface of the fabric, hardening effect and hardening effect interlaminar can be more highly shown compared to the case where the first resin only adheres to the fabric, and for consequently, the mechanical properties (especially CAI) of compound obtained by rolling the layers of the reinforced substrate With carbon fibers it can be greatly improved.

The reason why the second resin can show more highly the effects than those of the first resin is why the second resin has a melting point or temperature of initiation of flow higher than that of the first resin, or that the second resin does not melt or does not flow at the temperature in the which the first resin is molten or begins to flow. Also, already that the first adhesive resin already exists, does not absolutely require that the second resin itself is adhesive, and it can also be used a highly resistant but non-adhesive resin or a resin unable to contribute to the improvement of the properties of substrate management. Thus, the second resin can be selected of a fairly wide range of resins in terms of material and form that the first resin.

Considering the mechanisms mentioned above, if a resin that becomes adhesive at a relatively temperature low and not lower mechanical properties (preferably improves mechanical properties) is used as the first resin while a resin capable of showing more highly the mechanical properties It is used as the second resin that adheres to dry cloth, a more carbon fiber substrate can be obtained favorite.

The second resin can adhere inside of the fabric or adheres relatively more densely on a fabric surface, but to show the effects so efficient, it is preferable that the second resin adhere relatively more densely considerably on a surface of the fabric as the first resin.

The amount of the second resin deposited on the fabric is in the range between 1 and 10 parts by weight per 100 parts by weight of the fabric. It is more preferable than amount deposited is in the range between 2 and 9 parts by weight per 100 parts by weight of the fabric. Another interval Preferable is 3 to 7 parts by weight, and an index especially Preferable is 4 to 6 parts by weight.

If the deposited amount of the second resin It is less than 1 part by weight, the effect of improvement in properties  Mechanical can be small. If the amount deposited from the second resin is more than 10 parts by weight, it may be that the compound obtained is not especially excellent in CHW after that wet hot conditioning, and fiber content Carbon compound is too small. In addition, when obtain the compound, the permeability of the third resin described below as the matrix resin in the substrate reinforced with carbon fibers.

The meaning of use of the second Resin is explained more particularly in reference to drawings.

Fig. 7 is a typical vertical sectional view which shows yet another mode of the fiber reinforced substrate carbon of the invention. In Fig. 7, a substrate reinforced with Carbon fibers 71 comprise a fabric (bidirectional fabric) 76 comprising warp threads 72 formed by fiber bundles of carbon and weft threads 73 formed by carbon fiber beams, and a first resin 74 and a second resin 75 that adhere to the fabric 76 respectively. In the fiber reinforced substrate carbon 71, the second resin 75 adheres to the fabric in addition to the first resin 74, unlike the fiber reinforced substrate carbon 31 of Fig. 3. The second resin 75 adheres as particles relatively more densely on a surface of the fabric 76.

Fig. 8 is a typical vertical sectional view which shows yet another mode of the fiber reinforced substrate carbon of the invention different from the mode of Fig. 7. In Fig. 8, a substrate reinforced with carbon fibers 81 comprises a fabric (unidirectional fabric) 86 consisting of warp threads 82 formed by carbon fiber beams and auxiliary weft threads 83 formed by auxiliary fiber beams, and a first resin 84 and a second resin 85 adhered to the fabric 86 respectively. In the carbon fiber reinforced substrate 81, the second resin 85 adheres to the fabric in addition to the first resin 84, unlike  of the carbon fiber reinforced substrate 41 of Fig. 4. The second resin 85 adheres as relatively more particles densely on a surface of the fabric 86.

The second resin can adhere to the fabric by the first resin or it can adhere independently to the fabric, but it is preferable that the second resin adheres to the fabric by the first resin. That is, the second resin can adhere to the fabric as integrated with the first resin or you can adhere independently to the fabric without being integrated with the First resin However, it is preferable that the second resin be integrate with the first resin as in the previous case.

If the second resin is integrated with the first resin, can adhere reliably on a surface of the cloth. Also, if the second resin itself is made to adhere directly to the fabric, a higher temperature is necessary than the temperature used to make the first resin adhere. On the contrary, if the second resin is made for adhere to the fabric by means of the first resin, the second resin can be made to adhere to the fabric at a temperature lower.

Therefore, the production efficiency of Carbon fiber reinforced substrate can be improved. In addition, the second resin is not required to be adhesive. So, the second resin can be selected from a wider range of resins, and a resin capable of showing more can be selected Highly mechanical properties.

Being integrated means that both resins do not They are separated from each other. For example, a mere dry mix consisting of particles of the first resin and particles of the second resin cannot be mentioned as an integrated state, since that the respective resins are separated from each other.

In the case where the second resin integrated with the first resin adheres, if the second resin is not considerably compatible with the first resin, the reactivity chemistry between the first resin and the second resin can be minimized So, even if the first resin and the second resin are melted and mixed for integration, increasing viscosity can be prevented to the fullest. In addition, since the range selectable resins in terms of material and form for Second resin is less limited, the selectable range can be expanded, and the mechanical properties (especially CAI) of compound obtained can be further improved advantageously. From these points of view, it is preferable that the second resin is not considerably compatible with the first resin.

In the case where the first resin and the second resin are integrated with each other, it is preferable that surfaces of the second resin particles are partially (preferably 50% or more of the total surface area, plus preferably 90% or more) covers of the first resin. If the first resin and the second resin in this state adhere to the fabric, the second resin can be made to adhere to the fabric by the first resin more reliably compared to a case where a mere dry mixture is used consisting of the first resin and the second resin (not integrated).

To integrate the first resin and the second resin, both resins can be melted and mixed to obtain a mixture in a desired way. As another method, both resins they can be mixed using a solvent capable of dissolving them, and the solvent can be removed to obtain a mixture in one way wanted. As for the work environment, a mixture is preferable cast. For a molten mixture, it can be used with discretion selective a suitable apparatus as a single extruder spindle, a double spindle extruder, a mixer Banbury, a kneader or a three-cylinder mill.

The shape of the second resin is not especially limited, and any desired form can be used, for example, a fabric such as a fabric, non-woven fabric or mattress, particles, discontinuous pieces or any combination of the above. It is preferable to select a convenient way for the objective of the compound, but in terms of homogeneity microscopic, the mechanical characteristic is more preferable than improves the effect and inhibition of water absorption, a form of particles (preferably spherical) or discontinuous pieces.

In the case where the second resin is shaped of particles, it is preferable that the average particle diameter is in the range between 1 and 500 µm, to uniformly disperse the particles on a surface of the cloth. Another average particle diameter more preferable is between 1 and 150 µm, and another interval Even more preferable is between 3 and 100 µm. If the average diameter of particle is less than 1 µm, more particles enter the free spaces between the carbon filaments of the beams of carbon fiber that make up the fabric, and the amount of particles that adhere on the surface becomes small. If the average particle diameter is more than 150 µm, the number of particles made to adhere to a predetermined weight of dispersed particles becomes small since the diameter of particle becomes large, and it can be difficult to disperse evenly. The average particle diameter refers to the D50 measured by the laser diffraction dispersion method. For The measurement, LMS-24 produced by Seishin Enterprise Co, Ltd.

It is preferable that the water absorption coefficient of the second resin at 23 ° C and 50 RH is 2.5% by weight or less. A more preferable water absorption coefficient is 1.8% by weight, and yet another more preferable water absorption coefficient is 1.5% by weight or less. An especially preferable water absorption coefficient is 1.1% by weight or less. If the water absorption coefficient is greater than 2.5% by weight, the compound obtained cannot be excellent in mechanical properties (especially CHW ). The water absorption coefficient refers to the value measured according to ASTM-D-570.

The second resin is also not especially limited as the first resin, if this is a resin capable of solve the problems of the invention. It is preferable that the main component of the second resin is an extremely resin thermoplastic resistant, and can be selected from the group of Examples listed above of the first resin. Especially, it is desirable to use at least one resin selected from the group that It consists of polyamide resins, polyimide resins, resins polyamide-imide, polyetherimide resins, resins polysulfone, polyether sulfone resins, ether resins polyphenylene, polyether ether ketone resins and resins of ketone polyether ketone. Especially at least one selected from the group of resins consisting of resins of polyamide, polyamide-imide resins, resins polyetherimide and polyether sulfone resins can easily show the effects mentioned above.

In the case where a polyamide is used As the main component of the second resin, it is preferable use a homopolyamide such as polyamide 6, polyamide 66, polyamide 12, polyamide 610, polyamide 612, dicarboxylic acid aromatic or diamine such as isophthalic acid, terephthalic acid, paraxylenediamine or metaxylenediamine, dicarboxylic acid alicyclic or diamine such as dimethylbis methane (p-aminocyclohexyl), or a copolyamide consisting in two or more of the above.

Commercially available polyamides Suitable for the second resin include the Transparent Nylon T-714E, the T-714H and the T-600 produced respectively by Toyobo Co, Ltd., Trogamid T5000 and CX7323 produced respectively by Daicelhuls Ltd., Grilamid TR55 and TR90 produced respectively by EMS-CHEMIE, SP500 (particles) produced by Toray Industries, Inc., Genestar PA-9T produced by Kuraray Co, Ltd., etc.

It is preferable that the glass transition temperature of the polyamide measured by DSC is 100 ° C or higher. More preferable that it is 125 ° C or higher, and even more preferable that it be 150 ° C or higher. The preferred polyamide has sufficient heat resistance when the compound is produced by molding, and can also increase the effects (especially CAI ) using the second resin. Meanwhile, for example, polyamide 12 shows high effects of improving CAI, even if it has a glass transition temperature lower than 100 ° C. That is, it is preferable that a polyamide having a melting point has a glass transition temperature that is in the range between 30 ° C and 280 ° C.

In the case where a resin is used thermoplastic as a second resin, if a resin is used thermosetting as an epoxy resin as the first resin for make both the first resin and the second resin fully adhere, both CAI and CHW can be increased to high levels. In addition, if a thermoplastic resin is used with a low melting point like a polyamide resin with a point of Low fusion as the first resin to make both resins fully adhere, CAI can be increased to a level especially tall.

It is preferable that the second resin contains a thermosetting resin as a subsidiary component that can be selected from the aforementioned of the listed examples of the first resin. Among them, an epoxy resin or phenol resin are preferable. If the subsidiary component covers the main component of the second resin or is at least partially (preferably fully) converted to form a polymer alloy {preferably an interpenetrating polymer network ( IPN )}, the chemical interaction with the third resin described further forward can be controlled. Accordingly, the above-mentioned effects (especially CAI) of using the second resin can be further increased. This also shows preferable effects in the improvement of the resistance of chemical substances and the heat resistance of the second resin and in the inhibition of water absorption.

These effects can be especially noticeably shown in the case where a thermoplastic resin (especially a polyamide resin) is used as the second resin. In the case where a thermosetting resin is contained as a subsidiary component (especially when IPN is formed), it may be that the second resin has no melting point or flow initiation temperature, but only the second resin is not required It melts or flows at the melting point or at the flow initiation temperature of the first resin.

The preform of the invention has at least two layers of the above-mentioned substrate carbon fiber reinforced laminate, in which the layers of the substrate reinforced with carbon fibers are fully bonded by the first resin or the second resin.

If the union prevails on the surfaces whole layers of the substrate reinforced with the fiber of carbon, it may turn out that the handling properties of the preform become poor, and the permeability of Matrix resin It is only required that the linkage be such that the substrate layers reinforced with the plural laminated fiber of carbon can be fully managed, and it is preferable that Substrate layers are partially attached to each other.

Instead of laminating the layers of a carbon fiber reinforced substrate, carbon fiber reinforced substrates in different amounts of the first resin or the second resin that adheres to the fabric can also be laminated. Especially in the case of a preform produced by the RTM process that uses one half of the male mold and one half of the female mold, or in the case of a preform used for vacuum molding, in which a cavity formed by both a half of male mold or for half of female mold and a bag material is reduced in pressure to allow resin injection that uses the pressure difference between reduced pressure and atmospheric pressure, if carbon fiber substrates in different quantities of the first resin or the second resin that adhere to the fabric are used positively, the steps of the third resin described below can be secured and controlled.

This is explained more particularly in reference to a drawing Fig. 9 is a typical vertical sectional view that shows a mode of the preform of the invention. In Fig. 9, a carbon fiber reinforced substrate 90 of the invention, in which a first resin 93 and a second resin 94 that adheres relatively more densely on the surfaces of respective fabrics 92 consisting of carbon fiber beams, is a laminate consisting of four layers. The four layers of carbon fiber reinforced substrate 90 are attached one to the another by the first resin 93 or the second resin 94, to form a preform 91. Preform 91 is a dry preform, in the which the four layers of the carbon fiber reinforced substrate 90 are integrated, and the fiber beam volume fraction is minimized due to interlaminar bonding by first resin 93 or the second resin 94. Therefore, the preform 91 is excellent in handling properties.

The compound of the invention is obtained by a impregnation method of the preform formed of a third resin used as a matrix resin different from the first resin, and subsequently solidifying the resin. The third resin impregnated in the preform solidifies (cured or polymerized). The solidification of the third resin causes the formation of compound.

This is explained more particularly in reference to a drawing Fig. 10 is a typical vertical sectional view that shows a mode of the compound of the invention. In Fig. 10, the free spaces between the layers of the fiber reinforced substrate carbon 90 laminated in preform 91 shown in Fig. 9 are impregnated with a third resin 102 which is then cured or polymerized for solidification to form a compound 101.

The third resin 102 is not especially limited as the first resin 93, if it is a resin capable of solving the problems of the invention, but a resin is preferable thermosetting in view of the ability to conform and mechanical properties. It can be selected from said group above of the examples listed above from the First resin However, unlike the first resin, in the case where injection molding is used, the third Resin must be a liquid at injection temperature.

It is preferable that the thermosetting resin as the third resin is at least one selected from the group consisting of epoxy resins, phenol resins, vinyl ester resins, unsaturated polyester resins, ester cyanate resins, bismaleimide resins and benzoxacin resins, since The problems of this invention can be easily solved. In addition, resins containing an elastomer, rubber, hardening agent, hardener accelerator, catalyst or the like can also be used. Above all, in order to achieve, for example, very high mechanical properties (especially CAI and CHW ) required for the primary or main aircraft structure elements, an epoxy resin or bismaleimide resin is preferable. An epoxy resin is especially preferable.

Since the third resin and the first resin are used respectively for different functions, it is desirable use at least partially different resins from each other. Is that is, it is preferable to use an excellent permeability resin (having a low viscosity at the injection temperature and a long gel time) and excellent mechanical properties as the third resin, and use a resin capable of improving fabric handling properties and high delivery mechanical properties like the first resin. Of course, the first resin and the third resin may contain a component common without any problem, and may be preferable as to the compatibility between both.

In the case where the third resin 102 is impregnated in preform 91 in the injection or infusion molding  described below, if the third resin has a low viscosity, the molding cycle can be reduced since the resin It can be easily impregnated. It is preferable that the viscosity in the injection temperature is 400 mPa · or less. Plus Preferably, it is 200 mPa · or less. It is preferable that the injection temperature is 100 ° C or lower, since it can be used simple equipment.

The compound can be obtained by anyone of various molding methods such as injection or molding of Infusion (TRM, RFI, RIM, vacuum molding, etc.) and molding of press, or a combination of said molding methods.

A more preferable molding method to obtain the compound is a high productivity injection molding method such as RTM . In one of the RTM methods, a resin is injected under pressurization into a cavity formed by a half of male mold and half of female mold. In this case, it is preferable that the cavity be reduced in pressure for resin injection. Another preferable molding method is a vacuum molding method. In vacuum molding, for example, a cavity formed by a half of a male mold or a half of a female mold and a bag material such as a film, in particular a nylon film, silicone rubber or the like, is It reduces in pressure, and the pressure difference between the reduced pressure and the atmospheric pressure is used to inject a resin. In this case, it is preferable to have a resin distribution means on the preform in the cavity to accelerate the resin infiltration, and to separate the medium from the compound after the completion of the molding. These particular molding methods can preferably be used in view of the molding cost.

The applications of the compound of the invention They are not especially limited. Since the compound has excellent mechanical properties (especially CAI and CHW), it shows its effects to the maximum extent, if used as an element of primary or primary structure, structure element secondary, outer element, inner element or any part of them in transport machines such as airplanes, cars and boats.

Fig. 11 is a schematic perspective view showing the primary structure elements of an airplane. In Fig. 11, an aircraft 111 consists of several structure elements such as main wings 112, a keel beam 113, fuselage 114, a vertical fin 115 and horizontal stabilizers 116. If the compound obtained by a method of impregnating a compound is used preform composed of the carbon fiber reinforced substrate of the invention with a matrix and molded resin, a structure element having excellent mechanical properties (especially CAI and CHW ) with high productivity can be produced.

Fig. 12 is a schematic perspective view showing an example of a structural element in which the compound of the invention is applied. Fig. 13 is a schematic perspective view showing another example of a structural element in which the compound of the invention is applied. In Fig. 12, a structure element 121 is composed of a film 122, a stringer123 and hardeners 124. In Fig. 13, a structure element 131 is composed of films 132, a stringer 133 and hardeners 134. In elements of conventional structure, films 122 and 132, stringers 123 and 133 and hardeners 124 and 134 are respectively molded separately, and they are joined by rivets or adhesive, to produce the structure elements to which they are intended. However, in the compound of the invention, films, stringers and hardeners can be fully molded, to greatly reduce the cost of molding elements of
structure.

The invention will be further explained with examples. In the examples, raw materials were used following.

Carbon fiber bundles A: PAN- system carbon fibers, each beam consists of 24,000 filaments, and has a fineness of 1,000 tex, a tensile strength limit of 5,830 MPa, a tensile modulus of 294 GPa and a tension fracture energy of 58 MJ / m 3.

Carbon fiber bundles B: PAN- system carbon fibers, each beam consists of 12,000 filaments, and has a fineness of 800 tex, a tensile strength limit of 4,900 MPa, a tensile modulus of 235 GPa and a stress fracture energy of 52 MJ / m3.

Carbon fiber bundles C: PAN- system carbon fibers, each beam consists of 6,006 filaments, and has a fineness of 396 tex, a resistance limit at a tensile strength of 3,530 MPa, a tensile modulus of 235 GPa and a tension fracture energy of 27 MJ / m 3.

Fiberglass beams: ECE225 1/0 1Z, each beam has a fineness of 22.5 tex and a binder type is used "DP" (produced by Nitto Bouseki Co, Ltd.).

First resin A: A resin composition obtained by hot melt kneading 60% by weight of a polyether sulfone resin (fine ground "Sumika Excel" 5003P produced by Sumitomo Chemical Co, Ltd.) and 40% by weight of a epoxy resin (AK-601 produced by Nippon Kayaku Co, Ltd.) using a twin-screw extruder, having a glass transition temperature of 75 ° C.

First resin B: An epoxy resin ("Epikote" 1004AF produced by Japan Epoxi Resin Co, Ltd.), which has a flow initiation temperature of 100 ° C.

First resin C: An epoxy resin (PT500 produced by 3M).

Second resin: Spherical particles obtained by converting 90% by weight of a polyamide resin ("Grilamide" TR55 produced by SMS-SHOWA Denko KK, which has a glass transition temperature of 162 ° C) and 10% by weight of a resin epoxy and a hardening agent in a polymer alloy ( IPN ). The average particle size (D50) measured by the laser diffraction dispersion method is 13 µm.

Third resin: An epoxy resin composition liquid obtained by adding 32 parts of weight of the following curing solution with 100 weight parts of the main solution next preheated to 70 ° C and stirring until the mixture is It made homogeneous. The viscosity at 70 ° C measured using the Model E viscometer is 250 mPa.

Main solution: 30 parts by weight "of Araldite (R) "MY 721 produced by Vantico Inc., 20 parts in Weight of "Epikote" 825 produced by Japan Epoxi Resins Co, Ltd., 20 parts by weight of AK-601 produced by Nippon Kayaku Co, Ltd., 30 parts by weight of "Epiclon (R)" HP-7200L produced by Dainippon Ink and Chemicals, Inc., and 1.4 parts by weight of N-propyl p-toluenesulfonate as a curing accelerator were respectively weighed and removed at 100 ° C, until the mixture became homogeneous.

Curing solution: 18.1 parts by weight of W "Epikure" produced by Japan Epoxi Resins Co, Ltd. as a aromatic polyamine, 7.2 parts by weight of 3,3'-diaminodiphenylsulfone produced by Mitsui Kagaku Fine Chemicals, Inc. and 7.2 parts by weight of S "Sumicure" produced by Sumitomo Chemical Co., Ltd. were respectively weighed and removed at 90 ° C, until the mixture is It made homogeneous.

Reference Example one

The first resin A was crushed by particle freezing The average particle size D50 of The particles were 124 µm.

Using carbon fiber bundles A as warp threads and fiberglass beams as auxiliary threads weft formed a unidirectional tissue A. Tissue A was a Taffeta ligament, and had a thickness of 0.3 mm, one weight per unit of 295 g / m2 carbon fiber, 2.8 warp ends / cm and 3 ends / cm of plot. The unidirectional tissue obtained A was of 3.5 mm in the width of each carbon fiber beam used as a warp thread and more than 10 in the proportion of the width with the thickness of the carbon fiber beam, and it was a flat fabric. Before knitting, each of the bundles of carbon fibers A had a width of 5.8 mm and a thickness of 0.15 mm.

The particles of the first were allowed resin A will fall naturally to cover the tissue obtained unidirectional A by a vibration network for dispersion uniform, while they were weighed using an embossing roller and a scraper In this coating layer, 100 parts of the weight of Tissue were covered by 10 parts of the first resin's weight. In addition, while the covered fabric was heated at an interval between 180 and 200 ° C using a far infrared heater, treated metal touch rollers were used to allow a release were used to pressurize the fabric, to leave to the particles of the first resin to adhere to the tissue unidirectional A, which was then cooled and mounted as a carbon fiber reinforced substrate A. In this example, the weaver step process including a weaver machine to the step of Cooling was performed on the same line continuously. He reinforced carbon fiber substrate obtained A had a thickness of 0.36 mm, an air permeability of 23.7 cm 3 / cm 2 • and a cover factor of 99%.

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Example 1

Fifty parts by weight of the first resin B and 50 parts by weight of the second resin were kneaded at 170 ° C using a mixer, and freezing of soil (freeze ground), to obtain particles consisting of both resins integrated. The average particle diameter D50 of the particles was of 38 µm. The second resin was not melted or did not flow to the flow initiation temperature of the first resin B, and both Resins were not compatible with each other.

The particles obtained were loaded electrically using a powder paint system produced "Tricomatic (R)" II by Nordson Corporation, while they were uniformly dispersed by compressed air, to be applied to unidirectional tissue A obtained as described in the Reference Example 1. In this coating layer, 100 parts tissue weights were covered by 14 parts of the weight of the particles In addition, the covered fabric was heated at an interval which is between 140 and 160 ° C, using a press roller hot, to let the particles adhere to the tissue unidirectional A, which was then cooled and taken as a substrate reinforced with carbon fibers B. In this example, the weave to the process of the steps of the coating layer, the joint and cooling were performed in discontinuously different lines. The particles were more evenly dispersed on the tissue unidirectional A than those of Reference Example 1, showing that the coating and bonding methods of Example 1 were much better than those in Reference Example 1.

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Reference Example 2

Carbon fiber A beams were used as warp threads, and fiberglass beams were covered respectively of a nylon thread with a low melting point ("Elder" produced by Toray Industries, Inc., 6 tex) for use them as auxiliary weft threads, to form a fabric unidirectional C. Tissue C was a taffeta ligament, and had a 0.26mm thickness, a weight per unit of 193 carbon fiber g / m2, 1.8 ends / cm warp and 3 ends / cm weft. He fabric C was 5.5 mm wide for each beam of carbon fibers used as a warp thread and more than 20 in proportion to the width with the thickness of the carbon fiber beam, and it was a fabric flatter than the unidirectional fabric A of the Reference Example 1. A substrate reinforced with C carbon fibers was obtained as described for Reference Example 1, but the tissue C and that 100 parts weight of tissue C were covered by 14 parts of weight of the first resin A.

The substrate obtained reinforced with fibers of carbon C had a thickness of 0.37 mm, an air permeability of 72.0 cm3 / cm2 \ cdotsec, and a cover factor of 93%

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Reference Example 3

A bidirectional fabric D was woven using carbon fiber bundles B as warp threads and threads of plot. Tissue D was a taffeta ligament, and had a thickness of 0.19 mm, a weight per unit of carbon fiber of 19.3 g / m2, 1.21 ends / cm warp, and 1.21 ends / cm warp. It was obtained a substrate reinforced with carbon fibers D such as described for Reference of example 1, but the tissue D and that 100 parts of tissue weight was covered by 5 weight parts of the first resin A. The substrate obtained reinforced with carbon fibers D had a thickness of 0.24 mm, a air permeability of 15.6 cm3 / cm2 \ cdotsec, and a 99% coverage factor.

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Example 2

The substrate reinforced with carbon fibers A and the substrate reinforced with carbon fibers B were cut respectively to have a length of 340 mm and a width of 340 mm. For each substrate, a stack architecture [-45º / 0º / + 45º / 90º] was repeated twice to form a game, and another identical game was also manufactured. Both sets were glued to each other with the layers at 90 ° C facing each other, to provide a symmetrical laminate of a cross-folded symmetrical laminate of each substrate. The laminate was placed in a plate mold and a sealant and a bag material (polyamide film) was used to seal to form a cavity. The cavity was provided with a suction port for evacuation. A vacuum pump was used to evacuate the cavity from the suction port, reduce the vacuum pressure in the cavity, and the preform mold was adjusted to 80 ° C. The laminate was maintained in this state for 1 hour and cooled to room temperature, and the suction was stopped. In this way, a quasiisotropic preform A and a quasiisotropic preform B were obtained.

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Reference Example 4

It was used the substrate fiber reinforced carbon C and the substrate fiber reinforced carbon was repeated D. architecture stack (stack architecture) as described in Example 2 three times to form a game. Another identical game was also manufactured. Both games were glued to each other to provide a cross-folded symmetrical laminate. A pressure of 150 kPa was applied to the laminate at 130 ° C using a press machine containing a preform mold for 5 minutes, and in succession with the pressure maintained as it was, the laminate was cooled to room temperature and depressurized. In this way, a quasiisotropic C preform and a quasiisotropic preform D.

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Example 3

A unidirectional preform A, a unidirectional preform B and a unidirectional preform C as described in example 2, but four layers of a stack architecture [of 0 °] for the substrate reinforced with Carbon fibers A and the substrate reinforced with carbon fibers B, and six layers of a stack architecture [of 0 °] were used for the substrate reinforced with carbon fibers C.

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Example 4

Any of the pre-quasi-isotropic preform, the quasiisotropic preform B, quasiisotropic preform C, preform Quasi-isotropic D, the unidirectional preform A, the preform unidirectional B and unidirectional preform C were placed in a mold at 80 ° C, and a resin distribution medium was placed (34- metal mesh net) on the preform. Then they used a sealer and a bag material (film of polyamide) to seal forming a cavity. The cavity was provided with a resin injection port and a suction port For the evaluation. A vacuum pump was used to evacuate the cavity through the suction port, reduce the vacuum pressure in the cavity, and the mold and preform were adjusted at 80 ° C. So, the third resin was injected, prepared preliminary and Vacuum-worn, from the resin injection port used by the atmospheric pressure, keeping it at 80 ° C. When the third resin reached the suction port for evacuation, the port of resin injection was closed to stop the injection of resin. Thereafter, while the cavity was evacuated continuously by the vacuum pump of the suction port, the third resin impregnated in the preform was cured with the temperature maintained at 180 ° C for 2 hours. In this way, they were obtained a quasiisotropic A plate, a quasiisotropic B plate, a quasiisotropic C plate, a quasiisotropic D plate, a plate unidirectional A, a unidirectional plate B and a plate unidirectional C.

The volume fraction of carbon fibers Vf in the quasiisotropic plate A it was 54% in vol; the fraction of volume of carbon fibers Vf in the quasiisotropic plate B, 56% in vol; the volume fraction of carbon fibers Vf on the plate Quasiisotropic C, 55% in vol; and fiber volume fraction carbon Vf in the quasiisotropic D plate, 53% in vol.

The volume fraction of carbon fibers Vf in the unidirectional plate A it was 55% in vol; the fraction of volume of carbon fibers Vf in the unidirectional plate B, 56% in vol; and the volume fraction of carbon fibers Vf on the plate unidirectional C, 56% in vol.

These compounds were quite free of free and empty spaces, and it was shown that a good molded

From each of the quasiisotropic A plates, the quasiisotropic B plate, the quasiisotropic C plate and the quasiisotropic D plate obtained, a 152 mm long by 102 mm wide plate was cut as a coupon. A weight of 5.44 kilograms (12 pounds) was dropped in the center of the coupon, to give a fall weight impact of 6.67 kJ / m (1500 in · cd / in), and the compression force was measured after of impact ( CAI ).

In addition, from each of the unidirectional plates A, the unidirectional plate B and the unidirectional plate C obtained, a coupon according to SACMA SRM 1R-94 was obtained. The coupon was submerged at 70 ° C of water for 14 days (hot wet conditioning), and the compressive strength of 0 ° of the coupon was immediately measured at the evaluated temperature (82 ° C) ( CHW ). In addition, the 0 ° compression force of the unidirectional plate A coupon or the unidirectional plate C at room temperature (CS), not subjected to wet hot conditioning was also measured.

In addition, it was obtained from each of the plate unidirectional A, unidirectional plate B and plate unidirectional C, a coupon according to SACMA SRM 4R-94. The tensile force of 0º of the coupon in the room temperature (TS) was measured.

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Comparative Example one

The unidirectional woven fabric A produced as has been described in Reference Example 1, but the first resin A did not cause adhesion, it was used as a substrate reinforced with carbon fibers E.

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Comparative Example 2

The carbon fiber C beams were used as warp threads and fiberglass beams were used as auxiliary weft threads, to form a unidirectional tissue F. The tissue F was a taffeta ligament, and It had a thickness of 0.2 mm, a weight per unit of carbon fiber of 193 g / m2, 4.87 ends / cm warp and 3 ends / cm of plot. A substrate reinforced with carbon fibers F was obtained as described for Reference Example 1, but 100 weight parts of tissue F were covered with 5 weight parts of the first resin C.

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Comparative Example 3

They were obtained a quasiisotropic preform E, a quasiisotropic preform F, a unidirectional preform E and a unidirectional preform F respectively, as described for process the substrate reinforced with carbon fibers A and the substrate reinforced with C carbon fibers, but were used the substrate reinforced with carbon fibers E and the substrate reinforced with carbon fibers F.

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Comparative Example 4

They were molded respectively a plate quasiisotropic E, a quasiisotropic plate F, a unidirectional plate  E and a unidirectional plate F as described in example 4, for testing, but the quasiisotropic preform E was used, quasiisotropic preform F, unidirectional preform E and preform unidirectional F. The volume fraction of carbon fibers Vf in the quasiisotropic E plate was 59% in Vol, and the fraction of volume of carbon fibers Vf in the quasiisotropic F plate, 56% in vol. The volume fraction of carbon fibers Vf on the plate unidirectional was 60% in vol, and the volume fraction of Vf carbon fibers in the unidirectional plate F, 56% in vol.

The results of the above mentioned are shown in table 1.

TABLE 1

one

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TABLE 1 (continuation)

2

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As you can see in table 1, the substrates Carbon fiber reinforced A, B, C and D were easier to handle that the substrates produced using prepreg, due to The first resin that adheres to each tissue. They were excellent at handling properties such as stiffness, shape stability of the fabric in terms of slipping and misalignment, portability and ability to adapt. When they were trained in preforms, showed excellent stickiness, and substrates reinforced with carbon fiber laminates obtained from them They were not delaminated. Thus, strong preforms could be obtained bulky

On the other hand, the fiber reinforced substrate of carbon E that lacked the first resin was poor in handling properties, and since it was not sticky, the layers respective were delaminated, not allowing to obtain a bulky preform.

In view of the mechanical properties, the carbon fiber reinforced substrates A, B, C and D according to the invention were markedly higher in CAI , and not as low in CHW or TS as the carbon fiber reinforced substrate E. On the other hand, the substrate reinforced with carbon fibers F not according to the invention was very poor especially in CAI, which is unsuitable for uses as structural elements that require high mechanical properties, even if it contained the first resin.

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Industrial applicability

The invention can provide a compound good in matrix resin permeability and excellent in mechanical properties such as compression force after impact and compression force after conditioning Hot wet with high productivity. In addition, the invention can provide an excellent carbon fiber reinforced substrate in rigidity, in form stability, in capacity to adapt and stickiness in lamination, a preform formed by rolling layers of the substrate, and a compound obtained by impregnating the preform with a matrix resin.

The compound thus obtained is convenient as any of several elements as a structure element, internal element and external element in transport machines such as airplanes, cars and boats and other large areas. Is especially suitable as a structure element of a airplane.

Claims (22)

1. Substrate reinforced with carbon fibers (21, 41, 81) comprising a fabric composed of fiber bundles of carbon (22, 42, 52, 62, 82) and a first resin (24, 74, 84) that adheres to said fabric, in which said fiber bundles of carbon respectively comprise numerous carbon filaments continuous, the tensile modulus of said fiber bundles of Carbon is 210 GPa or more, the fracture tension energy of said carbon fiber bundles is 40 MJ / m3 or more, and the amount of said first resin that adheres to said tissue whose value is in the range between 1 and 20 parts by weight per 100 parts by weight of said fabric, in which the amount of the second highest resin (75, 85) at the melting point or the flow initiation temperature than said first resin (84) and adhering to said tissue is in the interval between 1 and 10 parts by weight per 100 parts by weight of said fabric. 2. Substrate reinforced with carbon fibers according to claim 1, wherein the amount of said first resin (74, 84) is in the range between 1 and 10 parts by weight per 100 parts by weight of said fabric. 3. Substrate reinforced with carbon fibers according to claim 1, wherein the first resin (74, 84) that adheres to said tissue adheres in a way relatively denser on a surface of said tissue (76, 86) that inside said bundles of carbon fibers. 4. Substrate reinforced with carbon fibers according to claim 1, wherein said tensile module of the said carbon fiber bundles is in the range between more than 280 GPa and less than 500 GPa, and the voltage energy of fracture of said carbon fiber beams is 53 of MJ / m 3 or more. 5. Substrate reinforced with carbon fibers according to claim 1, wherein said tissue (76, 86) is a unidirectional tissue, bidirectional tissue or sheet unidirectional, the specific weight of the carbon fiber of the carbon fiber substrate is in the interval between 50 g / m2 and 500 g / m2, and the thickness of the fiber substrate Carbon is in the range between 0.1 mm and 0.8 mm. 6. Carbon fiber reinforced substrate according to claim 1, wherein said tissue (86) is a unidirectional tissue or a unidirectional sheet, and permeability to the air of the substrate in carbon fiber is comprised in a range from 10 cm3 / cm2 .sec to 200 cm3 / cm2 .sec. 7. Carbon fiber reinforced substrate according to claim 1, wherein said first resin is cover on a surface of said fabric (86), and the diameters of the covered parts are 1 mm or less. 8. Carbon fiber reinforced substrate according to claim 1, wherein said first resin (74, 84) adheres discontinuously on a surface of said fabric (86). 9. Carbon fiber reinforced substrate according to claim 1, wherein said first resin (84) is adheres on a surface of said fabric (86), and the thickness middle of the first resin (84) adhering on the surface it is located in the range between 5 µm to 250 µm. 10. Carbon fiber reinforced substrate according to claim 1, wherein the melting temperature or the flow start temperature of said first resin (84) is located in the range between 50 ° C to 150 ° C. 11. Carbon fiber reinforced substrate according to claim 1, wherein the main component of said first resin (84) is a thermosetting resin. 12. Carbon fiber reinforced substrate according to claim 1, wherein the main component of said first resin (84) is a thermoplastic resin. 13. Carbon fiber reinforced substrate according to claim 12, wherein the amount of said resin thermoplastic is in the range between 70% to 100% by weight based on the weight of said first resin (84). 14. Carbon fiber reinforced substrate according to claim 1, wherein the main component of said first resin (84) is at least one resin chosen from the group consisting of epoxy resins, polyamide resins, polyetherimide resins, polyphenylene ether resins, polyethersulfone resins and phenoxy resins. 15. Carbon fiber reinforced substrate according to claim 1, wherein the amount of a second resin (85) that is not molten or flows at the melting temperature or at the flow start temperature of said first resin (84) and that adheres to said tissue is in the range between 1 to 10 parts by weight for 100 parts by weight of said fabric. 16. Carbon fiber reinforced substrate according to claim 1, wherein said second resin (85) is adheres on a surface of said fabric by means of said first resin (84). 17. Carbon fiber reinforced substrate according to any one of claims 1 or 15 or 16, in the which said second resin (85) is in the form of particles that they have an average particle diameter of 1 µm to 500 µm. 18. Carbon fiber reinforced substrate according to any one of claims 1, or 15 to 17, in the which the main component of said second resin (85) is a thermoplastic resin 19. Carbon fiber reinforced substrate according to any one of claims 5 to 18, wherein the main component of said second resin (85) is at least a thermoplastic resin that has a transition temperature glass from 30ºC to 280ºC chosen in the group constituted by the polyamide resins, resins of polyamide-imide, polyetherimide resins and polyethersulfone resins. 20. Preform comprising a laminate that comprises at least two or more than two layers of the reinforced substrate  with carbon fibers (90) according to any one of the claims 1 to 19, wherein the substrate layers reinforced with carbon fibers, they are fully attached to the others by means of said first resin (84) or said second resin (85). 21. Compound comprising at least the preform (91) according to claim 20 and the third resin (102), in which said preform (91) is impregnated with said third resin (102) which is different from said first resin (93) 22. Compound according to claim 21, which is used as an element of primary structure, as an element of secondary structure, as an external element, as an element interior and / or as parts that form these elements in an airplane, a motor vehicle or a boat.