CN102057087A

CN102057087A - Nonwoven fabric, felt and manufacturing method thereof

Info

Publication number: CN102057087A
Application number: CN2009801220453A
Authority: CN
Inventors: 樱井博志; 原宽; 佐野弘树; 尾上周平; 中本幸夫; 大泽好雄; 高木正一
Original assignee: Teijin Ltd
Current assignee: Teijin Ltd
Priority date: 2008-06-12
Filing date: 2009-02-25
Publication date: 2011-05-11
Also published as: EP2287374A4; KR20110036531A; JPWO2009150874A1; EP2287374A1; TW201009146A; WO2009150874A1

Abstract

The objective of the present invention is to provide a nonwoven fabric containing pitch-based carbon fibers having improved tensile elongation, which is a problem for carbon fibers derived from mesophase pitch, and high elongation and elasticity, which cannot be provided with conventional technology. Provided is a nonwoven fabric containing pitch-based carbon fibers, wherein for the pitch-based carbon fibers, (i) the average fiber diameter (D1) as observed with an optical microscope is greater than 2 [mu]m and no more than 20 [mu]m, (ii) the percentage of fiber diameter dispersion (S1) with respect to the average fiber size (D1) as observed with an optical microscope is 3-20%, (iii) the tensile elasticity is in the range of 80-300 GPa, and (iv) the tensile elongation is in the range of 1.4-2.5%. Also provided are a felt made of said nonwoven fabric and a manufacturing method thereof.

Description

Bondedfibre fabric, felt and their manufacture method

Technical field

The present invention relates to contain the bondedfibre fabric of pitch-based carbon fiber, felt therefrom, heat-insulating material and their manufacture method with high elongation rate and spring rate.More specifically, relate to that to contain with the mesophase pitch be raw material, under given conditions the felt and the heat-insulating material of the bondedfibre fabric of pitch-based carbon fiber, durability therefrom, oxidative resistance excellence through not melting, being fired into.

Background technology

Be intensity and the spring rate that the carbon fiber of raw material has balance with the polyacrylonitrile, be widely used as the structural elements of industrial robot arm or airborne vehicle.For carbon fiber is realized reducing cost the more expansion of extensive use with member etc. as automobile.But, be that the initiation material of the carbon fiber of raw material is a synthetic resin with the polyacrylonitrile, so it is limited to reduce cost.

As carbon fiber cheaply, it is that pitch is the pitch-based carbon fiber of raw material that the residue with oil or coal is arranged.Pitch-based carbon fiber can roughly be divided into the isotropic pitch to be the carbon fiber of raw material and to be the carbon fiber of raw material with the mesophase pitch.

Be that the pitch-based carbon fiber of raw material has patent documentation 1 described percentage elongation for example to surpass the carbon fiber of 2% high elongation rate with the isotropic pitch.But, on the other hand, the shortcoming that the graphite voltinism is low, can't obtain the carbon fiber of high elasticity rate is arranged.On the other hand, the carbon fiber that with the mesophase pitch is raw material can easily be realized the high elasticity rate because of its excellent graphite voltinism.Yet though the growth of the graphite crystallization due to burning till by high temperature can realize the high elasticity rateization, percentage elongation reduces, the shortcoming that the result has intensity to reduce.Therefore, make the unusual difficulty of pitch-based carbon fiber with high elongation rate and high elasticity rate.

As the means that are used to address the above problem, the scheme with the material asphalt modification is proposed.For example propose in the patent documentation 2 to make the condensation polycyclic hydrocarbon in the presence of hydrogen fluoride and the boron trifluoride after 100～400 ℃ of polymerizations obtain pitch that optical anisotropy contains quantity not sufficient 5%, and then carry out under 250～450 ℃ that thermal polymerization obtains, hydrogen with respect to the atomic ratio of carbon be 0.5～0.7, all in the aromatic series carbon orientation carbon amount below 50%, the anisotropy spheroid of 5～150 μ m is 5～60%, the raw material of the insoluble composition of pyridine below 25 weight %.But, because this method uses strong acid such as hydrogen fluoride and boron trifluoride as catalyst, so exist the processing that needs to use special installation and react the spent acid that extracts the back to expend problems such as huge fund.

In addition, patent documentation 3 proposes to make crosslinkedization agent and mesophase pitch reaction, the reactant that obtains is used as the manufacture method of the carbon fiber of raw material.But, problems such as cost up are also arranged because use crosslinkedization agent in this method.

As the additive method that the intensity that makes pitch-based carbon fiber improves, in patent documentation 4, disclose at oxygen and iodine is included in the pitch fibers in the presence of not, then the manufacture method of the pitch-based carbon fiber of under inert atmosphere, heat-treating.But this method has the shortcomings such as remarkable reduction of the life-span that iodine breaks away from, the result makes stove that are adsorbed on the pitch in carbonation process.

Patent documentation 5 has proposed and will not melt by the carbon fiber precursor that spinning obtains, in inert atmosphere in being that fusion-free fibre applies tension force to the pitch that generates below 700 ℃, implement heat treatment down in stretching, in inert atmosphere, fusion-free fibre is not carried out carbonization and graphitizing method in having under the stretching then.Yet,, for example exist and can't adopt so that the carbon fiber precursor of making by meltblown becomes the problem of non-woven fabric-shaped though this method is possible at carbon fiber precursor during for long fiber.

Introduced at the NO that contains 0.1～40 capacity % in the patent documentation 6 ₂And the H of 4～40 capacity % ₂In 100～400 ℃ temperature range, implement melt processed not under the oxidisability atmosphere of O, improved the manufacture method of the carbon fiber of intensity.But this method is as described in the embodiment, the result that flexible rate reduces.

As mentioned above, it is very difficult making the pitch-based carbon fiber with high elongation rate and high elasticity rate.

(patent documentation 1) Japanese kokai publication hei 2-169727 communique

(patent documentation 2) Japanese kokai publication hei 9-279154 communique

(patent documentation 3) Japanese kokai publication hei 1-207420 communique

(patent documentation 4) Japanese kokai publication hei 8-27628 communique

(patent documentation 5) Japanese kokai publication sho 62-69826 communique

(patent documentation 6) Japanese kokai publication hei 2-6618 communique

Summary of the invention

As mentioned above, the carbon fiber that with the mesophase pitch is raw material has excellent spring rate, on the other hand, compares with the carbon fiber that with the isotropic pitch is raw material, exist tensile elongation low, for example launch the problem of difficulty as the purposes of the structural elements of industrial robot arm or airborne vehicle.

Therefore, the object of the present invention is to provide to contain and make the bondedfibre fabric that improves, has the pitch-based carbon fiber of the high elongation rate that do not have at present and high elasticity rate as tensile elongation from the shortcoming of the carbon fiber of mesophase pitch.And then, the object of the present invention is to provide the bondedfibre fabric that contains the pitch-based carbon fiber with high elongation rate and spring rate is implemented felt and the heat-insulating material therefrom that the acupuncture processing obtains.

Discoveries such as the inventor, in the not melt processed in the manufacturing process of carbon fiber that with the mesophase pitch is raw material, making the oxygen additional amount is the fusion-free fibre of 8～15 weight %, 800～1, burn till under 800 ℃, can obtain thus containing and improve tensile elongation, have the high elongation rate that does not have at present and had the bondedfibre fabric of the pitch-based carbon fiber of high elasticity rate, thereby finish the present invention.

That is, the present invention comprises following invention.

1, bondedfibre fabric, it is the bondedfibre fabric that comprises pitch-based carbon fiber, it is characterized in that pitch-based carbon fiber

(i) the average fiber footpath (D1) with the optics microscopic is greater than 2 μ m and below the 20 μ m,

(ii) directly disperseing 100 fens rates of (S1) with respect to the fiber with the average fiber of optics microscopic footpath (D1) is 3～20%,

(iii) tensile elasticity rate is 80～300GPa, and

(iv) tensile elongation is 1.4～2.5%.

2, preceding paragraph 1 described bondedfibre fabric, wherein, the tensile elasticity rate of pitch-based carbon fiber is 100～300GPa, tensile elongation is 1.5～2.4%.

3, preceding paragraph 1 described bondedfibre fabric, wherein, the average fiber footpath (D1) with the optics microscopic of pitch-based carbon fiber is greater than 10 μ m and below the 20 μ m.

4, preceding paragraph 1 described bondedfibre fabric, wherein, TENSILE STRENGTH is more than the 10N/5cm sheet.

5, the manufacture method of bondedfibre fabric comprises following each operation:

(1) with the mesophase pitch spinning, make the precursor net that comprises carbon fiber precursor,

(2) the precursor net is not melted under the oxidizing gas atmosphere, make comprise the oxygen additional amount be 8～15 weight % carbon fiber do not melt net, and

(3) will not melt net, burn till under 800 ℃ 800～1.

6, preceding paragraph 5 described manufacture methods wherein, are carried out spinning with meltblown.

7, preceding paragraph 5 described manufacture methods, wherein, the average fiber length of the carbon fiber precursor of precursor net is 4～25cm.

8, preceding paragraph 5 described manufacture methods, wherein, the oxygen additional amount that does not melt the carbon fiber of net is 9～12 weight %.

9, preceding paragraph 5 described manufacture methods, wherein, the fibre length conservation rate (%) of following formula (1) expression before and after burning till is more than 90%.

Fibre length conservation rate=100 * L ¹/ L ⁰(1)

L ⁰: the fibre length before burning till

L ¹: the fibre length after burning till

10, felt obtains by preceding paragraph 1 described bondedfibre fabric being carried out the acupuncture processing.

11, preceding paragraph 10 described felts, wherein, the interlaminar strength of thickness direction is more than the 0.25N/5cm sheet.

12, preceding paragraph 10 described felts, wherein, the average fiber of carbon fiber directly is that weight per unit area is 250～1,000g/m greater than 10 μ m and below the 20 μ m ²

13, graphitization felt, be by further 2,000～3, preceding paragraph 10 described felts are heat-treated under 500 ℃ and obtain.

14, the manufacture method of felt comprises following each operation:

(2) the precursor net is not melted under the oxidizing gas atmosphere, make comprise the oxygen additional amount be 8～15 weight % carbon fiber do not melt net,

(3) will not melt net, burn till under 800 ℃, make bondedfibre fabric 800～1,

And (4) carry out acupuncture with bondedfibre fabric.

15, preceding paragraph 14 described manufacture methods wherein, are that the above pin of 0.15mm is with 15～100 times/cm with bondedfibre fabric with hangnail (the バ one Block) degree of depth ²Acupuncture number (パ Application チ number) carry out acupuncture.

16, complex, with resin impregnated in preceding paragraph 10 described felts and obtain.

17, complex, with resin impregnated in preceding paragraph 13 described graphitization felts and obtain.

18, heat-insulating material, be complex with preceding paragraph 16 500～2, heat-treat under 200 ℃ and obtain.

19, the manufacture method of heat-insulating material comprises following each operation:

(1) with resin impregnated in preceding paragraph 10 described felts and make complex,

(2) with complex 500～2, heat-treat under 200 ℃.

Description of drawings

Fig. 1 is the ideograph of the hangnail portion of pin.

Fig. 2 is the ideograph of pin.

Symbol description

The 1 hangnail degree of depth

Curved height on 2

3 felts

4 pins

5 base plates

6 hangnails (1st hangnail) the shortest with front end distance

The 7 pin degree of depth

8 in abutting connection with hangnail at interval

The specific embodiment

[bondedfibre fabric]

The present invention is the bondedfibre fabric that comprises pitch-based carbon fiber.The pitch-based carbon fiber that constitutes bondedfibre fabric is characterised in that:

(iii) tensile elasticity rate is 80～300GPa, and

(iv) tensile elongation is 1.4～2.5%.

(carbon fiber: tensile elasticity rate and tensile elongation)

Carbon fiber makes the mechanical property marked change because of its firing temperature.So tensile elasticity rate and tensile elongation are because of the thermal history marked change in the manufacture process of carbon fiber.The carbon fiber that for example with the isotropic pitch is raw material can fully realize surpassing 1.4% percentage elongation in the wide temperature zone from low temperature to high temperature.But its spring rate is difficult to surpass 50GPa.On the other hand, the carbon fiber that with the mesophase pitch is raw material is by making firing temperature more than 800 ℃, and spring rate can surpass 80GPa.But percentage elongation became and is lower than 1.4% when employing had manufacture method now.In addition, during 800 ℃ of firing temperature less thaies, can't realize the spring rate of 80GPa.Adopting prior art to be difficult to obtain tensile elasticity rate thus is 80～300GPa and the pitch-based carbon fiber of tensile elongation in 1.4～2.5% scope.

The invention is characterized in, making the oxygen additional amount in the not melt processed in the manufacturing process of pitch-based carbon fiber that with the mesophase pitch is raw material is the fusion-free fibre of 8～15 weight %, with fusion-free fibre 800～1, burn till under 800 ℃, manufacturing has the high tensile elongation that does not have at present, the pitch-based carbon fiber with high elasticity rate thus.

The tensile elasticity rate of the pitch-based carbon fiber of formation bondedfibre fabric of the present invention is 80～300GPa, be preferably 100～300GPa, 180～300GPa more preferably.The tensile elongation of the pitch-based carbon fiber of formation bondedfibre fabric of the present invention is 1.4～2.5%, is preferably 1.5～2.4%, more preferably 1.6～2.3%.Therefore, the preferred tensile elasticity rate of the pitch-based carbon fiber of formation bondedfibre fabric of the present invention is that 100～300GPa, tensile elongation are 1.5～2.4%, and more preferably tensile elasticity rate is that 180～300GPa, tensile elongation are 1.6～2.3%.

(carbon fiber: average fiber footpath (D1) and fiber directly disperse (S1))

The pitch-based carbon fiber of formation bondedfibre fabric of the present invention is owing to make tensile elasticity rate and tensile elongation in above-mentioned scope, so 100 fens rates that have specific average fiber footpath (D1) and directly disperse (S1) with respect to the fiber in average fiber footpath (D1).

The average fiber footpath (D1) with the optics microscopic of the pitch-based carbon fiber of formation bondedfibre fabric of the present invention is greater than 2 μ m and below the 20 μ m.If average fiber directly is greater than 10 μ m and below the 20 μ m, then become the fiber of oxidative resistance or excellent strength, and preferred.More preferably greater than 10 μ m and below the 15 μ m.

It is 3～20% that the fiber with respect to the average fiber of optics microscopic footpath (D1) of the pitch-based carbon fiber of formation bondedfibre fabric of the present invention directly disperses 100 fens rates of (S1), be preferably 5～15%, more preferably 8～13%.

(TENSILE STRENGTH of bondedfibre fabric)

The TENSILE STRENGTH of bondedfibre fabric of the present invention is preferably more than the 10N/5cm sheet, more preferably more than the 12N/5cm sheet.If the TENSILE STRENGTH of fabric is more than the 10N/5cm sheet, then handle the TENSILE STRENGTH raising of the felt that obtains by shapings such as acupunctures.This felt can be used in purposes such as heat-insulating material, acoustic material.The TENSILE STRENGTH of bondedfibre fabric is with the TENSILON determinator value that the sample of wide 5cm * long 20cm obtains that stretches at length direction.

[manufacture method of bondedfibre fabric]

Bondedfibre fabric of the present invention can be made by following each operation:

(1) with the mesophase pitch spinning, make the precursor net (operation (1)) that comprises carbon fiber precursor,

(2) the precursor net is not melted under the oxidizing gas atmosphere, make comprise the oxygen additional amount be 8～15 weight % carbon fiber do not melt net (operation (2)), and

(3) will not melt net, burn till (operation (3)) under 800 ℃ 800～1.

By this method, can obtain comprising the bondedfibre fabric of the present invention of pitch-based carbon fiber with high elongation rate and high elasticity rate.

Each operation of the present invention below is described in turn.

(operation (1): spinning)

As the raw material of pitch-based carbon fiber, preferred mesophase pitch.The middle one after another of mesophase pitch is preferably more than 90%, more preferably more than 95%, more preferably more than 99%.Need to prove that the middle one after another of mesophase pitch can be confirmed by the pitch that is in molten condition with polarized light microscope observing.As the raw material of mesophase pitch, for example can enumerate naphthalene or phenanthrene and so on condensation polycyclic hydrocarbon compound, oil is pitch or carbobitumen and so on condensed heterocyclic compounds etc.Wherein, preferred naphthalene or phenanthrene and so on condensation polycyclic hydrocarbon compound.

And then the softening point of material asphalt is preferably more than 230 ℃ below 340 ℃.The not melt processed of carbon fiber precursor must be handled under the temperature lower than softening point.So, if softening point is lower than 230 ℃, then need under the low temperature of not enough at least softening point, carry out not melt processed, the result does not melt to be needed for a long time, so not preferred.On the other hand, if softening point surpasses 340 ℃, then pyrolysis takes place in pitch easily, and the gas that occurs producing makes problems such as occurring bubble in the system, so not preferred.The more preferably scope of softening point is more than 250 ℃ below 320 ℃, more preferably more than 260 ℃ below 310 ℃.Need to prove that the softening point of material asphalt can be obtained by the METTLER method.Material asphalt can use appropriate combination more than two kinds.The middle one after another of the material asphalt of preferred compositions is at least more than 90%, and softening point is more than 230 ℃ below 340 ℃.

Operation (1) is with the mesophase pitch spinning, makes the operation of the precursor net that comprises carbon fiber precursor.Spinning process is not particularly limited, and can adopt so-called melt spinning method.Particularly, can enumerate the common spin-drawing method that the mesophase pitch of will discharge from tube head batches with winder,, utilize centrifugal force to batch the centrifugal spinning etc. of mesophase pitch the meltblown of hot blast as the atomizing source.Wherein consider, preferably use meltblown from the reasons such as form, productivity ratio height of control carbon fiber precursor.

Below put down in writing meltblown.In the present invention, the shape of the spinning-nozzle of formation carbon fiber precursor can be Any shape.Usually use the shape of round type, the nozzle that in good time uses special-shaped shape such as ellipse is also without any problem.Be preferably 2～20 scope as the length (LN) of nozzle bore and the ratio (LN/DN) of aperture (DN).If LN/DN surpasses 20, then, show radial structure at fibre profile to giving strong shearing force by the mesophase pitch of nozzle.The performance of radial structure makes fibre profile crackle occur sometimes in sintering process, causes that sometimes mechanical property reduces, so not preferred.On the other hand, during LN/DN less than 2, can't apply shearing to material asphalt, the result becomes the low carbon fiber precursor of orientation.So, also can't produce excellent mechanical property even burn till, not preferred.

In order to realize excellent mechanical property, need apply the shearing of appropriateness to middle asphalt phase.So the ratio (LN/DN) of the length of nozzle bore (LN) and aperture (DN) is preferably 2～20 scope, and then is preferably 3～12 scope especially.Shear rate during by nozzle of the temperature of the nozzle during to spinning, mesophase pitch, the air quantity that blows from nozzle, temperature of wind etc. also are not particularly limited, so long as can keep stable spinning state condition, be that the melt viscosity at the nozzle bore place of mesophase pitch gets final product in the scope of 1～100Pas.

During the melt viscosity of the mesophase pitch by nozzle is not enough 1Pas, melt viscosity is low excessively, can't keep filament shape, and is not preferred.On the other hand, when the melt viscosity of mesophase pitch surpasses 100Pas, middle asphalt phase is applied strong shearing force, form radial structure at fibre profile, so not preferred.In order to make the shearing force that middle asphalt phase is applied in suitable scope, and keep fiber shape, need the melt viscosity of control by the mesophase pitch of nozzle.So the melt viscosity of preferred mesophase pitch and then is preferably in the scope of 3～30Pas in the scope of 1～100Pas, more preferably in the scope of 5～25Pas.

The carbon fiber that constitutes bondedfibre fabric among the present invention is characterised in that average fiber footpath (D1) is greater than 2 μ m and below the 20 μ m.The control in the average fiber footpath of carbon fiber can recently be adjusted from the discharge rate of nozzle or by changing drawing-off by the aperture or the change material asphalt that change nozzle.The change of draw ratio can be by blowing the per minute 100～20 that is heated to 100～400 ℃ near refinement point, the gas of the linear velocity of 000m is realized.The gas that blows is not particularly limited, and considers to be preferably air from cost performance and security aspect.

Carbon fiber precursor become be trapped in wire netting etc. with on the precursor net.Can be adjusted to weight per unit area arbitrarily this moment by the band transfer rate, also can make it stacked by juxtaposition methods such as (Network ロスラ Star プ) as required.Consider productivity ratio and process stability, the weight per unit area of precursor net is preferably 150～1,000g/m ²

The average fiber length of carbon fiber precursor is preferably the scope of 4～25cm.During the average fiber length of carbon fiber precursor is not enough 4cm, become trapped in wire netting etc. with on the intensity of precursor net significantly reduce, be difficult to make it stacked by methods such as juxtapositions, cause that productivity ratio reduces, so not preferred.On the other hand, when surpassing 25cm, the precursor net quantity that becomes is very many, is difficult to remove the reaction heat that the reaction because of precursor net and oxidizing gas produces in not the melting of next operation, and is according to circumstances and existence such as causes burning at problem, not preferred.The more preferably scope of the average fiber length of carbon fiber precursor is 5～10cm.

The average fiber of the carbon fiber precursor that spinning obtains directly is preferably more than 2 μ m and below the 20 μ m.The average fiber footpath in the operation of fusion-free fibre that by carbon fiber precursor manufacturing oxygen additional amount is 8～15 weight %, is difficult to control the oxygen additional amount when 2 μ m are following.So, not only can't stablize quality, and according to circumstances lose, so not preferred because of infusible reaction heat causes carbon fiber precursor to burn by the carbon fiber that is fired into.On the other hand, when average fiber directly surpasses 20 μ m, in the operation of fusion-free fibre that by carbon fiber precursor manufacturing oxygen additional amount is 8～15 weight %, in order to make fusion-free fibre a lot of times of needs of oxygen additional amount above 8 weight %, cause productivity ratio significantly to reduce, so not preferred.The more preferably scope in the average fiber footpath of carbon fiber precursor is greater than 10 μ m and below the 20 μ m, more preferably greater than 10 μ m and below the 15 μ m.

Directly disperseing 100 fens rates of (S1) with respect to the fiber in the average fiber of carbon fiber precursor footpath is 3～20% scope.The CV value is the uneven index in fiber footpath, and more little, process stability is high more, means that inequality is more little.But, when wanting to make the CV value in fact, need do one's utmost to control the inequality of the amount of resin of discharging from each capillary of spinning tube head less than 3% product.So, reducing the spinning tube head, the result causes capillary number and reduces the remarkable productivity ratio reduction that causes.On the other hand, the CV value in the operation of fusion-free fibre that by carbon fiber precursor manufacturing oxygen additional amount is 7～15 weight %, was difficult to control the oxygen additional amount greater than 20% o'clock, and the result can't stablize the quality by the pitch-based carbon fiber that is fired into, so not preferred.The more preferably scope of CV value is 8～15%.

(operation (2): do not melt)

Operation (2) is that the precursor net is not melted under the oxidizing gas atmosphere, makes to comprise the operation that does not melt net that the oxygen additional amount is the carbon fiber of 8～15 weight %.

The invention is characterized in that the oxygen additional amount of the fusion-free fibre that obtains by operation (2) is 8～15 weight %.During the oxygen additional amount less than 8 weight % of fusion-free fibre, the tensile elongation of the carbon fiber that is fired in operation (3) can't surpass 1.4%.On the other hand, when the oxygen additional amount surpassed 15 weight %, causing with the mesophase pitch was that the promptly excellent spring rate of feature of pitch-based carbon fiber of raw material significantly reduces, not preferred.The scope that is used to obtain the preferred oxygen additional amount of excellent tensile elongation and spring rate is preferably 8～13 weight %, and then is preferably 9～12 weight % especially.

Not being melted under the oxidizing gas atmosphere of carbon fiber precursor implemented, and maybe can obtain the gas and the Air mixing gas of electronics but the alleged oxidizing gas of the present invention is meant air from carbon fiber precursor.As the gas that can from carbon fiber precursor, obtain electronics, can enumerate ozone, iodine, bromine, oxygen etc.But, if consider security, convenience, cost performance, then particularly preferably in implementing not melting of carbon fiber precursor in the air.

Not melting of carbon fiber precursor can be by batch processing, in handling continuously any handled, if consider productivity ratio, then preferably handles continuously.Infusible temperature is preferably 150～350 ℃, more preferably 160～340 ℃.In the batch processing, programming rate preferably adopts 1～10 ℃/minute.Consider productivity ratio and process stability, the more preferably scope of programming rate is 3～9 ℃/minute.When handling continuously,, can realize programming rate by making it in turn by being set at a plurality of reative cells of arbitrary temp.When making carbon fiber precursor, can use and transmit conveyer etc. in turn by a plurality of reative cell.The oxygen additional amount of fusion-free fibre depends on temperature and interior holdup time of stove in the stove to a great extent.In handling continuously, preferably transmit the speed of conveyer and the temperature of each reative cell by control, control the holdup time of each reative cell, the oxygen additional amount that makes pitch system not melt silk is 8～15 weight %.As the speed that transmits conveyer, also depend on the quantity and the size of reative cell, be preferably 0.1～1.5m/ minute.

(operation (3): burn till)

Operation (3) is not melt net 800～1, is fired into the operation of bondedfibre fabric under 800 ℃.

Do not melt net in a vacuum or use to burn till in the non-oxidizable atmosphere of inert gases such as nitrogen, argon, krypton and become bondedfibre fabric.Be considered to this aspect, burn till and handle preferably in normal pressure and the processing under the nitrogen atmosphere.In addition, can if consider productivity ratio, then be preferably continuous processing by any processing in batch processing, the continuous processing.

The oxygen additional amount of the fusion-free fibre by making operation (2) in the inventive method is 8～15 weight %, and can make the fibre length conservation rate (%) of following formula (I) expression in firing process is more than 90%.

Fibre length conservation rate=100 * L ¹/ L ⁰(I)

L ⁰: the fibre length before burning till

L ¹: the fibre length after burning till

The more preferably scope of fibre length conservation rate is more than 95%.If the fibre length conservation rate surpasses 90%, then the reason that the tensile elongation of pitch-based carbon fiber is higher than existing product is not still understood.The carbonization of present known mesophase pitch is via liquid phase.Infer that reason may be in the methods of the invention, the oxygen than prior art high concentration is attached on the carbon fiber precursor, make fusion-free fibre,, become the solid phase carbonization by the liquid phase carbonization so that carbon fiber precursor carries out oxygen is crosslinked.

[staple fibre]

In order to make pitch-based carbon fiber is desirable fibre length, can implement processing such as cut-out, broken pulverizing to the bondedfibre fabric that obtains.In addition, also can according to circumstances implement hierarchical processing.Processing mode is selected corresponding to desirable fibre length, cuts off the preferred cutters such as shear cut machine formula, single shaft, twin shaft and multi-shaft rotary that use.Broken, pulverize preferred hammer, pin type, ball formula, pearl formula and the rod-type that utilizes percussion that use, utilize the high-speed rotary of particle impact each other, the roll-type of utilizing compression tearing effect, circular cone type and disintegrating machine pulverizer such as spiral etc.

In order to obtain desirable fibre length, can become to cut off and broken the pulverizing by multiple multistage mechanism.Handle atmosphere and can be in wet type, the dry type any.Hierarchical processing is preferably used grading plants such as vibrating screen formula, centrifugation formula, inertia force formula, filtering type etc.Desirable fibre length not only obtains by machine is selected, between revolution that also can be by control rotor rotating knife etc., quantity delivered, sword in gap, the system holdup time etc. obtain.In addition, when using hierarchical processing, desirable fibre length also can obtain by adjusting mesh size etc.By the above-mentioned pitch that is treated as is carbon chopped fiber.

Above-mentioned bondedfibre fabric that contains pitch-based carbon fiber that obtains or the pitch that obtains by fragmentation etc. are that carbon chopped fiber can further be heated to 2,000～3,500 ℃ are carried out graphitization and make that finally to contain bondedfibre fabric or the pitch that pitch is graphitized fibre be the graphitization staple fibre.Graphitization is with enforcements such as acheson furnaces, electric furnace, in a vacuum or use the inferior enforcement of non-oxidizable atmosphere of inert gases such as nitrogen, argon, krypton.

[felt]

Bondedfibre fabric of the present invention is made of the pitch-based carbon fiber with high elongation rate and spring rate, handles so be fit to acupuncture, can preferably obtain felt by bondedfibre fabric of the present invention.The present invention includes by above-mentioned bondedfibre fabric being carried out acupuncture and handle the felt that obtains.

The interlaminar strength of the thickness direction of felt of the present invention is preferably above, the 0.35N/5cm sheet more preferably of 0.25N/5cm sheet.If interlaminar strength, has then been implemented stacked of juxtaposition interweaving (handing over Network) and insufficient less than the 0.25N/5cm sheet, peel off adding between the genetic horizon in man-hour, the property handled variation not only, and also become the occurrence cause of rerum natura inequality.Herein, interlaminar strength is represented the intensity that interweaves of the thickness direction of felt.Draw upper cut with cutter in the thickness direction centre position of felt abreast with a layer direction, by with its two ends with cupping machine the maximum intensity during with the speed stretching of 100mm/min and obtaining.

The carbon fiber that constitutes felt of the present invention directly is greater than 2 μ m and below the 20 μ m with the average fiber of optics microscopic preferably.Average fiber footpath is when 2 μ m are following, because space part is by refinement, to add the resin impregnated in man-hour not good so be shaped sometimes.On the contrary, if average fiber directly surpasses 20 μ m, then because space part by gigantism, so the thermal conductivity of the high-temperature area that strengthens in photothermal domination becomes big, thereby thermal insulation reduces sometimes.Consider that from the purpose that oxidative resistance, intensity increase the more preferably scope in average fiber footpath is preferably more than 10 μ m and below the 20 μ m, more preferably greater than 10 μ m and below the 15 μ m especially.

The weight per unit area of felt of the present invention is preferably 250～1,000g/m ²Weight per unit area can be adjusted corresponding to purposes, most preferably is 250～1,000g/m in order stably to produce continuously ²If weight per unit area is less than 250g/m ², then because the pitch-based carbon fiber net is thin, so take place sometimes that felting handles that the net that causes breaks or wrinkling.On the contrary, if weight per unit area greater than 1,000g/m ², then because thickness is big, so do not carry out the heat extraction that pitch is the fusion-free fibre net smoothly when melt processed not, fiber welding each other etc. takes place sometimes.The more preferably scope of weight per unit area is 400～700g/m ²

Therefore, the average fiber of the formation carbon fiber of felt of the present invention directly is greater than 10 μ m and below the 20 μ m, weight per unit area is preferably 250～1,000g/m ²The present invention includes by with above-mentioned felt further 2,000～3, heat-treat under 500 ℃ and the graphitization felt that obtains.

The average fiber of the preferred graphitized fibre of graphitization felt of the present invention directly is that weight per unit area is 250～1,000g/m greater than 2 μ m and below the 20 μ m ²Because the graphitization felt is made by above-mentioned felt, so weight per unit area is reduced because of graphitization processing weight by the weight per unit area of originally felt.The weight per unit area of graphitization felt can be by originally the selection of weight per unit area of felt suitably adjust.

If the weight per unit area of felt originally is less than 250g/m ², then because the pitch-based carbon fiber net is thin, so take place sometimes that felting handles that the net that causes breaks or wrinkling.On the contrary, if weight per unit area greater than 1,000g/m ², then because thickness is big, so do not carry out the heat extraction that pitch is the fusion-free fibre net smoothly during melt processed, fiber welding each other etc. takes place sometimes.The more preferably scope of weight per unit area is 400～700g/m ²

In addition, graphitization felt of the present invention preferably the weight in air, when heating up with 3 ℃/minute reduce the 10wt% of not enough initial stage weight.If weight is reduced to more than the 10wt% of initial stage weight, then oxidative resistance significantly reduces, and the characteristic in the time of can't fully satisfying as heat-insulating material is not preferred.Weight when heating up with 3 ℃/minute in air reduces, and is preferably below the 8wt%, more preferably below the 5wt%.Need to prove that the weight when heating up with 3 ℃/minute reduces and can measure with for example hot differential weight fraction parser etc. in air.

It is low that graphitization felt of the present invention and the graphitization felt of being made by the felt of prior art are compared the graphite voltinism.Therefore, thermal conductivity is step-down also, during for example as heat-insulating material, shows excellent insulating characteristics.The reason that the graphite voltinism of graphitization felt of the present invention is low is not still understood, infer that reason may be that the inventive method must make the oxygen than existing high concentration be attached on the carbon fiber precursor, make fusion-free fibre,, become the solid phase carbonization by the liquid phase carbonization so that carbon fiber precursor carries out oxygen is crosslinked.

[manufacture method of felt]

The present invention comprises the manufacture method of felt, and this method comprises following each operation:

(2) the precursor net is not melted under the oxidizing gas atmosphere, make comprise the oxygen additional amount be 8～15 weight % fusion-free fibre do not melt net (operation (2)),

(3) will not melt net, burn till under 800 ℃, make bondedfibre fabric (operation (3)) 800～1, and

(4) bondedfibre fabric is carried out acupuncture (operation (4)).

Operation (1)～(3) are identical with the manufacture method of aforesaid bondedfibre fabric.Wherein, preferably with the transfer rate in operation (2) and the operation (3) than carrying out optimization with respect to thermal contraction.At present, known by capture the pitch-based carbon fiber that obtains with the meltblown spinning, the method for carrying out juxtaposition can make productivity ratio improve, but it is difficult that stacked of juxtaposition is interweaved.This is because brute force interweaves during the capture after spinning of the individual layer net of juxtaposition, so even stacked product being implemented felting such as acupuncture processing handles, carbon fiber also is difficult to move at thickness direction.And then, because carbon fiber is hard and crisp, can causes fiber and lose so just increase the acupuncture number, make that on the contrary intensity reduces, yield rate reduces.Therefore, for it being interweaved, preferably the shape of pin is carried out optimization with not increasing the acupuncture number.

To not melt net and burn till, when making bondedfibre fabric, thermal contraction take place, so, then do not melt net and when burning till, be stretched, so carbon fiber is in the state that is stretched in the net if make with series-operation.And then, net also usually takes place by the situation of tearing.If carbon fiber is in the state that is stretched in the net, then be difficult to carry out felting processing such as acupuncture, become the reason that fiber is lost, cause interlaminar strength to reduce.Therefore, need burn till the mitigating measures of the thermal contraction when handling, therefore preferably make transfer rate in operation (2) (not melting) and the operation (3) (burning till) than carrying out optimization with respect to thermal contraction.That is, preferably making the ratio V1/V2 of transfer rate V2 of the net of the transfer rate V1 of net of operation (2) and operation (3) is 1.01～1.10.

Operation (4) is the operation of bondedfibre fabric being carried out acupuncture.The acupuncture number of acupuncture is preferably 1～200 time/cm ², 15～100 times/cm more preferably ²The hangnail degree of depth of pin is preferably above, the 0.2～0.4mm more preferably of 0.15mm.Therefore, operation (4) is that pin more than the 0.15mm is with 15～100 times/cm with bondedfibre fabric with the hangnail degree of depth preferably ²The acupuncture number carry out acupuncture.

If the hangnail degree of depth less than 0.15mm, is 15～100 times/cm at the acupuncture number then ²Scope in interweave fewly, can't obtain sufficient interlaminar strength.If the acupuncture number is less than 15 times/cm ²Even then the hangnail degree of depth is more than the 0.15mm, it is also few to interweave, and can't obtain sufficient interlaminar strength.On the contrary, if greater than 100 times/cm ², fiber then takes place in a large number to be lost, intensity reduces, and causes yield rate to reduce.The more preferably scope of the hangnail degree of depth is more than the 0.20mm, and the more preferably scope of acupuncture number is 15～50 times/cm ²

Need to prove that the hangnail degree of depth is the degree of depth of otch that is called as the hangnail of pin as shown in Figure 1.Hangnail portion also has and is called as curved projection.

Correspondence is carried out the weight per unit area, thickness of the bondedfibre fabric that felting handles etc., suitably selects the curved height of going up of pin, hangnail number, in abutting connection with hangnail interval, the pin degree of depth.Go up and bend highly and can in the scope of 0～0.15mm, suitably select.If go up curved height greater than 0.15mm, fiber then takes place in a large number to be lost, intensity reduction, yield rate reduction take place sometimes.The hangnail number can suitably be selected in 3～18 scope.If the hangnail number less than 3, then interweaves few, can't obtain sufficient interlaminar strength sometimes.On the contrary, if more than 18, fiber then taking place in a large number lose, causes intensity reduction, yield rate to reduce sometimes.Can from the scope of 0.3～3mm, suitably select at interval in abutting connection with hangnail.Need to prove, be meant the interval of adjacency between the heterotaxy that comprises scraper at interval in abutting connection with hangnail among the present invention.If at interval less than 0.3mm, fiber then takes place in a large number lose, cause intensity reduction, yield rate to reduce sometimes in abutting connection with hangnail.If opposite to 3mm, it is few then to interweave, and can't obtain sufficient interlaminar strength sometimes.The pin degree of depth can suitably be selected in the scope of 0～20mm.How dark the pin depth representing stick a needle into respect to felt, expression during acupuncture base plate and be positioned at distance with the hangnail (being generally called first hangnail) of pin front end beeline.If the pin degree of depth less than 0mm, then interweaves few, can't obtain sufficient interlaminar strength sometimes.On the contrary, if greater than 20mm, fiber then taking place in a large number lose, causes intensity reduction, yield rate to reduce sometimes.

The expression of Fig. 1 and Fig. 2 pattern ground goes up curved height, the pin degree of depth, in abutting connection with the hangnail interval.

Because the carbon fiber of formation bondedfibre fabric of the present invention has high elongation rate and high elasticity rate, handle so be fit to acupuncture.Preferably making the bulk density of felt by acupuncture is 0.01～0.5g/cm ³, 0.03～0.3g/cm more preferably ³The thickness of felt is not particularly limited as long as select according to purposes, is 1～100mm for example, is preferably about 5～50mm.Felt of the present invention goes for heat-insulating material, acoustic material etc.

[complex]

The present invention comprises the complex that resin impregnated is obtained in above-mentioned felt.Resin is preferably thermosetting resin.Thermosetting resin can be infiltrated in felt, after carrying out extrusion forming, make its heat cure obtain complex usually.

As thermosetting resin, can enumerate phenolic resins, epoxies, acrylic compounds, polyurethanes, silicone based, acid imide, thermohardening type MODIFIED PP E class and thermohardening type PPE class, polybutadiene is rubber and copolymer, acrylic rubber and copolymer thereof, silicon-type rubber and copolymer, natural rubber etc., wherein can be used alone, also appropriate combination more than two kinds can be used.The weight of resin is preferably 50～1,000 weight portion, more preferably 100～700 weight portions with respect to 100 weight portion felts.As above-mentioned felt, can use above-mentioned graphitization felt.

[heat-insulating material]

The present invention comprises above-mentioned complex 500～2, heat-treats the heat-insulating material that obtains under 200 ℃.That is, heat-insulating material of the present invention can followingly be made:

(1) resin impregnated is made complex in above-mentioned felt,

(2) with above-mentioned complex 500～2, heat-treating under 200 ℃ is carbonization treatment.

The heat treatment of this moment is that the temperature of carbonization treatment is preferably more than 800 ℃ below 2,000 ℃.

The average fiber of the carbon fiber of Gou Chenging is directly as long as be greater than 2 μ m and the scope below the 20 μ m as mentioned above, preferred especially average fiber directly is greater than 10 μ m and below the 20 μ m, more preferably be greater than 10 μ m and 15 μ m when following, oxidative resistance or excellent strength, even at high temperature also be difficult to take place oxidative degradation, excellent in te pins of durability is preferably used as the high temperature furnace heat-insulating material.

Heat-insulating material comprises 50～1 with respect to 100 weight portion pitch-based carbon fiber felts, 000 weight portion carbide.Carbide herein means that thermosetting resin was carbonized the composition that obtains when above-mentioned complex heat-treated.When carbide is lower than 50 weight portions, mean that the space of felt is few, promptly the bulk density height of felt causes thermal insulation to reduce.On the contrary, when carbide surpassed 1,000 weight portion, the major part of heat-insulating material is the carbide from thermosetting resin, can expect that the felt of oxidative resistance is few, and was not preferred., be 100～700 weight portion carbide preferably with respect to 100 weight portion felts.The weight ratio of carbide and felt can be obtained the weight of carbide by the weight that deducts the pitch-based carbon fiber felt of measuring in advance from the weight of the compound that obtains, calculates thus.

Generally speaking, heat-insulating material uses under the severe cruel condition of condition of high temperature and so on, so require high-durability.At high temperature also be difficult to oxidative degradation even comprise the felt of pitch-based carbon fiber of the present invention, and also be difficult to oxidative degradation under the state of composite making.So the excellent in te pins of durability of heat-insulating material of the present invention is so also can be used in the stove that carries out high-temperature process.

Embodiment

Be described more specifically the present invention by the following examples, but the present invention is not subjected to any qualification.

Each rerum natura is measured by following method in embodiment 1～13 and the comparative example 1～5.

(1) average fiber of carbon fiber footpath (D1) and fiber directly disperse (S1)

Average fiber footpath (D1) usage ratio chi under light microscope is measured the fiber of 60 carbon fibers and is directly asked its mean value to obtain.In addition, the ratio that average fiber footpath (D1) that the conduct of CV value obtains and fiber directly disperse (S1) is determined by following formula.

CV＝S1/D1×100

Herein, X is an observation, and n is the observation number.

(2) average fiber length of carbon fiber precursor

3 fibers of the position of the average fiber length of carbon fiber precursor by being arranged on 30cm under the tube head capture and brush the bundle that captures carbon fiber precursor, measure the length of above-mentioned bundle and carry out equalization and obtain.

(3) fibre length conservation rate

Fibre length (L by the carbon fiber that under 800 ℃, burns till ¹) and burn till preceding fibre length (L ⁰) value obtain the fibre length conservation rate with following formula (I).

Fibre length conservation rate=100 * L ¹/ L ⁰(I)

L ⁰: the fibre length before burning till

L ¹: the fibre length after burning till

Need to prove the fibre length (L of carbon fiber ¹) by extracting 10 the bondedfibre fabric that under 800 ℃, burns till out, measuring its length and carry out equalization and estimate.In addition, burn till preceding fibre length (L ⁰) by never extracting 10 out in the fusing net, measuring its length and carry out equalization and estimate.

(4) the oxygen additional amount of fusion-free fibre

The oxygen additional amount of fusion-free fibre is measured by CHNS-O Analyzer (Thermo ELECTRON CORPORATION system FLASH EA 1112Series).

(5) TENSILE STRENGTH of the tensile elongation of carbon fiber, tensile elasticity rate, bondedfibre fabric

The tensile elongation of carbon fiber, tensile elasticity rate are by 120 carbon fiber wires that stretch, after measuring fiber footpath separately, measure 120 mechanical strength with TENSILON determinator (ORIENTEC RTC-1150A), obtain the total mean value of tensile elongation, tensile elasticity rate and determine.

(6) TENSILE STRENGTH of bondedfibre fabric

From bondedfibre fabric in the width left, center, right each 2 amount to 6 samples that extract wide 5cm * long 20cm, stretch at length direction with the speed of cupping machine with 100mm/min, calculate the mean value of its intensity and determine.

(7) interlaminar strength of felt

From felt in the width left, center, right each 2 amount to 6 samples that extract wide 5cm * long 10cm, draw upper cut with cutter in sample thickness direction centre position abreast with a layer direction, the mean value of the maximum intensity when its two ends are stretched with the speed of 100mm/min with cupping machine and obtaining.

(8) weight per unit area of felt

From felt, in each 2 of width left, center, right amount at 6, mark the otch of A4 size, measure weight, calculate weight per unit area thus.

(9) TENSILE STRENGTH of heat-insulating material

(Japan Baldwin system, SS-207-5P) measures with large-scale characteristic test apparatus.

(10) be the section of the composite of resin with phenolic aldehyde

Observe with 1,000 times multiplying power with scanning electron microscope, confirm the space.

(11) thermal conductivity of heat-insulating material

Use capital of a country electronics system QTM-500, obtain with sonde method.

(12) weight ratio of carbide and carbon fiber felt

Obtain the weight of carbide by the weight that from the weight of the compound that obtains, deducts the carbon fiber felt of measuring in advance, calculate.

(13) oxidative resistance of graphitization felt

Use hot differential gravimetric analysis device (motor system of science, TG8120), in air, heat up with 3 ℃/minute, the weight reduction under estimating 700 ℃ from room temperature.

Embodiment 1

(spinning)

The mesophase pitch that will comprise 278 ℃ of middle one after another 100%, the softening temperatures of aromatic hydrocarbon uses down at 335 ℃ and comprises diameter 0.2mm

The tube head capillaceous of length 2mm, with per minute 8,000m blows 339 ℃ air from the other slit of capillary, and traction fusion mesophase pitch is made the precursor net of the carbon containing of average diameter 13.0 μ m.Carbon fiber precursor under the tube head is captured with metal plug, is 8.4cm when confirming its average fiber length.

(not melting)

Then, the precursor net was warmed up to 340 ℃ with 30 minutes from 200 ℃ under air atmosphere, make comprise fusion-free fibre do not melt net.The oxygen additional amount of fusion-free fibre is 10.9 weight %.In addition, the average fiber length of fusion-free fibre is 8.5cm.

(burning till)

In the nitrogen atmosphere, burn till processing continuously then, make the bondedfibre fabric that comprises carbon fiber in 800 ℃ of enforcements.The transfer rate V1 of the net when at this moment, making melt processed not and the ratio V1/V2 that burns till the transfer rate V2 of the net when handling are 1.03.The average fiber of the carbon fiber that obtains directly is 12.1 μ m, and the CV value in fiber footpath is 10.2%.In addition, the average fiber length of carbon fiber is 8.1cm, and the fibre length conservation rate is 95%.Need to prove, be the 15.5N/5cm sheet when measuring the TENSILE STRENGTH of the bondedfibre fabric comprise carbon fiber.

In addition, will not melt net and under argon gas body atmosphere, burn till 1,500 ℃ with 1 hour, obtain comprising the bondedfibre fabric of carbon fiber from room temperature.When estimating the mechanical property of this carbon fiber, tensile elongation is 1.61%, and TENSILE STRENGTH is 3.0GPa, and tensile elasticity rate is 240GPa.

Embodiment 2 (felt)

With the bondedfibre fabric that comprises carbon fiber that obtains among the embodiment 1 use to go up curved height 0.05mm, several 9 of hangnail, in abutting connection with the hangnail pin of 3mm, hangnail degree of depth 0.25mm at interval, be 20 times/cm with the acupuncture number ², the pin degree of depth is that 10mm implements acupuncture and handles, and obtains felt.The interlaminar strength of the felt that obtains is the 0.45N/5cm sheet, and average fiber directly is 12.1 μ m, and weight per unit area is 445g/m ²

Embodiment 3 (complex～heat-insulating material)

The felt of making is immersed in the phenolic resins (group Rong Huaxue (strain) system, PL-2211, viscosity 0.1Pas), compresses with roll squeezer, extrude unnecessary phenolic resins after, under 250 ℃, form, make complex, burn till in 800 ℃.And then, under 2,000 ℃, heat-treat, obtain the heat-insulating material of carbon fiber-containing.With respect to 100 weight portion carbon fiber felts, comprise 400 weight portion carbide.When observing the section of sintered body, do not observe the space.The TENSILE STRENGTH of heat-insulating material is 0.74MPa, and thermal conductivity is 0.048W/mK.In 2,000 ℃, TENSILE STRENGTH after handling 24 hours with the oxygen concentration of 20ppm is 0.68MPa.

Embodiment 4 (graphitization felt)

The felt of making among the embodiment 2 is burnt till 2,000 ℃ from room temperature with 3 hours under argon gas body atmosphere, obtain the graphitization felt.Weight per unit area is 438g/m ², the average fiber that constitutes the monofilament of graphitization felt directly is 11.3 μ m.In addition, with the graphitization felt in air with 3 ℃/minute when room temperature is warming up to 700 ℃, 700 ℃ weight is reduced to the 4.8wt% of initial stage weight.

Embodiment 5 (graphitization felt～heat-insulating material)

The graphitization felt of making among the embodiment 4 is immersed in the phenolic resins (group Rong Huaxue (strain) system, PL-2211, viscosity 0.1Pas), compress with roll squeezer, extrude unnecessary phenolic resins after, under 250 ℃, form, make complex, burn till in 800 ℃.And then, under 2,000 ℃, heat-treat, obtain containing the heat-insulating material of graphitized fibre.With respect to 100 weight portion graphitized fibre felts, comprise 405 weight portion carbide.When observing the section of sintered body, do not observe the space.The TENSILE STRENGTH of heat-insulating material is 1.23MPa, and thermal conductivity is 0.078W/mK.TENSILE STRENGTH after 2,000 ℃, oxygen concentration 20ppm are handled 24 hours down is 1.18MPa.

Embodiment 6

(spinning)

The mesophase pitch that will comprise 278 ℃ of middle one after another 100%, the softening temperatures of aromatic hydrocarbon comprises diameter 0.2mm 331 ℃ of uses With per minute 8,000m blows 336 ℃ air to the tube head capillaceous of length 2mm from the other slit of capillary, and traction fusion mesophase pitch is made the precursor net of average diameter 11.0 μ m.Carbon fiber precursor under the tube head is captured with metal plug, is 15.3cm when confirming its average fiber length.

(not melting)

Then, the precursor net was warmed up to 340 ℃ with 30 minutes from 200 ℃ under air atmosphere, what obtain comprising fusion-free fibre does not melt net.The oxygen additional amount of fusion-free fibre is 11.8 weight %.In addition, the average fiber length of fusion-free fibre is 15.2cm.

(burning till)

In the nitrogen atmosphere, burn till processing continuously then, make the bondedfibre fabric that comprises carbon fiber in 800 ℃ of enforcements.The transfer rate V1 of the net when at this moment, making melt processed not and the ratio V1/V2 that burns till the transfer rate V2 of the net when handling are 1.02.The average fiber of carbon fiber directly is 10.3 μ m, and the CV value in fiber footpath is 8.2%.The average fiber length of carbon fiber is 14.2cm, and the fibre length conservation rate is 93%.Need to prove, be the 14.6N/5cm sheet when measuring the TENSILE STRENGTH of the bondedfibre fabric comprise carbon fiber.

In addition, the net that do not melt that obtains is burnt till 1,500 ℃ from room temperature with 1 hour under argon gas body atmosphere, obtain comprising the bondedfibre fabric of carbon fiber.When estimating the mechanical property of this carbon fiber, tensile elongation is 1.55%, and TENSILE STRENGTH is 3.1GPa, and tensile elasticity rate is 235GPa.

Embodiment 7 (felt)

With the bondedfibre fabric that comprises carbon fiber that obtains among the embodiment 6 use to go up curved height 0.04mm, several 9 of hangnail, in abutting connection with hangnail at interval the pin of 3mm, hangnail degree of depth 0.20mm with the several 25 times/cm of acupuncture ², pin degree of depth 10mm implements acupuncture and handles, and obtains felt.The interlaminar strength of the felt that obtains is the 0.48N/5cm sheet, and average fiber directly is 10.5 μ m, and weight per unit area is 390g/m ²

Embodiment 8 (complex～heat-insulating material)

The felt of making among the embodiment 7 is immersed in the phenolic resins (group Rong Huaxue (strain) system, PL-2211, viscosity 0.1Pas), compresses with roll squeezer, extrude unnecessary phenolic resins after, under 250 ℃, form, make complex, burn till in 800 ℃.And then, under 2,000 ℃, heat-treat, obtain the heat-insulating material of carbon fiber-containing.With respect to 100 weight portion felts, comprise 400 weight portion carbide.When observing the section of sintered body, do not observe the space.The TENSILE STRENGTH of heat-insulating material is 0.79MPa, and thermal conductivity is 0.049W/mK.In 2,000 ℃, TENSILE STRENGTH after handling 24 hours with the oxygen concentration of 20ppm is 0.76MPa.

Embodiment 9 (graphitization felt)

The felt of making among the embodiment 7 is burnt till 2,500 ℃ from room temperature with 3 hours under argon gas body atmosphere, obtain the graphitization felt.Weight per unit area is 385g/m ², the average fiber that constitutes the monofilament of graphitization felt directly is 9.8 μ m.In addition, with the graphitization felt in air with 3 ℃/minute when room temperature is warming up to 700 ℃ 700 ℃ weight be reduced to the 3.8wt% of initial stage weight.

Embodiment 10

(spinning)

The mesophase pitch that will comprise 278 ℃ of middle one after another 100%, the softening temperatures of aromatic hydrocarbon comprises diameter 0.2mm 336 ℃ of uses

With per minute 5,000m blows 339 ℃ air to the tube head capillaceous of length 2mm from the other slit of capillary, and traction fusion mesophase pitch is made the precursor net that comprises carbon fiber precursor of average diameter 15.1 μ m.Carbon fiber precursor under the tube head is captured with metal plug, is 10.4cm when confirming its average fiber length.

(not melting)

Then, the precursor net was warmed up to 340 ℃ with 30 minutes from 200 ℃ under air atmosphere, what obtain comprising fusion-free fibre does not melt net.The oxygen additional amount of fusion-free fibre is 8.4 weight %.In addition, the average fiber length of fusion-free fibre is 10.4cm.

(burning till)

In the nitrogen atmosphere, burn till processing continuously then, make the bondedfibre fabric that comprises carbon fiber in 800 ℃ of enforcements.The transfer rate V1 of the net when at this moment, making melt processed not and the ratio V1/V2 that burns till the transfer rate V2 of the net when handling are 1.04.The average fiber of carbon fiber directly is 14.3 μ m, and the CV value in fiber footpath is 10.5%.In addition, the average fiber length of carbon fiber is 9.5cm, and the fibre length conservation rate is 91%.Need to prove, be the 15.6N/5cm sheet when measuring the TENSILE STRENGTH of the bondedfibre fabric comprise carbon fiber.In addition, what comprise fusion-free fibre burnt till 1,500 ℃ from room temperature with 1 hour with bondedfibre fabric under argon gas body atmosphere, obtain comprising the bondedfibre fabric of carbon fiber.When estimating the mechanical property of this carbon fiber, tensile elongation is 1.48%, and TENSILE STRENGTH is 2.6GPa, and tensile elasticity rate is 253GPa.

Embodiment 11 (felt)

With the bondedfibre fabric that comprises carbon fiber that obtains among the embodiment 10 use to go up curved height 0.05mm, several 9 of hangnail, in abutting connection with hangnail at interval the pin of 3mm, hangnail degree of depth 0.30mm with the several 30 times/cm of acupuncture ², pin degree of depth 10mm implements acupuncture and handles and obtain felt.The interlaminar strength of the felt that obtains is the 0.39N/5cm sheet, and average fiber directly is 14.3 μ m, and weight per unit area is 460g/m ²

Embodiment 12 (complex～heat-insulating material)

The felt of making among the embodiment 11 is immersed in the phenolic resins (group Rong Huaxue (strain) system, PL-4222, viscosity 0.5Pas), compress with roll squeezer, extrude unnecessary phenolic resins after, under 250 ℃, form, make complex, burn till in 800 ℃.And then, under 2,000 ℃, heat-treat, obtain the heat-insulating material of carbon fiber-containing.With respect to 100 weight portion carbon fiber felts, comprise 400 weight portion carbide.When observing the section of sintered body, do not observe the space.The TENSILE STRENGTH of heat-insulating material is 0.83MPa, and thermal conductivity is 0.049W/mK.In 2,000 ℃, TENSILE STRENGTH after handling 24 hours with the oxygen concentration of 20ppm is 0.78MPa.

Embodiment 13 (graphitization felt)

The felt of making among the embodiment 11 is burnt till 3,000 ℃ from room temperature with 3 hours under argon gas body atmosphere, obtain the graphitization felt.Weight per unit area is 452g/m ², the average fiber that constitutes the monofilament of graphitization felt directly is 13.8 μ m.In addition, with the graphitization felt in air with 3 ℃/minute when room temperature is warming up to 700 ℃, 700 ℃ weight is reduced to the 3.1wt% of initial stage weight.

Comparative example 1

(spinning)

The mesophase pitch that will comprise 278 ℃ of middle one after another 100%, the softening temperatures of aromatic hydrocarbon uses down at 335 ℃ and comprises diameter 0.2mm The tube head capillaceous of length 2mm, with per minute 8,000m blows 339 ℃ air from the other slit of capillary, and traction fusion mesophase pitch is made the precursor net of the carbon fiber precursor that comprises average diameter 13.0 μ m.Carbon fiber precursor under the tube head is captured with metal plug, is 8.4cm when confirming its average fiber length.

(not melting)

Then, the precursor net was warmed up to 290 ℃ with 30 minutes from 200 ℃ under air atmosphere, obtain comprising do not melt carbon fiber do not melt net.The oxygen additional amount that does not melt carbon fiber is 6.5 weight %.In addition, the average fiber length of fusion-free fibre is 8.5cm.

(burning till)

The transfer rate V1 of the net when making melt processed not then and the ratio V1/V2 that burns till the transfer rate V2 of the net when handling are 1.00, in the nitrogen atmosphere, burn till processing continuously in 800 ℃ of enforcements, want to obtain comprising the bondedfibre fabric of carbon fiber, but the bondedfibre fabric that the contraction of affirmation net causes comprising carbon fiber is cut off.The average fiber of carbon fiber directly is 12.1 μ m, and the CV value in fiber footpath is 10.2%.In addition, the average fiber length of pitch-based carbon fiber is 7.3cm, and the fibre length conservation rate is 86%.Need to prove, be the 6.7N/5cm sheet when measuring the TENSILE STRENGTH of the bondedfibre fabric comprise pitch-based carbon fiber.

In addition, the net that do not melt that obtains is burnt till 1,500 ℃ from room temperature with 1 hour under argon gas body atmosphere, obtain comprising the bondedfibre fabric of pitch-based carbon fiber.When estimating the mechanical property of this pitch-based carbon fiber, tensile elongation is 1.2%, and TENSILE STRENGTH is 1.7GPa, and tensile elasticity rate is 216GPa.

Comparative example 2 (felt)

With the bondedfibre fabric that comprises carbon fiber that obtains in the comparative example 1 use to go up curved height 0.05mm, several 9 of hangnail, in abutting connection with hangnail at interval the pin of 3mm, hangnail degree of depth 0.25mm with the several 20 times/cm of acupuncture ², pin degree of depth 10mm implements acupuncture and handles, and obtains felt.The interlaminar strength of the felt that obtains is the 0.15N/5cm sheet, and average fiber directly is 12.1 μ m, and weight per unit area is 218g/m ²In order to make heat-insulating material, attempt making impregnated phenolic resin in the felt that obtains (group Rong Huaxue (strain) system, PL-4222, viscosity 0.5Pas), but because of undercapacity, so felt breaks.

Comparative example 3

(spinning)

The mesophase pitch that will comprise 278 ℃ of middle one after another 100%, the softening temperatures of aromatic hydrocarbon comprises diameter 0.2mm 328 ℃ of uses

The tube head capillaceous of length 2mm, with per minute 3,000m blows 335 ℃ air from the other slit of capillary, and traction fusion mesophase pitch is made the precursor net of the carbon fiber precursor that comprises average diameter 21.5 μ m.Carbon fiber precursor under the tube head is captured with metal plug, is 30.4cm when confirming its average fiber length.

(not melting)

Then, the precursor net was warmed up to 340 ℃ with 30 minutes from 200 ℃ under air atmosphere, obtain comprising do not melt carbon fiber do not melt net.The oxygen additional amount that does not melt carbon fiber is 6.6 weight %.In addition, pitch is that the average fiber length of fusion-free fibre is 30.5cm.

(burning till)

The transfer rate V1 of the net when making melt processed not then and the ratio V1/V2 that burns till the transfer rate V2 of the net when handling are 1.00, in the nitrogen atmosphere, burn till processing continuously in 800 ℃ of enforcements, want to obtain comprising the bondedfibre fabric of carbon fiber, but confirmed to make the bondedfibre fabric that comprises carbon fiber be cut off because of net shrinks.The average fiber of carbon fiber directly is 20.5 μ m, and the CV value in fiber footpath is 9.2%.In addition, the average fiber length of carbon fiber is 25.9cm, and the fibre length conservation rate is 85%.Need to prove, be the 8.4N/5cm sheet when measuring the TENSILE STRENGTH of the bondedfibre fabric comprise carbon fiber.

In addition, the net that do not melt that obtains is burnt till 1,500 ℃ from room temperature with 1 hour under argon gas body atmosphere, obtain comprising the bondedfibre fabric of carbon fiber.When estimating the mechanical property of this carbon fiber, tensile elongation is 1.3%, and TENSILE STRENGTH is 1.6GPa, and tensile elasticity rate is 235GPa.

Comparative example 4

(spinning)

The isotropic pitch that will comprise 258 ℃ of middle one after another 0%, the softening temperatures of aromatic hydrocarbon comprises diameter 0.2mm in 295 ℃ of uses The tube head capillaceous of length 2mm, with per minute 5,000m blows 305 ℃ air from the other slit of capillary, the traction molten asphalt, manufacturing comprises the precursor net of the carbon fiber precursor of average diameter 13.5 μ m.Carbon fiber precursor under the tube head is captured with metal plug, is 17.4cm when confirming its average fiber length.

(not melting)

Then, the precursor net was warmed up to 320 ℃ with 40 minutes from 200 ℃ under air atmosphere, obtain comprising do not melt carbon fiber do not melt net.The oxygen additional amount that does not melt carbon fiber is 8.6 weight %.In addition, the average fiber length of fusion-free fibre is 17.5cm.

(burning till)

In the nitrogen atmosphere, burn till processing continuously then, make the bondedfibre fabric that comprises carbon fiber in 800 ℃ of enforcements.The transfer rate V1 of the net when at this moment, making melt processed not and the ratio V1/V2 that burns till the transfer rate V2 of the net when handling are 1.00.The average fiber of carbon fiber directly is 12.5 μ m, and the CV value in fiber footpath is 11.2%.In addition, the average fiber length of carbon fiber is 16.9cm, and the fibre length conservation rate is 96.6%.Need to prove, be the 9.5N/5cm sheet when measuring the TENSILE STRENGTH of the bondedfibre fabric comprise carbon fiber.

In addition, the net that do not melt that obtains is burnt till 1,500 ℃ from room temperature with 1 hour under argon gas body atmosphere, obtain comprising the bondedfibre fabric of carbon fiber.When estimating the mechanical property of this carbon fiber, tensile elongation is 2.2%, and TENSILE STRENGTH is 0.7GPa, and tensile elasticity rate is 29GPa.

Comparative example 5

The net of making among the embodiment 1 that do not melt that does not melt carbon fiber that comprises is burnt till 2,300 ℃ from room temperature with 2 hours under argon atmospher, obtain comprising the bondedfibre fabric of carbon fiber.When estimating the mechanical property of this carbon fiber, tensile elongation is 0.63%, and TENSILE STRENGTH is 2.4GPa, and tensile elasticity rate is 510GPa.

The invention effect

Adhesive-bonded fabric of the present invention is because contain the carbon fiber of high elongation rate and high resiliency rate, so the mechanical strength excellence is fit to acupuncture and processes, is fit to felting. According to the manufacture method of adhesive-bonded fabric of the present invention, can in particular range, improve the tensile elongation of pitch-based carbon fiber by making oxygen additional amount in the fusion-free fibre. The mechanical strength excellence of felt of the present invention, interlaminar strength are especially excellent. According to the manufacture method of felt of the present invention, can access the especially excellent felt of mechanical strength excellence, interlaminar strength. The mechanical strength of heat-insulating material of the present invention and thermal insulation excellence.

Utilizability on the industry

Adhesive-bonded fabric of the present invention, felt and heat-insulating material can be as the structural elements of industrial robot arm or airborne vehicle.

Claims

1. bondedfibre fabric, it is the bondedfibre fabric that comprises pitch-based carbon fiber, it is characterized in that pitch-based carbon fiber

(iii) tensile elasticity rate is 80～300GPa, and

(iv) tensile elongation is 1.4～2.5%.

2. bondedfibre fabric as claimed in claim 1, wherein, the tensile elasticity rate of pitch-based carbon fiber is 100～300GPa, tensile elongation is 1.5～2.4%.

3. bondedfibre fabric as claimed in claim 1, wherein, the average fiber footpath (D1) with the optics microscopic of pitch-based carbon fiber is greater than 10 μ m and below the 20 μ m.

4. bondedfibre fabric as claimed in claim 1, wherein, TENSILE STRENGTH is more than the 10N/5cm sheet.

5. the manufacture method of bondedfibre fabric comprises following each operation:

(3) will not melt net, burn till under 800 ℃ 800～1.

6. manufacture method as claimed in claim 5 wherein, is carried out spinning with meltblown.

7. manufacture method as claimed in claim 5, wherein, the average fiber length of the carbon fiber precursor of precursor net is 4～25cm.

8. manufacture method as claimed in claim 5, wherein, the oxygen additional amount that does not melt the carbon fiber of net is 9～12 weight %.

9. manufacture method as claimed in claim 5, wherein, the fibre length conservation rate (%) of following formula (I) expression before and after burning till is more than 90%,

Fibre length conservation rate=100 * L ¹/ L ⁰(I)

L ⁰: the fibre length before burning till

L ¹: the fibre length after burning till.

10. felt obtains by the described nonwoven fabric of claim 1 being carried out the acupuncture processing.

11. felt as claimed in claim 10, wherein, the interlaminar strength of thickness direction is more than the 0.25N/5cm sheet.

12. felt as claimed in claim 10, wherein, the average fiber of carbon fiber directly is that weight per unit area is 250～1,000g/m greater than 10 μ m and below the 20 μ m ²

13. the graphitization felt, be by with the described felt of claim 10 further 2,000～3, heat-treat under 500 ℃ and obtain.

14. the manufacture method of felt comprises following each operation:

(3) will not melt net, burn till under 800 ℃, make bondedfibre fabric 800～1, and

(4) bondedfibre fabric is carried out acupuncture.

15. manufacture method as claimed in claim 14 wherein, is that pin more than the 0.15mm is with 15～100 times/cm with bondedfibre fabric with the hangnail degree of depth ²The acupuncture number carry out acupuncture.

16. complex, with resin impregnated in the described felt of claim 10 and obtain.

17. complex, with resin impregnated in the described graphitization felt of claim 13 and obtain.

18. heat-insulating material, be complex with claim 16 500～2, heat-treat under 200 ℃ and obtain.

19. the manufacture method of heat-insulating material comprises following each operation:

(1) with resin impregnated in the described felt of claim 10 and make complex,

(2) with complex 500～2, heat-treat under 200 ℃.