TW201802318A - Nonwoven long-fiber fabric - Google Patents

Abstract

Nonwoven long-fiber fabric containing a liquid-film-breaking agent.

Description

Long fiber nonwoven

The present invention relates to a long-fiber nonwoven fabric.

As for the front sheet and the like of an absorbent article, a hot air nonwoven fabric or the like using staple fibers as a raw material has been mainly used in the past. In recent years, from the viewpoint of manufacturing cost and productivity, studies have been conducted using a non-woven fabric (hereinafter, referred to as a long-fiber non-woven fabric) using a long fiber such as a spunbond non-woven fabric as a raw material as a front sheet. However, compared with non-woven fabrics using short fibers as raw materials, long-fiber non-woven fabrics have problems such as shorter inter-fiber distances, thinner thicknesses, and higher rigidity of the heat-fused portion that bundles the long fibers. Therefore, the previous long-fiber non-woven fabrics are still not fully satisfactory in terms of the suppression of liquid residue or liquid return required for the front sheet, and the texture. There are several proposals for this. For example, Patent Document 1 describes that in the long-fiber nonwoven fabric, a portion of the long fibers bundled by the thermal fusion portion is broken and erected. Regarding the raised fibers, long fibers having a lower hydrophilicity than the unbroken fibers are described. Therefore, it is intended to provide cushioning properties to a thinner spunbond nonwoven fabric in order to improve the liquid permeability and the prevention of liquid return. As a technique different from this, Patent Document 2 describes an absorbent article in which a blood sheet is contained in the front sheet in order to improve the dry feeling. The blood modifier is intended to reduce the viscosity and surface tension of blood, stabilize the blood cells, and not easily form a coin string structure, so that the absorber can easily absorb menstrual blood. In addition, Patent Document 3 describes that from the viewpoint of making it difficult for the body fluid of the front sheet to flow or bleed back, the back sheet of the front sheet is rendered more hydrophilic than the front sheet. [Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2014-139359 [Patent Literature 2] Japanese Patent Laid-Open No. 2013-63245 [Patent Literature 3] Japanese Patent Laid-Open No. 2005-87659 Bulletin

The invention provides a long-fiber nonwoven fabric containing a liquid film cracking agent. The present invention also provides a long-fiber non-woven fabric containing a compound (C1) having a water solubility of 0 g or more and 0.025 g or less and a spreading factor of 15 for a liquid having a surface tension of 50 mN / m. mN / m or more. The present invention also provides a long-fiber non-woven fabric containing a compound (C2) having a water solubility of 0 g or more and 0.025 g or less and a spreading coefficient for a liquid having a surface tension of 50 mN / m greater than 0. mN / m, the interfacial tension for liquids with a surface tension of 50 mN / m is 20 mN / m or less. The above and other features and advantages of the present invention will be made clearer by referring to the accompanying drawings as appropriate and from the following description.

式(1)～(11)中，M¹ 、L¹ 、R²¹ 、及R²² 表示以下之1價或多價(2價或2價以上)之基。R²³ 、及R²⁴ 表示以下之1價或多價(2價或2價以上)之基、或單鍵。 M¹ 表示具有聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等組合而成之聚氧伸烷基的基；或赤藻糖醇基、木糖醇基、山梨糖醇基、甘油基或乙二醇基等具有複數個羥基之親水基(自赤藻糖醇等具有複數個羥基之上述化合物去除1個氫原子而成之親水基)、羥基、羧酸基、巰基、烷氧基(較佳為碳數1～20。例如較佳為甲氧基)、胺基、醯胺基、亞胺基、苯酚基、磺酸基、四級銨基、磺基甜菜鹼基、羥基磺基甜菜鹼基、膦基甜菜鹼基、咪唑鎓甜菜鹼基、羰基甜菜鹼基、環氧基、甲醇基、(甲基)丙烯酸基、或將其等組合而成之官能基。再者，於M¹ 為多價基之情形時，M¹ 表示自上述各基或官能基進而去除1個以上之氫原子而成之基。 L¹ 表示醚基、胺基(可作為L¹ 採用之胺基係由＞NR^C (R^C 表示氫原子或一價基)表示)、醯胺基、酯基、羰基、碳酸酯基之鍵結基。 R²¹ 、R²² 、R²³ 、及R²⁴ 分別獨立地表示烷基(較佳為碳數1～20。例如較佳為甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基)、烷氧基(較佳為碳數1～20。例如較佳為甲氧基、乙氧基)、芳基(較佳為碳數6～20。例如較佳為苯基)、氟烷基、或芳烷基、或者將其等組合而成之烴基、或者鹵素原子(例如較佳為氟原子)。再者，於R²² 及R²³ 為多價基之情形時，係表示自上述烴基進而去除1個以上之氫原子或氟原子而成之多價烴基。 又，於R²² 或R²³ 與M¹ 鍵結之情形時，可作為R²² 或R²³ 採用之基除上述各基、上述烴基或鹵素原子外，亦可列舉可作為R³² 採用之亞胺基。 關於液膜開裂劑，其中，較佳為如下化合物，該化合物具有(1)、(2)、(5)及(10)式中之任一者所表示之結構作為X，且具有其等式以外之上述式中之任一者所表示之結構作為X之末端、或包含X之末端與Y之基。進而較佳為如下化合物，該化合物包含具有X、或包含X之末端與Y之基由上述(2)、(4)、(5)、(6)、(8)及(9)式中之任一者所表示之結構至少1個的矽氧烷鏈。 作為上述化合物之具體例，可列舉聚矽氧系界面活性劑之有機改性聚矽氧(聚矽氧烷)。例如作為經反應性之有機基改性之有機改性聚矽氧，可列舉：胺基改性者、環氧改性者、羧基改性者、二醇改性者、甲醇改性者、(甲基)丙烯酸基改性者、巰基改性者、酚改性者。又，作為經非反應性之有機基改性之有機改性聚矽氧，可列舉：聚醚改性者(包括聚氧伸烷基改性者)、甲基苯乙烯基改性者、長鏈烷基改性者、高級脂肪酸酯改性者、高級烷氧基改性者、高級脂肪酸改性者、氟改性者等。視其等有機改性之種類，例如可藉由適當變更聚矽氧鏈之分子量、改性率、改性基之加成莫耳數等而獲得發揮出上述之液膜開裂作用之展佈係數。此處，所謂「長鏈」係指碳數為12以上、較佳為12～20者。又，所謂「高級」係指碳數為6以上、較佳為6～20者。 其中，聚氧伸烷基改性聚矽氧或環氧改性聚矽氧、甲醇改性聚矽氧、二醇改性聚矽氧等作為改性聚矽氧之液膜開裂劑較佳為具有於改性基中具有至少一個氧原子之結構之改性聚矽氧，尤佳為聚氧伸烷基改性聚矽氧。聚氧伸烷基改性聚矽氧由於具有聚矽氧烷鏈，故而難以滲透至纖維之內部而容易殘留於表面。又，因加成有親水性之聚氧伸烷基鏈，故而與水之親和性提高，而界面張力較低，因此容易於上述之液膜表面上移動，故而較佳。因此，容易於上述之液膜表面上移動，故而較佳。又，即便實施壓紋等熱熔融加工，於該部分聚氧伸烷基改性聚矽氧亦容易殘留於纖維之表面從而液膜開裂作用不易降低。尤其於液體容易蓄積之壓紋部分液膜開裂作用會充分地表現，故而較佳。 作為聚氧伸烷基改性聚矽氧，可列舉下述式[I]～[IV]所表示者。進而，就液膜開裂作用之觀點而言，較佳為該聚氧伸烷基改性聚矽氧具有上述範圍之質量平均分子量。 [化2]

[化3]

[化4]

[化5]

式中，R³¹ 表示烷基(較佳為碳數1～20。例如較佳為甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基)。R³² 表示單鍵或伸烷基(較佳為碳數1～20。例如較佳為亞甲基、伸乙基、伸丙基、伸丁基)，較佳為表示上述伸烷基。複數個R³¹ 、複數個R³² 各自相互可相同亦可不同。M¹¹ 表示具有聚氧伸烷基之基，較佳為聚氧伸烷基。作為上述之聚氧伸烷基，可列舉：聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等構成單體共聚合而成者等。m、n分別獨立為1以上之整數。再者，其等重複單元之符號係於各式(I)～(IV)中分別決定者，未必表示相同整數，亦可不同。 又，聚氧伸烷基改性聚矽氧亦可具有聚氧伸乙基改性基及聚氧伸丙基改性基中之任一者或兩者。又，為了不溶於水且具有較低之界面張力，較理想為於聚矽氧鏈之烷基R³¹ 具有甲基。作為具有該改性基、聚矽氧鏈者，並無特別限制，例如存在日本專利特開2002-161474之段落[0006]及[0012]所記載者。更具體而言，可列舉：聚氧伸乙基(POE)聚氧伸丙基(POP)改性聚矽氧、或聚氧伸乙基(POE)改性聚矽氧、聚氧伸丙基(POP)改性聚矽氧等。作為POE改性聚矽氧，可列舉：加成有3莫耳之POE之POE(3)改性二甲基聚矽氧等。作為POP改性聚矽氧，可列舉：加成有10莫耳、12莫耳、或24莫耳之POP之POP(10)改性二甲基聚矽氧、POP(12)改性二甲基聚矽氧、POP(24)改性二甲基聚矽氧等。 關於上述之第1實施形態之展佈係數與水溶解度，於聚氧伸烷基改性聚矽氧之情況下例如可根據聚氧伸烷基之加成莫耳數(對聚氧伸烷基改性聚矽氧1莫耳之形成聚氧伸烷基之氧伸烷基之鍵結數)、下述改性率等而設為特定之範圍。於該液膜開裂劑中，亦可與表面張力及界面張力同樣地分別設為特定之範圍。 就上述觀點而言，較佳為該聚氧伸烷基之加成莫耳數為1以上者。若未達1，則對於上述之液膜開裂作用而言，由於界面張力變高而展佈係數變小，因此液膜開裂效果變弱。就該觀點而言，加成莫耳數更佳為3以上，進而較佳為5以上。另一方面，若加成莫耳數過多，則變得親水而水溶解度變高。就該觀點而言，加成莫耳數較佳為30以下，更佳為20以下，進而較佳為10以下。 關於改性聚矽氧之改性率，若過低，則有損親水性，因此較佳為5%以上，更佳為10%以上，進而較佳為20%以上。又，若過高，則會溶解於水中，因此較佳為95%以下，更佳為70%以下，進而較佳為40%以下。再者，所謂上述改性聚矽氧之改性率，係改性聚矽氧1分子中之經改性之矽氧烷鍵結部之重複單元之個數相對於矽氧烷鍵結部之重複單元之總個數的比率。例如於上述式[I]及[IV]中為(n/m+n)×100%，於式[II]中為(2/m)×100%，於式[III]中為(1/m)×100%。 又，關於上述之展佈係數及水溶解度，於聚氧伸烷基改性聚矽氧之情況下除上述者以外，亦可分別藉由如下方式等而設定為特定之範圍：併用水可溶性之聚氧伸乙基與水不溶性之聚氧伸丙基及聚氧伸丁基作為改性基；使水不溶性之聚矽氧鏈之分子量變化；及除聚氧伸烷基改性基外，亦導入胺基、環氧基、羧基、羥基、甲醇基等作為改性基等。 該可用作液膜開裂劑之聚伸烷基改性聚矽氧以相對於纖維質量之含有比率(Oil Per Unit)計較佳為含有0.02質量%以上且5質量%以下。該聚伸烷基改性聚矽氧之含有比率(OPU)更佳為1質量%以下，進而較佳為0.4質量%以下。藉此，長纖維不織布成為觸感較佳者。又，就充分地發揮利用該聚伸烷基改性聚矽氧之液膜開裂效果之觀點而言，上述含有比率(OPU)更佳為0.04質量%以上，進而較佳為0.1質量%以上。 作為第2實施形態中之液膜開裂劑，較佳為如下述般具有選自由下述之結構Z、Z-Y、及Y-Z-Y所組成之群中之至少1種結構之化合物。 結構Z表示將＞C(A)-(C：碳原子)、-C(A)₂ -、-C(A)(B)-、＞C(A)-C(R³ )＜、＞C(R³ )-、-C(R³ )(R⁴ )-、-C(R³ )₂ -、＞C＜中之任一種基本結構重複、或者組合2種以上而成之結構之烴鏈。於結構Z之末端具有氫原子、或選自由-C(A)₃ 、-C(A)₂ B、-C(A)(B)₂ 、-C(A)₂ -C(R³ )₃ 、-C(R³ )₂ A、-C(R³ )₃ 所組成之群中之至少1種基。 上述之R³ 或R⁴ 分別獨立地表示氫原子、烷基(較佳為碳數1～20。例如較佳為甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基)、烷氧基(較佳為碳數1～20。例如較佳為甲氧基、乙氧基)、芳基(較佳為碳數6～20。例如較佳為苯基)、氟烷基、芳烷基、或將其等組合而成之烴基、或者氟原子等各種取代基。A、B分別獨立地表示羥基或羧酸基、胺基、醯胺基、亞胺基、苯酚基等包含氧原子或氮原子之取代基。於結構Z內R³ 、R⁴ 、A、B各自存在複數個之情形時其等相互可相同亦可不同。又，所連接之C(碳原子)間之鍵通常為單鍵，但亦可包含雙鍵或三鍵，C間之鍵亦可包含醚基、醯胺基、酯基、羰基、碳酸酯基等連結基。一個C與另一個C鍵結之數為1個～4個，因此亦可存在長鏈之烴鏈分支，或者具有放射狀之結構之情形。 Y表示包含選自氫原子、碳原子、氧原子、氮原子、磷原子、硫原子中之原子的具有親水性之親水基。例如為包含羥基、羧酸基、胺基、醯胺基、亞胺基、苯酚基；或者聚氧伸烷基(氧伸烷基之碳數較佳為1～4。例如較佳為聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等組合而成之聚氧伸烷基)；或者赤藻糖醇基、木糖醇基、山梨糖醇基、甘油基、乙二醇基等具有複數個羥基之親水基；或者磺酸基、硫酸基、磷酸基、磺基甜菜鹼基、羰基甜菜鹼基、膦基甜菜鹼基、四級銨基、咪唑鎓甜菜鹼基、環氧基、甲醇基、甲基丙烯酸基等親水基單獨；或者其等之組合之親水基等。再者，於Y為複數個之情形時，相互可相同亦可不同。 結構Z-Y及Y-Z-Y中，Y係鍵結於Z、或Z之末端之基。於Y鍵結於Z之末端之基之情形時，Z之末端之基例如將同與Y之鍵結數相同數量之氫原子等去除而與Y鍵結。 於該結構中，自具體說明過之基中選擇親水基Y、A、B而可滿足上述之展佈係數、水溶解度、界面張力。如此表現出目標之液膜開裂效果。 上述之液膜開裂劑較佳為將作為上述之結構Z、Z-Y、Y-Z-Y之具體例之下述(12)～(25)式所表示的結構任意地組合而成之化合物。進而，就液膜開裂作用之觀點而言，較佳為該化合物具有上述範圍之質量平均分子量。 [化6]

式(12)～(25)中，M² 、L² 、R⁴¹ 、R⁴² 、及R⁴³ 表示以下之1價或多價基(2價或2價以上)。 M² 表示具有聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等組合而成之聚氧伸烷基的基；或赤藻糖醇基、木糖醇基、山梨糖醇基、甘油基或乙二醇基等具有複數個羥基之親水基、羥基、羧酸基、巰基、烷氧基(較佳為碳數1～20。例如較佳為甲氧基)、胺基、醯胺基、亞胺基、苯酚基、磺酸基、四級銨基、磺基甜菜鹼基、羥基磺基甜菜鹼基、膦基甜菜鹼基、咪唑鎓甜菜鹼基、羰基甜菜鹼基、環氧基、甲醇基、(甲基)丙烯酸基、或將其等組合而成之官能基。 L² 表示醚基、胺基、醯胺基、酯基、羰基、碳酸酯基、或者聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等組合而成之聚氧伸烷基等鍵結基。 R⁴¹ 、R⁴² 、及R⁴³ 分別獨立地表示包含氫原子、烷基(較佳為碳數1～20。例如較佳為甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基)、烷氧基(較佳為碳數1～20。例如較佳為甲氧基、乙氧基)、芳基(較佳為碳數6～20。例如較佳為苯基)、氟烷基、芳烷基、或將其等組合而成之烴基、或者鹵素原子(例如較佳為氟原子)之各種取代基。 於R⁴² 為多價基之情形時，R⁴² 表示自上述各取代基進而去除1個以上之氫原子而成之基。 再者，於各結構所記載之鍵結鍵之前可任意地連接其他結構，亦可導入氫原子。 進而作為上述化合物之具體例，可列舉如下之化合物，但並不限定於此。 第1，可列舉聚醚化合物或非離子界面活性劑。具體而言，可列舉：式(V)之任一者所表示之聚氧伸烷基(POA)烷基醚、或式(VI)所表示之質量平均分子量1000以上之聚氧伸烷基二醇、硬脂醇聚醚、山萮醇聚醚、PPG肉豆蔻基醚、PPG硬脂基醚、PPG山萮基醚等。作為聚氧伸烷基烷基醚，較佳為加成有3莫耳以上且24莫耳以下、較佳為5莫耳之POP之月桂醚等。作為聚醚化合物，較佳為加成有17莫耳以上且180莫耳以下、較佳為約50莫耳之聚丙二醇(PPG)之質量平均分子量為1000～10000、較佳為3000之聚丙二醇等。再者，上述質量平均分子量之測定可利用上述之測定方法進行。 該聚醚化合物或非離子界面活性劑以相對於纖維質量之含有比率(Oil Per Unit)計較佳為含有0.10質量%以上且5質量%以下。該聚醚化合物或非離子界面活性劑之含有比率(OPU)更佳為1質量%以下，進而較佳為0.4質量%以下。藉此，不織布成為觸感較佳者。又，就充分地發揮利用該聚醚化合物或非離子界面活性劑之液膜開裂效果之觀點而言，上述含有比率(OPU)更佳為0.15質量%以上，進而較佳為0.2質量%以上。 [化7]

[化8]

式中，L²¹ 表示醚基、胺基、醯胺基、酯基、羰基、碳酸酯基、聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等組合而成之聚氧伸烷基等鍵結基。R⁵¹ 表示包含氫原子、甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基、甲氧基、乙氧基、苯基、氟烷基、芳烷基、或將其等組合而成之烴基、或者氟原子之各種取代基。又，a、b、m及n分別獨立為1以上之整數。此處，C_m H_n 表示烷基(n=2m+1)，C_a H_b 表示伸烷基(a=2b)。再者，其等碳原子數及氫原子數係於各式(V)及(VI)中各自獨立地決定者，未必表示相同之整數，亦可不同。以下，式(VII)～(XV)之m、m'、m''、n、n'及n''亦相同。再者，-(C_a H_b O)_m -之「m」係1以上之整數。該重複單元之值係於各式(V)及(VI)中各自獨立地決定者，未必表示相同之整數，亦可不同。 關於上述之第2實施形態之展佈係數、表面張力及水溶解度，於聚醚化合物或非離子界面活性劑之情況下例如可根據聚氧伸烷基之莫耳數等而分別設定為特定範圍。就該觀點而言，較佳為聚氧伸烷基之莫耳數為1以上且70以下者。藉由設為1以上，而充分地發揮上述之液膜開裂作用。就該觀點而言，莫耳數更佳為5以上，進而較佳為7以上。另一方面，加成莫耳數較佳為70以下，更佳為60以下，進而較佳為50以下。藉此，分子鏈之連結適度地變弱，而於液膜內之擴散性優異，故而較佳。 又，關於上述之展佈係數、表面張力、界面張力及水溶解度，於聚醚化合物或非離子界面活性劑之情況下分別可藉由如下方式而設定為特定之範圍：併用水溶性之聚氧伸乙基與水不溶性之聚氧伸丙基及聚氧伸丁基；使烴鏈之鏈長變化；使用烴鏈具有支鏈者；使用烴鏈具有雙鍵者；使用烴鏈具有苯環或萘環者；或者將上述適當組合等。 第2，可列舉碳原子數5以上之烴化合物。就液體更容易於液膜表面擴張之觀點而言，碳原子數較佳為100以下，更佳為50以下。該烴化合物係將聚有機矽氧烷除外者，且並不限定於直鏈，亦可為支鏈，該鏈並不特別限定於飽和鏈、不飽和鏈。又，於其中間及末端亦可具有酯或醚等取代基。其中，可較佳地單獨使用常溫下為液體者。該烴化合物以相對於纖維質量之含有比率(Oil Per Unit)計較佳為含有0.1質量%以上且5質量%以下。該烴化合物之含有比率(OPU)較佳為1質量%以下，更佳為0.99質量%以下，進而較佳為0.4質量%以下。藉此，長纖維不織布成為觸感較佳者。又，就充分地發揮基於該烴化合物之液膜開裂效果之觀點而言，上述含有比率(OPU)更佳為0.15質量%以上，進而較佳為0.2質量%以上。 作為烴化合物，可列舉：油或脂肪、例如天然油或天然脂肪。作為具體例，可列舉：椰子油、山茶油、蓖麻油、可可椰子油、玉米油、橄欖油、葵花籽油、妥爾油、及其等之混合物等。 又，可列舉：辛酸、癸酸、油酸、月桂酸、棕櫚酸、硬脂酸、肉豆蔻酸、山萮酸、及其等之混合物等如式(VII)所表示之脂肪酸。 [化9]

式中，m及n分別獨立為1以上之整數。此處，C_m H_n 表示上述各脂肪酸之烴基。 作為直鏈或支鏈、飽和或不飽和、經取代或未經取代之多元醇脂肪酸酯或者多元醇脂肪酸酯之混合物之例，可列舉：如式(VIII-I)或(VIII-II)所表示之甘油脂肪酸酯或季戊四醇脂肪酸酯，具體而言，可列舉：甘油三辛酸酯、甘油三棕櫚酸酯及其等之混合物等。再者，關於甘油脂肪酸酯、或季戊四醇脂肪酸酯之混合物，典型而言，包含若干之單酯、二酯、及三酯。作為甘油脂肪酸酯之較佳例，可列舉：甘油三辛酸酯、甘油三辛酸酯之混合物等。又，就使界面張力降低而獲得更高之展佈係數之觀點而言，亦可使用導入聚氧伸烷基至可維持水不溶性之程度之多元醇脂肪酸酯。 [化10]

[化11]

式中，m、m'、m''、n、n'及n''分別獨立為1以上之整數。複數個m、複數個n各自相互可相同亦可不同。此處，C_m H_n 、C_m 'H_n '及C_m ''H_n ''分別表示上述各脂肪酸之烴基。 作為直鏈或支鏈、飽和或不飽和之脂肪酸與具有多個羥基之多元醇形成酯，且一部分羥基未被酯化而殘存之脂肪酸或脂肪酸混合物之例，可列舉：如式(IX)之任一者、式(X)之任一者、或式(XI)之任一者所表示之甘油脂肪酸酯、或山梨醇酐脂肪酸酯、季戊四醇脂肪酸酯之部分酯化物。具體而言，可列舉：乙二醇單肉豆蔻酸酯、乙二醇二肉豆蔻酸酯、乙二醇棕櫚酸酯、乙二醇二棕櫚酸酯、甘油二肉豆蔻酸酯、甘油二棕櫚酸酯、甘油單油酸酯、山梨醇酐單油酸酯、山梨醇酐單硬脂酸酯、山梨醇酐二油酸酯、山梨醇酐三硬脂酯、季戊四醇單硬脂酸酯、季戊四醇二月桂酸酯、季戊四醇三硬脂酸酯、及其等之混合物等。再者，關於包含甘油脂肪酸酯、或山梨醇酐脂肪酸酯、季戊四醇脂肪酸酯等之部分酯化物之混合物，典型而言，包含若干經完全酯化之化合物。 [化12]

式中，m及n分別獨立為1以上之整數。複數個m、複數個n各自相互可相同亦可不同。此處，C_m H_n 表示上述各脂肪酸之烴基。 [化13]

式中，R⁵² 表示碳原子數2以上且22以下之直鏈或支鏈、飽和或不飽和之烴基(烷基、烯基、炔基等)。具體而言，可列舉：2-乙基己基、月桂基、肉豆蔻基、棕櫚基、硬脂基、山萮基、油醯基、亞麻油基等。 [化14]

式中，m及n分別獨立為1以上之整數。複數個m、複數個n各自相互可相同亦可不同。此處，C_m H_n 表示上述各脂肪酸之烴基。 又，可列舉：固醇、植固醇及固醇衍生物。作為具體例，可列舉：具有式(XII)之固醇結構之膽固醇、穀固醇、豆固醇、麥角固醇、及其等之混合物等。 [化15]

作為醇之具體例，可列舉：如式(XIII)所表示之月桂醇、肉豆蔻醇、鯨蠟醇、硬脂醇、鯨蠟硬脂醇、山萮醇、及其等之混合物等。 [化16]

式中，m及n分別獨立為1以上之整數。此處，C_m H_n 表示上述各醇之烴基。 作為脂肪酸酯之具體例，可列舉：如式(XIV)所表示之肉豆蔻酸異丙酯、棕櫚酸異丙酯、乙基己酸鯨蠟酯、三異辛酸甘油酯、肉豆蔻酸辛基十二烷基酯、棕櫚酸乙基己酯、硬脂酸乙基己酯、硬脂酸丁酯、肉豆蔻酸肉豆蔻酯、硬脂酸硬脂酯、異硬脂酸膽固醇基酯及其等之混合物等。 [化17]

式中，m及n分別獨立為1以上之整數。此處，兩個C_m H_n 可相同亦可不同。C_m H_n -COO-之C_m H_n 表示上述各脂肪酸之烴基。-COOC_m H_n 之C_m H_n 表示源自形成酯之醇之烴基。 又，作為蠟之具體例，可列舉：如式(XV)所表示之地蠟、石蠟、凡士林、礦物油、流動異構石蠟等。 [化18]

式中，m及n分別獨立為1以上之整數。 關於上述之第2實施形態之展佈係數、表面張力、水溶解度及界面張力，於上述之碳原子數5以上之烴化合物之情況下分別可藉由如下方式而設定為特定之範圍：例如少量導入親水性之聚氧伸乙基至可維持水不溶性之程度；導入雖為疏水性，但可使界面張力降低之聚氧伸丙基或聚氧伸丁基；使烴鏈之鏈長變化；使用烴鏈具有支鏈者；使用烴鏈具有雙鍵者；使用烴鏈具有苯環或萘環者等。 於本發明之長纖維不織布中，除上述之液膜開裂劑以外，亦可視需要而含有其他成分。又，第1實施形態之液膜開裂劑、第2實施形態之液膜開裂劑除各自所使用之形態以外，亦可組合兩者之劑而使用。該方面對於第2實施形態之液膜開裂劑中之第1化合物與第2化合物而言亦相同。 再者，於對本發明之長纖維不織布中所含有之液膜開裂劑或磷酸酯型之陰離子界面活性劑進行鑑定之情形時，可使用上述之液膜(表面張力為50 mN/m之液體)之表面張力(γ_w )等之測定方法中所述的鑑定方法。 又，於液膜開裂劑之成分為主鏈具有矽氧烷鏈之化合物或碳原子數1以上且20以下之烴化合物的情形時，液膜開裂劑相對於纖維質量之含有比率(OPU)可藉由如下方式求出：基於藉由上述之分析方法而獲得之物質之質量，用該液膜開裂劑之含量除以纖維之質量。 繼而，對本發明之長纖維不織布中之親水度，更詳細地進行說明。 親水度係構成纖維之親水度，可將去離子水相對於構成纖維之接觸角作為指標而進行判斷。接觸角係纖維狀之水滴與纖維表面之角度，親水度之降低係與接觸角之增大含義相同。該接觸角可藉由下述之測定方法而獲得。 於本發明之長纖維不織布中，具有自成為受液面側(肌膚抵接面側)之第1面側向第2面側(非肌膚抵接面側)之厚度方向之親水度梯度時，上述第1面側之纖維之接觸角(V1)就減少附著於肌膚之液量之觀點而言，較佳為80°以上，更佳為85°以上，進而較佳為90°以上。又，上述接觸角(V1)就防止於表面之液體流動之觀點而言，較佳為100°以下，更佳為97°以下，進而較佳為95°以下。 另一方面，關於上述第2面側(非肌膚抵接面側)之纖維之接觸角(V2)，就提高液體之吸抽性之觀點而言，較佳為90°以下，更佳為85°以下，進而較佳為80°以下。又，關於上述接觸角(V2)，就提高於作為正面片材載置於吸收體之狀態下向吸收體之液體交接性之觀點而言，較佳為30°以上，更佳為40°以上，進而較佳為50°以上。 進而，關於上述第1面側之纖維之接觸角(V1)與上述第2面側(非肌膚抵接面側)之纖維之接觸角(V2)的差(V1-V2)，就提高液體向厚度方向之透過性之觀點而言，較佳為3°以上，更佳為5°，進而較佳為10°。又，關於上述接觸角之差(V1-V2)，就兼顧液體向厚度方向之透過性與不易回液之觀點而言，較佳為5°以上，更佳為7°，進而較佳為10°。 (接觸角之測定方法) 上述之接觸角之測定可藉由以下之方法進行。 即，自長纖維不織布之特定部位取出纖維，對水相對於該纖維之接觸角進行測定。使用協和界面科學股份有限公司製造之自動接觸角計MCA-J作為測定裝置。於接觸角之測定中使用蒸餾水。於溫度25℃、相對濕度(RH)65%之測定條件下進行。將自噴墨式水滴噴出部(Cluster Technology公司製造，噴出部孔徑為25 μm之脈衝噴射器CTC-25)噴出之液量設定為20微微升，向纖維之正上方滴下水滴。將滴下之情況錄影於連接於水平設置之相機之高速錄影裝置中。關於錄影裝置，就其後進行圖像解析之觀點而言，較理想為安裝有高速擷取裝置之個人電腦。於本測定中，每隔17 msec對圖像進行錄影。於所錄影之影像中，將水滴滴至自積層不織布取出之纖維時之最初圖像利用附屬軟體FAMAS(設為：軟體之版本為2.6.2，解析手法為液滴法，解析方法為θ/2法，圖像處理演算法為無反射，圖像處理影像模式為圖框，臨限位準為200，且未進行曲率修正)進行圖像解析，算出水滴之接觸於空氣之面與纖維所成之角度，而設為接觸角。自積層不織布取出之纖維係剪裁為纖維長度1 mm，將該纖維置於接觸角計之樣品台，並水平維持。對每根該纖維測定不同之2個部位之接觸角。對N=5根之接觸角進行測量直至小數點以下1位，將平均合計10個部位之測定值而獲得之值(於小數點以下第2位四捨五入)定義為接觸角。 作為賦予如上述之接觸角之親水化劑，可無特別限制地採用此種物品所使用者。具體而言，例如可列舉：陰離子性、陽離子性、兩性及非離子性之界面活性劑，可使用羧酸鹽系之陰離子界面活性劑、磺酸鹽系之陰離子界面活性劑、硫酸酯鹽系之陰離子界面活性劑、磷酸酯型之陰離子界面活性劑(特別是烷基磷酸酯鹽)等陰離子界面活性劑；山梨醇酐脂肪酸酯、二乙二醇單硬脂酸酯、二乙二醇單油酸酯、甘油單硬脂酸酯、甘油單油酸酯、丙二醇單硬脂酸酯等多元醇單脂肪酸酯、油酸醯胺、硬脂酸醯胺、芥酸醯胺等脂肪酸醯胺、N-(3-油醯氧基-2-羥基丙基)二乙醇胺、聚氧乙烯氫化蓖麻油、聚氧乙烯山梨糖醇蜂蠟、聚氧乙烯山梨醇酐倍半硬脂酸酯、聚氧乙烯單油酸酯、聚氧乙烯山梨醇酐倍半硬脂酸酯、聚氧乙烯甘油單油酸酯、聚氧乙烯單硬脂酸酯、聚氧乙烯單月桂酸酯、聚氧乙烯單油酸酯、聚氧乙烯鯨蠟基醚、聚氧乙烯月桂醚等非離子系界面活性劑；四級銨鹽、胺鹽或胺等陽離子界面活性劑；含有羧基、磺酸酯基、硫酸酯基之二級胺或三級胺之脂肪族衍生物、或雜環式二級胺或三級胺之脂肪族衍生體等兩性界面活性劑等。其等較佳之界面活性劑及較佳之界面活性劑之組合只要包含其等界面活性劑即可，亦可進而包含其他界面活性劑等。再者，此處所謂磷酸酯型之陰離子界面活性劑，係實際上與作為可與上述之液膜開裂劑一併含有者所列舉之磷酸酯型之陰離子界面活性劑相同之劑。即，磷酸酯型之陰離子界面活性劑具有如下兩種功能，即賦予親水性之功能、與提高與血液或尿所含有之磷脂質之親和性而促進液膜開裂劑之作用之功能。 繼而，對本發明之長纖維不織布之製造方法進行說明。 首先，基礎之長纖維不織布之製造方法可無特別限制地採用此種物品所使用之方法。例如紡黏不織布係經由如下步驟而製造：(1)將原料樹脂熔融紡出並將長纖維集聚於輸送器上之步驟；(2)對所獲得之長纖維之纖維網實施熱壓紋(利用壓紋凸滾筒與平坦輥等)而形成熱熔合部之步驟而製造。再者，熱熔合部可藉由除熱壓紋以外，進行超音波熔合，或間斷性地施以熱風而進行局部熔合之方法等各種方法而形成。 於該製造步驟中，作為含有上述之液膜開裂劑或該液膜開裂劑及磷酸酯型之陰離子界面活性劑、或上述之親水化劑之方法，可列舉：(A)塗佈於不織布化後之原料長纖維不織布之方法、(B)塗佈於不織布化前之纖維表面之方法、(C)添加於成為纖維之原料之樹脂中之方法等。此時，可以纖維處理劑之形式進行塗佈，該纖維處理劑係將上述之液膜開裂劑或該液膜開裂劑及磷酸酯型之陰離子界面活性劑與上述之親水化劑全部進行混合並進行稀釋所得，亦可將各自以不同之纖維處理劑之形式分別地進行塗佈。作為纖維處理劑之塗佈方法，例如可列舉：利用噴霧之塗佈、利用狹縫式塗佈機之塗佈、利用凹版方式、軟版方式、浸漬方式之塗佈等。 液膜開裂劑、或液膜開裂劑及磷酸酯型之陰離子界面活性劑向纖維之含有可於任一步驟中進行。例如可於上述(B)或(C)之步驟中，於纖維之紡絲時通常所使用之纖維用紡絲油劑中調配液膜開裂劑、或液膜開裂劑及磷酸型陰離子界面活性劑之混合物而進行塗佈；亦可於上述(A)之不織布化後進行塗佈；亦可於纖維之延伸前後之纖維用潤飾油劑中調配液膜開裂劑、或液膜開裂劑及磷酸型陰離子界面活性劑之混合物而進行塗佈。又，可於不織布之製造通常所使用之纖維處理劑中調配液膜開裂劑或磷酸酯型之陰離子界面活性劑而塗佈於纖維，亦可於不織布化後進行塗佈。 另一方面，關於親水化劑，為了對長纖維不織布賦予親水度梯度，必須分塗不同之至少2種親水化劑。於利用上述(A)之方法含有親水化劑之情形時，原料長纖維不織布有較將其他短纖維作為原料之不織布薄之傾向，因此親水化劑容易滲出而分塗困難。又，於利用上述(B)或(C)之方法含有親水化劑之情形時，由於將自長纖維之熔融紡出直至利用熱熔合之不織布化於同一生產線中連續地進行，故而亦難以於不織布化前每個纖維分塗不同之親水化劑，或者難以將含有不同之親水化劑之纖維彼此於不織布化前進行積層。因此，可採用如下方法：將含有不同之親水化劑之複數個原料長纖維不織布彼此進行積層，而製成包含複數層之本發明之長纖維不織布。即，可列舉製成圖1(C)之複數層之長纖維不織布之方法。又，即便為單層，亦可採用如下方法，即藉由所使用之親水化劑，配合由熱風處理所產生之熱量而使親水度於厚度方向上進行變化之方法。 或者，即便為單層，於圖1(B)之長纖維不織布20中，亦藉由用以形成豎立性纖維4之延伸加工，而使豎立性纖維4之親水度變得低於纖維集合層3之纖維之親水度。藉此，第1面5側之豎立性纖維4之親水度低於第2面6側之纖維集合層3之纖維之親水度，在厚度方向上看，存在自有豎立性纖維4之層向纖維集合層3升高之2階段親水度梯度。其原因在於：對塗佈有親水化劑之原料長纖維不織布實施下述之起毛加工時，成為豎立性纖維4之長纖維較纖維集合層3之纖維得到延伸而斷裂。認為其原因在於：伴隨著纖維之延伸，親水化劑亦會追隨，伴隨此，於纖維得到延伸之部分親水化劑之濃度變薄。又，反之於親水化劑對延伸之纖維之追隨性較低之情形時，認為因纖維之延伸而親水化劑之一部分斷裂，而於纖維上產生存在油劑之部分與不存在油劑之部分，而未產生親水度之梯度(於不均一表面之潤濕係取決於各親水化劑成分之面積率)。 (起毛加工) 圖4(A)～(D)係表示由塗佈有親水化劑之原料長纖維不織布200形成具有自由端部42之豎立性纖維4等而製造圖1(B)之長纖維不織布20的方法。具體而言，可為僅包含圖4(C)所示之起毛加工之製造方法，亦可為包含依序進行圖4(A)及(B)所示之局部延伸加工(預加工)及圖4(C)所示之起毛加工之二階段起毛加工的製造方法。為了獲得肌膚觸感良好且柔軟之長纖維不織布，較佳為二階段起毛加工。 於二階段起毛加工中，進行圖4(A)及(B)所示之部分延伸加工。具體而言，對於塗佈有親水化劑之原料長纖維不織布200，藉由凹凸輥74、75之凹凸之相互嚙合而將原料長纖維不織布200進行挾壓。藉此，對原料長纖維不織布200之複數個部位實施局部延伸加工並帶來損傷。繼而，於圖4(C)所示之斷裂加工中，利用搬送輥76、76將經局部延伸加工之原料長纖維不織布200進行搬送並賦予相對於起毛輥77之角度。關於起毛輥77，具有用以起毛之突起部79。藉由該起毛輥77之滾動，經局部延伸加工之原料長纖維不織布200之一面之表面之長纖維一部分斷裂並起毛，而成為豎立性纖維4。豎立性纖維4於上述之起毛處理中，較構成未起毛之基質部分即纖維集合層3之纖維更得到延伸。藉由以上述方式進行延伸，豎立性纖維4之親水度變得低於構成纖維集合層3之纖維之親水度。 再者，起毛輥77亦可相對於經局部延伸加工之原料長纖維不織布200之搬送方向，向反方向、順方向之任一方法進行滾動，但就高效率地形成豎立性纖維4之觀點而言，較佳為向反方向進行滾動。 長纖維不織布20中，關於起毛之纖維之根數，就提高緩衝性之觀點、與肌膚接觸時肌膚觸感變良好之觀點而言，較佳為8根/cm以上，更佳為12根/cm以上，進而較佳為15根/cm以上。此處所謂起毛之纖維，包含具有自由端部42之豎立性纖維4及環狀纖維。又，就確保充分之斷裂強度之觀點而言，較佳為100根/cm以下，就防止外觀上起絨毛而不可見之觀點而言，更佳為40根/cm以下，進而較佳為30根/cm以下。再者，上述起毛之纖維係藉由以下之測定法進行測定。本案中所謂「具備起毛之纖維之長纖維不織布」係指於下述之測定法中，起毛之纖維為5根/cm以上之長纖維不織布。 (起毛之纖維之根數之測定法) 圖5(A)～(C)係表示於22℃65%RH環境下，對構成長纖維不織布20之纖維中起毛之纖維之根數進行測定之方法的模式圖。首先，利用鋒利之剃刀，自供測定之長纖維不織布20切出20 cm×20 cm之測定片，如圖5(A)所示般，於測定片之起毛之面進行凸折而形成測定樣品104。繼而，將該測定樣品104載置於A4尺寸之黑色襯紙上，如圖5(B)所示般，進而於其上載置開有長1 cm×寬1 cm之孔107之A4尺寸之黑色襯紙。此時，如圖5(B)所示般，將測定樣品104之折縫105以自上側之黑色襯紙之孔107可見之方式進行配置。兩襯紙係使用富士共和製紙股份有限公司之「KENRAN(黑色)連量265 g」。其後，於自上側之襯紙之孔107之兩側分別沿著折縫105向外側離開5 cm之位置上，分別載置50 g之重物，而製作測定樣品104完全摺疊之狀態。繼而，如圖5(C)所示般，使用顯微鏡(KEYENCE股份有限公司製造之VHX-900)，以30倍之倍率對襯紙之孔107內進行觀察，計測存在於假想線108之上方之每1 cm之纖維之根數，該假想線108係在測定樣品104之自折縫105往上0.2 mm處進行平行移動之位置上所形成。對9個部位進行計測，將平均值(將小數點第二位進行四捨五入)設為起毛之纖維之根數。 又，計數起毛之纖維之數量時，例如於存在如圖5(C)所示之纖維106a般，橫穿過處於自折縫105往上0.2 mm處之假想線108兩次之纖維的情形時，該纖維係計數為2根。具體而言，於圖5(C)所示之例中，橫穿過假想線108一次之纖維存在4根，橫穿過假想線108兩次之纖維106a存在1根，但橫穿過2次之纖維106a係計數為2根，起毛之纖維之根數為6根。 就提高與肌膚接觸時之肌膚觸感之觀點而言，長纖維不織布20較佳為起毛之纖維(橫穿過假想線108之纖維。此處，如上所述，包含具有自由端部42之豎立性纖維4及環狀纖維兩者)之平均纖維徑小於同一面之未起毛之部位之表面纖維(未橫穿過假想線108且未到達假想線108之纖維，即構成纖維集合體3之未起毛之纖維)的平均纖維徑。平均纖維徑係指利用顯微鏡(光學顯微鏡、或掃描式電子顯微鏡等)對起毛之纖維、及未起毛之纖維各12個部位的纖維徑進行測量所得之纖維徑。起毛之纖維之平均纖維徑較佳為未起毛之纖維之平均纖維徑的98%以下且40%以上，若為96%以下且70%以上，則肌膚觸感優異，故而更佳。同樣地，具有自由端部42之豎立性纖維4之平均纖維徑及環狀纖維之平均纖維徑較佳為均小於構成纖維集合體3之纖維(未起毛之纖維)之平均纖維徑，較佳為未起毛之纖維之纖維徑之98%以下且40%以上，若為96%以下且70%以上，則肌膚觸感優異，故而更佳。 進而，豎立性纖維4較佳為於自由端部42之部分變粗。作為變粗者之形狀，較佳為自由端部42之剖面為扁平狀(橢圓或潰縮之形狀)者。藉此，獲得前端柔軟之豎立性纖維4，而獲得對肌膚之刺激較少之長纖維不織布20。 又，長纖維不織布20較佳為如上述般，起毛之纖維(包含具有自由端部42之豎立性纖維4及環狀纖維之纖維)之根數為8根/cm以上且起毛之纖維之起毛高度為1.5 mm以下。藉此，獲得緩衝性得到提高而肌膚觸感得以提高之吸收性物品。就不易起球、不易脫毛之觀點而言，進而較佳為起毛之纖維之起毛高度為1 mm以下。另一方面，若0.2 mm以上，則獲得良好之肌膚觸感者。進而，在體液之吸收特性中之回液量減少之方面上，起毛高度較佳為0.5 mm以上。於與肌膚接觸之面側使用起毛面之情形時，在不易緊黏著肌膚而觸感較佳之方面上，起毛高度進而較佳為1 mm以下。又，起毛之纖維為15根/cm以上之情況於獲得緩衝性提高、及體液之吸收速度較快者之方面上較佳。又，為了防止成為類似起毛之外觀，或因於使用時摩擦而起球或脫毛，較佳為起毛之纖維之高度為5 mm以下。 此處，所謂起毛高度，與纖維之長度不同，意指於測定時不拉伸纖維，於自然狀態下之纖維之高度。若起毛之纖維之長度值較大或纖維之剛性較高，則有起毛之纖維之起毛高度變高之傾向。起毛之纖維之起毛高度係利用以下之測定法進行測定。 (起毛之纖維之起毛高度之測定方法) 起毛之纖維之起毛高度係於對起毛之纖維(包含具有自由端部42之豎立性纖維4及環狀纖維之纖維)之根數進行測定時，同時進行測定。具體而言，如圖5(C)所示般，對襯紙之孔107內進行觀察，自折縫105起每0.05 mm平行地劃線直至起毛之纖維不再相交處為止。繼而，與以上述方式測得之起毛之纖維之根數(根據處於0.2 mm上方之假想線108進行判斷)相比，選擇與平行之線相交之纖維成為一半之平行線，將自此處直至折縫之距離設為起毛高度。藉由以上之操作，對供測定之不織布3片進行計測，並以每片3個部位之方式取3片合計9個部位之平均值，而設為起毛之纖維之起毛高度。 除起毛之纖維之起毛高度、及起毛之纖維之根數以外，於獲得於與肌膚接觸時柔軟者，而肌膚觸感優異之方面上，較佳為長纖維不織布20之整體柔度為8 cN以下。於成為如嬰兒或幼兒之繈褓之柔軟者之方面上，長纖維不織布20之整體柔度進而較佳為0.5 cN以上且3 cN以下。整體柔度係藉由以下之測定法進行測定。 (整體柔度之測定方法) 關於長纖維不織布20之整體柔度，將長纖維不織布20於MD方向上切出150 mm，於CD方向上切出30 mm，並使用釘書機，將端部於上下2個部位進行固定而成為直徑45 mm之環狀。此時，纖維切斷機(stapler)之芯係設為於MD方向上變長。使用拉伸試驗機(例如，Orientec股份有限公司製造之Tensilon拉伸試驗機「RTA-100」)，於試樣台上將上述環筒狀地豎立，自上方利用與試樣台大致平行之平板以壓縮速度10 mm/分鐘之速度進行壓縮，測定此時之最大負荷，而設為CD方向之整體柔度。繼而，改變MD方向與CD方向而製作環，以相同之方式對MD方向之整體柔度進行測定。MD方向及CD方向各製作2個環而進行測定，將其等CD方向與MD方向之平均值設為長纖維不織布20之整體柔度。 再者，所謂MD方向，意指不織布之製造階段之機械搬出方向(MD：Machine Direction)，且意指所製造之不織布中之長度方向。於將不織布作為原料片材而製成輥狀之情形時，或自輥狀之狀態捲出之情形時，意指將該不織布捲出之方向。另一方面，所謂CD方向，意指不織布之製造階段之與機械搬出方向正交之寬度方向(CD：Cross Direction)，且意指所製造之不織布中之與上述長度方向正交之寬度方向。於上述原料片材之狀態下，意指輥軸方向。進而，於將不織布剪裁為特定尺寸而作為吸收性物品之正面片材之情形時，MD方向係與上述吸收性物品之長度方向一致之方向，上述CD方向係與吸收性物品之寬度方向一致之方向。 本發明之長纖維不織布係不管纖維之粗細或纖維間距離如何，均液體透過性較高者。然而，本發明之長纖維不織布尤其於使用較細之纖維之情形具有效果。若為了製成肌膚觸感較通常柔軟之長纖維不織布而使用較細之纖維，則纖維間距離變小，而纖維間之狹窄區域變多。相對於此，即便於本發明之長纖維不織布中使纖度低於先前，上述液膜開裂劑亦會確實地使多發之液膜開裂而減少液體殘留。如下所述，液膜面積率係藉由源自長纖維不織布表面之圖像解析而算出之液膜面積率，且與表面材之最表面之液體殘留狀態密切相關。因此，若液膜面積率減少，則處於肌膚附近之液體被去除，而排泄後之舒適性提高，從而成為排泄後亦穿戴感良好之吸收性物品。 另一方面，下述之液體殘留量意指長纖維不織布整體所保持之液量。若液膜面積率變小，則使液膜開裂而不穩定之液體增加，該液因親水度之梯度而自親水度較低之纖維層沿單向被抽向親水度較高之纖維層，從而液體殘留減少。又，關於表面之白色度，存在因表面之液膜破裂而液體殘留量降低從而白色度變高之傾向，從而於視覺上發白變得容易顯眼。本發明之包含液膜開裂劑之長纖維不織布即便使纖維變細，亦可使液膜面積率及液體殘留量降低而使表面發白，因此可以高水準兼顧乾爽感與藉由使纖維變細而賦予之柔軟之肌膚觸感。又，藉由使用本發明之長纖維不織布作為吸收性物品之表面材等構成構件，可提供如下吸收性物品，該吸收性物品由於與肌膚接觸之部分之乾爽感較高，且因視覺上發白而由體液導致之污染不易顯眼，故而實現安心感與穿戴感良好之舒適性。 關於此種含有液膜開裂劑，且具有親水度梯度之長纖維不織布，就提高肌膚觸感之柔軟性之觀點而言，長纖維不織布之纖維間距離較佳為300 μm以下，更佳為250 μm以下。又，關於其下限，就抑制由於纖維間變得過於狹窄而有損通液性之觀點而言，較佳為30 μm以上，更佳為50 μm以上。具體而言，較佳為30 μm以上且300 μm以下，更佳為50 μm以上且250 μm以下。 該情形時之上述纖維之纖度較佳為3.3 dtex以下，更佳為2.4 dtex以下。又，關於其下限，較佳為0.5 dtex以上，更佳為0.7 dtex以上。具體而言，較佳為0.5 dtex以上且3.3 dtex以下，更佳為0.7 dtex以上且2.4 dtex以下。 (纖維間距離之測定方法) 纖維間距離以下述方式對測定對象之長纖維不織布之厚度進行測定，並套入下述數式(2)而求出。 首先，將測定對象之長纖維不織布切割成長度方向50 mm×寬度方向50 mm而製作該長纖維不織布之切割片。於在將測定對象之不織布組入至生理用品或拋棄式尿布等吸收性物品中之情形時等未獲得該尺寸之切割片之情形時，切割成所獲得之最大限度之尺寸而製作切割片。 於49 Pa加壓下對該切割片之厚度進行測定。測定環境係溫度20±2℃、相對濕度65±5%，測定機器係使用顯微鏡(KEYENCE股份有限公司製造，VHX-1000)。首先，獲得上述長纖維不織布剖面之放大照片。於放大照片中同時顯示出已知尺寸者。將上述不織布剖面之放大照片對照比例尺而測定長纖維不織布之厚度。進行以上之操作3次，將3次之平均值設為乾燥狀態之長纖維不織布之厚度[mm]。再者，於積層品之情形時，根據纖維徑辨別其交界而算出厚度。 繼而，構成測定對象之長纖維不織布之纖維之纖維間距離係藉由以下所示之基於Wrotnowski之假定的式而求出。基於Wrotnowski之假定之式係通常於求出構成不織布之纖維之纖維間距離時使用。根據基於Wrotnowski之假定之式，纖維間距離A(μm)係根據長纖維不織布之厚度h(mm)、基重(單位面積重量)e(g/m² )、構成長纖維不織布之纖維之纖維徑d(μm)、纖維密度ρ(g/cm³ )，利用以下之數式(2)求出。再者，於具有凹凸之情形時，使用凸部之長纖維不織布厚度h(mm)作為代表值而算出。 纖維徑d(μm)係使用掃描式電子顯微鏡(Seiko Instruments股份有限公司製造之DSC6200)，對10根切取之纖維之纖維剖面進行測定，將其平均值設為纖維徑。 纖維密度ρ(g/cm³ )係使用密度梯度管，依據JIS L1015化學纖維短纖維試驗方法所記載之密度梯度管法之測定方法進行測定。 基重e(g/m² )係將測定對象之長纖維不織布切割成特定(0.12 m×0.06 m等)之尺寸，於質量測定後，利用「質量÷自特定之尺寸求出之面積=基重(g/m² )」之式進行計算而求出基重。 [數1]

(構成纖維之纖度之測定方法) 一面藉由電子顯微鏡等測量纖維之剖面形狀而測量纖維之剖面積(若為由複數種樹脂形成之纖維，則為各樹脂成分之剖面積)，一面藉由DSC(differential scanning calorimetry，示差熱分析裝置)特定樹脂之種類(於複數種樹脂之情形時，亦特定大致之成分比)，算出比重從而算出纖度。例如，若為僅由PET(polyethylene terephthalate，聚對苯二甲酸乙二酯)構成之短纖維，則首先觀察剖面，算出其剖面積。其後，藉由利用DSC進行測定，而根據熔點或峰形狀鑑定為由單成分之樹脂構成，且其為PET芯。其後，使用PET樹脂之密度與剖面積，算出纖維之質量，藉此算出纖度。 構成本發明之長纖維不織布之纖維主要含有熱熔合性纖維，可無特別限制地採用此種物品通常所使用者。作為熱熔合性纖維，例如可列舉：聚烯烴系樹脂、聚酯系樹脂、聚醯胺系樹脂、丙烯腈系樹脂、乙烯系樹脂、亞乙烯基系樹脂等。作為聚烯烴系樹脂，可列舉：聚乙烯、聚丙烯、聚丁烯等。作為聚酯系樹脂，可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等。作為聚醯胺系樹脂，可列舉：尼龍等。作為乙烯系樹脂，可列舉：聚氯乙烯等。作為亞乙烯基系樹脂，可列舉：聚偏二氯乙烯等。可將其等各種樹脂之1種單獨地使用或混合2種以上使用，亦可使用其等各種樹脂之改性物。又，亦可使用複合纖維作為長纖維。作為複合纖維，可使用並排(side by side)纖維、芯鞘纖維、偏心之具有捲曲之芯鞘纖維、分割纖維等。於使用複合纖維之情形時，若使用芯包含聚丙烯、鞘包含聚乙烯之芯鞘纖維，則於獲得柔軟之長纖維不織布之方面上較佳。關於長纖維之纖維徑，於下述之加工前，較佳為5 μm以上且30 μm以下，進而較佳為10 μm以上且20 μm以下。 就紡絲性之觀點而言，較佳為由作為聚烯烴系樹脂之聚丙烯樹脂所形成。作為聚丙烯樹脂，就潤滑而與肌膚接觸時肌膚觸感提高之觀點、斷裂之容易性之觀點而言，較佳為包含無規共聚物、均聚物、嵌段共聚物中之任一種以上5質量%以上且100質量%以下、更佳為25質量%以上且80質量%以下之樹脂。又，可將其等共聚物或均聚物進行混合，亦可將其他樹脂進行混合，但就於成形時不易斷頭之方面而言，較佳為聚丙烯之均聚物與無規共聚物之混合。藉此，使纖維之結晶性降低，而起毛之纖維本身變柔軟，而與肌膚接觸時之肌膚觸感變良好，並且可與不織布斷裂強度兼顧，而起毛之纖維容易在壓紋等熔合部被切斷。因此，獲得於壓紋熔合點等熱熔合部3之剝離不會產生，起毛之纖維變短，不易起球，且外觀亦良好者。又，由於熔點之分佈變廣，故而密封性變得良好。進而較佳為將丙烯成分作為基質並使之與作為無規共聚物之乙烯或α-烯烴進行共聚合而成者，特佳為乙烯丙烯共聚物樹脂。作為聚丙烯樹脂，就同樣之觀點而言，較佳為包含乙烯丙烯共聚物樹脂5質量%以上之樹脂，進而較佳為包含乙烯丙烯共聚物樹脂25質量%以上之樹脂。於乙烯丙烯共聚物樹脂中，較佳為包含乙烯濃度1質量%以上且20質量%以下者，尤其於無黏膩感，而且於延伸時容易延伸，脫毛較少，維持斷裂強度之方面上，更佳為乙烯濃度為3%以上且8%以下。又，作為聚丙烯樹脂，就環境之觀點而言，較佳為包含再生聚丙烯樹脂50質量%以上之樹脂，進而較佳為包含再生聚丙烯樹脂70質量%以上之樹脂。再者，於基於紡黏層與熔噴層之複數層之長纖維不織布而形成不織布之情形時亦相同。 本發明之長纖維不織布之基重(單位面積重量)較佳為10 g/m² 以上且80g/m² 以下、特別是15 g/m² 以上且60 g/m² 以下。再者，於本發明之長纖維不織布包含複數層之情形時，較佳為構成之各層之合計基重(單位面積重量)處於上述之較佳數值範圍內。 本發明之長纖維不織布由於具有親水度梯度，且包含液膜開裂劑、或於其中進而包含磷酸酯型之陰離子界面活性劑，故而應對各種纖維構造，液體殘留及回液抑制優異。因此，即便長纖維不織布被淋上大量液體，亦始終確保纖維間之液體之透過通路，液體透過性優異。藉此，不會受纖維間距離與液膜形成之問題限制，可賦予長纖維不織布各種功能。例如亦可為包含3層以上之複數層者。又，長纖維不織布之形狀可平坦，亦可一面側或兩面側設有凹凸，亦可對纖維之基重或密度加以各種變化者。進而，與吸收體之組合之選項之範圍亦擴大。又，包含複數層之情形時之液膜開裂劑可含有於所有層中，亦可含有於一部分層中。較佳為至少含有於直接接受液體之側之層中。例如於將本發明之長纖維不織布作為吸收性物品之正面片材之情形時，較佳為至少於肌膚抵接面側之層中含有液膜開裂劑。 本發明之長纖維不織布較佳為於至少一部分之纖維交絡點附近或纖維熔合點附近液膜開裂劑局部存在。此處所謂液膜開裂劑之「局部存在」，並非於構成長纖維不織布之纖維之表面整體均等地附著有液膜開裂劑之狀態，而係指如下狀態，即較各纖維之表面，液膜開裂劑偏向附著於纖維交絡點附近或纖維熔合點附近。具體而言，可定義為：相比纖維表面(交絡點間或熔合點間之纖維表面)，交絡點或熔合點附近之液膜開裂劑濃度較高。此時，存在於纖維交絡點附近或纖維熔合點附近之液膜開裂劑亦可以如下方式附著，即以纖維交絡點或纖維熔合點為中心而局部覆蓋纖維間之空間。交絡點或熔合點附近之液膜開裂劑濃度係越濃越佳。該濃度由於會根據所使用之液膜開裂劑之種類或所使用之纖維之種類、與其他劑混合之情形時之有效成分比率等而變化，故而無法一概而定，但就發揮上述之液膜開裂作用之觀點而言，可適當決定。 由於液膜開裂劑局部存在，而變得更容易表現出液膜開裂作用。即，纖維交絡點附近或纖維熔合點附近係液膜特別容易產生之位置，因此，藉由使更多之液膜開裂劑存在於該位置，而變得容易直接作用於液膜。 如上所述，液膜開裂劑之局部存在較佳為以長纖維不織布整體之纖維交絡點附近或纖維熔合點附近之30%以上產生，更佳為以40%以上產生，進而較佳為以50%以上產生。長纖維不織布中，纖維交絡點或纖維熔合點彼此之距離相對較短時，纖維間之空間較小而特別容易產生液膜。因此，若於纖維間之空間較小時之纖維交絡點附近或纖維熔合點附近有選擇地局部存在液膜開裂劑，則特別有效地表現出液膜開裂作用，故而較佳。又，於如上述之有選擇地局部存在之情形時，液膜開裂劑較佳為使對相對較小之纖維間空間之被覆率變大，且使對相對較大之纖維間空間之被覆率變小。藉此，可一面保持長纖維不織布中之液體透過性，一面有效地表現出於毛細管力較大而液膜容易產生之部分之開裂作用，從而長纖維不織布整體之液體殘留減少效果變高。此處所謂「相對較小之纖維間空間」係指相對於利用上述之(纖維間距離之測定方法)所求出之纖維間距離，具有1/2以下之纖維間距離的纖維間空間。 (液膜開裂劑之局部存在狀態之確認方法) 上述之液膜開裂劑之局部存在狀態可藉由以下之方法而確認。 首先，將長纖維不織布切割成5 mm×5 mm，並使用碳帶安裝至試樣台。將試樣台以無蒸鍍之狀態放入至掃描式電子顯微鏡(S4300SE/N，日立製作所股份有限公司製造)中，設為低真空或真空狀態。由於使用環形反射電子檢測器(附屬品)進行檢測，故而原子序越大，越容易釋出反射電子，因此塗佈有包含較多原子序大於主要構成聚乙烯(PE)或聚丙烯(PP)或聚酯(PET)之碳原子或氫原子之氧原子或矽原子的液膜開裂劑之部分發白地顯現，因此可藉由發白而確認局部存在之狀態。再者，關於其白色度，原子序越大、或附著量越多，白色度越增加。 於本發明之長纖維不織布之製造方法中，於如上所述般於不織布化後塗佈液膜開裂劑之情形時，可列舉：於包含液膜開裂劑之溶液中浸漬原料不織布之方法。上述溶液例如可列舉液膜開裂劑經溶劑稀釋所得之溶液等(以下，亦將該溶液稱為液膜開裂劑溶液)。作為進行稀釋之溶劑，可列舉乙醇等醇。又，作為其他方法，可列舉：對原料不織布塗佈液膜開裂劑單獨成分、或包含上述液膜開裂劑之溶液之方法。再者，亦可於包含上述液膜開裂劑之溶液中混合磷酸酯型之陰離子界面活性劑。該情形時之液膜開裂劑與磷酸酯型之陰離子界面活性劑之含有比率較佳為如上所述。作為上述溶劑，可無特別限制地使用可使水溶解度極小之液膜開裂劑適度溶解或分散於溶劑中並乳化以便容易塗佈於不織布者。例如，作為使液膜開裂劑溶解者，可使用乙醇、甲醇、丙酮、己烷等有機溶劑，或者於製成乳化液之情形時，當然亦可使用水作為溶劑或分散介質，作為乳化時所使用之乳化劑，可列舉：包含磷酸烷基酯、脂肪醯胺、烷基甜菜鹼、烷基磺基琥珀酸鈉等之各種界面活性劑。再者，所謂原料不織布係指塗佈液膜開裂劑之前者，作為其製造方法，可無特別限制地使用如上所述之通常所使用之製造方法。 作為塗佈於上述之原料不織布之方法，可無特別限制地採用可用於該不織布之製造方法者。例如可列舉：利用噴霧之塗佈、利用狹縫式塗佈機之塗佈、利用凹版方式、軟版方式、浸漬方式之塗佈等。 就液膜開裂劑於上述之纖維交絡點附近或纖維熔合點附近局部存在化之觀點而言，較佳為塗佈於不織布化後之原料不織布，更佳為不浸漬而塗佈於原料不織布之方法。塗佈之方法中，就使液膜開裂劑之局部存在化更明顯之觀點而言，特佳為利用柔版方式之塗佈方法。 又，作為原料不織布，可無特別限制地使用各種不織布。特別是就保持液膜開裂劑之局部存在化之觀點而言，較佳為纖維交絡點熱熔合或熱壓接在一起者，更佳為使用藉由上述之熱風處理或熱壓紋將纖維彼此進行熱接著而獲得之不織布。 於使液膜開裂劑附著於纖維時，較佳為以包含液膜開裂劑之纖維處理劑之形式使用。此處進行說明之所謂「纖維處理劑」係指如下者，即利用水與界面活性劑等將水溶解度極小之油狀液膜開裂劑進行乳化等而設為容易對原料不織布或纖維進行塗佈處理之狀態。於用以塗佈液膜開裂劑之纖維處理劑中，液膜開裂劑之含有比率較佳為相對於纖維處理劑之質量為50質量%以下。藉此，纖維處理劑可成為已使成為油狀成分之液膜開裂劑於溶劑中穩定地乳化之狀態。就穩定之乳化之觀點而言，液膜開裂劑之含有比率更佳為相對於纖維處理劑之質量為40質量%以下，進而較佳為30質量%以下。又，就塗佈後液膜開裂劑於適度之黏度下於纖維上移動而實現上述之不織布中之液膜開裂劑之局部存在化的觀點而言，較佳為設為上述之含有比率。關於液膜開裂劑之含有比率，就表現出充分之液膜開裂效果之觀點而言，較佳為相對於纖維處理劑之質量為5質量%以上，更佳為15質量%以上，進而較佳為25質量%以上。再者，含有液膜開裂劑之纖維處理劑亦可於不抑制液膜開裂劑之作用之範圍內含有其他劑。例如亦可含有上述之磷酸酯型之陰離子界面活性劑。該情形時之液膜開裂劑與磷酸酯型之陰離子界面活性劑之含有比率較佳為如上所述。除此以外，亦可含有纖維加工時所使用之抗靜電劑或耐摩擦劑、又對長纖維不織布賦予適度之親水性之親水化劑、賦予乳化穩定性之乳化劑等。 本發明之長纖維不織布可有效利用其柔軟之肌膚觸感與液體殘留之減少而應用於各種領域。例如可較佳地用作經期衛生棉、衛生護墊、拋棄式尿布、失禁護墊等自身體排出之液體之吸收所使用之吸收性物品中的正面片材、第二片材(配置於正面片材與吸收體之間之片材)、背面片材、防漏片材、或對人用擦拭片材、肌膚護理用片材、進而物鏡用之拭布等。於使用本發明之長纖維不織布作為吸收性物品之正面片材或第二片材之情形時，較佳為使用該長纖維不織布之第1層側作為肌膚對向面側。 關於自身體排出之液體之吸收所使用之吸收性物品，典型而言，具備正面片材、背面片材及介存於兩片材間之液體保持性之吸收體。作為使用本發明之長纖維不織布作為正面片材之情形時之吸收體及背面片材，可無特別限制地使用該等技術領域中通常所使用之材料。例如作為吸收體，可使用以衛生紙或不織布等被覆片材被覆包含紙漿纖維等纖維材料之纖維集合體或於其中保持有吸收性聚合物而成者。作為背面片材，可使用熱塑性樹脂之膜、或該膜與不織布之層壓體等液體不透過性或撥水性之片材。背面片材亦可具有水蒸氣透過性。吸收性物品亦可進而具備對應該吸收性物品之具體用途之各種構件。上述構件對業者而言公知。例如於將吸收性物品用於拋棄式尿布或經期衛生棉之情形時，可於正面片材上之左右兩側部配置一對或二對以上之立體防護。 關於上述之實施形態，本發明進而揭示以下之長纖維不織布。 ＜1＞ 一種長纖維不織布，其含有液膜開裂劑。 ＜2＞ 如上述＜1＞記載之長纖維不織布，其中上述液膜開裂劑之水溶解度為0 g以上且0.025 g以下。 ＜3＞ 如上述＜2＞記載之長纖維不織布，其中上述液膜開裂劑對表面張力為50 mN/m之液體之展佈係數為15 mN/m以上。 ＜4＞ 一種長纖維不織布，其含有化合物(C1)，該化合物(C1)係水溶解度為0 g以上且0.025 g以下，對表面張力為50 mN/m之液體之展佈係數為15 mN/m以上者。 ＜5＞ 如上述＜1＞至＜4＞中任一項記載之長纖維不織布，其中上述化合物(C1)或上述液膜開裂劑對表面張力為50 mN/m之液體之界面張力為20 mN/m以下。 ＜6＞ 如上述＜1＞至＜5＞中任一項記載之長纖維不織布，其中上述化合物(C1)或上述液膜開裂劑包含具有選自由下述之結構X、X-Y、及Y-X-Y所組成之群中之至少1種結構之化合物。 結構X表示將＞C(A)-(C表示碳原子。又，＜、＞及-表示鍵結鍵。以下相同)、-C(A)₂ -、-C(A)(B)-、＞C(A)-C(R¹ )＜、＞C(R¹ )-、-C(R¹ )(R² )-、-C(R¹ )₂ -、＞C＜及、-Si(R¹ )₂ O-、-Si(R¹ )(R² )O-中之任一種基本結構重複、或者組合2種以上而成之結構之矽氧烷鏈、或其混合鏈。於結構X之末端具有氫原子、或選自由-C(A)₃ 、-C(A)₂ B、-C(A)(B)₂ 、-C(A)₂ -C(R¹ )₃ 、-C(R¹ )₂ A、-C(R¹ )₃ 、及-OSi(R¹ )₃ 、-OSi(R¹ )₂ (R² )、-Si(R¹ )₃ 、-Si(R¹ )₂ (R² )所組成之群中之至少1種基。 上述之R¹ 或R² 分別獨立地表示氫原子、烷基、烷氧基、芳基、或鹵素原子。A、B分別獨立地表示包含氧原子或氮原子之取代基。於結構X內R¹ 、R² 、A、B各自存在複數個之情形時，其等相互可相同亦可不同。 Y表示包含選自氫原子、碳原子、氧原子、氮原子、磷原子、硫原子中之原子的具有親水性之親水基。Y為複數個之情形時相互可相同亦可不同。 ＜7＞ 如上述＜1＞至＜6＞中任一項記載之長纖維不織布，其中上述化合物(C1)或上述液膜開裂劑包含聚矽氧系界面活性劑之有機改性聚矽氧，且作為該有機改性聚矽氧，包含選自由胺基改性聚矽氧、環氧改性聚矽氧、羧基改性聚矽氧、二醇改性聚矽氧、甲醇改性聚矽氧、(甲基)丙烯酸基改性聚矽氧、巰基改性聚矽氧、酚改性聚矽氧、聚醚改性聚矽氧、甲基苯乙烯基改性聚矽氧、長鏈烷基改性聚矽氧、高級脂肪酸酯改性聚矽氧、高級烷氧基改性聚矽氧、高級脂肪酸改性聚矽氧及氟改性聚矽氧所組成之群中之至少1種。 ＜8＞ 如上述＜1＞至＜7＞中任一項記載之長纖維不織布，其中上述化合物(C1)或上述液膜開裂劑包含聚氧伸烷基改性聚矽氧，且該聚氧伸烷基改性聚矽氧為選自由下述式[I]～[IV]所表示之化合物所組成之群中之至少1種。 [化19]

[化20]

[化21]

[化22]

式中，R³¹ 表示烷基(較佳為碳數1～20。例如較佳為甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基)。R³² 表示單鍵或伸烷基(較佳為碳數1～20。例如較佳為亞甲基、伸乙基、伸丙基、伸丁基)，較佳為表示上述伸烷基。複數個R³¹ 、複數個R³² 各自相互可相同亦可不同。M¹¹ 表示具有聚氧伸烷基之基，較佳為聚氧伸烷基。作為上述之聚氧伸烷基，可列舉：聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等構成單體共聚合而成者等。m、n分別獨立為1以上之整數。再者，其等重複單元之符號係於各式[I]～[IV]中分別決定者，未必表示相同整數，亦可不同。 ＜9＞ 如上述＜2＞記載之長纖維不織布，其中上述液膜開裂劑對表面張力為50 mN/m之液體之展佈係數大於0 mN/m，對表面張力為50 mN/m之液體之界面張力為20 mN/m以下。 ＜10＞ 一種長纖維不織布，其含有化合物(C2)，該化合物(C2)係水溶解度為0 g以上且0.025 g以下，且對表面張力為50 mN/m之液體之展佈係數大於0 mN/m，對表面張力為50 mN/m之液體之界面張力為20 mN/m以下。 ＜11＞ 如上述＜1＞、＜2＞、＜9＞及＜10＞中之任一項記載之長纖維不織布，其中上述化合物(C2)或上述液膜開裂劑包含具有選自由下述之結構Z、Z-Y、及Y-Z-Y所組成之群中之至少1種結構之化合物。 結構Z表示將＞C(A)-(C：碳原子)、-C(A)₂ -、-C(A)(B)-、＞C(A)-C(R³ )＜、＞C(R³ )-、-C(R³ )(R⁴ )-、-C(R³ )₂ -、＞C＜中之任一種基本結構重複、或者組合2種以上而成之結構之烴鏈。於結構Z之末端具有氫原子、或選自由-C(A)₃ 、-C(A)₂ B、-C(A)(B)₂ 、-C(A)₂ -C(R³ )₃ 、-C(R³ )₂ A、-C(R³ )₃ 所組成之群中之至少1種基。 上述之R³ 或R⁴ 分別獨立地表示氫原子、烷基、烷氧基、芳基、氟烷基、芳烷基、或將其等組合而成之烴基、或者氟原子。A、B分別獨立地表示包含氧原子或氮原子之取代基。於結構Z內R³ 、R⁴ 、A、B各自存在複數個之情形時，其等相互可相同亦可不同。 Y表示包含選自氫原子、碳原子、氧原子、氮原子、磷原子、硫原子中之原子的具有親水性之親水基。Y於複數個之情形時相互可相同亦可不同。 ＜12＞ 如上述＜1＞、＜2＞及＜9＞～＜11＞中任一項記載之長纖維不織布，其中上述化合物(C2)或上述液膜開裂劑包含選自由下述式[V]之任一者所表示之聚氧伸烷基(POA)烷基醚、以及下述式[VI]所表示之質量平均分子量1000以上之聚氧伸烷基二醇、硬脂醇聚醚、山萮醇聚醚、PPG肉豆蔻基醚、PPG硬脂基醚及PPG山萮基醚所組成之群中之至少1種化合物。 [化23]

[化24]

式中，L²¹ 表示醚基、胺基、醯胺基、酯基、羰基、碳酸酯基、聚氧伸乙基、聚氧伸丙基、聚氧伸丁基、或將其等組合而成之聚氧伸烷基等鍵結基。R⁵¹ 表示包含氫原子、甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、2-乙基己基、壬基、癸基、甲氧基、乙氧基、苯基、氟烷基、芳烷基、或將其等組合而成之烴基、或者氟原子之各種取代基。又，a、b、m及n分別獨立為1以上之整數。此處，C_m H_n 表示烷基(n=2m+1)，C_a H_b 表示伸烷基(a=2b)。再者，其等碳原子數及氫原子數係於各式[V]及[VI]中各自獨立地決定者，未必表示相同之整數，亦可不同。再者，-(C_a H_b O)_m -之「m」係1以上之整數。該重複單元之值係於各式[V]及[VI]中各自獨立地決定者，未必表示相同之整數，亦可不同。 ＜13＞ 如上述＜1＞、＜2＞及＜9＞至＜12＞中任一項記載之長纖維不織布，其中上述化合物(C2)或上述液膜開裂劑包含選自由下述式[VII]所表示之脂肪酸、下述式[VIII-I]或[VIII-II]所表示之甘油脂肪酸酯及季戊四醇脂肪酸酯、下述式[IX]之任一者、下述式[X]之任一者、或下述式[XI]之任一者所表示之甘油脂肪酸酯、山梨醇酐脂肪酸酯、及季戊四醇脂肪酸酯之部分酯化物、具有下述式[XII]之固醇結構之化合物、下述式[XIII]所表示之醇、下述式[XIV]所表示之脂肪酸酯、以及下述式[XV]所表示之蠟所組成之群中之至少1種。 [化25]

式[VII]中，m及n分別獨立地為1以上之整數。此處，C_m H_n 表示上述各脂肪酸之烴基。 [化26]

[化27]

式[VIII-I]及[VIII-II]中，m、m'、m''、n、n'及n''分別獨立為1以上之整數。複數個m、複數個n各自相互可相同亦可不同。此處，C_m H_n 、C_m 'H_n '及C_m ''H_n ''分別表示上述各脂肪酸之烴基。 [化28]

式[IX]中，m及n分別獨立為1以上之整數。複數個m、複數個n各自相互可相同亦可不同。此處，C_m H_n 係表示上述各脂肪酸之烴基。 [化29]

式[X]中，R⁵² 表示碳原子數2以上且22以下之直鏈或支鏈、飽和或不飽和之烴基(烷基、烯基、炔基等)。具體而言，可列舉：2-乙基己基、月桂基、肉豆蔻基、棕櫚基、硬脂基、山萮基、油醯基、亞麻油基等。 [化30]

式[XI]中，m及n分別獨立為1以上之整數。複數個m、複數個n各自相互可相同亦可不同。此處，C_m H_n 表示上述各脂肪酸之烴基。 [化31]

[化32]

式[XIII]中，m及n分別獨立為1以上之整數。此處，C_m H_n 表示上述各醇之烴基。 [化33]

式[XIV]中，m及n分別獨立為1以上之整數。此處，2個C_m H_n 可相同亦可不同。C_m H_n -COO-之C_m H_n 表示上述各脂肪酸之烴基。-COOC_m H_n 之C_m H_n 表示源自形成酯之醇之烴基。 [化34]

式[XV]中，m及n分別獨立為1以上之整數。 ＜14＞ 如上述＜1＞至＜13＞中任一項記載之長纖維不織布，其中上述化合物(C1)、上述化合物(C2)或上述液膜開裂劑之水溶解度較佳為0.0025 g以下，更佳為0.0017 g以下，進而較佳為未達0.0001 g，且為0 g以上，較佳為1.0×10^-9 g以上。 ＜15＞ 如上述＜1＞至＜14＞中任一項記載之長纖維不織布，其中於上述長纖維不織布之至少一部分之纖維交絡點附近或纖維熔合點附近上述化合物或上述液膜開裂劑局部存在。 ＜16＞ 如上述＜1＞至＜15＞中任一項記載之長纖維不織布，其包含熱熔合性纖維，具有第1面與位於該第1面之相反側之第2面，且 上述第1面側之纖維之親水度低於上述第2面側之纖維之親水度。 ＜17＞ 如上述＜1＞至＜16＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且具備藉由熱熔合部將長纖維間斷性地固定之纖維集合層。 ＜18＞ 如上述＜1＞至＜17＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且該長纖維不織布之長纖維之纖維長度為30 mm以上，較佳之纖維長度為150 mm以上。 ＜19＞ 如上述＜1＞至＜18＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且上述第1面側之纖維之接觸角(V1)較佳為80°以上，更佳為85°以上，進而較佳為90°以上，且較佳為100°以下，更佳為97°以下，進而較佳為95°以下。 ＜20＞ 如上述＜1＞至＜19＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且上述第2面側之纖維之接觸角(V2)較佳為90°以下，更佳為85°以下，進而較佳為80°以下，且較佳為30°以上，更佳為40°以上，進而較佳為50°以上。 ＜21＞ 如上述＜1＞至＜20＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且上述第1面側之纖維之接觸角(V1)與上述第2面側(非肌膚抵接面側)之纖維之接觸角(V2)的差(V1-V2)較佳為3°以上，更佳為5°以上，進而較佳為7°，尤佳為10°。 ＜22＞ 如上述＜1＞至＜21＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且含有親水化劑。 ＜23＞ 如上述＜1＞至＜22＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且含有選自由陰離子性、陽離子性、兩性及非離子性之界面活性劑所組成之群中之至少1種。 ＜24＞ 如上述＜1＞至＜23＞中任一項記載之長纖維不織布，其中上述長纖維不織布包含單層，且含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且上述第1面側之纖維之親水度低於上述第2面側之纖維之親水度，具有親水度之梯度。 ＜25＞ 如上述＜1＞至＜24＞中任一項記載之長纖維不織布，其中上述長纖維不織布含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且上述第1面側之纖維為具有固定在纖維集合層之基底部及未與該纖維集合層固定之自由端部且豎立之豎立性纖維。 ＜26＞ 如上述＜25＞記載之長纖維不織布，其具有上述豎立性纖維之親水度低於上述纖維集合層之纖維之親水度的至少2階段之親水度梯度。 ＜27＞ 如上述＜26＞記載之長纖維不織布，其中上述豎立性纖維之接觸角為75°以上，較佳為80°以上，更佳為85°以上，進而較佳為90°以上。 ＜28＞ 如上述＜1＞至＜23＞中任一項記載之長纖維不織布，其中上述長纖維不織布包含複數層，且含有熱熔合性纖維，並具有第1面與位於該第1面之相反側之第2面，且使上述複數層之每層具有親水度之差並使親水度階段性地變高。 ＜29＞ 一種吸收性物品用之正面片材，其使用如上述＜1＞至＜28＞中任一項記載之長纖維不織布。 ＜30＞ 一種吸收性物品，其使用如上述＜14＞至＜28＞中任一項記載之長纖維不織布作為將上述第1面朝向肌膚抵接面側進行配置之正面片材。 [實施例] 以下，基於實施例而對本發明進一步詳細地進行說明，但本發明並不應受其限定地解釋。再者，本實施例中，「份」及「%」只要無特別事先說明，則均為質量基準。 下述實施例中之液膜開裂劑之表面張力、水溶解度及界面張力係藉由上述之測定方法進行。 (實施例1) 作為原料長纖維不織布，係製作積層有由包含聚丙烯均聚物樹脂之長纖維所構成之紡黏不織布兩層之紡黏-紡黏不織布(SS不織布)。兩層(第1不織布層及第2不織布層)均設為長纖維之纖維徑16 μm、單位面積重量10 g/m² 。 對於上述第1不織布層及第2不織布層，於積層前藉由下述所示之塗佈方法將下述之液膜開裂劑及親水化劑進行塗佈處理，藉由利用壓紋輥之熱壓接將兩層進行接合固定，而製成實施例1之長纖維不織布試樣。於該長纖維不織布試樣中，將第1不織布層之兩面規定為第1面側(a)及第2面側(b)，將第2不織布層之兩面規定為第1面側(a')及第2面側(b')，作為上述長纖維不織布試樣整體，將積層兩層後之兩面規定為第1面5側(第1不織布層之第1面側)(a)及第2面6側(第2不織布層之第2面側)(b')而進行試驗(以下，實施例2～4、比較例1及2亦相同)。 ＜液膜開裂劑＞ 作為液膜開裂劑，係結構X-Y中之X包含含有-Si(CH₃ )₂ O-之二甲基聚矽氧鏈、Y包含含有-(C₂ H₄ O)-之POE鏈，POE鏈之末端基為甲基(CH₃ )，改性率為20%，聚氧伸乙基加成莫耳數為3，且質量平均分子量為4000之聚氧伸乙基(POE)改性二甲基聚矽氧(信越化學工業股份有限公司製造 KF-6015)。 對表面張力為50 mN/m之液體之展佈係數：28.8 mN/m 表面張力為21.0 mN/m 對表面張力為50 mN/m之液體之界面張力：0.2 mN/m 水溶解度：未達0.0001 g 再者，其等4個數值係藉由上述之測定方法而測得。此時，「表面張力為50 mN/m之液體」係使用如下溶液，其係利用微量吸管(ACURA825、Socorex Isba SA公司製造)於100 g之去離子水中添加作為非離子系界面活性物質之聚氧乙烯山梨醇酐單月桂酸酯(花王股份有限公司製造，商品名RHEODOL SUPER TW-L120)3.75 μL，而將表面張力調整至50±1 mN/m(以下，相同)。又，水溶解度係每次添加0.0001 g之劑而測得。其結果，觀察到連0.0001 g都未溶解者係設為「未達0.0001 g」，觀察到溶解0.0001 g但未溶解0.0002 g者係設為「0.0001 g」。關於其以外之數值，亦藉由相同之方法而測得。 ＜液膜開裂劑及親水化劑之塗佈方法＞ 製作將上述聚氧伸乙基(POE)改性二甲基聚矽氧作為溶質溶解於乙醇溶液中而成之稀釋液與親水化劑之混合溶液，將各不織布浸漬於該稀釋液中，之後進行乾燥。 於所獲得之長纖維不織布試樣中，第1不織布層及第2不織布層均液膜開裂劑相對於纖維質量之含有比率(OPU)為0.1質量%。又，第1不織布層之第1面側(a)及第2面側(b)之纖維之接觸角、第2不織布層之第1面側(a')及第2面側(b')之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，且如下述表1所示。因此，作為所獲得之長纖維不織布試樣整體之第1面5側(a)之纖維之接觸角與第2面6側(b')之接觸角的差為10°，第1面5側(a)之親水度低於第2面6側(b')之親水度，具有第1面5側(a)向第2面6側(b')之親水度梯度。 (實施例2) 使用下述之劑作為液膜開裂劑，且將第1不織布層中之接觸角如下述表1般設置，除此以外，以與實施例1相同之方式製作實施例2之長纖維不織布試樣。 ＜液膜開裂劑＞ 作為液膜開裂劑，係結構X-Y中之X包含含有-Si(CH₃ )₂ O-之二甲基聚矽氧鏈、Y包含含有-(C₃ H₆ O)-之POP鏈，POP鏈之末端基為甲基(CH₃ )，改性率為10%，聚氧伸丙基加成莫耳數為10，且質量平均分子量為4340之聚氧伸丙基(POP)改性二甲基聚矽氧(藉由使聚矽氧油與烴化合物進行羥基化反應而取得)。 對表面張力為50 mN/m之液體之展佈係數：26.9 mN/m 表面張力：21.5 mN/m 對表面張力為50 mN/m之液體之界面張力：1.6 mN/m 水溶解度：0.0002 g 於所獲得之長纖維不織布試樣中，第1不織布層及第2不織布層均液膜開裂劑相對於纖維質量之含有比率(OPU)為0.1質量%。又，第1不織布層之第1面側(a)及第2面側(b)之纖維之接觸角、第2不織布層之第1面側(a')及第2面側(b')之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，且如下述表1所示。因此，作為所獲得之長纖維不織布試樣整體之第1面5側(a)之纖維之接觸角與第2面6側(b')之接觸角的差為11°，第1面5側(a)之親水度低於第2面6側(b')之親水度，具有自第1面5側(a)向第2面6側(b')之親水度梯度。 (實施例3) 使用下述之劑作為液膜開裂劑，且將第2不織布層中之接觸角如下述表1般設置，除此以外，以與實施例1相同之方式製作實施例3之長纖維不織布試樣。 ＜液膜開裂劑＞ 作為液膜開裂劑，係結構Z-Y中之Z為*-O-CH(CH₂ O-*)₂ (*表示鍵結部)，Y包含C₈ H₁₅ O-或C₁₀ H₁₉ O-之烴鏈，脂肪酸組成包含辛酸82%、癸酸18%，且質量平均分子量為550的三辛酸/癸酸甘油酯(花王股份有限公司製造之COCONAD MT)。 對表面張力為50 mN/m之液體之展佈係數：8.8 mN/m 表面張力：28.9 mN/m 對表面張力為50 mN/m之液體之界面張力：12.3 mN/m 水溶解度：未達0.0001 g 於所獲得之長纖維不織布試樣中，第1不織布層及第2不織布層均液膜開裂劑相對於纖維質量之含有比率(OPU)為0.5質量%。又，第1不織布層之第1面側(a)及第2面側(b)之纖維之接觸角、第2不織布層之第1面側(a')及第2面側(b')之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表1所示。因此，作為所獲得之長纖維不織布試樣整體之第1面5側之纖維(a)之接觸角與第2面6側(b')之接觸角的差為9°，第1面5側(a)之親水度低於第2面6側(b')之親水度，具有自第1面5側(a)向第2面6側(b')之親水度梯度。 (實施例4) 使用下述之劑作為液膜開裂劑，且將第1不織布層及第2不織布層中之接觸角如下述表1般設置，除此以外，以與實施例1相同之方式製作實施例4之長纖維不織布試樣。 ＜液膜開裂劑＞ 作為液膜開裂劑，係結構Z-Y中之Z包含含有-CH₂ -之烴鏈、Y包含含有-(C₃ H₆ O)-之POP鏈，聚氧伸丙基加成莫耳數為5，且質量平均分子量為500之POP烷基醚(花王股份有限公司製造消泡劑No.8)。 對表面張力為50 mN/m之液體之展佈係數：13.7 mN/m 表面張力：30.4 mN/m 對表面張力為50 mN/m之液體之界面張力：5.9 mN/m 水溶解度：未達0.0001 g 於所獲得之長纖維不織布試樣中，第1不織布層及第2不織布層均液膜開裂劑相對於纖維質量之含有比率(OPU)為5.0質量%。又，第1不織布層之第1面側(a)及第2面側(b)之纖維之接觸角、第2不織布層之第1面側(a')及第2面側(b')之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表1所示。因此，作為所獲得之長纖維不織布試樣整體之第1面5側(a)之纖維之接觸角與第2面6側(b')之接觸角的差為9°，第1面5側(a)之親水度低於第2面6側(b')之親水度，具有自第1面5側(a)向第2面6側(b')之親水度梯度。 (實施例5) 將單位面積重量設為20 g/m² ，且設為下述表2所示之接觸角，除此以外，以與實施例1相同之方式製作第1不織布層，將其設為原料長纖維不織布。 繼而，對於上述原料長纖維不織布，實施圖4所示之起毛加工處理而形成第1不織布層之第1面側(a)具有自由端部42之豎立性纖維4，從而製成包含豎立性纖維4與纖維集合層3之實施例5之長纖維不織布試樣。該長纖維不織布試樣整體中之兩面係相當於第1不織布層之兩面，規定為第1面5側(a)及第2面6側(b)而進行試驗(以下，實施例6～8、比較例3亦相同)。 該長纖維不織布試樣之起毛之纖維之根數係藉由圖5所示之測定方法進行測定，為18根/cm。即，於第1不織布層之第1面側(a)形成有上述豎立性纖維4。 於所獲得之長纖維不織布試樣中，第1面5側(a)之纖維(具有自由端部42之豎立性纖維4。實施例6～8、比較例3亦相同)及第2面6側(b)之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表2所示。因此，所獲得之長纖維不織布試樣之第1面5側(a)之纖維之接觸角與第2面6側(b)之接觸角的差為10°，第1面5側(a)之親水度低於第2面6側(b)之親水度，具有自第1面5側(a)向第2面6側(b)之親水度梯度。 (實施例6) 將單位面積重量設為20 g/m² ，並設為下述表2所示之接觸角，除此以外，以與實施例2相同之方式製作第1不織布層，將其設為原料長纖維不織布。 繼而，對於上述原料長纖維不織布，以與實施例5相同之方式實施起毛加工處理而製成實施例6之長纖維不織布試樣。該長纖維不織布試樣之豎立之纖維之根數係藉由圖5所示之測定方法進行測定，為17根/cm。 於所獲得之長纖維不織布試樣中，第1面5側(a)及第2面6側(b)之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表2所示。因此，所獲得之長纖維不織布試樣之第1面5側(a)之纖維之接觸角與第2面6側(b)之接觸角的差為12°，第1面5側(a)之親水度低於第2面6側(b)之親水度，具有自第1面5側(a)向第2面6側(b)之親水度梯度。 (實施例7) 將單位面積重量設為20 g/m² ，並設為下述表2所示之接觸角，除此以外，以與實施例3相同之方式製作第1不織布層，將其設為原料長纖維不織布。 繼而，對於上述原料長纖維不織布，以與實施例5相同之方式實施起毛加工處理而製成實施例7之長纖維不織布試樣。該長纖維不織布試樣之豎立之纖維之根數係藉由圖5所示之測定方法進行測定，為18根/cm。 於所獲得之長纖維不織布試樣中，第1面5側(a)及第2面6側(b)之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表2所示。因此，所獲得之長纖維不織布試樣之第1面5側之纖維(a)之接觸角與第2面6側(b)之接觸角的差為10°，第1面5側(a)之親水度低於第2面6側(b)側之親水度，具有自第1面5側(a)向第2面6側(b)之親水度梯度。 (實施例8) 將單位面積重量設為20 g/m² ，並設為下述表2所示之接觸角，除此以外，以與實施例4相同之方式製作第1不織布層，將其設為原料長纖維不織布。 繼而，對於上述原料長纖維不織布，以與實施例5相同之方式實施起毛加工處理而製成實施例8之長纖維不織布試樣。該長纖維不織布試樣之豎立之纖維之根數係藉由圖5所示之測定方法進行測定，為18根/cm。 於所獲得之長纖維不織布試樣中，第1面5側(a)及第2面6側(b)之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表2所示。因此，所獲得之長纖維不織布試樣之第1面5側之纖維(a)之接觸角與第2面6側(b)之接觸角的差為11°，第1面5側(a)側之親水度低於第2面6側(b)側之親水度，具有自第1面5側(a)向第2面6側(b)之親水度梯度。 (比較例1) 不塗佈液膜開裂劑、親水化劑，除此以外，以與實施例1相同之方式製作比較例1之長纖維不織布試樣。 所獲得之長纖維不織布試樣中之各面之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表3所示，接觸角無差值而無親水度之梯度。 (比較例2) 不塗佈液膜開裂劑，且設為下述表3所示之接觸角，除此以外，以與實施例1相同之方式製作比較例2之長纖維不織布試樣。 所獲得之長纖維不織布試樣中之各面之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表3所示，接觸角無差值而無親水度之梯度。 (比較例3) 不塗佈液膜開裂劑，且設為下述表3所示之接觸角，除此以外，以與實施例5相同之方式製作比較例3之長纖維不織布試樣。 所獲得之長纖維不織布試樣中之各面之纖維之接觸角係藉由上述之接觸角之測定方法進行測定，並如下述表3所示。所獲得之長纖維不織布試樣之第1面5側之纖維(a)之接觸角與第2面6側(b)之接觸角的差為10°，第1面5側(a)之親水度低於第2面6側(b)之親水度，具有自第1面5側(a)向第2面6側(b)之親水度梯度。 (評價試驗) 關於下述「1.液體殘留量試驗」、「3.回液量試驗」及「4.液體吸收時間試驗」之評價試驗，係自作為吸收性物品之一例之拋棄式尿布(花王股份有限公司製造：Merries(註冊商標) Merries pants L尺寸，2014年製造)去除正面片材，代替其將各長纖維不織布試樣作為正面片材進行積層，將其周圍進行固定而獲得評價用拋棄式尿布，使用該評價用拋棄式尿布進行評價。再者，每個試驗都製作實施例1～8、比較例1～3之評價用拋棄式尿布。關於「2.液體流動長度試驗」，如下所述，將各試樣作為正面片材而另外製作評價用試樣。 1.液體殘留量試驗 自各評價用之拋棄式尿布去除腰圍皺褶與腿皺褶，於展開狀態下將正面片材朝上固定在水平面上。於無加壓之狀態下，於尿布之自覆蓋吸收體的被覆片材之長度方向腹側部側之端部前端起125 mm之位置之該正面片材上注入總量160 g之人工尿。人工尿係每間隔10分鐘注入40 g，且以注入速度5 g/秒分4次注入。於第4次注入後10分鐘後，於以人工尿注入點為中心之邊長100 mm之正方形上切取正面片材，測定正面片材之重量(W1)。繼而，將切取之上述正面片材進行乾燥，測定乾燥後之正面片材之重量(W2)，將乾燥前後之重量差(W1-W2)作為液體殘留量而算出。進行以上之操作3次，將3次之平均值設為液體殘留量(mg)。液體殘留量係穿著者之肌膚濕潤至何種程度之指標，液體殘留量越少，越為良好之結果。再者，人工尿係使用組成為脲1.94重量%、氯化鈉0.795重量%、硫酸鎂0.11重量%、氯化鈣0.062重量%、硫酸鉀0.197重量%、紅色2號(染料)0.010重量%、水96.88重量%及聚氧乙烯月桂醚(約0.07%)，且將表面張力調整至53±1 dyne/cm(23℃)者。 2.液體流動長度試驗 試驗裝置係使用具有試驗樣品之載置面相對於水平面傾斜45°之載置部者。準備將各試樣作為正面片材並將該正面片材與對折之2片衛生紙重疊而製成吸收體之試樣樣品，將上述各評價用之試驗樣品以正面片材朝上之方式載置於該載置部上。將作為試驗液之經著色之去離子水以1 g/10 sec之速度滴至試驗樣品上。測定自最初不織布濕潤之地點至試驗液最初被吸收體吸收之地點為止之距離。將以上之操作進行3次，將3次之平均值設為液體流動長度(mm)。液體流動長度係液體未被試驗樣品吸收而於表面上流動，於穿著時何種程度地容易與肌膚接觸，而是否變得容易洩漏之指標，液體流動長度越短，評價越高。 3.回液量試驗 自上述各評價用之拋棄式尿布去除腰圍皺褶與腿皺褶，於展開狀態下將正面片材朝上固定在水平面上。於正面片材之上載置圓筒狀之附帶注入口之丙烯酸系板，進而於丙烯酸系板上，於尿布之背側部側及腹側部側分別載置2 kg之重物以施加負荷。設置於丙烯酸系板之注入口係形成內徑36 mm之圓筒(高度53 mm)狀，於丙烯酸系板上，在長度方向之1/3之位置且寬度方向之中心之位置上形成有軸線與該圓筒狀之注入口之中心一致且將該圓筒狀注入口之內部與丙烯酸系板之正面片材對向面之間連通的內徑36 mm之貫通孔。將丙烯酸系板以丙烯酸系板之圓筒狀注入口之中心軸位於尿布之自覆蓋吸收體的被覆片材之長度方向腹側部側之端部前端起125 mm之位置之方式進行配置，注入總量160 g之人工尿。人工尿係每間隔10分鐘注入40 g，且分4次注入。第4次之注入後10分鐘後，去除丙烯酸系板，於以人工尿注入點作為中心之邊長100 mm之正面片材上重疊濾紙(Toyo Roshi Kaisha公司製造 5C)16片，進而於其上施加負荷2分鐘，而使人工尿被濾紙吸收。負荷係對100 mm×100 mm之面積施加3.5 kg。經過2分鐘後去除負荷，對吸收了人工尿之濾紙之重量(W4)進行測定，將與預先所測得之吸收前之濾紙之重量(W3)的差(W4-W3)作為回液量而算出。將以上之操作進行3次，將3次之平均值設為回液量(g)，回液量越少，越難以發生回液而成為高評價。 4.液體吸收時間試驗 於上述之回液量試驗之評價時，測量直至160 g全部被尿布吸收為止之時間。將以上之操作進行3次，將3次之平均值設為液體吸收時間(秒)，液體吸收時間越短，液體之通過越快，越成為高評價。 [表1]

[表2]

[表3]

如上述表1～3所示，與無液膜開裂劑、親水度梯度及起毛纖維之比較例1及2相比，實施例1～8均所有之評價項目優異。 又，與不具有液膜開裂劑之比較例3相比，實施例1～8均表現出液體殘留量較少之良好結果。此外，實施例1～8於液體流動量、液體殘留量及液體吸收時間上，表現出與具有親水度梯度及起毛纖維之比較例3同等或比較例3以上之良好結果。 將本發明與其實施形態及實施例一起進行了說明，但只要本發明者沒有特別指定，則本發明不受說明之任何細節限定，認為應於不會背離隨附之申請專利範圍所示之發明之精神與範圍的情況下廣範圍地進行解釋。 本申請案係主張基於2016年5月31日於日本提出專利申請之日本專利特願2016-109599之優先權者，其等係參照此處並將其內容作為本說明書之記載之一部分併入本文中。The present invention relates to a long-fiber non-woven fabric having a shorter distance between fibers than a non-woven fabric using short fibers as a raw material, which can reduce the liquid film formed between the fibers, suppress the liquid residue and the liquid return through the liquid residue, and achieve higher Long-fiber non-woven fabric with standard dryness. In the long-fiber non-woven fabric, even if the fiber having free ends is erected as described in Patent Document 1, the expansion of the distance between the fibers using the fiber is limited to a part. For example, the fiber-to-fiber collection portion or the periphery of the thermal fusion portion where the long fibers are not broken and bundled by the thermal fusion portion has a short distance between fibers. In the area where the distance between the fibers is short, even if there is a space through which fecal fluid (such as urine or menstrual blood; also simply referred to as liquid) exists, it is also due to the capillary force of the meniscus between fibers or the surface activity produced by plasma proteins , And high blood surface viscosity, so it will form a stable liquid film between the fibers and easily retain liquid. The liquid film becomes a stable film between shorter fibers. Therefore, once it is generated, it is difficult to eliminate blood modifiers that use a gradient of hydrophilicity or stabilize blood cells. Even with the previous blood modifiers, there is still room for improvement in the dryness felt by the wearer. That is, there is still room for improvement in the suppression of liquid remnants or the return of liquid from the absorbent body through the liquid remnants. In addition, the liquid to be absorbed is not limited to blood, and urine also has surface activity caused by phospholipids, and a liquid film is formed in the same manner as described above, and the liquid residue and the liquid return through the liquid residue are not sufficiently suppressed, and the dry feeling remains. There is room for improvement. As described above, a technology for removing a liquid film formed in a narrow portion between fibers in a non-woven fabric and absorbing it to an absorber is required. However, since the liquid film has high stability, it is difficult to remove the liquid film. In addition, it is also considered to apply a water-soluble surfactant to reduce the surface tension of the liquid and remove the liquid film. However, if such a surfactant is to be used in an absorbent article to achieve the removal of a liquid film, there is a possibility that the liquid may also pass through the liquid-repellent bottom sheet. The long-fiber nonwoven fabric of the present invention can reduce the liquid film formed between the fibers, suppress the liquid residue and the liquid returning through the liquid residue, and achieve a higher level of dryness. The long-fiber nonwoven fabric of the present invention contains a liquid film cracking agent. The long-fiber nonwoven fabric of the present invention preferably includes a heat-fusible fiber, has a first surface and a second surface located on the opposite side of the first surface, and the fibers on the first surface side have a lower hydrophilicity than the second surface. The hydrophilicity of the fibers on the side. The so-called liquid film cleaving agent refers to an agent that inhibits the formation of a liquid film by causing a liquid film, such as menstrual blood or a highly viscous liquid such as menstrual blood, or an excretion liquid such as urine, to contact a non-woven fabric to form a liquid film between the fibers of the non-woven fabric or the surface of the fiber. The effect of cracking of the formed liquid film and the effect of suppressing the formation of the liquid film. The former can be described as the main role, and the latter can be described as the subordinate role. The cracking of the liquid film is achieved by pushing a part of the liquid film layer of the liquid film cracking agent to make it unstable. The effect of the liquid film cleaving agent will not allow the liquid to remain in the narrow area between the fibers and make it easy to pass, and it is complementary to the absorption effect of the liquid using the above-mentioned hydrophilicity gradient, thereby improving the long-fiber nonwoven fabric of the present invention. Its liquid permeability helps to reduce liquid residue and liquid return. Accordingly, even if the fibers constituting the long-fiber non-woven fabric are thinned and the distance between the fibers is narrowed, both the softness of the skin feel and the suppression of liquid residue are taken into consideration. Such a long-fiber nonwoven fabric of the present invention can be used, for example, as a front sheet of absorbent articles such as menstrual tampons, baby diapers, and adult diapers. (Properties to make liquid film disappear) The liquid film cleavage agent used in the present invention has a property to make liquid film disappear. Based on this property, the liquid film cleavage agent is applied to a test solution mainly composed of a plasma component or In the case of artificial urine, the liquid film disappearing effect can be exhibited. The artificial urine system will have urea 1.940% by mass, sodium chloride 0.795% by mass, magnesium sulfate 0.110% by mass, calcium chloride 0.062% by mass, potassium sulfate 0.197% by mass, red No. 2 (dye) 0.010% by mass, and water (about 96.88%). Mass%) and polyoxyethylene lauryl ether (approximately 0.07% by mass) are adjusted to a surface tension of 53 ± 1 mN / m (23 ° C). Here, the so-called liquid film disappearing effect includes the following two effects: for a structure entrained with air due to a liquid film formed by a test solution or artificial urine, suppressing the formation of the liquid film of the structure, and causing the structure to be formed An agent that disappears and exhibits at least one effect has the property of exhibiting an effect of disappearing a liquid film. The above test solution is a liquid component extracted from defibrillated horse blood (manufactured by NIPPON BIOTEST Co., Ltd.). Specifically, if 100 mL of defibrillated horse blood is allowed to stand for 1 hour at a temperature of 22 ° C and a humidity of 65%, the defiber horse blood is separated into an upper layer and a lower layer, and at this time, the upper layer is the above-mentioned test solution. The upper layer contains mainly plasma components and the lower layer contains mainly blood cells. When only the upper layer is taken out of the defibrated horse blood separated into the upper layer and the lower layer, for example, a pipette (manufactured by Kensakizai Co., Ltd.) can be used. Regarding whether a certain agent has the above-mentioned "dissolving property of the liquid film", it is assumed that the structure is liable to generate a structure that is entrained with air due to the liquid film formed by the test liquid or artificial urine to which the agent is applied. At that time, the amount of the structure, that is, the amount of the liquid film, is judged. That is, the test solution or artificial urine was adjusted to a temperature of 25 ° C, and then 10 g was added to a spiral tube (No. 5, manufactured by Maruemu Co., Ltd., a tube diameter of 27 mm, and a total length of 55 mm) to obtain a standard sample. In addition, as a measurement sample, 0.01 g of the same as the standard sample was obtained by adding an agent to be measured to 25 ° C in advance. The standard sample and the measurement sample were oscillated vigorously in a reciprocating manner in the upward and downward directions of the spiral tube, and then quickly placed on a horizontal surface. By the oscillation of the sample, a liquid layer (lower layer) without the above structure and a structure layer (upper layer) containing a large number of the structures are formed inside the spiral tube after the oscillation. Ten seconds after the end of the shaking, the height of the structural layer (the height of the liquid layer to the upper surface of the structural layer) of the two samples was measured. Then, when the height of the structure layer of the measurement sample is 90% or less with respect to the height of the structure layer of the standard sample, the agent to be measured is considered to have a liquid film cracking effect. The liquid film cracking agent used in the present invention is a single compound that meets the above properties or a mixture of a plurality of single compounds that meet the above properties, or satisfies the above properties by a combination of multiple compounds Cracking) agent. That is, the liquid film cleaving agent means an agent limited to those having a liquid film cleaving effect based on the above definition. Therefore, when a compound applied to an absorbent article contains a third component that does not meet the above definition, it is distinguished from a liquid film cleaving agent. In addition, as for the liquid film cleaving agent and the third component, the so-called "single compound" is a concept including compounds having the same composition formula but different molecular weights due to different numbers of repeating units. The liquid film cracking agent can be appropriately selected and used from those described in paragraphs [0007] to [0186] of the specification of International Publication No. 2016/098796. In the present invention, the "long-fiber non-woven fabric" refers to a non-woven fabric having a fiber assembly layer in which long fibers are intermittently fixed by a heat fusion section. The "long fiber" means a fiber having a fiber length of 30 mm or more. In particular, if it is a so-called continuous long fiber having a fiber length of 150 mm or more, it is preferable in terms of obtaining a long-fiber nonwoven fabric having a high breaking strength. Examples of such a long-fiber nonwoven fabric include a spunbond nonwoven fabric, a nonwoven fabric including a plurality of layers of a spunbond layer and a meltblown layer, and a hot-rolled nonwoven fabric using a carding method. Examples of non-woven fabrics including a plurality of layers include spunbond-spunbond layer nonwovens, spunbond-spunbond-spunbond layer nonwovens, spunbond-meltblown-spunbond layer nonwovens, spunbond-spunbond-meltblown- Non-woven spunbonded layer. In the case of a single layer, a long-fiber non-woven fabric having fibers (standing fibers) erected in a state where one end of the long fibers is not fixed to the fiber assembly layer is mentioned. The upper limit of the fiber length in the "long fiber" is not particularly limited. In addition, the above-mentioned fibers on the first surface side and fibers on the second surface side also refer to the fibers on the outermost surface of the laminated long-fiber nonwoven fabric even in the case of a plurality of layers. Figs. 1 (A) to (C) show specific examples of the layer structure of the long-fiber nonwoven fabric of the present invention. However, the long-fiber nonwoven fabric of the present invention is not limited to these, and various forms can be adopted. In addition, the first surface 5 shown in FIGS. 1 (A) to (C) is a liquid-receiving surface side (that is, a skin abutting surface side) when a long-fiber nonwoven fabric is used as a front sheet of an absorbent article. The second surface 6 is a surface on the absorber side (that is, on the non-skin contact surface side). FIG. 1 (A) shows a single-layer long-fiber nonwoven fabric 10. The long-fiber nonwoven fabric 10 includes a fiber assembly layer 3 in which the long fibers 1 are intermittently fixed by the heat fusion portion 2. The long-fiber non-woven fabric 10 has the hydrophilicity of the fibers 11 on the first surface 5 side of the liquid-receiving surface lower than the hydrophilicity of the fibers 12 on the second surface 6 side as the opposite surface side, and has a gradient of hydrophilicity. Here, the fibers on the first surface 5 side are fibers on the surface on the first surface 5 side of the fiber assembly layer 3. The fibers on the second surface 6 side are fibers on the surface on the second surface 6 side of the fiber assembly layer 3. FIG. 1 (B) shows another single-layer long-fiber nonwoven fabric 20. Examples of the long-fiber non-woven fabric 20 include long-fiber non-woven fabric 20 having upstanding fibers 4 on one side of the first surface 5 that are not fixed to the fiber assembly layer 3. The erect fiber 4 has a base portion 41 fixed to the thermal fusion portion 2 of the fiber collection portion 3 and a free end portion 42 which is not fixed to the thermal fusion portion 2 of the fiber collection layer 3. The free end portion 42 can be erected upward from the fiber assembly layer 3 toward the first surface 5 side. In this case, the fibers on the first surface 5 side are the standing fibers 4 on the surface on the first surface 5 side of the fiber assembly layer 3. The fibers on the second surface 6 side are fibers 12 on the surface on the second surface 6 side of the fiber assembly layer 3. The hydrophilicity of the standing fibers 4 is lower than that of the fibers on the second surface 6 side. FIG. 1 (C) shows a long-fiber nonwoven fabric 30 having a plurality of layers. Examples of the long-fiber non-woven fabric 30 include a long-fiber non-woven fabric 30 obtained by laminating a plurality of fiber assembly layers bundled by the heat fusion section 2. The long-fiber nonwoven fabric 30 includes a first fiber assembly layer 31 on the first surface 5 side, and a second fiber assembly layer 32 on the second surface 6 side. Furthermore, the plural layers are not limited to two layers as shown in FIG. 1 (C), and may be three or more layers. The plurality of fiber assembly layers are preferably integrated in a laminated state. For example, they are preferably joined by thermal embossing or a hot-melt adhesive. When a hot-melt adhesive is used, from the viewpoint of liquid permeability, it is preferable to perform bonding between layers by an intermittent coating method such as spiral coating. Alternatively, it is more preferable to use hot-melt adhesives to join only the peripheries in the planar direction, and to take a large number of non-joined regions and leave the interface between the layers. In this case, the fibers on the first surface 5 side are the fibers 11 on the surface on the first surface 5 side of the first fiber layer 31. The fibers on the second surface 6 side are fibers 12 on the surface on the second surface 6 side of the second fiber layer 32. Furthermore, in the long-fiber non-woven fabric 30 having a plurality of layers shown in FIG. 1 (C), the first fiber assembly layer 31 on the first surface 5 side may be one having the erect fibers 4 shown in FIG. 1 (B). Fiber assembly layer 3 (not shown). Regarding the above-mentioned hydrophilicity of the long-fiber nonwoven fabric of the present invention, it is preferred that there is a gradient of hydrophilicity from the first surface side to the second surface side. The above-mentioned "hydrophilic gradient" means a state in which, in the thickness direction of the long-fiber non-woven fabric, the skin is in contact with the liquid surface (such as a front sheet of a diaper, etc.) unless otherwise specified in advance. Side), the opposite side (for example, the non-skin-contacting surface in the above-mentioned front sheet) has higher hydrophilicity. The "gradient" includes various aspects in which there is a difference in hydrophilicity between the liquid-receiving surface side and the opposite surface side, and may be a gradually increasing state or a stepwise increasing state. kind. When it is called stepwise, it may be two steps or three steps or more. The above-mentioned hydrophilicity gradient may be a gradient from the first surface side (liquid-receiving surface side) to the second surface side along the transmission direction of the liquid, and is not strictly limited to the first surface (receiving liquid that is perpendicular to the non-woven fabric). Surface). For example, when a plurality of layers are included, each layer may have a difference in hydrophilicity and gradually increase in level. In addition, it may be a state in which the layers are gradually or stepwise increased in each layer, and the entire long-fiber nonwoven fabric is gradually or stepwise increased from the liquid receiving surface side to the opposite surface side. Alternatively, the hydrophilicity of the layer receiving only the liquid surface side (the first surface 5 side in FIG. 1 (C)) may be lower than the 2-stage hydrophilicity gradient of the other layers. In addition, the hydrophilicity of the fiber on the outermost surface of the layer receiving only the liquid surface side may be lower than the two-stage hydrophilicity gradient of other fibers in the same layer and fibers in other layers. On the other hand, when a single layer is included, the hydrophilicity in the layer may gradually or gradually increase in the thickness direction. Alternatively, it may be a two-stage hydrophilicity gradient of the surface fibers that are only affected by the liquid surface side (the first surface 5 side in Figures 1 (A) and (B)) than the hydrophilicity of other fibers in the layer. Like this. In particular, in the long-fiber nonwoven fabric 20 shown in FIG. 1 (B), from the viewpoint of improving the liquid-absorbability along the erect fibers 4, it is preferable that the erect fibers 4 have a lower hydrophilicity than the fibers of the fiber assembly layer 3. The hydrophilicity gradient of at least 2 stages of hydrophilicity. In the long-fiber nonwoven fabric of the present invention, the above-mentioned liquid film cleaving agent is contained in the constituent fibers coated on at least a part of the area of the long-fiber nonwoven fabric. The so-called at least a part of the coating is preferably a part which particularly receives the most liquid. For example, when the long-fiber nonwoven fabric of the present invention is used as a front sheet of an absorbent article such as menstrual tampons, it is an area corresponding to the excretory part of the wearer directly receiving the excretory fluid such as menstrual blood. In the thickness direction of the long-fiber nonwoven fabric of the present invention, it is preferable that the liquid film cleaving agent is contained at least on the liquid receiving surface side (the side close to the skin in the absorbent article) for receiving liquid. As for the front sheet of the above example, it is preferable that a liquid film cleaving agent is contained at least on the skin abutting surface side which is in contact with the skin of the wearer. Furthermore, from the viewpoint of liquid permeability, it is more preferable to exist in the thickness direction as much as possible, and particularly when a plurality of layers are included, it is more preferable to exist in as many layers as possible. If a liquid film cleaving agent exists at least on the liquid-receiving surface side, the liquid film cleaving agent will be dispersed in a part of the liquid after passing through the liquid, and the fiber may not adhere to the liquid film cleaving agent with the passage of the liquid. Liquid film cracking agent. With this, the effect of the liquid film cracking agent will also be exerted when the liquid is passed for the second time or later. In the present invention, the so-called long-fiber non-woven fabric contains or contains a liquid film cleaving agent, which mainly refers to the surface attached to the fibers. However, as long as the liquid film cleaving agent remains on the surface of the fiber, the liquid film cleaving agent may be contained in the fiber, or may be contained in the fiber by internal addition. As a method for attaching the liquid film cleaving agent to the surface of the fiber, various methods generally used can be adopted without particular limitation. Examples include flexographic printing, inkjet printing, gravure printing, screen printing, spraying, and brush coating. These treatments may be performed after the fiber is web-formed by various methods, and thereafter, the fiber web may be made into a non-woven fabric or incorporated into an absorbent article. The fiber with the liquid film cracking agent adhered to the surface is dried at a temperature sufficiently lower than the melting point of the fiber resin (for example, 120 ° C. or lower) by a hot-air blower dryer, for example. In the case where the liquid film cracking agent is attached to the fiber by using the above-mentioned adhesion method, the liquid film cracking agent may be used without being diluted, or a liquid film containing a liquid film cracking agent dissolved in a solvent may be used if necessary. It is performed by the solution of a cracking agent, or the emulsion and dispersion of a liquid film cracking agent. Regarding the liquid film cleaving agent of the present invention, in order for the nonwoven fabric to have the following liquid film cleaving effect, the liquid film cleaving agent must exist in a liquid state when it comes into contact with body fluids. In this respect, the melting point of the liquid film cleaving agent of the present invention is preferably 40 ° C or lower, more preferably 35 ° C or lower. Furthermore, the melting point of the liquid film cleaving agent of the present invention is preferably -220 ° C or higher, and more preferably -180 ° C or higher. Here, the above-mentioned effect of the liquid film cleaving agent in the long-fiber nonwoven fabric of the present invention will be specifically described with reference to FIGS. 2 and 3. As shown in FIG. 2, in the narrow region between the fibers, the liquid film 7 is easily expanded by liquids with higher viscosity such as menstrual blood or urine. In view of this, the liquid film cleaving agent stabilizes the liquid film and breaks it in the following manner, thereby suppressing the formation of the liquid film and promoting drainage from the nonwoven fabric. First, as shown in FIGS. 3 (A1) and (B1), the liquid film cleaving agent 8 included in the fiber 1 of the long-fiber nonwoven fabric moves on the surface of the liquid film 7 while maintaining the interface with the liquid film 7. Next, the liquid film cracking agent 8 is as shown in FIGS. 3 (A2) and (B2), and a part of the liquid film 7 is pushed open and penetrates in the thickness direction, as shown in FIGS. 3 (A3) and (B3). The liquid film 7 is gradually made uneven and changes to a thinner film. As a result, as shown in FIGS. 3 (A4) and (B4), the liquid film 7 was cracked, and cracks appeared. The ruptured liquid such as menstrual blood becomes a droplet, and further, it becomes easy to pass between the fibers of the long-fiber non-woven fabric, thereby reducing the residual liquid. The effect of the above-mentioned liquid film cracking agent on the liquid film is not limited to the case of the liquid film between the fibers, and it also works similarly to the liquid film wound on the surface of the fibers. That is, the liquid film cracking agent can move on the liquid film wound on the surface of the fiber, thereby pushing away a part of the liquid film to crack the liquid film. In addition, for the liquid film wound on the surface of the fiber, even if the liquid film cleaving agent does not move on the position attached to the fiber, the liquid film may be cracked due to its hydrophobic effect, thereby suppressing the formation of the liquid film. As mentioned above, the liquid film cracking agent does not reduce the surface tension of the liquid film, that is, to perform liquid modification. Instead, it pushes apart the liquid film generated between the fibers or the fiber surface to crack the liquid film, thereby inhibiting the formation of the liquid film. To promote the drainage of liquid from long-fiber nonwovens. Thereby, the liquid residue of the long-fiber nonwoven can be reduced. In addition, if such a long-fiber nonwoven fabric is incorporated into an absorbent article as a front sheet, liquid retention between the fibers is suppressed, and a liquid passage to the absorbent body is ensured. Thereby, the liquid permeability is improved, the liquid flow on the surface of the sheet is suppressed, and the liquid absorption speed is increased. In particular, it can increase the absorption rate of liquids that tend to remain between the fibers such as menstrual blood with higher viscosity. In addition, stains such as red in the front sheet are less likely to be noticeable, and the absorbent article can be securely felt with a secure and reliable absorbent article. In the long-fiber non-woven fabric of the present invention, as described above, the liquid film cleaving agent acts as a driving force that breaks the fine and stable liquid film generated between the narrow fibers and renders it ineffective. stable. At the same time, the above-mentioned hydrophilicity gradient functions in the form of a driving force that will cause the liquid film to crack and become unstable, and the fiber layer with a lower hydrophilicity will be unidirectional before the fiber surface is stabilized again. Draw to the fiber layer with higher hydrophilicity. In addition, even if the liquid returns slightly due to pressure or the like, the liquid film cracking agent suppresses the formation of a stable liquid film, and is sucked back to a fiber layer with higher hydrophilicity. As described above, the driving forces of the above liquid film cleaving agent and the hydrophilicity gradient are synergistic, which hinders the stabilization of the liquid between the fibers, and improves the liquid permeability in the thickness direction of the liquid in the long-fiber nonwoven fabric to suppress the liquid residue. . This makes it possible to quickly respond to new liquid-receiving liquid permeability, thereby making it possible to reduce liquid residue or return liquid through the liquid residue. In addition, if a liquid film cleaving agent is also present in the thermal fusion portion 2 that bundles the long fibers, the liquid film on the surface of the film-shaped fiber of the thermal fusion portion can also be cracked, and the gradient of the hydrophilicity can reliably be used. The liquid is caused to fall in the thickness direction from between the fibers. As a result, the long-fiber non-woven fabric can reduce the liquid residue caused by the unique heat fusion portion or the liquid return caused by the liquid residue. Furthermore, in the long-fiber nonwoven fabric 20 shown in FIG. 1 (B), when the liquid is supplied, it is confirmed that the erect fibers 4 containing a liquid film cleaving agent and having low hydrophilicity have the following effects. That is, when the liquid is supplied to the first surface 5 side having the erect fibers 4, the erect fibers 4 having a lower hydrophilicity than the fiber assembly layer 3 are raised in the free end portion 42 side, that is, they are raised in a floating manner. Furthermore, the erect fibers 4 are in an erect state to a certain degree (to the extent that they float from the fiber assembly layer 3) when they are not in contact with the liquid. The so-called "standing of the erect fibers 4" caused by contact with the liquid mentioned above means that the degree of erecting becomes larger than the state before contact with the liquid, that is, the angle formed by the erect fibers 4 and the fiber assembly layer 3 changes. Big. The erect fibers 4 are in a state where they are erected to a large extent while being in contact with the liquid. In this state, the liquid film is eliminated on the surface of the erect fibers 4 by the above-mentioned action of the liquid film cleaving agent 3. The liquid moves along the erect fibers and is sucked to the fiber assembly layer 3 with relatively high hydrophilicity. Inside. Thereby, liquid residue is reduced. Furthermore, after the liquid is absorbed, the erect fibers 4 having a low hydrophilicity are restored to the original erect state with a small degree of erecting, and the first surface 5 side of the fiber assembly portion 3 is covered to a certain extent from above. Thereby, the erect fibers 4 having low hydrophilicity (hydrophobicity) can prevent liquid from returning from the second surface 6 side, and function as a lid. In particular, when the long-fiber nonwoven fabric 20 is used as the front sheet of an absorbent article with the first surface 5 side facing the skin contact surface side, the liquid repellency suppression effect is high. That is, in the state where the user's skin is in contact with the front sheet, the erect fibers 4 having a low hydrophilicity (hydrophobicity) lie down and cover the first surface 5 side of the fiber assembly portion 3, so that it can be particularly effective Liquid suppression effect. In addition, since the erect fibers 4 are completely separated from the fiber assembly layer 3, they are cushioned under pressure to provide excellent touch to the skin. In addition, in a state of no pressure, as described above, it stands up to a certain degree even when it is not in contact with the liquid, so it can provide a soft skin feel which is an original function. In the long-fiber nonwoven fabric 20, this phenomenon occurs repeatedly with the supply of liquid. As a result, the long-fiber nonwoven fabric 20 having the erect fibers 4 contains the liquid film cleaving agent and has a hydrophilicity gradient, and besides achieving a good skin feel brought by the erect fibers 4, it also realizes liquid residue and recovery. The reduction of liquid and the time of liquid passing are further shortened. As a result, the long-fiber non-woven fabric 20 as a non-woven fabric for a front sheet can achieve an excellent dry feeling that has not been achieved before. Regarding the erecting action of the erecting fibers 4, it was confirmed through experiments that no erecting phenomenon occurred in hydrophilic erecting fibers, and a erecting phenomenon occurred in hydrophobic erecting fibers. The term "hydrophobicity" herein means that it has low affinity with body fluids and is not easily wetted, and means that the contact angle described below is 75 ° or more, preferably 80 ° or more, more preferably 85 ° or more, and even more preferably Above 90 °. The term "hydrophilic" means that the contact angle is smaller than the above-mentioned value, and in terms of affinity with body fluids, it means 90 ° or less. Regarding the erection of the erect fibers 4, it is thought that this may be caused by the following factors. That is, it is considered that in a state where the liquid is supplied to the first surface 5 side and the erect fibers 4 are in contact with the hydrophilic liquid, the energy in a state where the hydrophobic erect fibers 4 are aggregated with each other is stabilized, and therefore, the erect fibers are hydrophobic. The state in which the sexual fibers 4 are gathered together, that is, the state in which the hydrophobic erect fibers 4 stand. When the erect fibers 4 are hydrophobic, it is considered that when the liquid is supplied to the first surface 5 side of the erect fibers 4 and the erect fibers 4 are in contact with the liquid, a thin air layer is generated around the fibers. , The buoyancy comes into play, so that the erect fibers 4 stand up. Furthermore, it is considered that the rise of the erect fibers 4 in contact with the liquid is also affected by the fact that the liquid film cleaving agent has extremely low water solubility. Moreover, regarding the above-mentioned erection operation, the difference in specific gravity is also considered to be a factor. However, in fact, even when the first surface 5 side of the erection fiber 4 is facing downward, the erection of the fiber is confirmed ( Hydrophilic erect fibers do not occur), so it is estimated that the specific gravity is affected by the difference in hydrophilicity. Next, a preferred embodiment of the long-fiber nonwoven fabric according to the present invention will be described. Furthermore, in any embodiment, the long-fiber nonwoven fabric may be any of a single layer and a plurality of layers. For example, Figs. 1 (A) to (C) are applicable. Regarding the gradient of the hydrophilicity, the various aspects described above can be applied to the embodiments described below. In addition to the gradient of hydrophilicity described above, the long-fiber nonwoven fabric of the first embodiment has at least one layer containing a liquid having a surface tension of 50 mN / m and a spreading coefficient of 15 mN / m or more, and a water solubility of 0 g. A layer of liquid film cracking agent above and below 0.025 g. Furthermore, a compound having the above-mentioned properties may be referred to as a compound C1. The "spreading factor for liquids with a surface tension of 50 mN / m" possessed by liquid film cleaving agents refers to the spreading factor for liquids that are supposed to be excretory fluid such as menstrual blood or urine. The so-called "spreading coefficient" is obtained based on the measured value obtained by the following measuring method in an environmental area of a temperature of 25 ° C and a relative humidity (RH) of 65%, based on the following formula (1) Value. In addition, the liquid film in the formula (1) means a liquid phase of "a liquid having a surface tension of 50 mN / m", and includes a liquid in a state where the film has been developed between fibers or on the surface of the fiber, and the film is developed Both liquids in the previous state are also referred to as liquids for short. In addition, the surface tension of formula (1) means the interfacial tension at the interface between the liquid film and the liquid film cleaving agent and the gas phase, which is different from the interfacial tension between the liquid film cleaving agent and the liquid film between the liquid phase. This difference is the same as in other descriptions of this specification. S = γ _w -γ _o -γ _wo (1) γ _w : Surface tension of liquid film (liquid) _o : Surface tension of liquid film cracking agent _wo : The interfacial tension between the liquid film cleaving agent and the liquid film According to the formula (1), it can be known that the spreading coefficient (S) of the liquid film cleaving agent depends on the surface tension of the liquid film cleaving agent (γ _o ) Becomes smaller and larger, and will be caused by the interfacial tension between the liquid film cracking agent and the liquid film (γ _wo ) Gets smaller and bigger. With this spreading factor of 15 mN / m or more, the liquid film cracking agent becomes the one having higher mobility, that is, diffusivity, on the surface of the liquid film generated in the narrow region between the fibers. From this viewpoint, the spreading coefficient of the liquid film cracking agent is more preferably 20 mN / m or more, more preferably 25 mN / m or more, and even more preferably 30 mN / m or more. On the other hand, the upper limit is not particularly limited, but according to formula (1), the upper limit is 50 mN / m when a liquid with a surface tension of 50 mN / m is used; the upper surface tension is 60 mN / In the case of a liquid of m, the upper limit becomes 60 mN / m; in the case of using a liquid with a surface tension of 70 mN / m, the upper limit becomes 70 mN / m, so the surface tension of the liquid forming the liquid film becomes the upper limit . Therefore, in the present invention, from the viewpoint of using a liquid having a surface tension of 50 mN / m, the upper limit of the spreading coefficient is 50 mN / m or less. The so-called "water solubility" of the liquid film cracking agent is based on the mass (g) that the liquid film cracking agent can dissolve in 100 g of deionized water, and is based on the following measurement method, at a temperature of 25 ° C and a relative humidity ( RH) 65% of the measured value in the environmental area. Since the water solubility is 0 g or more and 0.025 g or less, the liquid film cracking agent is difficult to dissolve and forms an interface with the liquid film, so that the above-mentioned diffusivity is more effectively exhibited. From the same viewpoint, the water solubility of the liquid film cracking agent is preferably 0.0025 g or less, more preferably 0.0017 g or less, and still more preferably 0.0001 g or less. In addition, the smaller the water solubility, the better, and it is 0 g or more. From the viewpoint of diffusibility to the liquid film, it is actually set to 1.0 × 10. ^-9 g or more. In addition, it is considered that the above-mentioned water solubility is also completely applicable to menstrual blood, urine, and the like containing water as a main component. Surface tension (γ of liquid film with surface tension of 50 mN / m) (γ _w ), Surface tension of liquid film cracking agent (γ _o ) 、 Interfacial tension between liquid film cracking agent and liquid film (γ _wo ), And the water solubility of the liquid film cracking agent were measured by the following method. When the long-fiber nonwoven fabric to be measured is a member (for example, a front sheet) incorporated in an absorbent article such as a physiological article or a disposable diaper, it is taken out and measured in the following manner. That is, for an absorbent article, the adhesive used for joining the member to be measured and other members is weakened by a cooling method such as cold spraying, and then the member to be measured is carefully peeled off and taken out. This take-out method is applicable to the measurement of the long-fiber nonwoven fabric of the present invention such as the measurement of the distance between fibers and the fineness described below. In the case of measuring the liquid film cleaving agent attached to the fiber, first, the fiber to which the liquid film cleaving agent is adhered is washed with a washing liquid such as hexane, methanol, or ethanol, and the cleaning used The solvent (cleaning solvent containing a liquid film cleaving agent) is dried and taken out. The mass of the material taken out at this time is suitable for calculating the content ratio (OPU) of the liquid film cracking agent with respect to the fiber mass. When the amount of the removed substance is small for measuring the surface tension or interfacial tension, an appropriate column and solvent are selected according to the composition of the extracted substance, and then each component is analyzed by high performance liquid chromatography. Classify each component, and then perform MS (mass spectrometry) measurement, NMR (nuclear magnetic resonance) measurement, and elemental analysis on each component to identify the structure of each component. When the liquid film cleaving agent contains a polymer compound, it becomes easier to identify the constituents by using a method such as gel permeation chromatography (GPC) in combination. If the substance is a commercially available product, it is purchased, and if the substance is not a commercially available product, it is synthesized to obtain a sufficient amount to measure the surface tension or interfacial tension. Especially when measuring the surface tension and interfacial tension, in the case where the liquid film cracking agent obtained in the above manner is solid, it is heated to the melting point of the liquid film cracking agent + 5 ° C to make the phase transfer into a liquid, and then The measurement was performed directly under temperature conditions. (Surface tension of liquid film (liquid) (γ _w (Measurement method of)) Measurement can be performed using a platinum plate by the plate method (Wilhelmy method) in an environmental area having a temperature of 25 ° C and a relative humidity (RH) of 65%. As the measuring device at this time, an automatic surface tension meter "CBVP-Z" (trade name, manufactured by Kyowa Interface Science Co., Ltd.) can be used. Platinum plates are those with a purity of 99.9%, dimensions of 25 mm in length and 10 mm in width. Furthermore, in the following measurement of the liquid film cracking agent, the above-mentioned measurement method is used, and the above-mentioned "liquid with a surface tension of 50 mN / m" uses the following solution, which is added as deionized water as Polyoxyethylene sorbitan monolaurate (for example, manufactured by Kao Corporation, trade name: RHEODOL SUPER TW-L120) and a surface tension adjusted to 50 ± 1 mN / m. (Surface tension of liquid film cracking agent (γ _o Method of measurement) can be related to the surface tension of the liquid film (γ _w The measurement of) is performed in the same manner in an environmental region with a temperature of 25 ° C. and a relative humidity (RH) of 65% by the plate method using the same device. When the measurement is performed, when the liquid film cracking agent obtained as described above is solid, it is heated to the melting point of the liquid film cracking agent + 5 ° C to make the phase transfer to a liquid, and directly under the temperature conditions Perform the measurement. (Interfacial tension between liquid film cracking agent and liquid film (γ _wo Measurement method of)) It can be measured by the hanging drop method in an environmental area with a temperature of 25 ° C and a relative humidity (RH) of 65%. As the measurement device at this time, an automatic interface viscoelasticity measurement device (manufactured by TECLIS-ITCONCEPT, trade name THE TRACKER; or KRUSS company, trade name DSA25S) can be used. In the hanging drop method, the adsorption of the non-ionic interface active substance contained in the liquid having a surface tension of 50 mN / m at the same time as the formation of the drops begins, and the interface tension decreases with time. Therefore, the interfacial tension when a drop is formed (at 0 seconds) is read. When the measurement is performed, when the liquid film cracking agent obtained as described above is solid, the liquid film cracking agent is heated to the melting point of the liquid film cracking agent + 5 ° C. and the phase is transferred to a liquid. The measurement was performed directly. When measuring the interfacial tension, when the density difference between the liquid film cracking agent and the liquid with a surface tension of 50 mN / m is very small, or when the viscosity is very high, if the interfacial tension value is the measurement limit of the suspension drop agent Hereinafter, the measurement of the interfacial tension by the hanging drop method may be difficult. In this case, the measurement can be performed by the spin-drop method in an environmental region where the temperature is 25 ° C and the relative humidity (RH) is 65%. As the measuring device at this time, a spin-drop interfacial tensiometer (trade name: SITE100, manufactured by KURUSS) can be used. For this measurement, the interfacial tension when the shape of the drop is stable is also read. When the obtained liquid film cracking agent is solid, it is heated to the melting point of the liquid film cracking agent + 5 ° C to make it phase. It was transferred to a liquid, and the measurement was performed directly under the temperature conditions. Furthermore, when the interfacial tension can be measured by both the above-mentioned measuring devices, a smaller interfacial tension value is used as the measurement result. (Measuring method for water solubility of liquid film cracking agent) While stirring 100 g of deionized water with a stirrer in an environment area with a temperature of 25 ° C and a relative humidity (RH) of 65%, slowly obtain the liquid film cracking agent obtained. Dissolve in situ, and the amount of dissolution at the point when it is no longer dissolved (suspension or precipitation, precipitation, white turbidity is visible) is set to water solubility. Specifically, it measured by adding 0.0001 g each time. As a result, those who did not dissolve even 0.0001 g were regarded as "below 0.0001 g", and those who observed 0.0001 g but not dissolved 0.0002 g were regarded as "0.0001 g". Furthermore, in the case where the liquid film cracking agent is a surfactant, the so-called "dissolution" means both monodisperse dissolution and micellar dissolution dissolution. It can be seen that the amount of dissolution at the time of suspension or precipitation, precipitation, and turbidity becomes water solubility. . The liquid film cracking agent of this embodiment has the above-mentioned spreading coefficient and water solubility, so that it will not dissolve and spread on the surface of the liquid film, but can push away the layer of the liquid film near the center of the liquid film. This makes the liquid film unstable and causes it to crack. In this embodiment, the liquid film cleaving agent further preferably has an interfacial tension of 20 mN / m or less for a liquid having a surface tension of 50 mN / m. That is, the value of the spread coefficient (S) in the above formula (1) is defined as a variable "Interfacial tension between the liquid film cleaving agent and the liquid film (γ _wo ) "Is preferably 20 mN / m or less. By applying "the interfacial tension between the liquid film cracking agent and the liquid film (γ _wo ") Is suppressed to a low level, and the spreading coefficient of the liquid film cleaving agent is increased, so that the liquid film cleaving agent becomes easy to move from the fiber surface to the vicinity of the center of the liquid film, so that the above-mentioned effect becomes more obvious. From this viewpoint, the "interfacial tension of a liquid film cracking agent with a surface tension of 50 mN / m" is more preferably 17 mN / m or less, further preferably 13 mN / m or less, and even more preferably 10 mN / m or less, particularly preferably 9 mN / m or less, and particularly preferably 1 mN / m or less. On the other hand, the lower limit is not particularly limited, and from the viewpoint of insolubility to the liquid film, it may be greater than 0 mN / m. Furthermore, when the interfacial tension is 0 mN / m, that is, when dissolving, the interface between the liquid film and the liquid film cleaving agent cannot be formed, so the formula (1) does not hold, and the expansion of the agent does not occur. As for the spreading coefficient, it can be known from the numerical formula that the numerical value changes depending on the surface tension of the liquid to be targeted. For example, when the surface tension of the target liquid is 72 mN / m, the surface tension of the liquid film cracking agent is 21 mN / m, and the interfacial tension thereof is 0.2 mN / m, the spreading coefficient becomes 50.8 mN / m. When the surface tension of the target liquid is 30 mN / m, the surface tension of the liquid film cleaving agent is 21 mN / m, and the interfacial tension thereof is 0.2 mN / m, the spreading coefficient becomes 8.8 mN / m. In either case, the more the agent with the larger spreading coefficient, the better the liquid film cracking effect becomes. In this specification, the value at the surface tension of 50 mN / m is defined. However, even if the surface tension is different, the relationship between the values of the spread coefficients of the substances will not change. Therefore, even if the surface tension of the body fluid is assumed to vary by day Changes in physical conditions, etc., the more the agent with the larger spread coefficient, the more excellent the liquid film cracking effect. In this embodiment, the surface tension of the liquid film cracking agent is preferably 32 mN / m or less, more preferably 30 mN / m or less, even more preferably 25 mN / m or less, and even more preferably 22 mN / m. the following. The lower the surface tension, the better. The lower limit is not particularly limited. From the viewpoint of the durability of the liquid film cleaving agent, it is actually 1 mN / m or more. Next, the long-fiber nonwoven fabric according to the second embodiment will be described. In addition to the gradient of hydrophilicity described above, the long-fiber nonwoven fabric of the second embodiment also has at least one layer containing a liquid with a surface tension of 50 mN / m and a spreading coefficient greater than 0 mN / m, which is a positive value. A layer of a liquid film cleaving agent having a solubility of 0 g or more and 0.025 g or less and an interfacial tension of a liquid having a surface tension of 50 mN / m or less and 20 mN / m or less. Furthermore, a compound having the above-mentioned properties may be referred to as a compound C2. Setting the "Interfacial tension to a liquid having a surface tension of 50 mN / m" to be 20 mN / m or less means that the diffusivity of the liquid film cleaving agent on the liquid film is improved as described above. Therefore, even when the "spreading coefficient for a liquid with a surface tension of 50 mN / m" is less than 15 mN / m, the spreading coefficient is relatively small, because of the high diffusivity, so The liquid film cleaving agent with a large surface is dispersed in the liquid film, and the liquid film is pushed open at a plurality of positions, thereby exerting the same effect as in the case of the first embodiment. Furthermore, the so-called "spreading coefficient for liquids with a surface tension of 50 mN / m", "water solubility", and "interfacial tension for liquids with a surface tension of 50 mN / m" are related to liquid film cracking agents. The definitions in the first embodiment are the same, and their measurement methods are also the same. In this embodiment, from the viewpoint of more effectively exerting the above-mentioned effects of the liquid film cracking agent, the "Interfacial tension to a liquid having a surface tension of 50 mN / m" is preferably 17 mN / m or less, more preferably It is 13 mN / m or less, more preferably 10 mN / m or less, still more preferably 9 mN / m or less, and particularly preferably 1 mN / m or less. The lower limit value is not particularly limited in the same manner as in the first embodiment, and is actually larger than 0 mN / m in terms of not dissolving in a liquid film (a liquid having a surface tension of 50 mN / m). In addition, regarding the "spreading coefficient for a liquid having a surface tension of 50 mN / m", from the viewpoint of more effectively exerting the aforementioned effects of the liquid film cracking agent, it is preferably 9 mN / m or more, and more preferably 10 mN / m or more, and more preferably 15 mN / m or more. The upper limit is not particularly limited, and from the viewpoint that the surface tension of the liquid film-forming liquid becomes the upper limit according to formula (1), it is actually 50 mN / m or less. In addition, the more preferable ranges of the surface tension and water solubility of the liquid film cleaving agent are the same as those of the first embodiment. The long-fiber nonwoven fabric of the first embodiment and the long-fiber nonwoven fabric of the second embodiment preferably contain a phosphate ester type anionic surfactant in addition to the above-mentioned liquid film cleaving agent. Thereby, the hydrophilicity of the fiber surface is improved, and the wettability is increased, so that the area where the liquid film and the liquid film cleaving agent come into contact becomes larger; and because blood or urine has a surface-active substance having a phosphate group derived from a living body Therefore, by using a surfactant having a phosphate group in combination, and because of the compatibility of the active agent, and the affinity with the phospholipids contained in blood or urine is also good, the liquid film cracking agent becomes easy to move to the liquid film, And further promote the cracking of the liquid film. The content ratio of the liquid film cleaving agent and the phosphate ester type anionic surfactant is preferably 1: 1 to 19: 1, and more preferably 2: in terms of mass ratio (liquid film cleaving agent: phosphate ester type anionic surfactant). 1 to 15: 1, and more preferably 3: 1 to 10: 1. In particular, the content ratio is preferably 5: 1 to 19: 1 in terms of mass ratio, more preferably 8: 1 to 16: 1, and even more preferably 11: 1 to 13: 1. As a phosphate-type anionic surfactant, it can be used without particular limitation. For example, specific examples thereof include alkyl ether phosphate, dialkyl phosphate, and alkyl phosphate. Among them, alkyl phosphate is preferred from the viewpoint of improving the affinity with the liquid film and imparting the processability of the long-fiber nonwoven fabric. As the alkyl ether phosphate, various ones can be used without particular limitation. Examples include polyoxyalkylene stearyl ether phosphate, polyoxyalkylene myristyl ether phosphate, polyoxyalkylene lauryl ether phosphate, polyoxyalkylene palmityl ether phosphate, and the like. Those with saturated carbon chains; or those with unsaturated carbon chains, such as polyoxyalkylene oleyl ether phosphates, polyoxyalkylene palmityl ether ether phosphates, and those with branched carbon chains. More preferred are fully or partially neutralized salts of mono- or dimeric oxyalkylene alkyl ether phosphates having a carbon chain of 16 to 18. Examples of the polyoxyalkylene group include polyoxyethylene, polyoxypropyl, polyoxybutyl, and copolymers of the constituent monomers. Examples of the salt of the alkyl ether phosphate include alkali metals such as sodium and potassium, ammonia, and various amines. The alkyl ether phosphate may be used singly or in combination of two or more kinds. Specific examples of the alkyl phosphate include those having a saturated carbon chain, such as stearyl phosphate, myristyl phosphate, lauryl phosphate, and palmitate phosphate; or oleyl phosphate, palmitate phosphate, and the like Saturated carbon chains and those with branched carbon chains. More preferred is a completely neutralized or partially neutralized salt of a monoalkyl phosphate or dialkyl phosphate having a carbon chain of 16 to 18. Examples of the salt of the alkyl phosphate include alkali metals such as sodium and potassium, ammonia, and various amines. The alkyl phosphate may be used singly or in combination of two or more kinds. Next, specific examples of the liquid film cleaving agent in the first embodiment and the second embodiment will be described. Since they are in the above-mentioned specific numerical range, they do not dissolve in water or have the property of being poorly soluble in water, thereby exerting the effect of cracking the liquid film. In contrast, the surfactants and the like previously used as fiber treatment agents are practically water-soluble ones that are practically dissolved in water and are not the liquid film cleaving agent of the present invention. As the liquid film cracking agent in the first embodiment and the second embodiment, a compound having a mass average molecular weight of 500 or more is preferable. This mass average molecular weight will have a large effect on the viscosity of the liquid film cracking agent. The liquid film cracking agent maintains a high viscosity, so the liquid is not easy to flow down when passing through the fibers, so that the liquid film cracking effect in the long-fiber nonwoven can be maintained. From the viewpoint of setting the viscosity of the liquid film cracking effect sufficiently, the mass average molecular weight of the liquid film cracking agent is more preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. On the other hand, from the viewpoint of maintaining the viscosity of the liquid film cleaving agent since the fibers provided with the liquid film cleaving agent move to the liquid film, that is, the diffusivity, it is preferably 50,000 or less, more preferably 20,000 or less, and more preferably It is preferably below 10,000. The measurement of the mass-average molecular weight was performed using a gel permeation chromatography (GPC) "CCPD" (trade name, manufactured by Tosoh Corporation). The measurement conditions are as follows. The calculation of the converted molecular weight was performed using polystyrene. Separation column: GMHHR-H + GMHHR-H (cation) Eluent: L Farmin DM20 / CHCl ₃ Solvent flow rate: 1.0 ml / min. Separation column temperature: 40 ° C. As the liquid film cracking agent in the first embodiment, it is preferable to have a structure selected from the group consisting of the following structures X, XY, and YXY as follows. A compound of at least one structure in the group. Structure X indicates that> C (A)-(C indicates a carbon atom. Also, <,>, and-indicate a bond. The same applies hereinafter), -C (A) ₂ -, -C (A) (B)-,> C (A) -C (R ¹ ) ＜ 、 ＞ C (R ¹ )-, -C (R ¹ ) (R ² )-, -C (R ¹ ) ₂ -,> C <and -Si (R ¹ ) ₂ O-, -Si (R ¹ ) (R ² ) A siloxane chain having a basic structure in which any one of O- is repeated, or a combination of two or more types, or a mixed chain thereof. Has a hydrogen atom at the end of structure X, or is selected from -C (A) ₃ , -C (A) ₂ B, -C (A) (B) ₂ , -C (A) ₂ -C (R ¹ ) ₃ , -C (R ¹ ) ₂ A, -C (R ¹ ) ₃ , And -OSi (R ¹ ) ₃ , -OSi (R ¹ ) ₂ (R ² ), -Si (R ¹ ) ₃ , -Si (R ¹ ) ₂ (R ² ) At least one base in the group. R above ¹ Or R ² Each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20. For example, methyl, ethyl, and propyl are preferred), and an alkoxy group (preferably has a carbon number of 1 to 20. For example, it is preferably Various substituents such as a methoxy group, an ethoxy group), an aryl group (preferably a carbon number of 6 to 20. For example, a phenyl group is preferred), a halogen atom (for example, a fluorine atom is preferred). A and B each independently represent a substituent including an oxygen atom or a nitrogen atom such as a hydroxy group or a carboxylic acid group, an amine group, a sulfonylamino group, an imino group, or a phenol group. Within structure X ¹ , R ² When there are a plurality of, A, and B, they may be the same as or different from each other. In addition, the bond between C (carbon atom) or Si to be connected is usually a single bond, but may also include a double or triple bond, and the bond between C or Si may also include an ether group (-O-), amidino group (-CONR ^A -: R ^A Is a hydrogen atom or a monovalent group), an ester group (-COO-), a carbonyl group (-CO-), a carbonate group (-OCOO-), and other linking groups. The number of bonds between one C and Si and another C or Si is one to four, so there may also be long-chain polysiloxane chains (siloxane chains) or mixed chain branches, or radial structures. situation. Y represents a hydrophilic group having a hydrophilic property including an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. For example, it is a hydroxyl group, a carboxylic acid group, an amine group, an amido group, an imine group, a phenol group, and a polyoxyalkylene group (the carbon number of the oxyalkylene group is preferably 1 to 4. The polyoxyethylene group is preferred, for example. (POE) group, polyoxypropylene (POP) group), sulfonic acid group, sulfate group, phosphate group, sulfobetaine group, carbonyl betaine group, phosphono betaine group (these betaine groups refer to A betaine residue obtained by removing one hydrogen atom from a betaine compound), a hydrophilic group such as a quaternary ammonium group alone, or a hydrophilic group including a combination thereof. In addition to these, it can also be listed in the following M ¹ The groups and functional groups listed in. When Y is plural, they may be the same as or different from each other. In the structures XY and YXY, Y is a base bonded to X or the end of X. In the case where Y is bonded to a radical at the end of X, the radical at the end of X is removed, for example, by the same number of hydrogen atoms as the number of bonds to Y, and is bonded to Y. In this structure, the hydrophilic groups Y, A, and B are selected from the bases that have been specifically described so as to satisfy the above-mentioned spreading coefficient, water solubility, and interfacial tension. This shows the target liquid film cracking effect. The above-mentioned liquid film cleaving agent is preferably a compound whose structure X is a siloxane structure. Further, the liquid film cleaving agent is preferably a compound containing a siloxane chain in which the structures represented by the following formulae (1) to (11) as specific examples of the above-mentioned structures X, XY, and YXY are arbitrarily combined. Furthermore, from the viewpoint of the cracking effect of the liquid film, it is preferable that the compound has a mass average molecular weight in the above range. [Chemical 1]

In formulas (1) to (11), M ¹ , L ¹ , R ^{twenty one} , And R ^{twenty two} Represents the following bases of one or more valences (two or more valences). R ^{twenty three} , And R ^{twenty four} Represents a base of one or more valences (two or more valences) below, or a single bond. M ¹ Represents a group having polyoxyethylene, polyoxypropyl, polyoxybutyl, or a combination of polyoxyalkylene; or erythritol, xylitol, and sorbose A hydrophilic group having a plurality of hydroxyl groups such as an alcohol group, a glyceryl group, or a glycol group (a hydrophilic group obtained by removing one hydrogen atom from the compound having a plurality of hydroxyl groups such as erythritol), a hydroxyl group, a carboxylic acid group, Mercapto group, alkoxy group (preferably carbon number 1 to 20. For example, methoxy group is preferred), amine group, amido group, imine group, phenol group, sulfonic group, quaternary ammonium group, sulfo beet Base, hydroxysulfobetaine, phosphinobetaine, imidazolium betaine, carbonyl betaine, epoxy group, methanol group, (meth) acrylic group, or a combination of these functions base. Furthermore, in M ¹ In the case of a multivalent base, M ¹ Represents a group obtained by removing one or more hydrogen atoms from each of the above-mentioned groups or functional groups. L ¹ Represents ether group, amine group (can be used as L ¹ The amine group used is from NR ^C (R ^C (A hydrogen atom or a monovalent group), a bonding group represented by), amidino group, ester group, carbonyl group, and carbonate group. R ^{twenty one} , R ^{twenty two} , R ^{twenty three} , And R ^{twenty four} Each independently represents an alkyl group (preferably a carbon number of 1 to 20. For example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, Nonyl, decyl), alkoxy (preferably having 1 to 20 carbons. For example, methoxy and ethoxy are preferred), aryl (preferably 6 to 20 carbons. For example, benzene is preferred) Group), a fluoroalkyl group, an aralkyl group, or a hydrocarbon group obtained by combining these, or a halogen atom (for example, a fluorine atom is preferred). Furthermore, in R ^{twenty two} And R ^{twenty three} When it is a polyvalent group, it means a polyvalent hydrocarbon group obtained by removing one or more hydrogen atoms or fluorine atoms from the above-mentioned hydrocarbon group. Again, in R ^{twenty two} Or R ^{twenty three} With M ¹ In the case of bonding, it can be used as R ^{twenty two} Or R ^{twenty three} In addition to the above-mentioned groups, the above-mentioned hydrocarbon groups, or halogen atoms, the groups that can be used may be listed as R ³² Used imine. As for the liquid film cleaving agent, among them, a compound having a structure represented by any one of the formulae (1), (2), (5), and (10) as X and having the following formula is preferable. The structure represented by any one of the above formulas is other than the terminal of X, or includes the terminal of X and the base of Y. It is further preferred that the compound includes a group having X, or a terminal containing X and a group consisting of Y, which is represented by the formula (2), (4), (5), (6), (8), and (9). At least one siloxane chain having a structure represented by any one. As a specific example of the said compound, the organic modified polysiloxane (polysiloxane) of a polysiloxane type surfactant is mentioned. For example, as the reactive organic-group-modified organic-modified polysiloxane, amine-group modified, epoxy-modified, carboxy-modified, glycol-modified, methanol-modified, (Meth) acrylic modified, mercapto modified, phenol modified. Examples of the non-reactive organic-group-modified organic modified polysiloxane include polyether-modified ones (including polyoxyalkylene-modified ones), methylstyrene-modified ones, and long Alkyl group modified, higher fatty acid ester modified, higher alkoxy modified, higher fatty acid modified, fluorine modified, etc. Depending on the type of the organic modification, for example, by appropriately changing the molecular weight of the polysiloxane chain, the modification rate, and the addition mole number of the modified group, the distribution coefficient that exerts the cracking effect of the liquid film described above can be obtained . Here, the "long chain" means a carbon having 12 or more carbon atoms, and preferably 12 to 20 carbon atoms. The term "high-grade" refers to those having a carbon number of 6 or more, and preferably 6 to 20 carbon atoms. Among them, polyoxyalkylene-modified polysiloxanes or epoxy-modified polysiloxanes, methanol-modified polysiloxanes, glycol-modified polysiloxanes, and the like are preferred as the liquid film cracking agents of modified polysiloxanes. The modified polysiloxane having a structure having at least one oxygen atom in the modified group is particularly preferably a polyoxyalkylene-modified polysiloxane. Polyoxyalkylene-modified polysiloxane has a polysiloxane chain, so it is difficult for it to penetrate into the fiber and easily remain on the surface. In addition, since a polyoxyalkylene chain having a hydrophilic property is added, the affinity with water is improved, and the interfacial tension is low. Therefore, it is easy to move on the surface of the liquid film, which is preferable. Therefore, it is easy to move on the surface of the liquid film, which is preferable. In addition, even if thermal melting processing such as embossing is performed, the polyoxyalkylene-modified polysiloxane is easily left on the surface of the fiber, and the cracking effect of the liquid film is not easily reduced. In particular, the cracking effect of the liquid film on the embossed part where the liquid is easy to accumulate is sufficiently exhibited, so it is preferable. Examples of the polyoxyalkylene-modified polysiloxane include those represented by the following formulas [I] to [IV]. Furthermore, from the viewpoint of the cracking effect of the liquid film, it is preferable that the polyoxyalkylene-modified polysiloxane has a mass average molecular weight in the above range. [Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

Where R ³¹ Represents an alkyl group (preferably a carbon number of 1 to 20. For example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, Decyl). R ³² A single bond or an alkylene group (preferably having 1 to 20 carbon atoms. For example, a methylene group, an ethylene group, a propyl group, or a butyl group) is preferable, and the above-mentioned alkylene group is preferable. Plural R ³¹ Plural R ³² Each may be the same as or different from each other. M ¹¹ The group having a polyoxyalkylene group is preferably a polyoxyalkylene group. Examples of the polyoxyalkylene group include polyoxyethyl groups, polyoxypropyl groups, polyoxybutyl groups, or those obtained by copolymerizing the constituent monomers. m and n are each independently an integer of 1 or more. In addition, the symbols of the repeating units are determined separately in each of the formulae (I) to (IV), and do not necessarily represent the same integer, and may be different. The polyoxyalkylene-modified polysiloxane may have any one or both of a polyoxyethylene-modified group and a polyoxypropylene-modified group. In addition, in order to be insoluble in water and have a low interfacial tension, an alkyl group R in a polysiloxane chain is preferred. ³¹ Has a methyl group. There is no particular limitation on those having the modified group and the polysiloxane chain. For example, there are those described in paragraphs [0006] and [0012] of Japanese Patent Laid-Open No. 2002-161474. More specifically, polyoxyethylene (POE) polyoxypropylene (POP) modified polysiloxane, or polyoxyethylene (POE) modified polysiloxane, polyoxypropylene (POP) modified polysiloxane. Examples of the POE-modified polysiloxane include POE (3) -modified dimethylpolysiloxane with 3 moles of POE added. Examples of the POP-modified polysiloxane include POP (10) -modified dimethylpolysiloxane and POP (12) -modified dimethicone added with 10 mol, 12 mol, or 24 mol POP. Polysiloxane, POP (24) modified dimethylpolysiloxane, etc. Regarding the spreading coefficient and water solubility of the first embodiment described above, in the case of polyoxyalkylene modified polysiloxane, for example, based on the addition mole number of polyoxyalkylene (for polyoxyalkylene) The number of modified polysiloxanes (1 mol, polyoxyalkylene group, oxyalkylene group, number of bonds), the following modification ratio, and the like are set to specific ranges. In this liquid film cleaving agent, similar to surface tension and interfacial tension, they can be set to specific ranges, respectively. From the viewpoints described above, it is preferred that the addition mol number of the polyoxyalkylene group is 1 or more. If it is less than 1, for the liquid film cracking effect described above, since the interfacial tension becomes high and the spreading coefficient becomes small, the liquid film cracking effect becomes weak. From this viewpoint, the addition mole number is more preferably 3 or more, and still more preferably 5 or more. On the other hand, if the number of added moles is too high, it becomes hydrophilic and the water solubility becomes high. From this viewpoint, the addition mole number is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Regarding the modification rate of the modified polysiloxane, if it is too low, hydrophilicity is impaired. Therefore, it is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more. If it is too high, it will dissolve in water, so it is preferably 95% or less, more preferably 70% or less, and even more preferably 40% or less. In addition, the so-called modification rate of the modified polysiloxane is the number of repeating units of the modified siloxane bond in the modified polysiloxane, relative to the number of repeat units in the siloxane bond. The ratio of the total number of repeating units. For example, (n / m + n) × 100% in the above formulas [I] and [IV], (2 / m) × 100% in the formula [II], and (1 / m) × 100%. In addition, regarding the above-mentioned spreading coefficient and water solubility, in the case of polyoxyalkylene-modified polysiloxane, in addition to the above, they can be set to specific ranges by the following methods, respectively: and water-soluble Polyoxyethylene and water-insoluble polyoxypropyl and polyoxybutylene are used as modification groups; the molecular weight of the water-insoluble polysiloxane chain is changed; and in addition to polyoxyalkylene modified groups, As the modifying group, an amine group, an epoxy group, a carboxyl group, a hydroxyl group, a methanol group, and the like are introduced. The polyalkylene-modified polysiloxane that can be used as a liquid film cracking agent preferably contains 0.02% by mass or more and 5% by mass or less in terms of the content ratio (Oil Per Unit) with respect to the fiber mass. The content ratio (OPU) of the polyalkylene-modified polysiloxane is more preferably 1% by mass or less, and still more preferably 0.4% by mass or less. Thereby, the long-fiber nonwoven fabric becomes a person with a better touch. From the viewpoint of sufficiently exerting the cracking effect of the liquid film using the polyalkylene-modified polysiloxane, the content ratio (OPU) is more preferably 0.04% by mass or more, and still more preferably 0.1% by mass or more. The liquid film cleaving agent in the second embodiment is preferably a compound having at least one structure selected from the group consisting of the following structures Z, ZY, and YZY as described below. Structure Z means that> C (A)-(C: carbon atom), -C (A) ₂ -, -C (A) (B)-,> C (A) -C (R ³ ) ＜ 、 ＞ C (R ³ )-, -C (R ³ ) (R ⁴ )-, -C (R ³ ) ₂ -A hydrocarbon chain in which any one of the basic structures of C, C is repeated, or two or more of them are combined. Has a hydrogen atom at the end of structure Z, or is selected from -C (A) ₃ , -C (A) ₂ B, -C (A) (B) ₂ , -C (A) ₂ -C (R ³ ) ₃ , -C (R ³ ) ₂ A, -C (R ³ ) ₃ At least one base in the group. R above ³ Or R ⁴ Each independently represents a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 20. For example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethyl Hexyl, nonyl, decyl), alkoxy (preferably 1 to 20 carbons. For example, methoxy and ethoxy are preferred), aryl (preferably 6 to 20 carbons. For example, more Various substituents such as a phenyl group), a fluoroalkyl group, an aralkyl group, or a hydrocarbon group formed by combining these, or a fluorine atom are preferred. A and B each independently represent a substituent including an oxygen atom or a nitrogen atom such as a hydroxy group or a carboxylic acid group, an amine group, a sulfonylamino group, an imino group, or a phenol group. In structure Z ³ , R ⁴ When there are a plurality of, A, and B, they may be the same as or different from each other. In addition, the bond between the C (carbon atom) to be connected is usually a single bond, but may also include a double bond or a triple bond. The bond between C may also include an ether group, amidino group, an ester group, a carbonyl group, and a carbonate group. And so on. The number of bonds between one C and another C is one to four, so there may be a case where a long-chain hydrocarbon chain is branched or has a radial structure. Y represents a hydrophilic group having a hydrophilic property including an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. For example, it contains a hydroxyl group, a carboxylic acid group, an amine group, an amido group, an imine group, and a phenol group; or a polyoxyalkylene group (the carbon number of the oxyalkylene group is preferably 1 to 4. For example, polyoxyalkylene is preferred Ethyl, polyoxypropyl, polyoxybutyl, or a combination of polyoxyalkylene); or erythritol, xylitol, sorbitol, glyceryl Hydrophilic groups having a plurality of hydroxyl groups, such as ethylene glycol groups, or sulfonic acid groups, sulfate groups, phosphate groups, sulfobetaines, carbonyl betaines, phosphinobetaines, quaternary ammonium groups, and imidazolium beets A hydrophilic group such as a base, an epoxy group, a methanol group, a methacrylic group alone; or a combination of such hydrophilic groups. When Y is plural, they may be the same as or different from each other. In the structures ZY and YZY, Y is a group bonded to Z or the terminal end of Z. In the case where Y is bonded to a base at the end of Z, the base at the end of Z is removed, for example, by the same number of hydrogen atoms as the number of bonds to Y, and is bonded to Y. In this structure, the hydrophilic groups Y, A, and B are selected from the bases that have been specifically described so as to satisfy the above-mentioned spreading coefficient, water solubility, and interfacial tension. This shows the target liquid film cracking effect. The liquid film cleaving agent described above is preferably a compound obtained by arbitrarily combining the structures represented by the following formulae (12) to (25) as specific examples of the structures Z, ZY, and YZY. Furthermore, from the viewpoint of the cracking effect of the liquid film, it is preferable that the compound has a mass average molecular weight in the above range. [Chemical 6]

In formulas (12) to (25), M ² , L ² , R ⁴¹ , R ⁴² , And R ⁴³ Represents the following monovalent or polyvalent bases (divalent or higher). M ² Represents a group having polyoxyethylene, polyoxypropyl, polyoxybutyl, or a combination of polyoxyalkylene; or erythritol, xylitol, and sorbose Hydrophilic groups having a plurality of hydroxyl groups, such as alcohol groups, glyceryl groups, or ethylene glycol groups, hydroxyl groups, carboxylic acid groups, mercapto groups, alkoxy groups (preferably having 1 to 20 carbon atoms. For example, methoxy groups are preferred), amines Group, amido, imino, phenol, sulfonic, quaternary ammonium, sulfobetaine, hydroxysulfobetaine, phosphinobetaine, imidazolium betaine, carbonylbetaine Group, epoxy group, methanol group, (meth) acrylic group, or a functional group obtained by combining them. L ² Ether group, amine group, amido group, ester group, carbonyl group, carbonate group, or polyoxyethylene, polyoxypropyl, polyoxybutyl, or a combination of polyoxyethylene Alkyl and other bonding groups. R ⁴¹ , R ⁴² , And R ⁴³ Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2- Ethylhexyl, nonyl, decyl), alkoxy (preferably having 1 to 20 carbons. For example, methoxy and ethoxy are preferred), aryl (preferably 6 to 20 carbons. For example It is preferably a phenyl group), a fluoroalkyl group, an aralkyl group, or a hydrocarbon group formed by combining them, or various substituents of a halogen atom (for example, a fluorine atom is preferred). In R ⁴² In the case of a multivalent base, R ⁴² Represents a group obtained by removing one or more hydrogen atoms from each of the above substituents. In addition, other structures may be arbitrarily connected before the bonding described in each structure, and a hydrogen atom may be introduced. Further, as specific examples of the above-mentioned compounds, the following compounds may be mentioned, but they are not limited thereto. First, polyether compounds or non-ionic surfactants are mentioned. Specifically, polyoxyalkylene (POA) alkyl ether represented by any one of formula (V), or polyoxyalkylene diester having a mass average molecular weight of 1,000 or more represented by formula (VI) can be listed. Alcohol, stearyl alcohol polyether, behenyl alcohol polyether, PPG myristyl ether, PPG stearyl ether, PPG behenyl ether and the like. As the polyoxyalkylene alkyl ether, lauryl ether having a POP of 3 mol or more and 24 mol or less, more preferably 5 mol is preferred. As the polyether compound, polypropylene glycol (PPG) having a molar average molecular weight of 1,000 to 10,000, and preferably 3,000 to 17 mol or more and 180 mol or less, preferably about 50 mol is preferable. Wait. The measurement of the mass average molecular weight can be performed by the above-mentioned measurement method. The polyether compound or nonionic surfactant is preferably contained in an amount of 0.10% by mass to 5% by mass in terms of a content ratio (Oil Per Unit) with respect to the mass of the fiber. The content ratio (OPU) of the polyether compound or nonionic surfactant is more preferably 1% by mass or less, and still more preferably 0.4% by mass or less. With this, the non-woven fabric becomes a person with a better touch. From the viewpoint of sufficiently exerting the cracking effect of the liquid film using the polyether compound or the nonionic surfactant, the content ratio (OPU) is more preferably 0.15 mass% or more, and further preferably 0.2 mass% or more. [Chemical 7]

[Chemical 8]

Where L ^{twenty one} Ether group, amine group, amido group, ester group, carbonyl group, carbonate group, polyoxyethylene, polyoxypropyl, polyoxybutyl, or a combination of them Base is bonded to the base. R ⁵¹ Contains hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, decyl, methoxy, ethoxy, benzene Group, a fluoroalkyl group, an aralkyl group, or a hydrocarbon group formed by combining them, or various substituents of a fluorine atom. In addition, a, b, m, and n are each independently an integer of 1 or more. Here, C _m H _n For alkyl (n = 2m + 1), C _a H _b Represents alkylene (a = 2b). The number of carbon atoms and the number of hydrogen atoms are independently determined in each of the formulae (V) and (VI), and they do not necessarily represent the same integer or may be different. Hereinafter, m, m ', m'', n, n', and n '' of Formula (VII)-(XV) are the same. Furthermore,-(C _a H _b O) _m -"M" is an integer of 1 or more. The value of the repeating unit is determined independently in each of the formulas (V) and (VI), and does not necessarily represent the same integer or may be different. The distribution coefficient, surface tension, and water solubility of the second embodiment described above can be set to specific ranges in the case of a polyether compound or a nonionic surfactant, for example, according to the mole number of polyoxyalkylene. . From this viewpoint, the molar number of the polyoxyalkylene group is preferably 1 or more and 70 or less. By setting it to 1 or more, the above-mentioned liquid film cracking effect is fully exerted. From this viewpoint, the Mohr number is more preferably 5 or more, and even more preferably 7 or more. On the other hand, the addition mole number is preferably 70 or less, more preferably 60 or less, and even more preferably 50 or less. Thereby, the connection of the molecular chain is moderately weakened, and the diffusibility in the liquid film is excellent, so it is preferable. In addition, the above-mentioned spreading coefficient, surface tension, interfacial tension, and water solubility can be set to specific ranges in the case of polyether compounds or nonionic surfactants by using water-soluble polyoxygen in combination. Ethyl and water-insoluble polyoxypropylene and polyoxybutylene; change the chain length of the hydrocarbon chain; use a hydrocarbon chain with a branched chain; use a hydrocarbon chain with a double bond; use a hydrocarbon chain with a benzene ring or Naphthalene ring; or an appropriate combination of the above. Second, a hydrocarbon compound having 5 or more carbon atoms can be mentioned. From the viewpoint that the liquid is easier to expand on the surface of the liquid film, the number of carbon atoms is preferably 100 or less, and more preferably 50 or less. This hydrocarbon compound excludes polyorganosiloxane, and is not limited to a straight chain, and may be a branched chain, and the chain is not particularly limited to a saturated chain and an unsaturated chain. Moreover, it may have substituents, such as an ester and an ether, in the middle and a terminal. Among them, those which are liquid at normal temperature can be used alone. The hydrocarbon compound is preferably contained in an amount of 0.1% by mass to 5% by mass in terms of a content ratio (Oil Per Unit) with respect to the fiber mass. The content ratio (OPU) of the hydrocarbon compound is preferably 1% by mass or less, more preferably 0.99% by mass or less, and still more preferably 0.4% by mass or less. Thereby, the long-fiber nonwoven fabric becomes a person with a better touch. From the viewpoint of sufficiently exerting the liquid film cracking effect based on the hydrocarbon compound, the content ratio (OPU) is more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more. Examples of the hydrocarbon compound include oils and fats, such as natural oils and natural fats. Specific examples include coconut oil, camellia oil, castor oil, coconut oil, corn oil, olive oil, sunflower oil, tall oil, and mixtures thereof. In addition, octanoic acid, capric acid, oleic acid, lauric acid, palmitic acid, stearic acid, myristic acid, behenic acid, and mixtures thereof, and the like are represented by the fatty acid represented by formula (VII). [Chemical 9]

In the formula, m and n are each independently an integer of 1 or more. Here, C _m H _n Represents a hydrocarbon group of each of the above fatty acids. Examples of linear or branched, saturated or unsaturated, substituted or unsubstituted polyhydric alcohol fatty acid esters or mixtures of polyhydric alcohol fatty acid esters include the following: formula (VIII-I) or (VIII-II) Specific examples of the glycerol fatty acid ester or pentaerythritol fatty acid ester represented by) include glycerol tricaprylate, glycerol tripalmitate, and mixtures thereof. Furthermore, the mixture of glycerin fatty acid esters or pentaerythritol fatty acid esters typically includes several mono-, di-, and tri-esters. Preferred examples of the glycerin fatty acid ester include glycerol tricaprylate, a mixture of glycerol tricaprylate, and the like. In addition, from the viewpoint of reducing the interfacial tension and obtaining a higher spreading coefficient, a polyhydric alcohol fatty acid ester may be used in which polyoxyalkylene is introduced to such an extent that water insolubility can be maintained. [Chemical 10]

[Chemical 11]

In the formula, m, m ', m'', n, n', and n '' are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same as or different from each other. Here, C _m H _n , C _m 'H _n 'And C _m '' H _n '' Represents a hydrocarbon group of each of the above fatty acids. As an example of a fatty acid or fatty acid mixture in which a linear or branched, saturated or unsaturated fatty acid and a polyhydric alcohol having a plurality of hydroxyl groups form an ester, and a part of the hydroxyl groups remain without being esterified, as shown in formula (IX): A glycerin fatty acid ester, a sorbitan fatty acid ester, or a partial esterification of a pentaerythritol fatty acid ester represented by any one, any one of formula (X), or any one of formula (XI). Specific examples include ethylene glycol monomyristate, ethylene glycol dimyristate, ethylene glycol palmitate, ethylene glycol dipalmitate, glycerol dimyristate, and glycerol dipalmitate. Esters, glycerol monooleate, sorbitan monooleate, sorbitan monostearate, sorbitan dioleate, sorbitan tristearate, pentaerythritol monostearate, pentaerythritol Dilaurate, pentaerythritol tristearate, and mixtures thereof. In addition, a mixture containing a partially esterified product of a glycerin fatty acid ester, a sorbitan fatty acid ester, a pentaerythritol fatty acid ester, and the like typically contains several fully esterified compounds. [Chemical 12]

In the formula, m and n are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same as or different from each other. Here, C _m H _n Represents a hydrocarbon group of each of the above fatty acids. [Chemical 13]

Where R ⁵² A straight or branched, saturated or unsaturated hydrocarbon group (alkyl, alkenyl, alkynyl, etc.) having 2 or more and 22 or less carbon atoms. Specific examples include 2-ethylhexyl, lauryl, myristyl, palmyl, stearyl, behenyl, oleyl, and linoleyl. [Chemical 14]

In the formula, m and n are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same as or different from each other. Here, C _m H _n Represents a hydrocarbon group of each of the above fatty acids. Further examples include sterols, phytosterols, and sterol derivatives. Specific examples include cholesterol, sitosterol, stigmasterol, ergosterol, and mixtures thereof having a sterol structure of formula (XII). [Chemical 15]

Specific examples of the alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cetylstearyl alcohol, behenyl alcohol, and a mixture thereof, as represented by formula (XIII). [Chemical 16]

In the formula, m and n are each independently an integer of 1 or more. Here, C _m H _n Represents a hydrocarbon group of each of the above alcohols. Specific examples of the fatty acid ester include isopropyl myristate, isopropyl palmitate, cetyl ethylhexanoate, glyceryl triisocaprylate, and octyl myristate as represented by formula (XIV). Dodecyl ester, ethylhexyl palmitate, ethylhexyl stearate, butyl stearate, myristyl myristate, stearyl stearate, cholesterol based stearate, and the like And so on. [Chemical 17]

In the formula, m and n are each independently an integer of 1 or more. Here, two C's _m H _n It can be the same or different. C _m H _n -COO- 之 C _m H _n Represents a hydrocarbon group of each of the above fatty acids. -COOC _m H _n C _m H _n Represents a hydrocarbon group derived from an ester-forming alcohol. Specific examples of the wax include terrestrial wax, paraffin wax, petrolatum, mineral oil, and fluid isomerized paraffin represented by the formula (XV). [Chemical 18]

In the formula, m and n are each independently an integer of 1 or more. The spreading coefficient, surface tension, water solubility, and interfacial tension of the second embodiment described above can be set to specific ranges in the case of the above-mentioned hydrocarbon compound having 5 or more carbon atoms, for example, in a small amount, such as a small amount. Introduction of hydrophilic polyoxyethylene to the extent that it can maintain water insolubility; introduction of polyoxypropyl or polyoxybutyl, which can reduce the interfacial tension, although hydrophobic, and change the chain length of the hydrocarbon chain; Those using a hydrocarbon chain having a branched chain; those using a hydrocarbon chain having a double bond; those using a hydrocarbon chain having a benzene ring or a naphthalene ring. In the long-fiber nonwoven fabric of the present invention, in addition to the above-mentioned liquid film cleaving agent, other components may be contained as necessary. In addition, the liquid film cleaving agent of the first embodiment and the liquid film cleaving agent of the second embodiment may be used in combination of the two agents in addition to the respective modes. This point is also the same for the first compound and the second compound in the liquid film cleaving agent of the second embodiment. When identifying the liquid film cleaving agent or phosphate anionic surfactant contained in the long-fiber nonwoven fabric of the present invention, the above-mentioned liquid film (a liquid having a surface tension of 50 mN / m) can be used. Surface tension (γ _w ) And the like. When the component of the liquid film cleaving agent is a compound having a siloxane chain as a main chain or a hydrocarbon compound having 1 to 20 carbon atoms, the content ratio (OPU) of the liquid film cleaving agent to the fiber mass may be It is determined by dividing the content of the liquid film cleaving agent by the mass of the fiber based on the mass of the substance obtained by the above-mentioned analysis method. Next, the hydrophilicity in the long-fiber nonwoven fabric of the present invention will be described in more detail. The hydrophilicity is the hydrophilicity of the constituent fibers, and the contact angle of the deionized water with respect to the constituent fibers can be used as an index to judge. The contact angle is the angle between the fibrous water droplets and the fiber surface, and the decrease in hydrophilicity has the same meaning as the increase in contact angle. This contact angle can be obtained by the following measurement method. When the long-fiber nonwoven fabric of the present invention has a hydrophilicity gradient in a thickness direction from a first surface side to a liquid-receiving surface side (skin contact surface side) to a second surface side (non-skin contact surface side), The contact angle (V1) of the fiber on the first surface side is preferably 80 ° or more, more preferably 85 ° or more, and even more preferably 90 ° or more from the viewpoint of reducing the amount of liquid adhered to the skin. The contact angle (V1) is preferably 100 ° or less, more preferably 97 ° or less, and even more preferably 95 ° or less from the viewpoint of preventing liquid flow on the surface. On the other hand, the contact angle (V2) of the fibers on the second surface side (non-skin contact surface side) is preferably 90 ° or less, more preferably 85, from the viewpoint of improving the suction property of the liquid. ° or less, and more preferably 80 ° or less. The contact angle (V2) is preferably 30 ° or more, and more preferably 40 ° or more, from the viewpoint of improving the liquid transferability to the absorbent body when it is placed on the absorbent body as a front sheet. , And more preferably 50 ° or more. Furthermore, regarding the difference (V1-V2) between the contact angle (V1) of the fiber on the first surface side and the contact angle (V2) of the fiber on the second surface side (non-skin contact surface side), the liquid direction is increased. From the viewpoint of the permeability in the thickness direction, it is preferably 3 ° or more, more preferably 5 °, and even more preferably 10 °. The difference between the contact angles (V1-V2) described above is preferably 5 ° or more, more preferably 7 °, and even more preferably 10 in terms of considering both the permeability of the liquid in the thickness direction and the difficulty of liquid return. °. (Measurement method of contact angle) The above-mentioned measurement of the contact angle can be performed by the following method. That is, the fiber is taken out from a specific part of the long-fiber nonwoven fabric, and the contact angle of water with respect to the fiber is measured. An automatic contact angle meter MCA-J manufactured by Kyowa Interface Science Co., Ltd. was used as a measuring device. For the measurement of the contact angle, distilled water was used. The measurement was performed under the conditions of a temperature of 25 ° C and a relative humidity (RH) of 65%. The amount of liquid ejected from the inkjet-type water droplet ejection section (pulse ejector CTC-25, manufactured by Cluster Technology, with an orifice diameter of 25 μm) was set to 20 picoliters, and water droplets were dripped directly above the fiber. Record the dropping situation in a high-speed recording device connected to a horizontally set camera. As for the recording device, from the viewpoint of subsequent image analysis, a personal computer equipped with a high-speed capture device is preferable. In this measurement, images were recorded every 17 msec. In the recorded video, the initial image when water droplets are dropped onto the fibers taken from the laminated nonwoven fabric is using the attached software FAMAS (set: the software version is 2.6.2, the analysis method is the droplet method, and the analysis method is θ / 2 method, the image processing algorithm is non-reflection, the image processing image mode is frame, the threshold level is 200, and no curvature correction is performed.) The image analysis is performed to calculate the surface of the water droplet in contact with the air and the fiber. And the contact angle. The fiber taken out from the laminated non-woven fabric was cut to a fiber length of 1 mm, and the fiber was placed on a sample table of a contact angle meter and maintained horizontally. For each of these fibers, the contact angles at two different locations were measured. Measure the contact angle of N = 5 roots to one digit below the decimal point, and define the value obtained by averaging the measured values of 10 locations in total (rounded to the second digit below the decimal point) as the contact angle. As the hydrophilizing agent imparting the contact angle as described above, a user of such an article can be used without particular limitation. Specific examples include anionic, cationic, amphoteric, and nonionic surfactants, and carboxylate anionic surfactants, sulfonate anionic surfactants, and sulfate salts can be used. Anionic surfactants, anionic surfactants of the phosphate type (especially alkyl phosphate salts) and other anionic surfactants; sorbitan fatty acid esters, diethylene glycol monostearate, diethylene glycol Polyol mono-fatty acid esters such as monooleate, glyceryl monostearate, glycerol monooleate, propylene glycol monostearate, fatty acids such as ammonium oleate, ammonium stearate, and erucamide Amine, N- (3-oleyloxy-2-hydroxypropyl) diethanolamine, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol beeswax, polyoxyethylene sorbitan sesquistearate, poly Oxyethylene monooleate, polyoxyethylene sorbitan sesquistearate, polyoxyethylene glycerol monooleate, polyoxyethylene monostearate, polyoxyethylene monolaurate, polyoxyethylene mono Nonionics such as oleate, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether Surfactants; Cationic surfactants such as quaternary ammonium salts, amine salts, or amines; aliphatic derivatives of secondary or tertiary amines containing carboxyl, sulfonate, and sulfate groups, or heterocyclic secondary Ampholytic surfactants such as aliphatic derivatives of amines or tertiary amines. The combination of these preferred surfactants and preferred surfactants may include such surfactants, and may further include other surfactants. It should be noted that the phosphate ester type anionic surfactant herein is actually the same agent as the phosphate ester type anionic surfactants that can be included together with the above-mentioned liquid film cleaving agent. That is, the phosphate ester type anionic surfactant has two functions, that is, the function of imparting hydrophilicity and the function of improving the affinity with the phospholipids contained in blood or urine to promote the function of a liquid film cleavage agent. Next, the manufacturing method of the long-fiber nonwoven fabric of this invention is demonstrated. First, the manufacturing method of the base long-fiber non-woven fabric may be a method used for such an article without any particular limitation. For example, spunbond non-woven fabrics are manufactured by the following steps: (1) the step of melt-spinning the raw resin and gathering the long fibers on the conveyor; (2) performing heat embossing (using Embossing a convex roller and a flat roller, etc.) to produce a thermal fusion section. In addition, the thermal fusion portion may be formed by various methods such as a method of performing ultrasonic fusion in addition to thermal embossing, or intermittently applying hot air to perform local fusion. In this manufacturing step, as the method containing the above-mentioned liquid film cleaving agent or the liquid film cleaving agent and an anionic surfactant of the phosphate type, or the above-mentioned hydrophilizing agent, there may be mentioned: (A) coating on a non-woven fabric The following method is a method of long-fiber non-woven fabric, (B) a method of coating the fiber surface before the non-woven fabric, and (C) a method of adding the resin to be a raw material of the fiber. In this case, the coating may be performed in the form of a fiber treating agent. The fiber treating agent is a mixture of the above-mentioned liquid film cleaving agent or the liquid film cleaving agent and a phosphate ester type anionic surfactant with the above-mentioned hydrophilic agent. It can also be obtained by diluting, respectively, respectively, and coating it as a different fiber treatment agent. Examples of the coating method of the fiber treatment agent include coating by spraying, coating by a slit coater, coating by a gravure method, a flexo method, and a dipping method. The liquid film cleaving agent, or the liquid film cleaving agent and the phosphate ester type anionic surfactant can be contained in the fiber in any step. For example, in the step (B) or (C) above, a liquid film cleaving agent, or a liquid film cleaving agent, and a phosphoric acid-type anionic surfactant can be prepared in a spinning oil agent for fibers usually used in the spinning of fibers. It can also be coated with the mixture; it can also be coated after the non-woven fabric of (A) above; it can also be formulated with a liquid film cracking agent, or a liquid film cracking agent and a phosphoric acid type in the finishing oil for the fiber before and after the fiber is stretched. A mixture of anionic surfactants is applied. In addition, a liquid film cleaving agent or a phosphate-type anionic surfactant can be blended in a fiber treatment agent usually used in the manufacture of nonwoven fabrics, and then applied to the fibers, or the nonwoven fabric can be coated. On the other hand, in order to impart a hydrophilicity gradient to the long-fiber nonwoven fabric, it is necessary to separately apply at least two different types of hydrophilizing agents. In the case where the method (A) contains a hydrophilizing agent, the long-fiber nonwoven fabric tends to be thinner than the non-woven fabric using other short fibers as a raw material. Therefore, the hydrophilizing agent tends to bleed out and it is difficult to separate the coating. Moreover, when the method of (B) or (C) is used to contain a hydrophilizing agent, since the continuous spinning from the long fibers to the non-woven fabric using thermal fusion is continuously performed in the same production line, it is also difficult to Before the non-woven fabric, each fiber is coated with a different hydrophilizing agent, or it is difficult to laminate the fibers containing different hydrophilizing agents to each other before the non-woven fabric. Therefore, the following method can be adopted: a plurality of raw material long-fiber nonwoven fabrics containing different hydrophilizing agents are laminated on each other to form a long-fiber nonwoven fabric of the present invention including a plurality of layers. That is, a method of forming a long-fiber nonwoven fabric having a plurality of layers as shown in FIG. 1 (C) is mentioned. In addition, even if it is a single layer, a method may be adopted in which the hydrophilicity is changed in the thickness direction by using the hydrophilicizing agent used in combination with the heat generated by the hot air treatment. Alternatively, even if it is a single layer, in the long-fiber nonwoven fabric 20 shown in FIG. 1 (B), the hydrophilicity of the erect fibers 4 becomes lower than that of the fiber assembly layer by the elongation process used to form the erect fibers 4. The hydrophilicity of the fiber of 3. As a result, the hydrophilicity of the erect fibers 4 on the first surface 5 side is lower than the hydrophilicity of the fibers of the fiber assembly layer 3 on the second surface 6 side. In the thickness direction, there is a layer direction of the erect fibers 4. The two-stage hydrophilicity gradient of the fiber assembly layer 3 rises. The reason is that when the raw long-fiber nonwoven fabric coated with a hydrophilizing agent is subjected to the following fluffing processing, the long fibers that become the standing fibers 4 are stretched and broken than the fibers of the fiber assembly layer 3. It is considered that the reason is that as the fiber is stretched, the hydrophilizing agent will also follow it. With this, the concentration of the hydrophilizing agent in the part where the fiber is stretched becomes thin. On the other hand, when the followability of the hydrophilizing agent to the extended fiber is low, it is considered that a part of the hydrophilizing agent is broken due to the extension of the fiber, and a part where the oil agent exists and a part where the oil agent does not exist are generated on the fiber. Without generating a gradient of hydrophilicity (wetting on a heterogeneous surface depends on the area ratio of each hydrophilizing agent component). (Raising processing) FIGS. 4 (A) to (D) show the production of the long fibers of FIG. 1 (B) by forming the standing fibers 4 with free ends 42 from the long-fiber nonwoven fabric 200 coated with a hydrophilizing agent. Non-woven 20 method. Specifically, it may be a manufacturing method including only the fluffing processing shown in FIG. 4 (C), or it may include performing the partial extension processing (pre-processing) and drawing shown in FIG. 4 (A) and (B) in order. The manufacturing method of the two-stage raising process shown in 4 (C). In order to obtain a long-fiber non-woven fabric with good skin feel and softness, a two-stage raising process is preferred. In the two-stage raising process, the partial extension process shown in FIG. 4 (A) and (B) is performed. Specifically, the raw long-fiber nonwoven fabric 200 coated with the hydrophilizing agent is pressed against the raw long-fiber nonwoven fabric 200 by the irregularities of the concave-convex rollers 74 and 75 being engaged with each other. Thereby, a plurality of portions of the raw long-fiber nonwoven fabric 200 are partially stretched and damaged. Next, in the fracture processing shown in FIG. 4 (C), the raw long-fiber nonwoven fabric 200 that has been partially stretched is conveyed by the conveying rollers 76 and 76, and an angle with respect to the raising roller 77 is imparted. The raising roller 77 has a raised portion 79 for raising. By the rolling of the fluffing roller 77, a part of the long fibers on the surface of one side of the raw long-fiber nonwoven fabric 200 that has undergone the partial stretching process is broken and fluffed to become the standing fibers 4. In the raising process described above, the erect fibers 4 are stretched more than the fibers constituting the non-fluffed matrix portion, that is, the fiber assembly layer 3. By extending in the manner described above, the hydrophilicity of the erect fibers 4 becomes lower than that of the fibers constituting the fiber assembly layer 3. In addition, the raising roller 77 may roll in either the reverse direction or the forward direction with respect to the conveying direction of the raw long-fiber nonwoven fabric 200 that has been partially stretched, but from the viewpoint of efficiently forming the erect fibers 4 In other words, it is preferable to scroll in the opposite direction. In the long-fiber nonwoven fabric 20, the number of fluffed fibers is preferably 8 / cm or more, and more preferably 12 / cm or more, more preferably 15 pieces / cm or more. The raised fibers here include the erect fibers 4 and the endless fibers having the free ends 42. From the viewpoint of ensuring sufficient breaking strength, the number is preferably 100 pieces / cm or less, and from the viewpoint of preventing fluff from being invisible on the appearance, it is more preferably 40 pieces / cm or less, and even more preferably 30. Root / cm or less. The fluffed fibers were measured by the following measurement method. In the present case, the "long-fiber non-woven fabric having fluffed fibers" refers to a long-fiber non-woven fabric having 5 fluffed fibers / cm or more in the measurement method described below. (Measurement method of the number of fluffed fibers) Figures 5 (A) to (C) show a method of measuring the number of fluffed fibers among the fibers constituting the long-fiber nonwoven fabric 20 at 22 ° C and 65% RH. Pattern illustration. First, a sharp razor was used to cut a 20 cm × 20 cm measurement piece from the long-fiber non-woven fabric 20 for measurement, as shown in FIG. 5 (A), and the raised surface of the measurement piece was convexly folded to form a measurement sample 104. . Next, the measurement sample 104 was placed on a black backing paper of A4 size, as shown in FIG. 5 (B), and then a black backing of A4 size with holes 107 of length 1 cm × width 1 cm was placed on it. paper. At this time, as shown in FIG. 5 (B), the crease 105 of the measurement sample 104 is arranged so as to be visible from the hole 107 of the black backing paper on the upper side. For the double-sided paper, "KENRAN (black) continuous weight 265 g" was used by Fuji Kyowa Paper Co., Ltd. Thereafter, 50 g weights were placed on the two sides of the hole 107 on the backing paper, which were separated from the outer side by 5 cm along the crease 105, to make the measurement sample 104 completely folded. Next, as shown in FIG. 5 (C), using a microscope (VHX-900 manufactured by KEYENCE Co., Ltd.), the inside of the hole 107 of the backing paper was observed at a magnification of 30 times, and the area above the virtual line 108 was measured For each 1 cm of fiber number, the imaginary line 108 is formed at a position where the measurement sample 104 moves 0.2 mm in parallel from the crease 105 upward. The measurement was performed on 9 parts, and the average value (rounded to the second decimal place) was set as the number of fluffed fibers. When the number of fluffed fibers is counted, for example, in the case where there are fibers 106a shown in FIG. 5 (C), the fibers cross the imaginary line 108 twice 0.2 mm from the crease 105 upward. The fiber count is two. Specifically, in the example shown in FIG. 5 (C), four fibers cross the imaginary line 108 once, and one fiber 106a crosses the imaginary line 108 twice, but crosses twice. The number of fibers 106a was 2 and the number of fluffed fibers was 6. From the viewpoint of improving the skin feel when in contact with the skin, the long-fiber non-woven fabric 20 is preferably a fluffed fiber (a fiber that crosses the imaginary thread 108. Here, as described above, the standing with the free end portion 42 is included The average fiber diameter of both the natural fiber 4 and the endless fiber is smaller than the surface fibers (fibers that do not cross the imaginary line 108 and do not reach the imaginary line 108) on the same side of the unfluffed portion, that is, the fibers that constitute the fiber assembly Fluffed fibers). The average fiber diameter refers to a fiber diameter obtained by measuring the fiber diameter of each of the fluffed fiber and the unfluffed fiber at 12 locations using a microscope (optical microscope, scanning electron microscope, or the like). The average fiber diameter of the fluffed fibers is preferably 98% or less and 40% or more of the average fiber diameter of the non-fluffed fibers. If the average fiber diameter is 96% or less and 70% or more, the skin feel is excellent, so it is more preferable. Similarly, the average fiber diameter of the erect fibers 4 and the endless fibers having the free ends 42 are preferably smaller than the average fiber diameter of the fibers (non-fluffed fibers) constituting the fiber assembly 3, and more preferably It is 98% or less and 40% or more of the fiber diameter of the non-fluffed fiber. If it is 96% or less and 70% or more, the skin feel is excellent, so it is better. Furthermore, it is preferable that the erect fibers 4 become thicker at the portion of the free end portion 42. As the shape of the thickened body, a flat shape (ellipse or collapsed shape) in cross section of the free end portion 42 is preferred. Thereby, the erect fibers 4 with a soft tip are obtained, and the long-fiber nonwoven fabric 20 with less irritation to the skin is obtained. Moreover, as for the long-fiber nonwoven fabric 20, it is preferable that the number of fluffed fibers (including the upright fiber 4 with the free end part 42 and the fiber of an endless fiber) is 8 pieces / cm or more and the fluffed fiber is as described above. The height is 1.5 mm or less. As a result, an absorbent article having improved cushioning properties and improved skin feel is obtained. From the standpoint of pilling resistance and hair removal resistance, it is more preferable that the raising height of the raised fibers is 1 mm or less. On the other hand, if it is 0.2 mm or more, a person with a good skin touch is obtained. Furthermore, it is preferable that the raising height is 0.5 mm or more from the viewpoint of reducing the amount of liquid return in the absorption characteristics of body fluids. When the raised surface is used on the side that comes in contact with the skin, the raised height is more preferably 1 mm or less in that it is not easy to adhere to the skin and has a better feel. In addition, the case where the number of fluffed fibers is 15 or more / cm is preferable in terms of obtaining improved cushioning properties and a faster absorption rate of body fluids. In addition, in order to prevent the appearance of fluffing, or to pilling or hair loss due to friction during use, the height of the fluffed fibers is preferably 5 mm or less. Here, the raising height is different from the length of the fiber, and means the height of the fiber in a natural state without stretching the fiber during measurement. If the length value of the fluffed fiber is large or the rigidity of the fiber is high, the fluff height of the fluffed fiber tends to be high. The fluffing height of the fluffed fiber was measured by the following measuring method. (Measurement method for raising height of fluffed fiber) The raising height of fluffed fiber is determined when the number of fluffed fibers (including the upright fiber 4 with a free end portion 42 and the endless fiber) is measured at the same time. Perform the measurement. Specifically, as shown in FIG. 5 (C), the inside of the hole 107 of the backing paper is observed, and the scribe line 105 is lined in parallel every 0.05 mm until the raised fibers no longer intersect. Then, compared with the number of fluffed fibers measured based on the above method (determined based on the imaginary line 108 above 0.2 mm), the fiber that intersects the parallel line is selected to become a half parallel line, which will run from here to The crease distance is set to the raising height. With the above operations, 3 pieces of non-woven fabric to be measured are measured, and an average value of 3 pieces and a total of 9 pieces is taken as 3 pieces of each piece, and it is set as the raising height of the fluffed fiber. In addition to the raising height of the raised fibers and the number of raised fibers, in terms of obtaining softness when in contact with the skin and excellent skin feel, the overall flexibility of the long-fiber nonwoven 20 is preferably 8 cN the following. The overall flexibility of the long-fiber nonwoven fabric 20 is more preferably 0.5 cN or more and 3 cN or less in terms of being a soft person such as a baby or a toddler. The overall compliance is measured by the following measurement method. (Measurement method of overall flexibility) Regarding the overall flexibility of the long-fiber nonwoven fabric 20, cut out the long-fiber nonwoven fabric 20 in the MD direction by 150 mm, cut out 30 mm in the CD direction, and use a stapler to cut the end It is fixed at two positions above and below to form a ring with a diameter of 45 mm. At this time, the core of the stapler is made longer in the MD direction. Using a tensile testing machine (for example, a Tensilon tensile testing machine "RTA-100" manufactured by Orientec Co., Ltd.), the ring is erected on a sample table, and a flat plate substantially parallel to the sample table is used from above. Compression was performed at a compression speed of 10 mm / minute, and the maximum load at this time was measured, and the overall flexibility in the CD direction was set. Then, the MD direction and the CD direction were changed to make a ring, and the overall flexibility in the MD direction was measured in the same manner. Two loops were made for each of the MD direction and the CD direction, and measurements were performed. The average value of the CD direction and the MD direction was set as the overall flexibility of the long-fiber nonwoven fabric 20. Furthermore, the MD direction means the machine direction (MD: Machine Direction) in the manufacturing stage of the nonwoven fabric, and means the length direction in the manufactured nonwoven fabric. When the nonwoven fabric is made into a roll shape as a raw material sheet, or when it is rolled out from a roll-shaped state, it means the direction in which the nonwoven fabric is rolled out. On the other hand, the CD direction means a width direction (CD: Cross Direction) orthogonal to the machine carrying-out direction at the manufacturing stage of the nonwoven fabric, and means a width direction orthogonal to the above-mentioned longitudinal direction in the manufactured nonwoven fabric. In the state of the above-mentioned raw material sheet, it means the direction of the roll axis. Furthermore, when the non-woven fabric is cut to a specific size as the front sheet of the absorbent article, the MD direction is a direction consistent with the length direction of the absorbent article, and the CD direction is consistent with the width direction of the absorbent article. direction. The long-fiber non-woven fabric of the present invention has a higher liquid permeability regardless of the thickness of the fibers or the distance between the fibers. However, the long-fiber nonwoven fabric of the present invention is effective especially in the case of using thinner fibers. If a thinner fiber is used to make a long-fiber non-woven fabric with a softer touch on the skin, the distance between the fibers becomes smaller and the narrow area between the fibers becomes larger. On the other hand, even if the fineness in the long-fiber nonwoven fabric of the present invention is lower than before, the above-mentioned liquid film cracking agent will surely crack multiple liquid films and reduce liquid residue. As described below, the area ratio of the liquid film is the area ratio of the liquid film calculated from the image analysis of the surface of the long-fiber nonwoven fabric, and is closely related to the state of the liquid remaining on the outermost surface of the surface material. Therefore, if the area ratio of the liquid film is reduced, the liquid in the vicinity of the skin is removed, and the comfort after excretion is improved, thereby becoming an absorbent article with a good wearing feeling even after excretion. On the other hand, the remaining amount of liquid below means the amount of liquid held by the entire long-fiber nonwoven fabric. If the area ratio of the liquid film becomes smaller, the liquid that is cracked and unstable is increased. The liquid is drawn from the fiber layer with lower hydrophilicity in one direction to the fiber layer with higher hydrophilicity due to the gradient of hydrophilicity. As a result, liquid residue is reduced. In addition, the whiteness of the surface tends to increase the whiteness due to a decrease in the amount of liquid remaining due to the rupture of the liquid film on the surface, and it becomes easy to visually become white. The long-fiber non-woven fabric containing a liquid film cracking agent of the present invention can reduce the liquid film area ratio and the amount of liquid residue and whiten the surface even if the fiber is thinned. Therefore, it is possible to achieve a high level of dryness and thinner fibers Gives a soft skin feel. In addition, by using the long-fiber nonwoven fabric of the present invention as a constituent member such as a surface material of an absorbent article, it is possible to provide an absorbent article having a high dryness feeling due to a part in contact with the skin and a visual development Pollution caused by body fluids is not easy to be noticeable, so it realizes comfort with good peace of mind and wearability. Regarding such a long-fiber nonwoven fabric containing a liquid film cleaving agent and having a hydrophilic gradient, from the viewpoint of improving the softness of the skin, the distance between the fibers of the long-fiber nonwoven fabric is preferably 300 μm or less, more preferably 250 μm or less. In addition, the lower limit is preferably 30 μm or more, and more preferably 50 μm or more, from the viewpoint of suppressing the liquid permeability from being impaired because the fibers become too narrow. Specifically, it is preferably 30 μm or more and 300 μm or less, and more preferably 50 μm or more and 250 μm or less. In this case, the fineness of the fiber is preferably 3.3 dtex or less, and more preferably 2.4 dtex or less. The lower limit is preferably 0.5 dtex or more, and more preferably 0.7 dtex or more. Specifically, it is preferably 0.5 dtex or more and 3.3 dtex or less, and more preferably 0.7 dtex or more and 2.4 dtex or less. (Measuring method of the inter-fiber distance) The inter-fiber distance is measured by measuring the thickness of the long-fiber nonwoven fabric to be measured in the following manner, and calculating it by inserting the following formula (2). First, a long-fiber nonwoven fabric to be measured is cut into a length of 50 mm × a width of 50 mm to produce a cut piece of the long-fiber nonwoven. When a non-woven fabric to be measured is incorporated into an absorbent article such as a physiological article or a disposable diaper, and the like, when a cut sheet of this size is not obtained, the cut sheet is cut to the maximum size obtained to produce a cut sheet. The thickness of the dicing sheet was measured under a pressure of 49 Pa. The measurement environment temperature was 20 ± 2 ° C and the relative humidity was 65 ± 5%. The measurement equipment was a microscope (manufactured by KEYENCE Corporation, VHX-1000). First, an enlarged photograph of the cross section of the long-fiber nonwoven fabric is obtained. Known sizes are displayed in the enlarged photo. The enlarged photo of the cross section of the nonwoven fabric was measured against a scale to measure the thickness of the long-fiber nonwoven fabric. The above operation was performed 3 times, and the average value of 3 times was set to the thickness [mm] of the long-fiber nonwoven fabric in a dry state. In the case of a laminated product, the thickness is calculated by discriminating the boundary based on the fiber diameter. Next, the inter-fiber distance of the fibers constituting the long-fiber non-woven fabric to be measured was determined by the following equation based on Wrotnowski's assumption. The formula based on Wrotnowski's assumption is usually used when determining the inter-fiber distance of the fibers constituting the non-woven fabric. According to the assumption based on Wrotnowski's assumption, the inter-fiber distance A (μm) is based on the thickness h (mm) of the long-fiber nonwoven fabric and the basis weight (weight per unit area) e (g / m). ² ), Fiber diameter d (μm), fiber density ρ (g / cm) ³ ), And it is calculated | required by the following formula (2). When there are irregularities, the thickness h (mm) of the long-fiber nonwoven fabric of the convex portion is used as a representative value to calculate. The fiber diameter d (μm) was measured using a scanning electron microscope (DSC6200 manufactured by Seiko Instruments Co., Ltd.), and the fiber cross sections of 10 cut fibers were measured, and the average value was defined as the fiber diameter. Fiber density ρ (g / cm ³ ) Is measured using a density gradient tube according to the density gradient tube method described in JIS L1015 chemical fiber staple fiber test method. Basis weight e (g / m ² ) Is to cut the long-fiber non-woven fabric of the measurement object into a specific size (0.12 m × 0.06 m, etc.), and after measuring the mass, use "mass ÷ area obtained from a specific size = basis weight (g / m ² ) "To calculate the basis weight. [Number 1]

(Method for measuring the fineness of constituent fibers) The cross-sectional area of the fiber is measured by measuring the cross-sectional shape of the fiber with an electron microscope or the like (if the fiber is formed of a plurality of resins, the cross-sectional area of each resin component). DSC (differential scanning calorimetry) specifies the type of resin (in the case of multiple resins, the approximate composition ratio is also specified), calculates the specific gravity, and calculates the fineness. For example, if it is a short fiber consisting only of PET (polyethylene terephthalate), the cross-section is first observed and the cross-sectional area is calculated. Then, it measured by DSC, and it was identified from the melting point or the peak shape to consist of a single-component resin, and it was a PET core. Thereafter, the density and cross-sectional area of the PET resin were used to calculate the fiber mass, thereby calculating the fineness. The fibers constituting the long-fiber non-woven fabric of the present invention mainly contain heat-fusible fibers, and such articles can be used without any particular restrictions by ordinary users. Examples of the heat-fusible fibers include polyolefin resins, polyester resins, polyamide resins, acrylonitrile resins, vinyl resins, and vinylidene resins. Examples of the polyolefin-based resin include polyethylene, polypropylene, and polybutene. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and the like. Examples of the polyamide-based resin include nylon and the like. Examples of the vinyl-based resin include polyvinyl chloride. Examples of the vinylidene resin include polyvinylidene chloride. One of these various resins may be used singly or in combination of two or more, and modified products of these various resins may also be used. Moreover, a composite fiber may be used as a long fiber. As the composite fiber, side by side fiber, core-sheath fiber, eccentric core-sheath fiber having crimp, split fiber, and the like can be used. In the case of using a composite fiber, it is preferable to obtain a soft long-fiber nonwoven fabric by using a core-sheath fiber having a core including polypropylene and a sheath including polyethylene. As for the fiber diameter of the long fiber, before the following processing, it is preferably 5 μm or more and 30 μm or less, and more preferably 10 μm or more and 20 μm or less. From the viewpoint of spinnability, it is preferably formed of a polypropylene resin as a polyolefin resin. As the polypropylene resin, it is preferable to include any one or more of a random copolymer, a homopolymer, and a block copolymer from the viewpoint of improving the feeling of the skin when it comes in contact with the skin while being lubricated and the ease of breaking. 5 mass% or more and 100 mass% or less, more preferably 25 mass% or more and 80 mass% or less of the resin. In addition, these copolymers or homopolymers can be mixed, and other resins can also be mixed. However, in terms of being difficult to break when molding, homopolymers and random copolymers of polypropylene are preferred. Of blending. As a result, the crystallinity of the fibers is reduced, and the fluffed fibers themselves become soft, and the skin feels good when they come into contact with the skin, and can take into account the strength of the non-woven fabric. Cut off. Therefore, peeling obtained at the heat fusion portion 3 such as the embossed fusion point does not occur, and the fluffed fibers become shorter, which is difficult to pilling, and the appearance is also good. In addition, since the distribution of the melting points is widened, the sealability is improved. It is more preferable that the propylene component is used as a matrix and copolymerized with ethylene or an α-olefin as a random copolymer, and particularly preferred is an ethylene-propylene copolymer resin. From the same viewpoint, the polypropylene resin is preferably a resin containing 5 mass% or more of an ethylene propylene copolymer resin, and more preferably a resin containing 25 mass% or more of an ethylene propylene copolymer resin. In the ethylene-propylene copolymer resin, it is preferable to include one having an ethylene concentration of 1% by mass or more and 20% by mass or less, especially in terms of no stickiness, easy extension during elongation, less hair loss, and maintaining break strength, More preferably, the ethylene concentration is 3% or more and 8% or less. In addition, as the polypropylene resin, in terms of environment, a resin containing 50% by mass or more of a recycled polypropylene resin is preferred, and a resin containing 70% by mass or more of a recycled polypropylene resin is more preferred. The same applies to the case where a nonwoven fabric is formed based on a plurality of layers of long-fiber nonwoven fabrics of a spunbond layer and a meltblown layer. The basis weight (weight per unit area) of the long-fiber nonwoven fabric of the present invention is preferably 10 g / m ² Above 80g / m ² Below, especially 15 g / m ² Above 60 g / m ² the following. Furthermore, when the long-fiber nonwoven fabric of the present invention includes a plurality of layers, it is preferable that the total basis weight (weight per unit area) of each of the constituent layers is within the above-mentioned preferred numerical range. Since the long-fiber nonwoven fabric of the present invention has a hydrophilicity gradient and contains a liquid film cleaving agent or a phosphate ester type anionic surfactant therein, the long-fiber nonwoven fabric is excellent in various fiber structures, and has excellent liquid residue and liquid repellency suppression. Therefore, even if the long-fiber nonwoven fabric is dripped with a large amount of liquid, the liquid permeation path between the fibers is always ensured, and the liquid permeability is excellent. Thereby, various functions can be imparted to the long-fiber nonwoven fabric without being limited by the problems of the distance between the fibers and the formation of the liquid film. For example, a plurality of layers may be used. In addition, the shape of the long-fiber nonwoven fabric may be flat, or unevenness may be provided on one side or both sides, and various changes may be made to the basis weight or density of the fiber. Furthermore, the range of options for combination with an absorber has also expanded. When a plurality of layers are included, the liquid film cleaving agent may be contained in all the layers, or may be contained in a part of the layers. It is preferably contained in at least the layer directly receiving the liquid. For example, when the long-fiber nonwoven fabric of the present invention is used as a front sheet of an absorbent article, it is preferable to include a liquid film cleaving agent in at least the layer on the skin-contacting surface side. The long-fiber non-woven fabric of the present invention is preferably present locally in the vicinity of at least a portion of the fiber entanglement point or near the fiber fusion point. The "local presence" of the liquid film cleaving agent here is not a state where the liquid film cleaving agent is uniformly attached to the entire surface of the fibers constituting the long-fiber nonwoven fabric, but refers to a state where the liquid film is more than the surface of each fiber. The cleavage agent tends to adhere near the fiber entanglement point or the fiber fusion point. Specifically, it can be defined as: the concentration of the liquid film cleaving agent near the entanglement point or the fusion point is higher than the fiber surface (the fiber surface between the entanglement points or the fusion point). At this time, the liquid film cracking agent existing near the fiber entanglement point or the fiber fusion point may also be attached in such a manner that the space between the fibers is partially covered with the fiber entanglement point or the fiber fusion point as the center. The thicker the liquid film cracking agent near the intersection or fusion point, the better the concentration. The concentration varies depending on the type of liquid film cracking agent used, the type of fiber used, and the effective ingredient ratio when mixed with other agents, so it cannot be determined uniformly, but the above-mentioned liquid film is used. From the viewpoint of cracking effect, it can be appropriately determined. Because the liquid film cracking agent exists locally, it becomes easier to show the liquid film cracking effect. That is, the position where the liquid film is particularly prone to occur near the fiber entanglement point or the fiber fusion point. Therefore, by allowing more liquid film cleaving agents to exist at this position, it becomes easy to directly act on the liquid film. As mentioned above, the local existence of the liquid film cracking agent is preferably generated at a position near the fiber intersection point or the fiber fusion point of the entire long-fiber non-woven fabric, and more preferably at 40% or more, and more preferably at 50% or more. More than% produced. In long-fiber non-woven fabrics, when the distance between the fiber entanglement point or the fiber fusion point is relatively short, the space between the fibers is small and a liquid film is particularly prone to occur. Therefore, if the liquid film cracking agent is selectively present locally near the fiber entanglement point or the fiber fusion point when the space between the fibers is small, it is particularly effective to exhibit the liquid film cracking effect, which is preferable. In addition, in the case where it is selectively present locally as described above, the liquid film cleaving agent is preferably made to increase the coverage ratio to a relatively small inter-fiber space and to increase the coverage ratio to a relatively large inter-fiber space. Get smaller. Thereby, while maintaining the liquid permeability in the long-fiber nonwoven fabric, the cracking effect of the portion where the liquid film is easily generated due to the large capillary force can be effectively exhibited, so that the effect of reducing the liquid residue in the entire long-fiber nonwoven fabric becomes higher. The "relatively small inter-fiber space" herein refers to an inter-fiber space having an inter-fiber distance of 1/2 or less with respect to the inter-fiber distance obtained by the above-mentioned (method for measuring the inter-fiber distance). (Confirmation method of local existence state of liquid film cleaving agent) The above-mentioned local existence state of liquid film cleaving agent can be confirmed by the following method. First, a long-fiber non-woven fabric was cut into 5 mm × 5 mm and mounted on a sample stand using a carbon ribbon. The sample stage was placed in a scanning electron microscope (S4300SE / N, manufactured by Hitachi, Ltd.) without vapor deposition, and set to a low vacuum or vacuum state. Because the ring-shaped reflection electron detector (accessory) is used for detection, the larger the atomic order is, the easier it is to emit reflected electrons. Therefore, it is coated with polyethylene (PE) or polypropylene (PP) that contains more atomic orders than the main constituent. The part of the liquid film cracking agent of carbon atom or hydrogen atom or oxygen atom or silicon atom of polyester (PET) appears whitish, so the state of local existence can be confirmed by whitishness. Moreover, as for the whiteness, the larger the atomic order or the larger the amount of adhesion, the more the whiteness is increased. In the method for producing a long-fiber non-woven fabric of the present invention, when a liquid film cleaving agent is applied after the non-woven fabric is formed as described above, a method of immersing a raw material non-woven fabric in a solution containing the liquid film cleaving agent can be cited. Examples of the solution include a solution obtained by diluting a liquid film cracking agent with a solvent (hereinafter, this solution is also referred to as a liquid film cracking agent solution). Examples of the solvent for dilution include alcohols such as ethanol. Moreover, as another method, the method of coating a raw material nonwoven fabric with a separate component of a liquid film cleaving agent, or the solution containing the said liquid film cleaving agent is mentioned. Furthermore, a phosphate ester type anionic surfactant may be mixed in a solution containing the liquid film cleaving agent. In this case, the content ratio of the liquid film cleaving agent to the phosphate ester type anionic surfactant is preferably as described above. As the above-mentioned solvent, a liquid film cleaving agent having a very small water solubility can be used without any particular limitation, or it can be moderately dissolved or dispersed in a solvent and emulsified so as to be easily applied to a non-woven fabric. For example, as a dissolving agent for a liquid film, an organic solvent such as ethanol, methanol, acetone, or hexane can be used, or when an emulsion is prepared, of course, water can be used as a solvent or a dispersion medium for emulsification. Examples of the emulsifier to be used include various surfactants including alkyl phosphate, fatty ammonium, alkyl betaine, sodium alkyl sulfosuccinate, and the like. In addition, the raw material nonwoven fabric refers to the former method of applying a liquid film cleaving agent, and as the production method thereof, a production method generally used as described above can be used without particular limitation. As a method for coating the above-mentioned raw material non-woven fabric, a method that can be used for the non-woven fabric can be employed without particular limitation. Examples include coating by spraying, coating by a slit coater, coating by a gravure method, a flexo method, and a dipping method. From the viewpoint of localization of the liquid film cleaving agent near the fiber entanglement point or the fiber fusion point described above, it is preferably a non-woven raw material coated with a non-woven material, more preferably a non-impregnated raw material coated with a non-woven material. method. In the coating method, a coating method using a flexographic method is particularly preferred from the viewpoint of making the local presence of the liquid film cracking agent more apparent. Moreover, as a raw material nonwoven fabric, various nonwoven fabrics can be used without a restriction | limiting in particular. In particular, from the viewpoint of maintaining the localized existence of the liquid film cracking agent, it is preferable that the fiber intersection points are thermally fused or thermally bonded together, and it is more preferable to use the above-mentioned hot air treatment or thermal embossing to separate the fibers with each other. The obtained non-woven fabric was heat-bonded. When the liquid film cleaving agent is attached to the fibers, it is preferably used in the form of a fiber treatment agent containing the liquid film cleaving agent. The "fiber treatment agent" described here refers to the use of water and a surfactant to emulsify an oily liquid film cracking agent with very little water solubility, etc., to make it easy to coat the raw nonwoven fabric or fibers. Status of processing. In the fiber treatment agent for coating a liquid film cleaving agent, the content ratio of the liquid film cleaving agent is preferably 50% by mass or less based on the mass of the fiber treatment agent. Thereby, the fiber treatment agent can be in a state where the liquid film cleaving agent which becomes an oily component has been stably emulsified in a solvent. From the viewpoint of stable emulsification, the content ratio of the liquid film cracking agent is more preferably 40% by mass or less, and more preferably 30% by mass or less with respect to the mass of the fiber treating agent. In addition, from the viewpoint of achieving localized existence of the liquid film cleaving agent in the non-woven fabric described above, the liquid film cleaving agent moves on the fibers under a moderate viscosity after coating, and is preferably set to the above-mentioned content ratio. Regarding the content ratio of the liquid film cracking agent, from the viewpoint of exhibiting a sufficient liquid film cracking effect, it is preferably 5 mass% or more, more preferably 15 mass% or more, and more preferably relative to the mass of the fiber treatment agent. It is 25 mass% or more. Furthermore, the fiber treatment agent containing a liquid film cleaving agent may contain other agents within a range that does not inhibit the effect of the liquid film cleaving agent. For example, the above-mentioned phosphate anionic surfactant may be contained. In this case, the content ratio of the liquid film cleaving agent to the phosphate ester type anionic surfactant is preferably as described above. In addition, it may contain an antistatic agent or an anti-friction agent used in fiber processing, a hydrophilic agent that imparts moderate hydrophilicity to long-fiber nonwovens, and an emulsifier that imparts emulsion stability. The long-fiber nonwoven fabric of the present invention can be used in various fields by effectively utilizing its soft skin feel and reduction of liquid residue. For example, it can be preferably used as a front sheet, a second sheet (arranged on the front surface) in an absorbent article for absorption of liquid discharged from the body such as menstrual cotton, sanitary pads, disposable diapers, incontinence pads and the like. Sheet between the sheet and the absorbent body), back sheet, leak-proof sheet, wipe sheet for humans, sheet for skin care, and cloth for objective lenses. When the long-fiber nonwoven fabric of the present invention is used as a front sheet or a second sheet of an absorbent article, it is preferable to use the first-layer side of the long-fiber nonwoven fabric as the skin-facing surface side. The absorbent article used for the absorption of liquid discharged from the body is typically an absorbent body having a front sheet, a back sheet, and a liquid-retaining property interposed between the two sheets. As the absorbent body and the back sheet when the long-fiber nonwoven fabric of the present invention is used as the front sheet, materials generally used in these technical fields can be used without particular limitation. For example, as the absorbent body, a fiber aggregate containing a fibrous material such as pulp fiber or a covering sheet with a covering sheet such as toilet paper or nonwoven fabric, or an absorbent polymer held therein can be used. As the back sheet, a liquid-impermeable or water-repellent sheet such as a film of a thermoplastic resin or a laminate of the film and a nonwoven fabric can be used. The back sheet may have water vapor permeability. The absorbent article may further include various members corresponding to specific uses of the absorbent article. The aforementioned components are well known to the practitioner. For example, when an absorbent article is used in disposable diapers or menstrual tampons, one or two or more pairs of three-dimensional protection can be arranged on the left and right sides of the front sheet. Regarding the embodiment described above, the present invention further discloses the following long-fiber nonwoven fabric. <1> A long-fiber non-woven fabric containing a liquid film cleaving agent. <2> The long-fiber nonwoven fabric according to the above <1>, wherein the water solubility of the liquid film cleaving agent is 0 g or more and 0.025 g or less. <3> The long-fiber nonwoven fabric according to the above <2>, wherein the spreading coefficient of the liquid film cleaving agent to a liquid having a surface tension of 50 mN / m is 15 mN / m or more. <4> A long-fiber non-woven fabric containing a compound (C1) having a water solubility of 0 g to 0.025 g and a spreading coefficient of 15 mN / for a liquid having a surface tension of 50 mN / m m or more. <5> The long-fiber nonwoven fabric according to any one of the above <1> to <4>, wherein the compound (C1) or the liquid film cleaving agent has an interfacial tension of 20 mN for a liquid having a surface tension of 50 mN / m / m or less. <6> The long-fiber nonwoven fabric according to any one of the above <1> to <5>, wherein the compound (C1) or the liquid film cleaving agent has a structure selected from the group consisting of the following structures X, XY, and YXY A compound of at least one structure in the group. Structure X indicates that> C (A)-(C indicates a carbon atom. Also, <,>, and-indicate a bond. The same applies hereinafter), -C (A) ₂ -, -C (A) (B)-,> C (A) -C (R ¹ ) ＜ 、 ＞ C (R ¹ )-, -C (R ¹ ) (R ² )-, -C (R ¹ ) ₂ -,> C <and, -Si (R ¹ ) ₂ O-, -Si (R ¹ ) (R ² ) A siloxane chain having a basic structure in which any one of O- is repeated, or a combination of two or more types, or a mixed chain thereof. Has a hydrogen atom at the end of structure X, or is selected from -C (A) ₃ , -C (A) ₂ B, -C (A) (B) ₂ , -C (A) ₂ -C (R ¹ ) ₃ , -C (R ¹ ) ₂ A, -C (R ¹ ) ₃ , And -OSi (R ¹ ) ₃ , -OSi (R ¹ ) ₂ (R ² ), -Si (R ¹ ) ₃ , -Si (R ¹ ) ₂ (R ² ) At least one base in the group. R above ¹ Or R ² Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a halogen atom. A and B each independently represent a substituent containing an oxygen atom or a nitrogen atom. Within structure X ¹ , R ² When there are a plurality of, A, and B, they may be the same as or different from each other. Y represents a hydrophilic group having a hydrophilic property including an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. When Y is plural, they may be the same as or different from each other. <7> The long-fiber nonwoven fabric according to any one of the above <1> to <6>, in which the compound (C1) or the liquid film cleaving agent contains a polysiloxane-based organically modified polysiloxane, And as the organic modified polysiloxane, it is selected from the group consisting of amine-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, glycol-modified polysiloxane, and methanol-modified polysiloxane. (Meth) acrylic-based modified polysiloxane, mercapto-modified polysiloxane, phenol-modified polysiloxane, polyether-modified polysiloxane, methylstyrene-modified polysiloxane, long-chain alkyl At least one of the group consisting of modified polysiloxane, higher fatty acid ester modified polysiloxane, higher alkoxy modified polysiloxane, higher fatty acid modified polysiloxane, and fluorine-modified polysiloxane. <8> The long-fiber nonwoven fabric according to any one of the above <1> to <7>, wherein the compound (C1) or the liquid film cleaving agent contains polyoxyalkylene-modified polysiloxane, and the polyoxygen The alkylene-modified polysiloxane is at least one selected from the group consisting of compounds represented by the following formulas [I] to [IV]. [Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical 22]

Where R ³¹ Represents an alkyl group (preferably a carbon number of 1 to 20. For example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, Decyl). R ³² A single bond or an alkylene group (preferably having 1 to 20 carbon atoms. For example, a methylene group, an ethylene group, a propyl group, or a butyl group) is preferable, and the above-mentioned alkylene group is preferable. Plural R ³¹ Plural R ³² Each may be the same as or different from each other. M ¹¹ The group having a polyoxyalkylene group is preferably a polyoxyalkylene group. Examples of the polyoxyalkylene group include polyoxyethyl groups, polyoxypropyl groups, polyoxybutyl groups, or those obtained by copolymerizing the constituent monomers. m and n are each independently an integer of 1 or more. In addition, the symbols of the repeating units are determined separately in each of the formulas [I] to [IV], and do not necessarily represent the same integers, and may be different. <9> The long-fiber non-woven fabric according to the above <2>, wherein the liquid film cracking agent has a spreading coefficient of greater than 0 mN / m for a liquid having a surface tension of 50 mN / m, and a liquid having a surface tension of 50 mN / m The interfacial tension is 20 mN / m or less. <10> A long-fiber non-woven fabric containing a compound (C2) having a water solubility of 0 g to 0.025 g and a spreading coefficient for a liquid having a surface tension of 50 mN / m greater than 0 mN / m, the interfacial tension for liquids with a surface tension of 50 mN / m is 20 mN / m or less. <11> The long-fiber nonwoven fabric according to any one of the above <1>, <2>, <9>, and <10>, wherein the compound (C2) or the liquid film cleaving agent contains a compound selected from the group consisting of Compounds of at least one structure in the group consisting of structures Z, ZY, and YZY. Structure Z means that> C (A)-(C: carbon atom), -C (A) ₂ -, -C (A) (B)-,> C (A) -C (R ³ ) ＜ 、 ＞ C (R ³ )-, -C (R ³ ) (R ⁴ )-, -C (R ³ ) ₂ -A hydrocarbon chain in which any one of the basic structures of C, C is repeated, or two or more of them are combined. Has a hydrogen atom at the end of structure Z, or is selected from -C (A) ₃ , -C (A) ₂ B, -C (A) (B) ₂ , -C (A) ₂ -C (R ³ ) ₃ , -C (R ³ ) ₂ A, -C (R ³ ) ₃ At least one base in the group. R above ³ Or R ⁴ Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group, an aralkyl group, or a hydrocarbon group or a fluorine atom in which these are combined. A and B each independently represent a substituent containing an oxygen atom or a nitrogen atom. In structure Z ³ , R ⁴ When there are a plurality of, A, and B, they may be the same as or different from each other. Y represents a hydrophilic group having a hydrophilic property including an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. In a plurality of cases, Y may be the same as or different from each other. <12> The long-fiber nonwoven fabric according to any one of the above <1>, <2>, and <9> to <11>, wherein the compound (C2) or the liquid film cleaving agent is selected from the group consisting of the following formula [V ], A polyoxyalkylene (POA) alkyl ether represented by any one of the following, and a polyoxyalkylene glycol having a mass average molecular weight of 1,000 or more represented by the following formula [VI], stearyl alcohol polyether, At least one compound in the group consisting of behenyl alcohol polyether, PPG myristyl ether, PPG stearyl ether, and PPG behenyl ether. [Chemical 23]

[Chemical 24]

Where L ^{twenty one} Ether group, amine group, amido group, ester group, carbonyl group, carbonate group, polyoxyethylene, polyoxypropyl, polyoxybutyl, or a combination of them Base is bonded to the base. R ⁵¹ Contains hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, decyl, methoxy, ethoxy, benzene Group, a fluoroalkyl group, an aralkyl group, or a hydrocarbon group formed by combining them, or various substituents of a fluorine atom. In addition, a, b, m, and n are each independently an integer of 1 or more. Here, C _m H _n For alkyl (n = 2m + 1), C _a H _b Represents alkylene (a = 2b). The number of carbon atoms and the number of hydrogen atoms are independently determined in each of the formulas [V] and [VI], and they do not necessarily represent the same integers or may be different. Furthermore,-(C _a H _b O) _m -"M" is an integer of 1 or more. The value of the repeating unit is determined independently in each of the formulas [V] and [VI], and does not necessarily represent the same integer or may be different. <13> The long-fiber nonwoven fabric according to any one of the above <1>, <2>, and <9> to <12>, wherein the compound (C2) or the liquid film cleaving agent contains a member selected from the following formula [VII Fatty acid represented by], glycerol fatty acid ester and pentaerythritol fatty acid ester represented by the following formula [VIII-I] or [VIII-II], any one of the following formula [IX], and the following formula [X] Any one of them, or a partial esterified product of a glycerin fatty acid ester, a sorbitan fatty acid ester, and a pentaerythritol fatty acid ester represented by any one of the following formula [XI], having a solid formula of the following formula [XII] At least one selected from the group consisting of a compound having an alcohol structure, an alcohol represented by the following formula [XIII], a fatty acid ester represented by the following formula [XIV], and a wax represented by the following formula [XV]. [Chemical 25]

In Formula [VII], m and n are each independently an integer of 1 or more. Here, C _m H _n Represents a hydrocarbon group of each of the above fatty acids. [Chemical 26]

[Chemical 27]

In Formulas [VIII-I] and [VIII-II], m, m ', m'', n, n', and n '' are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same as or different from each other. Here, C _m H _n , C _m 'H _n 'And C _m '' H _n '' Represents a hydrocarbon group of each of the above fatty acids. [Chemical 28]

In Formula [IX], m and n are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same as or different from each other. Here, C _m H _n Represents a hydrocarbon group of each of the above fatty acids. [Chemical 29]

In formula [X], R ⁵² A straight or branched, saturated or unsaturated hydrocarbon group (alkyl, alkenyl, alkynyl, etc.) having 2 or more and 22 or less carbon atoms. Specific examples include 2-ethylhexyl, lauryl, myristyl, palmyl, stearyl, behenyl, oleyl, and linoleyl. [Chemical 30]

In Formula [XI], m and n are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same as or different from each other. Here, C _m H _n Represents a hydrocarbon group of each of the above fatty acids. [Chemical 31]

[Chemical 32]

In Formula [XIII], m and n are each independently an integer of 1 or more. Here, C _m H _n Represents a hydrocarbon group of each of the above alcohols. [Chemical 33]

In Formula [XIV], m and n are each independently an integer of 1 or more. Here, 2 C _m H _n It can be the same or different. C _m H _n -COO- 之 C _m H _n Represents a hydrocarbon group of each of the above fatty acids. -COOC _m H _n C _m H _n Represents a hydrocarbon group derived from an ester-forming alcohol. [Chem 34]

In the formula [XV], m and n are each independently an integer of 1 or more. <14> The long-fiber nonwoven fabric according to any one of the above <1> to <13>, wherein the water solubility of the compound (C1), the compound (C2), or the liquid film cleaving agent is preferably 0.0025 g or less, More preferably 0.0017 g or less, still more preferably 0.0001 g or less, and more than 0 g, more preferably 1.0 × 10 ^-9 g or more. <15> The long-fiber nonwoven fabric according to any one of the above <1> to <14>, wherein the compound or the liquid film cleaving agent is partially near the fiber intersection point or the fiber fusion point of at least a part of the long-fiber nonwoven fabric. presence. <16> The long-fiber nonwoven fabric according to any one of the above <1> to <15>, which includes a heat-fusible fiber, has a first surface and a second surface located on the opposite side of the first surface, and the first The hydrophilicity of the fibers on one side is lower than that of the fibers on the second side. <17> The long-fiber nonwoven fabric according to any one of the above <1> to <16>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface located on the opposite side of the first surface. Surface, and has a fiber assembly layer that intermittently fixes long fibers by a thermal fusion section. <18> The long-fiber nonwoven fabric according to any one of the above-mentioned <1> to <17>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface located on the opposite side of the first surface. Surface, and the long fiber length of the long-fiber non-woven fabric is 30 mm or more, and the preferred fiber length is 150 mm or more. <19> The long-fiber nonwoven fabric according to any one of the above <1> to <18>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber, and has a first surface and a second surface located on the opposite side of the first surface. Surface, and the contact angle (V1) of the fibers on the first surface side is preferably 80 ° or more, more preferably 85 ° or more, even more preferably 90 ° or more, and preferably 100 ° or less, and more preferably 97 ° or less, and more preferably 95 ° or less. <20> The long-fiber nonwoven fabric according to any one of the above-mentioned <1> to <19>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface on the opposite side of the first surface. Surface, and the contact angle (V2) of the fibers on the second surface side is preferably 90 ° or less, more preferably 85 ° or less, even more preferably 80 ° or less, and more preferably 30 ° or more, more preferably 40 ° or more, and more preferably 50 or more. <21> The long-fiber nonwoven fabric according to any one of the above <1> to <20>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface on the opposite side of the first surface. Surface, and the difference (V1-V2) between the contact angle (V1) of the fiber on the first surface side and the contact angle (V2) of the fiber on the second surface side (non-skin contact surface side) is preferably 3 ° The above is more preferably 5 ° or more, even more preferably 7 °, and even more preferably 10 °. <22> The long-fiber nonwoven fabric according to any one of the above-mentioned <1> to <21>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface on the opposite side of the first surface. Noodles, and contains a hydrophilizing agent. <23> The long-fiber nonwoven fabric according to any one of the above <1> to <22>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface on the opposite side of the first surface. Surface, and contains at least one selected from the group consisting of anionic, cationic, amphoteric, and nonionic surfactants. <24> The long-fiber non-woven fabric according to any one of the above <1> to <23>, wherein the long-fiber non-woven fabric includes a single layer, and contains heat-fusible fibers, and has a first surface and a surface on the first surface. The second surface on the opposite side, and the hydrophilicity of the fibers on the first surface side is lower than the hydrophilicity of the fibers on the second surface side, and has a gradient of hydrophilicity. <25> The long-fiber nonwoven fabric according to any one of the above-mentioned <1> to <24>, wherein the long-fiber nonwoven fabric contains a heat-fusible fiber and has a first surface and a second surface on the opposite side of the first surface. Surface, and the fiber on the first surface side is an erect fiber having a base portion fixed to the fiber collection layer and a free end portion not fixed to the fiber collection layer. <26> The long-fiber non-woven fabric according to the above <25>, which has a hydrophilicity gradient of at least two stages in which the hydrophilicity of the standing fibers is lower than that of the fibers of the fiber assembly layer. <27> The long-fiber nonwoven fabric according to the above <26>, wherein the contact angle of the erect fibers is 75 ° or more, preferably 80 ° or more, more preferably 85 ° or more, and even more preferably 90 ° or more. <28> The long-fiber non-woven fabric according to any one of the above <1> to <23>, wherein the long-fiber non-woven fabric includes a plurality of layers, and contains heat-fusible fibers, and has a first surface and a surface on the first surface. The second surface on the opposite side has a difference in hydrophilicity between each of the plurality of layers and increases the hydrophilicity in stages. <29> A front sheet for an absorbent article, using a long-fiber nonwoven fabric as described in any one of <1> to <28> above. <30> An absorbent article using the long-fiber nonwoven fabric according to any one of the above <14> to <28> as a front sheet in which the first surface is arranged toward the skin-contacting surface side. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention should not be construed as being limited thereto. In addition, in this embodiment, as long as "part" and "%" are not specified in advance, they are all based on quality. The surface tension, water solubility, and interfacial tension of the liquid film cleaving agent in the following examples were performed by the above-mentioned measurement methods. (Example 1) As a raw long fiber nonwoven fabric, a spunbond-spunbond nonwoven fabric (SS nonwoven fabric) having two layers of a spunbond nonwoven fabric composed of long fibers containing a polypropylene homopolymer resin was produced. Both layers (the first non-woven layer and the second non-woven layer) have a fiber diameter of 16 μm and a basis weight of 10 g / m. ² . The first non-woven fabric layer and the second non-woven fabric layer were coated with the following liquid film cracking agent and hydrophilizing agent by the following coating method before lamination, and the heat of the embossing roller was used. The two layers were bonded and fixed by pressure bonding to prepare a long-fiber nonwoven fabric sample of Example 1. In this long-fiber nonwoven fabric sample, the two surfaces of the first nonwoven fabric layer are defined as the first surface side (a) and the second surface side (b), and the two surfaces of the second nonwoven fabric layer are specified as the first surface side (a ' ) And the second surface side (b '), as the entire long-fiber nonwoven fabric sample, the two surfaces of the laminated two layers are defined as the first surface 5 side (the first surface side of the first nonwoven fabric layer) (a) and the first Tests were performed on two sides and six sides (second side of the second nonwoven fabric layer) (b ') (hereinafter, the same applies to Examples 2 to 4, and Comparative Examples 1 and 2). <Liquid film cracking agent> As a liquid film cracking agent, X in the system structure XY contains -Si (CH ₃ ) ₂ O-dimethyl polysiloxane chain, Y contains-(C ₂ H ₄ O)-of the POE chain, the terminal group of the POE chain is methyl (CH ₃ ), The modification rate is 20%, the polyoxyethylene addition mole number is 3, and the mass average molecular weight is 4000 polyoxyethylene (POE) modified dimethylpolysiloxane (Shin-Etsu Chemical Industry Co., Ltd. KF-6015). Spreading factor for liquids with a surface tension of 50 mN / m: 28.8 mN / m Surface tension of 21.0 mN / m Interfacial tension for liquids with a surface tension of 50 mN / m: 0.2 mN / m Water solubility: less than 0.0001 g Further, these four numerical values are measured by the above-mentioned measurement method. At this time, the "liquid with a surface tension of 50 mN / m" was a solution using a micropipette (ACURA825, manufactured by Socorex Isba SA) in 100 g of deionized water to add a polymer as a non-ionic interface active substance. Oxyethylene sorbitan monolaurate (manufactured by Kao Corporation, trade name RHEODOL SUPER TW-L120) was 3.75 μL, and the surface tension was adjusted to 50 ± 1 mN / m (hereinafter, the same). The water solubility was measured by adding 0.0001 g of the agent each time. As a result, it was observed that even 0.0001 g was not dissolved, it was set to "below 0.0001 g", and it was observed that 0.0001 g was dissolved but 0.0002 g was not dissolved, it was set to "0.0001 g". Other values are also measured by the same method. <Coating method of liquid film cracking agent and hydrophilizing agent> Preparation of a diluent and a hydrophilizing agent prepared by dissolving the above polyoxyethylene (POE) modified dimethylpolysiloxane as a solute in an ethanol solution The solutions were mixed, and each of the nonwoven fabrics was immersed in the diluted solution, followed by drying. In the obtained long-fiber nonwoven fabric sample, the content ratio (OPU) of the liquid-film cracking agent of the first nonwoven fabric layer and the second nonwoven fabric layer to the fiber mass was 0.1% by mass. The contact angle of the fibers on the first surface side (a) and the second surface side (b) of the first nonwoven layer, and the first surface side (a ') and the second surface side (b') of the second nonwoven layer The contact angle of the fiber was measured by the above-mentioned method for measuring the contact angle, and is shown in Table 1 below. Therefore, the difference between the contact angle of the fibers on the first side 5 side (a) and the second side 6 side (b ') of the obtained long-fiber nonwoven fabric sample was 10 °, and the first side 5 sides (a) has a hydrophilicity lower than that of the second surface 6 side (b '), and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b'). (Example 2) In the same manner as in Example 1, except that the following agent was used as the liquid film cracking agent, and the contact angle in the first nonwoven fabric layer was set as shown in Table 1 below, Long fiber nonwoven fabric sample. <Liquid film cracking agent> As a liquid film cracking agent, X in the system structure XY contains -Si (CH ₃ ) ₂ O-dimethyl polysiloxane chain, Y contains-(C ₃ H ₆ O)-of POP chain, the terminal group of POP chain is methyl (CH ₃ ), The modification rate is 10%, the polyoxypropylene addition mol number is 10, and the mass average molecular weight is 4340 polyoxypropylene (POP) modified dimethylpolysiloxane (by making the polymer It is obtained by a hydroxylation reaction between a silicone oil and a hydrocarbon compound). Spreading factor for liquids with a surface tension of 50 mN / m: 26.9 mN / m Surface tension: 21.5 mN / m Interfacial tension for liquids with a surface tension of 50 mN / m: 1.6 mN / m Water solubility: 0.0002 g in In the obtained long-fiber nonwoven fabric sample, the content ratio (OPU) of the liquid-film cracking agent of the first nonwoven fabric layer and the second nonwoven fabric layer to the mass of the fibers was 0.1% by mass. The contact angle of the fibers on the first surface side (a) and the second surface side (b) of the first nonwoven layer, and the first surface side (a ') and the second surface side (b') of the second nonwoven layer The contact angle of the fiber was measured by the above-mentioned method for measuring the contact angle, and is shown in Table 1 below. Therefore, the difference between the contact angle of the fibers on the first side 5 side (a) and the second side 6 side (b ') of the obtained long-fiber nonwoven fabric sample was 11 °, and the first side 5 sides (a) has a hydrophilicity lower than that of the second surface 6 side (b '), and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b'). (Example 3) In the same manner as in Example 1, except that the following agent was used as a liquid film cracking agent, and the contact angle in the second nonwoven fabric layer was set as shown in Table 1 below, Long fiber nonwoven fabric sample. <Liquid film cracking agent> As a liquid film cracking agent, Z in the system structure ZY is * -O-CH (CH ₂ O- *) ₂ (* Indicates the bonding part), Y contains C ₈ H ₁₅ O- or C ₁₀ H ₁₉ O- hydrocarbon chain, fatty acid composition containing 82% caprylic acid, 18% capric acid, and a mass average molecular weight of 550 tricaprylic acid / capric acid glyceride (COCONAD MT manufactured by Kao Corporation). Spreading factor for liquids with a surface tension of 50 mN / m: 8.8 mN / m Surface tension: 28.9 mN / m Interfacial tension for liquids with a surface tension of 50 mN / m: 12.3 mN / m Water solubility: less than 0.0001 g In the obtained long-fiber nonwoven fabric sample, the content ratio (OPU) of the liquid-film cracking agent of the first nonwoven fabric layer and the second nonwoven fabric layer to the fiber mass was 0.5% by mass. The contact angle of the fibers on the first surface side (a) and the second surface side (b) of the first nonwoven layer, and the first surface side (a ') and the second surface side (b') of the second nonwoven layer The contact angle of the fibers was measured by the above-mentioned method for measuring the contact angle, and is shown in Table 1 below. Therefore, the difference between the contact angle of the fiber (a) on the first surface 5 side and the second surface 6 side (b ') as the entire long-fiber nonwoven fabric sample obtained was 9 °, and the first surface 5 sides (a) has a hydrophilicity lower than that of the second surface 6 side (b '), and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b'). (Example 4) In the same manner as in Example 1, except that the following agents were used as the liquid film cracking agent, and the contact angles in the first nonwoven fabric layer and the second nonwoven fabric layer were set as shown in Table 1 below. A long-fiber nonwoven fabric sample of Example 4 was prepared. <Liquid film cracking agent> As a liquid film cracking agent, Z in the system structure ZY contains -CH ₂ -Hydrocarbon chain, Y contains-(C ₃ H ₆ O)-, a POP alkyl ether having a polyoxypropylene addition mole number of 5 and a mass average molecular weight of 500 (defoamer No. 8 manufactured by Kao Corporation). Spreading factor for liquids with a surface tension of 50 mN / m: 13.7 mN / m Surface tension: 30.4 mN / m Interfacial tension for liquids with a surface tension of 50 mN / m: 5.9 mN / m Water solubility: less than 0.0001 g In the obtained long-fiber nonwoven fabric sample, the content ratio (OPU) of the liquid film cracking agent of the first nonwoven fabric layer and the second nonwoven fabric layer to the fiber mass was 5.0% by mass. The contact angle of the fibers on the first surface side (a) and the second surface side (b) of the first nonwoven layer, and the first surface side (a ') and the second surface side (b') of the second nonwoven layer The contact angle of the fibers was measured by the above-mentioned method for measuring the contact angle, and is shown in Table 1 below. Therefore, the difference between the contact angle of the fibers on the first side 5 side (a) and the second side 6 side (b ') of the obtained long-fiber nonwoven fabric sample was 9 °, and the first side 5 sides (a) has a hydrophilicity lower than that of the second surface 6 side (b '), and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b'). (Example 5) The weight per unit area was 20 g / m ² The first non-woven fabric layer was produced in the same manner as in Example 1 except that the contact angle was set as shown in Table 2 below, and this was made into a long-fiber non-woven fabric. Next, the above-mentioned raw long-fiber nonwoven fabric was subjected to a fluffing process as shown in FIG. 4 to form a standing fiber 4 having a free end portion 42 on the first surface side (a) of the first nonwoven fabric layer, thereby forming a standing fiber. 4 and the fiber assembly layer 3 of the long fiber nonwoven fabric sample of Example 5. Both sides of the entire long-fiber nonwoven fabric sample correspond to both sides of the first nonwoven fabric layer, and the test is defined as the first side 5 side (a) and the second side 6 side (b) (hereinafter, Examples 6 to 8) The same applies to Comparative Example 3). The number of fluffed fibers in this long-fiber nonwoven fabric sample was measured by the measurement method shown in FIG. 5 and was 18 fibers / cm. That is, the erect fibers 4 are formed on the first surface side (a) of the first nonwoven fabric layer. Among the obtained long-fiber nonwoven fabric samples, the fibers on the first side 5 side (a) (the standing fibers 4 with the free ends 42. The same applies to Examples 6 to 8, and Comparative Example 3) and the second surface 6 The contact angle of the fiber on the side (b) was measured by the above-mentioned method for measuring the contact angle, and is shown in Table 2 below. Therefore, the difference between the contact angle of the fibers on the first surface 5 side (a) and the second surface 6 side (b) of the obtained long-fiber nonwoven fabric sample was 10 °, and the first surface 5 side (a) The hydrophilicity is lower than that of the second surface 6 side (b), and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b). (Example 6) The weight per unit area was 20 g / m ² The first non-woven fabric layer was produced in the same manner as in Example 2 except that the contact angles shown in Table 2 below were used, and this was made into a long-fiber non-woven fabric. Next, the raw long-fiber nonwoven fabric was subjected to a fluffing treatment in the same manner as in Example 5 to prepare a long-fiber nonwoven fabric sample of Example 6. The number of standing fibers of this long-fiber nonwoven fabric sample was measured by the measurement method shown in FIG. 5 and was 17 fibers / cm. In the obtained long-fiber nonwoven fabric samples, the contact angles of the fibers on the first side 5 side (a) and the second side 6 side (b) were measured by the above-mentioned method for measuring the contact angle, and are shown in the following table. 2 shown. Therefore, the difference between the contact angle of the fibers on the first side 5 side (a) and the second side 6 side (b) of the obtained long-fiber nonwoven fabric sample was 12 °, and the first side 5 side (a) The hydrophilicity is lower than that of the second surface 6 side (b), and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b). (Example 7) The weight per unit area was 20 g / m ² The first non-woven fabric layer was produced in the same manner as in Example 3 except that the contact angle was set as shown in Table 2 below, and this was made into a long-fiber non-woven fabric. Next, about the raw long-fiber nonwoven fabric, a fuzzing treatment was performed in the same manner as in Example 5 to prepare a long-fiber nonwoven fabric sample of Example 7. The number of standing fibers in the long-fiber nonwoven fabric sample was measured by the measuring method shown in FIG. 5 and was 18 fibers / cm. In the obtained long-fiber nonwoven fabric samples, the contact angles of the fibers on the first side 5 side (a) and the second side 6 side (b) were measured by the above-mentioned method for measuring the contact angle, and are shown in the following table. 2 shown. Therefore, the difference between the contact angle of the fiber (a) on the first surface 5 side and the second surface 6 side (b) of the obtained long-fiber nonwoven fabric sample was 10 °, and the first surface 5 side (a) The hydrophilicity is lower than that on the second surface 6 side (b) side, and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b). (Example 8) The basis weight was set to 20 g / m ² The first nonwoven fabric layer was produced in the same manner as in Example 4 except that the contact angles shown in Table 2 below were used, and this was made into a long-fiber nonwoven fabric. Next, about the raw long-fiber nonwoven fabric, a fuzzing treatment was performed in the same manner as in Example 5 to prepare a long-fiber nonwoven fabric sample of Example 8. The number of standing fibers in the long-fiber nonwoven fabric sample was measured by the measuring method shown in FIG. 5 and was 18 fibers / cm. In the obtained long-fiber nonwoven fabric samples, the contact angles of the fibers on the first side 5 side (a) and the second side 6 side (b) were measured by the above-mentioned method for measuring the contact angle, and are shown in the following table. 2 shown. Therefore, the difference between the contact angle of the fiber (a) on the first side 5 side and the contact angle on the second side 6 side (b) of the obtained long-fiber nonwoven fabric sample was 11 °, and the first side 5 side (a) The hydrophilicity of the side is lower than the hydrophilicity of the second surface 6 side (b) side, and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b). (Comparative Example 1) A long-fiber nonwoven fabric sample of Comparative Example 1 was produced in the same manner as in Example 1 except that the liquid film cleaving agent and the hydrophilizing agent were not applied. The contact angle of the fibers on each side of the obtained long-fiber nonwoven fabric sample was measured by the above-mentioned method for measuring the contact angle, and as shown in Table 3 below, there was no difference in contact angle and no gradient in hydrophilicity. (Comparative Example 2) A long-fiber nonwoven fabric sample of Comparative Example 2 was produced in the same manner as in Example 1 except that the liquid film cleaving agent was not applied and the contact angle shown in Table 3 below was used. The contact angle of the fibers on each side of the obtained long-fiber nonwoven fabric sample was measured by the above-mentioned method for measuring the contact angle, and as shown in Table 3 below, there was no difference in contact angle and no gradient in hydrophilicity. (Comparative Example 3) A long-fiber nonwoven fabric sample of Comparative Example 3 was produced in the same manner as in Example 5 except that the liquid film cleaving agent was not applied and the contact angle shown in Table 3 below was used. The contact angle of the fibers on each side in the obtained long-fiber nonwoven fabric sample was measured by the above-mentioned method for measuring the contact angle, and is shown in Table 3 below. The difference between the contact angle of the fiber (a) on the first side 5 side and the contact angle on the second side 6 side (b) of the obtained long-fiber nonwoven fabric sample was 10 °, and the hydrophilicity of the first side 5 side (a) was hydrophilic. The degree of hydrophilicity is lower than that of the second surface 6 side (b) and has a hydrophilicity gradient from the first surface 5 side (a) to the second surface 6 side (b). (Evaluation test) The evaluation tests of the following "1. Liquid Residual Amount Test", "3. Liquid Return Test" and "4. Liquid Absorption Time Test" are disposable diapers which are examples of absorbent articles ( Kao Co., Ltd .: Merries (registered trademark) Merries pants L size, manufactured in 2014) Instead of the front sheet, each long fiber nonwoven fabric sample is laminated as the front sheet, and the periphery is fixed for evaluation. A disposable diaper was evaluated using this evaluation. In addition, for each test, disposable diapers for evaluation of Examples 1 to 8 and Comparative Examples 1 to 3 were produced. Regarding "2. Liquid flow length test", as described below, each sample was used as a front sheet, and a sample for evaluation was prepared separately. 1. Liquid Residue Test The waist creases and leg creases were removed from the disposable diapers used for each evaluation, and the front sheet was fixed upward on a horizontal surface in the unfolded state. In the non-pressurized state, a total amount of 160 g of artificial urine was injected into the front sheet at a position of 125 mm from the front end of the end portion of the cover sheet covering the absorbent body in the lengthwise direction on the ventral portion side. The artificial urinary system was infused with 40 g every 10 minutes, and was injected 4 times at an injection rate of 5 g / second. Ten minutes after the fourth injection, a front sheet was cut out on a square with a length of 100 mm centered on the artificial urine injection point, and the weight of the front sheet (W1) was measured. Next, the cut-out front sheet was dried, the weight (W2) of the front sheet after drying was measured, and the weight difference (W1-W2) before and after drying was calculated as the liquid residual amount. The above operation was performed 3 times, and the average value of 3 times was made into liquid residual amount (mg). The amount of liquid residue is an indicator of how wet the wearer's skin is. The smaller the amount of liquid residue, the better the result. In addition, the artificial urine system uses a composition of 1.94% by weight of urea, 0.795% by weight of sodium chloride, 0.11% by weight of magnesium sulfate, 0.062% by weight of calcium chloride, 0.197% by weight of potassium sulfate, 0.010% by weight of red No. 2 (dye), 96.88% by weight of water and polyoxyethylene lauryl ether (about 0.07%), and the surface tension was adjusted to 53 ± 1 dyne / cm (23 ° C). 2. Liquid flow length test The test device uses a mounting portion having a mounting surface with a test sample inclined at 45 ° with respect to the horizontal plane. Each sample was prepared as a front sheet, and the front sheet was overlapped with two folds of two toilet papers to prepare an absorbent sample. The test samples for each evaluation were placed with the front sheet facing upward. On the mounting portion. The colored deionized water as a test solution was dropped onto the test sample at a rate of 1 g / 10 sec. The distance from the point where the nonwoven fabric was initially wet to the point where the test solution was first absorbed by the absorbent was measured. The above operation was performed 3 times, and the average value of 3 times was made into liquid flow length (mm). The liquid flow length is an indicator of how much liquid flows on the surface without being absorbed by the test sample, and how easily it comes into contact with the skin when worn, and whether it becomes easy to leak. The shorter the liquid flow length, the higher the evaluation. 3. Liquid return test The waist folds and leg folds were removed from the disposable diapers used in the above evaluations, and the front sheet was fixed upward on a horizontal surface in the unfolded state. A cylindrical acrylic board with an injection port was placed on the front sheet, and then a 2 kg weight was placed on the acrylic board on the back side and the ventral side of the diaper to apply a load. The injection port provided on the acrylic plate is formed into a cylinder (height 53 mm) with an inner diameter of 36 mm. On the acrylic plate, an axis is formed at a position of 1/3 in the longitudinal direction and at the center of the width direction. A through-hole with an inner diameter of 36 mm, which coincides with the center of the cylindrical injection port and communicates between the inside of the cylindrical injection port and the facing surface of the acrylic sheet. The acrylic board was arranged so that the central axis of the cylindrical injection port of the acrylic board was located at a position 125 mm from the front end of the end portion of the cover sheet of the diaper in the longitudinal direction of the cover sheet. A total of 160 g of artificial urine. The artificial urinary system was infused with 40 g every 10 minutes and divided into 4 injections. Ten minutes after the fourth injection, the acrylic board was removed, and 16 pieces of filter paper (5C manufactured by Toyo Roshi Kaisha) were superimposed on a front sheet with a side length of 100 mm centered on the artificial urine injection point, and further on The load was applied for 2 minutes, and the artificial urine was absorbed by the filter paper. The load is 3.5 kg on an area of 100 mm × 100 mm. After 2 minutes, the load was removed, and the weight (W4) of the filter paper that absorbed the artificial urine was measured. The difference (W4-W3) from the weight (W3) of the filter paper before absorption that was previously measured was used as the liquid return amount. Figure it out. The above operation was performed three times, and the average value of the three times was set as the liquid return amount (g). The smaller the liquid return amount, the more difficult it is for liquid return to occur, and the evaluation becomes high. 4. Liquid absorption time test In the evaluation of the liquid return amount test described above, the time until 160 g is completely absorbed by the diaper is measured. The above operation was performed three times, and the average value of the three times was taken as the liquid absorption time (second). The shorter the liquid absorption time, the faster the passage of the liquid, and the higher the evaluation. [Table 1]

[Table 2]

[table 3]

As shown in the above Tables 1 to 3, all of the evaluation items of Examples 1 to 8 were superior to Comparative Examples 1 and 2 having no liquid film cracking agent, hydrophilicity gradient, and fluff fibers. Moreover, compared with the comparative example 3 which does not have a liquid film cleaving agent, Examples 1-8 all showed the favorable result that a liquid residual amount was small. In addition, Examples 1 to 8 showed good results with respect to the liquid flow amount, the liquid residual amount, and the liquid absorption time, which were equivalent to or higher than Comparative Example 3 having a hydrophilicity gradient and fluff fibers. The present invention has been described together with its embodiments and examples, but as long as the inventor has not specifically specified it, the present invention is not limited by any details of the description, and it should be considered that the invention should not depart from the scope of the attached patent application. Explain the spirit and scope of a broad range. This application claims priority based on Japanese Patent Application No. 2016-109599, filed in Japan on May 31, 2016, the contents of which are hereby incorporated by reference as part of the description of this specification. in.

1‧‧‧ long fiber
2‧‧‧Hot Fusion Department
3‧‧‧ fiber assembly layer
4‧‧‧ erect fiber
5‧‧‧Part 1
6‧‧‧ second side
7‧‧‧ liquid film
8‧‧‧Liquid film cracking agent
10, 20, 30‧‧‧ long fiber nonwoven
11‧‧‧Fiber of the first side
12‧‧‧ 2nd side fiber
31‧‧‧The first fiber layer
32‧‧‧ 2nd fiber layer
41‧‧‧base end
42‧‧‧ free end
74, 75‧‧‧ uneven roller
76‧‧‧ transport roller
77‧‧‧Fuzzing roller
79‧‧‧ protrusion
104‧‧‧Measurement sample
105‧‧‧ Crease
106a‧‧‧ fiber
107‧‧‧ Holes in stabilizer
108‧‧‧imaginary line
200‧‧‧ Raw Long Fiber Non-Woven

FIG. 1 is a schematic diagram showing a preferred specific example of the long-fiber nonwoven fabric of the present invention, (A) is a diagram showing a single-layer long-fiber nonwoven fabric, and (B) is a diagram showing another single-layer long-fiber nonwoven fabric, ( C) is a view showing a plurality of layers of long-fiber nonwoven fabrics. Fig. 2 is a schematic view showing a liquid film formed in a gap between fibers of a long-fiber nonwoven fabric. Fig. 3 (A1) to (A4) are explanatory views schematically showing the state of the liquid film cracking agent from the side to crack the liquid film, and (B1) to (B4) schematically show the liquid film cracking agent from the top to liquid state An illustration of a state where the film is cracked. Fig. 4 is an explanatory diagram showing the raising processing steps, (A) is a schematic diagram showing a partially extended processing step, and (B) is a partially enlarged representation of the meshing state of the concave-convex roller in one of the partially extended processing steps of (A) The cross-sectional view (C) is a schematic diagram showing a fracture processing step. Fig. 5 is an explanatory diagram schematically showing a method for measuring the number of fluffed fibers, (A) is a diagram showing a state after the long-fiber nonwoven is embossed, and (B) is a diagram showing the length of (A) (C) is a diagram illustrating a state in which a black non-woven paper with an opening is superimposed on the fiber non-woven fabric, and the opening of the black silk interleaving paper is shown in (B), and a method for measuring the fluffed fiber from the opening is shown.

no

Claims (12)

A long-fiber non-woven fabric containing a liquid film cracking agent. For example, the long-fiber non-woven fabric of claim 1, wherein the water solubility of the liquid film cleaving agent is 0 g or more and 0.025 g or less. For example, the long-fiber non-woven fabric of claim 2, wherein the spreading coefficient of the liquid film cleaving agent for a liquid having a surface tension of 50 mN / m is 15 mN / m or more. A long-fiber non-woven fabric containing a compound (C1) having a water solubility of 0 g to 0.025 g and a spreading coefficient of a liquid having a surface tension of 50 mN / m of 15 mN / m or more . The long-fiber nonwoven fabric according to any one of claims 1 to 4, wherein the interfacial tension of the compound (C1) or the liquid film cleaving agent for a liquid having a surface tension of 50 mN / m is 20 mN / m or less. The long-fiber nonwoven fabric according to any one of claims 1 to 4, wherein the compound (C1) or the liquid film cleaving agent includes at least one selected from the group consisting of the following structures X, XY, and YXY A compound of the structure, the structure X represents that> C (A)-(C represents a carbon atom; and <,> and-represent a bond; the same applies hereinafter), -C (A) _2- , -C (A) ( B)-,> C (A) -C (R ¹ ) <,> C (R ¹ )-, -C (R ¹ ) (R ² )-, -C (R ¹ ) ₂ -,> C <and Any one of -Si (R ¹ ) ₂ O-, -Si (R ¹ ) (R ² ) O- has a repeating basic structure, or a combination of two or more structures of a siloxane chain, or a mixed chain thereof; Has a hydrogen atom at the end of Structure X, or is selected from -C (A) ₃ , -C (A) ₂ B, -C (A) (B) ₂ , -C (A) ₂ -C (R ¹ ) ₃ , -C (R ¹ ) ₂ A, -C (R ¹ ) ₃ , and -OSi (R ¹ ) ₃ , -OSi (R ¹ ) ₂ (R ² ), -Si (R ¹ ) ₃ , -Si ( At least one group in the group consisting of R ¹ ) ₂ (R ² ); each of R ¹ or R ² above independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a halogen atom; A, B each independently represent an oxygen atom or a nitrogen atom comprising a substituent of; the inner structure ^{X R 1, R 2, A} , B each When there are a plurality of cases, they may be the same as or different from each other; Y represents a hydrophilic hydrophilic group having an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom; Y When there are a plurality of cases, they may be the same as or different from each other. For example, the long-fiber non-woven fabric of claim 2, wherein the spreading coefficient of the liquid film cleaving agent for a liquid with a surface tension of 50 mN / m is greater than 0 mN / m and the interfacial tension for a liquid with a surface tension of 50 mN / m is 20 mN / m or less. A long-fiber non-woven fabric containing a compound (C2) having a water solubility of 0 g to 0.025 g and a spreading coefficient for a liquid having a surface tension of 50 mN / m greater than 0 mN / m. The interfacial tension of a liquid with a surface tension of 50 mN / m is 20 mN / m or less. The long-fiber nonwoven fabric according to any one of 2, 7, and 8, wherein the compound (C2) or the liquid film cleaving agent includes at least one structure selected from the group consisting of the following structures Z, ZY, and YZY Compound, the structure Z means that> C (A)-(C: carbon atom), -C (A) _2- , -C (A) (B)-,> C (A) -C (R ³ ) <,> C (R ³ )-, -C (R ³ ) (R ⁴ )-, -C (R ³ ) ₂ -,> C <Any one of the basic structures is repeated, or a combination of two or more types Hydrocarbon chain; has a hydrogen atom at the end of structure Z, or is selected from -C (A) ₃ , -C (A) ₂ B, -C (A) (B) ₂ , -C (A) ₂ -C ( R ³ ) ₃ , -C (R ³ ) ₂ A, -C (R ³ ) ₃ , at least one type of group; each of the above R ³ or R ⁴ independently represents a hydrogen atom, an alkyl group, or an alkane An oxy group, an aryl group, a fluoroalkyl group, an aralkyl group, or a hydrocarbon group or a fluorine atom formed by combining them; A and B each independently represent a substituent including an oxygen atom or a nitrogen atom; R in the structure Z ³ , R ⁴ , A, and B may be the same or different from each other when there are a plurality of them; Y means that it is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, and phosphorogen. A hydrophilic group having a hydrophilic property as an atom of a proton or a sulfur atom; when Y is plural, they may be the same as or different from each other. The long-fiber non-woven fabric according to any one of claims 1 to 4, 7, and 8, which contains heat-fusible fibers, has a first surface and a second surface located on the opposite side of the first surface, and the first surface side The hydrophilicity of the fibers is lower than that of the fibers on the second surface side. The long-fiber non-woven fabric according to any one of claims 1 to 4, 7, and 8, which contains heat-fusible fibers, has a first surface and a second surface located on the opposite side of the first surface, and the first surface side The fibers are erect fibers having a base portion fixed to the fiber collection layer and a free end portion not fixed to the fiber collection layer. An absorbent article using a long-fiber nonwoven fabric as claimed in claim 10 or 11 as a front sheet in which the first surface is arranged toward the skin contact surface side.