WO2011004713A1 - Water permeability-imparting agent, water-permeable fiber to which the water permeability-imparting agent is applied, and method for producing nonwoven fabric - Google Patents

Water permeability-imparting agent, water-permeable fiber to which the water permeability-imparting agent is applied, and method for producing nonwoven fabric Download PDF

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Publication number
WO2011004713A1
WO2011004713A1 PCT/JP2010/060702 JP2010060702W WO2011004713A1 WO 2011004713 A1 WO2011004713 A1 WO 2011004713A1 JP 2010060702 W JP2010060702 W JP 2010060702W WO 2011004713 A1 WO2011004713 A1 WO 2011004713A1
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Prior art keywords
imparting agent
water permeability
water
acid
group
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PCT/JP2010/060702
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French (fr)
Japanese (ja)
Inventor
善治 藤本
正人 好岡
和喜 伊東
美幸 比嘉
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松本油脂製薬株式会社
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Priority to JP2010535140A priority Critical patent/JP4644318B1/en
Publication of WO2011004713A1 publication Critical patent/WO2011004713A1/en

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53Polyethers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D06M13/295Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507Polyesters

Definitions

  • the present invention relates to a water permeability imparting agent, a water permeable fiber to which it is attached, and a method for producing a nonwoven fabric. Specifically, by imparting the water permeability-imparting agent of the present invention to the hydrophobic synthetic fiber for nonwoven fabric production, excellent permeability is obtained in the card process during nonwoven fabric production, and the resulting nonwoven fabric is instantly water permeable.
  • the present invention relates to a method for producing a water permeability imparting agent, a water permeable fiber to which it is attached, and a non-woven fabric, which have both properties, durable water permeability and liquid return prevention properties and are excellent in safety.
  • absorbent articles such as sanitary goods such as disposable diapers and synthetic napkins, topsheets that impart hydrophilicity to various nonwoven fabrics mainly composed of hydrophobic synthetic fibers (polyolefin fibers, polyester fibers, etc.) It has a structure formed by three layers in which a material made of cotton-like pulp, a polymer absorber or the like is disposed between the absorbent material and the water-repellent back sheet.
  • a material made of cotton-like pulp, a polymer absorber or the like is disposed between the absorbent material and the water-repellent back sheet.
  • the water permeability imparting agent is required to have the contradictory required properties of water permeability to the surface of hydrophobic synthetic fibers and to maintain water permeability even for repeated liquid water permeability.
  • Alkyl phosphate salts, cationic properties It was compensated by adjusting the blending ratio of surfactants and amphoteric surfactants.
  • durable water permeability is insufficient, or even when durable water permeability is obtained to some extent, instantaneous water permeability is insufficient.
  • a product satisfying both durable water permeability was not obtained.
  • the card process which is a process for manufacturing a nonwoven fabric, there is a problem that scum is generated in the card machine or napping is generated in the web. Furthermore, there was a problem that there were many things with strong irritation to skin.
  • Patent Document 1 discloses a method in which polyether-modified silicone is used in combination with an alkyl phosphate ester salt, but durability and water repellent prevention properties are insufficient.
  • Patent Document 2 discloses a method in which two types of amphoteric surfactants are used in combination with an alkyl phosphate ester salt, but the durable water permeability is insufficient.
  • Patent Document 3 proposes a method in which an acylated polyamine cationized product of polyoxyalkylene fatty acid amide, an alkyl phosphate salt, an amphoteric surfactant, and a polyoxyalkylene-modified silicone are used in combination. Run short.
  • Patent Document 4 discloses a treatment agent containing a betaine amphoteric activator, a dicarboxylic acid ester of a polyalkylene adduct of an oxy fatty acid ester, and an anionic surfactant. However, the card passing property, instantaneous water permeability and durable water permeability are disclosed. Lack of sex. Patent Document 5 proposes a method of treating fibers by using an alkyl phosphate salt in combination with an amphoteric surfactant, an alkoxylated ricinolein type compound, and a polyoxyalkylene-modified silicone, but is insufficient in card passage and liquid return prevention properties. To do.
  • Patent Document 6 at least one of an alkyl phosphate salt, a cationized product of (poly) amine having a polyoxyalkylene group and an acyl group, and a condensate of a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and a dicarboxylic acid
  • a method has been proposed for treating fibers using a combination of an ester having a hydroxyl group blocked with a fatty acid, a dialkylsulfosuccinate salt, a trialkylglycine derivative, and a polyoxyalkylene-modified silicone. Run short.
  • these treatment agents are not only at an insufficient level for the instantaneous water permeability, durable water permeability, and liquid return prevention required for current sanitary material applications, but also are cards that are a manufacturing process for nonwoven fabrics.
  • the skin irritation is strong, and safety issues have arisen.
  • these treatment agents cannot satisfy all performance levels. Therefore, a high-performance treatment agent having both a high performance level and safety in hygiene material applications is desired.
  • the present invention solves the conventional problems and has a high level of performance in terms of instantaneous water permeability, durable water permeability, liquid return prevention properties and card passage properties, and has excellent water permeability.
  • An agent, a method for producing a water-permeable fiber and a nonwoven fabric to which the agent is attached are provided.
  • the present inventors have found that the above problems can be solved if the water permeability imparting agent contains a specific polyether polyester compound (A) as an essential component.
  • the invention has been completed.
  • the water permeability imparting agent according to the present invention contains a polyether polyester compound (A) represented by the following general formula (1) as an essential component.
  • R 1 and R 3 are each independently a residue obtained by removing an OH group from a monovalent aliphatic alcohol
  • AO is an oxyalkylene group having 2 to 4 carbon atoms
  • a and b Are each independently an integer of 1 to 100
  • R 2 is a divalent organic group.
  • the water-permeability imparting agent according to the present invention further contains an alkyl phosphate salt (B) represented by the following general formula (2).
  • B alkyl phosphate salt
  • R 4 is an alkyl group having 6 to 22 carbon atoms
  • AO is an oxyalkylene group having 2 to 4 carbon atoms
  • c is an integer of 0 to 15
  • n is an integer of 1 to 2
  • Y + is an ionic residue selected from the group consisting of hydrogen ion, sodium ion, potassium ion, ammonium ion, diethanolammonium ion and triethanolammonium ion.
  • the weight ratio of the polyether polyester compound (A) in the entire nonvolatile content of the water permeability imparting agent is preferably 10 to 90% by weight. Further, the weight ratio of the alkyl phosphate salt (B) to the whole nonvolatile content of the water permeability imparting agent is preferably 5 to 80% by weight.
  • the water-permeability imparting agent according to the present invention may further contain at least one leveling agent (C) selected from ester oils and mineral oils, and the smoothness occupying the entire nonvolatile content of the water-permeability imparting agent.
  • the weight ratio of the agent (C) is preferably 0.2 to 40% by weight.
  • the ester oil may be a monohydric alcohol and / or a fatty acid ester obtained from a (poly) ether compound obtained by adding a C 2-4 alkylene oxide to a monohydric alcohol and a fatty acid, and a polyhydric alcohol and / or polyhydric alcohol. It is preferably at least one selected from fatty acid esters obtained from a (poly) ether compound obtained by adding a C 2-4 alkylene oxide to a monohydric alcohol and a fatty acid.
  • the mineral oil is preferably at least one selected from machine oil, spindle oil and liquid paraffin.
  • the water permeability imparting agent according to the present invention is an ester in which at least one hydroxyl group of a condensate of dialkylsulfosuccinate salt (D1), polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid is blocked with a fatty acid.
  • D1 dialkylsulfosuccinate salt
  • D2 polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid
  • D3 at least one component selected from a nitrogen-containing surfactant
  • the weight ratio of the component (D) in the entire nonvolatile content of the water-permeability imparting agent Is preferably 0.2 to 40% by weight.
  • the water-permeability imparting agent according to the present invention is used for hydrophobic synthetic fibers for producing nonwoven fabrics.
  • the water-permeable fiber according to the present invention is obtained by treating the hydrophobic synthetic fiber for producing a nonwoven fabric with the water-permeability imparting agent according to any one of claims 1 to 6, and imparting water permeability to the obtained fiber.
  • the adhesion rate of the non-volatile content of the agent is 0.1 to 2% by weight.
  • the manufacturing method of the nonwoven fabric concerning this invention includes the process of producing the fiber web by accumulating the said water-permeable fiber, and heat-processing the obtained fiber web.
  • the water-permeability imparting agent according to the present invention, the water-permeable fiber and the nonwoven fabric to which the water-permeability imparting agent is attached have high performance levels in terms of instantaneous water permeability, durable water permeability, liquid return prevention property and card passability. Excellent safety.
  • the water permeability imparting agent of the present invention contains the polyether polyester compound (A) represented by the general formula (1) as an essential component. Details will be described below.
  • the polyether polyester compound (A) represented by the general formula (1) (hereinafter sometimes referred to as component (A)) is a component that is extremely excellent in instantaneous water permeability and durable water permeability.
  • R 1 and R 3 are residues (aliphatic hydrocarbon groups) obtained by removing OH groups from monovalent aliphatic alcohols. The number of carbon atoms of the aliphatic hydrocarbon group may be distributed, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. It may have a polycyclic structure.
  • the aliphatic hydrocarbon group may have 1 to 60 carbon atoms, but is preferably 10 to 60, more preferably 12 to 60, and particularly preferably 14 to 60 from the viewpoint of improving durable water permeability.
  • Examples of the monovalent aliphatic alcohol include methanol, ethanol, butanol, 2-ethylhexanol, lauryl alcohol, palmityl alcohol, palmitolyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosanol, docosanol, tetrocosanol, hexa Cosanol, octacosanol, nonacosanol, triacontanol, C24-26 alcohol (made by Ito Oil Co., Ltd., trade name: Hysokol 246), C32-36 alcohol (made by Shin Nippon Rika Co., Ltd., trade name: NJ Cole 3236) ), C14-60 alcohol (trade name: Unilin alcohol 450, manufactured by Petrolite, USA), C30-60 alcohol (trade name: lanolin alcohol A, manufactured by Nippon Seika Co., Ltd.), and the like.
  • the aliphatic alcohol preferably has a distribution in the range of 1 to 60 carbon atoms from the viewpoint of improving the durable water permeability. That is, a plurality of aliphatic alcohols having different carbon numbers in the range of 1 to 60 carbon atoms are preferable.
  • the range of the number of carbon atoms having a distribution is preferably 10 to 60, more preferably 12 to 60, and still more preferably 14 to 60.
  • the distribution may be part of this carbon number range, or may be in the entire range.
  • the aliphatic alcohols having different carbon numbers are preferably 3 or more, more preferably 5 to 60, further preferably 10 to 55, and particularly preferably 15 to 50. .
  • AO is an oxyalkylene group having 2 to 4 carbon atoms.
  • a and b, which are repeating numbers of oxyalkylene units, are each independently an integer of 2 to 100, preferably 5 to 50, more preferably 6 to 30.
  • (AO) a and (AO) b are preferably polyoxyalkylene groups having 50 mol% or more of oxyethylene units as oxyalkylene units.
  • R 2 is a divalent organic group, and examples thereof include a divalent organic group obtained by removing a carboxyl group (or an acid anhydride group) from dicarboxylic acid and dicarboxylic acid anhydride.
  • R 2 includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, thiodipropion
  • Examples thereof include divalent organic groups obtained by removing a carboxyl group (or acid anhydride group) from acids, thiodioctanoic acid, thiodilauric acid, thiodistearic acid and the like and anhydrides of these dicarboxylic acids.
  • Component (A) is a condensate obtained by a dehydration condensation reaction between an alkylene oxide adduct of a monovalent aliphatic alcohol and a dicarboxylic acid.
  • the carboxyl group molar equivalent of dicarboxylic acid per molar equivalent of hydroxyl group of the alkylene oxide adduct of monovalent aliphatic alcohol is in the range of 0.2 to 1. 0.4 to 0.8 is more preferable.
  • esterification method, reaction conditions, and the like when producing component (A), and any known method or ordinary conditions can be employed.
  • heating is performed while distilling off the generated water in a nitrogen gas stream in the presence of a catalyst. It is obtained by reacting.
  • the weight ratio of the component (A) in the non-volatile content of the water permeability imparting agent is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, further preferably 30 to 80% by weight, and 40 to 70% by weight. Is particularly preferred.
  • the nonvolatile content of the water-permeability imparting agent of the present invention means a component in the water-permeability imparting agent remaining on the fiber surface even after the heat drying step for removing moisture and the like. It means a component that remains without being volatilized when it reaches a constant weight by removing heat and the like by heat treatment.
  • the water permeability-imparting agent of the present invention preferably further contains an alkyl phosphate salt (B) represented by the aforementioned general formula (2) (hereinafter sometimes referred to as component (B)) in addition to component (A). .
  • the component (B) is a component excellent in card passing performance, performance for maintaining durable water permeability, and performance for reducing liquid return.
  • R 4 is an alkyl group having 6 to 22 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and further preferably 10 to 14 carbon atoms.
  • the card process passability may decrease and the odor of the product may become strong.
  • the alkyl group has more than 22 carbon atoms, the water solubility of the compound, the card passability, and the instantaneous Water permeability may decrease.
  • the carbon number of the alkyl group may be distributed, the alkyl group may be linear or branched, and may be saturated or unsaturated.
  • AO is an oxyalkylene group having 2 to 4 carbon atoms.
  • C which is the number of repeating oxyalkylene units, is an integer of 0 to 15, preferably 0 to 10, more preferably 0 to 3, and particularly preferably c is 0 and no polyoxyalkylene group is contained.
  • (AO) c is preferably a polyoxyalkylene group having 50 mol% or more of oxyethylene units as oxyalkylene units.
  • n is an integer of 1 to 2
  • Y + is an ionic residue selected from the group consisting of hydrogen ion, sodium ion, potassium ion, ammonium ion, diethanolammonium ion and triethanolammonium ion. These may be a mixture, or one or more may be used.
  • the component (B) is composed of decyl phosphate potassium salt, lauryl phosphate potassium salt, tridecyl phosphate potassium salt, myristyl phosphate potassium salt, cetyl phosphate potassium, for the purpose of improving the performance of maintaining card permeability and durable water permeability.
  • Salt, oleyl phosphate potassium salt, polyoxyethylene 2 mol addition cetyl phosphate potassium salt, polyoxyethylene 3 mol addition lauryl phosphate diethanolammonium salt, polyoxyethylene 3 mol addition lauryl phosphate triethanolammonium salt are preferred, lauryl phosphate potassium salt is preferred Further preferred.
  • the weight ratio of the component (B) in the entire nonvolatile content of the water permeability imparting agent is preferably 5 to 80% by weight, more preferably 10 to 60% by weight, further preferably 20 to 50% by weight, and 20 to 40% by weight. Is particularly preferred.
  • the water-permeability imparting agent of the present invention has a component (A) that is particularly excellent in instantaneous water-permeable performance and durable water-permeable performance, and in particular, card-passing performance and performance that retains durable water-permeable properties in order to further exert its effects.
  • the weight ratio (A) / (B) to the component (B) excellent in performance for reducing the liquid return amount is preferably 30/70 to 90/10, and preferably 40/60 to 80/20. Is more preferable, and 50/50 to 70/30 is particularly preferable.
  • the water permeability imparting agent of the present invention may further contain a smoothing agent (C) and / or a component (D) described later in addition to the component (A) or in addition to the component (A) and the component (B). .
  • the smoothing agent (C) (hereinafter sometimes referred to as “component (C)”) is at least one selected from ester oils and mineral oils, and is a component that can further improve the card passability and the like. In particular, since there is little wrapping around the cylinder and it is difficult for the web to be nipped, a nonwoven fabric with excellent surface quality can be obtained.
  • the weight ratio of the component (C) to the whole non-volatile content of the water-permeability imparting agent is preferably 0.2 to 40% by weight, more preferably 5 to 30% by weight. 20% by weight is particularly preferred. If the weight ratio exceeds 40% by weight, the water permeability of the water-permeability imparting agent may be insufficient, resulting in a decrease in solution stability and an antistatic property in a card process.
  • the ester oil of component (C) is not particularly limited, but a fatty acid ester obtained from a monohydric alcohol and / or a (poly) ether compound in which an alkylene oxide having 2 to 4 carbon atoms is added to the monohydric alcohol and a fatty acid,
  • at least one fatty acid ester selected from fatty acid esters obtained from (poly) ether compounds obtained by adding a polyhydric alcohol and / or a polyhydric alcohol with a C 2-4 alkylene oxide and a fatty acid is preferable.
  • a monohydric aliphatic alcohol etc. are mentioned.
  • the carbon number of the monovalent aliphatic alcohol may be distributed. Moreover, it may be saturated or unsaturated, may be linear, and may have a branch.
  • the aliphatic alcohol preferably has 1 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, still more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 18 carbon atoms.
  • Examples of the monohydric alcohol include methanol, ethanol, butanol, 2-ethylhexanol, lauryl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, and behenyl alcohol.
  • the number of moles of alkylene oxide added in the (poly) ether compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a monohydric alcohol is preferably 0 to 150, more preferably 0 to 50, particularly when no alkylene oxide is contained. preferable.
  • the raw material polyhydric alcohol constituting the fatty acid ester is not particularly limited, and examples thereof include divalent to hexavalent alcohols.
  • the polyhydric alcohol include diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, glycerin, trimethylolpropane, sorbitol, sorbitan, pentaerythritol, sucrose, etc. Polyols.
  • polyglycerin such as diglycerin, triglycerin, tetraglycerin and hexaglycerin, which is a condensate of glycerin, is also included.
  • the number of moles of alkylene oxide added in the (poly) ether compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a polyhydric alcohol is preferably 0 to 150, more preferably 0 to 50, and particularly preferably 0 to 20.
  • the starting fatty acid constituting the fatty acid ester is not particularly limited, and may be a saturated fatty acid or an unsaturated fatty acid. Of these, saturated fatty acids are preferable, and the number of carbon atoms of the fatty acids is preferably 10 to 30, more preferably 12 to 18, and particularly preferably 14 to 18.
  • Saturated fatty acids include caproic acid, caprylic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, serotic acid, montanic acid, Examples include melicic acid.
  • the unsaturated fatty acid include oleic acid, elaidic acid, erucic acid, linoleic acid, linolenic acid and the like.
  • fatty acid esters are prepared by appropriately selecting the above-mentioned monohydric alcohols and polyhydric alcohols and / or (poly) ether compounds in which alkylene oxides having 2 to 4 carbon atoms are added to these alcohols and fatty acids, and by known synthesis methods. Obtainable.
  • Examples of the fatty acid ester obtained from a (poly) ether compound obtained by adding a monohydric alcohol and / or a monohydric alcohol with a C 2-4 alkylene oxide and a fatty acid include lauryl oleate, stearyl oleate, oleyl oleate, Octyl oleate, isooctyl palmitate, isooctyl stearate, tridecyl oleate, butyl stearate, 2-ethylhexyl oleate, oleyl stearate, oleyl palmitate, oleyl laurate, oleyl isostearate, polyoxyethylene ( 10 mol) Stearyl ether oleate and the like.
  • Examples of the fatty acid ester obtained from a (poly) ether compound obtained by adding a C 2-4 alkylene oxide to a polyhydric alcohol and / or a monohydric alcohol and a fatty acid include glycerin monooleate, glycerin monostearate, hexa Examples include glycerol monostearate, trimethylolpropane monopalmitate, sorbitan monooleate, polyoxyethylene (20 mol) glycerol monostearate and the like. Among these, isooctyl palmitate and isooctyl stearate are particularly preferable as the fatty acid ester.
  • the mineral oil of component (C) is preferably at least one selected from machine oil, spindle oil and liquid paraffin.
  • the viscosity of the mineral oil at 30 ° C. is preferably 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 5 m 2 / s, and more preferably 1 ⁇ 10 ⁇ 6 to 4 ⁇ 10 ⁇ 5 m 2 / s.
  • As the mineral oil liquid paraffin is preferable.
  • the water-permeability imparting agent of the present invention contains at least one hydroxyl group of a condensate of a dialkyl sulfosuccinate salt (D1), a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and a dicarboxylic acid as a component for assisting durable water permeability.
  • At least one component (D) selected from an ester (D2) blocked with a fatty acid and a nitrogen-containing surfactant (D3) may be included within a range not impairing safety.
  • the weight ratio of the component (D) in the entire nonvolatile content of the water permeability imparting agent is preferably 0.2 to 40% by weight, more preferably 5 to 40% by weight, further preferably 5 to 30% by weight, and 5 to 20% by weight. % Is particularly preferred. When the weight ratio exceeds 40% by weight, the card passing property may deteriorate.
  • component (D1) and / or component (D3) is essential, the total amount of component (D1) and component (D3) in the entire nonvolatile content of the water permeability imparting agent is 0.2 to 30 wt. %, More preferably 5 to 20% by weight, still more preferably 5 to 10% by weight.
  • the dialkylsulfosuccinate salt (D1) (sometimes referred to as component (D1)) is a dialkyl ester of succinic acid having a sulfonate group at the ⁇ -position.
  • the number of carbon atoms of the alkyl group constituting the dialkyl ester may be distributed, and the alkyl group may be linear or branched, and may be saturated or unsaturated.
  • the alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 18 carbon atoms, still more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 14 carbon atoms. If the alkyl group has less than 6 carbon atoms, the card passing property may decrease. On the other hand, if the carbon number of the alkyl group exceeds 18, the instantaneous water permeability may decrease.
  • Examples of the sulfonate salt of component (D1) include alkali metal salts such as sodium salt and potassium salt, and amine salts.
  • the salt is sodium salt and / or potassium salt, the fiber to which the water permeability-imparting agent has adhered is attached. This is preferable because the liquid penetrates quickly.
  • component (D1) examples include dihexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate sodium salt, dilauryl sulfosuccinate sodium salt, dicoco alkylsulfosuccinate sodium salt, ditridecyl sulfosuccinate sodium salt Salt, dimyristyl sulfosuccinate sodium salt, distearyl sulfosuccinate sodium salt and the like. These dialkyl sulfosuccinate salts may be used alone or in combination of two or more.
  • Component (D2) An ester (D2) (component (D2)) in which at least one hydroxyl group of a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester (hereinafter sometimes referred to as polyhydroxy ester) and a dicarboxylic acid is blocked with a fatty acid.
  • polyhydroxy ester a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester
  • dicarboxylic acid is blocked with a fatty acid.
  • the polyhydroxyester is structurally an ester of a polyoxyalkylene group-containing hydroxy fatty acid and a polyhydric alcohol, and two or more (preferably all) hydroxyl groups of the polyhydric alcohol are esterified. Therefore, the polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester is an ester having a plurality of hydroxyl groups.
  • the polyoxyalkylene group-containing hydroxy fatty acid has a structure in which a polyoxyalkylene group is bonded to a fatty acid hydrocarbon group via an oxygen atom, and one end that is not bonded to the fatty acid hydrocarbon group of the polyoxyalkylene group is It is a hydroxyl group.
  • the polyhydroxyester include an alkylene oxide adduct of an esterified product of a hydroxy fatty acid having 6 to 22 carbon atoms (preferably 12 to 22 carbon atoms) and a polyhydric alcohol.
  • Examples of the hydroxy fatty acid having 6 to 22 carbon atoms include hydroxycaprylic acid, hydroxycapric acid, hydroxyundecanoic acid, hydroxylauric acid, hydroxystearic acid, and ricinoleic acid, and hydroxystearic acid and ricinoleic acid are preferable.
  • Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, sorbitan, trimethylolpropane, pentaerythritol and the like, and glycerin is preferable.
  • Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide.
  • the number of added moles of alkylene oxide is preferably 80 or less, more preferably 5 to 30 per mole equivalent of hydroxyl group of the hydroxy fatty acid polyhydric alcohol ester. If the added mole number exceeds 80, the liquid return amount may increase, which is not preferable. In order to obtain high durable water permeability, it is important to adjust the balance between the hydrophilic group and the hydrophobic group.
  • the proportion of ethylene oxide in the alkylene oxide is preferably 50 mol% or more, more preferably 80 mol% or more. If the ratio of ethylene oxide is less than 50 mol%, the hydrophobicity becomes strong and sufficient durable water permeability may not be obtained.
  • the polyhydroxyester can be produced, for example, by esterifying a polyhydric alcohol and a hydroxy fatty acid (hydroxymonocarboxylic acid) under ordinary conditions to obtain an esterified product, and then subjecting the esterified product to an addition reaction with an alkylene oxide.
  • the polyhydroxyester can be suitably produced also by using an oil and fat obtained from nature such as castor oil or a hardened castor oil obtained by adding hydrogen to this, and further subjecting it to an addition reaction with an alkylene oxide.
  • the carboxyl group molar equivalent of hydroxy fatty acid per molar equivalent of hydroxyl group of polyhydric alcohol is preferably in the range of 0.5-1.
  • the carbon number of the dicarboxylic acid is preferably 2 to 10, more preferably 2 to 8. If the carbon number of the dicarboxylic acid exceeds 10, sufficient hydrophilicity may not be imparted.
  • dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and phthalic acid.
  • the carboxyl group molar equivalent of dicarboxylic acid per molar equivalent of hydroxyl group of polyhydroxyester is preferably in the range of 0.2 to 1, More preferred is 0.8.
  • D2 the method of esterification, reaction conditions, etc. at the time of manufacturing a component (D2), A well-known method and normal conditions are employable.
  • Component (D2) of the present invention has at least one hydroxyl group blocked with a fatty acid in the above-mentioned condensate of polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid (hereinafter sometimes referred to as condensate).
  • condensate of polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid
  • Ester Esters that are not capped with fatty acids have insufficient durable water permeation performance, and the viscosity of the compound increases with time, resulting in an increase in water-insoluble matter, thus reducing the solution stability of the imparting agent.
  • the number of carbon atoms of the fatty acid blocking at least one or more hydroxyl groups of the condensate is preferably 10 to 50, and more preferably 12 to 36.
  • the hydrophilicity becomes strong and sufficient durable water permeability may not be obtained.
  • the carbon number of the hydrocarbon group in the fatty acid may be distributed, the hydrocarbon group may be linear or branched, may be saturated or unsaturated, It may have a polycyclic structure.
  • Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, icosanoic acid, behenic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melicic acid, and lanolin fatty acid.
  • lanolin fatty acid having 12 to 36 carbon atoms which is a lanolin derivative obtained by purifying behenic acid or wool grease, is preferable.
  • the carboxyl group molar equivalent of the fatty acid per molar equivalent of the hydroxyl group of the condensate is preferably in the range of 0.2 to 1, and more preferably 0.4 to 1. There are no particular limitations on the reaction conditions for esterification.
  • Component (D3) examples of the nitrogen-containing surfactant (D3) (sometimes referred to as component (D3)) include ammonium salt type cationic surfactant (D3a), imidazolinium type cationic surfactant (D3b), and alkylbetaine surfactant. It is preferably at least one selected from (D3c), alkylimidazole type betaine surfactant (D3d), amide group-containing betaine surfactant (D3e) and higher fatty acid alkanolamide type surfactant (D3f).
  • the component (D3) of the present invention is a component excellent in instantaneous water permeability and durable water permeability, but it is preferably used in a minimum amount because the card passing property and safety may be inferior.
  • the ammonium salt type cationic surfactant (D3a) is not particularly limited.
  • dilauryl dimethyl ammonium chloride did
  • the imidazolinium type cationic surfactant (D3b) is not particularly limited, but the substituent at the 2-position of the imidazolinium ring is an aliphatic hydrocarbon group having 11 to 21 carbon atoms, and the anionic group is methylsulfuric acid. Those that are ionic residues selected from the group consisting of ions, ethyl sulfate ions and dimethyl phosphate ions are preferred.
  • imidazolinium type cationic surfactants include 1-hydroxyethyl-1-ethyl-2-laurylimidazolinium ethyl sulfate, 1-hydroxyethyl-1-ethyl-2-oleylimidazolinium ethyl sulfate, 1 -Hydroxyethyl-1-ethyl-2-stearylimidazolinium ethyl sulfate, 1-hydroxyethyl-1-methyl-2-tetradecylimidazolinium methyl sulfate, 1-hydroxyethyl-1-methyl-2-lauryl imidazoli 1-hydroxyethyl-1-methyl-2-oleylimidazolinium methylsulfate, 1-hydroxyethyl-1-methyl-2-stearylimidazolinium methylsulfate, 1-hydroxyethyl-1- Chill 2-oleyl imidazolinium dimethyl phosphate. Of these, 1-hydroxyethyl-1
  • the alkylbetaine surfactant (D3c) is not particularly limited, and examples thereof include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, lauryldimethylaminosulfopropylbetaine, and lauryldimethylhydroxysulfobetaine. Among these, stearyldimethylaminoacetic acid betaine is preferable.
  • the alkylimidazole type betaine surfactant (D3d) is not particularly limited, and examples thereof include 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-oleyl-N-carboxymethyl-N-hydroxy. Examples include ethyl imidazolinium betaine. Of these, 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine is preferred.
  • the amide group-containing betaine surfactant (D3e) is not particularly limited, and examples thereof include lauric acid amidopropyldimethylaminoacetic acid betaine, oleic acid amidopropyldimethylaminoacetic acid betaine, and stearic acid amidopropyldimethylaminoacetic acid betaine. Among these, stearate amidopropyldimethylaminoacetic acid betaine is preferable.
  • the higher fatty acid alkanolamide type surfactant (D3f) is not particularly limited, and examples thereof include lauric acid diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, behenic acid diethanolamide, lauric acid monoethanolamide, and lauric acid monoester. Isopropanolamide etc. are mentioned. Further, the higher fatty acid alkanolamide type surfactant may also contain an alkylene oxide adduct having 2 to 4 carbon atoms. Among these, stearic acid diethanolamide and behenic acid diethanolamide are preferable.
  • the water permeability-imparting agent of the present invention may contain polyoxyalkylene-modified silicone (E) (sometimes referred to as component (E)) as long as it does not impair the effects of the present invention, but lacks liquid return prevention properties.
  • the weight ratio of the silicone compound (E) in the entire nonvolatile content of the water permeability imparting agent is less than 20% by weight, less than 15% by weight, less than 10% by weight, It is preferable in the order of less than 7% by weight, less than 5% by weight, and less than 3% by weight.
  • Component (E) has a molecular weight of 1,000 to 100,000 and a Si content of 20 to 70% by weight.
  • the polyoxyalkylene is polyoxyethylene or polyoxypropylene, and the ratio of the polyoxyethylene in the total polyoxyalkylene is 20% by weight or more.
  • the water permeability imparting agent of the present invention may contain water and / or a solvent as required, and preferably contains water essentially.
  • the water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like.
  • the weight ratio of the non-volatile component in the entire water-permeability imparting agent when producing the water-permeability imparting agent is preferably 10 to 40% by weight, and particularly preferably 18 to 30% by weight.
  • the water permeability imparting agent of the present invention further contains an antibacterial agent, an antioxidant, a preservative, a matting agent, a pigment, an antirust agent, an aromatic, an antifoaming agent, and the like as necessary. Also good.
  • Method for producing water permeability imparting agent As a method for producing the water-permeability imparting agent of the present invention, a known method can be employed. For example, the component (A) and the component (C) are blended as necessary and stirred at a temperature of about 70 ° C. Next, if necessary, an aqueous solution of the component (B) is blended and stirred uniformly at a temperature of about 70 ° C. Next, a component (D) is mix
  • the water-permeable fiber of the present invention is a water-permeable fiber composed of a hydrophobic synthetic fiber (fiber body) for manufacturing a nonwoven fabric and the water-permeability imparting agent attached to the fiber, and is generally cut to a predetermined length. Short fiber.
  • the adhesion rate of the non-volatile component of the water permeability imparting agent is 0.1 to 2% by weight, preferably 0.3 to 1% by weight, based on the water permeable fiber. When the adhesion rate of the nonvolatile content of the water permeability imparting agent to the water permeable fiber is less than 0.1% by weight, the instantaneous water permeability and the durable water permeability may be lowered.
  • the adhesion rate of the non-volatile content of the water permeability imparting agent exceeds 2% by weight, the wrapping increases when the fiber is carded, resulting in a significant reduction in productivity, and a nonwoven fabric obtained by a method such as a dry method. Such a fiber product may become sticky after water permeation.
  • hydrophobic synthetic fiber (fiber body) for manufacturing a nonwoven fabric examples include, for example, polyolefin fibers, polyester fibers, nylon fibers, polyvinyl chloride fibers, composite fibers composed of two or more types of thermoplastic resins, etc.
  • polyolefin resin / polyolefin resin for example, high density polyethylene / polypropylene, linear high density polyethylene / polypropylene, low density polyethylene / polypropylene, binary copolymer of propylene and other ⁇ -olefin or ternary Examples include copolymer / polypropylene, linear high-density polyethylene / high-density polyethylene, and low-density polyethylene / high-density polyethylene.
  • polyolefin resin / polyester resin for example, polypropylene / polyethylene terephthalate, high-density polyethylene / polyethylene terephthalate, linear high-density polyethylene / polyethylene terephthalate, and low-density polyethylene / polyethylene terephthalate.
  • polyester-type resin / polyester-type resin copolymer polyester / polyethylene terephthalate etc. are mentioned, for example.
  • the fiber which consists of polyamide-type resin / polyester-type resin, polyolefin-type resin / polyamide-type resin etc. can be illustrated.
  • polyolefin fibers (polyolefin fibers and polyolefin fibers for manufacturing nonwoven fabrics) are used because the attached water permeability imparting agent is difficult to fall off by liquids such as urine and body fluids.
  • the water permeability-imparting agent of the present invention is suitable for hydrophobic synthetic fibers such as polyester fibers for producing non-woven fabrics (polyester fibers and composite fibers containing polyester fibers), and polyolefin fibers for producing non-woven fabrics.
  • the water permeability imparting agent of the present invention is suitable.
  • Examples of the cross-sectional structure of the fiber include a sheath-core type, a parallel-type, an eccentric sheath-core type, a multilayer type, a radiation type, and a sea-island type.
  • the sheath includes eccentricity.
  • a core type or a parallel type is preferred.
  • the cross-sectional shape can be a circular shape or an irregular shape. In the case of an irregular shape, for example, a flat shape, a polygonal shape such as a triangle to an octagon, a T shape, a hollow shape, a multileaf shape, and the like can be used.
  • the water-permeability-imparting agent of the present invention may be adhered to the fiber main body without being diluted as it is, and diluted with water or the like to a concentration such that the weight ratio of the entire nonvolatile content is 0.5 to 5% by weight as an emulsion. You may make it adhere to a fiber main body.
  • the step of attaching the water permeability imparting agent to the fiber body may be any of a spinning process, a stretching process, a crimping process, and the like of the fiber body.
  • the means for attaching the water permeability imparting agent of the present invention to the fiber body is not particularly limited, and means such as roller lubrication, nozzle spray lubrication, and dip lubrication may be used.
  • a method for obtaining a desired adhesion amount more uniformly and efficiently may be employed in accordance with the fiber manufacturing process and its characteristics. Moreover, as a drying method, you may use the method of drying with a hot air and infrared rays, the method of making it contact with a heat source, and drying.
  • Method for producing nonwoven fabric As a manufacturing method of a nonwoven fabric, a well-known method is employable without particular limitation. Short fibers or long fibers can be used as the raw fiber. Examples of the web forming method in which the raw fibers are short fibers include a dry method such as a card method and an airlaid method, and a wet method such as a papermaking method. Examples of the web forming method in which the raw fibers are long fibers include a spunbond method, a melt blow method, and a flash spinning method. Examples of the interfiber bonding method include a chemical bond method, a thermal bond method, a needle punch method, a spunlace method, and a stitch bond method.
  • the method for producing the nonwoven fabric of the present invention preferably includes a step of producing a fiber web by passing the water-permeable fibers (for example, short fibers) of the present invention through a card machine or the like and heat-treating the obtained fiber web. That is, the water-permeability imparting agent of the present invention is particularly preferably used when it has a step of heat-treating the fiber web in the production of the nonwoven fabric.
  • the method for bonding the fiber web by heat treatment include thermal fusion methods such as thermocompression using a heated roll or ultrasonic waves, thermal fusion using heated air, and a thermocompression bonding (point bonding) method.
  • the water-permeable fiber (short fiber) of the present invention is mixed and heat-treated and bonded as described above.
  • a fiber molded body obtained by a spunbond method, a melt blow method, a flash spinning method, or the like is heat-treated with a heating roll or heated air or the like, to which the water permeability imparting agent of the present invention is attached, or heated.
  • a method of manufacturing a nonwoven fabric by attaching the water permeability imparting agent of the present invention to a material heat treated with a roll or heated air is also included.
  • a composite fiber resin is spun, then the spun composite long fiber filament is cooled with a cooling fluid, and tension is applied to the filament with drawn air to obtain the desired fineness. Thereafter, the spun filament is collected on a collection belt and subjected to a bonding treatment to obtain a spunbonded nonwoven fabric.
  • the joining means include thermocompression bonding using a heating roll or ultrasonic waves, heat fusion using heated air, and a thermocompression bonding (point bonding) method.
  • a method for imparting the water permeability imparting agent of the present invention to the obtained spunbond nonwoven fabric it can be performed by a gravure method, a flexo method, a roll coating method such as a gate roll method, a spray coating method, etc. There is no particular limitation as long as the coating amount can be adjusted for each side.
  • a drying method you may use the method of drying with a hot air and infrared rays, the method of making it contact with a heat source, and drying.
  • the water-permeable fiber of the present invention has physical properties excellent in liquid return prevention properties.
  • the liquid return amount of the water-permeable fiber is usually 1.2 g or less, preferably 1.0 g or less, more preferably 0.8 g or less, more preferably 0.6 g or less, particularly preferably 0.4 g or less, and most preferably 0. .2 g or less.
  • the water-permeable fiber of the present invention is excellent in durable water permeability.
  • the disappearance time of the physiological saline is measured at 20 places in the third evaluation, and the number of places where the disappearance time is less than 5 seconds is usually 10 or more, preferably 12 Or more, more preferably 14 or more, more preferably 16 or more, particularly preferably 18 or more, and most preferably 20.
  • the water-permeable fiber of the present invention is excellent in safety. In sanitary material applications, high safety is required because it is in direct contact with the human body. In order to evaluate the safety of the water-permeable fiber, a cytotoxicity (IC 50 ) test is performed, and 70% or more is preferable.
  • IC 50 cytotoxicity
  • the above physical properties can be obtained by attaching the water permeability imparting agent of the present invention to the fiber body.
  • Examples 1 to 10 and Comparative Examples 1 to 11 The components and water shown in Tables 1 and 2 were mixed, and the water permeability imparting agents of Examples 1 to 10 and Comparative Examples 1 to 11 having a non-volatile content of 25% by weight in the entire water permeability imparting agent were respectively obtained. Prepared. The obtained water-permeability imparting agent was diluted with warm water of about 60 ° C. so that the weight ratio of nonvolatile content was 0.8% by weight to obtain a diluted solution.
  • the fiber body is a polypropylene (core) -polyethylene (sheath) composite fiber to which a fiber treatment agent such as a water permeability imparting agent is not attached, and has a single fiber fineness of 1.5 Dtex and a fiber length of 38 mm. It was.
  • the fibers to which the respective liquid permeability imparting agents were attached were placed in a 60 ° C. hot air dryer for 2 hours and then allowed to dry at room temperature for 8 hours or more to obtain water permeable fibers. .
  • the obtained water-permeable fibers were respectively passed through a blended cotton process and a card process using a card testing machine to prepare webs with a basis weight of 30 g / m 2 .
  • the physical properties in the card process (card passing property: presence of cylinder winding and occurrence of scum) were evaluated by the following evaluation method.
  • the obtained web was heat-treated at 130 ° C. in an air-through hot air circulating dryer to fix the web to obtain a nonwoven fabric.
  • the physical properties instant water permeability, durable water permeability, and liquid return prevention property) were evaluated by the evaluation methods shown below. The results are shown in Tables 3 and 4.
  • Nep number 0 is the most excellent.
  • the disappearance time of physiological saline was measured at 20 locations by the instantaneous water permeability test method of the nonwoven fabric, and the number of disappearance time less than 5 seconds was determined. displayed. If this number is 18 or more, the durable water permeability is good. The same operation is repeated for the nonwoven fabric subjected to the test. In this repeated test, it is better that the number of disappearances of physiological saline (the number of places where the disappearance time is less than 5 seconds) is large even if the number of times is repeated.
  • Cytotoxicity test (IC 50 ) Cell lines by colony formation method using V79 cells were examined in a concentration range of water extract 3 to 100% was IC 50 concentration (%) to inhibit colony formation by 50%. Extraction conditions, treatment conditions, and the like were performed in accordance with the cytotoxicity test of the plastic drug container test method of “15th revision Japanese Pharmacopoeia 2006”. In the pass / fail judgment, a density of 70% or more was regarded as acceptable ( ⁇ ), and a density of less than 70% was regarded as unacceptable (x).
  • Adhesion rate of water permeability imparting agent adhering to water permeable fiber The adhering rate of the non-volatile content of the water permeability imparting agent adhering to the water permeable fiber is water permeability adjusted for 24 hours at 25 ° C. ⁇ 40% RH temperature and humidity
  • the conductive fiber (W1) was extracted with methanol using a rapid residual oil extractor R-11 (manufactured by Tokai Keiki Co., Ltd.), and the non-volatile content (W2) of the water permeability imparting agent was determined.
  • providing agent was calculated
  • C W2 / W1 ⁇ 100 (%)
  • Component a1 Maleate ester of polyoxyethylene (10 mol) stearyl ether
  • Component a2 Maleate ester of polyoxyethylene (10 mol) C14-60 alkyl ether component b1: Lauryl phosphate potassium salt
  • Component b2 Tridecyl phosphate potassium salt
  • Component b3 Polyoxyethylene 2 mol cetyl phosphate potassium salt component c1: Isooctyl palmitate component c2: Isooctyl stearate component d 1 1: Dioctyl alkyl sulfosuccinate sodium salt component d 1 2: Ditridecyl sulfosuccinate sodium salt component d 2 1: polyoxyethylene (20 moles) Custer blocked the ester component in 1 mole of the hydroxyl groups 1 molar equivalent per equivalent of stearic acid maleic acid condensation of wax d 2 2: polyoxyethylene ( 0 mole) to 1 mole of the hydroxyl groups capped
  • Component b4 Stearyl phosphate potassium salt
  • Component f1 Cationic compound obtained by reacting epichlorohydrin of polyoxyethylene behenate diethylenetriamine (number of polyoxyethylene groups: 15)
  • Component f2 Polyoxyethylene (10 mol) behenic acid diethanolamide
  • Component f3 Polyoxyethylene (20 mol) castor wax maleic acid condensate (unsealed product)
  • the water-permeable fibers supplied with the water-permeability imparting agent of Examples 1 to 10 have good card passing properties, and the instantaneous water permeability, durable water permeability and liquid of the water-permeable nonwoven fabric are excellent. The return amount was small and good. Furthermore, it passed the cytotoxicity test. If this water permeability imparting agent is added, the fiber can be given instant water permeability, durable water permeability, and liquid return prevention property, and further the irritation to the skin can be reduced, confirming the effect of the present invention. . On the other hand, as is apparent from Table 4, Comparative Examples 1 to 11 that deviate from these component composition ranges could not satisfy all necessary characteristics.
  • the water permeability imparting agent of the present invention is effective when imparting water permeability to hydrophobic synthetic fibers.
  • the water-permeable fiber of the present invention has excellent permeability in the carding process, and the obtained nonwoven fabric has both instantaneous water permeability, durable water permeability and liquid return prevention properties, and is excellent in safety. Is. Therefore, the water-permeability imparting agent and water-permeable fiber of the present invention are effective for producing a high-quality nonwoven fabric.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Nonwoven Fabrics (AREA)

Abstract

Disclosed is an excellently safe water permeability-imparting agent which provides fibers with excellent card passing properties in a carding step during the production of a nonwoven fabric, and which enables the resulting nonwoven fabric to have instantaneous water permeability, long-term water permeability, and liquid return-preventing properties at the same time. Specifically disclosed is a water permeability-imparting agent which contains a polyether polyester compound (A) represented by general formula (1) as an essential ingredient. (In the formula, R1 and R3 each independently represents a residue that is obtained by removing an OH group from a monohydric aliphatic alcohol; AO represents an oxyalkylene group having 2-4 carbon atoms; a and b each independently represents an integer of 2-100; and R2 represents a divalent organic group.)

Description

透水性付与剤、それが付着した透水性繊維および不織布の製造方法Water permeability imparting agent, water permeable fiber to which it is attached, and method for producing nonwoven fabric
 本発明は、透水性付与剤、それが付着した透水性繊維および不織布の製造方法に関する。詳細には、不織布製造用疎水性合成繊維に対して、本発明の透水性付与剤を付与することにより、不織布製造時のカード工程で優れた通過性が得られ、得られた不織布が瞬時透水性、耐久透水性、液戻り防止性を併せ持ち、かつ安全性にも優れる、透水性付与剤、それが付着した透水性繊維および不織布の製造方法に関する。 The present invention relates to a water permeability imparting agent, a water permeable fiber to which it is attached, and a method for producing a nonwoven fabric. Specifically, by imparting the water permeability-imparting agent of the present invention to the hydrophobic synthetic fiber for nonwoven fabric production, excellent permeability is obtained in the card process during nonwoven fabric production, and the resulting nonwoven fabric is instantly water permeable. The present invention relates to a method for producing a water permeability imparting agent, a water permeable fiber to which it is attached, and a non-woven fabric, which have both properties, durable water permeability and liquid return prevention properties and are excellent in safety.
 一般に、紙おむつや合成ナプキンを代表とする生理用品等の吸収性物品は、疎水性合成繊維(ポリオレフィン系繊維、ポリエステル系繊維等)を主材とする各種不織布に親水性を付与したトップシートと、吸収材及び撥水性を付与したバックシートの間に綿状パルプや高分子吸収体等からなる材料を配置した3層から形成される構造になっている。尿や体液等の液体はトップシートを通過して吸収体に吸収されるが、透水性のよいこと、すなわち液体がトップシート上から内部の吸収体に完全に吸収される迄の時間が極めて短い瞬時透水性が必要である。加えて一度吸収体に吸収された液体が再びトップシート上に戻らないようにすること、すなわち液戻り防止性が必要である。さらに、僅か1回から2回の液体の吸収によってトップシート上の処理剤が流出して透水性が急激に低下するのは、おむつの取り替え回数が増すことになって好ましくないので、トップシートには繰り返しの液体吸収に耐える耐久透水性が要求される。また、不織布の製造面からは、カード工程の高速化に伴いシリンダーへの巻付きやスカムが発生したり、ウェブにネップが発生して表面品位の優れた不織布が得られなくなるので、良好なカード通過性が要求される。さらに、安全性への配慮から皮膚への刺激性の少ない要求が一層強くなってきている。親水性に極めて劣る疎水性合成繊維について、上記のような要求に応える透水性付与剤およびそれが付着した透水性繊維が要求されている。 In general, absorbent articles such as sanitary goods such as disposable diapers and synthetic napkins, topsheets that impart hydrophilicity to various nonwoven fabrics mainly composed of hydrophobic synthetic fibers (polyolefin fibers, polyester fibers, etc.) It has a structure formed by three layers in which a material made of cotton-like pulp, a polymer absorber or the like is disposed between the absorbent material and the water-repellent back sheet. Although liquids such as urine and body fluid pass through the top sheet and are absorbed by the absorber, the water permeability is good, that is, the time until the liquid is completely absorbed from the top sheet to the internal absorber is extremely short. Instant water permeability is required. In addition, it is necessary to prevent the liquid once absorbed by the absorber from returning to the top sheet again, that is, to prevent liquid return. Furthermore, it is not preferable that the treatment agent on the top sheet flows out due to absorption of the liquid only once or twice and the water permeability decreases rapidly, because this increases the number of diaper replacements. Is required to have durable water permeability to withstand repeated liquid absorption. In addition, from the non-woven fabric manufacturing side, winding of the cylinder and scum occur with the speeding up of the card process, or the web is nipped and a non-woven fabric with excellent surface quality cannot be obtained. Passability is required. Furthermore, the demand for less irritation to the skin has become stronger due to safety considerations. For hydrophobic synthetic fibers that are extremely inferior in hydrophilicity, there is a demand for a water-permeability imparting agent that meets the above requirements and a water-permeable fiber to which it adheres.
 これらの特性を透水性付与剤によって改善する技術が提案されている。疎水性合成繊維の表面に対して、瞬時透水性がよく、かつ繰り返しの液体透水に対しても透水性を維持するという相反する要求特性を透水性付与剤に求められ、アルキルホスフェート塩、カチオン性界面活性剤および両性界面活性剤等の配合割合の調整等で補っていた。しかし、瞬時透水性が得られる場合でも耐久透水性が不足したり、耐久透水性がある程度得られる場合でも瞬時透水性が不足したりして、現在の衛生材料用途に要求される瞬時透水性・耐久透水性の両者を満足するものが得られていなかった。また、不織布の製造工程であるカード工程においても、カード機にスカムが発生したり、ウェブにネップが発生する問題があった。さらには、皮膚への刺激性の強いものが多いという問題点があった。 A technique for improving these characteristics by using a water permeability imparting agent has been proposed. The water permeability imparting agent is required to have the contradictory required properties of water permeability to the surface of hydrophobic synthetic fibers and to maintain water permeability even for repeated liquid water permeability. Alkyl phosphate salts, cationic properties It was compensated by adjusting the blending ratio of surfactants and amphoteric surfactants. However, even when instantaneous water permeability is obtained, durable water permeability is insufficient, or even when durable water permeability is obtained to some extent, instantaneous water permeability is insufficient. A product satisfying both durable water permeability was not obtained. Further, even in the card process, which is a process for manufacturing a nonwoven fabric, there is a problem that scum is generated in the card machine or napping is generated in the web. Furthermore, there was a problem that there were many things with strong irritation to skin.
 たとえば、特許文献1ではアルキル燐酸エステル塩にポリエーテル変性シリコーンを併用する方法が開示されているが、耐久透水性や液戻り防止性が不足する。特許文献2ではアルキル燐酸エステル塩に2種類の両性界面活性剤を併用する方法が開示されているが、耐久透水性が不足する。特許文献3ではポリオキシアルキレン脂肪酸アミドのアシル化ポリアミンカチオン化物、アルキルホスフェート塩、両性界面活性剤、ポリオキシアルキレン変性シリコーンを併用する方法が提案されているが、カード通過性や液戻り防止性が不足する。特許文献4ではベタイン型両性活性剤とオキシ脂肪酸エステルのポリアルキレン付加物のジカルボン酸エステルおよびアニオン性界面活性剤を配合した処理剤が開示されているが、カード通過性や瞬時透水性および耐久透水性が不足する。特許文献5ではアルキルホスフェート塩に両性界面活性剤、アルコキシル化リシノレイン型化合物、ポリオキシアルキレン変性シリコーンを併用して繊維を処理する方法が提案されているが、カード通過性や液戻り防止性が不足する。特許文献6ではアルキルホスフェート塩、ポリオキシアルキレン基とアシル基とを有した(ポリ)アミンのカチオン化物、ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルとジカルボン酸との縮合物の少なくとも1つ以上の水酸基を脂肪酸で封鎖したエステル、ジアルキルスルホサクシネート塩、トリアルキルグリシン誘導体、ポリオキシアルキレン変性シリコーンを併用して繊維を処理する方法が提案されているが、カード通過性や液戻り防止性が不足する。 For example, Patent Document 1 discloses a method in which polyether-modified silicone is used in combination with an alkyl phosphate ester salt, but durability and water repellent prevention properties are insufficient. Patent Document 2 discloses a method in which two types of amphoteric surfactants are used in combination with an alkyl phosphate ester salt, but the durable water permeability is insufficient. Patent Document 3 proposes a method in which an acylated polyamine cationized product of polyoxyalkylene fatty acid amide, an alkyl phosphate salt, an amphoteric surfactant, and a polyoxyalkylene-modified silicone are used in combination. Run short. Patent Document 4 discloses a treatment agent containing a betaine amphoteric activator, a dicarboxylic acid ester of a polyalkylene adduct of an oxy fatty acid ester, and an anionic surfactant. However, the card passing property, instantaneous water permeability and durable water permeability are disclosed. Lack of sex. Patent Document 5 proposes a method of treating fibers by using an alkyl phosphate salt in combination with an amphoteric surfactant, an alkoxylated ricinolein type compound, and a polyoxyalkylene-modified silicone, but is insufficient in card passage and liquid return prevention properties. To do. In Patent Document 6, at least one of an alkyl phosphate salt, a cationized product of (poly) amine having a polyoxyalkylene group and an acyl group, and a condensate of a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and a dicarboxylic acid A method has been proposed for treating fibers using a combination of an ester having a hydroxyl group blocked with a fatty acid, a dialkylsulfosuccinate salt, a trialkylglycine derivative, and a polyoxyalkylene-modified silicone. Run short.
 このように、これらの処理剤では、現在の衛生材料用途に要求される瞬時透水性、耐久透水性、液戻り防止性には不十分なレベルにあるだけでなく、不織布の製造工程であるカード工程においてカード機にスカムが発生したり、カード工程の高速化に伴い、ウェブにネップが発生する問題が多くなってきている。さらに、皮膚への刺激性が強く、安全性の問題が出てきている。
 以上のように、これらの処理剤では全ての性能レベルを満足することができない。従って、衛生材料用途において、高い性能レベルと安全性を併せ持つ高性能の処理剤が望まれている。
As described above, these treatment agents are not only at an insufficient level for the instantaneous water permeability, durable water permeability, and liquid return prevention required for current sanitary material applications, but also are cards that are a manufacturing process for nonwoven fabrics. There are increasing problems that scum is generated in a card machine in the process, and that a nep is generated in the web with an increase in the speed of the card process. Furthermore, the skin irritation is strong, and safety issues have arisen.
As described above, these treatment agents cannot satisfy all performance levels. Therefore, a high-performance treatment agent having both a high performance level and safety in hygiene material applications is desired.
特開平4-82961号公報Japanese Patent Laid-Open No. 4-82961 特開2000-170076号公報JP 2000-170076 A 特開2002-161474号公報JP 2002-161474 A 特開2000-34672号公報JP 2000-34672 A 特開2002-161477号公報JP 2002-161477 A 特開2007-247128号公報JP 2007-247128 A
 そこで本発明は、従来の問題点を解決して、瞬時透水性、耐久透水性、液戻り防止性およびカード通過性のいずれについても高い性能レベルを有し、安全性にも優れた透水性付与剤、それが付着した透水性繊維および不織布の製造方法を提供するものである。 Accordingly, the present invention solves the conventional problems and has a high level of performance in terms of instantaneous water permeability, durable water permeability, liquid return prevention properties and card passage properties, and has excellent water permeability. An agent, a method for producing a water-permeable fiber and a nonwoven fabric to which the agent is attached are provided.
 本発明者等は、前記課題を解決するために鋭意検討した結果、特定のポリエーテルポリエステル化合物(A)を必須成分として含有する透水性付与剤であれば、前記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved if the water permeability imparting agent contains a specific polyether polyester compound (A) as an essential component. The invention has been completed.
 すなわち、本発明にかかる透水性付与剤は、下記一般式(1)で示されるポリエーテルポリエステル化合物(A)を必須成分として含有するものである。
Figure JPOXMLDOC01-appb-C000003
(式中、RおよびRは、それぞれ独立して、1価の脂肪族アルコールからOH基を除いた残基であり、AOは炭素数2~4のオキシアルキレン基であり、aおよびbは、それぞれ独立して1~100の整数であり、Rは2価の有機基である。)
That is, the water permeability imparting agent according to the present invention contains a polyether polyester compound (A) represented by the following general formula (1) as an essential component.
Figure JPOXMLDOC01-appb-C000003
Wherein R 1 and R 3 are each independently a residue obtained by removing an OH group from a monovalent aliphatic alcohol, AO is an oxyalkylene group having 2 to 4 carbon atoms, a and b Are each independently an integer of 1 to 100, and R 2 is a divalent organic group.)
 また、本発明にかかる透水性付与剤は、下記一般式(2)で示されるアルキルホスフェート塩(B)をさらに含有することが好ましい。
Figure JPOXMLDOC01-appb-C000004
 (式中、Rは炭素数6~22のアルキル基であり、AOは炭素数2~4のオキシアルキレン基であって、cは0~15の整数であり、nは1~2の整数であり、Yは水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、ジエタノールアンモニウムイオンおよびトリエタノールアンモニウムイオンからなる群から選択されるイオン性残基である。)
Moreover, it is preferable that the water-permeability imparting agent according to the present invention further contains an alkyl phosphate salt (B) represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000004
(Wherein R 4 is an alkyl group having 6 to 22 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, c is an integer of 0 to 15, and n is an integer of 1 to 2) Y + is an ionic residue selected from the group consisting of hydrogen ion, sodium ion, potassium ion, ammonium ion, diethanolammonium ion and triethanolammonium ion.)
 前記透水性付与剤の不揮発分全体に占める前記ポリエーテルポリエステル化合物(A)の重量割合は10~90重量%であることが好ましい。また、前記透水性付与剤の不揮発分全体に占めるアルキルホスフェート塩(B)の重量割合は5~80重量%であることが好ましい。 The weight ratio of the polyether polyester compound (A) in the entire nonvolatile content of the water permeability imparting agent is preferably 10 to 90% by weight. Further, the weight ratio of the alkyl phosphate salt (B) to the whole nonvolatile content of the water permeability imparting agent is preferably 5 to 80% by weight.
 また、本発明にかかる透水性付与剤は、エステル油および鉱物油から選ばれる少なくとも1種の平滑剤(C)をさらに含有してもよく、前記透水性付与剤の不揮発分全体に占める前記平滑剤(C)の重量割合は0.2~40重量%であることが好ましい。 Moreover, the water-permeability imparting agent according to the present invention may further contain at least one leveling agent (C) selected from ester oils and mineral oils, and the smoothness occupying the entire nonvolatile content of the water-permeability imparting agent. The weight ratio of the agent (C) is preferably 0.2 to 40% by weight.
 また、前記エステル油は、1価アルコールおよび/または1価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステル、および多価アルコールおよび/または多価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステルから選ばれる少なくとも1種であることが好ましい。前記鉱物油は、マシン油、スピンドル油および流動パラフィンから選ばれる少なくとも1種であることが好ましい。 The ester oil may be a monohydric alcohol and / or a fatty acid ester obtained from a (poly) ether compound obtained by adding a C 2-4 alkylene oxide to a monohydric alcohol and a fatty acid, and a polyhydric alcohol and / or polyhydric alcohol. It is preferably at least one selected from fatty acid esters obtained from a (poly) ether compound obtained by adding a C 2-4 alkylene oxide to a monohydric alcohol and a fatty acid. The mineral oil is preferably at least one selected from machine oil, spindle oil and liquid paraffin.
 また、本発明にかかる透水性付与剤は、ジアルキルスルホサクシネート塩(D1)、ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルとジカルボン酸との縮合物の少なくとも1つの水酸基を脂肪酸で封鎖したエステル(D2)および含窒素系界面活性剤(D3)から選ばれる少なくとも1種の成分(D)を含有してもよく、前記透水性付与剤の不揮発分全体に占める前記成分(D)の重量割合が0.2~40重量%であることが好ましい。 The water permeability imparting agent according to the present invention is an ester in which at least one hydroxyl group of a condensate of dialkylsulfosuccinate salt (D1), polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid is blocked with a fatty acid. (D2) and at least one component (D) selected from a nitrogen-containing surfactant (D3) may be contained, and the weight ratio of the component (D) in the entire nonvolatile content of the water-permeability imparting agent Is preferably 0.2 to 40% by weight.
 また、本発明にかかる透水性付与剤は、不織布製造用疎水性合成繊維に用いられることが好ましい。
 本発明にかかる透水性繊維は、不織布製造用疎水性合成繊維に対して、請求項1~6のいずれかに記載の透水性付与剤を処理して得られ、得られた繊維に対する透水性付与剤の不揮発分の付着率が0.1~2重量%である。
 本発明にかかる不織布の製造方法は、前記の透水性繊維を集積させて繊維ウェブを作製し、得られた繊維ウェブを熱処理する工程を含むものである。
Moreover, it is preferable that the water-permeability imparting agent according to the present invention is used for hydrophobic synthetic fibers for producing nonwoven fabrics.
The water-permeable fiber according to the present invention is obtained by treating the hydrophobic synthetic fiber for producing a nonwoven fabric with the water-permeability imparting agent according to any one of claims 1 to 6, and imparting water permeability to the obtained fiber. The adhesion rate of the non-volatile content of the agent is 0.1 to 2% by weight.
The manufacturing method of the nonwoven fabric concerning this invention includes the process of producing the fiber web by accumulating the said water-permeable fiber, and heat-processing the obtained fiber web.
 本発明にかかる透水性付与剤、この透水性付与剤が付着した透水性繊維および不織布は、瞬時透水性、耐久透水性、液戻り防止性およびカード通過性のいずれについても高い性能レベルを有し、安全性にも優れる。 The water-permeability imparting agent according to the present invention, the water-permeable fiber and the nonwoven fabric to which the water-permeability imparting agent is attached have high performance levels in terms of instantaneous water permeability, durable water permeability, liquid return prevention property and card passability. Excellent safety.
 本発明の透水性付与剤は、上記一般式(1)で示されるポリエーテルポリエステル化合物(A)を必須成分として含有するものである。以下、詳細に説明する。 The water permeability imparting agent of the present invention contains the polyether polyester compound (A) represented by the general formula (1) as an essential component. Details will be described below.
〔ポリエーテルポリエステル化合物(A)〕
 上記一般式(1)で示されるポリエーテルポリエステル化合物(A)(以下、成分(A)ということがある)は、瞬時透水性と耐久透水性において非常に優れる成分である。一般式(1)中、R、Rは1価の脂肪族アルコールからOH基を除いた残基(脂肪族炭化水素基)である。脂肪族炭化水素基の炭素数は分布があってもよく、脂肪族炭化水素基は、飽和であっても不飽和であってもよく、直鎖状であっても分岐を有していてもよく、多環構造を有していてもよい。脂肪族炭化水素基の炭素数は、1~60が挙げられるが、耐久透水性を向上させる点から、10~60がより好ましく、12~60がさらに好ましく、14~60が特に好ましい。
[Polyether polyester compound (A)]
The polyether polyester compound (A) represented by the general formula (1) (hereinafter sometimes referred to as component (A)) is a component that is extremely excellent in instantaneous water permeability and durable water permeability. In General Formula (1), R 1 and R 3 are residues (aliphatic hydrocarbon groups) obtained by removing OH groups from monovalent aliphatic alcohols. The number of carbon atoms of the aliphatic hydrocarbon group may be distributed, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. It may have a polycyclic structure. The aliphatic hydrocarbon group may have 1 to 60 carbon atoms, but is preferably 10 to 60, more preferably 12 to 60, and particularly preferably 14 to 60 from the viewpoint of improving durable water permeability.
 1価の脂肪族アルコールとしては、例えば、メタノール、エタノール、ブタノール、2-エチルヘキサノール、ラウリルアルコール、パルミチルアルコール、パルミトレイルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコール、エイコサノール、ドコサノール、テトロコサノール、ヘキサコサノール、オクタコサノール、ノナコサノール、トリアコンタノール、C24~26アルコール(伊藤製油(株)製、商品名:ハイソコール246)、C32~36アルコール(新日本理化(株)製、商品名:NJコール3236)、C14~60アルコール(米国ペトロライト社製、商品名:ユニリンアルコール450)、C30~60アルコール(日本精化(株)製、商品名:ラノリンアルコールA)等が挙げられる。これらの中でも、C24~26アルコール、C32~36アルコール、C14~60、C30~60アルコール等の炭素数が14以上のものが好ましい。これらの脂肪族アルコールは、1種から構成されていてもよく、また2種以上から構成されていてもよい。
 また、脂肪族アルコールは、耐久透水性を向上させる点から、炭素数1~60の範囲で分布を有することが好ましい。つまり、炭素数1~60の範囲で、炭素数が異な複数の脂肪族アルコールであることが好ましい。分布を有する炭素数の範囲は10~60が好ましく、12~60がより好ましく、14~60がさらに好ましい。分布は、この炭素数範囲の一部で有していてもよく、全範囲で有していてもよい。この炭素数範囲の一部で分布を有する場合、炭素数が異なる脂肪族アルコールは3種以上が好ましく、5~60種がより好ましく、10~55種がさらに好ましく、15~50種が特に好ましい。
Examples of the monovalent aliphatic alcohol include methanol, ethanol, butanol, 2-ethylhexanol, lauryl alcohol, palmityl alcohol, palmitolyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosanol, docosanol, tetrocosanol, hexa Cosanol, octacosanol, nonacosanol, triacontanol, C24-26 alcohol (made by Ito Oil Co., Ltd., trade name: Hysokol 246), C32-36 alcohol (made by Shin Nippon Rika Co., Ltd., trade name: NJ Cole 3236) ), C14-60 alcohol (trade name: Unilin alcohol 450, manufactured by Petrolite, USA), C30-60 alcohol (trade name: lanolin alcohol A, manufactured by Nippon Seika Co., Ltd.), and the like. That. Among these, those having 14 or more carbon atoms such as C24-26 alcohol, C32-36 alcohol, C14-60, C30-60 alcohol and the like are preferable. These aliphatic alcohols may be composed of one kind or two or more kinds.
The aliphatic alcohol preferably has a distribution in the range of 1 to 60 carbon atoms from the viewpoint of improving the durable water permeability. That is, a plurality of aliphatic alcohols having different carbon numbers in the range of 1 to 60 carbon atoms are preferable. The range of the number of carbon atoms having a distribution is preferably 10 to 60, more preferably 12 to 60, and still more preferably 14 to 60. The distribution may be part of this carbon number range, or may be in the entire range. When having a distribution in a part of this carbon number range, the aliphatic alcohols having different carbon numbers are preferably 3 or more, more preferably 5 to 60, further preferably 10 to 55, and particularly preferably 15 to 50. .
 AOは炭素数2~4のオキシアルキレン基である。オキシアルキレン単位の繰り返し数であるaおよびbは、それぞれ独立して2~100の整数であり、5~50が好ましく、6~30がより好ましい。(AO)および(AO)は、オキシアルキレン単位としてオキシエチレン単位を50モル%以上有するポリオキシアルキレン基が好ましい。 AO is an oxyalkylene group having 2 to 4 carbon atoms. A and b, which are repeating numbers of oxyalkylene units, are each independently an integer of 2 to 100, preferably 5 to 50, more preferably 6 to 30. (AO) a and (AO) b are preferably polyoxyalkylene groups having 50 mol% or more of oxyethylene units as oxyalkylene units.
 Rは2価の有機基であり、ジカルボン酸およびジカルボン酸の無水物からカルボキシル基(または酸無水物基)を除いた2価の有機基を挙げることができる。Rとしては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、チオジプロピオン酸、チオジオクタン酸、チオジラウリン酸、チオジステアリン酸等およびこれらのジカルボン酸の無水物等からカルボキシル基(または酸無水物基)を除いた2価の有機基を挙げられる。これらの中でも、(無水)コハク酸、(無水)マレイン酸からカルボキシル基(または酸無水物基)を除いた2価の有機基が好ましい。 R 2 is a divalent organic group, and examples thereof include a divalent organic group obtained by removing a carboxyl group (or an acid anhydride group) from dicarboxylic acid and dicarboxylic acid anhydride. R 2 includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, thiodipropion Examples thereof include divalent organic groups obtained by removing a carboxyl group (or acid anhydride group) from acids, thiodioctanoic acid, thiodilauric acid, thiodistearic acid and the like and anhydrides of these dicarboxylic acids. Among these, a divalent organic group obtained by removing a carboxyl group (or an acid anhydride group) from (anhydrous) succinic acid or (anhydrous) maleic acid is preferable.
 成分(A)は、1価の脂肪族アルコールのアルキレンオキシド付加物とジカルボン酸とを脱水縮合反応して得られる縮合物である。成分(A)の縮合物を製造する場合、1価の脂肪族アルコールのアルキレンオキシド付加物の水酸基1モル当量あたりのジカルボン酸のカルボキシル基モル当量は、0.2~1の範囲であることが好ましく、0.4~0.8がさらに好ましい。成分(A)を製造する際のエステル化の方法、反応条件等については特に限定はなく、公知の方法、通常の条件を採用できる。例えば、1価の脂肪族アルコールのアルキレンオキシド付加物1モルと無水マレイン酸0.5モルとの割合で、触媒存在下の窒素ガス気流下で、生成する水を留去しながら加温して反応させることにより得られる。 Component (A) is a condensate obtained by a dehydration condensation reaction between an alkylene oxide adduct of a monovalent aliphatic alcohol and a dicarboxylic acid. When preparing the condensate of component (A), the carboxyl group molar equivalent of dicarboxylic acid per molar equivalent of hydroxyl group of the alkylene oxide adduct of monovalent aliphatic alcohol is in the range of 0.2 to 1. 0.4 to 0.8 is more preferable. There are no particular limitations on the esterification method, reaction conditions, and the like when producing component (A), and any known method or ordinary conditions can be employed. For example, in a ratio of 1 mol of an alkylene oxide adduct of a monovalent aliphatic alcohol and 0.5 mol of maleic anhydride, heating is performed while distilling off the generated water in a nitrogen gas stream in the presence of a catalyst. It is obtained by reacting.
 透水性付与剤の不揮発分全体に占める成分(A)の重量割合は、10~90重量%が好ましく、10~80重量%がより好ましく、30~80重量%がさらに好ましく、40~70重量%が特に好ましい。
 なお、本発明の透水性付与剤の不揮発分とは、水分などを除くための熱乾燥工程後においても繊維表面に残存する透水性付与剤中の成分を意味し、透水性付与剤を105℃で熱処理して水分などを除去し、恒量に達したときの揮発せずに残存した成分を意味する。
The weight ratio of the component (A) in the non-volatile content of the water permeability imparting agent is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, further preferably 30 to 80% by weight, and 40 to 70% by weight. Is particularly preferred.
The nonvolatile content of the water-permeability imparting agent of the present invention means a component in the water-permeability imparting agent remaining on the fiber surface even after the heat drying step for removing moisture and the like. It means a component that remains without being volatilized when it reaches a constant weight by removing heat and the like by heat treatment.
〔アルキルホスフェート塩(B)〕
 本発明の透水性付与剤は、成分(A)に加え、前述の一般式(2)で示されるアルキルホスフェート塩(B)(以下、成分(B)ということがある)をさらに含むことが好ましい。成分(B)は、特にカード通過性能、耐久透水性を保持する性能、液戻り量を少なくする性能に優れた成分である。
 一般式(2)中、Rは炭素数6~22のアルキル基であり、炭素数は10~18が好ましく、10~16がより好ましく、10~14がさらに好ましい。アルキル基の炭素数が6未満では、カード工程通過性が低下すると共に製品の臭気が強くなることがあり、アルキル基の炭素数が22超であると、化合物の水溶性、カード通過性、瞬時透水性が低下することがある。アルキル基の炭素数は分布があってもよく、アルキル基は直鎖状であっても分岐を有していてもよく、飽和であっても不飽和であってもよい。
 AOは炭素数2~4のオキシアルキレン基である。オキシアルキレン単位の繰り返し数であるcは0~15の整数であり、0~10が好ましく、0~3がさらに好ましく、cが0でポリオキシアルキレン基を含有しない場合が特に好ましい。(AO)は、オキシアルキレン単位としてオキシエチレン単位を50モル%以上有するポリオキシアルキレン基が好ましい。nは1~2の整数であり、Yは水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、ジエタノールアンモニウムイオンおよびトリエタノールアンモニウムイオンからなる群から選択されるイオン性残基である。これらは混合物であってもよく、また、1種または2種以上を用いてもよい。
[Alkyl phosphate salt (B)]
The water permeability-imparting agent of the present invention preferably further contains an alkyl phosphate salt (B) represented by the aforementioned general formula (2) (hereinafter sometimes referred to as component (B)) in addition to component (A). . The component (B) is a component excellent in card passing performance, performance for maintaining durable water permeability, and performance for reducing liquid return.
In the general formula (2), R 4 is an alkyl group having 6 to 22 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and further preferably 10 to 14 carbon atoms. If the carbon number of the alkyl group is less than 6, the card process passability may decrease and the odor of the product may become strong. If the alkyl group has more than 22 carbon atoms, the water solubility of the compound, the card passability, and the instantaneous Water permeability may decrease. The carbon number of the alkyl group may be distributed, the alkyl group may be linear or branched, and may be saturated or unsaturated.
AO is an oxyalkylene group having 2 to 4 carbon atoms. C, which is the number of repeating oxyalkylene units, is an integer of 0 to 15, preferably 0 to 10, more preferably 0 to 3, and particularly preferably c is 0 and no polyoxyalkylene group is contained. (AO) c is preferably a polyoxyalkylene group having 50 mol% or more of oxyethylene units as oxyalkylene units. n is an integer of 1 to 2, and Y + is an ionic residue selected from the group consisting of hydrogen ion, sodium ion, potassium ion, ammonium ion, diethanolammonium ion and triethanolammonium ion. These may be a mixture, or one or more may be used.
 これらの中でもカード通過性や耐久透水性を保持する性能の向上という理由から、成分(B)は、デシルホスフェートカリウム塩、ラウリルホスフェートカリウム塩、トリデシルホスフェートカリウム塩、ミリスチルホスフェートカリウム塩、セチルホスフェートカリウム塩、オレイルホスフェートカリウム塩、ポリオキシエチレン2モル付加セチルホスフェートカリウム塩、ポリオキシエチレン3モル付加ラウリルホスフェートジエタノールアンモニウム塩、ポリオキシエチレン3モル付加ラウリルホスフェートトリエタノールアンモニウム塩が好ましく、ラウリルホスフェートカリウム塩がさらに好ましい。 Among these, the component (B) is composed of decyl phosphate potassium salt, lauryl phosphate potassium salt, tridecyl phosphate potassium salt, myristyl phosphate potassium salt, cetyl phosphate potassium, for the purpose of improving the performance of maintaining card permeability and durable water permeability. Salt, oleyl phosphate potassium salt, polyoxyethylene 2 mol addition cetyl phosphate potassium salt, polyoxyethylene 3 mol addition lauryl phosphate diethanolammonium salt, polyoxyethylene 3 mol addition lauryl phosphate triethanolammonium salt are preferred, lauryl phosphate potassium salt is preferred Further preferred.
 透水性付与剤の不揮発分全体に占める成分(B)の重量割合は、5~80重量%が好ましく、10~60重量%がより好ましく、20~50重量%がさらに好ましく、20~40重量%が特に好ましい。
 また、本発明の透水性付与剤は、その効果をより一層発揮させるために、特に瞬時透水性能と耐久透水性能に優れた成分(A)と、特にカード通過性能、耐久透水性を保持する性能、液戻り量を少なくする性能に優れた成分(B)との重量比(A)/(B)を30/70~90/10となるようにすることが好ましく、40/60~80/20がさらに好ましく、50/50~70/30が特に好ましい。
The weight ratio of the component (B) in the entire nonvolatile content of the water permeability imparting agent is preferably 5 to 80% by weight, more preferably 10 to 60% by weight, further preferably 20 to 50% by weight, and 20 to 40% by weight. Is particularly preferred.
In addition, the water-permeability imparting agent of the present invention has a component (A) that is particularly excellent in instantaneous water-permeable performance and durable water-permeable performance, and in particular, card-passing performance and performance that retains durable water-permeable properties in order to further exert its effects. The weight ratio (A) / (B) to the component (B) excellent in performance for reducing the liquid return amount is preferably 30/70 to 90/10, and preferably 40/60 to 80/20. Is more preferable, and 50/50 to 70/30 is particularly preferable.
 本発明の透水性付与剤は、成分(A)に加え、または成分(A)と成分(B)に加え、後述の平滑剤(C)および/または成分(D)をさらに含有してもよい。 The water permeability imparting agent of the present invention may further contain a smoothing agent (C) and / or a component (D) described later in addition to the component (A) or in addition to the component (A) and the component (B). .
〔平滑剤(C)〕
 平滑剤(C)(以下、成分(C)ということがある)は、エステル油および鉱物油から選ばれる少なくとも1種であり、より一層のカード通過性等を向上することができる成分である。とくに、シリンダーへの巻付きが少なくウェブにネップが発生しにくいので、表面品位の優れた不織布が得られる。
 成分(C)をさらに含む場合において、透水性付与剤の不揮発分全体に占める成分(C)の重量割合は、0.2~40重量%が好ましく、5~30重量%がさらに好ましく、10~20重量%が特に好ましい。重量割合が、40重量%超になると、透水性付与剤の水溶性が不足し溶液安定性の低下やカード工程での制電性が低下することがある。
[Smoothing agent (C)]
The smoothing agent (C) (hereinafter sometimes referred to as “component (C)”) is at least one selected from ester oils and mineral oils, and is a component that can further improve the card passability and the like. In particular, since there is little wrapping around the cylinder and it is difficult for the web to be nipped, a nonwoven fabric with excellent surface quality can be obtained.
In the case where the component (C) is further included, the weight ratio of the component (C) to the whole non-volatile content of the water-permeability imparting agent is preferably 0.2 to 40% by weight, more preferably 5 to 30% by weight. 20% by weight is particularly preferred. If the weight ratio exceeds 40% by weight, the water permeability of the water-permeability imparting agent may be insufficient, resulting in a decrease in solution stability and an antistatic property in a card process.
 成分(C)のエステル油について、特に限定はないが、1価アルコールおよび/または1価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステル、および多価アルコールおよび/または多価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステルから選ばれる少なくとも1種の脂肪酸エステルが好ましい。 The ester oil of component (C) is not particularly limited, but a fatty acid ester obtained from a monohydric alcohol and / or a (poly) ether compound in which an alkylene oxide having 2 to 4 carbon atoms is added to the monohydric alcohol and a fatty acid, In addition, at least one fatty acid ester selected from fatty acid esters obtained from (poly) ether compounds obtained by adding a polyhydric alcohol and / or a polyhydric alcohol with a C 2-4 alkylene oxide and a fatty acid is preferable.
 脂肪酸エステルを構成する原料の1価アルコールとしては、特に限定はないが、1価の脂肪族アルコール等が挙げられる。1価の脂肪族アルコールの炭素数は分布があってもよい。また、飽和であっても不飽和あってもよく、直鎖状であってもよく、分岐を有していてもよい。脂肪族アルコールの炭素数は、1~22が好ましく、8~18がより好ましく、10~18がさらに好ましく、12~18が特に好ましい。
 1価アルコールとしては、例えば、メタノール、エタノール、ブタノール、2-エチルヘキサノール、ラウリルアルコール、パルミチルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコール、ベヘニルアルコール等が挙げられる。
 1価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物のアルキレンオキサイドの付加モル数は、0~150が好ましく、0~50がさらに好ましく、アルキレンオキサイドを含有しない場合が特に好ましい。
Although it does not specifically limit as a monohydric alcohol of the raw material which comprises fatty acid ester, A monohydric aliphatic alcohol etc. are mentioned. The carbon number of the monovalent aliphatic alcohol may be distributed. Moreover, it may be saturated or unsaturated, may be linear, and may have a branch. The aliphatic alcohol preferably has 1 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, still more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 18 carbon atoms.
Examples of the monohydric alcohol include methanol, ethanol, butanol, 2-ethylhexanol, lauryl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, and behenyl alcohol.
The number of moles of alkylene oxide added in the (poly) ether compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a monohydric alcohol is preferably 0 to 150, more preferably 0 to 50, particularly when no alkylene oxide is contained. preferable.
 脂肪酸エステルを構成する原料の多価アルコールとしては、特に限定はないが、2~6価のアルコール等が挙げられる。
 多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、ジエチレングリコールなどのジオール類、グリセリン、トリメチロールプロパン、ソルビトール、ソルビタン、ペンタエリスリトール、ショ糖などのポリオール類が挙げられる。さらに、グリセリンの縮合物であるジグリセリン、トリグリセリン、テトラグリセリン、ヘキサグリセリン等のポリグリセリンも含まれる。さらに、これらの(ポリ)オキシアルキレン付加物も挙げられる。
 多価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物のアルキレンオキサイドの付加モル数は、0~150が好ましく、0~50がさらに好ましく、0~20が特に好ましい。
The raw material polyhydric alcohol constituting the fatty acid ester is not particularly limited, and examples thereof include divalent to hexavalent alcohols.
Examples of the polyhydric alcohol include diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, glycerin, trimethylolpropane, sorbitol, sorbitan, pentaerythritol, sucrose, etc. Polyols. Furthermore, polyglycerin such as diglycerin, triglycerin, tetraglycerin and hexaglycerin, which is a condensate of glycerin, is also included. Furthermore, these (poly) oxyalkylene adducts are also mentioned.
The number of moles of alkylene oxide added in the (poly) ether compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a polyhydric alcohol is preferably 0 to 150, more preferably 0 to 50, and particularly preferably 0 to 20.
 脂肪酸エステルを構成する原料の脂肪酸としては、特に限定はなく、飽和脂肪酸であってもよく、不飽和脂肪酸であってもよい。この中でも、飽和脂肪酸が好ましく、脂肪酸の炭素数は、10~30が好ましく、12~18がさらに好ましく、14~18が特に好ましい。
 飽和脂肪酸としては、カプロン酸、カプリル酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ステアリン酸、ノナデカン酸、アラキジン酸、ベヘニン酸、セロチン酸、モンタン酸、メリシン酸等が挙げられる。不飽和脂肪酸としては、オレイン酸、エライジン酸、エルカ酸、リノール酸、リノレン酸等が挙げられる。
The starting fatty acid constituting the fatty acid ester is not particularly limited, and may be a saturated fatty acid or an unsaturated fatty acid. Of these, saturated fatty acids are preferable, and the number of carbon atoms of the fatty acids is preferably 10 to 30, more preferably 12 to 18, and particularly preferably 14 to 18.
Saturated fatty acids include caproic acid, caprylic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, serotic acid, montanic acid, Examples include melicic acid. Examples of the unsaturated fatty acid include oleic acid, elaidic acid, erucic acid, linoleic acid, linolenic acid and the like.
 これらの脂肪酸エステルは、前述の1価アルコールや多価アルコールおよび/またはそれらアルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とを適宜選択して公知の合成法により得ることができる。 These fatty acid esters are prepared by appropriately selecting the above-mentioned monohydric alcohols and polyhydric alcohols and / or (poly) ether compounds in which alkylene oxides having 2 to 4 carbon atoms are added to these alcohols and fatty acids, and by known synthesis methods. Obtainable.
 1価アルコールおよび/または1価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステルとしては、ラウリルオレエート、ステアリルオレエート、オレイルオレエート、イソオクチルオレエート、イソオクチルパルミテート、イソオクチルステアレート、トリデシルオレエート、ブチルステアレート、2-エチルヘキシルオレエート、オレイルステアレート、オレイルパルミテート、オレイルラウレート、オレイルイソステアレート、ポリオキシエチレン(10モル)ステアリルエーテルのオレイン酸エステル等が挙げられる。
 また、多価アルコールおよび/または1価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステルとしては、グリセリンモノオレエート、グリセリンモノステアレート、ヘキサグリセリンモノステアレート、トリメチロールプロパンモノパルミテート、ソルビタンモノオレエート、ポリオキシエチレン(20モル)グリセリンモノステアレート等が挙げられる。
 これらの中でも、脂肪酸エステルとしては、イソオクチルパルミテートやイソオクチルステアレートが特に好ましい。
Examples of the fatty acid ester obtained from a (poly) ether compound obtained by adding a monohydric alcohol and / or a monohydric alcohol with a C 2-4 alkylene oxide and a fatty acid include lauryl oleate, stearyl oleate, oleyl oleate, Octyl oleate, isooctyl palmitate, isooctyl stearate, tridecyl oleate, butyl stearate, 2-ethylhexyl oleate, oleyl stearate, oleyl palmitate, oleyl laurate, oleyl isostearate, polyoxyethylene ( 10 mol) Stearyl ether oleate and the like.
Examples of the fatty acid ester obtained from a (poly) ether compound obtained by adding a C 2-4 alkylene oxide to a polyhydric alcohol and / or a monohydric alcohol and a fatty acid include glycerin monooleate, glycerin monostearate, hexa Examples include glycerol monostearate, trimethylolpropane monopalmitate, sorbitan monooleate, polyoxyethylene (20 mol) glycerol monostearate and the like.
Among these, isooctyl palmitate and isooctyl stearate are particularly preferable as the fatty acid ester.
 成分(C)の鉱物油としては、マシン油、スピンドル油および流動パラフィンから選ばれる少なくとも1種であることが好ましい。鉱物油の30℃の粘度は、1×10-6~5×10-5/sが好ましく、1×10-6~4×10-5/sがより好ましい。鉱物油としては流動パラフィンが好ましい。 The mineral oil of component (C) is preferably at least one selected from machine oil, spindle oil and liquid paraffin. The viscosity of the mineral oil at 30 ° C. is preferably 1 × 10 −6 to 5 × 10 −5 m 2 / s, and more preferably 1 × 10 −6 to 4 × 10 −5 m 2 / s. As the mineral oil, liquid paraffin is preferable.
〔成分(D)〕
 本発明の透水性付与剤は、耐久透水性を補助する成分として、ジアルキルスルホサクシネート塩(D1)、ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルとジカルボン酸との縮合物の少なくとも1つの水酸基を脂肪酸で封鎖したエステル(D2)および含窒素系界面活性剤(D3)から選ばれる少なくとも1種の成分(D)を、安全性を損なわない範囲で含んでもよい。透水性付与剤の不揮発分全体に占める成分(D)の重量割合は0.2~40重量%が好ましく、5~40重量%がより好ましく、5~30重量%がさらに好ましく、5~20重量%が特に好ましい。重量割合が40重量%超になると、カード通過性等が悪化することがある。また、成分(D1)および/または成分(D3)を必須に含む場合は、透水性付与剤の不揮発分全体に占める成分(D1)と成分(D3)の合計量は、0.2~30重量%が好ましく、5~20重量%がより好ましく、5~10重量%がさらに好ましい。
[Component (D)]
The water-permeability imparting agent of the present invention contains at least one hydroxyl group of a condensate of a dialkyl sulfosuccinate salt (D1), a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and a dicarboxylic acid as a component for assisting durable water permeability. At least one component (D) selected from an ester (D2) blocked with a fatty acid and a nitrogen-containing surfactant (D3) may be included within a range not impairing safety. The weight ratio of the component (D) in the entire nonvolatile content of the water permeability imparting agent is preferably 0.2 to 40% by weight, more preferably 5 to 40% by weight, further preferably 5 to 30% by weight, and 5 to 20% by weight. % Is particularly preferred. When the weight ratio exceeds 40% by weight, the card passing property may deteriorate. When component (D1) and / or component (D3) is essential, the total amount of component (D1) and component (D3) in the entire nonvolatile content of the water permeability imparting agent is 0.2 to 30 wt. %, More preferably 5 to 20% by weight, still more preferably 5 to 10% by weight.
〔成分(D1)〕
 前記のジアルキルスルホサクシネート塩(D1)(成分(D1)ということがある)は、α位にスルホン酸塩の基を有するコハク酸のジアルキルエステルである。ジアルキルエステルを構成するアルキル基の炭素数は分布があってもよく、アルキル基は直鎖状であっても分岐を有していてもよく、飽和であっても不飽和であってもよい。アルキル基の炭素数は6~18が好ましく、8~18がより好ましく、10~18がさらに好ましく、12~14が特に好ましい。アルキル基の炭素数が6未満ではカード通過性が低下することがある。一方、アルキル基の炭素数が18超であると、瞬時透水性が低下することがある。
[Component (D1)]
The dialkylsulfosuccinate salt (D1) (sometimes referred to as component (D1)) is a dialkyl ester of succinic acid having a sulfonate group at the α-position. The number of carbon atoms of the alkyl group constituting the dialkyl ester may be distributed, and the alkyl group may be linear or branched, and may be saturated or unsaturated. The alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 18 carbon atoms, still more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 14 carbon atoms. If the alkyl group has less than 6 carbon atoms, the card passing property may decrease. On the other hand, if the carbon number of the alkyl group exceeds 18, the instantaneous water permeability may decrease.
 成分(D1)のスルホン酸塩としては、ナトリウム塩やカリウム塩等のアルカリ金属塩、アミン塩を挙げることができ、ナトリウム塩および/またはカリウム塩であると、透水性付与剤が付着した繊維に液体が速やかに浸透するので好ましい。 Examples of the sulfonate salt of component (D1) include alkali metal salts such as sodium salt and potassium salt, and amine salts. When the salt is sodium salt and / or potassium salt, the fiber to which the water permeability-imparting agent has adhered is attached. This is preferable because the liquid penetrates quickly.
 成分(D1)としては、たとえば、ジヘキシルスルホサクシネートナトリウム塩、ジ-2-エチルヘキシルスルホサクシネートナトリウム塩、ジラウリルスルホサクシネートナトリウム塩、ジ椰子アルキルスルホサクシネートナトリウム塩、ジトリデシルスルホサクシネートナトリウム塩、ジミリスチルスルホサクシネートナトリウム塩、ジステアリルスルホサクシネートナトリウム塩等が挙げられる。これらのジアルキルスルホサクシネート塩は、1種または2種以上を併用してもよい。 Examples of the component (D1) include dihexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate sodium salt, dilauryl sulfosuccinate sodium salt, dicoco alkylsulfosuccinate sodium salt, ditridecyl sulfosuccinate sodium salt Salt, dimyristyl sulfosuccinate sodium salt, distearyl sulfosuccinate sodium salt and the like. These dialkyl sulfosuccinate salts may be used alone or in combination of two or more.
〔成分(D2)〕
 ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステル(以下、ポリヒドロキシエステルということがある)とジカルボン酸との縮合物の少なくとも1つの水酸基を脂肪酸で封鎖したエステル(D2)(成分(D2)ということがある)は、疎水性繊維との親和性が高く、成分(D2)を含む付与剤は水と接触しても繊維から脱落し難くなることから、耐久透水性をより向上できる成分である。
[Component (D2)]
An ester (D2) (component (D2)) in which at least one hydroxyl group of a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester (hereinafter sometimes referred to as polyhydroxy ester) and a dicarboxylic acid is blocked with a fatty acid. Is a component that has a high affinity with hydrophobic fibers, and the imparting agent containing the component (D2) is less likely to fall off from the fibers even when it comes into contact with water, and thus is a component that can further improve durable water permeability.
 ポリヒドロキシエステルは、構造上、ポリオキシアルキレン基含有ヒドロキシ脂肪酸と多価アルコールとのエステルであり、多価アルコールの水酸基のうち、2個以上(好ましくは全部)の水酸基がエステル化されている。したがって、ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルは、複数の水酸基を有するエステルである。 The polyhydroxyester is structurally an ester of a polyoxyalkylene group-containing hydroxy fatty acid and a polyhydric alcohol, and two or more (preferably all) hydroxyl groups of the polyhydric alcohol are esterified. Therefore, the polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester is an ester having a plurality of hydroxyl groups.
 ポリオキシアルキレン基含有ヒドロキシ脂肪酸は、脂肪酸の炭化水素基に酸素原子を介してポリオキシアルキレン基が結合した構造を有し、ポリオキシアルキレン基の脂肪酸の炭化水素基と結合していない片末端が水酸基となっている。
 ポリヒドロキシエステルとしては、たとえば、炭素数6~22(好ましくは12~22)のヒドロキシ脂肪酸と多価アルコールとのエステル化物のアルキレンオキシド付加物を挙げることができる。ヒドロキシ脂肪酸の炭素数が6未満であると、親水性が強くなり、一方、22を超えると疎水性が強くなる。いずれの場合も他の成分との相溶性が悪くなるため、十分な耐久透水性を得られないことがある。
The polyoxyalkylene group-containing hydroxy fatty acid has a structure in which a polyoxyalkylene group is bonded to a fatty acid hydrocarbon group via an oxygen atom, and one end that is not bonded to the fatty acid hydrocarbon group of the polyoxyalkylene group is It is a hydroxyl group.
Examples of the polyhydroxyester include an alkylene oxide adduct of an esterified product of a hydroxy fatty acid having 6 to 22 carbon atoms (preferably 12 to 22 carbon atoms) and a polyhydric alcohol. When the number of carbon atoms of the hydroxy fatty acid is less than 6, the hydrophilicity becomes strong, while when it exceeds 22, the hydrophobicity becomes strong. In either case, the compatibility with other components deteriorates, so that sufficient durable water permeability may not be obtained.
 炭素数6~22のヒドロキシ脂肪酸としては、たとえば、ヒドロキシカプリル酸、ヒドロキシカプリン酸、ヒドロキシウンデカン酸、ヒドロキシラウリン酸、ヒドロキシステアリン酸、リシノール酸挙げられ、ヒドロキシステアリン酸、リシノール酸が好ましい。多価アルコールとしては、たとえば、エチレングリコール、グリセリン、ソルビトール、ソルビタン、トリメチロールプロパン、ペンタエリスリトール等が挙げられ、グリセリンが好ましい。アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等の炭素数2~4のアルキレンオキシドが挙げられる。 Examples of the hydroxy fatty acid having 6 to 22 carbon atoms include hydroxycaprylic acid, hydroxycapric acid, hydroxyundecanoic acid, hydroxylauric acid, hydroxystearic acid, and ricinoleic acid, and hydroxystearic acid and ricinoleic acid are preferable. Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, sorbitan, trimethylolpropane, pentaerythritol and the like, and glycerin is preferable. Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide.
 アルキレンオキシドの付加モル数は、上記ヒドロキシ脂肪酸多価アルコールエステルの水酸基1モル当量当り、好ましくは80以下、さらに好ましくは5~30である。付加モル数が80を超えると液戻り量が増加することがあるので好ましくない。高い耐久透水性を得るためには、親水基と疎水基のバランスを調整することが重要である。アルキレンオキシドに占めるエチレンオキシドの割合は、好ましくは50モル%以上、さらに好ましくは80モル%以上である。エチレンオキシドの割合が50モル%未満では、疎水性が強くなるために十分な耐久透水性が得られないことがある。 The number of added moles of alkylene oxide is preferably 80 or less, more preferably 5 to 30 per mole equivalent of hydroxyl group of the hydroxy fatty acid polyhydric alcohol ester. If the added mole number exceeds 80, the liquid return amount may increase, which is not preferable. In order to obtain high durable water permeability, it is important to adjust the balance between the hydrophilic group and the hydrophobic group. The proportion of ethylene oxide in the alkylene oxide is preferably 50 mol% or more, more preferably 80 mol% or more. If the ratio of ethylene oxide is less than 50 mol%, the hydrophobicity becomes strong and sufficient durable water permeability may not be obtained.
 ポリヒドロキシエステルは、たとえば、多価アルコールとヒドロキシ脂肪酸(ヒドロキシモノカルボン酸)を通常の条件でエステル化してエステル化物を得て、次いでこのエステル化物にアルキレンオキシドを付加反応させることによって製造できる。ポリヒドロキシエステルは、ひまし油などの天然から得られる油脂やこれに水素を添加した硬化ひまし油を用い、さらにアルキレンオキシドを付加反応させることによっても、好適に製造できる。
 ポリヒドロキシエステルを製造する場合、多価アルコールの水酸基1モル当量あたりのヒドロキシ脂肪酸のカルボキシル基モル当量は、0.5~1の範囲であることが好ましい。
The polyhydroxyester can be produced, for example, by esterifying a polyhydric alcohol and a hydroxy fatty acid (hydroxymonocarboxylic acid) under ordinary conditions to obtain an esterified product, and then subjecting the esterified product to an addition reaction with an alkylene oxide. The polyhydroxyester can be suitably produced also by using an oil and fat obtained from nature such as castor oil or a hardened castor oil obtained by adding hydrogen to this, and further subjecting it to an addition reaction with an alkylene oxide.
In the case of producing a polyhydroxyester, the carboxyl group molar equivalent of hydroxy fatty acid per molar equivalent of hydroxyl group of polyhydric alcohol is preferably in the range of 0.5-1.
 ポリヒドロキシエステルとジカルボン酸との縮合物において、ジカルボン酸の炭素数については、2~10が好ましく、2~8がさらに好ましい。ジカルボン酸の炭素数が10を超えると十分な親水性を付与できないことがある。このようなジカルボン酸としては、たとえば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フタル酸等が挙げられる。ジカルボン酸と共に、ラウリン酸、オレイン酸、ステアリン酸、ベヘン酸、安息香酸等のジカルボン酸以外のカルボン酸を20%以下(好ましくは10%以下)含有してもよい。ポリヒドロキシエステルとジカルボン酸との縮合物を製造する場合、ポリヒドロキシエステルの水酸基1モル当量あたりのジカルボン酸のカルボキシル基モル当量は、0.2~1の範囲であることが好ましく、0.4~0.8がさらに好ましい。成分(D2)を製造する際のエステル化の方法、反応条件等については特に限定はなく、公知の方法、通常の条件を採用できる。 In the condensate of polyhydroxyester and dicarboxylic acid, the carbon number of the dicarboxylic acid is preferably 2 to 10, more preferably 2 to 8. If the carbon number of the dicarboxylic acid exceeds 10, sufficient hydrophilicity may not be imparted. Examples of such dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and phthalic acid. Along with the dicarboxylic acid, 20% or less (preferably 10% or less) of a carboxylic acid other than the dicarboxylic acid such as lauric acid, oleic acid, stearic acid, behenic acid and benzoic acid may be contained. When producing a condensate of polyhydroxyester and dicarboxylic acid, the carboxyl group molar equivalent of dicarboxylic acid per molar equivalent of hydroxyl group of polyhydroxyester is preferably in the range of 0.2 to 1, More preferred is 0.8. There is no limitation in particular about the method of esterification, reaction conditions, etc. at the time of manufacturing a component (D2), A well-known method and normal conditions are employable.
 本発明の成分(D2)は、上述のポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルとジカルボン酸との縮合物(以下、縮合物ということがある)において、少なくとも1つの水酸基を脂肪酸で封鎖したエステルである。脂肪酸で封鎖していないエステルでは、耐久透水性能が不足し、また化合物が経時的に増粘し水不溶物が増加するので、付与剤の溶液安定性が低下する。
 縮合物の少なくとも1つ以上の水酸基を封鎖する脂肪酸の炭素数は10~50が好ましく、12~36がさらに好ましい。また、脂肪酸の炭素数が10未満であると親水性が強くなり、十分な耐久透水性を得ることができないことがある。脂肪酸中の炭化水素基の炭素数は分布があってもよく、炭化水素基は直鎖状であっても分岐を有していてもよく、飽和であっても不飽和であってもよく、多環構造を有していてもよい。このような脂肪酸としては、たとえば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、イコサン酸、ベヘン酸、リグノセリン酸、ネルボン酸、セロチン酸、モンタン酸、メリシン酸、ラノリン脂肪酸等が挙げられるが、ベヘン酸やウールグリースを精製したラノリン誘導体である炭素数12~36のラノリン脂肪酸が好ましい。縮合物と脂肪酸とのエステルを製造する場合、縮合物の水酸基1モル当量あたりの脂肪酸のカルボキシル基モル当量は0.2~1の範囲であることが好ましく、0.4~1がさらに好ましい。エステル化の反応条件については特に限定はない。
Component (D2) of the present invention has at least one hydroxyl group blocked with a fatty acid in the above-mentioned condensate of polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid (hereinafter sometimes referred to as condensate). Ester. Esters that are not capped with fatty acids have insufficient durable water permeation performance, and the viscosity of the compound increases with time, resulting in an increase in water-insoluble matter, thus reducing the solution stability of the imparting agent.
The number of carbon atoms of the fatty acid blocking at least one or more hydroxyl groups of the condensate is preferably 10 to 50, and more preferably 12 to 36. Further, if the fatty acid has less than 10 carbon atoms, the hydrophilicity becomes strong and sufficient durable water permeability may not be obtained. The carbon number of the hydrocarbon group in the fatty acid may be distributed, the hydrocarbon group may be linear or branched, may be saturated or unsaturated, It may have a polycyclic structure. Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, icosanoic acid, behenic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melicic acid, and lanolin fatty acid. However, lanolin fatty acid having 12 to 36 carbon atoms, which is a lanolin derivative obtained by purifying behenic acid or wool grease, is preferable. When an ester of a condensate and a fatty acid is produced, the carboxyl group molar equivalent of the fatty acid per molar equivalent of the hydroxyl group of the condensate is preferably in the range of 0.2 to 1, and more preferably 0.4 to 1. There are no particular limitations on the reaction conditions for esterification.
〔成分(D3)〕
 含窒素系界面活性剤(D3)(成分(D3)ということがある)としては、アンモニウム塩型カチオン界面活性剤(D3a)、イミダゾリニウム型カチオン界面活性剤(D3b)、アルキルベタイン界面活性剤(D3c)、アルキルイミダゾール型ベタイン界面活性剤(D3d)、アミド基含有ベタイン界面活性剤(D3e)および高級脂肪酸アルカノールアミド型界面活性剤(D3f)から選ばれる少なくとも1種であることが好ましい。
 本発明の成分(D3)は、瞬時透水性や耐久透水性に優れた成分であるが、カード通過性や安全性が劣ることがあるので最少量の使用が好ましい。
[Component (D3)]
Examples of the nitrogen-containing surfactant (D3) (sometimes referred to as component (D3)) include ammonium salt type cationic surfactant (D3a), imidazolinium type cationic surfactant (D3b), and alkylbetaine surfactant. It is preferably at least one selected from (D3c), alkylimidazole type betaine surfactant (D3d), amide group-containing betaine surfactant (D3e) and higher fatty acid alkanolamide type surfactant (D3f).
The component (D3) of the present invention is a component excellent in instantaneous water permeability and durable water permeability, but it is preferably used in a minimum amount because the card passing property and safety may be inferior.
 アンモニウム塩型カチオン界面活性剤(D3a)としては特に限定はないが、例えば、ジオクチルジメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライド、ジラウリルジメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド、ジ椰子アルキルジメチルアンモニウムクロライド、ジ硬化牛脂アルキルジメチルアンモニウムクロライド、ベヘニルトリメチルアンモニウムクロライド、ジラウリルジメチルアンモニウムメトサルフェート、ジラウリルメチルエチルアンモニウムエトサルフェート、ジステアリルジメチルアンモニウムメトサルフェート、ジ(オレイロキシエチル)ヒドロキシエチルメチルアンモニウムメトサルフェート、ジ(ステアリン酸アミドエチル)ヒドロキシエチルメチルアンモニウムメトサルフェート等が挙げられる。これらのなかでも、ジラウリルジメチルアンモニウムクロライドやジステアリルジメチルアンモニウムクロライドが好ましい。 The ammonium salt type cationic surfactant (D3a) is not particularly limited. For example, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, dicoco alkyldimethylammonium chloride, Di-cured tallow alkyldimethylammonium chloride, behenyltrimethylammonium chloride, dilauryldimethylammonium methosulfate, dilaurylmethylethylammonium etosulphate, distearyldimethylammonium methosulfate, di (oleyloxyethyl) hydroxyethylmethylammonium methosulfate, di ( Amidoethyl stearate) hydroxyethylmethyla Methosulfate, and the like. Among these, dilauryl dimethyl ammonium chloride and distearyl dimethyl ammonium chloride are preferable.
 イミダゾリニウム型カチオン界面活性剤(D3b)としては特に限定はないが、イミダゾリニウム環の2位の置換基が炭素数11~21の脂肪族炭化水素基であって、アニオン基がメチル硫酸イオン、エチル硫酸イオンおよびジメチル燐酸イオンからなる群から選択されるイオン性残基である場合のものが好ましい。かかるイミダゾリニウム型カチオン界面活性剤としては、例えば1-ヒドロキシエチル-1-エチル-2-ラウリルイミダゾリニウムエチルサルフェート、1-ヒドロキシエチル-1-エチル-2-オレイルイミダゾリニウムエチルサルフェート、1-ヒドロキシエチル-1-エチル-2-ステアリルイミダゾリニウムエチルサルフェート、1-ヒドロキシエチル-1-メチル-2-テトラデシルイミダゾリニウムメチルサルフェート、1-ヒドロキシエチル-1-メチル-2-ラウリルイミダゾリニウムメチルサルフェート、1-ヒドロキシエチル-1-メチル-2-オレイルイミダゾリニウムメチルサルフェート、1-ヒドロキシエチル-1-メチル-2-ステアリルイミダゾリニウムメチルサルフェート、1-ヒドロキシエチル-1-メチル-2-オレイルイミダゾリニウムジメチルホスフェート等が挙げられる。これらのなかでも、1-ヒドロキシエチル-1-エチル-2-オレイルイミダゾリニウムエチルサルフェートが好ましい。 The imidazolinium type cationic surfactant (D3b) is not particularly limited, but the substituent at the 2-position of the imidazolinium ring is an aliphatic hydrocarbon group having 11 to 21 carbon atoms, and the anionic group is methylsulfuric acid. Those that are ionic residues selected from the group consisting of ions, ethyl sulfate ions and dimethyl phosphate ions are preferred. Examples of such imidazolinium type cationic surfactants include 1-hydroxyethyl-1-ethyl-2-laurylimidazolinium ethyl sulfate, 1-hydroxyethyl-1-ethyl-2-oleylimidazolinium ethyl sulfate, 1 -Hydroxyethyl-1-ethyl-2-stearylimidazolinium ethyl sulfate, 1-hydroxyethyl-1-methyl-2-tetradecylimidazolinium methyl sulfate, 1-hydroxyethyl-1-methyl-2-lauryl imidazoli 1-hydroxyethyl-1-methyl-2-oleylimidazolinium methylsulfate, 1-hydroxyethyl-1-methyl-2-stearylimidazolinium methylsulfate, 1-hydroxyethyl-1- Chill 2-oleyl imidazolinium dimethyl phosphate. Of these, 1-hydroxyethyl-1-ethyl-2-oleylimidazolinium ethyl sulfate is preferred.
 アルキルベタイン界面活性剤(D3c)としては特に限定はないが、例えば、ラウリルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ラウリルジメチルアミノスルホプロピルベタイン、ラウリルジメチルヒドロキシスルホベタイン等が挙げられる。これらの中でも、ステアリルジメチルアミノ酢酸ベタインが好ましい。 The alkylbetaine surfactant (D3c) is not particularly limited, and examples thereof include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, lauryldimethylaminosulfopropylbetaine, and lauryldimethylhydroxysulfobetaine. Among these, stearyldimethylaminoacetic acid betaine is preferable.
 アルキルイミダゾール型ベタイン界面活性剤(D3d)としては特に限定はないが、例えば、2-ラウリル―N―カルボキシメチル―N-ヒドロキシエチルイミダゾリニウムベタイン、2-オレイル―N―カルボキシメチル―N-ヒドロキシエチルイミダゾリニウムベタイン等が挙げられる。これらのなかでも、2-ラウリル―N―カルボキシメチル―N-ヒドロキシエチルイミダゾリニウムベタインが好ましい。 The alkylimidazole type betaine surfactant (D3d) is not particularly limited, and examples thereof include 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-oleyl-N-carboxymethyl-N-hydroxy. Examples include ethyl imidazolinium betaine. Of these, 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine is preferred.
 アミド基含有ベタイン界面活性剤(D3e)としては特に限定はないが、例えば、ラウリン酸アミドプロピルジメチルアミノ酢酸ベタイン、オレイン酸アミドプロピルジメチルアミノ酢酸ベタイン、ステアリン酸アミドプロピルジメチルアミノ酢酸ベタイン等が挙げられ、これらの中でも、ステアリン酸アミドプロピルジメチルアミノ酢酸ベタインが好ましい。 The amide group-containing betaine surfactant (D3e) is not particularly limited, and examples thereof include lauric acid amidopropyldimethylaminoacetic acid betaine, oleic acid amidopropyldimethylaminoacetic acid betaine, and stearic acid amidopropyldimethylaminoacetic acid betaine. Among these, stearate amidopropyldimethylaminoacetic acid betaine is preferable.
 高級脂肪酸アルカノールアミド型界面活性剤(D3f)としては特に限定はないが、例えば、ラウリン酸ジエタノールアミド、オレイン酸ジエタノールアミド、ステアリン酸ジエタノールアミド、ベヘン酸ジエタノールアミド、ラウリン酸モノエタノールアミド、ラウリン酸モノイソプロパノールアミド等が挙げられる。さらに、高級脂肪酸アルカノールアミド型界面活性剤には、炭素数2~4のアルキレンオキサイド付加物も含んでもよい。これらの中でも、ステアリン酸ジエタノールアミドやベヘン酸ジエタノールアミドが好ましい。 The higher fatty acid alkanolamide type surfactant (D3f) is not particularly limited, and examples thereof include lauric acid diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, behenic acid diethanolamide, lauric acid monoethanolamide, and lauric acid monoester. Isopropanolamide etc. are mentioned. Further, the higher fatty acid alkanolamide type surfactant may also contain an alkylene oxide adduct having 2 to 4 carbon atoms. Among these, stearic acid diethanolamide and behenic acid diethanolamide are preferable.
〔その他の成分〕
 本発明の透水性付与剤は、本発明の効果を阻害しない範囲でポリオキシアルキレン変性シリコーン(E)(成分(E)ということがある)を含有してもよいが、液戻り防止性が不足するという問題とカード時にスカムが発生するという理由から、透水性付与剤の不揮発分全体に占めるシリコーン系化合物(E)の重量割合は、20重量%未満、15重量%未満、10重量%未満、7重量%未満、5重量%未満、3重量%未満の順で好ましい。
 成分(E)は、分子量が1,000~100,000であり、Si含有率が20~70重量%である。ポリオキシアルキレンがポリオキシエチレンやポリオキシプロピレンであり、ポリオキシアルキレン全体のうちポリオキシエチレンが占める割合が20重量%以上である。
[Other ingredients]
The water permeability-imparting agent of the present invention may contain polyoxyalkylene-modified silicone (E) (sometimes referred to as component (E)) as long as it does not impair the effects of the present invention, but lacks liquid return prevention properties. The weight ratio of the silicone compound (E) in the entire nonvolatile content of the water permeability imparting agent is less than 20% by weight, less than 15% by weight, less than 10% by weight, It is preferable in the order of less than 7% by weight, less than 5% by weight, and less than 3% by weight.
Component (E) has a molecular weight of 1,000 to 100,000 and a Si content of 20 to 70% by weight. The polyoxyalkylene is polyoxyethylene or polyoxypropylene, and the ratio of the polyoxyethylene in the total polyoxyalkylene is 20% by weight or more.
 本発明の透水性付与剤は、必要に応じて水および/または溶剤を含有していてもよく、水を必須に含有することが好ましい。本発明に使用する水としては、純水、蒸留水、精製水、軟水、イオン交換水、水道水等のいずれであってもよい。透水性付与剤を製造する際の透水性付与剤全体に占める不揮発分の重量割合は、10~40重量%が好ましく、18~30重量%が特に好ましい。 The water permeability imparting agent of the present invention may contain water and / or a solvent as required, and preferably contains water essentially. The water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like. The weight ratio of the non-volatile component in the entire water-permeability imparting agent when producing the water-permeability imparting agent is preferably 10 to 40% by weight, and particularly preferably 18 to 30% by weight.
 また、本発明の透水性付与剤には、必要に応じて、抗菌剤、酸化防止剤、防腐剤、艶消し剤、顔料、防錆剤、芳香剤、消泡剤等がさらに含まれていてもよい。 The water permeability imparting agent of the present invention further contains an antibacterial agent, an antioxidant, a preservative, a matting agent, a pigment, an antirust agent, an aromatic, an antifoaming agent, and the like as necessary. Also good.
〔透水性付与剤の製造方法〕
 本発明の透水性付与剤の製造方法としては、公知の方法を採用できる。例えば、成分(A)と必要に応じて成分(C)を配合し約70℃の温度で撹伴する。次に、必要に応じて成分(B)の水溶液を配合して約70℃の温度で均一に攪拌する。次に、必要に応じて成分(D)を配合して約70℃の温度で均一に攪拌する。次いで、攪拌しながら所定量の水を注入し希釈すると10~40重量%の透水性付与剤が得ることができる。
[Method for producing water permeability imparting agent]
As a method for producing the water-permeability imparting agent of the present invention, a known method can be employed. For example, the component (A) and the component (C) are blended as necessary and stirred at a temperature of about 70 ° C. Next, if necessary, an aqueous solution of the component (B) is blended and stirred uniformly at a temperature of about 70 ° C. Next, a component (D) is mix | blended as needed, and it stirs uniformly at the temperature of about 70 degreeC. Next, when a predetermined amount of water is poured and diluted while stirring, a water permeability imparting agent of 10 to 40% by weight can be obtained.
〔透水性繊維〕
 本発明の透水性繊維は、不織布製造用疎水性合成繊維(繊維本体)とこれに付着した上記透水性付与剤とから構成される透水性繊維であり、一般的には所定の長さに切断した短繊維である。透水性付与剤の不揮発分の付着率は、前記透水性繊維に対して0.1~2重量%であり、好ましくは0.3~1重量%である。透水性繊維に対する透水性付与剤の不揮発分の付着率が0.1重量%未満では、瞬時透水性、耐久透水性が低下することがある。一方、透水性付与剤の不揮発分の付着率が2重量%を超えると、繊維をカード処理する時に巻付きが多くなって生産性が大幅に低下し、乾式法等の方法により得られた不織布等の繊維製品が透水後にベトツキが大きくなることがある。
[Water-permeable fiber]
The water-permeable fiber of the present invention is a water-permeable fiber composed of a hydrophobic synthetic fiber (fiber body) for manufacturing a nonwoven fabric and the water-permeability imparting agent attached to the fiber, and is generally cut to a predetermined length. Short fiber. The adhesion rate of the non-volatile component of the water permeability imparting agent is 0.1 to 2% by weight, preferably 0.3 to 1% by weight, based on the water permeable fiber. When the adhesion rate of the nonvolatile content of the water permeability imparting agent to the water permeable fiber is less than 0.1% by weight, the instantaneous water permeability and the durable water permeability may be lowered. On the other hand, when the adhesion rate of the non-volatile content of the water permeability imparting agent exceeds 2% by weight, the wrapping increases when the fiber is carded, resulting in a significant reduction in productivity, and a nonwoven fabric obtained by a method such as a dry method. Such a fiber product may become sticky after water permeation.
 不織布製造用疎水性合成繊維(繊維本体)としては、たとえば、ポリオレフィン繊維、ポリエステル繊維、ナイロン繊維、塩ビ繊維、2種類以上の熱可塑性樹脂からなる複合繊維等であり、複合繊維の組み合わせとしては、ポリオレフィン系樹脂/ポリオレフィン系樹脂の場合、例えば、高密度ポリエチレン/ポリプロピレン、直鎖状高密度ポリエチレン/ポリプロピレン、低密度ポリエチレン/ポリプロピレン、プロピレンと他のα-オレフィンとの二元共重合体または三元共重合体/ポリプロピレン、直鎖状高密度ポリエチレン/高密度ポリエチレン、低密度ポリエチレン/高密度ポリエチレン等が挙げられる。また、ポリオレフィン系樹脂/ポリエステル系樹脂の場合、例えば、ポリプロピレン/ポリエチレンテレフタレート、高密度ポリエチレン/ポリエチレンテレフタレート、直鎖状高密度ポリエチレン/ポリエチレンテレフタレート、低密度ポリエチレン/ポリエチレンテレフタレート等が挙げられる。また、ポリエステル系樹脂/ポリエステル系樹脂の場合、例えば、共重合ポリエステル/ポリエチレンテレフタレート等が挙げられる。さらにポリアミド系樹脂/ポリエステル系樹脂、ポリオレフィン系樹脂/ポリアミド系樹脂等からなる繊維も例示することができる。これら不織布製造用疎水性合成繊維(繊維本体)のなかでも、付着した透水性付与剤が尿や体液等の液体によって脱落がし難いという理由から、不織布製造用ポリオレフィン系繊維(ポリオレフィン繊維やポリオレフィン繊維を含む複合繊維)、不織布製造用ポリエステル系繊維(ポリエステル繊維やポリエステル繊維を含む複合繊維)等の疎水性合成繊維に本発明の透水性付与剤は好適であり、さらには不織布製造用ポリオレフィン系繊維に本発明の透水性付与剤は好適である。 Examples of the hydrophobic synthetic fiber (fiber body) for manufacturing a nonwoven fabric include, for example, polyolefin fibers, polyester fibers, nylon fibers, polyvinyl chloride fibers, composite fibers composed of two or more types of thermoplastic resins, etc. In the case of polyolefin resin / polyolefin resin, for example, high density polyethylene / polypropylene, linear high density polyethylene / polypropylene, low density polyethylene / polypropylene, binary copolymer of propylene and other α-olefin or ternary Examples include copolymer / polypropylene, linear high-density polyethylene / high-density polyethylene, and low-density polyethylene / high-density polyethylene. In the case of polyolefin resin / polyester resin, for example, polypropylene / polyethylene terephthalate, high-density polyethylene / polyethylene terephthalate, linear high-density polyethylene / polyethylene terephthalate, and low-density polyethylene / polyethylene terephthalate. Moreover, in the case of polyester-type resin / polyester-type resin, copolymer polyester / polyethylene terephthalate etc. are mentioned, for example. Furthermore, the fiber which consists of polyamide-type resin / polyester-type resin, polyolefin-type resin / polyamide-type resin etc. can be illustrated. Among these hydrophobic synthetic fibers (fiber bodies) for manufacturing nonwoven fabrics, polyolefin fibers (polyolefin fibers and polyolefin fibers for manufacturing nonwoven fabrics) are used because the attached water permeability imparting agent is difficult to fall off by liquids such as urine and body fluids. The water permeability-imparting agent of the present invention is suitable for hydrophobic synthetic fibers such as polyester fibers for producing non-woven fabrics (polyester fibers and composite fibers containing polyester fibers), and polyolefin fibers for producing non-woven fabrics. The water permeability imparting agent of the present invention is suitable.
 繊維の断面構造は鞘芯型、並列型、偏心鞘芯型、多層型、放射型あるいは海島型が例示できるが、繊維製造工程での生産性や、不織布加工の容易さから、偏心を含む鞘芯型または並列型が好ましい。また、断面形状は円形または異形形状とすることができる。異形形状の場合、例えば扁平型、三角形~八角形等の多角型、T字型、中空型、多葉型等の任意の形状とすることができる。 Examples of the cross-sectional structure of the fiber include a sheath-core type, a parallel-type, an eccentric sheath-core type, a multilayer type, a radiation type, and a sea-island type. However, because of the productivity in the fiber manufacturing process and the ease of non-woven fabric processing, the sheath includes eccentricity. A core type or a parallel type is preferred. The cross-sectional shape can be a circular shape or an irregular shape. In the case of an irregular shape, for example, a flat shape, a polygonal shape such as a triangle to an octagon, a T shape, a hollow shape, a multileaf shape, and the like can be used.
 本発明の透水性付与剤は、そのまま希釈等せずに繊維本体に付着させてもよく、水等で不揮発分全体の重量割合が0.5~5重量%となる濃度に希釈してエマルジョンとして繊維本体に付着させてもよい。透水性付与剤を繊維本体へ付着させる工程は、繊維本体の紡糸工程、延伸工程、捲縮工程等のいずれであってもよい。本発明の透水性付与剤を繊維本体に付着させる手段については、特に限定はなく、ローラー給油、ノズルスプレー給油、ディップ給油等の手段を使用してもよい。繊維の製造工程やその特性に合わせ、より均一に効率よく目的の付着量が得られる方法を採用すればよい。また、乾燥の方法としては、熱風および赤外線により乾燥させる方法、熱源に接触させて乾燥させる方法等を用いてよい。 The water-permeability-imparting agent of the present invention may be adhered to the fiber main body without being diluted as it is, and diluted with water or the like to a concentration such that the weight ratio of the entire nonvolatile content is 0.5 to 5% by weight as an emulsion. You may make it adhere to a fiber main body. The step of attaching the water permeability imparting agent to the fiber body may be any of a spinning process, a stretching process, a crimping process, and the like of the fiber body. The means for attaching the water permeability imparting agent of the present invention to the fiber body is not particularly limited, and means such as roller lubrication, nozzle spray lubrication, and dip lubrication may be used. A method for obtaining a desired adhesion amount more uniformly and efficiently may be employed in accordance with the fiber manufacturing process and its characteristics. Moreover, as a drying method, you may use the method of drying with a hot air and infrared rays, the method of making it contact with a heat source, and drying.
〔不織布の製造方法〕
 不織布の製造方法として、特に限定なく、公知の方法を採用できる。原料繊維としては短繊維や長繊維を用いることができる。原料繊維が短繊維のウェブ形成方式としては、カード方式やエアレイド方式等の乾式法や抄紙方式等の湿式法が挙げられる。また原料繊維が長繊維のウェブ形成方式としては、スパンボンド法、メルトブロー法、フラッシュ紡糸法等が挙げられる。また、繊維間結合方式としては、ケミカルボンド法、サーマルボンド法、ニードルパンチ法、スパンレース法、スティッチボンド法等が挙げられる。
 本発明の不織布の製造方法は、本発明の透水性繊維(例えば短繊維)をカード機等に通し繊維ウェブを作製し、得られた繊維ウェブを熱処理する工程を含むものが好ましい。すなわち、本発明の透水性付与剤は、不織布の製造において繊維ウェブを熱処理する工程を有する場合に、特に好適に使用されるものである。
 繊維ウェブを熱処理して接合させる方法としては、加熱ロールまたは超音波によるによる熱圧着、加熱空気による熱融着、熱圧着点(ポイントボンディング)法等の熱融着法が挙げられる。繊維ウェブを熱処理して接合させる一例としては、芯に高融点の樹脂を使用し鞘に低融点の樹脂を使用する鞘芯型の複合繊維の場合、低融点の樹脂の融点付近で熱処理することで、繊維交点の熱接着を容易に行なうことができる。
 不織布の製造方法としては、透水性付与剤が付与された短繊維をカード機等に通しウェブとしたものを上述のように熱処理して接合させ一体化する方法、エアレイド法でパルプ等を積層する際に本発明の透水性繊維(短繊維)と混綿して、上述のように熱処理して接合させる方法等も挙げられる。その他、スパンボンド法、メルトブロー法、フラッシュ紡糸法等により得られた繊維成形体に対して、本発明の透水性付与剤を付着させたものを加熱ロールまたは加熱空気等で熱処理して、または加熱ロールまたは加熱空気等で熱処理したものに本発明の透水性付与剤を付着させて、不織布を製造する方法も挙げられる。
[Method for producing nonwoven fabric]
As a manufacturing method of a nonwoven fabric, a well-known method is employable without particular limitation. Short fibers or long fibers can be used as the raw fiber. Examples of the web forming method in which the raw fibers are short fibers include a dry method such as a card method and an airlaid method, and a wet method such as a papermaking method. Examples of the web forming method in which the raw fibers are long fibers include a spunbond method, a melt blow method, and a flash spinning method. Examples of the interfiber bonding method include a chemical bond method, a thermal bond method, a needle punch method, a spunlace method, and a stitch bond method.
The method for producing the nonwoven fabric of the present invention preferably includes a step of producing a fiber web by passing the water-permeable fibers (for example, short fibers) of the present invention through a card machine or the like and heat-treating the obtained fiber web. That is, the water-permeability imparting agent of the present invention is particularly preferably used when it has a step of heat-treating the fiber web in the production of the nonwoven fabric.
Examples of the method for bonding the fiber web by heat treatment include thermal fusion methods such as thermocompression using a heated roll or ultrasonic waves, thermal fusion using heated air, and a thermocompression bonding (point bonding) method. As an example of joining the fiber web by heat treatment, in the case of a sheath-core type composite fiber using a high melting point resin for the core and a low melting point resin for the sheath, heat treatment is performed near the melting point of the low melting point resin. Thus, thermal bonding of the fiber intersection can be easily performed.
As a method for producing a nonwoven fabric, a method in which short fibers to which a water permeability-imparting agent has been applied is made into a web through a card machine or the like is heat-treated and joined as described above, and pulp or the like is laminated by an airlaid method. In some cases, there may be mentioned a method in which the water-permeable fiber (short fiber) of the present invention is mixed and heat-treated and bonded as described above. In addition, a fiber molded body obtained by a spunbond method, a melt blow method, a flash spinning method, or the like is heat-treated with a heating roll or heated air or the like, to which the water permeability imparting agent of the present invention is attached, or heated. A method of manufacturing a nonwoven fabric by attaching the water permeability imparting agent of the present invention to a material heat treated with a roll or heated air is also included.
 スパンボンド法の一例としては、複合繊維樹脂を紡糸し、次に、紡出された複合長繊維フィラメントを冷却流体により冷却し、延伸空気によってフィラメントに張力を加えて所期の繊度とする。その後、紡糸されたフィラメントを捕集ベルト上に捕集し、接合処理を行ってスパンボンド不織布を得る。接合手段としては、加熱ロールまたは超音波によるによる熱圧着、加熱空気による熱融着、熱圧着点(ポイントボンディング)法等がある。
 得られたスパンボンド不織布に本発明の透水性付与剤を付与する方法としては、グラビア法、フレキソ法、ゲートロール法等のロールコーティング法、スプレーコーティング法等で行うことができるが、不織布への塗布量を片面ずつ調節できるものであれば特に限定されるものではない。また、乾燥の方法としては、熱風および赤外線により乾燥させる方法、熱源に接触させて乾燥させる方法等を用いてよい。
As an example of the spunbond method, a composite fiber resin is spun, then the spun composite long fiber filament is cooled with a cooling fluid, and tension is applied to the filament with drawn air to obtain the desired fineness. Thereafter, the spun filament is collected on a collection belt and subjected to a bonding treatment to obtain a spunbonded nonwoven fabric. Examples of the joining means include thermocompression bonding using a heating roll or ultrasonic waves, heat fusion using heated air, and a thermocompression bonding (point bonding) method.
As a method for imparting the water permeability imparting agent of the present invention to the obtained spunbond nonwoven fabric, it can be performed by a gravure method, a flexo method, a roll coating method such as a gate roll method, a spray coating method, etc. There is no particular limitation as long as the coating amount can be adjusted for each side. Moreover, as a drying method, you may use the method of drying with a hot air and infrared rays, the method of making it contact with a heat source, and drying.
〔透水性繊維の物性〕
 本発明の透水性繊維は、液戻り防止性に優れた物性を有している。透水性繊維の液戻り量は、通常1.2g以下、好ましくは1.0g以下、さらに好ましくは0.8g以下、より好ましくは0.6g以下、特に好ましくは0.4g以下、最も好ましくは0.2g以下である。
[Physical properties of water-permeable fibers]
The water-permeable fiber of the present invention has physical properties excellent in liquid return prevention properties. The liquid return amount of the water-permeable fiber is usually 1.2 g or less, preferably 1.0 g or less, more preferably 0.8 g or less, more preferably 0.6 g or less, particularly preferably 0.4 g or less, and most preferably 0. .2 g or less.
 本発明の透水性繊維は、耐久透水性に優れている。透水性繊維の耐久透水性評価は、繰り返しの評価が3回目において生理食塩水の消失時間を20箇所で測定し、消失時間5秒未満となる箇所の個数は、通常10個以上、好ましくは12個以上、さらに好ましくは14個以上、より好ましくは16個以上、特に好ましくは18個以上、最も好ましくは20個である。 The water-permeable fiber of the present invention is excellent in durable water permeability. In the durable water permeability evaluation of the water permeable fiber, the disappearance time of the physiological saline is measured at 20 places in the third evaluation, and the number of places where the disappearance time is less than 5 seconds is usually 10 or more, preferably 12 Or more, more preferably 14 or more, more preferably 16 or more, particularly preferably 18 or more, and most preferably 20.
 本発明の透水性繊維は、安全性に優れている。衛生材料用途では、人体に直接接することから、高い安全性が求められている。透水性繊維の安全性を評価するためには、細胞毒性(IC50)試験を実施し、70%以上が好ましい。本発明の透水性付与剤を繊維本体に付着させることによって、上記物性が得られる。 The water-permeable fiber of the present invention is excellent in safety. In sanitary material applications, high safety is required because it is in direct contact with the human body. In order to evaluate the safety of the water-permeable fiber, a cytotoxicity (IC 50 ) test is performed, and 70% or more is preferable. The above physical properties can be obtained by attaching the water permeability imparting agent of the present invention to the fiber body.
 以下に本発明を実施例によって説明するが、本発明はこれに限定されるものではない。なお、各実施例および比較例における評価項目と評価方法は以下の通りである。なお、例中の「部」および「%」とあるのは、それぞれ「重量部」および「重量%」を表す。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In addition, the evaluation items and the evaluation method in each example and comparative example are as follows. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
(実施例1~10および比較例1~11)
 表1および2に示す各成分および水を混合して、透水性付与剤全体に占める不揮発分の重量割合が25重量%の実施例1~10、比較例1~11の透水性付与剤をそれぞれ調製した。得られた透水性付与剤をそれぞれ約60℃の温水で不揮発分の重量割合が0.8重量%の濃度になるよう希釈して希釈液を得た。
 次に、繊維本体300gに対しそれぞれの透水性付与剤の希釈液150gをスプレーで付着させ、透水性繊維に付着する透水性付与剤の不揮発分の付着量を0.4重量%にした。繊維本体は、透水性付与剤等の繊維処理剤が付着していない、ポリプロピレン(芯)-ポリエチレン(鞘)系複合繊維であり、単繊維繊度が1.5Dtex、繊維長が38mmのものであった。それぞれの透水性付与剤の希釈液を付着させた繊維を、60℃の温風乾燥機の中に2時間入れた後、室温で8時間以上放置して乾燥させて、透水性繊維を得た。
(Examples 1 to 10 and Comparative Examples 1 to 11)
The components and water shown in Tables 1 and 2 were mixed, and the water permeability imparting agents of Examples 1 to 10 and Comparative Examples 1 to 11 having a non-volatile content of 25% by weight in the entire water permeability imparting agent were respectively obtained. Prepared. The obtained water-permeability imparting agent was diluted with warm water of about 60 ° C. so that the weight ratio of nonvolatile content was 0.8% by weight to obtain a diluted solution.
Next, 150 g of the diluted solution of each water permeability imparting agent was attached to the fiber body 300 g by spraying, so that the non-volatile content of the water permeability imparting agent adhering to the water permeable fiber was 0.4% by weight. The fiber body is a polypropylene (core) -polyethylene (sheath) composite fiber to which a fiber treatment agent such as a water permeability imparting agent is not attached, and has a single fiber fineness of 1.5 Dtex and a fiber length of 38 mm. It was. The fibers to which the respective liquid permeability imparting agents were attached were placed in a 60 ° C. hot air dryer for 2 hours and then allowed to dry at room temperature for 8 hours or more to obtain water permeable fibers. .
 得られた透水性繊維をそれぞれ混打綿工程およびカード試験機を用いたカード工程に通し、目付30g/mのウェブを作製した。その際、それぞれの透水性繊維について、下記に示す評価方法でカード工程における物性(カード通過性:シリンダー巻付きおよびスカム発生の有無)を評価した。得られたウェブをエァースルー型熱風循環乾燥機中130℃で熱処理してウェブを固定し、不織布を得た。得られた不織布について、下記に示す評価方法で物性(瞬時透水性、耐久透水性および液戻り防止性)をそれぞれ評価した。その結果を表3および4に示す。 The obtained water-permeable fibers were respectively passed through a blended cotton process and a card process using a card testing machine to prepare webs with a basis weight of 30 g / m 2 . At that time, for each water-permeable fiber, the physical properties in the card process (card passing property: presence of cylinder winding and occurrence of scum) were evaluated by the following evaluation method. The obtained web was heat-treated at 130 ° C. in an air-through hot air circulating dryer to fix the web to obtain a nonwoven fabric. About the obtained nonwoven fabric, the physical properties (instant water permeability, durable water permeability, and liquid return prevention property) were evaluated by the evaluation methods shown below. The results are shown in Tables 3 and 4.
〔評価方法〕
(1)シリンダー巻付き
 カード試験機を用いて30℃×70%RHの条件で試料短繊維40gをカーディングした後にシリンダーを観察し、以下の基準で評価した。なお、5が最も良い評価である。
5…巻付きなし、4…シリンダー面の1/10に巻付きあり、3…シリンダー面の1/5に巻付きあり、2…シリンダー面の1/3に巻付きあり、1…全面に巻付きあり
〔Evaluation methods〕
(1) Cylinder winding The card | curd was observed after carding 40 g of sample short fibers on the conditions of 30 degreeC x 70% RH using the card test machine, and the following references | standards evaluated. Note that 5 is the best evaluation.
5 ... No winding, 4 ... winding to 1/10 of the cylinder surface, 3 ... winding to 1/5 of the cylinder surface, 2 ... winding to 1/3 of the cylinder surface, 1 ... winding to the entire surface With
(2)スカム発生の有無
 カード試験機を用いて30℃×70%RHの条件で試料短繊維200gをカーディングした後にローラーに付着したスカムを観察し、スカム発生の有無を評価した。
(2) Presence or absence of scum generation After carding 200 g of sample short fibers under a condition of 30 ° C. and 70% RH using a card testing machine, the scum adhering to the roller was observed to evaluate the presence or absence of scum generation.
(3)ネップ発生の数
 カード試験機を用いて25℃×65%RHの条件で試料短繊維20gをカーディングした後にウェブを観察し、発生したネップ数を数えた。なお、ネップ数0が最も優れる。
(3) Number of Nep Generation The web was observed after carding 20 g of the sample short fiber under the condition of 25 ° C. × 65% RH using a card testing machine, and the number of generated neps was counted. Nep number 0 is the most excellent.
(4)不織布の瞬時透水性
 不織布を濾紙(東洋濾紙、No.5)の上に重ね、不織布表面から10mmの高さに設置したビューレットより1滴(約0.05ml)の生理食塩水を滴下して、不織布表面から水滴が消失するまでの時間を測定する。不織布表面の20箇所でこの測定を行って5秒未満の個数を表示する。この個数が18個以上であれば瞬時透水性は良好である。
(4) Instantaneous water permeability of non-woven fabric The non-woven fabric is layered on filter paper (Toyo filter paper, No. 5), and 1 drop (about 0.05 ml) of physiological saline is added from a burette placed at a height of 10 mm from the non-woven fabric surface. It is dripped and the time until water droplets disappear from the nonwoven fabric surface is measured. This measurement is performed at 20 points on the surface of the nonwoven fabric, and the number of less than 5 seconds is displayed. If this number is 18 or more, the instantaneous water permeability is good.
(5)不織布の耐久透水性
 不織布(10cm×10cm)を市販の紙おむつに重ね、その上に内径60mmの円筒を置き、生理食塩水80mlを円筒内に注入して不織布を通して紙おむつに吸収させた。注水後3分間放置した後に、不織布を2枚の濾紙(東洋濾紙、No.5)の間に挟み、その上に板(10cm×10cm)と重り(合計3.5kg)を乗せて3分間放置して脱水し、その後さらに5分間風乾した。風乾後の試料不織布に上記円筒内で生理食塩水が通過した箇所について、不織布の瞬時透水性の試験方法によって、生理食塩水の消失時間を20箇所で測定し、消失時間5秒未満の個数を表示した。この個数が18個以上であれば耐久透水性は良好である。試験に供した不織布について、同様の作業を繰り返して行う。この繰り返し試験では回数を重ねても生理食塩水の消失個数(消失時間5秒未満となる箇所の個数)が多い方がよい。
(5) Durable water permeability of nonwoven fabric A nonwoven fabric (10 cm × 10 cm) was placed on a commercially available paper diaper, a cylinder with an inner diameter of 60 mm was placed thereon, 80 ml of physiological saline was injected into the cylinder, and the nonwoven fabric was absorbed through the nonwoven fabric. After leaving for 3 minutes after water injection, the nonwoven fabric is sandwiched between two filter papers (Toyo filter paper, No. 5), and a plate (10 cm × 10 cm) and weight (total 3.5 kg) are placed on it for 3 minutes. And dehydrated, then air dried for another 5 minutes. About the location where physiological saline passed through the sample nonwoven fabric after air drying in the cylinder, the disappearance time of physiological saline was measured at 20 locations by the instantaneous water permeability test method of the nonwoven fabric, and the number of disappearance time less than 5 seconds was determined. displayed. If this number is 18 or more, the durable water permeability is good. The same operation is repeated for the nonwoven fabric subjected to the test. In this repeated test, it is better that the number of disappearances of physiological saline (the number of places where the disappearance time is less than 5 seconds) is large even if the number of times is repeated.
(6)不織布の液戻り防止性
 市販の紙おむつの上に不織布(10cm×10cm)を置き、さらにその上に内径60mmの円筒を置き、生理食塩水100mlを円筒内に注入して不織布を通して紙おむつに吸収させた。生理食塩水が全て紙おむつに吸収されたら円筒を取り除き、予め秤量した濾紙(東洋濾紙、No.5)を20枚重ね、これに5kgの荷重を乗せた。5分間放置後、濾紙の重さを計り、重量増加分を測定して液戻り量(g)とした。1.2g以下を許容範囲としているが、1.0g以下が望ましい。
(6) Preventing liquid return of nonwoven fabric Place a nonwoven fabric (10 cm x 10 cm) on a commercially available paper diaper, place a cylinder with an inner diameter of 60 mm on it, inject 100 ml of physiological saline into the cylinder, and pass through the nonwoven fabric into the paper diaper. Absorbed. When all the physiological saline was absorbed by the paper diaper, the cylinder was removed, 20 sheets of pre-weighed filter paper (Toyo Filter Paper, No. 5) were stacked, and a 5 kg load was placed thereon. After standing for 5 minutes, the filter paper was weighed and the weight increase was measured to obtain the liquid return amount (g). Although the allowable range is 1.2 g or less, 1.0 g or less is desirable.
(7)細胞毒性試験(IC50
 細胞株はV79細胞を用いるコロニー形成法により、水抽出液3~100%の濃度範囲で検討し、コロニー形成を50%阻害する濃度(%)をIC50とした。抽出条件および処理条件等は「第15改正 日本薬局方 2006年度」のプラスチック製医薬品容器試験法の細胞毒性試験に準拠して実施した。合否の判定は、濃度70%以上を合格(○)とし、70%未満を不合格(×)とした。
(7) Cytotoxicity test (IC 50 )
Cell lines by colony formation method using V79 cells were examined in a concentration range of water extract 3 to 100% was IC 50 concentration (%) to inhibit colony formation by 50%. Extraction conditions, treatment conditions, and the like were performed in accordance with the cytotoxicity test of the plastic drug container test method of “15th revision Japanese Pharmacopoeia 2006”. In the pass / fail judgment, a density of 70% or more was regarded as acceptable (◯), and a density of less than 70% was regarded as unacceptable (x).
(8)透水性繊維に付着する透水性付与剤の付着率
 透水性繊維に付着する透水性付与剤の不揮発分の付着率は、25℃×40%RHの温湿度で24時間調湿した透水性繊維(W1)を、メタノールを用いて、迅速残脂抽出装置R-11型(東海計器(株)製)で抽出し、透水性付与剤の不揮発分の付着量(W2)を求めた。そして下記の式より、透水性付与剤の不揮発分の付着率C%を求めた。
  C=W2/W1×100(%)
(8) Adhesion rate of water permeability imparting agent adhering to water permeable fiber The adhering rate of the non-volatile content of the water permeability imparting agent adhering to the water permeable fiber is water permeability adjusted for 24 hours at 25 ° C. × 40% RH temperature and humidity The conductive fiber (W1) was extracted with methanol using a rapid residual oil extractor R-11 (manufactured by Tokai Keiki Co., Ltd.), and the non-volatile content (W2) of the water permeability imparting agent was determined. And the adhesion rate C% of the non volatile matter of the water-permeability | providing agent was calculated | required from the following formula.
C = W2 / W1 × 100 (%)
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
成分a1:ポリオキシエチレン(10モル)ステアリルエーテルのマレイン酸エステル
成分a2:ポリオキシエチレン(10モル)C14~60アルキルエーテルのマレイン酸エステル
成分b1:ラウリルホスフェートカリウム塩
成分b2:トリデシルホスフェートカリウム塩
成分b3:ポリオキシエチレン2モルセチルホスフェートカリウム塩
成分c1:イソオクチルパルミテート
成分c2:イソオクチルステアレート
成分d1:ジ椰子アルキルスルホサクシネートナトリウム塩
成分d2:ジトリデシルスルホサクシネートナトリウム塩
成分d1:ポリオキシエチレン(20モル)カスターワックスのマレイン酸縮合物の水酸基1モル当量あたりステアリン酸1モル当量で封鎖したエステル
成分d2:ポリオキシエチレン(20モル)カスターワックスのマレイン酸縮合物の水酸基1モル当量あたりベヘン酸1モル当量で封鎖したエステル
成分d1:ジステアリルジメチルアンモニウムクロライド
成分d2:1-ヒドロキシエチル-1-エチル-2-オレイルイミダゾリニウムエチルサルフェート
成分d3:ステアリルジメチルアミノ酢酸ベタイン
成分d4:2-ラウリル―N―カルボキシメチル―N-ヒドロキシエチルイミダゾリニウムベタイン
成分d5:ステアリン酸アミドプロピルジメチルアミノ酢酸ベタイン
成分d6:ステアリン酸ジエタノールアミド
成分e:ポリオキシエチレン/ポリオキシプロピレン変性シリコーン(Si含有率:65%、POE含有率:100%、分子量:10000)。なお、POE含有率は、ポリオキシアルキレン中のポリオキシエチレンの含有率(重量%)を示す。
Component a1: Maleate ester of polyoxyethylene (10 mol) stearyl ether Component a2: Maleate ester of polyoxyethylene (10 mol) C14-60 alkyl ether component b1: Lauryl phosphate potassium salt Component b2: Tridecyl phosphate potassium salt Component b3: Polyoxyethylene 2 mol cetyl phosphate potassium salt component c1: Isooctyl palmitate component c2: Isooctyl stearate component d 1 1: Dioctyl alkyl sulfosuccinate sodium salt component d 1 2: Ditridecyl sulfosuccinate sodium salt component d 2 1: polyoxyethylene (20 moles) Custer blocked the ester component in 1 mole of the hydroxyl groups 1 molar equivalent per equivalent of stearic acid maleic acid condensation of wax d 2 2: polyoxyethylene ( 0 mole) to 1 mole of the hydroxyl groups capped with ester component per equivalent behenate 1 molar equivalent of maleic acid condensation product of castor wax d 3 1: distearyl dimethyl ammonium chloride component d 3 2: 1-hydroxyethyl-1-ethyl -2 -Oleylimidazolinium ethyl sulfate component d 3 3: Stearyldimethylaminoacetic acid betaine component d 3 4: 2-lauryl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine component d 3 5: amidopropyldimethylamino stearate Betaine acetate component d 3 6: stearic acid diethanolamide component e: polyoxyethylene / polyoxypropylene-modified silicone (Si content: 65%, POE content: 100%, molecular weight: 10,000). In addition, POE content rate shows the content rate (weight%) of the polyoxyethylene in polyoxyalkylene.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
成分b4:ステアリルホスフェートカリウム塩
成分f1:ポリオキシエチレンベヘン酸ジエチレントリアミンのエピクロルヒドリンを反応させたカチオン化物(ポリオキシエチレン基の数:15)
成分f2:ポリオキシエチレン(10モル)ベヘン酸ジエタノールアミド
成分f3:ポリオキシエチレン(20モル)カスターワックスのマレイン酸縮合物(未封鎖物)
Component b4: Stearyl phosphate potassium salt Component f1: Cationic compound obtained by reacting epichlorohydrin of polyoxyethylene behenate diethylenetriamine (number of polyoxyethylene groups: 15)
Component f2: Polyoxyethylene (10 mol) behenic acid diethanolamide Component f3: Polyoxyethylene (20 mol) castor wax maleic acid condensate (unsealed product)
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 表3から明らかなように、実施例1~10の本発明の透水性付与剤を給油した透水性繊維は、カード通過性が良好であり、透水性不織布の瞬時透水性、耐久透水性および液戻り量も少なく良好であった。さらには、細胞毒性試験にも合格した。この透水性付与剤を付与すれば、繊維に瞬時透水性、耐久透水性、および液戻り防止性を付与し、さらに皮膚への刺激性も低減することができ、本発明の効果が確認された。一方、表4から明らかなように、これらの成分組成範囲から外れる比較例1~11は、総ての必要特性を満足することはできなかった。 As is apparent from Table 3, the water-permeable fibers supplied with the water-permeability imparting agent of Examples 1 to 10 have good card passing properties, and the instantaneous water permeability, durable water permeability and liquid of the water-permeable nonwoven fabric are excellent. The return amount was small and good. Furthermore, it passed the cytotoxicity test. If this water permeability imparting agent is added, the fiber can be given instant water permeability, durable water permeability, and liquid return prevention property, and further the irritation to the skin can be reduced, confirming the effect of the present invention. . On the other hand, as is apparent from Table 4, Comparative Examples 1 to 11 that deviate from these component composition ranges could not satisfy all necessary characteristics.
 本発明の透水性付与剤は、疎水性の合成繊維に対して、透水性を付与するときに有効である。本発明の透水性繊維は、カード工程で優れた通過性を有しており、さらに得られた不織布は、瞬時透水性、耐久透水性、液戻り防止性を併せ持ち、かつ安全性にも優れたものである。従って、本発明の透水性付与剤及び透水性繊維は、高品位の不織布を製造するために有効である。 The water permeability imparting agent of the present invention is effective when imparting water permeability to hydrophobic synthetic fibers. The water-permeable fiber of the present invention has excellent permeability in the carding process, and the obtained nonwoven fabric has both instantaneous water permeability, durable water permeability and liquid return prevention properties, and is excellent in safety. Is. Therefore, the water-permeability imparting agent and water-permeable fiber of the present invention are effective for producing a high-quality nonwoven fabric.

Claims (10)

  1.  下記一般式(1)で示されるポリエーテルポリエステル化合物(A)を必須成分として含有する、透水性付与剤。
    Figure JPOXMLDOC01-appb-C000001
    (式中、RおよびRは、それぞれ独立して、1価の脂肪族アルコールからOH基を除いた残基であり、AOは炭素数2~4のオキシアルキレン基であり、aおよびbは、それぞれ独立して1~100の整数であり、Rは2価の有機基である。)
    A water permeability imparting agent containing a polyether polyester compound (A) represented by the following general formula (1) as an essential component.
    Figure JPOXMLDOC01-appb-C000001
    Wherein R 1 and R 3 are each independently a residue obtained by removing an OH group from a monovalent aliphatic alcohol, AO is an oxyalkylene group having 2 to 4 carbon atoms, a and b Are each independently an integer of 1 to 100, and R 2 is a divalent organic group.)
  2.  下記一般式(2)で示されるアルキルホスフェート塩(B)をさらに含有する、請求項1に記載の透水性付与剤。
    Figure JPOXMLDOC01-appb-C000002
     (式中、Rは炭素数6~22のアルキル基であり、AOは炭素数2~4のオキシアルキレン基であって、cは0~15の整数であり、nは1~2の整数であり、Yは水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、ジエタノールアンモニウムイオンおよびトリエタノールアンモニウムイオンからなる群から選択されるイオン性残基である。)
    The water permeability imparting agent according to claim 1, further comprising an alkyl phosphate salt (B) represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000002
    (Wherein R 4 is an alkyl group having 6 to 22 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, c is an integer of 0 to 15, and n is an integer of 1 to 2) Y + is an ionic residue selected from the group consisting of hydrogen ion, sodium ion, potassium ion, ammonium ion, diethanolammonium ion and triethanolammonium ion.)
  3.  前記ポリエーテルポリエステル化合物(A)と前記アルキルホスフェート塩(B)との重量比(A/B)が、30/70~90/10である、請求項2に記載の透水性付与剤。 The water permeability imparting agent according to claim 2, wherein a weight ratio (A / B) of the polyether polyester compound (A) and the alkyl phosphate salt (B) is 30/70 to 90/10.
  4.  前記透水性付与剤の不揮発分全体に占めるポリエーテルポリエステル化合物(A)の重量割合が10~90重量%であり、前記アルキルホスフェート塩(B)の重量割合が5~80重量%である、請求項2または3に記載の透水性付与剤。 The weight ratio of the polyether polyester compound (A) in the nonvolatile content of the water permeability imparting agent is 10 to 90% by weight, and the weight ratio of the alkyl phosphate salt (B) is 5 to 80% by weight. Item 4. The water permeability imparting agent according to Item 2 or 3.
  5.  エステル油および鉱物油から選ばれる少なくとも1種の平滑剤(C)をさらに含有し、前記透水性付与剤の不揮発分全体に占める前記平滑剤(C)の重量割合が0.2~40重量%である、請求項1~4のいずれかに記載の透水性付与剤。 It further contains at least one smoothing agent (C) selected from ester oil and mineral oil, and the weight ratio of the smoothing agent (C) to the whole non-volatile content of the water permeability imparting agent is 0.2 to 40% by weight. The water permeability imparting agent according to any one of claims 1 to 4, wherein
  6.  前記エステル油が、1価アルコールおよび/または1価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステル、および多価アルコールおよび/または多価アルコールに炭素数2~4のアルキレンオキサイドを付加した(ポリ)エーテル化合物と脂肪酸とから得られる脂肪酸エステルから選ばれる少なくとも1種であり、前記鉱物油が、マシン油、スピンドル油および流動パラフィンから選ばれる少なくとも1種である、請求項5に記載の透水性付与剤。 Fatty acid ester obtained from ester alcohol and monohydric alcohol and / or (poly) ether compound obtained by adding C2-C4 alkylene oxide to monohydric alcohol and fatty acid, and polyhydric alcohol and / or polyhydric alcohol Is a fatty acid ester obtained from a (poly) ether compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fatty acid, and the mineral oil is selected from machine oil, spindle oil and liquid paraffin The water-permeability imparting agent according to claim 5, which is at least one kind.
  7.  ジアルキルスルホサクシネート塩(D1)、ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルとジカルボン酸との縮合物の少なくとも1つの水酸基を脂肪酸で封鎖したエステル(D2)および含窒素系界面活性剤(D3)から選ばれる少なくとも1種の成分(D)をさらに含み、前記透水性付与剤の不揮発分全体に占める前記成分(D)の重量割合が0.2~40重量%である、請求項1~6のいずれかに記載の透水性付与剤。 Dialkyl sulfosuccinate salt (D1), ester (D2) obtained by blocking at least one hydroxyl group of a polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester and dicarboxylic acid with a fatty acid, and a nitrogen-containing surfactant (D3) The component (D) further comprises at least one component (D) selected from the group (1), and the weight ratio of the component (D) to the entire nonvolatile content of the water permeability-imparting agent is 0.2 to 40% by weight. 6. The water permeability-imparting agent according to any one of 6.
  8.  不織布製造用疎水性合成繊維に用いられる、請求項1~7のいずれかに記載の透水性付与剤。 The water permeability imparting agent according to any one of claims 1 to 7, which is used for a hydrophobic synthetic fiber for producing a nonwoven fabric.
  9.  不織布製造用疎水性合成繊維に対して、請求項1~8のいずれかに記載の透水性付与剤を処理して得られ、得られた繊維に対する透水性付与剤の不揮発分の付着率が0.1~2重量%である、透水性繊維。 A hydrophobic synthetic fiber for producing a nonwoven fabric is obtained by treating the water-permeability-imparting agent according to any one of claims 1 to 8, and the adhesion rate of the nonvolatile content of the water-permeability-imparting agent to the obtained fiber is 0. Water permeable fiber that is 1-2% by weight.
  10.  請求項9に記載の透水性繊維を集積させて繊維ウェブを作製し、得られた繊維ウェブを熱処理する工程を含む、不織布の製造方法。 A method for producing a nonwoven fabric, comprising a step of accumulating the water-permeable fibers according to claim 9 to produce a fiber web and heat-treating the obtained fiber web.
PCT/JP2010/060702 2009-07-09 2010-06-24 Water permeability-imparting agent, water-permeable fiber to which the water permeability-imparting agent is applied, and method for producing nonwoven fabric WO2011004713A1 (en)

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KR20210152001A (en) 2019-06-13 2021-12-14 다케모토 유시 가부시키 가이샤 Treatment agents for synthetic fibers and synthetic fibers
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