JP4018550B2 - Carbon fiber spun yarn fabric and method for producing the same - Google Patents

Description

【００８２】
比較例１
実施例１と同じＰＡＮ系酸化繊維を用い、表２に示すように、織物用のタテ方向の紡績糸〔紡績糸(タテ)〕として、より数４５０回／ｍ、太さ(Ｏ_A)５５０ｄｔｅｘの双糸、織物用のヨコ方向の紡績糸〔紡績糸(ヨコ)〕として、より数４５０回／ｍ、太さ(Ｏ_B)４００ｄｔｅｘの双糸を作製した。紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｏ_B／Ｏ_A)は０．７２であった。
【００８３】
次いで、上記紡績糸(タテ)を打込本数３７本／インチ(２．５４ｃｍ)、上記紡績糸(ヨコ)を打込本数３７本／インチ(２．５４ｃｍ)の条件で製織し、目付１９０ｇ／ｍ²、厚さ０．４２ｍｍの平織りの酸化繊維紡績糸織物を得た。
【００８４】
さらに、この酸化繊維紡績糸織物をＰＶＡ水溶液(０．３質量％)にて浸漬処理(樹脂処理)し、ＰＶＡを０．５質量％添着せしめた後、２５０℃、２０ＭＰａにて圧縮処理し、目付１９１ｇ／ｍ²、厚さ０．２０ｍｍ、嵩密度０．９６ｇ／ｃｍ³の樹脂処理・圧縮処理後の酸化繊維紡績糸織物を得た。
【００８５】
この樹脂処理・圧縮処理後の酸化繊維紡績糸織物を、１６００℃、窒素雰囲気下、２分間焼成し炭素化することによって炭素繊維紡績糸織物を得た。
【００８６】
得られた炭素繊維紡績糸織物は、目付が１１４ｇ／ｍ²、厚さが０．２４ｍｍ、嵩密度が０．４８ｇ／ｃｍ³、タテ方向の炭素繊維紡績糸〔紡績糸(タテ)〕の太さ(Ｃ_A)が３３０ｄｔｅｘ、ヨコ方向の炭素繊維紡績糸〔紡績糸(ヨコ)〕の太さ(Ｃ_B)が２４０ｄｔｅｘ、紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｃ_B／Ｃ_A)が０．７３、厚さ方向の電気抵抗値が１０．１ｍΩであり、良好な物性の炭素繊維紡績糸織物ではなかった。表２中×で示す箇所が本発明の構成から逸脱している。
【００８７】
比較例２
実施例１と同じＰＡＮ系酸化繊維を用い、表２に示すように、織物用のタテ方向の紡績糸〔紡績糸(タテ)〕として、より数４５０回／ｍ、太さ(Ｏ_A)５５０ｄｔｅｘの双糸、織物用のヨコ方向の紡績糸〔紡績糸(ヨコ)〕として、より数４５０回／ｍ、太さ(Ｏ_B)１９０ｄｔｅｘの双糸を作製した。紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｏ_B／Ｏ_A)は０．３５であった。
【００８８】
次いで、上記紡績糸(タテ)を打込本数３７本／インチ(２．５４ｃｍ)、上記紡績糸(ヨコ)を打込本数５５本／インチ(２．５４ｃｍ)の条件で製織し、目付１３０ｇ／ｍ²、厚さ０．２８ｍｍの平織りの酸化繊維紡績糸織物を得た。
【００８９】
さらに、この酸化繊維紡績糸織物をＰＶＡ水溶液(０．３質量％)にて浸漬処理(樹脂処理)し、ＰＶＡを０．５質量％添着せしめた後、１５０℃、１５ＭＰａにて圧縮処理し、目付１３１ｇ／ｍ²、厚さ０．１７ｍｍ、嵩密度０．７７ｇ／ｃｍ³の樹脂処理・圧縮処理後の酸化繊維紡績糸織物を得た。
【００９０】
この樹脂処理・圧縮処理後の酸化繊維紡績糸織物を、１６００℃、窒素雰囲気下、２分間焼成し炭素化することによって炭素繊維紡績糸織物を得た。
【００９１】
得られた炭素繊維紡績糸織物は、目付が７８ｇ／ｍ²、厚さが０．１８ｍｍ、嵩密度が０．４３ｇ／ｃｍ³、タテ方向の炭素繊維紡績糸〔紡績糸(タテ)〕の太さ(Ｃ_A)が３３３ｄｔｅｘ、ヨコ方向の炭素繊維紡績糸〔紡績糸(ヨコ)〕の太さ(Ｃ_B)が１１０ｄｔｅｘ、紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｃ_B／Ｃ_A)が０．３３、厚さ方向の電気抵抗値が４．２ｍΩであり、良好な物性の炭素繊維紡績糸織物ではなかった。表２中×で示す箇所が本発明の構成から逸脱している。
【００９２】
比較例３
実施例１と同じＰＡＮ系酸化繊維を用い、表２に示すように、織物用のタテ方向の紡績糸〔紡績糸(タテ)〕として、より数４５０回／ｍ、太さ(Ｏ_A)１７０ｄｔｅｘの双糸、織物用のヨコ方向の紡績糸〔紡績糸(ヨコ)〕として、より数４５０回／ｍ、太さ(Ｏ_B)１５０ｄｔｅｘの双糸を作製した。紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｏ_B／Ｏ_A)は０．８８であった。
【００９３】
次いで、上記紡績糸(タテ)を打込本数６０本／インチ(２．５４ｃｍ)、上記紡績糸(ヨコ)を打込本数６０本／インチ(２．５４ｃｍ)の条件で製織し、目付７６ｇ／ｍ²、厚さ０．２４ｍｍの平織りの酸化繊維紡績糸織物を得た。
【００９４】
さらに、この酸化繊維紡績糸織物をＰＶＡ水溶液(０．３質量％)にて浸漬処理(樹脂処理)し、ＰＶＡを０．５質量％添着せしめた後、２５０℃、２０ＭＰａにて圧縮処理し、目付７６ｇ／ｍ²、厚さ０．１２ｍｍ、嵩密度０．６３ｇ／ｃｍ³の樹脂処理・圧縮処理後の酸化繊維紡績糸織物を得た。
【００９５】
この樹脂処理・圧縮処理後の酸化繊維紡績糸織物を、１６００℃、窒素雰囲気下、２分間焼成し炭素化することによって炭素繊維紡績糸織物を得た。
【００９６】
得られた炭素繊維紡績糸織物は、目付が４７ｇ／ｍ²、厚さが０．１５ｍｍ、嵩密度が０．３１ｇ／ｃｍ³、タテ方向の炭素繊維紡績糸〔紡績糸(タテ)〕の太さ(Ｃ_A)が１００ｄｔｅｘ、ヨコ方向の炭素繊維紡績糸〔紡績糸(ヨコ)〕の太さ(Ｃ_B)が９０ｄｔｅｘ、紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｃ_B／Ｃ_A)が０．９０、厚さ方向の電気抵抗値が１５．０ｍΩであり、良好な物性の炭素繊維紡績糸織物ではなかった。表２中×で示す箇所が本発明の構成から逸脱している。
【００９７】
【表２】

【００９８】
比較例４
実施例１と同じＰＡＮ系酸化繊維を用い、表３に示すように、織物用のタテ方向の紡績糸〔紡績糸(タテ)〕として、より数４００回／ｍ、太さ(Ｏ_A)８８０ｄｔｅｘの双糸、織物用のヨコ方向の紡績糸〔紡績糸(ヨコ)〕として、より数４００回／ｍ、太さ(Ｏ_B)４００ｄｔｅｘの双糸を作製した。紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｏ_B／Ｏ_A)は０．４６であった。
【００９９】
次いで、上記紡績糸(タテ)を打込本数２３本／インチ(２．５４ｃｍ)、上記紡績糸(ヨコ)を打込本数３７本／インチ(２．５４ｃｍ)の条件で製織し、目付２３０ｇ／ｍ²、厚さ０．４８ｍｍの平織りの酸化繊維紡績糸織物を得た。
【０１００】
さらに、この酸化繊維紡績糸織物をＰＶＡ水溶液(０．３質量％)にて浸漬処理(樹脂処理)し、ＰＶＡを０．５質量％添着せしめた後、２５０℃、２０ＭＰａにて圧縮処理し、目付２３３ｇ／ｍ²、厚さ０．２４ｍｍ、嵩密度０．７７ｇ／ｃｍ³の樹脂処理・圧縮処理後の酸化繊維紡績糸織物を得た。
【０１０１】
この樹脂処理・圧縮処理後の酸化繊維紡績糸織物を、１６００℃、窒素雰囲気下、２分間焼成し炭素化することによって炭素繊維紡績糸織物を得た。
【０１０２】
得られた炭素繊維紡績糸織物は、目付が１４０ｇ／ｍ²、厚さが０．３２ｍｍ、嵩密度が０．４４ｇ／ｃｍ³、タテ方向の炭素繊維紡績糸〔紡績糸(タテ)〕の太さ(Ｃ_A)が５００ｄｔｅｘ、ヨコ方向の炭素繊維紡績糸〔紡績糸(ヨコ)〕の太さ(Ｃ_B)が２４０ｄｔｅｘ、紡績糸(ヨコ)と紡績糸(タテ)との太さ比(Ｃ_B／Ｃ_A)が０．４８、厚さ方向の電気抵抗値が８．２ｍΩであり、良好な物性の炭素繊維紡績糸織物ではなかった。表３中×で示す箇所が本発明の構成から逸脱している。
【０１０３】
【表３】

【０１０４】
【発明の効果】
本発明の炭素繊維紡績糸織物は、厚さ、嵩密度、並びに、タテ方向の炭素繊維紡績糸の太さＣ_Aとヨコ方向の炭素繊維紡績糸の太さＣ_Bとが所定の範囲になるように構成されているので、強度特性に優れ、厚さ方向の電気抵抗値が低く高分子電解質型燃料電池用の電極材として有用な素材であって、且つ薄い素材である。
【０１０５】
また、原料の酸化繊維の物性、その酸化繊維の紡績加工、製織、圧縮処理、焼成等を所定の条件で行うことにより、上記炭素繊維紡績糸織物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thin-layer carbon fiber spun yarn fabric and a method for producing the same.
[0002]
[Prior art]
Polyacrylonitrile (PAN) -based oxidized fibers exhibit the same tensile elongation as ordinary organic fibers and are easy to spin. Using this PAN-based oxidized fiber, a spun yarn (twisted yarn) or the like is spun to obtain a spun yarn, and then the spun yarn is woven and further carbonized to produce a carbon fiber spun yarn fabric. it can.
[0003]
Carbon fiber spun yarn fabric is a material that is excellent in strength characteristics, has a low electric resistance value in the thickness direction, and is useful as an electrode material for polymer electrolyte fuel cells. As described above, since the PAN-based oxidized fiber is suitable for obtaining a carbon fiber spun yarn fabric, its application as a raw material for the electrode material is being promoted.
[0004]
When applied to an electrode material, in the case of a polymer electrolyte fuel cell, the electrode material, the electrolyte membrane, and the separator are integrated to form a set (single cell), and a large number of these are stacked to assemble the battery. . When the battery is used for an automobile or the like that requires high output, the stack stack number is 300 to 400. In these applications, the thicker the set of stacks, the greater the overall battery volume.
[0005]
For this reason, the electrode material is required to be as thin as possible. However, at present, the electrode material is as thick as 0.3 to 0.4 mm.
[0006]
In addition, there exist some which were described in patent document 1, 2 etc. as a conventional manufacturing technique of a carbon fiber spun yarn fabric.
[0007]
In Patent Document 1, a carbon cloth in which warps and wefts made of carbon fibers are plain woven is used as an electrode material, and a carbon cloth to be used as an electrode material (woven yarn made of carbon short fibers, thickness 0.4mm).
[0008]
However, any of the carbon cloths described in Patent Document 1 is different from a carbon fabric using a spun yarn obtained by spinning an oxidized fiber as in the present invention. Also, the described thicknesses are thicker than the scope of the present invention.
[0009]
Patent Document 2 describes a method of producing a carbon fiber spun yarn fabric after shortening the carbon fiber.
[0010]
However, the carbon fiber spun yarn fabric described in Patent Document 2 is completely different from the present invention in the manufacturing method. Moreover, there is no description about the thickness, and there is no description about the use of the electrode material.
[0011]
[Patent Document 1]
JP 7-335234 A (paragraph numbers [0004] and [0027])
[Patent Document 2]
JP 10-280246 A (Claims)
[0012]
[Problems to be solved by the invention]
While the present inventors have been variously studied to obtain a thin-layer carbon fiber spun yarn fabric,
1. By using a PAN-based oxidized fiber having a knot strength higher than that of carbon fiber as a raw material, it becomes possible to produce a fine spun yarn.
2. The spun yarn at the time of weaving is preferably as thin as possible, but the warp yarn is subject to the tension in the winding direction and is also affected by the yarn tension in the transverse direction. For this reason, by placing a spun yarn that is thicker in the warp direction than the warp direction (strong spun yarn) and driving a spun yarn that is thinner in the warp direction than in the warp direction, weaving workability is improved and thickness is reduced. .
3. Further, the manufactured spun yarn fabric is subjected to resin treatment or heat compression without resin treatment to reduce the thickness.
4). The resulting spun yarn fabric is carbonized.
By applying such items and operations, it is possible to obtain a thin carbon fiber spun yarn fabric that has excellent strength characteristics, has a low electrical resistance value in the thickness direction, is useful as an electrode material for polymer electrolyte fuel cells, and is thin It has been found that this can be done, and the present invention has been completed.
[0013]
Accordingly, an object of the present invention is to provide a carbon fiber spun yarn fabric and a method for producing the same, which have solved the above problems.
[0014]
[Means for Solving the Problems]
The present invention for achieving the above object is described below.
[0015]
[1] Thickness is 0.08 to 0.15 mm, bulk density is 0.45 to 0.70 g / cm ^Three The thickness C of the carbon fiber spun yarn in the vertical direction _A (dtex) and width C of carbon fiber spun yarn in the horizontal direction _B (dtex) is the formula 1
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
Carbon fiber spun yarn fabric that meets the requirements.
[0016]
[2] Polyacrylonitrile-based oxidized fiber spun yarn having a dry strength of 1.5 gf / dtex or more and a knot strength of 0.3 gf / dtex or more, and a thickness O of the oxidized fiber spun yarn in the vertical direction _A (dtex) and width of oxidized fiber spun yarn in the horizontal direction O _B (dtex) is the formula 3
250 <O _A <660 Equation 3
And Equation 4
0.40 <O _B / O _A <0.62 Formula 4
The oxidized fiber spun yarn fabric woven from the oxidized fiber spun yarn satisfying the above conditions is compressed at a temperature of 100 to 350 ° C. and a pressure of 0.5 to 20 MPa, and the oxidized fiber spun yarn fabric after the compression treatment is carbonized. 0.08 to 0.15 mm, bulk density 0.45 to 0.70 g / cm ^Three The thickness C of the carbon fiber spun yarn in the vertical direction _A (dtex) and width C of carbon fiber spun yarn in the horizontal direction _B (dtex) is the formula 1
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
The manufacturing method of the carbon fiber spun yarn fabric which satisfy | fills.
[0017]
[3] Polyacrylonitrile-based oxidized fiber spun yarn having a dry strength of 1.5 gf / dtex or more and a knot strength of 0.3 gf / dtex or more, and the thickness O of the oxidized fiber spun yarn in the vertical direction _A (dtex) and width of oxidized fiber spun yarn in the horizontal direction O _B (dtex) is the formula 3
250 <O _A <660 Equation 3
And Equation 4
0.40 <O _B / O _A <0.62 Formula 4
Oxidized fiber spun yarn fabric woven with oxidized fiber spun yarn satisfying the above conditions is resin-treated and the resin is applied in the range of 0.2 to 10% by mass, and then compressed at a temperature of 100 to 350 ° C. and a pressure of 0.5 to 20 MPa. And carbonizing the oxidized fiber spun yarn fabric after the resin treatment / compression treatment, the thickness is 0.08 to 0.15 mm, and the bulk density is 0.45 to 0.70 g / cm. ^Three The thickness C of the carbon fiber spun yarn in the vertical direction _A (dtex) and width C of carbon fiber spun yarn in the horizontal direction _B (dtex) is the formula 1
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
The manufacturing method of the carbon fiber spun yarn fabric which satisfy | fills.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0019]
The carbon fiber spun yarn fabric of the present invention has a thickness of 0.08 to 0.15 mm, preferably 0.08 to 0.14 mm.
[0020]
When the thickness of the carbon fiber spun yarn fabric exceeds 0.15 mm, when this spun yarn fabric is used as an electrode material for a polymer electrolyte fuel cell, it is difficult to make the fuel cell stack compact, and the battery volume is small. This is not preferable because it causes problems such as enlargement.
[0021]
The bulk density of the carbon fiber spun yarn fabric of the present invention is 0.45 to 0.70 g / cm. ^Three It is.
[0022]
The bulk density of carbon fiber spun yarn fabric is 0.45 g / cm ^Three If the ratio is less than 1, the electrical resistance value in the thickness direction of the carbon fiber spun yarn fabric increases (electric conductivity decreases), which is not preferable. Carbon fiber spun yarn fabric has a bulk density of 0.70 g / cm ^Three When this spun yarn fabric is used as an electrode material for a polymer electrolyte fuel cell, a high current density (1.6 A / cm due to a decrease in gas diffusibility during battery operation) ² ) Side voltage drop occurs, which is not preferable.
[0023]
Thickness C of the vertical carbon fiber spun yarn (spun yarn (vertical)) constituting the carbon fiber spun yarn fabric of the present invention _A (dtex) and the thickness C of the carbon fiber spun yarn in the horizontal direction [spun yarn (horizontal)] _B (dtex) is expressed by Equation 1
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
Meet.
[0024]
Carbon fiber spun yarn (vertical) thickness C _A Is more than 400 dtex, it is not preferable because a carbon fiber spun yarn fabric having a desired thickness cannot be obtained.
[0025]
Carbon fiber spun yarn (width) thickness C _B And carbon fiber spun yarn (vertical) thickness C _A Ratio C _B / C _A Is more than 0.62, it is not preferable because a carbon fiber spun yarn fabric having a desired thickness cannot be obtained.
[0026]
The electrical resistance value in the thickness direction of the carbon fiber spun yarn fabric is preferably 4 mΩ. When this spun yarn fabric is used as an electrode material for a polymer electrolyte fuel cell, the lower the electric resistance value, the better the battery performance. If this electrical resistance value exceeds 4 mΩ, the electromotive force is lowered, and the battery performance is deteriorated.
[0027]
In addition, the electrical resistance value in the thickness direction of the carbon fiber spun yarn fabric is measured by a measurement method described later.
[0028]
Hereinafter, an example of the method for producing the carbon fiber spun yarn fabric of the present invention will be described in detail.
[0029]
[Oxidized fiber (single fiber)]
Oxidized fiber (single fiber) of carbon fiber spun yarn fabric raw material is a PAN-based oxidized fiber. For example, a commercially available PAN-based fiber is treated in air at high temperature to cause a cyclization reaction and increase the amount of oxygen bonds. It is possible to use those obtained by flameproofing treatment that makes them infusible and flame-retardant.
[0030]
The dry strength and knot strength in the PAN-based oxidized fiber are physical property values measured according to JIS L 1015.
[0031]
The dry strength of the oxidized fiber is 1.5 gf / dtex (14.7 mN / dtex) or more. When the oxidized fiber dry strength is less than 1.5 gf / dtex (14.7 mN / dtex), the strength of the oxidized fiber spun yarn obtained by spinning the oxidized fiber is reduced, and the oxidized fiber spun yarn is carbonized. This is not preferable because the generation of fine powder due to a decrease in strength of the carbon fiber spun yarn increases.
[0032]
The knot strength of the oxidized fiber is 0.3 gf / dtex (2.9 mN / dtex) or more. When the oxidized fiber knot strength is less than 0.3 gf / dtex (2.9 mN / dtex), it is difficult to obtain a target fine oxidized fiber spun yarn. Even when it is obtained, the spun yarn strength is low and the fabric processing is difficult.
[0033]
The specific gravity of the oxidized fiber is not particularly limited, but is preferably 1.35 to 1.45.
[0034]
The fineness of the oxidized fiber is more preferably in the range of 0.9 to 4.5 dtex and in the range of 1.0 to 2.5 dtex.
[0035]
The number of crimps of the oxidized fiber is not particularly limited, but is preferably 5 to 20 pieces / inch (2.54 cm).
[0036]
The crimp rate of the oxidized fiber is not particularly limited, but is preferably 7 to 15%.
[0037]
The cut length of the oxidized fiber is not particularly limited, but is preferably 25 to 100 mm.
[0038]
[Spinning processing]
The above-described oxidized fibers are spun into oxidized fiber spun yarn (warp yarn) in the warp direction during weaving and oxidized fiber spun yarn (weft yarn) in the warp direction during weaving.
[0039]
Here, the thickness of the warp thread O _A Is 250 to 660 dtex, and the thickness of the weft thread O _B And warp thread thickness O _A Ratio to _B / O _A Is 0.40 to 0.62.
[0040]
Warp thread thickness O _A Is less than 250 dtex, it is not preferable because it tends to cause elongation due to the tension in the driving direction during fabric processing and also tends to cause spun yarn breakage when spun in the horizontal direction. Warp thread thickness O _A Is more than 660 dtex, the spun yarn is too thick, so that the thickness of the woven fabric is increased during the fabric processing, and a carbon fiber woven fabric having a target thickness cannot be obtained.
[0041]
Weft thickness O _B And warp thread thickness O _A Ratio to _B / O _A Is less than 0.40, weaving is difficult due to a decrease in yarn strength. Weft thickness O _B And warp thread thickness O _A Ratio to _B / O _A Is more than 0.62, it is difficult to produce a carbon fiber fabric having a target thickness.
[0042]
Both warp yarn and weft yarn are preferably 350 to 820 times / m. If the number is less than 350 times / m, the strength is lowered and cracking is likely to occur, which is not preferable. If the number is more than 820 times / m, it is not preferable because problems such as a decrease in spinning processability, a single fiber breakage easily occur, and a tendency to flakes occur.
[0043]
[Weaving]
An oxidized fiber spun yarn fabric is produced by weaving the oxidized fiber spun yarn described above.
[0044]
The form of the oxidized fiber fabric is not particularly limited, but plain weave, cedar weave, satin weave and the like are preferable.
[0045]
The thickness of the oxidized fiber fabric is preferably 0.08 to 0.20 mm.
[0046]
The bulk density of the oxidized fiber fabric is 1.0 g / cm. ^Three The following is preferable because it is easy to control the thickness by the compression treatment in the subsequent step. The bulk density of the oxidized fiber fabric is 1.0 g / cm ^Three If it exceeds 1, it is difficult to control the thickness reduction.
[0047]
The number of warp yarns and weft yarns of the oxidized fiber spun yarn is adjusted depending on the thickness of the spun yarn, but is preferably in the range of 30 to 70 yarns / inch (2.54 cm).
[0048]
[Resin treatment]
The oxidized fiber spun yarn woven fabric described above may be subjected to a resin treatment for the purpose of further exhibiting a reduction effect before the compression treatment. Resin treatment suppresses restoration of thickness during carbonization and facilitates obtaining a thin material.
[0049]
The type of the resin may be either thermoplastic or thermosetting resin, but it softens when it is compressed at a high temperature (100 to 350 ° C.) in the subsequent process, fuses between the fibers, and calcined carbonized (nitrogen) It is preferable to use a resin that remains carbonized even in a slight amount (950 to 2300 ° C.) in the atmosphere. For example, resins such as polyvinyl alcohol, carboxymethyl cellulose, epoxy, phenol novolac, aramid, and polyimide are preferable.
[0050]
The optimum amount of the resin adhesion varies depending on the type of resin and the target hardness of the woven fabric after carbonization, but is usually preferably in the range of 0.2 to 10% by mass. When the adhesion amount of the resin exceeds 10% by mass, the carbon fiber spun yarn woven fabric obtained by calcination carbonization is not preferable because it loses flexibility and becomes brittle.
[0051]
The resin treatment method is preferably an immersion method. According to this method, the resin can be applied most uniformly. The temperature during the resin treatment is preferably in the range of room temperature (25 ° C.) to 90 ° C.
[0052]
[Compression processing]
The above-mentioned oxidized fiber spun yarn fabric is subjected to a compression treatment at a temperature of 100 to 350 ° C. and a pressure of 0.5 to 20 MPa after or without the resin treatment.
[0053]
The temperature and pressure during the compression treatment are appropriately adjusted according to the type of resin during the resin treatment and the target thickness of the carbon fiber spun yarn fabric.
[0054]
[Firing / Carbonization]
After the compression treatment, the oxidized fiber spun yarn fabric is preferably carbonized by firing at 950 to 2300 ° C. for 0.5 to 20 minutes in an inert gas atmosphere such as a nitrogen atmosphere.
[0055]
When the temperature during firing is less than 950 ° C., the electrical conductivity of the resulting carbon fiber spun yarn fabric is lowered, which is not preferable. When the temperature during firing exceeds 2300 ° C., the strength of the carbon fiber spun yarn fabric deteriorates and fine powder is generated, which is not preferable.
[0056]
【Example】
The present invention is described in detail by the following examples and comparative examples.
[0057]
Carbon fiber spun yarn fabrics were produced under the conditions of the following examples and comparative examples. Various physical properties of raw material oxidized fiber, oxidized fiber spun yarn fabric before resin / compression treatment, oxidized fiber spun yarn fabric after resin / compression treatment, and carbon fiber spun yarn fabric after firing were measured by the following methods.
[0058]
Specific gravity of oxidized fiber: Measured by Archimedes method (solvent acetone).
[0059]
Fiber performance: Dry strength, knot strength, number of crimps, crimp rate, fineness of oxidized fiber, thickness of spun yarn, and the number were measured according to JIS L 1015.
[0060]
Thickness of spun yarn fabric: The thickness when a load of 200 gf was applied to a circular pressure plate with a diameter of 30 mm (2.8 kPa) was measured.
[0061]
Weight per unit area of the spun yarn fabric was calculated from a mass obtained by drying a spun yarn fabric of 50 mm square at 120 ° C. for 2 hours.
[0062]
Bulk density of spun yarn fabric: calculated from the thickness and basis weight measured under the above conditions.
[0063]
Specific surface area: The surface area per unit mass was calculated from the nitrogen adsorption amount at a relative pressure (nitrogen / helium) of 0.30 by the BET adsorption method.
[0064]
Number of spun yarns: The number of spun yarns / inch (2.54 cm) in the warp direction and the horizontal direction was measured for the woven fabric cut into 50 mm squares.
[0065]
Electrical resistance value: sandwiched between two 50 mm square (thickness 10 mm) gold-plated electrodes so that the entire surface of the carbon fiber fabric was in contact, and the electrical resistance value (mΩ) between the two electrodes was measured.
[0066]
Example 1
PAN-based oxidized fiber [specific gravity 1.39, fineness 2.2 dtex, crimp number 9.0 pcs / inch (2.54 cm), crimp rate 11.0%, cut length 51 mm, dry strength 2.1 gf / dtex (20. 6 mN / dtex) and knot strength 0.4 gf / dtex (3.9 mN / dtex)], and as shown in Table 1, warp-direction spun yarn for fabric (spun yarn (warp)) is several 450 more Times / m, thickness (O _A ) 550 dtex double yarn, horizontal spun yarn for fabric [spun yarn (horizontal)], several 450 times / m, thickness (O _B ) A 250 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.45.
[0067]
Next, the spun yarn (warp) is woven under conditions of 37 yarns / inch (2.54 cm) and the spun yarn (width) is 50 yarns / inch (2.54 cm). m ² A plain weave oxidized fiber spun yarn fabric having a thickness of 0.30 mm was obtained.
[0068]
Furthermore, this oxidized fiber spun yarn fabric was immersed in a PVA aqueous solution (0.3% by mass) (resin treatment), and after 0.5% by mass of PVA was added, it was compressed at 150 ° C. and 15 MPa, 131g / m ² , Thickness 0.14mm, bulk density 0.93g / cm ^Three Oxidized fiber spun yarn fabric after resin treatment / compression treatment was obtained.
[0069]
The oxidized fiber spun yarn fabric after the resin treatment / compression treatment was baked and carbonized at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0070]
The obtained carbon fiber spun yarn fabric has a basis weight of 131 g / m. ² , Thickness is 0.14 mm, bulk density is 0.93 g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 330 dtex, the thickness of carbon fiber spun yarn (spun yarn (horizontal)) in the horizontal direction (C) _B ) Is 150 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.45, the electric resistance value in the thickness direction was 2.0 mΩ, and the carbon fiber spun yarn fabric had good physical properties.
[0071]
Example 2
Using the same PAN-based oxidized fiber as in Example 1, as shown in Table 1, a warp-direction spun yarn for fabric (spun yarn (warp)) was several 420 times / m, and the thickness (O _A ) Twist yarn of 290 dtex, woven spun yarn for fabric (spun yarn (horizontal)), more than 420 times / m, thickness (O _B ) 150 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.52.
[0072]
Subsequently, the spun yarn (warp) is woven under the conditions of 50 yarns / inch (2.54 cm) and the spun yarn (width) is 60 yarns / inch (2.54 cm). m ² A plain weave oxidized fiber spun yarn fabric having a thickness of 0.18 mm was obtained.
[0073]
Furthermore, this oxidized fiber spun yarn fabric was subjected to a compression treatment at 150 ° C. and 15 MPa without resin treatment, and a basis weight of 97 g / m. ² , Thickness 0.11mm, bulk density 0.88g / cm ^Three An oxidized fiber spun yarn woven fabric after compression treatment was obtained.
[0074]
The oxidized fiber spun yarn fabric after the compression treatment was calcinated at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0075]
The obtained carbon fiber spun yarn fabric has a basis weight of 58 g / m. ² , Thickness is 0.12 mm, bulk density is 0.48 g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 170 dtex, the carbon fiber spun yarn in the horizontal direction (spun yarn (width)) (C) _B ) Is 90 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.52 and the electrical resistance value in the thickness direction was 2.5 mΩ, and the carbon fiber spun yarn fabric had good physical properties.
[0076]
Example 3
Using the same PAN-based oxidized fiber as in Example 1, as shown in Table 1, a warp-direction spun yarn for fabric (spun yarn (warp)) was several 420 times / m, and the thickness (O _A ) Twist yarn of 290 dtex, woven spun yarn for fabric (spun yarn (horizontal)), more than 420 times / m, thickness (O _B ) 150 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.52.
[0077]
Subsequently, the spun yarn (warp) is woven under the conditions of 50 yarns / inch (2.54 cm) and the spun yarn (width) is 60 yarns / inch (2.54 cm). m ² A plain weave oxidized fiber spun yarn fabric having a thickness of 0.18 mm was obtained.
[0078]
Furthermore, this oxidized fiber spun yarn fabric was immersed in a PVA aqueous solution (0.3% by mass) (resin treatment), and after 0.5% by mass of PVA was added, it was compressed at 150 ° C. and 15 MPa, 98 g / m ² , Thickness 0.11mm, bulk density 0.89g / cm ^Three Oxidized fiber spun yarn fabric after resin treatment / compression treatment was obtained.
[0079]
The oxidized fiber spun yarn fabric after the resin treatment / compression treatment was baked and carbonized at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0080]
The obtained carbon fiber spun yarn fabric has a basis weight of 59 g / m. ² , Thickness is 0.10 mm, bulk density is 0.59 g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 170 dtex, the carbon fiber spun yarn in the horizontal direction (spun yarn (width)) (C) _B ) Is 90 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.52 and the electric resistance value in the thickness direction was 1.8 mΩ, and it was a carbon fiber spun yarn fabric with good physical properties.
[0081]
[Table 1]

[0082]
Comparative Example 1
Using the same PAN-based oxidized fiber as in Example 1, as shown in Table 2, as a spun yarn (spun yarn (warp)) in the warp direction for fabric, several 450 times / m, thickness (O _A ) 550 dtex double yarn, horizontal spun yarn for fabric [spun yarn (horizontal)], several 450 times / m, thickness (O _B ) A 400 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.72.
[0083]
Next, the spun yarn (warp) is woven under conditions of 37 yarns / inch (2.54 cm) and the spun yarn (width) is 37 yarns / inch (2.54 cm). m ² A plain woven oxidized fiber spun yarn woven fabric having a thickness of 0.42 mm was obtained.
[0084]
Furthermore, this oxidized fiber spun yarn fabric was immersed in a PVA aqueous solution (0.3% by mass) (resin treatment), and after 0.5% by mass of PVA was added, it was compressed at 250 ° C. and 20 MPa, 191g / m ² , Thickness 0.20mm, bulk density 0.96g / cm ^Three Oxidized fiber spun yarn fabric after resin treatment / compression treatment was obtained.
[0085]
The oxidized fiber spun yarn fabric after the resin treatment / compression treatment was baked and carbonized at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0086]
The obtained carbon fiber spun yarn fabric has a basis weight of 114 g / m. ² , Thickness is 0.24 mm, bulk density is 0.48 g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 330 dtex, the thickness of carbon fiber spun yarn (spun yarn (horizontal)) in the horizontal direction (C) _B ) Is 240 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.73, the electric resistance value in the thickness direction was 10.1 mΩ, and it was not a carbon fiber spun yarn fabric with good physical properties. The part shown by x in Table 2 deviates from the configuration of the present invention.
[0087]
Comparative Example 2
Using the same PAN-based oxidized fiber as in Example 1, as shown in Table 2, as a spun yarn (spun yarn (warp)) in the warp direction for fabric, several 450 times / m, thickness (O _A ) 550 dtex double yarn, horizontal spun yarn for fabric [spun yarn (horizontal)], several 450 times / m, thickness (O _B ) A 190 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.35.
[0088]
Next, the spun yarn (warp) is woven under the conditions of 37 yarns / inch (2.54 cm) and the spun yarn (width) is 55 yarns / inch (2.54 cm). m ² A plain woven oxidized fiber spun yarn fabric having a thickness of 0.28 mm was obtained.
[0089]
Furthermore, this oxidized fiber spun yarn fabric was immersed in a PVA aqueous solution (0.3% by mass) (resin treatment), and after 0.5% by mass of PVA was added, it was compressed at 150 ° C. and 15 MPa, 131g / m ² , Thickness 0.17mm, bulk density 0.77g / cm ^Three Oxidized fiber spun yarn fabric after resin treatment / compression treatment was obtained.
[0090]
The oxidized fiber spun yarn fabric after the resin treatment / compression treatment was baked and carbonized at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0091]
The obtained carbon fiber spun yarn fabric has a basis weight of 78 g / m. ² , Thickness is 0.18mm, bulk density is 0.43g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 333 dtex, the carbon fiber spun yarn in the horizontal direction (spun yarn (horizontal)) (C _B ) Is 110 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.33 and the electrical resistance value in the thickness direction was 4.2 mΩ, and it was not a carbon fiber spun yarn fabric with good physical properties. The part shown by x in Table 2 deviates from the configuration of the present invention.
[0092]
Comparative Example 3
Using the same PAN-based oxidized fiber as in Example 1, as shown in Table 2, as a spun yarn (spun yarn (warp)) in the warp direction for fabric, several 450 times / m, thickness (O _A ) 170 dtex double yarn, horizontal spun yarn for fabric [spun yarn (horizontal)], several 450 times / m, thickness (O _B ) 150 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.88.
[0093]
Next, the spun yarn (warp) is woven under the conditions of 60 yarns / inch (2.54 cm) and the spun yarn (width) is 60 yarns / inch (2.54 cm). m ² A plain woven oxidized fiber spun yarn fabric having a thickness of 0.24 mm was obtained.
[0094]
Furthermore, this oxidized fiber spun yarn fabric was immersed in a PVA aqueous solution (0.3% by mass) (resin treatment), and after 0.5% by mass of PVA was added, it was compressed at 250 ° C. and 20 MPa, 76g / m ² , Thickness 0.12mm, bulk density 0.63g / cm ^Three Oxidized fiber spun yarn fabric after resin treatment / compression treatment was obtained.
[0095]
The oxidized fiber spun yarn fabric after the resin treatment / compression treatment was baked and carbonized at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0096]
The obtained carbon fiber spun yarn fabric has a basis weight of 47 g / m. ² , Thickness is 0.15 mm, bulk density is 0.31 g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 100 dtex, the carbon fiber spun yarn (spun yarn (width)) in the horizontal direction (C) _B ) Is 90 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.90, the electric resistance value in the thickness direction was 15.0 mΩ, and it was not a carbon fiber spun yarn fabric with good physical properties. The part shown by x in Table 2 deviates from the configuration of the present invention.
[0097]
[Table 2]

[0098]
Comparative Example 4
Using the same PAN-based oxidized fiber as in Example 1, as shown in Table 3, the warp direction spun yarn for fabric (spun yarn (warp)) was several 400 times / m, and the thickness (O _A ) As an 880 dtex double yarn, a horizontal spun yarn for fabrics (spun yarn (width)), several 400 times / m, thickness (O _B ) A 400 dtex double yarn was produced. Thickness ratio of spun yarn (horizontal) and spun yarn (vertical) (O _B / O _A ) Was 0.46.
[0099]
Next, the spun yarn (warp) is woven under the conditions of 23 yarns / inch (2.54 cm) and the spun yarn (width) is 37 yarns / inch (2.54 cm). m ² A plain woven oxidized fiber spun yarn fabric having a thickness of 0.48 mm was obtained.
[0100]
Furthermore, this oxidized fiber spun yarn fabric was immersed in a PVA aqueous solution (0.3% by mass) (resin treatment), and after 0.5% by mass of PVA was added, it was compressed at 250 ° C. and 20 MPa, 233g / m ² , Thickness 0.24mm, bulk density 0.77g / cm ^Three Oxidized fiber spun yarn fabric after resin treatment / compression treatment was obtained.
[0101]
The oxidized fiber spun yarn fabric after the resin treatment / compression treatment was baked and carbonized at 1600 ° C. in a nitrogen atmosphere for 2 minutes to obtain a carbon fiber spun yarn fabric.
[0102]
The obtained carbon fiber spun yarn fabric has a basis weight of 140 g / m. ² , Thickness is 0.32mm, bulk density is 0.44g / cm ^Three , Thickness of carbon fiber spun yarn [spun yarn (vertical)] (C _A ) Is 500 dtex, the thickness (C) _B ) Is 240 dtex, the thickness ratio of the spun yarn (horizontal) and the spun yarn (vertical) (C _B / C _A ) Was 0.48, and the electrical resistance value in the thickness direction was 8.2 mΩ, which was not a carbon fiber spun yarn fabric with good physical properties. The part shown by x in Table 3 deviates from the configuration of the present invention.
[0103]
[Table 3]

[0104]
【The invention's effect】
The carbon fiber spun yarn fabric of the present invention has a thickness, a bulk density, and a thickness C of the carbon fiber spun yarn in the vertical direction. _A Width of carbon fiber spun yarn in the horizontal direction _B Is a material that is excellent in strength characteristics, has a low electrical resistance value in the thickness direction, is useful as an electrode material for polymer electrolyte fuel cells, and is a thin material It is.
[0105]
Further, the carbon fiber spun yarn fabric can be obtained by performing physical properties of the oxidized fiber as a raw material, spinning processing, weaving, compression treatment, firing, and the like of the oxidized fiber under predetermined conditions.

Claims (3)

The thickness is 0.08 to 0.15 mm, the bulk density is 0.45 to 0.70 g / cm ³ , and the length C _A (dtex) of the carbon fiber spun yarn in the vertical direction and the carbon fiber spun yarn in the horizontal direction The thickness C _B (dtex) of Equation 1
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
Carbon fiber spun yarn fabric that meets the requirements. A spun yarn of polyacrylonitrile-based oxidized fiber having a dry strength of 1.5 gf / dtex or more and a knot strength of 0.3 gf / dtex or more, and the thickness of the oxidized fiber spun yarn in the vertical direction O _A (dtex) and the oxidation in the horizontal direction fibers spun yarn thickness O _B (dtex) is the formula 3
250 <O _A <660 Formula 3
And Equation 4
_{0.40 <O B / O A <} 0.62 Equation 4
The oxidized fiber spun yarn fabric woven from the oxidized fiber spun yarn satisfying the above conditions is compressed at a temperature of 100 to 350 ° C. and a pressure of 0.5 to 20 MPa, and the oxidized fiber spun yarn fabric after the compression treatment is carbonized. 0.08 to 0.15 mm, the bulk density is 0.45 to 0.70 g / cm ³ , the thickness C _A (dtex) of the carbon fiber spun yarn in the vertical direction and the thickness of the carbon fiber spun yarn in the horizontal direction. C _B (dtex) is expressed by Equation 1
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
The manufacturing method of the carbon fiber spun yarn fabric which satisfy | fills. A spun yarn of polyacrylonitrile-based oxidized fiber having a dry strength of 1.5 gf / dtex or more and a knot strength of 0.3 gf / dtex or more, and the thickness of the oxidized fiber spun yarn in the vertical direction O _A (dtex) and the oxidation in the horizontal direction fibers spun yarn thickness O _B (dtex) is the formula 3
250 <O _A <660 Formula 3
And Equation 4
_{0.40 <O B / O A <} 0.62 Equation 4
Oxidized fiber spun yarn fabric woven with oxidized fiber spun yarn satisfying the above conditions is treated with resin, and the resin is applied in the range of 0.2 to 10% by mass, and then compressed at a temperature of 100 to 350 ° C. and a pressure of 0.5 to 20 MPa. And carbonizing the oxidized fiber spun yarn fabric after the resin treatment / compression treatment, the thickness is 0.08 to 0.15 mm, the bulk density is 0.45 to 0.70 g / cm ³ , The thickness C _A (dtex) of the carbon fiber spun yarn in the direction and the thickness C _B (dtex) of the carbon fiber spun yarn in the horizontal direction
150 <C _A <400 Formula 1
And Equation 2
0.40 <C _B / C _A <0.62 Formula 2
The manufacturing method of the carbon fiber spun yarn fabric which satisfy | fills.