JP2004293026A - Polyvinyl alcohol-based binder fiber, and paper and nonwoven fabric comprising the same - Google Patents
Polyvinyl alcohol-based binder fiber, and paper and nonwoven fabric comprising the same Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 130
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 117
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 117
- 239000011230 binding agent Substances 0.000 title claims abstract description 58
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 15
- 239000000123 paper Substances 0.000 title abstract 2
- 230000008961 swelling Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 238000010828 elution Methods 0.000 claims description 20
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 125000005372 silanol group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 abstract description 37
- 238000007602 hot air drying Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000009987 spinning Methods 0.000 description 17
- 238000007127 saponification reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Nonwoven Fabrics (AREA)
- Paper (AREA)
Abstract
Description
本発明は、熱風乾燥方式のような高速乾燥や、マルチシリンダー方式のような低温乾燥等の低熱量の乾燥条件下で溶解可能であり、得られた紙または不織布が高い強力を発現させることを特徴とするポリビニルアルコール系バインダー繊維およびそれを用いてなる紙または不織布に関する。 The present invention is capable of dissolving under low-calorie drying conditions such as high-speed drying such as a hot-air drying method and low-temperature drying such as a multi-cylinder method, and that the obtained paper or nonwoven fabric exhibits high strength. The present invention relates to a polyvinyl alcohol-based binder fiber and paper or a nonwoven fabric using the same.
現在、ポリビニルアルコール（以下、ＰＶＡと略記する）系繊維は、その水溶性と強い接着性を有するという特徴を生かして、製紙用バインダー繊維として用いられている。ＰＶＡ系バインダー繊維の十分な接着性は、抄紙工程において繊維が分散した水中で膨潤し、乾燥工程の熱により十分溶解し、乾燥しながら結晶化することにより達成される。
従来、ＰＶＡ系繊維を用いて紙または不織布を製造する場合、乾燥工程において熱ドラム方式のヤンキードライヤーが一般的に使用されている。ヤンキードライヤーは乾燥熱量が大きいため乾燥時にＰＶＡ系バインダー繊維が十分に溶解し、接着性を発現する。しかし、近年になって乾燥の効率化や生産性向上のため、エアースルードライヤー等が用いられるケースが増加してきているが、エアースルードライヤーを用いて乾燥した場合、エアースルードライヤーは乾燥時間が短く、また乾燥熱量が小さいため、従来のＰＶＡ系バインダー繊維では十分に溶解できず、その結果、十分な接着性を発現できないという問題がある。
At present, polyvinyl alcohol (hereinafter abbreviated as PVA) fibers are used as papermaking binder fibers, taking advantage of their water solubility and strong adhesiveness. Sufficient adhesiveness of the PVA-based binder fiber is achieved by swelling in water in which the fiber is dispersed in the papermaking process, sufficiently dissolving by the heat of the drying process, and crystallizing while drying.
Conventionally, when paper or nonwoven fabric is manufactured using PVA-based fibers, a Yankee dryer of a heat drum type is generally used in a drying process. Since the Yankee dryer has a large amount of drying heat, the PVA-based binder fibers are sufficiently dissolved during drying, and exhibit adhesiveness. However, in recent years, in order to increase the efficiency of drying and improve productivity, the number of cases where an air through dryer is used has been increasing.When drying using an air through dryer, the drying time of the air through dryer is short. In addition, since the amount of drying heat is small, conventional PVA-based binder fibers cannot be sufficiently dissolved, and as a result, there is a problem that sufficient adhesiveness cannot be exhibited.
上記問題点を解決するために、一般的に原料であるＰＶＡ系樹脂に低ケン化度の樹脂を用いたり、またはＰＶＡ系樹脂にカルボキシル基やスルホン酸基、シリル基、四級アンモニウム塩等のカチオン性基などイオン性の官能基を導入することにより、溶解性を向上させる手法がとられている。例えば、樹脂の溶解性を向上させるために、ＰＶＡ樹脂のケン化度を低下させ、かつＰＶＡ樹脂の重合度を低下させ溶解性を高める手法が提案されている（例えば、特許文献１、２参照。）。また、ＰＶＡ樹脂にシリル基を導入したり、エチレン基の導入を行うことにより、溶解性および接着強力の向上を達成する技術が提案されている（例えば、特許文献３、４、５、６参照。）。
In order to solve the above problems, generally, a low saponification degree resin is used as a PVA-based resin as a raw material, or a carboxyl group, a sulfonic acid group, a silyl group, a quaternary ammonium salt, or the like is used as a PVA-based resin. A method of improving the solubility by introducing an ionic functional group such as a cationic group has been adopted. For example, in order to improve the solubility of the resin, a technique has been proposed in which the degree of saponification of the PVA resin is reduced, and the degree of polymerization of the PVA resin is reduced to increase the solubility (for example, see
上記特許文献１〜６では、バインダー繊維の接着性向上を達成するために、ＰＶＡ樹脂の改質を中心とした検討がなされているが、これらのバインダー繊維は丸孔の紡糸口金を用いて溶融紡糸あるいは湿式紡糸により製造されるため、繊維断面形状は丸型〜繭型形状となり、繊維断面から断面充実度を算出する式より計算した断面充実度は３５％以上となる。そのため、特許文献１〜６で得られるバインダー繊維は熱ドラム方式のヤンキードライヤー方式のような乾燥熱量の大きい乾燥方法では十分な接着性が得られるが、熱風乾燥方式のような高速乾燥や、マルチシリンダー方式のような低温・低熱量の乾燥条件下では接着性が不十分であるという問題点があった。
In the above-mentioned
上記課題点を鑑みて、本発明者等は鋭意検討を重ねた結果、断面充実度が３０％以下となるような紡糸口金を用いて紡糸し、繊維断面を扁平形状にして繊維の表面積を向上させることにより、従来の熱ドラム方式のヤンキードライヤー方式のような乾燥熱量の大きい乾燥方法を必要とせず、低温・低熱量の乾燥条件下でも高い紙力が得られ、しかも乾燥の効率化や生産性の向上が実現できる紙または不織布が得られることを見出した。 In view of the above problems, the present inventors have conducted intensive studies, and as a result, spun using a spinneret having a cross-sectional degree of 30% or less to improve the surface area of the fiber by making the fiber cross section flat. This eliminates the need for a drying method that requires a large amount of drying heat as in the conventional Yankee dryer method using a thermal drum, and provides high paper strength even under low-temperature, low-heat drying conditions. It has been found that a paper or a non-woven fabric which can achieve improvement in the properties can be obtained.
すなわち本発明は、繊維の断面充実度が３０％以下であり、３０℃の水中における繊維の膨潤度が１００％以上、かつ溶出量が２０％以下であることを特徴とするＰＶＡ系バインダー繊維であり、好ましくは繊維断面が扁平形状しており、その長辺の長さをＡ、その長辺の中央部（１／２Ａ）の厚さをＢ、その長辺の端部より１／４Ａの部分の厚さをＣとしたときに、Ａ／Ｂ≧３かつ０．６≦Ｃ／Ｂ≦１．２である上記のＰＶＡ系バインダー繊維であり、より好ましくは長辺の中央部（１／２Ａ）の厚さＢが６μｍ以下である上記のＰＶＡ系バインダー繊維であり、さらに好ましくはＰＶＡ系樹脂が、カルボン酸基、スルホン酸基、エチレン基、シラン基、シラノール基、アミン基、アンモニウム基のいずれかを０．１〜１５モル％共重合されてなる樹脂である上記のＰＶＡ系バインダー繊維に関するものであり、さらに上記のＰＶＡ系バインダー繊維を１〜５０質量％含有してなる紙または不織布に関するものである。 That is, the present invention relates to a PVA-based binder fiber, characterized in that the fiber has a cross-sectional integrity of 30% or less, a swelling degree of the fiber in water at 30 ° C. of 100% or more, and an elution amount of 20% or less. Yes, preferably the cross section of the fiber is flat, the length of the long side is A, the thickness of the central part (1 / 2A) of the long side is B, and 1 / 4A is larger than the end of the long side. When the thickness of the portion is C, the PVA-based binder fiber satisfies A / B ≧ 3 and 0.6 ≦ C / B ≦ 1.2, and more preferably the central part (1/1 / 2A) is a PVA-based binder fiber having a thickness B of 6 μm or less, more preferably a PVA-based resin having a carboxylic acid group, a sulfonic acid group, an ethylene group, a silane group, a silanol group, an amine group, and an ammonium group. Is 0.1 to 15 mol% copolymerized Relates above PVA binder fibers is a resin comprising Te, it relates more paper or nonwoven comprising a PVA binder fibers of the containing from 1 to 50% by weight.
本発明の単繊維の断面充実度が３０％以下であり、３０℃の水中における繊維の膨潤度が１００％以上かつ溶出量が２０％以下であるＰＶＡ系バインダー繊維を用いることにより、熱風乾燥方式のような高速乾燥や、マルチシリンダー方式のような低温乾燥等の低熱量の乾燥条件下でも高強力な紙または不織布を得ることが可能となる。 The hot air drying method is performed by using a PVA-based binder fiber in which the cross-sectional degree of the single fiber of the present invention is 30% or less and the swelling degree of the fiber in water at 30 ° C. is 100% or more and the elution amount is 20% or less. A high-strength paper or nonwoven fabric can be obtained even under low heat drying conditions such as high-speed drying as described above and low-temperature drying as in a multi-cylinder system.
ＰＶＡ系バインダー繊維の十分な接着性は、抄紙工程において繊維が分散した水中で膨潤し、乾燥工程の熱により十分溶解し、乾燥しながら結晶化することにより達成される。しかしながら従来のＰＶＡ系バインダー繊維では近年増加傾向のある高速乾燥、低温乾燥など低熱量の乾燥条件では溶解性が不十分なため、十分な接着性を得ることは困難である。従来の技術では溶解性の向上すなわちその指標である結晶融解温度を低下させるために、前記したようにケン化度の低下や変性基導入による結晶サイズの低下を利用したのに対し、本発明では繊維の断面充実度を大幅に低下させ、接着面積を増大させることで紙力の向上を達成することに特徴を有する。 Sufficient adhesiveness of the PVA-based binder fiber is achieved by swelling in water in which the fiber is dispersed in the papermaking process, sufficiently dissolving by the heat of the drying process, and crystallizing while drying. However, conventional PVA-based binder fibers have insufficient solubility under low-calorie drying conditions such as high-speed drying and low-temperature drying, which tend to increase in recent years, so that it is difficult to obtain sufficient adhesiveness. In the prior art, in order to improve the solubility, that is, to lower the crystal melting temperature, which is an indicator thereof, a reduction in the degree of saponification or a reduction in the crystal size due to the introduction of a modifying group was used as described above. It is characterized in that the cross-sectional integrity of the fiber is significantly reduced and the bonding area is increased, thereby improving the paper strength.
本発明のＰＶＡ系バインダー繊維は繊維の断面充実度が３０％以下であるような断面形状をとる必要がある。繊維断面を断面充実度が３０％以下であるような断面形状にして繊維の表面積を向上させることにより、後述するが本発明のＰＶＡ系バインダー繊維を用いて紙または不織布を製造した場合、低温・低熱量の乾燥条件下でも高い紙力を得ることが可能となる。好ましくは２７％以下、より好ましくは２５％以下である。繊維の断面充実度を３０％以下にする方法として好適なのは扁平形状とすることである。好ましくは図１に示すように扁平形状の長辺の長さをＡ、その長辺の中央部（１／２Ａ）の厚さをＢ、その長辺の端部より１／４Ａの部分の厚さをＣとしたときに、Ａ／Ｂ≧３かつ０．６≦Ｃ／Ｂ≦１．２であることが好ましい。Ａ／Ｂ＜３である場合、断面充実度が３０％よりも大きくなり好ましくない。またＣ／Ｂ＜０．６あるいはＣ／Ｂ＞１．２となる場合、本発明の目的とする扁平形状を形成しないためバインダー繊維の表面積が低下し、効率的なバインダー効果が発現しない。より好ましくはＡ／Ｂ≧５かつ０．８≦Ｃ／Ｂ≦１．２であり、さらに好ましくはＡ／Ｂ≧６かつ０．９≦Ｃ／Ｂ≦１．１である。また好ましくは厚さＢを６μｍ以下、より好ましくは５μｍ以下とすることで接着効率はより一層向上する。
なお、繊維の断面充実度、断面形状は走査型電子顕微鏡にて測定されたものを示す。
The PVA-based binder fiber of the present invention needs to have a cross-sectional shape such that the cross-sectional degree of the fiber is 30% or less. As will be described later, when a paper or nonwoven fabric is produced using the PVA-based binder fiber of the present invention, the fiber cross section is formed so that the cross section of the fiber has a cross-sectional degree of 30% or less and the fiber surface area is improved. High paper strength can be obtained even under a low calorie drying condition. It is preferably at most 27%, more preferably at most 25%. A preferable method for reducing the fiber cross-sectional solidity to 30% or less is a flat shape. Preferably, as shown in FIG. 1, the length of the long side of the flat shape is A, the thickness of the central portion (１ ／ A) of the long side is B, and the thickness of the
The fiber cross-sectional degree and cross-sectional shape are those measured with a scanning electron microscope.
また本発明のＰＶＡ系バインダー繊維は３０℃の水中における繊維の膨潤度が１００％以上である必要がある。膨潤度が１００％未満であるとバインダーとしての性能が十分に発現しない。好ましくは１２０％以上、より好ましくは１４０％以上である。 Further, the PVA-based binder fiber of the present invention needs to have a swelling degree of the fiber in water at 30 ° C. of 100% or more. When the degree of swelling is less than 100%, the performance as a binder is not sufficiently exhibited. It is preferably at least 120%, more preferably at least 140%.
本発明において使用されるＰＶＡ系樹脂は特に制限はなく、例えば低ケン化度ＰＶＡやカルボン酸基、スルホン酸基、エチレン基、シラン基、シラノール基、アミン基、アンモニウム基のいずれか一つまたは二つ以上共重合していても構わないが、中でもカルボン酸基、スルホン酸基、エチレン基、シラン基、シラノール基、アミン基、アンモニウム基のいずれかを０．１〜１５モル％共重合されていることがより好ましい。しかしながら共重合成分のないＰＶＡ系樹脂あるいは上記共重合成分が共重合されたＰＶＡ系樹脂から得られる本発明のＰＶＡ系バインダー繊維は、３０℃の水中における繊維の溶出量が２０％以下である必要がある。溶出量が２０％を超えると、歩留まり悪化によるコストアップ、白水（抄紙中に使用する水）への溶出による排水負荷の上昇や、例えば紙にした場合、溶出したＰＶＡの再付着による紙品位の低下（紙の風合いが硬くなる等）が生じる。好ましくは１０％以下、より好ましくは５％以下である。 The PVA-based resin used in the present invention is not particularly limited. For example, a low saponification degree PVA or any one of a carboxylic acid group, a sulfonic acid group, an ethylene group, a silane group, a silanol group, an amine group, an ammonium group or Although two or more copolymers may be copolymerized, any of carboxylic acid groups, sulfonic acid groups, ethylene groups, silane groups, silanol groups, amine groups, and ammonium groups is copolymerized in an amount of 0.1 to 15 mol%. Is more preferable. However, the PVA-based binder fiber of the present invention obtained from a PVA-based resin having no copolymerized component or a PVA-based resin obtained by copolymerizing the above-mentioned copolymerized component must have a fiber elution amount of 20% or less in water at 30 ° C. There is. If the amount of elution exceeds 20%, the cost will increase due to the decrease in yield, the drainage load will increase due to elution into white water (water used during papermaking), and if paper is used, the paper quality will be reduced due to the reattachment of the eluted PVA. Degradation (such as hardening of paper texture) occurs. It is preferably at most 10%, more preferably at most 5%.
本発明で用いるＰＶＡ系樹脂の重合度については、得られるＰＶＡ系バインダー繊維の溶出量の面からは３００以上、一方生産性、コストの面からは３０００以下であることが好ましい。より好ましくは８００〜２０００である。またＰＶＡのケン化度についてはＰＶＡの溶出の面からは９５モル％以上であることが好ましい。ＰＶＡのケン化度が９５モル％よりも低いと、バインダー使用時のＰＶＡの溶出が著しく、歩留まりの悪化および排水への溶出等の問題が発生したり、またバインダーとして使用された後も耐水性が極めて低く、特に湿潤条件でバインダー性能が著しく低下する。より好ましくはケン化度９６〜９９．９モル％の範囲である。 The degree of polymerization of the PVA-based resin used in the present invention is preferably 300 or more in terms of the amount of PVA-based binder fiber to be eluted, and 3000 or less in terms of productivity and cost. More preferably, it is 800 to 2000. The degree of saponification of PVA is preferably at least 95 mol% from the viewpoint of PVA elution. If the degree of saponification of PVA is lower than 95 mol%, the dissolution of PVA at the time of use of the binder is remarkable, causing problems such as deterioration in yield and dissolution into drainage, and water resistance even after being used as a binder. Is extremely low, and particularly under wet conditions, the binder performance is significantly reduced. The saponification degree is more preferably in the range of 96 to 99.9 mol%.
本発明のＰＶＡ系バインダー繊維は、上記したＰＶＡ系樹脂を水に対して８〜１８質量％溶解させた紡糸原液を、該樹脂に対して固化能を有する塩類の水溶液からなる凝固浴中に吐出させ繊維状とした後、２〜５倍湿延伸を行い、乾燥することにより得られる。水に溶解するＰＶＡ系樹脂の濃度が１８質量％より高い場合、ＰＶＡポリマーが溶解した溶液の粘度が高くなり、紡糸が不可能となる。好ましくは１０〜１６質量％である。 The PVA-based binder fiber of the present invention discharges a spinning solution obtained by dissolving the above-mentioned PVA-based resin in water in an amount of 8 to 18% by mass into a coagulation bath comprising an aqueous solution of a salt having a solidifying ability for the resin. It is obtained by performing 2 to 5 times wet stretching after drying into a fibrous form and drying. When the concentration of the PVA-based resin dissolved in water is higher than 18% by mass, the viscosity of the solution in which the PVA polymer is dissolved becomes high, and spinning becomes impossible. Preferably it is 10 to 16% by mass.
固化能を有する塩類の水溶液としては、硫酸ナトリウム（芒硝）、硫酸アンモニウム、炭酸ナトリウム等が挙げられる。上記した固化能を有する塩類の水溶液からなる凝固浴中に吐出させ繊維状とした後に湿延伸を行うが、湿延伸倍率が２倍より低いと正常な紡糸が行えず、一方湿延伸倍率が５倍を越える延伸を行うと、ＰＶＡ分子の配向が著しく進行するため結晶融解温度が上昇し、得られた繊維は水に対する膨潤度が低下し、バインダーとして機能しなくなる。 Examples of the aqueous solution of a salt having a solidifying ability include sodium sulfate (Glauber's salt), ammonium sulfate, sodium carbonate, and the like. The wet drawing is performed after discharging into a coagulation bath comprising an aqueous solution of a salt having the above-mentioned solidifying ability to form a fiber. If the wet drawing ratio is lower than 2 times, normal spinning cannot be performed. If the stretching is performed more than twice, the orientation of PVA molecules is remarkably advanced, so that the crystal melting temperature is increased, and the obtained fiber has a reduced degree of swelling in water and does not function as a binder.
本発明の断面形状が断面充実度３０％以下のＰＶＡ系バインダー繊維を製造するためには幅８０〜８００μｍ、厚さ２０〜８０μｍの矩形孔の紡糸口金を使用して紡糸原液を固化能を有する塩類の水溶液中に吐出させ、紡糸口金の金板面と第一ローラーとの間の張力を０．００３〜０．０１ｃＮ／ｄｔｅｘの範囲になるようにして紡糸することが好ましい。この張力が０．００３ｃＮ／ｄｔｅｘ未満であると、繊維の断面が変形して断面形状が繭型となってしまい、本発明の目的とする断面形状の繊維を得ることができない。一方、張力が０．０１ｃＮ／ｄｔｅｘ以上になると凝固浴中で繊維が断糸し、正常に紡糸することができない。より好ましくは０．００３５〜０．００６ｃＮ／ｄｔｅｘである。 In order to produce a PVA-based binder fiber having a cross-sectional shape of 30% or less in cross-section according to the present invention, a spinneret having a rectangular hole having a width of 80 to 800 μm and a thickness of 20 to 80 μm is used, and has a solidifying ability for a spinning solution. It is preferable that the spinning is performed by discharging the solution into an aqueous solution of a salt so that the tension between the metal plate surface of the spinneret and the first roller is in the range of 0.003 to 0.01 cN / dtex. If this tension is less than 0.003 cN / dtex, the cross section of the fiber is deformed and the cross section becomes a cocoon shape, and the fiber having the cross section aimed at by the present invention cannot be obtained. On the other hand, if the tension is not less than 0.01 cN / dtex, the fibers break in the coagulation bath and cannot be spun normally. More preferably, it is 0.0035 to 0.006 cN / dtex.
本発明で用いられるＰＶＡ系バインダー繊維の単繊維の平均繊度に特に制限はないが、０．０１〜５０ｄｔｅｘの範囲であることが好ましい。平均繊度が０．０１ｄｔｅｘより小さい場合は繊維の製造が困難となり生産性が低下し、コストアップとなる。一方、平均繊度が５０ｄｔｅｘよりも大きくなると、単繊維の繊維径自体が太くなるため接着性が低下するようになる。より好ましくは０．１〜５．０ｄｔｅｘである。本発明の繊維はあらゆる形態で使用することができ、例えばカットファイバー、フィラメントヤーン、紡績糸等としても構わない。 The average fineness of the single fibers of the PVA-based binder fibers used in the present invention is not particularly limited, but is preferably in the range of 0.01 to 50 dtex. If the average fineness is smaller than 0.01 dtex, it becomes difficult to produce fibers, the productivity is reduced, and the cost is increased. On the other hand, when the average fineness is larger than 50 dtex, the fiber diameter itself of the single fiber becomes large, so that the adhesiveness decreases. More preferably, it is 0.1 to 5.0 dtex. The fiber of the present invention can be used in any form, and may be, for example, a cut fiber, a filament yarn, a spun yarn, or the like.
本発明のＰＶＡ系バインダー繊維を用いて紙または不織布を製造するが、紙または不織布中の該ＰＶＡ系バインダー繊維は全固形分に対して１〜５０質量％含んでいることが好ましい。紙または不織布中の該ＰＶＡ系バインダー繊維の含有量が１質量％よりも少ないと、繊維の構成本数が少ないためバインダーとして機能せず、したがって接着性が発現しなくなる。一方、紙または不織布中の該ＰＶＡ系バインダー繊維の含有量が５０質量％よりも多いと、バインダー繊維が主体となるため、バインダー繊維の収縮による紙または不織布の表面平滑性の低下や、風合いが硬くなる等の品位の低下を招く恐れがある。より好ましくは２〜３０質量％、より好ましくは５〜２５質量％である。 A paper or nonwoven fabric is produced using the PVA-based binder fiber of the present invention, and the PVA-based binder fiber in the paper or nonwoven fabric preferably contains 1 to 50% by mass based on the total solid content. If the content of the PVA-based binder fiber in the paper or nonwoven fabric is less than 1% by mass, the number of fibers constituting the fiber is so small that the fiber does not function as a binder, and therefore, the adhesiveness is not exhibited. On the other hand, when the content of the PVA-based binder fiber in the paper or nonwoven fabric is more than 50% by mass, the binder fiber is mainly used, and thus the surface smoothness of the paper or nonwoven fabric is reduced due to shrinkage of the binder fiber, and the texture is reduced. There is a risk of lowering the quality such as hardening. More preferably, it is 2 to 30% by mass, more preferably 5 to 25% by mass.
以下実施例により本発明を説明するが、本発明はこれら実施例により限定されるものではない。なお本発明の実施例において、ＰＶＡ樹脂の重合度、ＰＶＡバインダー繊維の断面充実度、断面形状、溶出量、膨潤度、およびＰＶＡバインダー繊維を用いて製造した紙の湿裂断長（ＷＢ）、乾裂断長（ＤＢ）は以下の測定方法によって測定されたものを示す。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In Examples of the present invention, the degree of polymerization of the PVA resin, the degree of cross-sectional solidity of the PVA binder fiber, the cross-sectional shape, the elution amount, the degree of swelling, and the wet breaking length (WB) of the paper produced using the PVA binder fiber, The dry crack length (DB) indicates a value measured by the following measurement method.
［ＰＶＡ樹脂の重合度］
ＰＶＡ系ポリマーを１〜１０ｇ／ｌの濃度（Ｃｖ）になるように熱水で溶解して得られた溶液の相対粘度ηｒｅｌをＪＩＳ Ｋ６７２６試験法に準拠して３０℃で測定し、下記（１）式より極限粘度［η］を求め、さらに（２）式より重合度ＰＡを算出する。
［η］＝２．３０３ｌｏｇ（ηｒｅｌ）／Ｃｖ ・・・（１）
ＰＡ＝（［η］×１０４／８．２９）×１．６１３ ・・・（２）
[Polymerization degree of PVA resin]
The relative viscosity η rel of a solution obtained by dissolving a PVA-based polymer with hot water so as to have a concentration (Cv) of 1 to 10 g / l was measured at 30 ° C. in accordance with JIS K6726 test method. The intrinsic viscosity [η] is determined from the equation (1), and the polymerization degree PA is calculated from the equation (2).
[Η] = 2.303 log (η rel ) / Cv (1)
PA = ([η] × 104 / 8.29) × 1.613 (2)
［ＰＶＡバインダー繊維の断面充実度 ％］
走査型電子顕微鏡〔（株）日立製作所製〕にて繊維の断面形状を測定し、繊維の断面積をＳ１、その繊維を取り囲む最小円の面積をＳ２とし、以下の式により求める。
断面充実度（％）＝（Ｓ１／Ｓ２）×１００
[Cross section of PVA binder fiber%]
The cross-sectional shape of the fiber is measured by a scanning electron microscope (manufactured by Hitachi, Ltd.), and the cross-sectional area of the fiber is S1, and the area of the smallest circle surrounding the fiber is S2, and is obtained by the following equation.
Cross section solidity (%) = (S1 / S2) x 100
［ＰＶＡバインダー繊維の断面形状 Ａ／Ｂ、Ｃ／Ｂ、Ｂ（μｍ）］
走査型電子顕微鏡〔（株）日立製作所製〕にて繊維の断面形状を測定し、求めた。
[Cross-sectional shape of PVA binder fiber A / B, C / B, B (μm)]
The cross-sectional shape of the fiber was measured with a scanning electron microscope (manufactured by Hitachi, Ltd.) and determined.
［ＰＶＡバインダー繊維のＰＶＡ溶出量 ％］
繊維中のＰＶＡ樹脂純分が１ｇとなるように換算量を秤量したのち、３０℃の水１００ｍｌ中に浸漬し、液温を３０℃に保ったまま３０分静置する。静置後、未溶解部分を除去した上澄み液５０ｍｌを採取し、水蒸気浴上で蒸発乾固したのち、１０５℃の乾燥機中で４時間乾燥させ、乾燥後乾燥残分ａ（ｇ）を計量する。この乾燥残分にはＰＶＡと硫酸ナトリウム等の無機分が含まれるため、さらに５００〜８００℃でＰＶＡ成分が完全に無くなるまで焼成する。焼成後、残分ｂ（ｇ）を測定し、下記の式から溶出量を求める。
溶出量（％）＝（ａ−ｂ）×２００
[PVA elution amount of PVA binder fiber%]
After weighing the converted amount so that the pure content of PVA resin in the fiber becomes 1 g, the fiber is immersed in 100 ml of water at 30 ° C., and allowed to stand for 30 minutes while keeping the liquid temperature at 30 ° C. After standing, 50 ml of the supernatant liquid from which the undissolved portion was removed was collected, evaporated to dryness on a steam bath, dried in a dryer at 105 ° C. for 4 hours, and the dried residue a (g) was measured after drying. I do. Since the dried residue contains PVA and inorganic components such as sodium sulfate, it is further fired at 500 to 800 ° C. until the PVA component is completely eliminated. After the calcination, the residue b (g) is measured, and the elution amount is determined from the following equation.
Elution amount (%) = (ab) × 200
［ＰＶＡバインダー繊維の膨潤度 ％］
繊維中のＰＶＡ樹脂純分が１ｇとなるように換算量を秤量したのち、３０℃の水１００ｍｌ中に浸漬し、液温を３０℃に保ったまま３０分静置する。静置後、繊維分を濾取して回転数３０００ｒｐｍの延伸脱水機で１０分間脱水し、脱水後の質量（Ｍ１）を測定する。質量測定したサンプルを１０５℃の熱風乾燥機中で４時間乾燥後、質量（Ｍ２）を測定し、以下の式から膨潤度を求める。
膨潤度（％）＝［（Ｍ１−Ｍ２）／Ｍ２］×１００
[Swelling degree of PVA binder fiber%]
After weighing the converted amount so that the pure content of PVA resin in the fiber becomes 1 g, the fiber is immersed in 100 ml of water at 30 ° C., and allowed to stand for 30 minutes while keeping the liquid temperature at 30 ° C. After standing, the fiber content is collected by filtration and dewatered for 10 minutes with a drawing dehydrator having a rotation speed of 3000 rpm, and the mass after dehydration (M1) is measured. After the sample whose mass has been measured is dried in a hot-air dryer at 105 ° C. for 4 hours, the mass (M2) is measured, and the degree of swelling is determined from the following equation.
Swelling degree (%) = [(M1-M2) / M2] × 100
［紙の湿裂断長ＷＢ、乾裂断長ＤＢ Ｎ・ｍ／ｇ］
紙の湿裂断長ＷＢは紙を２０℃の水中で２４時間吸水させた後、幅１５ｍｍ、長さ１７０ｍｍの試料を把持長さ１００ｍｍ、引張速度５０ｍｍ／分で測定した強力ＷＳ（Ｎ）と試料の秤量Ｗ（ｇ／ｍ２）より下記式にて求めた。
ＷＢ＝ＷＳ／（１５×Ｗ）×１０００（Ｎ・ｍ／ｇ）
一方、紙の乾裂断長ＤＢは、２３℃×５０％ＲＨ室内で２４時間調湿した後、幅１５ｍｍ、長さ１７０ｍｍの試料を把持長さ１００ｍｍ、引張速度５０ｍｍ／分で測定した強力ＤＳ（Ｎ）と試料の秤量Ｗ（ｇ／ｍ２）より下記式にて求めた。
ＤＢ＝ＤＳ／（１５×Ｗ）×１０００（Ｎ・ｍ／ｇ）
[Wet breaking length WB, Dry breaking length DB N · m / g of paper]
The wet tear length WB of the paper was determined by measuring the strength of the sample (15 mm wide and 170 mm long) with a strong WS (N) measured at a gripping length of 100 mm and a pulling speed of 50 mm / min after absorbing the paper in water at 20 ° C. for 24 hours. It was determined by the following equation from the weight W (g / m 2 ) of the sample.
WB = WS / (15 × W) × 1000 (N · m / g)
On the other hand, the dry crack length DB of the paper was determined by controlling the humidity in a chamber at 23 ° C. × 50% RH for 24 hours, and then measuring the strength DS (measuring a sample having a width of 15 mm and a length of 170 mm at a gripping length of 100 mm and a tensile speed of 50 mm / min). N) and the weight W (g / m 2 ) of the sample were determined by the following equation.
DB = DS / (15 × W) × 1000 (N · m / g)
［実施例１］
（１）平均重合度１７００、ケン化度９８．０モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を孔数４０００、縦３０μｍ×横１８０μｍの長方形のスリット型の紡糸口金より飽和硫酸ナトリウムからなる凝固浴中に吐出させ、紡糸口金の金板面と第一ローラーとの間の張力が０．０３５〜０．０４５ｃＮ／ｄｔｅｘとなるように第１ローラーで巻き取った後、４倍の湿延伸を行い、定長乾燥機中にて１２０℃で１０分間乾燥させ、表１に示すように、断面充実度２３％、断面形状がＡ／Ｂ＝６．３、Ｃ／Ｂ＝０．９７、Ｂ＝４．５μｍの繊度１．５ｄｔｅｘの扁平形状ＰＶＡ繊維を得た。また得られた扁平状ＰＶＡ繊維の膨潤度は１８２％、ＰＶＡの溶出量は６．９％であった。
（２）上記（１）で得られたＰＶＡ繊維を３ｍｍにカットしたものを繊維純分として２０質量部、ガラス繊維（旭ファイバーグラス株式会社製「ＧＰ０２４」、繊維径９μｍ、繊維長６ｍｍ）を８０質量部混合して均一に混合攪拌してスラリーを調製した。かかるスラリーを用いてＴＡＰＰＩ式抄紙機に供給して抄造した後、乾燥温度２１０℃のネット式エアースルードライヤーを用いて乾燥し、秤量４０ｇ／ｍ２の紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々４．５９Ｎ・ｍ／ｇ、０．３４Ｎ・ｍ／ｇであった。
[Example 1]
(1) A spinning solution comprising a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 98.0 mol% was prepared from saturated sodium sulfate by a rectangular slit type spinneret having 4,000 holes and a length of 30 μm × 180 μm. Into a coagulation bath, and wound up with the first roller so that the tension between the metal plate surface of the spinneret and the first roller is 0.035 to 0.045 cN / dtex. The film is stretched and dried in a fixed-length dryer at 120 ° C. for 10 minutes. As shown in Table 1, the cross-sectional solidity is 23%, the cross-sectional shape is A / B = 6.3, and the C / B is 0.97. , B = 4.5 μm and a flat PVA fiber having a fineness of 1.5 dtex. The swelling degree of the obtained flat PVA fiber was 182%, and the elution amount of PVA was 6.9%.
(2) The PVA fiber obtained in the above (1) was cut into 3 mm, and 20 parts by mass of glass fiber (“GP024” manufactured by Asahi Fiberglass Co., Ltd., fiber diameter 9 μm, fiber length 6 mm) as a pure fiber was used. 80 parts by mass were mixed and uniformly mixed and stirred to prepare a slurry. The slurry was supplied to a TAPPI-type paper machine to form a paper, and then dried using a net-type air-through dryer at a drying temperature of 210 ° C. to produce a paper weighing 40 g / m 2 . As shown in Table 1, the DB and WB of the obtained paper were 4.59 N · m / g and 0.34 N · m / g, respectively.
［実施例２］
（１）平均重合度１７００、ケン化度９８．０モル％、エチレン含有量５モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を実施例１と同一条件にて紡糸、延伸、熱処理を行い、表１に示すように、断面充実度２３％、断面形状がＡ／Ｂ＝６．１、Ｃ／Ｂ＝０．９７、Ｂ＝４．５μｍの繊度１．５ｄｔｅｘの扁平形状ＰＶＡ繊維を得た。また得られた扁平状ＰＶＡ繊維の膨潤度は１５４％、ＰＶＡの溶出量は２．３％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々４．６３Ｎ・ｍ／ｇ、０．７８Ｎ・ｍ／ｇであった。
[Example 2]
(1) A spinning dope composed of a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700, a saponification degree of 98.0 mol%, and an ethylene content of 5 mol% was spun, stretched and heat-treated under the same conditions as in Example 1. As shown in Table 1, a flat-shaped PVA fiber having a fineness of 1.5 dtex and a cross-sectional shape of 23% and a cross-sectional shape of A / B = 6.1, C / B = 0.97, and B = 4.5 μm was obtained. Was. The swelling degree of the obtained flat PVA fiber was 154%, and the elution amount of PVA was 2.3%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. As shown in Table 1, the DB and WB of the obtained paper were 4.63 N · m / g and 0.78 N · m / g, respectively.
［実施例３］
（１）平均重合度１７００、ケン化度９９．９モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を実施例１と同一条件にて紡糸、延伸、熱処理を行い、表１に示すように、断面充実度２３％、断面形状がＡ／Ｂ＝６．２、Ｃ／Ｂ＝０．９９、Ｂ＝４．４μｍの繊度１．５ｄｔｅｘの扁平形状ＰＶＡ繊維を得た。また得られた扁平状ＰＶＡ繊維の膨潤度は１４３％、ＰＶＡの溶出量は０．９％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々２．８０Ｎ・ｍ／ｇ、０．３８Ｎ・ｍ／ｇであった。
[Example 3]
(1) A spinning dope composed of a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 99.9 mol% was spun, stretched, and heat-treated under the same conditions as in Example 1, and as shown in Table 1. A flat PVA fiber having a fineness of 1.5 dtex and a cross-sectional degree of 23%, a cross-sectional shape of A / B = 6.2, C / B = 0.99, and B = 4.4 μm was obtained. The swelling degree of the obtained flat PVA fiber was 143%, and the PVA elution amount was 0.9%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. The DB and WB of the obtained paper were 2.80 N · m / g and 0.38 N · m / g, respectively, as shown in Table 1.
［実施例４］
（１）平均重合度１７００、ケン化度９８．０モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を孔数４０００、縦３０μｍ×横４５０μｍの長方形のスリット型の紡糸口金より飽和硫酸ナトリウムからなる凝固浴中に吐出させ、紡糸口金の金板面と第一ローラーとの間の張力が０．０３５〜０．０４５ｃＮ／ｄｔｅｘとなるように第１ローラーで巻き取った後、４倍の湿延伸を行い、定長乾燥機中にて１２０℃で１０分間乾燥させ、表１に示すように、断面充実度９％、断面形状がＡ／Ｂ＝１６、Ｃ／Ｂ＝０．９８、Ｂ＝４．５μｍの繊度３．８ｄｔｅｘの扁平形状ＰＶＡ繊維を得た。また得られた扁平状ＰＶＡ繊維の膨潤度は１６２％、ＰＶＡの溶出量は３．１％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々４．４８Ｎ・ｍ／ｇ、０．３５Ｎ・ｍ／ｇであった。
[Example 4]
(1) An undiluted spinning solution composed of a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 98.0 mol% was prepared from saturated sodium sulfate from a rectangular slit-type spinneret having 4,000 holes and a length of 30 μm × width of 450 μm. Into a coagulation bath, and wound up with the first roller so that the tension between the metal plate surface of the spinneret and the first roller is 0.035 to 0.045 cN / dtex. The film was stretched, dried at 120 ° C. for 10 minutes in a fixed-length dryer, and as shown in Table 1, the cross-sectional solidity was 9%, the cross-sectional shape was A / B = 16, C / B = 0.98, B = 4.5 μm and a flat PVA fiber having a fineness of 3.8 dtex. The swelling degree of the obtained flat PVA fiber was 162%, and the elution amount of PVA was 3.1%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. As shown in Table 1, DB and WB of the obtained paper were 4.48 N · m / g and 0.35 N · m / g, respectively.
［実施例５］
（１）平均重合度１７００、ケン化度９８．０モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を実施例１と同一条件で紡糸、湿延伸を行い、さらに１５〜３０℃の水中にて定長水洗した後、定長乾燥機中にて１２０℃で１０分間乾燥させ、表１に示すように、断面充実度２３％、断面形状がＡ／Ｂ＝６．１、Ｃ／Ｂ＝０．９７、Ｂ＝４．４μｍの繊度１．５ｄｔｅｘのソルトフリーの扁平形状ＰＶＡ繊維を得た。また得られた扁平状ＰＶＡ繊維の膨潤度は１６０％、ＰＶＡの溶出量は１．１％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々４．２２Ｎ・ｍ／ｇ、０．３３Ｎ・ｍ／ｇであった。
[Example 5]
(1) A spinning stock solution comprising a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 98.0 mol% was spun and wet stretched under the same conditions as in Example 1, and further placed in water at 15 to 30 ° C. And then dried in a constant-length drier at 120 ° C. for 10 minutes. As shown in Table 1, the solidity was 23% in cross-section, A / B = 6.1, and C / B = 0.97, B = 4.4 μm, and a salt-free flat PVA fiber having a fineness of 1.5 dtex were obtained. The swelling degree of the obtained flat PVA fiber was 160%, and the elution amount of PVA was 1.1%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. As shown in Table 1, the DB and WB of the obtained paper were 4.22 N · m / g and 0.33 N · m / g, respectively.
［実施例６］
（１）平均重合度１７００、ケン化度９８．０モル％のＰＶＡ樹脂１８質量％のＤＭＳＯ（ジメチルスルホキシド）溶液からなる紡糸原液を孔数２００００、縦３０μｍ×横１８０μｍの長方形のスリット型の紡糸口金よりメタノールからなる固化浴中に吐出させ、紡糸口金の金板面と第一ローラーとの間の張力が０．０３５〜０．０４５ｃＮ／ｄｔｅｘとなるように第１ローラーで巻き取った後、３倍の湿延伸を行い、定長乾燥機中にて１４０℃で１０分間乾燥させ、表１に示すように、断面充実度２５％、断面形状がＡ／Ｂ＝５．５、Ｃ／Ｂ＝０．９５、Ｂ＝４．７μｍの繊度２．２ｄｔｅｘのソルトフリーの扁平形状ＰＶＡ繊維を得た。また得られた扁平状ＰＶＡ繊維の膨潤度は１７０％、ＰＶＡの溶出量は３．３％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々４．３２Ｎ・ｍ／ｇ、０．３４Ｎ・ｍ／ｇであった。
[Example 6]
(1) A rectangular spinning spinning solution having a number of pores of 20,000, a length of 30 μm and a width of 180 μm was prepared by spinning a spinning dope comprising a DMSO (dimethyl sulfoxide) solution containing 18% by mass of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 98.0 mol% After discharging into a solidification bath made of methanol from the spinneret and winding it up with the first roller so that the tension between the metal plate surface of the spinneret and the first roller is 0.035 to 0.045 cN / dtex, After performing 3 times wet stretching and drying in a constant-length dryer at 140 ° C. for 10 minutes, as shown in Table 1, the cross-sectional solidity is 25%, the cross-sectional shape is A / B = 5.5, and the C / B is = 0.95, B = 4.7 µm, and a salt-free flat PVA fiber having a fineness of 2.2 dtex was obtained. The swelling degree of the obtained flat PVA fiber was 170%, and the elution amount of PVA was 3.3%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. As shown in Table 1, DB and WB of the obtained paper were 4.32 N · m / g and 0.34 N · m / g, respectively.
［比較例１］
（１）平均重合度１７００、ケン化度９９．９モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を孔径６０μｍ、孔数４０００の紡糸口金より飽和硫酸ナトリウムからなる凝固浴中に吐出させ、第１ローラーで巻き取った後、４倍の湿延伸を行い、定長乾燥機中にて１２０℃で１０分間乾燥させ、表１に示すように、断面充実度３９％、繊度１．０ｄｔｅｘの繭型形状のＰＶＡ繊維を得た。また得られた繭型形状ＰＶＡ繊維の膨潤度は１４５％、ＰＶＡの溶出量は１．０％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々０．３５Ｎ・ｍ／ｇ、０．０５Ｎ・ｍ／ｇであり、紙力が本発明で得られたＰＶＡバインダー繊維を用いた紙（実施例１〜６）と比べて著しく劣るものであった。
[Comparative Example 1]
(1) A spinning stock solution comprising a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 99.9 mol% is discharged from a spinneret having a pore diameter of 60 μm and a number of holes of 4000 into a coagulation bath composed of saturated sodium sulfate, After being wound up by the first roller, the film is wet stretched 4 times, dried in a constant-length dryer at 120 ° C. for 10 minutes, and as shown in Table 1, has a cross-sectional area of 39% and a fineness of 1.0 dtex. A cocoon-shaped PVA fiber was obtained. The degree of swelling of the obtained cocoon-shaped PVA fiber was 145%, and the amount of eluted PVA was 1.0%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. The DB and WB of the obtained paper are 0.35 N · m / g and 0.05 N · m / g, respectively, as shown in Table 1, and the paper strength is a paper using the PVA binder fiber obtained by the present invention. It was significantly inferior to (Examples 1 to 6).
［比較例２］
（１）平均重合度１７００、ケン化度９８．０モル％のＰＶＡ樹脂１４質量％水溶液からなる紡糸原液を比較例１と同一条件にて紡糸、延伸、熱処理を行い、表１に示すように、断面充実度３９％、繊度１．０ｄｔｅｘの繭型形状のＰＶＡ繊維を得た。また得られた繭型形状ＰＶＡ繊維の膨潤度は１６２％、ＰＶＡの溶出量は３．１％であった。
（２）上記（１）で得られたＰＶＡ繊維を実施例１と同一条件にて紙を製造した。得られた紙のＤＢ、ＷＢは表１に示すように各々１．５２Ｎ・ｍ／ｇ、０．２９Ｎ・ｍ／ｇであり、紙力が本発明で得られたＰＶＡバインダー繊維を用いた紙（実施例１〜６）と比べて劣るものであった。
[Comparative Example 2]
(1) A spinning dope composed of a 14% by mass aqueous solution of a PVA resin having an average degree of polymerization of 1700 and a saponification degree of 98.0 mol% was spun, stretched, and heat-treated under the same conditions as in Comparative Example 1, and as shown in Table 1. A cocoon-shaped PVA fiber having a cross-sectional degree of 39% and a fineness of 1.0 dtex was obtained. The cocoon-shaped PVA fiber obtained had a swelling degree of 162% and an elution amount of PVA of 3.1%.
(2) Paper was produced from the PVA fiber obtained in the above (1) under the same conditions as in Example 1. The DB and WB of the obtained paper are 1.52 N · m / g and 0.29 N · m / g, respectively, as shown in Table 1, and the paper strength is a paper using the PVA binder fiber obtained by the present invention. It was inferior to (Examples 1 to 6).
［比較例３］
ＰＶＡバインダー繊維として、株式会社ニチビ製の断面充実度４３％、断面形状がＡ／Ｂ＝３．７、Ｃ／Ｂ＝１．４、Ｂ＝７．１μｍのダンベル型断面形状のソルブロン「ＮＬ２００３」を用いて紙を製造した。表１に示すように該バインダー繊維の膨潤度は１６０％、ＰＶＡの溶出量は１０％であり、得られた紙のＤＢ、ＷＢは各々１．８１Ｎ・ｍ／ｇ、０．０１Ｎ・ｍ／ｇであり、紙力が本発明で得られたＰＶＡバインダー繊維を用いた紙（実施例１〜６）と比べて著しく劣るものであった。
[Comparative Example 3]
As a PVA binder fiber, NL2003 manufactured by Nichibi Co., Ltd. has a dumbbell-shaped cross-sectional shape of 43% cross-section, A / B = 3.7, C / B = 1.4, and B = 7.1 μm. Was used to produce paper. As shown in Table 1, the swelling degree of the binder fiber was 160%, the elution amount of PVA was 10%, and the DB and WB of the obtained paper were 1.81 Nm / g and 0.01 Nm / g, respectively. g, and the paper strength was remarkably inferior to the paper using the PVA binder fiber obtained in the present invention (Examples 1 to 6).
本発明の単繊維の断面充実度が３０％以下であり、３０℃の水中における繊維の膨潤度が１００％以上かつ溶出量が２０％以下であるＰＶＡ系バインダー繊維を用いることにより、熱風乾燥方式のような高速乾燥や、マルチシリンダー方式のような低温乾燥等の低熱量の乾燥条件下でも高強力な紙または不織布を得ることが可能となる。 The hot air drying method is performed by using a PVA-based binder fiber in which the cross-sectional degree of the single fiber of the present invention is 30% or less and the swelling degree of the fiber in water at 30 ° C. is 100% or more and the elution amount is 20% or less. A high-strength paper or nonwoven fabric can be obtained even under low heat drying conditions such as high-speed drying as described above and low-temperature drying as in a multi-cylinder system.
Claims (5)
A paper or nonwoven fabric comprising 1 to 50% by mass of the polyvinyl alcohol-based binder fiber according to any one of claims 1 to 4.
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