CN105074082B - Carbon fiber nonwoven fabric - Google Patents

Carbon fiber nonwoven fabric Download PDF

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Publication number
CN105074082B
CN105074082B CN201480012664.8A CN201480012664A CN105074082B CN 105074082 B CN105074082 B CN 105074082B CN 201480012664 A CN201480012664 A CN 201480012664A CN 105074082 B CN105074082 B CN 105074082B
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carbon fiber
nonwoven fabric
bundle
fiber nonwoven
fiber bundle
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CN105074082A (en
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三好且洋
桥本贵史
成濑惠宽
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Toray Industries Inc
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Toray Industries Inc
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A kind of carbon fiber nonwoven fabric, wherein, carbon fiber is through having the aliphatic compound of a plurality of epoxy radicals or specific aromatic compound starching, in carbon fiber bundle in carbon fiber nonwoven fabric, constitute the average x of quantity of radical of the carbon fiber of carbon fiber bundle (1) in the range of 90～1000/bundle, constitute the standard deviation of radical of the carbon fiber of carbon fiber bundle (1) in the range of 50～500, in described carbon fiber bundle (1), the radical of the carbon fiber constituting carbon fiber bundle is more than 90.The present invention can provide the carbon fiber nonwoven fabric that the deviation of high fluidity when can simultaneously realize carbon fibre composite molding and high mechanical property and mechanical property plastic property the least, carbon fiber felt is also excellent.

Description

Carbon fiber nonwoven fabric
Technical field
The present invention relates to carbon fiber nonwoven fabric, particularly relate to using this carbon fiber nonwoven fabric to make carbon fiber composite High fluidity and the carbon fiber nonwoven fabric of high mechanical property can be realized during the products formed expected simultaneously.
Background technology
The carbon fibre composite formed by carbon fiber and thermoplastic resin is used for the manufacture of various products formed, always with Come, it is proposed that the scheme as target of good mobility when the high mechanical property of the various products formeds to manufacture, manufacture.Its In, there is the scheme of the form that carbon fiber is non-woven fabrics made in carbon fibre composite, such as patent documentation 1 proposes one Particular carbon fibre bundle in carbon fiber nonwoven fabric is suppressed in low-level relative to the ratio of fiber total amount and makes this particular carbon fine The average fiber radical in dimension bundle carbon fiber nonwoven fabric in particular range.
But, as the carbon fiber nonwoven fabric (carbon fiber bundle in carbon fiber nonwoven fabric such described in this patent documentation 1 Carefully, the ratio of bundle is low, carbon fiber fibrillation) for, although the machinery using its carbon fibre composite products formed manufactured is special Property excellent, but mobility during molding is low, insufficient formability.Its reason is, owing to the carbon fiber as reinforcing fiber fully divides Dissipating, so stress is not easy to concentrate, can give full play to the reinforced effects of carbon fiber, but then, carbon fiber is intersected with each other, system About activity each other, causes becoming to be difficult to activity.
On the other hand, patent documentation 2 proposes a kind of by particular carbon fibre bundle same as described above in carbon fiber nonwoven fabric It is set in higher level relative to the ratio of fiber total amount and makes the average fiber radical in this particular carbon fibre bundle special at another Composite in the range of Ding.But, as carbon fiber nonwoven fabric (wherein, carbon fiber bundle such described in this patent documentation 2 Slightly, the ratio of bundle is high) for, although using mobility during its manufacture carbon fibre composite products formed high, mouldability is excellent, But mechanical property is low, deviation is the biggest.Its reason is, owing to carbon fiber bundle is thick, so the impregnation that resin is in bundle is poor, and stress Easily concentrate on the end of carbon fiber, but owing to carbon fiber is formed without network (net work), so easily movable.
Patent documentation 1: Japanese Unexamined Patent Publication 2012-158846 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-158847 publication
Summary of the invention
Therefore, the problem of the present invention be to provide that a kind of conventional carbon fiber nonwoven fabric as described above cannot be reached, High fluidity when can simultaneously realize carbon fibre composite molding and the deviation of high mechanical property and mechanical property is the least, The carbon fiber nonwoven fabric that the plastic property of carbon fiber felt is also excellent.
In order to solve above-mentioned problem, the carbon fiber nonwoven fabric that the present invention relates to has following composition.
(1) a kind of carbon fiber nonwoven fabric, it is the carbon fiber nonwoven fabric comprising carbon fiber, it is characterised in that carbon fiber warp There is the aliphatic compound starching of a plurality of epoxy radicals, in the carbon fiber bundle in carbon fiber nonwoven fabric, constitute carbon fiber bundle (1) the average x of quantity of the radical of carbon fiber, in the range of 90～1000/bundle, constitutes the carbon fiber of carbon fiber bundle (1) The standard deviation of radical is in the range of 50～500, in described carbon fiber bundle (1), constitutes the radical of the carbon fiber of carbon fiber bundle It it is more than 90.
(2) a kind of carbon fiber nonwoven fabric, it is the carbon fiber nonwoven fabric comprising carbon fiber, it is characterised in that carbon fiber warp Aromatic compound starching, described aromatic compound be the atomic number between epoxy radicals and aromatic rings be more than 6, have multiple The aromatic compound of several epoxy radicals, in the carbon fiber bundle in carbon fiber nonwoven fabric, constitutes the carbon fiber of carbon fiber bundle (1) The average x of quantity of radical in the range of 90～1000/bundle, constitute the standard of radical of the carbon fiber of carbon fiber bundle (1) Deviations is in the range of 50～500, in described carbon fiber bundle (1), constitute the radical of carbon fiber of carbon fiber bundle be 90 with On.
(3) carbon fiber nonwoven fabric as described in (1) or (2), wherein, above-mentioned there is a plurality of epoxy radicals compound be Two ends of the longest atomic link have the compound of epoxy radicals.
(4) carbon fiber nonwoven fabric as described in (3), wherein, the above-mentioned compound with a plurality of epoxy radicals is only Two ends of long atomic link have the compound of epoxy radicals.
(5) carbon fiber nonwoven fabric as described in (1) or (3), wherein, the above-mentioned aliphatic compound with a plurality of epoxy radicals The atomic number of the longest atomic link of thing is 20～200.
(6) carbon fiber nonwoven fabric as according to any one of (1), (3)～(5), wherein, above-mentioned have a plurality of epoxy radicals Aliphatic compound be sweet selected from the many glycidyl ethers of glycerol, the two many glycidyl ethers of glycerol, polyethylene glycol diglycidyl Oil base ethers, the compound of at least one of polypropylene glycol diglycidyl ether apoplexy due to endogenous wind.
(7) carbon fiber nonwoven fabric as described in (2), wherein, the atomic number between above-mentioned epoxy radicals and aromatic rings is more than 6 , the aromatic compound with a plurality of epoxy radicals be the compound shown in followingization 1.
[changing 1]
(here, in formula [I], R1For followingization 2, R2For the alkylidene of carbon number 2～30, R3For-H or-CH3, m, n are The integer of 2～48, m+n is 4～50.)
[changing 2]
(8) carbon fiber nonwoven fabric as described in (7), wherein, above-mentioned R2For-CH2CH2-or-CH (CH3)CH2-。
(9) carbon fiber nonwoven fabric as described in (2), wherein, above-mentioned aromatic compound is condensed polycyclc aromatic chemical combination Thing.
(10) carbon fiber nonwoven fabric as described in (9), wherein, the skeleton of above-mentioned condensed polycyclc aromatic compound be naphthalene, Any one in anthracene, phenanthrene, pyrene.
(11) a kind of carbon fiber nonwoven fabric, it is the carbon fiber nonwoven fabric comprising carbon fiber, it is characterised in that at carbon fiber On be attached with for carbon fiber weight 100 weight % be 0.1～5.0 weight % selected from followingization 3～change shown in 5 The compound of at least one in chemistry formula (III), (IV) and (V), in the carbon fiber bundle in carbon fiber nonwoven fabric, constitutes carbon The average x of quantity of the radical of the carbon fiber of fibre bundle (1), in the range of 90～1000/bundle, constitutes the carbon of carbon fiber bundle (1) The standard deviation of the radical of fiber is in the range of 50～500, in described carbon fiber bundle (1), constitutes the carbon fiber of carbon fiber bundle Radical be more than 90.
[changing 3]
[changing 4]
[changing 5]
In above formula, R1For H, OH, followingization 6 or followingization 7, R2For H or OH, m, n are 1～49, and wherein m+n is 10～50.
[changing 6]
[changing 7]
(12) carbon fiber nonwoven fabric as according to any one of (1)～(11), wherein, above-mentioned composition carbon fiber bundle (1) The standard deviation of the radical of carbon fiber is in the range of 50～350.
(13) carbon fiber nonwoven fabric as according to any one of (1)～(12), wherein, the weight of above-mentioned carbon fiber bundle (1) Relative to the ratio of carbon fiber gross weight in the range of 5～80 weight %.
(14) carbon fiber nonwoven fabric as according to any one of (1)～(13), wherein, when carbon fiber nonwoven fabric is by 25 DEG C Pendency value (cm)/monofilament bending stiffness (Pa cm4) 1.4 × 103～4.0 × 103(cm/(Pa·cm4)) in the range of Carbon fiber bundle is formed.
(15) carbon fiber nonwoven fabric as according to any one of (1)～(14), wherein, the carbon constituting carbon fiber nonwoven fabric is fine The monofilament bending stiffness of dimension is 1.0 × 10-11～2.8 × 10-11(Pa·m4In the range of).
(16) carbon fiber nonwoven fabric as according to any one of (1)～(15), wherein, the carbon constituting carbon fiber nonwoven fabric is fine Fibre length Ln (number average fiber length) of dimension is in the range of scope, more preferably 3～the 25mm of 3～50mm.
For the carbon fiber nonwoven fabric of the present invention as above, by meeting the model of regulation in the invention described above Enclose, as shown in the result of embodiment as mentioned below, high fluidity, Er Qieneng can not only be obtained when using its molding Enough realizing the high mechanical property of products formed, the deviation of its mechanical property is the least, and can present the plastic property of excellence.This Outward, in order to that more reliably realize high fluidity and high mechanical property and deposit, as set forth above, it is possible to use preferred chemical combination Thing, the standard deviation of radical of carbon fiber, carbon fiber bundle (1) weight relative to the scope of the ratio of carbon fiber gross weight, outstanding Value of hanging down (cm)/monofilament bending stiffness (Pa cm4) scope, the scope etc. of monofilament bending stiffness of carbon fiber.
As it has been described above, according to the carbon fiber nonwoven fabric that the present invention relates to, it is provided that it is combined using its molding carbon fiber The deviation that can simultaneously realize high fluidity and high mechanical property and mechanical property during material is the least, carbon fiber is to delicate area The also excellent carbon fiber nonwoven fabric of tracing ability.
Accompanying drawing explanation
Fig. 1 is the structure diagram of the example representing carding apparatus.
Fig. 2 is the structure diagram of the example representing airflow net forming apparatus.
Fig. 3 is the structure diagram of the determinator representing pendency values determination method.
Detailed description of the invention
Hereinafter, the present invention is together explained with embodiment, comparative example.
It is not particularly limited firstly, for the carbon fiber used in the present invention, the carbon of high intensity, high elastic modulus can be used Fiber, they may be used singly or in combination of two or more kinds.Wherein, the carbon that can enumerate PAN system, asphalt series, artificial silk system etc. is fine Dimension.From the viewpoint of the intensity of the products formed obtained with the harmony of elastic modelling quantity, further preferred PAN based carbon fiber.Carbon The density of fiber is preferably 1.65～1.95g/cm3, more preferably 1.70～1.85g/cm3.The excessive carbon fiber of density exists The situation of the lightweight poor performance of the carbon fibre reinforced plastic arrived, there is the carbon fibre reinforced plastic obtained in the too small carbon fiber of density The situation of mechanical property step-down.
Additionally, from the viewpoint of productivity ratio, it is more that carbon fiber is preferably bundle, preferably the monofilament number in bundle.As making Monofilament number during carbon fiber bundle, can use in the range of 1000～350,000, particularly preferably 10,000～100, Use in the range of 000.
Preferably, the monofilament bending stiffness of carbon fiber is preferably 1.0 × 10-11～2.8 × 10-11Pa·m4In the range of, More preferably 1.0 × 10-11～1.5 × 10-11Pa·m4.By monofilament bending stiffness within the above range, it is described below Manufacture in the operation of carbon fiber nonwoven fabric, it is possible to make the stay in grade of the carbon fiber nonwoven fabric obtained.
For purposes such as the cementabilities improved carbon fiber during carbon fibre composite molding and matrix resin, the most right Carbon fiber carries out surface process.The method processed as surface, has electrolysis process, ozone process, UV treatment etc..
Additionally, in the carbon fiber nonwoven fabric that the 1st scheme of the present invention relates to, carbon fiber is through having a plurality of epoxy radicals Aliphatic compound has carried out starching.So-called above-mentioned aliphatic compound in the present invention, refers to non-ring type straight-chain saturated hydrocarbons, props up Chain saturated hydrocarbons, non-ring type straight-chain unsaturated hydrocarbons, branched unsaturated hydrocarbons or by the carbon atom (CH of above-mentioned hydrocarbon3, CH2, CH, C) oxygen atom (O), nitrogen-atoms (NH, N), sulphur atom (SO it are substituted by3H, SH), the chemical combination of the chain structure of carbonyl atom group (CO) Thing.
Additionally, the above-mentioned aliphatic compound with a plurality of epoxy radicals is preferably two end tools at the longest atomic link There is a compound of epoxy radicals, be wherein preferably the most only two ends at the longest atomic link and there is the compound of epoxy radicals.The present invention In, for there is the aliphatic compound of a plurality of epoxy radicals, the carbon of the chain structure linked between 2 epoxy radicals will be constituted Atom, the atomic link that the sum of hetero atom (oxygen atom, nitrogen-atoms etc.) is maximum are referred to as the longest atomic link, will constitute the longest atomic link The sum of atom as the atomic number of the longest atomic link.It should be noted that with the atomic linkage constituting the longest atomic link The equiatomic quantity of hydrogen is not included in sum.
Structure for side chain is not particularly limited, but in order to avoid the density of the intermolecular cross-linking of sizing agent compound becomes Too much, preferably it is difficult to become the structure of crosslinking points.
When the epoxy radicals that sizing agent compound has is less than 2, it is impossible to effectively carry out the bridging of carbon fiber and matrix resin. Therefore, in order to effectively carry out the bridging of carbon fiber and matrix resin, epoxy radix is necessary for more than 2.
On the other hand, when epoxy radix is too much, the density of the intermolecular cross-linking of sizing agent compound becomes big, becomes fragility Upper pulp layer, the hot strength of result complex reduces, and therefore, epoxy radix is preferably less than 6, more preferably less than 4, enters One step preferably can be 2.And then, it is preferred that these 2 epoxy radicals are positioned at two ends of the longest atomic link.That is, by Two ends of the longest atomic link have epoxy radicals, prevent the crosslink density of local from increasing, and therefore, the stretching for complex is strong It is preferred for degree.
As the structure of epoxy radicals, it is preferably reactive high glycidyl.
From prevent too low or too high due to resin viscosity and cause as collecting agent operability deteriorate from the viewpoint of, institute State the molecular weight of aliphatic compound and be preferably more than 80, less than 3200, more preferably more than 100, less than 1500, the most excellent Elect more than 200, less than 1000 as.
As the concrete example of the aliphatic compound with a plurality of epoxy radicals in the present invention, such as, shrink for two For glyceryl ether compound, can enumerate ethylene glycol diglycidyl base ether and polyethylene glycol diglycidyl base ethers, the third two Alcohol diglycidyl ether and polypropylene glycol diglycidyl ether class, BDO diglycidyl ether, neopentyl glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, ployalkylene glycol diglycidyl ether class etc..Additionally, for For the most glycidyl etherified compound, the many glycidyl ethers of glycerol, the two many glycidyl ethers of glycerol, polyglycereol can be enumerated Many glycidyls ethers, sorbitol polyglycidyl base ethers, arabitol many glycidyls ethers, trimethylolpropane Many glycidyls ethers, tetramethylolmethane many glycidyls ethers, many glycidyls ethers etc. of aliphatic polyol.
Preferably there is the how glycidyl etherified compound of aliphatic of reactive high glycidyl.It is highly preferred that Polyethylene glycol diglycidyl base ethers, polypropylene glycol diglycidyl ether class, alkanediol diglycidyl ether class and The compound with structure shown below is preferred.
G-O-(R1-O)m-G [I]
G-O-R2 n-O-G [II]
CH2-O-(R1-O)x-R3
|
CH-O-(R1-O)y-R4 [III]
|
CH2-O-(R1-O)z-R5
Here, G is glycidyl, R1For-CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-, R2For-CH2-, R3、R4、 R5In at least 2 be-G, other be-H or-G, m be the integer of 1～25, n is the integer of 2～75, and, x, y, z is 0 or just Integer, x+y+z is preferably 0～25.In addition it is also possible to use the mixture of above-claimed cpd.
The atomic number with the longest atomic link in the aliphatic compound of a plurality of epoxy radicals is preferably more than 20.That is, If this atomic number is less than 20, then the crosslink density gone up in pulp layer uprises, and therefore easily becomes the structure that toughness is low, and result is the most difficult In the hot strength presenting complex.And in contrast, if the atomic number of the longest atomic link is relatively big, then goes up pulp layer softness and hold Easily becoming the structure that toughness is high, the hot strength of result complex easily increases, and especially has for drawing during more crisp resin Stretching the feature that intensity is high, therefore, the atomic number of the longest atomic link is more preferably more than 25, can be further preferably more than 30.
But, although the atomic number of the longest atomic link is the biggest, and structure is the most soft, but can bend time long and functional group be sealed Closing, result causes carbon fiber sometimes to reduce with the bonding force of resin, it is therefore preferable that atomic number is less than 200, can be more preferably Less than 100.
When aliphatic compound has annular aliphatic skeleton, as long as epoxy radicals is sufficiently far from cyclic skeleton, specifically, As long as being calculated as more than 6 with atomic number, then can use.
In the carbon fiber nonwoven fabric that the 2nd scheme of the present invention relates to, it is 6 by the atomic number between epoxy radicals and aromatic rings Above, to have a plurality of epoxy radicals aromatic compound is used as sizing agent.Atom between so-called epoxy radicals and aromatic rings Number, refers to constitute shackle epoxide and the fragrance carbon atom of chain structure of interannular, hetero atom (oxygen atom, nitrogen-atoms etc.), carbonyl The sum of base atomic group.
If the atomic number between the epoxy radicals of sizing agent and aromatic rings is less than 6, then can make the boundary of carbon fiber and matrix resin Compound bigger for existing in face on upright and outspoken and three-dimensional, therefore, with the surface functional group of the most surface being present in carbon fiber Reactivity do not increase, result is it could not be expected that the improve of lateral characteristics of composite.
Specifically can enumerate the compound that following formula [I] (changing 9) represents.
[changing 9]
(here, in formula [I], R1For followingization 10, R2For the alkylidene of carbon number 2～30, R3For-H or-CH3, m, n Being the integer of 2～48, m+n is 4～50.)
[changing 10]
Now, upright and outspoken and three-dimensional in order to not make carbon fiber in carbon fibre composite and the interface of matrix resin exist Compound bigger on, strand is straight-chain, have flexibility and compound that molecular weight is little is preferred, therefore, Make m, n in above formula [I] be respectively more than 2, be preferably more than 3, more preferably more than 5, make m+n be more than 4, be preferably More than 6, more preferably more than 10.When being each less than the compound of 4 less than 2 or m+n for m, n, exist as the present invention's The situation that the matrix resin of purpose and the cementability of carbon fiber also reduce.On the other hand, when m+n is more than 50, exist and matrix tree The situation that the cementability of the compatibility reduction of fat, matrix resin and carbon fiber reduces.Additionally, in formula [I], R2Be preferably- CH2CH2-or-CH (CH3)CH2-。
Here, the bisphenol A moieties in above formula [I] or F part have the effect of raising and the compatibility of matrix resin and carry The effect of high resistance to fluffing.
Above, the atomic number between epoxy radicals and aromatic rings be more than 6, the aromatic series with a plurality of epoxy radicals The skeleton of compound can be condensed polycyclc aromatic compound.As the skeleton of condensed polycyclc aromatic compound, example can be enumerated As naphthalene, anthracene, phenanthrene,, pyrene, aphthacene, benzo [9,10] luxuriant and rich with fragrance, 1,2-benzanthracene, benzopyrene etc..Can be preferably naphthalene that skeleton is little, Anthracene, phenanthrene, pyrene.
About the epoxide equivalent of the condensed polycyclc aromatic compound with a plurality of epoxy radicals, from the raising making cementability From the viewpoint of effect is abundant, preferably in the range of 150～350, further preferably in the range of 200～300.
About the molecular weight of the condensed polycyclc aromatic compound with a plurality of epoxy radicals, increase from preventing resin viscosity From the viewpoint of operability high, as collecting agent deteriorates, preferably in the range of 400～800, further preferably 400～ In the range of 600.
Additionally, for adjust viscosity, improve mar proof, improve resistance to fluffing, improve convergence, improve high order processability Etc. purpose, it is also possible to add the bis-phenol that the molecular weight of " Epikote " 828, " Epikote " 834 etc is little in above-mentioned sizing agent Type epoxide, straight-chain low molecular weight epoxy compound, Polyethylene Glycol, polyurethane, polyester, emulsifying agent or surfactant Deng other compositions.
And then, that adds the rubber such as nitrile rubber or epoxy radicals end-blocking nitrile rubber etc has the straight of elastomer properties The epoxy-modified compounds of chain etc. are the most out of question.
About the sizing agent adhesion amount to carbon fiber, from the viewpoint of increase with the improvement amplitude of the cementability of resin, On the other hand, from the consumption avoiding sizing agent become excessive from the viewpoint of, preferably to per unit weight carbon fiber give 0.01 More than weight %, below 10 weight %, more preferably give below more than 0.05 weight %, 5 weight %, further preferably give More than 0.1 weight %, below 2 weight %.
In the present invention, sizing agent is preferably by similarly coating, coating.That is, the thickness of starching oxidant layer be 20～200 angstroms and The maximum of thickness is preferred less than 2 times of minima.By such uniform starching oxidant layer, it is possible to more effectively in Reveal coupling effect.
In the carbon fiber nonwoven fabric that the 3rd scheme of the present invention relates to, the carbon fiber of carbon fiber nonwoven fabric is attached with For carbon fiber weight 100 weight % be 0.1～5.0 weight % selected from above-mentionedization 3～change the chemical formula shown in 5 (III), the specific compound of at least one in (IV) and (V) (below, is the most also referred to as sizing agent.).As above institute Polyoxyethylene moieties and/or polypropylene oxide part in the compound stated give flatness to carbon fiber, have reduction and rub Wipe the effect of coefficient, when giving to carbon fiber nonwoven fabric hereinafter described, it is possible to reduce and produced by carbon fiber interlacing each other Raw frictional force, can improve mobility and plastic property.On the other hand, bisphenol A moieties has the compatibility improved with matrix resin Effect.Compared with the situation being used in mixed way each single component, use above-mentioned each composition by copolymerization, it is possible to maintain and resin The compatibility, it is possible to further enhance the effect reducing coefficient of friction.
Additionally, for above-mentioned sizing agent, when being less than the compound of 10 for the m+n in above-mentioned chemical formula, reduce friction The effect of coefficient is little, the most preferably.During additionally, m+n is more than 50, the compatibility with matrix resin reduces, matrix resin and carbon fiber Cementability reduce, therefore the most preferred.
Process as sizing agent mentioned above, following processing method can be applied, i.e. make by generally well-known surface Treatment process and washing step etc. and be spontaneously wet out by water, moisture content is that the water-wet carbon fiber bundle about 20～80 weight % is dried After, the processing method of the attachment liquid (sizing liquor) containing sizing agent.
As the imparting means of sizing agent, it is not particularly limited, such as, has following method: impregnate in sizing liquor via roller Method；The method contacted with the roller being attached with sizing liquor；With the vaporific method etc. blowing and spraying sizing liquor.Additionally, be batch (-type), company Any one in continuous formula, but preferably productivity ratio is good and can reduce the continuous way of deviation.In the case of Gai, preferably control starching Liquid concentration, temperature, spinline tension etc. so that sizing agent effective ingredient is to the adhesion amount of carbon fiber in proper range and equably Attachment.Additionally, it is highly preferred that when giving sizing agent, make carbon fiber vibrate with ultrasound wave.
Baking temperature and drying time should adjust according to the adhesion amount of compound, but from completely removing the tax of sizing agent From the viewpoint of giving the solvent of use, shortening and be dried the required time, on the other hand, from preventing the heat deterioration of sizing agent, Prevent carbon fiber bundle hardening thus cause bundle spreadability deteriorate from the viewpoint of, baking temperature be preferably more than 130 DEG C, 350 Below DEG C, more preferably more than 180 DEG C, less than 250 DEG C.
As in sizing agent use solvent, can enumerate water, methanol, ethanol, dimethylformamide, dimethyl acetylamide, Acetone etc., from processing ease, take precautions against natural calamities from the viewpoint of, preferably water.Therefore, compound conduct that is insoluble or that be insoluble in water is used During sizing agent, emulsifying agent, surfactant etc. can be added and become water dispersible and use.Specifically, as Emulsifying agent, surfactant, it is possible to use styrene-maleic anhydride copolymer, alkene-copolymer-maleic anhydride, naphthalene sulfonate Formaldehyde condensation products, the anionic emulsifier such as sodium polyacrylate, the cationic breast such as polymine, polyvinyl imidazol quinoline Agent, nonyl phenol EO addition product, polyvinyl alcohol, the copolymer of polyoxyethylene ether-ester, Isosorbide Dinitrate oxirane The nonionic emulsifier etc. such as addition product, but preferably little with the interaction of epoxy radicals nonionic emulsifier.
For the single quality of carbon fiber, sizing agent adhesion amount is preferably more than 0.01 mass %, 10 mass % Hereinafter, more than more preferably 0.05 mass %, below 5 mass %, further preferably give more than 0.1 mass %, 2 mass % with Under.When being below 0.01 mass %, it is difficult to present cementability and improve effect.When being more than 10 mass %, by carbon fiber nonwoven fabric Mechanical properties when making carbon fibre composite products formed reduces sometimes.
For carbon fiber bundle, in order to obtain carbon fiber-integrated body hereinafter described, (it is for representing carbon fiber bundle for pendency value The index of hardness) divided by monofilament bending stiffness, i.e. pendency value/monofilament bending stiffness preferably 1.4 × 103～4.0 × 103cm/ (Pa·cm4In the range of), more preferably 1.5 × 103～3.0 × 103cm/(Pa·cm4In the range of).If pendency value/monofilament Bending stiffness is less than 1.4 × 103cm/(Pa·cm4), then the convergence of fiber is poor, and be described below obtains carbon fiber nonwoven fabric Operation (air lay, combing etc.) in the easy fibrillation of fiber, exist when making carbon fibre composite mouldability deteriorate Situation, if more than 4.0 × 103cm/(Pa·cm4), then dislike with the wettability of matrix resin when making carbon fibre composite Changing, mechanical characteristic may reduce.
As obtaining the operation of carbon fiber nonwoven fabric, combing, air lay etc. can be enumerated.So-called combing in the present invention, Refer to operations described below: by the aggregation of discontinuous fiber being applied power with rake along the most same direction, make not connect The direction of continuous fiber is consistent or by the operation of fiber detaching.The carding apparatus with following roller is generally used to carry out, described Roller is: possesses the roller of a large amount of nadel on surface and/or is wound with the roller wiry of the bladed projection with saw.
When stating combing on the implementation, in order to prevent carbon fiber from fractureing, preferably shorten carbon fiber present in the carding apparatus Time (holdup time).Specifically, carbon fiber present on tinsel (wire) is made to divide a word with a hyphen at the end of a line the most at short notice To doffer (doffer roll), described tinsel is entangled on the cylinder (cylinder roll) of carding apparatus.Therefore, in order to Dividing a word with a hyphen at the end of a line described in promotion, the preferably rotating speed at cylinder is to rotate under the such high rotating speed of such as more than 150rpm.Additionally, due to Identical reason, the most for example, more than 10m/ minute such fast speed of the superficial velocity of doffer.
The operation of combing carbon fiber bundle is not particularly limited, it is possible to use common operation.Such as, as it is shown in figure 1, combing Device 1 is mainly constituted by with lower part: cylinder 2, is arranged at the licker-in (take in roll) of upstream side near its outer surface 3, with licker-in 3 be opposition side the doffer 4 that arranges near the outer surface of cylinder 2 of downstream, between licker-in 3 and doffer 4 The a plurality of working rolls (worker roller) 5 arranged near the outer surface of cylinder 2, the stripping of arranging near working roll 5 Roller (stripper roller) 6, the feed roll motor (feed roller) 7 arranged near licker-in 3 and belt conveyer 8.
Discontinuous carbon fiber bundle 9 is supplied to belt conveyer 8, and carbon fiber bundle 9 passes sequentially through the appearance of feed roll motor The outer surface of face and licker-in 3 is fed on the outer surface of cylinder 2.To this stage, carbon fiber bundle is disengaged, and forms cotton The aggregation of cotton-shaped carbon fiber bundle.The flocculence carbon fiber bundle aggregation being fed on cylinder 2 outer surface is partially wrapped in On the outer surface of working roll 5, but this carbon fiber is peeled by stripper roller 6 and is returned again on the outer surface of cylinder 2.? Feed roll motor 7, licker-in 3, cylinder 2, working roll 5, stripper roller 6 each roller outer surface on, substantial amounts of pin, projection are to erect State exist, in above-mentioned operation carbon fiber bundle because of the effect of pin by fibrillation to regulation bundle, to be to a certain degree orientated.Warp The carbon fiber bundle crossing said process and extremely specified by fibrillation, using the fleece of the lamellar of a kind of form as carbon fiber-integrated body The form of 10 moves to the outer surface of doffer 4.
Air lay is the manufacture method of the non-woven fabrics of chopped fiber, and it is not particularly limited, and common air-flow can be used to become Net method.As common air laid, Honshu paper process, Kroyer method, Dan-Web method, J&J method, KC method, this section can be enumerated Special (Scott) method etc..
Such as, as in figure 2 it is shown, airflow net forming apparatus 11 has the cylindrical shape of mutually opposing rotation and has punctulate rotary drum 12 and the evener roller (pin cylinder) 13 that is arranged in each rotary drum 12, carbon fiber bundle monomer or carbon fiber bundle and thermoplasticity Resin fibre is delivered to rotary drum 12 by wind together with large quantity of air, by evener roller 13 fibrillation in rotary drum 12, discharges from pore, under Drop down onto on the tinsel 14 thereunder advanced.Now, the air for air-supply is arranged at the air-suction trunk under tinsel 14 Carbon fiber bundle and the thermoplastic resin of the carbon fiber bundle monomer of (suction box) 15 suction, the most fibrillation or fibrillation are fine Dimension is stayed on tinsel 14, forms carbon fiber nonwoven fabric.
Additionally, the most so-called carbon fiber nonwoven fabric, refer to become net or combing fine at discontinuous carbon by said flow Under the dimension state that oriented by fibrillation of bundle, keep the carbon fiber nonwoven fabric of form by fiber entanglement each other and friction, can Enumerate laminar fleece, by fleece lamination, make its complexation, the bonding and non-woven fabrics etc. that obtains as required.For For the carbon fiber nonwoven fabric arrived, from preventing carbon fiber from fractureing, bending, and can suppress fiber interlacing power each other from And when making carbon fibre composite from the viewpoint of good fluidity, preferably obtained by air lay；From non-woven fabrics Uniformity from the viewpoint of, preferably obtained by combing.
Carbon fiber nonwoven fabric can be only made up of carbon fiber but it also may containing thermoplastic resin fibre and/or thermoplasticity Resin particle.Add thermoplastic resin fibre can air lay, combing operation in prevent the fracture of carbon fiber, so excellent Choosing.Owing to carbon fiber is rigidity and more crisp, so being difficult to be wound around and easily snap off.Therefore, the carbon fiber only formed by carbon fiber There is easily disconnection in non-woven fabrics in it manufactures or carbon fiber holds caducous problem.For air laid, by containing Thermoplastic fibre and/or thermoplastic resin particle, can utilize following method to improve carbon fiber nonwoven fabric in subsequent handling Operability, described method is: by using the crimping of hot calender roll or heat embossing roller etc., heat treatment to make the side of fiber thermal welding Method, the method making fiber interlacing by acupuncture (needle punch) or spun lacing (water jet needle) etc..With regard to combing method For, by containing soft and being difficult to the thermoplastic resin fibre fractureing, being easily wound around, the carbon fiber that uniformity is high can be formed Aggregation.In the present invention, in the case of containing thermoplastic resin fibre in carbon fiber-integrated body, carbon in carbon fiber-integrated body The containing ratio of fiber is preferably 20～95 mass %, more preferably 50～95 mass %, more preferably 70～95 mass %. If the ratio of carbon fiber is low, then it is difficult to obtain high mechanical property when making carbon fibre composite, otherwise, if thermoplastic resin The ratio of fat fiber is too low, then can not get the effect of the uniformity of above-mentioned raising carbon fiber-integrated body.
In carbon fiber bundle in carbon fiber nonwoven fabric, constitute carbon fiber bundle (1) and (wherein constitute the carbon fiber of carbon fiber bundle Radical is more than 90) the average x of quantity of radical of carbon fiber in the range of 90～1000.From improving hereinafter described From the viewpoint of the appearance of the rate of utilization of strength of carbon fiber and the products formed in time making carbon fibre composite, structure The average x of quantity of bundles of carbon fiber radical preferably in the range of 90～600, the scope of more preferably 90～500.From From the viewpoint of increasing carbon fiber content when making carbon fibre composite, obtaining high elastic modelling quantity, average x is preferred for quantity In the range of 300～1000, more preferably 500～1000.When the average x of quantity of carbon fiber bundle is less than 90, fiber Interlacing number each other increases, and mobility deteriorates.During more than 1000, the delicate area such as rib are followed by mechanical property and carbon fiber Property deteriorate, the deviation of mechanical property becomes big.
For the carbon fiber bundle in carbon fiber nonwoven fabric, the radical of the carbon fiber constituting carbon fiber bundle is more than 90 Carbon fiber bundle (1) be preferably more than 5 weight %, 80 weights relative to the ratio of the carbon fiber gross weight in carbon fiber nonwoven fabric Amount below %.From the viewpoint of the appearance improving the rate of utilization of strength of carbon fiber and products formed, preferably 5 weight % with Below upper, 50 weight %, more than more preferably 5 weight %, below 45 weight %.From improving mobility further, increasing and make Carbon fiber content during carbon fibre composite, obtain high elastic modelling quantity from the viewpoint of, preferably greater than 30 weight % and be Below 80 weight %, more preferably greater than 35 weight % and be below 80 weight %.From rate of utilization of strength and the products formed of carbon fiber Appearance, from the standpoint of harmony between mobility, preferably greater than 30 weight % and be below 50 weight %.Carbon fiber When the ratio of bundle (1) is less than 5 weight %, fiber interlacing number each other increases, and mobility deteriorates.During more than 80 weight %, machinery The tracing ability of the delicate area such as rib is deteriorated by characteristic and carbon fiber, and the deviation of mechanical property becomes big.
By the above-mentioned carbon fiber bundle (1) in carbon fiber nonwoven fabric, hereinafter described constitute carbon fiber bundle carbon fiber Radical xnStandard deviation meet the scope of 50≤σ≤500, carbon fiber bundle is distributed in carbon fiber nonwoven fabric dispersedly, by This can obtain can realize that the deviation of high fluidity and high mechanical property and mechanical property is the least simultaneously, carbon fiber is to fine portion The carbon fiber nonwoven fabric that the tracing ability of position is also excellent.When above-mentioned standard deviation is less than 50, mobility deteriorates, above-mentioned standard deviation During more than 500, mechanical property deteriorates, and the deviation of mechanical property becomes big.Above-mentioned standard deviation is preferably the model of 100≤σ≤350 Enclose, more preferably the scope of 150≤σ≤350, be even more preferably the scope of 150≤σ≤300.
In the present invention, containing in the case of thermoplastic resin fibre in carbon fiber-integrated body, as long as at attainable cost In the range of the purpose (that is, keep the form of carbon fiber-integrated body, prevent coming off of carbon fiber) of invention, then thermoplastic resin is fine The fibre length of dimension is not particularly limited, and generally can use the thermoplastic resin fibre of 3～about 100mm.Need explanation It is that the fibre length of thermoplastic resin fibre relatively can also determine according to the fibre length of carbon fiber.
Additionally, in above-mentioned combing method, in order to improve the effect of the entanglement brought by thermoplastic resin fibre, preferably to heat Plastic resin fiber gives curling.As long as in the range of the purpose of attainable cost invention, then the degree crimped limits the most especially The thermoplastic resin fibre that fixed, generally can to use crispation number be 5～25/about 25mm, crimp percent is 3～about 30%.
Containing in the case of thermoplastic resin particle in carbon fiber-integrated body, spherical, fine platy, granule can be enumerated (pellet) columned thermoplastic resin particle as.Preferred mean diameter when making ball is 0.01～1000 μm.
As the material of thermoplastic resin fibre as above, it is not particularly limited, can be combined making carbon fiber Do not make during material products formed mechanical property be greatly reduced in the range of suitably select.If example, then can use following resin Spinning and the fiber that obtains, described resin is: the polyolefin-based resins such as polyethylene, polypropylene, nylon 6, nylon 6,6 polyamide such as grade It is polyester based resin, polyether-ketone, polyether sulfone, the virtues such as resin, polyethylene terephthalate, polybutylene terephthalate (PBT) Fragrant polyamide etc..The material of described thermoplastic resin fibre preferably suitably selects according to the combination of matrix resin.Use down The thermoplastic resin fibre stating resin does not make the mechanical property of carbon fibre reinforced plastic reduce, so particularly preferably, described Resin is: the resin identical with matrix resin and matrix resin have the resin of the compatibility or high with the cementability of matrix resin Resin.If example, then thermoplastic resin fibre be preferably selected from by Fypro, polyphenylene sulfide fibre, polypropylene fibre, The fiber of at least one in the group of polyetheretherketonefiber fiber and phenoxy resin fiber composition.
In the present invention, when matrix resin is impregnated in carbon fiber nonwoven fabric, can make containing thermoplastic resin fine The carbon fiber nonwoven fabric of dimension, is directly used as matrix resin by the thermoplastic resin fibre contained in carbon fiber nonwoven fabric；Can also The carbon fiber nonwoven fabric not containing thermoplastic resin fibre is used as raw material, contains in any stage manufacturing carbon fibre composite Leaching matrix resin.Even additionally, the carbon fiber nonwoven fabric containing thermoplastic resin fibre being used as in the case of raw material, also Any stage impregnation matrix resin of carbon fibre composite can manufactured.In these cases, thermoplastic resin is constituted fine The resin of dimension and matrix resin can be identical resin, it is also possible to for different resins.Constitute the tree of thermoplastic resin fibre In the case of fat is different from matrix resin, preferably both have the compatibility or affinity is high.
When manufacturing carbon fibre composite, impregnation operation (using as the thermoplastic resin of matrix resin containing being immersed in as above In described carbon fiber nonwoven fabric thus make the operation of carbon fibre composite) pressuring machine with heating function can be used Implement.As pressuring machine, as long as temperature, pressure necessary to the impregnation of matrix resin can be realized, then it is not particularly limited, permissible Use following pressuring machine: there is the common pressuring machine of the plane platen of lifting, there is the mechanism of 1 pair of ring steel belt traveling So-called biobelt pressuring machine.In described impregnation operation, after matrix resin can being made the lamellars such as film, non-woven fabrics, fabric, with carbon Fabric nonwoven cloth lamination, and use the melted impregnation matrix resins such as above-mentioned pressuring machine in this condition.In addition it is also possible to use Following method: use matrix resin to make discontinuous fiber, mixes with inorfil in the operation making carbon fiber nonwoven fabric Close, thus make containing matrix resin and the carbon fiber nonwoven fabric of inorfil, use pressuring machine etc. to this carbon fiber nonwoven fabric The method carrying out heating pressurization.
It follows that embodiments of the invention, comparative example are illustrated.
First, characteristic, the assay method used in embodiment, comparative example is illustrated.
(1) assay method of fibre bundle
The sample of 100mm × 100mm is cut from carbon fiber nonwoven fabric, then, right in being heated to the electric furnace of 500 DEG C Sample heats about 1 hour, burns the Organic substances such as thermoplastic resin fibre.Measure after cooling to room temperature the carbon fiber of residual without Spin the quality of cloth, then from carbon fiber nonwoven fabric, take out whole carbon fiber bundle with tweezers.For the whole carbon fiber bundles taken out, Use can measure the balance to 1/10000g, measures weight Mn and length Ln of each carbon fiber bundle.After mensuration, to each bundle meter Calculate the carbon mono-filaments radical x constituting carbon fiber bundlen=Mn/ (Ln × F).Here, F is the fiber number of carbon fiber, xnFor carbon fiber bundle Composition monofilament radical.By the composition monofilament radical x of carbon fiber bundlenBe the carbon fiber bundle of more than 90 as carbon fiber bundle (1), Gross weight is calculated as M1, bundle sum is calculated as N, is measured.Additionally, monofilament radical x will be constitutednCarbon fiber bundle less than 90 As fibre bundle (2), the gross weight of carbon fiber bundle (2) is calculated as M2, it is measured.By fibrillation to the journey cannot taken out with tweezers The fibre bundle of degree is concentrated, last gravimetry.Additionally, in the case of mensuration short in fibre length, weight becomes difficulty, permissible With the interval of about 0.2mm, fibre length is classified, by gravimetry in categorized plurality of fibers constriction, use average Value.After all carrying out classifying, measuring, calculate the quantity average x=∑ of structure bundles of carbon fiber radical for carbon fiber bundle (1) { Mn/ (Ln × F) }/N, the carbon fiber radical x of composition carbon fiber bundlenStandard deviation={ 1/N × ∑ (xn-x)2}1/2, obtain The average x of quantity of structure bundles of carbon fiber radical and the carbon fiber radical x of composition carbon fiber bundlenStandard deviation.Need explanation , N is the bundle sum of carbon fiber bundle (1).Additionally, carbon fiber bundle (A) can lead to relative to the ratio of carbon fiber bundle gross weight Cross
M1/(M1+M2)×100
Obtain.
(2) flow test (punch forming)
The carbon fibre composite that 2 chip sizes are 100 × 100mm × 2mm is preheated to the fusing point+40 DEG C of thermoplastic resin Then 2 overlaps are arranged in warmed up to the pressurization disk of 120 DEG C by (such as, be 260 DEG C during Ny6), pressurization 5 under 20Mpa Second.Measure the area A2 after this compression and the area A1 of sheet material before compression, using A2/A1 as mobility (%).
(3) Vf (containing ratio of the carbon fiber in carbon fibre composite)
From the products formed of carbon fibre composite, cut the sample of about 2g, measure its quality.Then, it is being heated to Sample is heated 1 hour by the electric furnace of 550 DEG C, burns the Organic substances such as matrix resin.After being cooled to room temperature, the carbon measuring residual is fine The quality of dimension.Measure the quality ratio relative to the quality burning the sample before the Organic substances such as matrix resin of carbon fiber, as The containing ratio of carbon fiber.
(4) bend test
Bending strength is measured according to JIS-K7171.
(5) fibre strength utilization rate
Calculated by following formula.
Fibre strength utilization rate=bending strength/Vf
(6) monofilament bending stiffness (Pa m4)
Calculated by monofilament bending stiffness=E × I.Here,
E: monofilament elastic modelling quantity,
I: cross sectional moment of inertia.
Assume that fibre section is positive round, fibre diameter D obtain cross sectional moment of inertia, by filament stretch elastic modelling quantity and cross section The moment of inertia obtains bending stiffness.
(7) pendency value/monofilament bending stiffness
With represent the pendency value of hardness of carbon fiber bundle divided by the bending stiffness of monofilament, thus as sizing agent (Sz agent) The index of convergence.
(8) the pendency value (cm) of carbon fiber bundle
As shown in Fig. 3 (A), the carbon fiber bundle 21 pulled out not applying tension force on bobbin cuts into the length of 40cm, One end fixation adhesive tape 22 is fixed, at the counterweight 23 of other end suspention 100g, after correcting twisting and bending, is measuring temperature Atmosphere is placed 30 minutes.Then, take off counterweight 23, as shown in Fig. 3 (B), carbon fiber bundle 25 is placed on the water that angle is 90 ° On flat rectangle platform 24 so that carbon fiber bundle 25 exposes 25cm from platform, it is supported making the carbon fiber bundle of 40cm not bend, With fixation adhesive tape 26, the carbon fiber portion on platform is fixed simultaneously, then remove the support of the part exposed from platform and make it hang down Under, measure after 2 seconds from the length of horizontal range L lighted, using meansigma methods that n number is 3 times as pendency value.
(9) coefficient of friction
Using following rubbing device, in described rubbing device, by the stainless steel bar of 5 a diameter of 10mm, (chromium plating, surface is thick Rugosity is 1～1.5s) configure the most abreast with the interval of 50mm, and rod is configured z-shape so that carbon fiber strand energy Enough pass through while the surface with the contact angle contact rod of 120 °.Utilize this device that carbon fiber wire bar is applied 0.09g/ denier Enter side tension force so that it is pass through with the silk speed of 3m/ minute, the warp tension ratio of strand the entry side and the exit side obtain friction system by following formula Number.
Coefficient of friction=(3/8 π) ln (T2/T1)
T1: strand enters side tension force
T2: strand goes out side tension force
[embodiment]
First, carbon fiber bundle and the sizing agent used in embodiments of the invention 1～7, comparative example 1～3 is illustrated.
[carbon fiber bundle (A)]
For fibre diameter be 7 μm, tensile modulus of elasticity be 230GPa, monofilament bending stiffness be 2.71 × 10-11Pa· m4, fibril number be the continuous print carbon fiber bundle of 24000, as sizing agent, by glycerol triglycidyl group ether dimethyl methyl It is 1 weight % that amide (hreinafter referred to as DMF) dilution makes resinous principle, prepares sizing agent mother solution, fine to carbon by infusion process Dimension gives sizing agent, is dried in 230 DEG C.Adhesion amount is 0.4 weight %.
[carbon fiber bundle (B)]
Sizing agent is changed to glycerol diglycidyl ether, in addition, operates in the same manner as carbon fiber bundle (A), To carbon fiber bundle.
[carbon fiber bundle (C)]
Sizing agent is changed to polyethylene glycol diglycidyl base ether (in formula [I], R1For-CH2CH2-, m=9), except this with Outward, operate in the same manner as carbon fiber bundle (A), obtain carbon fiber bundle.
[carbon fiber bundle (D)]
Sizing agent is changed to the two many glycidyl ethers of glycerol, in addition, operates in the same manner as carbon fiber bundle (A), Obtain carbon fiber bundle.
[carbon fiber bundle (E)]
Sizing agent is changed to diethylene glycol diglycidyl glyceryl ether, in addition, grasps in the same manner as carbon fiber bundle (A) Make, obtain carbon fiber bundle.
[carbon fiber bundle (F)]
Sizing agent is changed to has the bisphenol A-type diglycidyl ether of aromatic rings, YUKA SHELL EPOXY Co., Ltd. system " Epikote " 828 (having the epoxide of aromatic rings), in addition, operates in the same manner as carbon fiber bundle (A), Obtain carbon fiber bundle.
[carbon fiber bundle (G)]
Sizing agent is changed to phenol Novolacs type glycidyl ether, YUKA SHELL EPOXY Co., Ltd. system " Epikote " 154 (having the epoxide of aromatic rings), in addition, operates in the same manner as carbon fiber bundle (A), obtains carbon Fibre bundle.
Embodiment 1:
Carbon fiber bundle (A) is cut into fibre length is 15mm, according to be by quality ratio 90: 10 ratio by cleaved Carbon fiber bundle (A) and nylon 6 chopped fiber (chopped fiber fiber number is 1.7dtex, and Cutting Length is 51mm, crispation number is 12/ 25mm, crimp percent is 15%) mixing, put in carding apparatus.By fleece juxtaposition out, formed by carbon fiber bundle (A) and nylon 6 fiber formed per unit area weight be 100g/cm2Lamellar carbon fiber nonwoven fabric.In carbon fiber nonwoven fabric The weight of carbon fiber bundle (1) be 18 weight % relative to the ratio of carbon fiber gross weight, the number of structure bundles of carbon fiber radical Measuring average x is 160, and standard deviation is 70.
The coiling direction of lamellar carbon fiber nonwoven fabric is calculated as 0 °, lamination carbon-fibre nonwoven in the way of becoming 0 °/90 ° Cloth, and then with overall with polyamide resin film (" CM1001 ", η r=2.3, east beautiful (strain) system) layer through the carbon fiber nonwoven fabric of lamination Close so that carbon fiber becomes 30: 70 with the volume ratio of thermoplastic resin, then entirety corrosion resistant plate is clamped, pre-in 260 DEG C Heat is after 90 seconds, in 260 DEG C of hot pressing 180 seconds while applying the pressure of 2.0MPa.Then, 50 it are cooled under pressurised conditions DEG C, obtain the flat board of the carbon fibre composite that thickness is 2mm.Relative to 0 ° of direction on the top layer of the flat board obtained, measure 0 ° With the bending strength on 90 ° of directions, the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 485MPa as a result, fibre strength profit It is that 16.2MPa/%, CV value is less than 5% by rate.
In the way of becoming the size of 100mm × 100mm, from the flat board obtained, cut sample, carry out flow test, knot Fruit can obtain the high-quality product that mobility is 270% flowing.Condition, mensuration, evaluation result are shown in table 1.
Embodiment 2:
The weight forming the carbon fiber bundle (1) in carbon fiber nonwoven fabric is 40 weights relative to the ratio of carbon fiber gross weight Amount %, the average x of quantity of structure bundles of carbon fiber radical are 320, standard deviation is the carbon fiber nonwoven fabric of 200, except this with Outward, same as in Example 1.Measuring the bending strength on 0 ° of flat board and 90 ° of directions obtained and mobility, result can obtain Following high-quality product: the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 480MPa, and fibre strength utilization rate is 16.0MPa/%, CV value is less than 5%, and mobility is 290% flowing.
Embodiment 3:
The weight forming the carbon fiber bundle (1) in carbon fiber nonwoven fabric is 62 weights relative to the ratio of carbon fiber gross weight Amount %, the average x of quantity of structure bundles of carbon fiber radical are 615, standard deviation is the carbon fiber nonwoven fabric of 320, except this with Outward, same as in Example 1.Measuring the bending strength on 0 ° of flat board and 90 ° of directions obtained and mobility, result can obtain Following high-quality product: the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 463MPa, and fibre strength utilization rate is 15.4MPa/%, CV value is less than 5%, and mobility is 313% flowing.
Embodiment 4～7, comparative example 1～2:
For embodiment 2, as shown in Table 1 and Table 2 carbon fiber bundle (A) is changed to carbon fiber bundle (B), (C), (D), (E), (F), (G), in addition, operate similarly to Example 2, obtain carbon fiber nonwoven fabric and by carbon fiber nonwoven fabric The flat board of the carbon fibre composite formed.Condition, mensuration, evaluation result are shown in Tables 1 and 2 in the lump.
Comparative example 3:
The weight forming the carbon fiber bundle (1) in carbon fiber nonwoven fabric is 84 weights relative to the ratio of carbon fiber gross weight Amount %, the average x of quantity of structure bundles of carbon fiber radical are 1100, standard deviation is the carbon fiber nonwoven fabric of 630, except this In addition, same as in Example 1.Measure the bending strength on 0 ° of flat board and 90 ° of directions obtained and mobility, as a result 0 ° with The meansigma methods of the bending strength on 90 ° of directions is 300MPa, and fibre strength utilization rate is that 10.0MPa/%, CV value is less than 5%, stream Dynamic property is 320%, although mobility is excellent, but bending strength and fiber utilization rate are low, and deviation is also big, mechanical properties.
[table 2]
Comparative example 1 2 3
The carbon fiber bundle used before cutting (F) (G) (A)
Carbon fiber Cutting Length [mm] 15 15 15
The ratio of carbon fiber bundle (1) [%] 39 41 84
The meansigma methods of the bundles of number of fiber of x: structure [root] 314 330 1100
σ: standard deviation 197 220 630
Resin CM1001 CM1001 CM1001
Vf [%] 30 30 30
Mobility [%] 280 288 320
Bending strength (JIS-K7171) [MPa] 421 417 310
CV value ○ ○ ×
Fibre strength utilization rate [MPa/%] 14.0 13.9 10.3
Zero: CV value is less than 5%
×: CV value is more than 5%
Then, carbon fiber and the sizing agent used in embodiments of the invention 8～14, comparative example 4～6 is illustrated.
[carbon fiber bundle (A1)]
For fibre diameter be 7 μm, tensile modulus of elasticity be 230GPa, monofilament bending stiffness be 2.71 × 10-11Pa· m4, fibril number be the continuous print carbon fiber bundle of 24000, as sizing agent, make the R in above-mentioned formula [I]2For-CH2CH2-、R3For- CH3, m be 2, n be 2, use sizing agent the aqueous emulsion that resinous principle is 1 weight %, by infusion process to carbon fiber give Sizing agent, is dried in 180 DEG C.Adhesion amount is 0.8 weight %.
[carbon fiber bundle (B1)]
As sizing agent, it is changed to the R in above-mentioned formula [I]2For-CH2CH2-、R3For-CH3, m be 5, n be the sizing agent of 5, In addition, operate in the same manner as carbon fiber bundle (A1), obtain carbon fiber bundle.
[carbon fiber bundle (C1)]
Sizing agent is changed to the R in above-mentioned formula [I]2For-CH2CH2-、R3For-CH3, m be 10, n be the sizing agent of 10, remove Beyond this, operate in the same manner as carbon fiber bundle (A1), obtain carbon fiber bundle.
[carbon fiber bundle (D1)]
Sizing agent is changed to the R in above-mentioned formula [I]2For-CH2CH2-、R3For-H, m be 15, n be the sizing agent of 15, remove Beyond this, operate in the same manner as carbon fiber bundle (A1), obtain carbon fiber bundle.
[carbon fiber bundle (E1)]
Sizing agent is changed to the R in above-mentioned formula [I]2For-CH2CH2-、R3For-CH3, m be 30, n be the sizing agent of 30, remove Beyond this, operate in the same manner as carbon fiber bundle (A1), obtain carbon fiber bundle.
[carbon fiber bundle (F1)]
Sizing agent is changed to the R in above-mentioned formula [I]1For-OH, R2For-CH2CH2-、R3For-CH3, m be 15, n be 15 Sizing agent, in addition, operates in the same manner as carbon fiber bundle (A1), obtains carbon fiber bundle.
[carbon fiber bundle (G1)]
Sizing agent is changed to the R in above-mentioned formula [I]2For-CH2CH2-、R3For-CH3, m be 1, n be the sizing agent of 1, except this In addition, operate in the same manner as carbon fiber bundle (A1), obtain carbon fiber bundle.
Embodiment 8:
Carbon fiber bundle (A1) is cut into fibre length is 15mm, will be through cutting according to the ratio being 90: 10 by quality ratio (chopped fiber fiber number is 1.7dtex to the carbon fiber bundle (A1) cut, and Cutting Length is 51mm, and crispation number is 12 with nylon 6 chopped fiber Individual/25mm, crimp percent is 15%) mixing, put in carding apparatus.By fleece juxtaposition out, formed by carbon fiber The per unit area weight that bundle (A1) and nylon 6 fiber are formed is 100g/cm2Lamellar carbon fiber nonwoven fabric.Carbon-fibre nonwoven The weight of the carbon fiber bundle (1) in cloth is 18 weight % relative to the ratio of carbon fiber gross weight, structure bundles of carbon fiber radical The average x of quantity be 160, standard deviation is 70.
The coiling direction of lamellar carbon fiber nonwoven fabric is calculated as 0 °, lamination carbon-fibre nonwoven in the way of becoming 0 °/90 ° Cloth, and then with overall with polyamide resin film (" CM1001 ", η r=2.3, east beautiful (strain) system) layer through the carbon fiber nonwoven fabric of lamination Close so that carbon fiber becomes 30: 70 with the volume ratio of thermoplastic resin, then entirety corrosion resistant plate is clamped, pre-in 260 DEG C Heat is after 90 seconds, in 260 DEG C of hot pressing 180 seconds while applying the pressure of 2.0MPa.Then, 50 it are cooled under pressurised conditions DEG C, obtain the flat board of the carbon fibre composite that thickness is 2mm.Relative to 0 ° of direction on the top layer of the flat board obtained, measure 0 ° With the bending strength on 90 ° of directions, the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 467MPa as a result, fibre strength profit It is that 15.6MPa/%, CV value is less than 5% by rate.
In the way of becoming the size of 100mm × 100mm from the flat plate cutting obtained sample, carry out flow test, result The high-quality product that mobility is 275% flowing can be obtained.Condition, mensuration, evaluation result are shown in table 3.
Embodiment 9:
The weight forming the carbon fiber bundle (1) in carbon fiber nonwoven fabric is 40 weights relative to the ratio of carbon fiber gross weight Amount %, the average x of quantity of structure bundles of carbon fiber radical are 320, standard deviation is the carbon fiber nonwoven fabric of 200, except this with Outward, the same as in Example 8.Measuring the bending strength on 0 ° of flat board and 90 ° of directions obtained and mobility, result can obtain Following high-quality product: the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 461MPa, and fiber utilization rate is 15.4MPa/%, CV Value is less than 5%, and mobility is 297% flowing.
Embodiment 10:
The weight forming the carbon fiber bundle (1) in carbon fiber nonwoven fabric is 62 weights relative to the ratio of carbon fiber gross weight Amount %, the average x of quantity of structure bundles of carbon fiber radical are 615, standard deviation is the carbon fiber nonwoven fabric of 320, except this with Outward, the same as in Example 8.Measuring the bending strength on 0 ° of flat board and 90 ° of directions obtained and mobility, result can obtain Following high-quality product: the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 449MPa, and fibre strength utilization rate is 15.0MPa/%, CV value is less than 5%, and mobility is 318% flowing.
Embodiment 11～14, comparative example 4～5:
For embodiment 9, as shown in Table 3 and Table 4 carbon fiber bundle (A1) is changed to carbon fiber bundle (B1), (C1), (D1), (E1), (F1), (G1), in addition, operate similarly to Example 9, obtain carbon fiber nonwoven fabric and by carbon The flat board of the carbon fibre composite that fabric nonwoven cloth is formed.Condition, mensuration, evaluation result are shown in the lump table 3 and table 4.
Comparative example 6:
The weight forming the carbon fiber bundle (1) in carbon fiber nonwoven fabric is 84 weights relative to the ratio of carbon fiber gross weight Amount %, the average x of quantity of structure bundles of carbon fiber radical are 1100, standard deviation is the carbon fiber nonwoven fabric of 630, except this In addition, the same as in Example 8.Measure the bending strength on 0 ° of flat board and 90 ° of directions obtained and mobility, as a result 0 ° with The meansigma methods of the bending strength on 90 ° of directions is 300MPa, and fibre strength utilization rate is that 10.0MPa/%, CV value is less than 5%, stream Dynamic property is 332%, although mobility is excellent, but bending strength and fibre strength utilization rate are low, and deviation is also big, mechanical properties.
[table 4]
Comparative example 4 5 6
The carbon fiber bundle used before cutting (F1) (G1) (A1)
Epoxy radicals/aromatic ring atoms number - 5 8
Carbon fiber Cutting Length [mm] 15 15 15
The ratio of carbon fiber bundle (1) [%] 39 41 84
The meansigma methods of the bundles of number of fiber of x: structure [root] 314 330 1100
σ: standard deviation 197 220 630
Resin CM1001 CM1001 CM1001
Vf [%] 30 30 30
Mobility [%] 275 295 332
Bending strength (JIS-K7171) [MPa] 416 411 300
CV value ○ ○ ×
Fibre strength utilization rate [MPa/%] 13.9 13.7 10.0
Zero: CV value is less than 5%
×: CV value is more than 5%
Then, carbon fiber bundle and the sizing agent used in embodiments of the invention 15～26, comparative example 7～9 is said Bright.
[carbon fiber bundle (A2)]
As sizing agent, prepare the R in the formula [III] of above-mentionedization 31=OH, R2=H, the bisphenol-A epoxy of m=15, n=15 The 1 water-dispersible emulsion of weight % concentration of ethane additive product derivant.It is 7 μm, tensile elasticity by dip roll by fibre diameter Modulus is 230GPa, monofilament bending stiffness is 2.71 × 10-11Pa·m4, fibril number be that the continuous print carbon fiber bundle of 24000 exists In this sizing agent emulsion dipping after, use hot air circulating dryer in 150 DEG C carry out 1 minute be dried.Measure sizing agent Adhesion amount, coefficient of friction, pendency value, result adhesion amount is 0.8 weight %, and coefficient of friction is 0.22, and pendency value is 5.3cm.
[carbon fiber bundle (B2)]
As sizing agent, make the R in the formula [III] of above-mentionedization 31Chemical combination for the chemical formula [VII] shown in above-mentionedization 7 Thing, R2=H, the 1 water-dispersible emulsion of weight % concentration of m=15, n=15, in addition, the carbon fiber of use, sizing agent are attached Method etc. identical with carbon fiber bundle (A2).Measuring the adhesion amount of sizing agent, coefficient of friction, pendency value, result adhesion amount is 0.9 Weight %, coefficient of friction is 0.23, and pendency value is 5.5cm.
[carbon fiber bundle (C2)]
As sizing agent, make the R in the formula [IV] of above-mentionedization 41=H, R2=OH, m=10, n=10 1 weight % dense Spending water-dispersible emulsion, in addition, the carbon fiber of use, sizing agent adherence method etc. are identical with carbon fiber bundle (A2).Measure The adhesion amount of sizing agent, coefficient of friction, pendency value, result adhesion amount is 0.6 weight %, and coefficient of friction is 0.21, and pendency value is 5.0cm。
[carbon fiber bundle (D2)]
Add in the polypropylene glycol that 260g hydroxyl value is 112 87g 2 4-/2 6-toluene di-isocyanate(TDI)s 80/20 Anisotropic body mixture, 34.4g N-methyl diethanol benzyl ammonium chloride, in blanket of nitrogen, make it react 2 hours in 40 DEG C, Obtain the carbamate compounds of the quaternary nitrogen of the NCO containing 2.23 weight %, 0.513 weight %.It is added thereto to 41.3g glycerol diglycidyl ether, 335.4g DMF (dimethylformamide), make it react about 3 hours in 50 DEG C, until different Cyanic acid ester group disappears.Product is the epoxide oxygen (oxirane oxygen) containing 0.743 weight %, containing 0.476 weight The compound that the water dispersible of quaternary nitrogen of amount % is good.
Ratio with 4: 1 add in the above-mentioned polyurethane obtained epoxide equivalent be 225～280, mean molecule quantity be about Liquid-state epoxy resin (Shell Chemicals Co., Ltd.'s system " Epikote " of the bisphenol-A diglycidyl ether type of 470 843) dimethyl formamide solution of 30 weight %, then adds water, obtains 1 weight % emulsion, as sizing agent, In addition, identical with carbon fiber bundle (A2).Measuring the adhesion amount of sizing agent, coefficient of friction, pendency value, result adhesion amount is 0.8 weight %, coefficient of friction is 0.34, and pendency value is 10.5cm.
[carbon fiber bundle (E2)]
As sizing agent, make the R in the formula [III] of above-mentionedization 31=OH, R2=H, the 1 weight % concentration of m=1, n=1 Water-dispersible emulsion, in addition, the carbon fiber of use, sizing agent adherence method etc. are identical with carbon fiber bundle (A2).In mensuration The slurry adhesion amount of agent, coefficient of friction, pendency value, result adhesion amount is 0.7 weight %, and coefficient of friction is 0.35, and pendency value is 6.2cm。
Embodiment 15:
Carbon fiber bundle (A2) is cut into fibre length 6mm, according to be by quality ratio 80: 20 ratio by cleaved Carbon fiber bundle mixes with nylon 6 chopped fiber (chopped fiber fiber number is 1.7dtex, and Cutting Length is 10mm), and input air flow becomes net dress Put.Non-woven fabrics out carries out heat treatment, and forming the per unit area weight formed by carbon fiber and nylon 6 fiber is 200g/cm2Lamellar carbon fiber nonwoven fabric.The fibre bundle of the non-woven fabrics formed is measured, the weight of result carbon fiber bundle (1) Amount is 13 weight % relative to the ratio of carbon fiber gross weight, and the average x of quantity of the radical of the bundles of carbon fiber of structure is 160, Standard deviation is 70.
The coiling direction of lamellar carbon fiber-integrated body is calculated as 0 °, lamination carbon fiber-integrated body in the same direction, Jin Eryong Carbon fiber-integrated body entirety and nylon resin melt spraying non-woven fabrics (" CM1001 ", η r=2.3, east beautiful (strain) system) layer through lamination Close so that carbon fiber becomes 30: 70 with the volume ratio of thermoplastic resin, then entirety corrosion resistant plate is clamped, pre-in 240 DEG C Heat is after 90 seconds, in 250 DEG C of hot pressing 180 seconds while applying the pressure of 2.0MPa.Then, it is cooled under pressurised conditions 50 DEG C, obtain the flat board of the carbon fibre composite that thickness is 2mm.Relative to 0 ° of direction on the top layer of the flat board obtained, measure Bending strength on 0 ° and 90 ° of directions, the meansigma methods of the bending strength on 0 ° and 90 ° of directions is 470MPa as a result, fiber utilization Rate is that 15.7MPa/%, CV value is less than 5%.
In the way of becoming the size of 100mm × 100mm from the flat plate cutting obtained sample, carry out flow test, result The high-quality product that mobility is 300% flowing can be obtained.Condition, mensuration, evaluation result are shown in table 5.
Embodiment 16～26:
For embodiment 15, change condition as shown in table 5, table 6, in addition, grasp similarly to Example 15 Make, obtain carbon fiber nonwoven fabric and the flat board of carbon fibre composite formed by carbon fiber nonwoven fabric.By condition, measure, comment Valency result is shown in table 5, table 6.
Comparative example 7:
Carbon fiber bundle (D2) is cut into fibre length 15mm, according to be by quality ratio 80: 20 ratio by cleaved Carbon fiber bundle and nylon 6 discontinuous fibre (chopped fiber fiber number is 1.7dtex, and Cutting Length is 10mm) mix, obtain carbon fine The average x of quantity of the radical that ratio is 23 weight %, the bundles of carbon fiber of structure of dimension bundle (1) is 250, standard deviation is 200 Carbon fiber nonwoven fabric, in addition, operate similarly to Example 15, obtain carbon fiber nonwoven fabric and by carbon fiber nonwoven fabric The flat board of the carbon fibre composite formed.Condition, mensuration, evaluation result are shown in table 7.The stream of the carbon fiber nonwoven fabric obtained Dynamic property is poor.
Comparative example 8:
Carbon fiber bundle (E2) is cut into fibre length 15mm, according to be by quality ratio 80: 20 ratio by cleaved Carbon fiber bundle and nylon 6 discontinuous fibre (chopped fiber fiber number is 1.7dtex, and Cutting Length is 10mm) mix, obtain carbon fine The average x of quantity of the radical that ratio is 22 weight %, the bundles of carbon fiber of structure of dimension bundle (1) is 260, standard deviation is 210 Carbon fiber nonwoven fabric, in addition, operate similarly to Example 15, obtain carbon fiber nonwoven fabric and by carbon fiber nonwoven fabric The flat board of the carbon fibre composite formed.Condition, mensuration, evaluation result are shown in table 7 in the lump.The carbon fiber nonwoven fabric obtained Poor fluidity.
Comparative example 9:
Carbon fiber bundle (A2) is cut into fibre length 15mm, according to be by quality ratio 80: 20 ratio by cleaved Carbon fiber bundle and nylon 6 discontinuous fibre (chopped fiber fiber number is 1.7dtex, and Cutting Length is 10mm) mix, obtain carbon fine The average x of quantity of the radical that ratio is 80 weight %, the bundles of carbon fiber of structure of dimension bundle (1) is 1200, standard deviation is The carbon fiber nonwoven fabric of 630, in addition, operates similarly to Example 15, obtain carbon fiber nonwoven fabric and by carbon fiber without Spin the flat board of the carbon fibre composite that cloth is formed.Condition, mensuration, evaluation result are shown in table 7 in the lump.The carbon fiber obtained without Although spinning cloth good fluidity, but fibre strength utilization rate being the lowest, the deviation of physical property is the biggest.
[table 7]
Comparative example 7 8 9
The carbon fiber bundle used before cutting (D2) (E2) (A2)
Pendency value/bending stiffness [cm/(Pa·cm4)] 3.87×103 2.29×103 1.96×103
Carbon fiber Cutting Length [mm] 15 15 15
The ratio of carbon fiber bundle (1) [%] 23 22 80
The meansigma methods of the bundles of number of fiber of x: structure [root] 250 260 1200
σ: standard deviation 200 210 630
Resin CM1001 CM1001 CM1001
Vf [%] 30 30 30
Mobility [%] 240 240 340
Bending strength (JIS-K7171) [MPa] 430 430 360
CV value ○ ○ ×
Fibre strength utilization rate [MPa/%] 14.3 14.3 12.0
Zero: CV value is less than 5%
×: CV value is more than 5%
Industrial applicability
The carbon fiber nonwoven fabric that the present invention relates to be applicable to that prior art cannot be reached, require high fluidity and high machine The manufacture of all fibre reinforced products formeds that mechanical property deviation is little is deposited and required to tool characteristic also.
Description of reference numerals
1 carding apparatus
2 cylinders
3 licker-ins
4 doffers
5 working rolls
6 stripper rollers
7 feed roll motor
8 belt conveyers
9 discontinuous carbon fibers
The fleece of 10 lamellars
11 airflow net forming apparatus
12 rotary drums
13 evener rollers
14 tinsels
15 air-suction trunks
21 carbon fiber bundles
22 fixation adhesive tapes
23 counterweights
24
25 carbon fiber bundles
26 fixation adhesive tapes

Claims (16)

1. a carbon fiber nonwoven fabric, it is the carbon fiber nonwoven fabric comprising carbon fiber, it is characterised in that carbon fiber is multiple through having The aliphatic compound starching of several epoxy radicals, in the carbon fiber bundle in carbon fiber nonwoven fabric, constitutes the carbon of carbon fiber bundle (1) The average x of quantity of the radical of fiber, in the range of 90～1000/bundle, constitutes the radical of the carbon fiber of carbon fiber bundle (1) Standard deviation is in the range of 50～500, and in described carbon fiber bundle (1), the radical of the carbon fiber constituting carbon fiber bundle is 90 Above.
2. a carbon fiber nonwoven fabric, it is the carbon fiber nonwoven fabric comprising carbon fiber, it is characterised in that carbon fiber is through aromatic series Compound starching, described aromatic compound be the atomic number between epoxy radicals and aromatic rings be more than 6, there is a plurality of ring The aromatic compound of epoxide, in the carbon fiber bundle in carbon fiber nonwoven fabric, constitutes the radical of the carbon fiber of carbon fiber bundle (1) The average x of quantity in the range of 90～1000/bundle, the standard deviation of radical of the carbon fiber constituting carbon fiber bundle (1) exists In the range of 50～500, in described carbon fiber bundle (1), the radical of the carbon fiber constituting carbon fiber bundle is more than 90.
3. carbon fiber nonwoven fabric as claimed in claim 1 or 2, wherein, described in have the compound of a plurality of epoxy radicals be Two ends of the longest atomic link have the compound of epoxy radicals.
4. carbon fiber nonwoven fabric as claimed in claim 3, wherein, described in have the compound of a plurality of epoxy radicals be only Two ends of long atomic link have the compound of epoxy radicals.
5. carbon fiber nonwoven fabric as claimed in claim 1, wherein, described in there is the aliphatic compound of a plurality of epoxy radicals The atomic number of the longest atomic link is 20～200.
6. carbon fiber nonwoven fabric as claimed in claim 1, wherein, described in there is the aliphatic compound of a plurality of epoxy radicals be Selected from the many glycidyl ethers of glycerol, the two many glycidyl ethers of glycerol, polyethylene glycol diglycidyl base ethers, polypropylene glycol The compound of at least one of diglycidyl ether apoplexy due to endogenous wind.
7. carbon fiber nonwoven fabric as claimed in claim 2, wherein, the atomic number between described epoxy radicals and aromatic rings be 6 with On, the aromatic compound with a plurality of epoxy radicals be the compound shown in followingization 1,
[changing 1]
Here, in formula [I], R1For followingization 2, R2For the alkylidene of carbon number 2～30, R3For-H or-CH3, m, n are 2～48 Integer, m+n is 4～50,
[changing 2]
8. carbon fiber nonwoven fabric as claimed in claim 7, wherein, described R2For-CH2CH2-or-CH (CH3)CH2-。
9. carbon fiber nonwoven fabric as claimed in claim 2, wherein, described aromatic compound is condensed polycyclc aromatic chemical combination Thing.
10. carbon fiber nonwoven fabric as claimed in claim 9, wherein, the skeleton of described condensed polycyclc aromatic compound be naphthalene, Any one in anthracene, phenanthrene, pyrene.
11. 1 kinds of carbon fiber nonwoven fabrics, it is the carbon fiber nonwoven fabric comprising carbon fiber, it is characterised in that attached on carbon fiber For carbon fiber weight 100 weight % be 0.1～5.0 weight % selected from followingization 3～change the chemistry shown in 5 The compound of at least one in formula (III), (IV) and (V), in the carbon fiber bundle in carbon fiber nonwoven fabric, constitutes carbon fiber The average x of quantity of the radical of the carbon fiber of bundle (1), in the range of 90～1000/bundle, constitutes the carbon fiber of carbon fiber bundle (1) The standard deviation of radical in the range of 50～500, in described carbon fiber bundle (1), constitute the root of the carbon fiber of carbon fiber bundle Number is more than 90,
[changing 3]
[changing 4]
[changing 5]
In above formula, R1For H, OH, followingization 6 or followingization 7, R2For H or OH, m, n are 1～49, and wherein m+n is 10～50,
[changing 6]
[changing 7]
12. carbon fiber nonwoven fabrics as according to any one of claim 1,2 or 11, wherein, described composition carbon fiber bundle (1) The standard deviation of the radical of carbon fiber is in the range of 50～350.
13. carbon fiber nonwoven fabrics as according to any one of claim 1,2 or 11, wherein, the weight of described carbon fiber bundle (1) Relative to the ratio of carbon fiber gross weight in the range of 5～80 weight %.
14. carbon fiber nonwoven fabrics as according to any one of claim 1,2 or 11, wherein, carbon fiber nonwoven fabric is by 25 DEG C Time pendency value/monofilament bending stiffness 1.4 × 103～4.0 × 103cm/Pa·cm4In the range of carbon fiber bundle formed, The unit of described pendency value is cm, and the unit of described monofilament bending stiffness is Pa cm4。
15. carbon fiber nonwoven fabrics as according to any one of claim 1,2 or 11, wherein, constitute the carbon of carbon fiber nonwoven fabric The monofilament bending stiffness of fiber is 1.0 × 10-11～2.8 × 10-11Pa·m4In the range of.
16. carbon fiber nonwoven fabrics as according to any one of claim 1,2 or 11, wherein, constitute the carbon of carbon fiber nonwoven fabric Fibre length Ln of fiber is in the range of 3～50mm.
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