Water permeability-imparting agent and use thereof

Abstract

The present invention provides a water permeability imparting agent which imparts excellent water permeability to fibers with excellent stability over time and excellent workability. The water permeability imparting agent comprises a nonionic surfactant (N) and at least one selected from an anionic surfactant containing S element (S) and an anionic surfactant containing P element (P), and the iodine value of the nonvolatile component of the water permeability imparting agent is 0.5 to 100 gI2 / 100 g, and the acid value is 0.5 to 100 mgKOH / g. The water permeability imparting agent comprises the above-mentioned active agent (P), and the above-mentioned active agent (P) must comprise a compound (A) represented by general formula (1) and a compound (B) represented by general formula (2), and preferably comprises a compound (C) represented by general formula (3).

Description

Technical Field

[0001] This invention relates to permeability-improving agents and their applications. Background Technology

[0002] Typically, absorbent products such as diapers and sanitary products consist of an absorbent core made of flocculent pulp, highly absorbent polymers, etc., placed between a liquid-permeable top sheet and a liquid-impermeable bottom sheet.

[0003] Urine or bodily fluids pass through the topsheet and are absorbed by the absorbent material. To avoid discomfort during this process, the time until the urine or bodily fluids are completely absorbed must be extremely short (instantaneous permeability). Furthermore, if the treatment agent on the topsheet leaks out due to the absorption of one or two amounts of urine or bodily fluids, causing a sharp decrease in permeability, the frequency of absorbent material replacement will increase. Therefore, permeable materials such as topsheets also require reusable permeability (durable permeability).

[0004] Therefore, research has been conducted on matters that meet the above-mentioned performance requirements. For example, in Patent Document 1, a treatment agent containing an alkyl oxide adduct of a multi-component active hydrogen compound was proposed.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2023-130314 Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] However, these treatment agents have problems such as insufficient permeability and long-term stability required for nonwoven fabrics used in current hygiene products, and insufficient operability of the treatment agents.

[0010] Therefore, the present invention was made in view of such actual circumstances, and its object is to provide a permeability imparting agent that imparts excellent permeability to fibers with good long-term stability and excellent workability. Furthermore, fibers and nonwoven fabrics coated with this permeability imparting agent are provided.

[0011] Technical means for solving problems

[0012] In order to solve the above-mentioned problems, the inventors conducted in-depth research and determined that as long as the permeability imparting agent contains at least one selected from nonionic surfactants and anionic surfactants containing sulfur and anionic surfactants containing phosphorus, and the iodine value and acid value are specific, the above-mentioned problems can be solved.

[0013] That is, the permeability imparting agent of the present invention comprises a nonionic surfactant (N) and at least one selected from anionic surfactants (S) containing sulfur and anionic surfactants (P) containing phosphorus, wherein the non-volatile component of the above-mentioned permeability imparting agent has an iodine value of 0.5 to 100 gI2 / 100g and an acid value of 0.5 to 100 mgKOH / g.

[0014] Preferably, the permeability imparting agent comprises the surfactant (P), which must comprise compound (A) of general formula (1) and compound (B) of general formula (2), and optionally compound (C) of general formula (3).

[0015] [Chemistry 1]

[0016]

[0017] (where R is in the formula) 1 It is a hydrocarbon group with 6 to 22 carbon atoms. R 1 It can be straight-chain or branched. AO is an oxoalkylene group with 2 to 4 carbon atoms, and m is an integer from 0 to 15. M 1 It is a hydrogen atom, an alkali metal, or an organic amine salt. M 2 It can be a hydrogen atom, an alkali metal, or an organic amine salt.

[0018] [Chemistry 2]

[0019]

[0020] (where R is in the formula) 2 and R 3 It is a hydrocarbon group with 6 to 22 carbon atoms. R 2 and R 3 It can be straight-chain or branched. AO is an oxoalkylene group with 2 to 4 carbon atoms, and m is an integer from 0 to 15. M 1 It consists of hydrogen atoms, alkali metals, or organic amine salts. There are two (AO) atoms within the molecule. m In this case, the two can be the same or different.

[0021] [Chemistry 3]

[0022]

[0023] (where R is in the formula) 4 It is a hydrocarbon group with 6 to 22 carbon atoms. R 4 It can be straight-chain or branched. AO is an oxoalkylene group with 2 to 4 carbon atoms, and m is an integer from 0 to 15. M 1 It is a hydrogen atom, an alkali metal, or an organic amine salt. M 2It is a hydrogen atom, an alkali metal, or an organic amine salt. Q is M. 2 Or (OA) m R 5 R 5 It is a hydrocarbon group with 6 to 22 carbon atoms. R 5 It can be a straight chain or a branched chain. Y is 1 or 2. There are more than 2 M molecules within the molecule. 2 Or (AO) m In this case, they can be the same or different.

[0024] Preferably, the surfactant (S) contains at least one selected from dialkyl sulfosuccinic acid, dialkyl sulfosuccinate, polyol fatty acid sulfate, and polyol fatty acid sulfate salt.

[0025] Preferably, the total amount of phosphorus in the non-volatile components is 0-15% by weight and / or the total amount of sulfur is 0-10% by weight.

[0026] Preferably, the above-mentioned water-permeable agent is used in nonwoven fabrics for menstrual blood.

[0027] Preferably, the permeability imparting agent comprises the surfactant (P), which must comprise: surfactant (P-1) having an alkyl group having 12 to 18 carbon atoms and / or an alkenyl group having 12 to 18 carbon atoms; and surfactant (P-2) having an alkyl group having 10 or fewer carbon atoms and / or an alkenyl group having 10 or fewer carbon atoms.

[0028] The fiber of the present invention is made by imparting the above-mentioned water-permeable agent to raw material fibers.

[0029] The nonwoven fabric of the present invention is made by imparting the above-mentioned water-permeable agent.

[0030] The absorbent articles of the present invention include the above-mentioned nonwoven fabric.

[0031] Invention Effects

[0032] The water-permeability imparting agent of the present invention exhibits excellent workability and can impart excellent water permeability stability to fibers over time. The fibers and nonwoven fabrics of the present invention demonstrate excellent water permeability stability over time. Detailed Implementation

[0033] [Nonionic surfactant (N)]

[0034] The permeability imparting agent of the present invention must contain a nonionic surfactant (N).

[0035] From the viewpoint that the agent has excellent operability and water permeability over time stability, the iodine value of the nonionic surfactant (N) is preferably 0 to 120 gI2 / 100g, more preferably 5 to 85 gI2 / 100g, and even more preferably 30 to 70 gI2 / 100g.

[0036] From the viewpoint that the agent has excellent operability and water permeability over time stability, the acid value of the nonionic surfactant (N) is preferably 0 to 120 mgKOH / g, more preferably 0.5 to 80 mgKOH / g, even more preferably 1 to 60 mgKOH / g, and particularly preferably 3 to 30 mgKOH / g.

[0037] The nonionic surfactant (N) is not particularly limited, but from the viewpoint of simultaneously excelling in both operability and water permeability over time stability, it is preferably selected from at least one of the following: polyoxyalkylene polyol ether (N1), polyoxyalkylene polyol fatty acid ester (N2), polyoxyalkylene aliphatic alcohol ether (N3), fatty acid ester of polyalkylene diol (N4), polyol fatty acid ester (N5), polyoxyalkylene-containing hydroxy fatty acid polyol ester (N6) (hereinafter, sometimes referred to as polyhydroxy ester), ester formed by capping at least one hydroxyl group of a polyhydroxy ester with fatty acid (N7), nonionic surfactant formed by capping at least one hydroxyl group of a condensate of a polyhydroxy ester and an unsaturated dicarboxylic acid with fatty acid (N8), and polyester-based nonionic surfactant (N9).

[0038] (Polyoxyalkylene polyol ether)(N1)

[0039] Polyoxyalkylene polyol ethers refer to compounds with structures formed by the addition of polyols to ethylene oxide, propylene oxide, butane oxide, and other epoxides.

[0040] Examples of polyols include: ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, diglycerol, sorbitan, sorbitol, di(trimethylolpropane), dipentaerythritol, and sucrose. Among these, glycerol, trimethylolpropane, and sucrose are preferred.

[0041] The preferred molar number of epoxides added is 3 to 100, more preferably 4 to 70, and even more preferably 5 to 50. The proportion of ethylene oxide in the epoxide is preferably 50 mol% or more, and even more preferably 80 mol% or more.

[0042] The weight-average molecular weight of the polyoxyalkylene polyol ether is preferably 300-10000, more preferably 400-8000, and even more preferably 500-5000.

[0043] Examples of polyoxyalkylene polyol ethers include: polyethylene glycol, glycerol ethylene oxide adducts, trimethylolpropane ethylene oxide adducts, pentaerythritol ethylene oxide adducts, diglycerol ethylene oxide adducts, sorbitan ethylene oxide adducts, sorbitan ethylene oxide propylene oxide adducts, sorbitol ethylene oxide adducts, sorbitol ethylene oxide propylene oxide adducts, di(trimethylolpropane) ethylene oxide adducts, dipentaerythritol ethylene oxide adducts, sucrose ethylene oxide adducts, etc., but are not limited to these.

[0044] (Polyoxyalkylene polyol fatty acid ester)(N2)

[0045] Polyoxyalkylene polyol fatty acid esters refer to compounds that have a structure formed by ester bonding of fatty acids with compounds formed by the addition of ethylene oxide, propylene oxide, butyl oxide, or other epoxides to polyols.

[0046] Examples of polyols include: glycerol, trimethylolpropane, pentaerythritol, erythritol, diglycerol, sorbitan, sorbitol, di(trimethylolpropane), dipentaerythritol, and sucrose. Among these, glycerol, diglycerol, sorbitan, and sorbitol are preferred.

[0047] As fatty acids, examples include: lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, isocetyl acid, stearic acid, isostearic acid, oleic acid, transoleic acid, linoleic acid, linolenic acid, arachidic acid, eicosapentaenoic acid, behenic acid, isoodocosanoic acid, erucic acid, tetracosanoic acid, isoodocosanoic acid, etc.

[0048] The preferred molar number of epoxides added is 3 to 100, more preferably 5 to 70, and even more preferably 10 to 50. The proportion of ethylene oxide in the epoxide is preferably 50 mol% or more, and even more preferably 80 mol% or more.

[0049] The weight-average molecular weight of the polyoxyalkylene polyol fatty acid ester is preferably 300-7000, more preferably 500-5000, and even more preferably 700-3000.

[0050] Examples of polyoxyalkylene polyol fatty acid esters include: glycerol ethylene oxide adduct monolaurate, glycerol ethylene oxide adduct dilaurate, glycerol ethylene oxide adduct trilaurate, trimethylolpropane ethylene oxide adduct trilaurate, sorbitan ethylene oxide adduct monooleate, sorbitan ethylene oxide adduct dioleate, sorbitan ethylene oxide adduct trioleate, sorbitan ethylene oxide adduct propylene oxide adduct monooleate, sorbitan ethylene oxide adduct propylene oxide adduct dioleate, sorbitan ethylene oxide adduct propylene oxide adduct trioleate, sorbitan ethylene oxide adduct propylene oxide adduct glycerol trilaurate, sucrose ethylene oxide adduct trilaurate, etc., but are not limited to these.

[0051] (Polyoxyalkylene aliphatic alcohol ether)(N3)

[0052] Polyoxyalkylene aliphatic alcohol ethers refer to compounds with structures formed by the addition of aliphatic monohydric alcohols to ethylene oxide, propylene oxide, butane oxide, and other epoxides.

[0053] Examples of polyoxyalkylene aliphatic alcohol ethers include epoxide adducts of aliphatic alcohols such as octanol, 2-ethylhexanol, decanol, lauryl alcohol, tridecanool, myristol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol.

[0054] The preferred molar number of ethylene oxide additions is 1 to 100 moles, more preferably 2 to 70 moles, and even more preferably 3 to 50 moles. Furthermore, the proportion of ethylene oxide relative to the total ethylene oxide is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more.

[0055] (Fatty acid esters of polyalkylene glycols) (N4)

[0056] Fatty acid esters of polyalkylene glycols refer to compounds having a structure formed by ester bonding of polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and fatty acids. The weight-average molecular weight of the polyalkylene glycol is preferably 100-1000, more preferably 150-800, and even more preferably 200-700.

[0057] Examples of polyalkylene glycol fatty acid esters include: polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene polypropylene glycol monolaurate, polyethylene polypropylene glycol dilaurate, polyethylene polypropylene glycol monooleate, polyethylene polypropylene glycol monooleate, etc., but are not limited to these.

[0058] (Polyol fatty acid esters)(N5)

[0059] Polyol fatty acid esters refer to compounds that have a structure formed by the ester bonding of polyols and fatty acids.

[0060] Examples of polyols include: ethylene glycol, trimethylolpropane, pentaerythritol, erythritol, diethylene glycol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, sorbitan, sorbitol, di(trimethylolpropane), and sucrose. Among these, ethylene glycol, glycerol, diglycerol, sorbitan, and sorbitol are preferred.

[0061] As fatty acids, examples include: lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, isocetyl acid, stearic acid, isostearic acid, oleic acid, transoleic acid, linoleic acid, linolenic acid, isoeicosanoic acid, codoleic acid, eicosaenoic acid, docosanoic acid, isoocosanoic acid, erucic acid, tetracosanoic acid, etc.

[0062] In addition, the polyol fatty acid ester has at least one or more hydroxyl groups.

[0063] The weight-average molecular weight of the polyol fatty acid ester is preferably 100-1000, more preferably 200-800, and even more preferably 300-600.

[0064] Examples of fatty acid esters include: glycerol monolaurate, glycerol dilaurate, trilaurate, hexaglycerol monolaurate, glycerol monopalmitate, glycerol dipalmitate, trilaurate, hexaglycerol monopalmitate, glycerol monopalmitate, glycerol distearate, tristearate, hexaglycerol monostearate, glycerol monooleate, glycerol monooleate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sucrose monolaurate, sucrose dilaurate, etc., but are not limited to these.

[0065] (Polyhydroxy fatty acid polyol esters containing polyoxyalkylene groups) (sometimes called polyhydroxy esters) (N6)

[0066] Structurally, polyhydroxy esters are esters of polyoxyalkylene-containing hydroxy fatty acids and polyols, preferably in which two or more hydroxyl groups of the polyol are esterified. Therefore, polyoxyalkylene-containing hydroxy fatty acid polyol esters are esters with multiple hydroxyl groups.

[0067] Hydroxy fatty acids containing polyoxyalkylene have a structure in which the polyoxyalkylene is bonded to the hydrocarbon group of the fatty acid via an oxygen atom, and the single end of the polyoxyalkylene that is not bonded to the hydrocarbon group of the fatty acid is a hydroxyl group.

[0068] Examples of polyhydroxy esters include alkylene oxide adducts of esters of hydroxy fatty acids with 6 to 22 carbon atoms (preferably 12 to 22) and polyols.

[0069] Examples of hydroxy fatty acids with 6 to 22 carbon atoms include: hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxylauric acid, hydroxystearic acid, and ricinoleic acid, with hydroxystearic acid and ricinoleic acid being preferred. Examples of polyols include: ethylene glycol, glycerol, sorbitol, sorbitan, trimethylolpropane, and pentaerythritol, with glycerol being preferred. Examples of epoxides include: ethylene oxide, propylene oxide, and butane oxide, which have 2 to 4 carbon atoms.

[0070] Relative to the molar equivalent of hydroxyl groups in the aforementioned hydroxy fatty acid polyol esters, the molar number of epoxide additions is preferably 80 or less, more preferably 5 to 30. If the molar number of additions exceeds 80, the amount of liquid return in absorbent articles may increase, which is therefore undesirable. Furthermore, the proportion of ethylene oxide in the total epoxide is preferably 50 mol% or more, more preferably 80 mol% or more. When the proportion of ethylene oxide is less than 50 mol%, the fibers or nonwoven fabrics may not achieve sufficient durable water permeability, which is therefore undesirable.

[0071] Polyhydroxy esters can be manufactured, for example, by esterifying a polyol with a hydroxy fatty acid (hydroxy monocarboxylic acid) under normal conditions to obtain an esterified product, followed by an addition reaction of an epoxide with the esterified product. Polyhydroxy esters can also be suitably manufactured by using hydrogenated castor oil, which is derived from naturally occurring oils such as castor oil, and further by adding hydrogen to an epoxide. In the manufacture of polyhydroxy esters, the molar equivalent of the carboxyl group in the hydroxy fatty acid is preferably in the range of 0.5 to 1 per molar equivalent of the hydroxyl group in the polyol.

[0072] (An ester formed by capping at least one hydroxyl group of a polyhydroxy ester with a fatty acid) (N7)

[0073] For an ester formed by capping at least one hydroxyl group of a polyhydroxy ester with a fatty acid, the ester is formed by capping at least one hydroxyl group with a fatty acid. The fatty acid used to cap at least one or more hydroxyl groups of the polyhydroxy ester preferably has 10 to 50 carbon atoms, more preferably 12 to 36. The number of carbon atoms in the hydrocarbon group of the fatty acid can be distributed, and the hydrocarbon group can be linear or branched, saturated or unsaturated, and can also have a polycyclic structure. Examples of such fatty acids include: lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, eicosanoic acid, behenic acid, nervonic acid, ceric acid, linalic acid, beeswax acid, lanolin fatty acid, etc., with stearic acid and behenic acid being preferred. In the case of producing an ester of a condensate and a fatty acid, the molar equivalent of the carboxyl group of the fatty acid is preferably in the range of 0.2 to 1, more preferably 0.4 to 1, relative to 1 molar equivalent of hydroxyl groups in the condensate. The reaction conditions for esterification are not particularly limited.

[0074] (Nonionic surfactant prepared by capping at least one hydroxyl group of a condensate of a polyhydroxy ester and an unsaturated dicarboxylic acid with a fatty acid) (N8)

[0075] Nonionic surfactants prepared by capping at least one hydroxyl group of a condensate of a polyhydroxy ester and an unsaturated dicarboxylic acid with a fatty acid are obtained by capping at least one hydroxyl group of a condensate of a polyoxyalkylene-containing hydroxy fatty acid polyol ester and a dicarboxylic acid with a fatty acid.

[0076] In the condensation product of a polyhydroxy ester and a dicarboxylic acid, the dicarboxylic acid preferably has 2 to 10 carbon atoms, more preferably 2 to 8. Examples of such dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, maleic acid, and phthalic acid. In the case of containing a dicarboxylic acid, it may also contain 20% or less (preferably 10% or less) of a carboxylic acid other than a dicarboxylic acid, such as lauric acid, oleic acid, stearic acid, benzyl acid, and benzoic acid. When manufacturing the condensation product of a polyhydroxy ester and a dicarboxylic acid, the molar equivalent of the carboxyl group of the dicarboxylic acid is preferably in the range of 0.2 to 1, more preferably 0.4 to 0.8, relative to 1 molar equivalent of hydroxyl groups in the polyhydroxy ester. The esterification method and reaction conditions are not particularly limited, and known methods and general conditions can be used.

[0077] The condensate of a polyhydroxy ester and a dicarboxylic acid is an ester obtained by capping at least one hydroxyl group with a fatty acid in the aforementioned condensate of a polyoxyalkylene-containing hydroxy fatty acid polyol ester and a dicarboxylic acid (hereinafter sometimes referred to as the condensate). The fatty acid capped with at least one or more hydroxyl groups of the condensate preferably has 10 to 50 carbon atoms, more preferably 12 to 36. The number of carbon atoms in the hydrocarbon group of the fatty acid can be distributed, and the hydrocarbon group can be linear or branched, saturated or unsaturated, and may also have a polycyclic structure. Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, nervonic acid, ceric acid, linalic acid, beeswax acid, lanolin fatty acid, etc., with stearic acid or behenic acid being preferred. In the case of producing an ester of the condensate and fatty acid, the molar equivalent of the carboxyl group of the fatty acid is preferably in the range of 0.2 to 1, more preferably 0.4 to 1, relative to 1 molar equivalent of hydroxyl groups in the condensate. The reaction conditions for esterification are not particularly limited.

[0078] (Polyester-based nonionic surfactant)(N9)

[0079] Polyester-based nonionic surfactants (N9) are compounds having a structure formed by ester bonding of the following polycarboxylic acids and the following polyols.

[0080] Polycarboxylic acids are binary or higher carboxylic acids with 10 to 66 carbon atoms (excluding aromatic carboxylic acids). Examples include sebacic acid, oleic acid dimer, erucic acid dimer, oleic acid trimer, and erucic acid trimer.

[0081] Among polycarboxylic acids, dimer acids of unsaturated fatty acids with 18 to 22 carbon atoms are preferred, and dimer acids of unsaturated fatty acids with 18 carbon atoms are even more preferred.

[0082] Polyols are di- or higher alcohols having 2 to 3 (poly)oxyalkylene units within their molecules. There are no particular limitations on polyols as long as they are di- or higher alcohols and have (poly)oxyalkylene units within their molecules. Examples include: polyalkylene glycols composed of oxyethylene units and / or oxypropylene units, polyalkylene sorbitan anhydrides, polyalkylene sorbitan fatty acid esters, polyalkylene glycerols, polyalkylene polyglycerols, polyalkylene polyglycerol esters, and polyalkylene-modified organosilicones. Polyalkylene glycols composed of oxyethylene units and / or oxypropylene units are preferred.

[0083] Examples of polyalkylene glycols composed of oxyethylidene units and / or oxypropylene units include: polyoxyethylidene glycol, polypropylene glycol, and polyoxyethylidene polyoxypropylene glycol.

[0084] Polyoxyethylene polyoxypropylene glycol can be either block or atactic. Polyoxyethylene glycol is preferred.

[0085] The number average molecular weight of the polyalkylene glycol is preferably 100 to 10,000, more preferably 200 to 2,000, and even more preferably 400 to 1,000.

[0086] It should be noted that the number-average molecular weight mentioned in this invention refers to the value obtained by measuring the molecular weight using gel permeation chromatography (GPC) under the following measurement conditions and converting it to polystyrene.

[0087] (GPC measurement conditions)

[0088] Apparatus: Apparatus name "HPLC LC-6A SYSTEM" (manufactured by SHIMAZU Corporation)

[0089] Columns: “KF-800P (10mm×4.6mmΦ)”, “KF-804 (300mm×8mmΦ)”, “KF-802.5 (300mm×8mmΦ)”, “KF-801 (300mm×8mmΦ)” (all manufactured by SHODEX)

[0090] Mobile phase: Tetrahydrofuran (THF)

[0091] Flow rate: 1.0 ml / min

[0092] Sample volume: 100 μl (100-fold dilution)

[0093] Column temperature: 50℃

[0094] Standard curve preparation standard material: polystyrene (PSt)

[0095] The weight-average molecular weight of the above-mentioned polyester-based nonionic surfactant is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 10,000.

[0096] There are no particular limitations on the methods and reaction conditions for manufacturing the above-mentioned polyester-based nonionic surfactants; well-known methods and common conditions can be used. For example, polycarboxylic acid and polyol can be mixed and heated to react, thereby obtaining a polyester-based nonionic surfactant.

[0097] Polycarboxylic acids and polyols can be used in combination with one or more of the above-mentioned components. Alternatively, polyester-based nonionic surfactants can be manufactured by reacting components other than polycarboxylic acids and polyols.

[0098] [Anionic surfactant (S)]

[0099] Anionic surfactants (S) are anionic surfactants containing sulfur (S) elements.

[0100] By using it in combination with the aforementioned nonionic surfactant (N), the agent exhibits excellent workability and water permeability stability over time.

[0101] From the viewpoint that the agent has excellent operability and water permeability over time stability, the iodine value of the anionic surfactant (S) is preferably 0 to 120 gI2 / 100g, more preferably 5 to 80 gI2 / 100g, and even more preferably 30 to 70 gI2 / 100g.

[0102] From the viewpoint that the agent has excellent operability and water permeability over time stability, the acid value of the anionic surfactant (S) is preferably 0 to 120 mgKOH / g, more preferably 3 to 80 mgKOH / g, and even more preferably 10 to 65 mgKOH / g.

[0103] Anionic surfactants (S) include sulfonic acid type and sulfuric acid type.

[0104] Examples of sulfonic acid types include: dialkyl sulfosuccinic acid and / or its salts (S-1), monoalkyl sulfosuccinic acid and / or its salts, alkylbenzene sulfonic acid and / or its salts, alkyl sulfonic acid and / or its salts, acylmethyl taurine, etc.

[0105] Examples of sulfate-type sulfates include: polyol fatty acid sulfate salts (S-2), alkyl sulfate salts, and polyoxyethylene alkyl sulfate salts.

[0106] Examples of sulfonic acid-based sulfonates include: sodium hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium octyl sulfonate, tetrabutylphosphine hexane sulfonate, sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, sodium didecyl sulfosuccinate, sodium ditridecyl sulfosuccinate, disodium monooctyl sulfosuccinate, disodium monohexyl sulfosuccinate, disodium mono-2-ethylhexyl sulfosuccinate, disodium monodecyl sulfosuccinate, disodium monotridecyl sulfosuccinate, petroleum sulfonates, etc. From the viewpoint of simultaneously achieving excellent operability and water permeability over time stability of the additive, sodium di-2-ethylhexyl sulfosuccinate and sodium ditridecyl sulfosuccinate are preferred.

[0107] Sulfuric acid type polyol fatty acid sulfate salts (S-2) can be listed as substances having a structure obtained by sulfation and neutralization of polyol fatty acid esters (a).

[0108] There are no particular limitations on the sulfation method; fuming sulfuric acid, concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide gas, etc., can be used, employing known methods. There are also no particular limitations on the neutralization method; known methods can be used. The alkaline substances used for neutralization include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; oxides and hydroxides of alkaline earth metals such as calcium oxide, calcium hydroxide, magnesium oxide, and magnesium hydroxide; ammonia; mono-, di-, and tri-alkyl alcohols with 2-4 carbon atoms in their hydroxyalkyl chains; and primary, secondary, and tertiary alkyl amines with 1-4 carbon atoms in their alkyl chains. Two or more alkaline substances can be used in combination.

[0109] The aforementioned polyol fatty acid ester (a) is an ester compound with a structure formed by the ester bonding of polyol and fatty acid. It can be a synthetic product or a natural product.

[0110] The polyols used in the synthesis of the above-mentioned polyol fatty acid esters (a) are polyols having two or more hydroxyl groups, such as: ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, etc.; polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, etc.; glycerol, trimethylolpropane, pentaerythritol, erythritol, diglycerol, polyglycerol, sorbitan, sorbitol, di(trimethylolpropane), dipentaerythritol, sucrose, etc. From the viewpoint that the operability and water permeability of the agent are excellent over time, glycerol and sorbitan are preferred, and glycerol is even more preferred.

[0111] For the fatty acids used in the synthesis of the above-mentioned polyol fatty acid esters (a), unsaturated fatty acids include, for example, oleic acid, ricinoleic acid, and linolenic acid; saturated fatty acids, hydroxy fatty acids, or hydroxyunsaturated fatty acids include, for example, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, benzyl acid, etc., limonene acid, nervonic acid, ceric acid, ligninic acid, beeswax acid, lanolin fatty acids, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxylauric acid, hydroxystearic acid, etc. Among these, ricinoleic acid, linolenic acid, and hydroxystearic acid are preferred.

[0112] The higher the molecular weight of the aforementioned polyol fatty acid ester (a), the better its durable water permeability. Therefore, the total number of carbon atoms in the aforementioned polyol fatty acid ester (a) is preferably 23 or more, more preferably 27 or more, even more preferably 31 or more, and particularly preferably 39 or more. The preferred upper limit for the total number of carbon atoms in the aforementioned polyol fatty acid ester (a) is 100, more preferably 90, and even more preferably 80. If the total number of carbon atoms in the aforementioned polyol fatty acid ester (a) exceeds 100, the instantaneous water permeability may decrease.

[0113] Examples of natural sources of the aforementioned polyol fatty acid esters (a) include: beef tallow, lard, horse tallow, mutton tallow, poultry tallow, whale oil, sea hog fat, sardine oil, cod oil, shark oil, castor oil, rapeseed oil, cottonseed oil, sesame oil, olive oil, soybean oil, coconut oil, palm oil, palm kernel oil, peanut oil, corn oil, and sunflower seed oil. From the perspective of durability and water permeability, beef tallow, castor oil, and rapeseed oil are preferred.

[0114] In addition to the natural products mentioned above, examples of the aforementioned polyol fatty acid esters (a) include hydrogenated oils and semi-hydrogenated oils that have a structure formed by hydrogenating the aforementioned natural products. Examples include: hydrogenated coconut oil, hydrogenated palm oil, semi-hydrogenated palm oil, hydrogenated palm kernel oil, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated castor oil, hydrogenated tallow, semi-hydrogenated tallow, hydrogenated lard, semi-hydrogenated sardine oil, hydrogenated cod oil, semi-hydrogenated cod oil, hydrogenated shark oil, and semi-hydrogenated shark oil.

[0115] As a sulfate-type alkyl sulfate salt, the alkyl group is preferably 1 to 30, more preferably 4 to 22, and even more preferably 6 to 18. The alkyl group can be any of the following: straight-chain or branched, saturated or unsaturated, aliphatic or aromatic, and may also have a distribution.

[0116] The alkyl sulfates used as the alkyl sulfate salts described above are not particularly limited, and examples include: methyl sulfate, ethyl sulfate, butyl sulfate, hexyl sulfate, octyl sulfate, decyl sulfate, lauryl sulfate, cetyl sulfate, stearyl sulfate, and oleyl sulfate. From the viewpoint of simultaneously achieving excellent workability and water permeability over time stability of the agent, lauryl sulfate, cetyl sulfate, stearyl sulfate, and oleyl sulfate are preferred, and lauryl sulfate, cetyl sulfate, stearyl sulfate, and oleyl sulfate are even more preferred. The salts used as the alkyl sulfate salts of the present invention are not particularly limited, and examples include: sodium salts, potassium salts, and ammonium salts.

[0117] As the aforementioned polyoxyalkylene alkyl sulfate salt, the alkyl group is preferably 1 to 30, more preferably 4 to 22, and even more preferably 6 to 18. This alkyl group can be any of the following: straight-chain or branched, saturated or unsaturated, aliphatic or aromatic, and can also have a distribution. The polyoxyalkylene alkyl group in the polyoxyalkylene alkyl sulfate salt of the present invention is polyoxyethylene and / or polyoxypropylene. When it is polyoxyethylene and polyoxypropylene, it can be a compound formed by random addition polymerization or a compound formed by block addition polymerization. From the viewpoint of productivity, a compound formed by random addition polymerization is preferred. From the viewpoint of simultaneously excellent operability and water permeability over time stability of the agent, the addition molar number of the polyoxyalkylene is 1 to 40, preferably 2 to 30, more preferably 3 to 25, and even more preferably 4 to 20. The salt as the aforementioned polyoxyalkylene alkyl sulfate salt is not particularly limited; for example, sodium salts, potassium salts, and ammonium salts can be mentioned.

[0118] [Anionic surfactant (P)]

[0119] Anionic surfactants (P) are anionic surfactants containing the phosphorus element.

[0120] Anionic surfactants (P) combined with the aforementioned nonionic surfactants (N) result in excellent workability and long-term stability of the agent's permeability.

[0121] Anionic surfactants (P) must contain compound (A) of general formula (1) and compound (B) of general formula (2).

[0122] (Compound (A))

[0123] Compound (A) is the compound represented by the general formula (1) above. Compound (A) has the function of simultaneously improving the workability and water permeability of the agent by being used in combination with the surfactant (S) or nonionic surfactant (N) described later.

[0124] In general formula (1), from the viewpoint that the workability and water permeability of the adjuvant are both excellent over time, R 1 The preferred hydrocarbon group has 6 to 22 carbon atoms, the more preferred hydrocarbon group has 6 to 18 carbon atoms, and the most preferred hydrocarbon group has 12 to 18 carbon atoms.

[0125] R 1 It can be a straight chain or a branch chain; from the perspective of maximizing the effect of this application, a straight chain is preferred. 1 It can be saturated or unsaturated.

[0126] AO is an oxoalkylene group with 2 to 4 carbon atoms. From the viewpoint of maximizing the effect of this application, AO preferably has 2 carbon atoms.

[0127] m is an integer from 0 to 15, and from the viewpoint of maximizing the effect of this application, it is preferably 0 to 10, and more preferably 0 to 8.

[0128] M 1 It is a hydrogen atom, an alkali metal, or an organic amine salt. M 2 It consists of hydrogen atoms, alkali metals, or organic amine salts.

[0129] (Compound (B))

[0130] Compound (B) is the compound represented by the general formula (2) above. Compound (B), when used in combination with a nonionic surfactant (N), has the function of simultaneously improving the workability and water permeability stability of the agent over time.

[0131] In general formula (2), from the viewpoint that the workability and water permeability of the agent are both excellent over time, R 2 and R 3 The preferred hydrocarbon group has 6 to 22 carbon atoms, the more preferred hydrocarbon group has 6 to 18 carbon atoms, and the most preferred hydrocarbon group has 12 to 18 carbon atoms.

[0132] R 2 and R 3 It can be a straight chain or a branch chain, but from the point of view of maximizing the effect of this application, a straight chain is preferred. 2 and R 3 It can be saturated or unsaturated.

[0133] AO is an oxoalkylene group with 2 to 4 carbon atoms. From the viewpoint of maximizing the effect of this application, AO preferably has 2 carbon atoms.

[0134] m is an integer from 0 to 15, and from the viewpoint of maximizing the effect of this application, it is preferably 0 to 10, and more preferably 0 to 8.

[0135] M 1 It can be a hydrogen atom, an alkali metal, ammonium, phosphonium, an organic amine salt, or a quaternary ammonium salt.

[0136] There are 2 (AO) molecules within the molecule. m In this case, the two can be the same or different.

[0137] (Compound (C))

[0138] Compound (C) is the compound represented by the above general formula (3), and is any component included in this invention. From the viewpoint of simultaneously achieving excellent operability and long-term stability of water permeability of the agent, this invention preferably includes compound (C).

[0139] In general formula (3), from the viewpoint that the workability and water permeability of the agent are both excellent over time, R 4 The preferred hydrocarbon group has 6 to 22 carbon atoms, the more preferred hydrocarbon group has 6 to 18 carbon atoms, and the most preferred hydrocarbon group has 12 to 18 carbon atoms.

[0140] R 4 It can be a straight chain or a branch chain; from the perspective of maximizing the effect of this application, a straight chain is preferred. 4 It can be saturated or unsaturated.

[0141] m is an integer from 0 to 15, and from the viewpoint of maximizing the effect of this application, it is preferably 0 to 10, and more preferably 0 to 8.

[0142] AO is an oxoalkylene group with 2 to 4 carbon atoms, and m is an integer from 0 to 15. M 1 and M 2 Each can be independently a hydrogen atom, an alkali metal, ammonium, phosphonium, or an organic amine salt or quaternary ammonium salt. Q is M. 2 Or (OA) m R 5 R 5 It is a hydrocarbon group with 3 to 5 carbon atoms. R 5 It can be a straight chain or a branch chain. Additionally, R... 5 It can be saturated or unsaturated. Y is 1 or 2. There are more than two M molecules within the molecule. 2 Or (AO) m In this case, they can be the same or different.

[0143] [Compound (D)]

[0144] Compound (D) is a compound represented by the following general formula (4). From the viewpoint that the permeability agent of the present invention is excellent in both operability and long-term stability of water permeability, it preferably contains compound (D).

[0145] [Chemistry 4]

[0146]

[0147] From the perspective of simultaneously achieving excellent operability and long-term stability of permeability of the additive, in the formula, R 6 R 7 and R 8 Each group is preferably a hydrocarbon group with 6 to 22 carbon atoms, with an upper limit of 18, more preferably 16, and even more preferably 14, and a lower limit of 6, more preferably 8, and even more preferably 12. Alternatively, 6 to 16, and more preferably 10 to 20, are preferred.

[0148] R 6 R 7 and R 8 It can be a straight chain or a branch chain, but from the point of view of maximizing the effect of this application, a straight chain is preferred. 6 R 7 and R 8 It can be saturated or unsaturated.

[0149] R 6 R 7 and R 8 They can be the same or different.

[0150] AO is an oxoalkylene group with 2 to 4 carbon atoms. From the viewpoint of maximizing the effects of this application, it is preferred that AO has 2 carbon atoms.

[0151] m is an integer from 0 to 15, and from the viewpoint of maximizing the effect of this application, it is preferably 0 to 10, and more preferably 0 to 8.

[0152] There are more than two (AO) molecules within the molecule. m In this case, the two can be the same or different.

[0153] Specific examples of compound (D) are not particularly limited, but can include: tris(2-ethylhexyl) phosphate, tris(polyoxyethylene 8-molar addition 2-ethylhexyl) phosphate, triisolauryl phosphate, tris(polyoxyethylene 9-molar addition isolauryl) phosphate, triisostearyl phosphate, tris(polyoxyethylene 15-molar addition isostearyl) phosphate, di(2-ethylhexyl) monooctyl phosphate, di(polyoxyethylene 8-molar addition 2-ethylhexyl) monooctyl phosphate, etc. Among these, from the perspective of achieving the effects of this application, tris(2-ethylhexyl) phosphate, triisolauryl phosphate, and triisostearyl phosphate are preferred. Furthermore, from the viewpoint of achieving the effects of this application, tris(polyoxyethylene 8-molar addition 2-ethylhexyl) phosphate, tris(polyoxyethylene 9-molar addition isolauryl) phosphate, and tris(polyoxyethylene 15-molar addition isostearyl) phosphate are preferred.

[0154] [Inorganic phosphate (IN)]

[0155] From the viewpoint that the permeability additive is excellent in both operability and long-term stability of water permeability, the water permeability additive of the present invention preferably contains inorganic phosphate (IN).

[0156] Inorganic phosphate (IN) is at least one selected from phosphoric acid, dihydrogen phosphate, dimetallic hydrogen phosphate, and trimetallic phosphate. Specifically, examples of dihydrogen phosphate include potassium dihydrogen phosphate and sodium dihydrogen phosphate; examples of dimetallic hydrogen phosphate include dipotassium hydrogen phosphate and disodium hydrogen phosphate; and examples of trimetallic phosphate include tripotassium phosphate and trisodium phosphate.

[0157] [Permeability enhancer]

[0158] The non-volatile component of the permeability-enhancing agent of the present invention has an iodine value of 0.5~100 gI2 / 100g. When the iodine value is less than 0.5 gI2 / 100g, the operability and long-term stability of the permeability of the agent are insufficient; when it exceeds 100 gI2 / 100g, the permeability and long-term stability of the permeability are insufficient.

[0159] From the viewpoint of simultaneously improving the operability and long-term stability of the permeability of the agent, the lower limit of the iodine value of the non-volatile component of the permeability agent of the present invention is preferably 2 gI2 / 100g, more preferably 5 gI2 / 100g, and even more preferably 10 gI2 / 100g.

[0160] From the viewpoint of simultaneously improving the operability and long-term stability of the permeability of the agent, the upper limit of the iodine value of the non-volatile component of the permeability agent of the present invention is preferably 85 gI2 / 100g, more preferably 50 gI2 / 100g, and even more preferably 30 gI2 / 100g.

[0161] The non-volatile component of the permeability-enhancing agent of the present invention has an acid value of 0.5~100 mgKOH / g. When the acid value is less than 0.5 mgKOH / g, the operability and long-term stability of the permeability of the agent are insufficient; when the acid value exceeds 100 mgKOH / g, the operability, permeability, and long-term stability of the permeability of the agent are insufficient.

[0162] From the viewpoint of simultaneously improving operability and the long-term stability of permeability, the lower limit of the acid value of the non-volatile component of the permeability imparting agent of the present invention is preferably 1.0 mgKOH / g, more preferably 3.0 mgKOH / g, and even more preferably 5.0 mgKOH / g.

[0163] From the viewpoint of simultaneously improving the operability and long-term stability of the permeability of the agent, the upper limit of the acid value of the non-volatile component of the permeability agent of the present invention is preferably 85 mgKOH / g, more preferably 55 mgKOH / g, and even more preferably 25 mgKOH / g.

[0164] The acid value of the non-volatile component of the permeability-improving agent of the present invention can be adjusted as needed after mixing various components. In this case, the adjustment method is not particularly limited, and known methods can be used. Examples of alkaline substances used for adjustment include: alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; oxides and hydroxides of alkaline earth metals such as calcium oxide, calcium hydroxide, magnesium oxide, and magnesium hydroxide; ammonia; mono-, di-, and tri-alkyl alcohol amines with 2 to 4 carbon atoms in the hydroxyalkyl chain; and primary, secondary, and tertiary alkyl amines with 1 to 4 carbon atoms in the alkyl chain. Two or more alkaline substances can be used together. Examples of acidic substances used for adjustment include: sulfuric acid, phosphoric acid, acetic acid, lactic acid, and citric acid. Two or more acidic substances can be used together.

[0165] From the viewpoint of simultaneously improving the operability and long-term stability of the permeability of the agent, the total amount of phosphorus in the non-volatile components of the permeability agent of the present invention is preferably 0 to 15% by weight.

[0166] From the viewpoint that the agent has excellent operability and water permeability stability over time, the upper limit of the total amount of phosphorus in the non-volatile component of the water permeability agent of the present invention is preferably 10% by weight, more preferably 9% by weight, and even more preferably 8% by weight.

[0167] From the viewpoint of simultaneously improving operability and the long-term stability of permeability, the lower limit of the total amount of phosphorus in the non-volatile component of the permeability imparting agent of the present invention is preferably 0% by weight, more preferably 0.5% by weight, further preferably 1.0% by weight, and particularly preferably 1.5% by weight.

[0168] From the viewpoint of simultaneously improving the operability and long-term stability of the permeability of the agent, the total amount of sulfur in the non-volatile components of the permeability agent of the present invention is 0 to 10% by weight.

[0169] From the viewpoint that the agent has excellent operability and water permeability stability over time, the upper limit of the total amount of sulfur in the non-volatile component of the water permeability agent of the present invention is preferably 8% by weight, more preferably 6% by weight, and even more preferably 4% by weight.

[0170] From the viewpoint of simultaneously improving the operability and long-term stability of the permeability of the agent, the lower limit of the total amount of sulfur in the non-volatile component of the permeability agent of the present invention is preferably 0% by weight, more preferably 0.3% by weight, further preferably 0.6% by weight, and particularly preferably 1.0% by weight.

[0171] The total amount of phosphorus and sulfur in the non-volatile components of the permeability-improving agent of the present invention is greater than 0% by weight and less than 25% by weight. From the viewpoint of maximizing the effects of this application, it is preferably 1.0% to 19.0% by weight, more preferably 1.5% to 13.0% by weight, and even more preferably 2.0% to 7.0% by weight.

[0172] (Determination of iodine value)

[0173] The determination was performed according to the method described in the "Test Method for Analysis of Standard Oils and Fats (2013 Edition)" formulated by the Japan Oil Chemistry Society (iodine value (Widmanstätten-carbon tetrachloride method)). It should be noted that a potentiometric titration apparatus can also be used during titration.

[0174] (Determination of acid value)

[0175] The determination was performed according to the method described in the "Test Method for Analysis of Standard Oils and Fats (2013 Edition)" formulated by the Japan Oil Chemistry Society (acid value (applicable to oils and fats)). It should be noted that a potentiometric titration apparatus can also be used during titration.

[0176] (Method for determining phosphorus and sulfur content based on ICP luminescence analysis)

[0177] (1) Preprocessing

[0178] Weigh an appropriate amount of the additive or its non-volatile component into a platinum crucible (adjust the amount to fall within the range of the standard curve), add 5% (w / w) potassium hydroxide ethanol solution and dissolve. Gradually heat on an electric heater, carbonize, and then ashing at 750°C. After cooling to room temperature, add 0.5 g of alkaline flux (a 1:1 weight mixture of sodium carbonate and potassium carbonate), slowly raise the temperature, and perform alkaline melting at 850°C for 10 minutes. After naturally cooling to room temperature, dilute to volume with ultrapure water to obtain the test sample.

[0179] (2) Standard Curve

[0180] Pre-adjusted standard solutions of 10 ppm and 100 ppm phosphorus and sulfur concentrations were respectively applied to ICP (analytical equipment: Shimadzu ICPS-8100, ICP luminescence analyzer) to prepare a standard curve.

[0181] (3) Measurement

[0182] The test sample prepared in (1) above is used in an ICP (test instrument: Shimadzu ICPS-8100, ICP luminescence analyzer), and the content of phosphorus and sulfur in the additive or the non-volatile components of the additive is determined using the standard curve prepared in (2) above. When the additive is used as the test sample, the ratio of the non-volatile components of the additive is determined, and the content of phosphorus and sulfur in the non-volatile components can be calculated by using its weight ratio.

[0183] The non-volatile component of the permeability-enhancing agent in this invention refers to the absolutely dry component when the agent is heat-treated to remove solvents and the like, and a constant amount is achieved. Methods for obtaining the non-volatile component include methods that directly heat-treat the agent, and methods that obtain it by solvent extraction from fibers or nonwoven fabrics coated with the agent and dried after heat treatment.

[0184] In cases where the permeability agent is directly heat-treated to obtain non-volatile components, 2.0~3.0 g of the permeability agent is spread flat on an aluminum sheet, dried at 110°C under infrared lamp irradiation, and the remaining portion on the aluminum sheet is recovered when the change in volatile components within 150 seconds reaches 0.15%.

[0185] In the case of obtaining non-volatile components from fibers and non-woven fabrics, the fibers with adsorbents are cleaned using cleaning solutions such as hexane, methanol, and ethanol, and the solvent used in the cleaning (the cleaning solvent containing the non-volatile components of the adsorbents) is dried and recovered.

[0186] If the extracted material contains components from fibers or nonwoven fabrics, the portion remaining after deducting these contents will be used as the non-volatile component of the additive.

[0187] In analyses related to the composition of the excipient, for the excipient and its non-volatile components (including extracts from fibers and nonwoven fabrics), after selecting an appropriate column and solvent based on the composition, high-performance liquid chromatography (HPLC) is used to fractionate each component. Subsequently, MS, NMR, and elemental analysis are performed on each component to identify its structure. Furthermore, when the non-volatile components of the excipient contain polymeric compounds, the identification of the constituent components is facilitated by using methods such as gel permeation chromatography (GPC).

[0188] From the viewpoint of simultaneously improving operability and the long-term stability of permeability, the proportion of nonionic surfactant (N) in the non-volatile component of the permeability-improving agent of the present invention is preferably 1.0 wt% to 95 wt%. The upper limit of this proportion is more preferably 90 wt%, further preferably 60 wt%, and particularly preferably 40 wt%. On the other hand, the lower limit of this proportion is more preferably 3.0 wt%, further preferably 5.0 wt%, and particularly preferably 10 wt%. Additionally, for example, it is more preferably 3.0 wt% to 90 wt%, and further preferably 5.0 wt% to 60 wt%.

[0189] When the permeability-improving agent of the present invention comprises an anionic surfactant (S) having an sulfur element, from the viewpoint of simultaneously excelling in both the operability of the agent and the long-term stability of permeability, the proportion of the anionic surfactant (S) in the permeability-improving agent of the present invention is preferably 5% to 80% by weight. The upper limit of this ratio is more preferably 75% by weight, further preferably 70% by weight, and particularly preferably 60% by weight. On the other hand, the lower limit of this ratio is more preferably 8% by weight, further preferably 13% by weight, and particularly preferably 15% by weight. Additionally, for example, it is more preferably 8% to 75% by weight, and further preferably 13% to 70% by weight.

[0190] When the permeability-improving agent of the present invention comprises an anionic surfactant (P) having a phosphorus element, from the viewpoint of simultaneously excelling in both the operability of the agent and the long-term stability of permeability, the proportion of the anionic surfactant (P) in the permeability-improving agent of the present invention is preferably 5% to 80% by weight. The upper limit of this ratio is more preferably 70% by weight, further preferably 60% by weight, and particularly preferably 50% by weight. On the other hand, the lower limit of this ratio is more preferably 10% by weight, further preferably 15% by weight, and particularly preferably 20% by weight. Additionally, for example, it is more preferably 10% to 70% by weight, and further preferably 15% to 60% by weight.

[0191] From the viewpoint that the agent has excellent operability and water permeability stability over time, the ratio of the following peak area P1 to the total of P1 to P3 (P1+P2+P3) in the spectrum obtained by measuring the non-volatile components of the water permeability agent of the present invention by P-nuclear NMR is preferably 40% to 100%.

[0192] P1: Peak area in the range of 0~10ppm

[0193] P2: Peak area in the range of -25 to -3 ppm

[0194] P3: Peak area in the range of -3 to 0 ppm

[0195] For compounds that show peaks in the -25 to 10 ppm spectrum, there is a tendency to classify them sequentially from the low magnetic field side as inorganic phosphate or compound (A), compound (B), compound (D), and compound (C).

[0196] If [P1 / (P1+P2+P3)] is 40% to 100%, the operability and water permeability of the agent are both excellent over time, which is therefore preferred. From the viewpoint that the operability and water permeability of the agent are both excellent over time, the upper limit of the ratio [P1 / (P1+P2+P3)] is preferably 90%, more preferably 80%, and even more preferably 75%. On the other hand, from the viewpoint that the operability and water permeability of the agent are both excellent over time, the lower limit of [P1 / (P1+P2+P3)] is preferably 40%, more preferably 45%, and even more preferably 50%. In addition, for example, it is preferred to be 40% to 90%, more preferably 45% to 85%, and even more preferably 50% to 75%. It should be noted that the method for measuring the peak area of ​​each of P1 to P3 is based on the method described in the following paragraphs.

[0197] [A / (A+B+C+D+IN)]

[0198] [A / (A+B+C+D+IN)] is the ratio of the P-nuclear NMR integral value (A) belonging to compound (A) of the following general formula (1) to the total of the P-nuclear NMR integral values ​​(A+B+C+D+IN) belonging to compound (A) of the above general formula (1), compound (B) belonging to the above general formula (2), compound (C) belonging to the above general formula (3), compound (D) belonging to the above inorganic phosphate (IN) (hereinafter referred to as the total of P-nuclear NMR integral values ​​(A+B+C+D+IN)).

[0199] Compound (A) can be 31 The p-NMR method is used for detection.

[0200] Weigh approximately 30 mg of the non-volatile component of the sample into a 5 mm diameter NMR sample tube, and add approximately 0.5 ml of heavy water (D₂O) or dichloroform (CDCl₃) as a deuteration solvent. 31 The measurements were performed using a BRUKER AVANCE400 (162MHz) and a JNM-ECZ400R (162MHz) from Nippon Electronics Co., Ltd.

[0201] From the viewpoint of maximizing the effect of this application, the lower limit value of [A / (A+B+C+D+IN)] is preferably 20%, 22%, 25%, and 30% respectively (the preferred values ​​described later are even higher, and the same applies below).

[0202] From the viewpoint of maximizing the effect of this application, the upper limit value of [A / (A+B+C+D+IN)] is preferably 98%, 95%, 92%, 90%, and 80%, respectively.

[0203] From the viewpoint of maximizing the effectiveness of this application, the lower limit value of [B / (A+B+C+D+IN)] is preferably 1%, 3%, 5%, and 7%, respectively.

[0204] From the viewpoint of maximizing the effect of this application, the upper limit value of [B / (A+B+C+D+IN)] is preferably 65%, 50%, 40%, and 30%, respectively.

[0205] [C / (A+B+C+D+IN)] represents the ratio of the P-nuclear NMR integral value (C) belonging to the above compound (C) to the total P-nuclear NMR integral values ​​(A+B+C+D+IN).

[0206] From the viewpoint of maximizing the effectiveness of this application, the lower limit values ​​of [C / (A+B+C+D+IN)] are preferably 0%, 4%, 8%, and 10%, respectively.

[0207] From the viewpoint of maximizing the effectiveness of this application, the upper limit values ​​of [C / (A+B+C+D+IN)] are preferably 40%, 30%, and 20%, respectively.

[0208] [D / (A+B+C+D+IN)] represents the ratio of the P-nuclear NMR integral value (D) belonging to the above compound (D) to the total P-nuclear NMR integral values ​​(A+B+C+D+IN).

[0209] From the viewpoint of maximizing the effect of this application, the lower limit values ​​of [D / (A+B+C+D+IN)] are preferably 0%, 4%, 8%, and 10%, respectively.

[0210] From the viewpoint of maximizing the effect of this application, the upper limit value of [D / (A+B+C+D+IN)] is preferably 10%, 5%, 4%, 2%, and 0%, respectively.

[0211] [IN / (A+B+C+D+IN)] represents the ratio of the P-nuclear NMR integral value (IN) belonging to the above inorganic phosphate (IN) to the total P-nuclear NMR integral values ​​(A+B+C+D+IN).

[0212] From the viewpoint of maximizing the effectiveness of this application, the lower limit values ​​of [IN / (A+B+C+D+IN)] are preferably 0%, 0.1%, 0.5%, and 1%, respectively.

[0213] From the viewpoint of maximizing the effectiveness of this application, the upper limit value of [IN / (A+B+C+D+IN)] is preferably 10%, 5%, 4%, 2%, and 0%, respectively.

[0214] From the viewpoint of maximizing the effects of this application, the weight ratio of the anionic surfactant in the total of anionic and nonionic surfactants in the permeability-imparting agent [anionic / (anionic + nonionic)] is preferably 5% to 99% by weight. The lower limit of the weight ratio of the anionic surfactant in the total of anionic and nonionic surfactants in the permeability-imparting agent [anionic / (anionic + nonionic)] is more preferably 10% by weight, further preferably 40% by weight, and particularly preferably 60% by weight. The upper limit is more preferably 97% by weight, further preferably 95% by weight, and particularly preferably 90% by weight.

[0215] From the viewpoint that the agent has excellent operability and water permeability stability over time, the pH of the aqueous solution of the non-volatile component of the above-mentioned water permeability agent with a concentration of 1% is preferably 4.0 to 11.0, more preferably 5.0 to 10.0, and even more preferably 6.0 to 9.0.

[0216] The permeability imparting agent of the present invention is preferred for use in menstrual blood permeability applications, as it can exert a better effect.

[0217] From the viewpoint of maximizing the effect of this application, the concentration of the non-volatile component of the above-mentioned permeability imparting agent is preferably 40% to 100% by weight, more preferably 45% to 95% by weight, and even more preferably 50% to 90% by weight.

[0218] In the permeability imparting agent of the present invention, from the viewpoint of maximizing the effect of this application, the ratio of the organosilicon compound to the non-volatile component of the permeability imparting agent is preferably in the following order: less than 25% by weight, less than 15% by weight, less than 5% by weight, less than 3% by weight, less than 1% by weight, and 0% by weight.

[0219] 〔fiber〕

[0220] The fiber of the present invention is formed by imparting the above-mentioned water-permeable agent to the fiber body. The fiber of the present invention can be a short fiber or a long fiber, but considering water permeability, a short fiber is preferred.

[0221] In terms of antistatic properties and water permeability, the non-volatile component of the water permeability agent preferably has an adhesion rate of 0.03% to 2% relative to the fiber matrix, and more preferably 0.1% to 1% relative to the fiber matrix.

[0222] The fiber matrix can be, for example, polyolefin fibers, polyester fibers, nylon fibers, vinyl chloride fibers, or composite fibers composed of two or more thermoplastic resins. In the case of polyolefin resin / polyolefin resin combinations, examples include: high-density polyethylene / polypropylene, linear high-density polyethylene / polypropylene, low-density polyethylene / polypropylene, binary or terpolymer of propylene with other α-olefins / polypropylene, linear high-density polyethylene / high-density polyethylene, and low-density polyethylene / high-density polyethylene. In the case of polyolefin resin / polyester resin combinations, examples include: polypropylene / polyethylene terephthalate, high-density polyethylene / polyethylene terephthalate, linear high-density polyethylene / polyethylene terephthalate, and low-density polyethylene / polyethylene terephthalate. In the case of polyester resin / polyester resin combinations, examples include: copolyester / polyethylene terephthalate. Examples of fibers composed of polyamide / polyester resins, polyolefin / polyamide resins, etc., can also be cited. Among these fiber bodies, for the sake of preferring a soft, skin-like feel, the water-permeability imparting agent of the present invention is suitable for hydrophobic synthetic fibers such as polyolefin fibers (polyolefin fibers, composite fibers containing polyolefin fibers) and polyester fibers (polyester fibers, composite fibers containing polyester fibers), and furthermore, the water-permeability imparting agent of the present invention is suitable for polyolefin fibers.

[0223] Furthermore, if the main body of these fibers is nonwoven fabric manufacturing fiber, it is preferred from the perspective of water permeability.

[0224] The cross-sectional structure of the fiber can be exemplified by sheath-core type, parallel type, eccentric sheath-core type, multi-layer type, radial type, or island type. However, considering the productivity of the fiber manufacturing process and the ease of nonwoven fabric processing, an eccentric sheath-core type or parallel type is preferred. Furthermore, the cross-sectional shape can be circular or irregular. In the case of irregular shapes, for example, it can be any shape such as flat, polygonal (triangular to octagonal), T-shaped, hollow, or multi-leaf type.

[0225] The water-permeability-enhancing agent of the present invention can be directly adhered to the fiber matrix without dilution, or it can be diluted with water or the like to a concentration of 0.5% to 5% by weight of the non-volatile components before adhering to the fiber matrix. The process of adhering the water-permeability-enhancing agent to the fiber matrix can be any process of the fiber matrix, such as spinning, stretching, or crimping. There are no particular limitations on the means by which the water-permeability-enhancing agent of the present invention is adhered to the fiber matrix; methods such as roller oiling, nozzle spraying, or impregnation can be used. Depending on the fiber manufacturing process and its characteristics, a method that can obtain the target adhesion amount more uniformly and efficiently can be adopted. Furthermore, as a drying method, methods using hot air and infrared rays, or methods of drying by contact with a heat source, can be used.

[0226] [Non-woven fabric]

[0227] The nonwoven fabric of the present invention can be made by imparting a water-permeable agent to a raw nonwoven fabric without such an agent, or by using fibers with an imparted water-permeable agent. There are no particular limitations on the manufacturing method of the nonwoven fabric of the present invention, and known methods can be used. Short fibers or long fibers can be used as the raw material fibers. Examples of web-forming methods using short fibers include dry methods such as carding and air-forming, and wet methods such as papermaking. Examples of web-forming methods using long fibers include spunbonding, meltblowing, and flash spinning. Examples of fiber bonding methods include chemical bonding, thermal bonding, needle punching, hydroentangling, and stitch bonding.

[0228] The method for manufacturing the nonwoven fabric of the present invention preferably includes a step of passing the fibers of the present invention through a carding machine or the like to form a fiber web, and then heat-treating the resulting fiber web. That is, the water-permeability imparting agent of the present invention is particularly preferred when the manufacturing process of the nonwoven fabric includes a step of heat-treating the fiber web.

[0229] Examples of methods for joining fibrous webs by heat treatment include: hot pressing using heated rollers or ultrasound, hot fusion bonding using heated air, and hot pressing joint (point bonding) methods. As an example of joining fibrous webs by heat treatment, in the case of a sheath-core type composite fiber where the core uses a high-melting-point resin and the sheath uses a low-melting-point resin, heat treatment near the melting point of the low-melting-point resin allows for easy thermal bonding of the fiber joints.

[0230] As a method for manufacturing nonwoven fabric, the following methods can also be cited: forming a web by passing short fibers endowed with a water-permeable agent through a carding machine or the like, and then heat-treating them as described above to bond them together; blending the water-permeable fibers (short fibers) of the present invention with the pulp during lamination using an air-laid method, and then heat-treating them as described above to bond them together. Furthermore, the following methods can also be cited: heat-treating a fiber molded body obtained by spunbonding, meltblowing, flash spinning, etc., by applying a heat-permeable agent of the present invention to the fiber molded body using a heated roller or heated air, or attaching the water-permeable agent of the present invention to the fiber molded body after heat treatment using a heated roller or heated air, to manufacture a nonwoven fabric.

[0231] As an example of spunbond bonding, composite fiber resin is spun into fibers. The spun composite long fiber filaments are then cooled with a cooling fluid, and tension is applied to the filaments using stretching air to achieve the desired fineness. The spun filaments are then collected on a collection belt and bonded to obtain spunbond nonwoven fabric. Bonding methods include hot pressing based on heated rollers or ultrasound, hot fusion bonding using heated air, and hot pressing point bonding (spot bonding).

[0232] As a method for imparting the permeability-improving agent of the present invention to the obtained spunbond nonwoven fabric, it can be performed by roller coating methods such as gravure coating, flexographic coating, and gate roller coating, or spray coating, etc., as long as the method can adjust the coating amount of the nonwoven fabric individually on one side. In addition, as a drying method, it can be performed by using hot air and infrared rays, or by drying it by contact with a heat source, etc.

[0233] [Absorbent items]

[0234] The absorbent articles of the present invention include the nonwoven fabric of the present invention. Examples of absorbent articles of the present invention include diapers, sanitary napkins (panty liners, etc.). In the absorbent articles of the present invention, the nonwoven fabric of the present invention is preferably used as the top sheet of sanitary materials such as diapers and sanitary napkins.

[0235] In addition, it can also be used for second sheets, absorbent bodies, and absorbent pads.

[0236] Example

[0237] The present invention will now be specifically described through examples and comparative examples, but the present invention is not limited to the examples described herein. It should be noted that, unless otherwise specified, "percentage (%)" and "parts" in the following examples refer to "weight %" and "parts by weight". It should also be noted that, in the examples and comparative examples, the evaluation of the various properties of the permeability-improving agents was performed according to the following methods.

[0238] (Examples 1 to 38 and Comparative Examples 1 to 7)

[0239] In addition, the components shown in Tables 4 to 9 are as described in Tables 1 and 2 and below.

[0240] The acid values ​​N-1~5, 7, 8, 15, and 17~20 in Table 2 come from unreacted fatty acids remaining during the esterification reaction. Additionally, the ester compounds contain small amounts of different partial and complete ester compounds as byproducts. Substances with the same name but different iodine values ​​in Table 2 originate from the purity of unsaturated fatty acids. Furthermore, p-1~p-12, shown in Tables 4~9, are contained in the integral ratios shown in Table 3.

[0241] [Table 1]

[0242]

[0243] [Table 2]

[0244]

[0245] A-1: Compound of general formula (1), R 1 = Hexobase, m=0, M 1 H or K, M 2 H or K

[0246] A-2: Compound of general formula (1), R 1 =octyl group, m=0, M 1 H or K, M 2 H or K

[0247] A-3: Compound of general formula (1), R 1 =Lauryl, m=0, M 1 H or K, M 2 H or K

[0248] A-4: Compound of general formula (1), R 1 =Lauryl, m=0, M 1 H or K, M 2 H or K

[0249] A-5: Compound of general formula (1), R 1 =Lauryl, m=0, M 1 H or K, M 2 H or K

[0250] A-6: Compound of general formula (1), R 1 =Stearyl group, cetyl group, m=0, M 1 H or K, M 2 H or K

[0251] A-7: Compound of general formula (1), R 1 =Stearyl group, m=0, M 1 H or K, M 2 H or K

[0252] A-8: Compound of general formula (1), R 1 =Stearyl group, m=0, M 1 H or K, M 2 H or K

[0253] A-9: Compound of general formula (1), R 1 =Olelene group, m=0, M 1 H or K, M 2 H or K

[0254] B-1: Compound of general formula (2), R 2 =N-hexylene, R 3 =N-hexane, m=0, M 1 H or K

[0255] B-2: Compound of general formula (2), R 2 = n-octyl, R 3 =octyl group, m=0, M 1 H or K

[0256] B-3: Compound of general formula (2), R 2 =Lauryl, R 3 =Lauryl, m=0, M 1 H or K

[0257] B-4: Compound of general formula (2), R 2 =Lauryl, R 3 =Lauryl, m=0, M 1 H or K

[0258] B-5: Compound of general formula (2), R 2 =Lauryl, R 3 =Lauryl, m=0, M 1 H or K

[0259] B-6: Compound of general formula (2), R 2 =Stearyl group, cetyl group, R 3 =Stearyl group, cetyl group, m=0, M 1 H or K

[0260] B-7: Compound of general formula (2), R 2 =Stearin base, R 3 =Stearyl group, m=0, M 1 H or K

[0261] B-8: Compound of general formula (2), R 2 =Stearin base, R 3 =Stearyl group, m=0, M 1 H or K

[0262] B-9: Compound of general formula (2), R 2 =Olelene group, R 3 =Olelene group, m=0, M 1 H or K

[0263] C-1: Compound of general formula (3), R 4 =N-hexane, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0264] C-2: Compound of general formula (3), R 4 =octyl group, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0265] C-3: Compound of general formula (3), R 4 =Lauryl, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0266] C-4: Compound of general formula (3), R 4 =Lauryl, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0267] C-5: Compound of general formula (3), R 4 =Lauryl, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0268] C-6: Compound of general formula (3), R 4 =Stearyl group, cetyl group, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0269] C-7: Compound of general formula (3), R 4 =Stearyl group, m=0, M 1 H or K, M 2H or K, Y=1, Q=M 2

[0270] C-8: Compound of general formula (3), R 4 =Stearyl group, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0271] C-9: Compound of general formula (3), R 4 =Olelene group, m=0, M 1 H or K, M 2 H or K, Y=1, Q=M 2

[0272] D-1 Trihexyl Phosphate

[0273] D-2 Trioctyl Phosphate

[0274] D-3 Trilauryl Phosphate

[0275] D-4 Trilauryl Phosphate

[0276] D-5 Trilauryl Phosphate

[0277] D-6 Tristearyl Cetyl Phosphate

[0278] D-7 Tristearate Phosphate

[0279] D-8 Tristearate Phosphate

[0280] D-9 Trioleyl Phosphate

[0281] The components shown in Tables 4 to 9 were mixed with water to prepare aqueous solutions of the permeability-enhancing agents for Examples 1 to 38 and Comparative Examples 1 to 7, respectively, in which the weight percentage of the non-volatile component in the total permeability-enhancing agent was 50% by weight. The obtained permeability-enhancing agents were diluted with warm water at approximately 60°C to a concentration of 0.9% by weight of the non-volatile component to obtain diluted solutions.

[0282] Next, using an immersion oil supply method, 150g of diluted solutions of various permeability-enhancing agents were applied to 300g of the fiber matrix, resulting in an application rate of 0.45% by weight of the non-volatile components of the permeability-enhancing agents to the permeable fiber. The fiber matrix consisted of polypropylene (core)-polyethylene (sheath) composite fibers without any fiber treatment agents such as permeability-enhancing agents, with a single fiber fineness of 2.2 Dtex and a fiber length of 38mm. The fibers with the diluted solutions of the various permeability-enhancing agents were placed in an 80°C hot air dryer for 2 hours, and then left at room temperature for at least 8 hours to dry, thus obtaining the permeable fiber.

[0283] The obtained water-permeable fibers were respectively subjected to a fiber-opening step and a carding step using a carding tester to produce a web with a basis weight of 25 g / m 2 . The obtained web was heat-treated at 135°C in a hot air circulation dryer to fix the web, thereby obtaining a nonwoven fabric. The obtained nonwoven fabric was evaluated for water permeability by the evaluation method described below. The results are shown in Tables 4 to 9.

[0284] [Operability]

[0285] The operability was evaluated for a 50% by concentration aqueous solution of a water permeability imparting agent, with the properties of the formulated product as evaluation targets: 1) no product separation occurs, and 2) fluidity is maintained. A rating of ○ or higher is acceptable.

[0286] [Judgment Criteria]

[0287] ◎ (Very good): Both 1) and 2) can be satisfied at the same time

[0288] ○+ (Good): Either one of 1) and 2) is slightly inferior, but at a level that poses no problem as a product

[0289] ○ (Fair): Both 1) and 2) are slightly inferior, but at a level that poses no problem as a product

[0290] △ (Poor): Either one of 1) and 2) is considerably inferior

[0291] × (Unacceptable): Both 1) and 2) are considerably inferior

[0292] [Water Permeability of Nonwoven Fabric]

[0293] (Instantaneous Water Permeability of Nonwoven Fabric)

[0294] The nonwoven fabric was overlaid on filter paper (Toyo Filter Paper, No.5), one drop (about 0.05 ml) of artificial urine was dropped from a burette arranged at a height of 10 mm from the surface of the nonwoven fabric, and the time until the water droplet disappeared from the surface of the nonwoven fabric was measured. This measurement was performed at 20 positions on the surface of the nonwoven fabric, and the number of positions where the time was less than 5 seconds was counted. The number was evaluated according to the following criteria. It should be noted that ◎ is the best evaluation, and a rating of ○ or higher is practically usable.

[0295] [Judgment Criteria]

[0296] ◎(Good)… 18 to 20 positions

[0297] ○(Fair)… 11 to 17 positions

[0298] △(Unacceptable)… 1 to 10 positions

[0299] (Durable Water Permeability of Nonwoven Fabric)

[0300] Following the Repeated Liquid Strike-Through Time (DLT) method of the EDANA assay, 0.9% physiological saline was passed through a 10cm x 10cm nonwoven fabric, and the permeation time was measured. After permeation, the nonwoven fabric was sandwiched between two sheets of filter paper (Toyo Filter Paper, No. 5), and a 10cm x 10cm plate and a 500g weight were placed on top for 3 minutes to dehydrate, followed by further air drying for 5 minutes.

[0301] The same procedure was repeated for the nonwoven fabric used in the test. In this repeated test, even with increased number of iterations, the shorter the water permeability time, the better. Evaluation was conducted according to the following criteria. It should be noted that ◎ represents the best evaluation; a score of ○ or higher indicates the fabric is suitable for practical use.

[0302] [Judgment Criteria]

[0303] ◎(Good)... The duration of water penetration is less than 3 seconds until the fourth water penetration.

[0304] ○(Okay)... The duration of water penetration is less than 3 seconds until the second or third time.

[0305] △(Not allowed)... Only the first water permeation indicator is less than 3 seconds.

[0306] (Evaluation of the long-term stability of permeability)

[0307] Nonwoven fabric (10cm × 10cm) was stored in an environmental test chamber at 60℃ and 80%RH for 14 days. After 14 days, the nonwoven fabric was removed from the environmental test chamber, and the instantaneous permeability and durable permeability of the nonwoven fabric as described above were evaluated. The smaller the difference between the instantaneous permeability and durable permeability before and after immersion in the environmental test chamber, the smaller the decrease in permeability over time. The smaller the decrease over time, the better. The evaluation of instantaneous permeability and durable permeability after time was carried out according to the following criteria. It should be noted that ◎ represents the best evaluation, and if it is ○ or above, it can be used for practical purposes.

[0308] (Instantaneous water permeability after a period of time)

[0309] [Judgment Criteria]

[0310] ◎(Good)... 14 to 20

[0311] ○(Optional)... 9 to 13

[0312] △(Defective)... 1 to 8

[0313] × (not allowed)... 0

[0314] (Permeability after a period of time)

[0315] [Judgment Criteria]

[0316] ◎(Good)... The duration of water penetration is less than 3 seconds until the third water penetration.

[0317] ○(Okay)... The duration is less than 3 seconds until the second water infiltration.

[0318] △(Poor)... Only the first water permeation indicator lasted less than 3 seconds.

[0319] × (Not allowed)... The first water infiltration should not exceed 3 seconds.

[0320] (blood permeability)

[0321] As an example of absorbent articles, an evaluation sanitary napkin was used, in which the surface sheet of a sanitary napkin (manufactured by Unicharm Inc.: Sofy Nude) was removed and replaced with a nonwoven fabric sample, which was then fixed around the sample.

[0322] An acrylic plate with a 1cm inner diameter through-hole was stacked, and 5.0g of defibrinated horse blood (adjusted to 10mPa / s), equivalent to menstrual blood, was poured in through the through-hole. After a total of 5.0g of defibrinated horse blood had been poured in, the acrylic plate was removed after 60 seconds. The L value at the location where the defibrinated horse blood was introduced was measured using a Konica Minolta CR-400 colorimeter. The higher the L value (lightness), the closer the color is to white, and the less red is visible on the surface sheet (non-woven fabric sample). That is, it indicates the blood permeability between fibers. It should be noted that ◎ represents the best evaluation, and values ​​of ○ or higher are suitable for practical use.

[0323] [Judgment Criteria]

[0324] ◎(Good)... indicates an L value of 60 or higher.

[0325] ○ (can)... indicates that the L value is 50 or higher and less than 60.

[0326] △ (not allowed)... indicates that the value of L is less than 50.

[0327] [Table 3]

[0328]

[0329] [Table 4]

[0330]

[0331] [Table 5]

[0332]

[0333] [Table 6]

[0334]

[0335] [Table 7]

[0336]

[0337] [Table 8]

[0338]

[0339] [Table 9]

[0340]

[0341] As shown in Tables 4-8, the permeability-improving agents in Examples 1-38 are permeability-improving agents containing at least one nonionic surfactant (N) and an anionic surfactant (S) containing sulfur (S) and an anionic surfactant (P) containing phosphorus (P). The iodine value and acid value of the non-volatile components of the above-mentioned permeability-improving agents are within a specific range, thus solving the problem of this application. In addition, it was confirmed that the effects of this application are also achieved when the nonwoven fabrics prepared in the examples are applied to diapers and menstrual products with surface sheets.

[0342] On the other hand, as can be seen from Table 9, when the acid value is not within a specific range (Comparative Example 1, Comparative Example 2, Comparative Example 6 and Comparative Example 7) or the iodine value is not within a specific range (Comparative Example 3, Comparative Example 4 and Comparative Example 5), the problem of this application, namely the permeability after time or the stability of the additive, cannot be solved.

[0343] Industrial practicality

[0344] Fibers and nonwoven fabrics treated with the permeability-improving agent of the present invention are used in absorbent articles such as sanitary napkins and other feminine hygiene products. Furthermore, they can also be used in food, medical, and industrial applications where absorbent sheets are required.

Claims

1. A permeability-enhancing agent, characterized in that, It comprises a nonionic surfactant (N) and at least one selected from anionic surfactants (S) containing sulfur and anionic surfactants (P) containing phosphorus. The non-volatile component of the permeability-enhancing agent has an iodine value of 0.5~100 gI2 / 100g and an acid value of 0.5~100 mgKOH / g.

2. The permeability-improving agent according to claim 1, wherein, The water-permeability imparting agent includes the surfactant (P). The active agent (P) must contain compound (A) of general formula (1) and compound (B) of general formula (2), and optionally contain compound (C) of general formula (3). [Chemistry 1] In the formula, R 1 It is a hydrocarbon group with 6 to 22 carbon atoms, R 1 It can be straight-chain or branched; AO is an alkylene group with 2 to 4 carbon atoms; m is an integer from 0 to 15; M 1 M is a hydrogen atom, an alkali metal, or an organic amine salt. 2 It consists of hydrogen atoms, alkali metals, or organic amine salts; [Chemistry 2] In the formula, R 2 and R 3 It is a hydrocarbon group with 6 to 22 carbon atoms, R 2 and R 3 It can be straight-chain or branched; AO is an oxoalkylene group with 2 to 4 carbon atoms; m is an integer from 0 to 15; M 1 It consists of hydrogen atoms, alkali metals, or organic amine salts, and contains two (AO) atoms within the molecule. m In this case, the two can be the same as each other or different; [Chemistry 3] In the formula, R 4 It is a hydrocarbon group with 6 to 22 carbon atoms, R 4 It can be straight-chain or branched; AO is an alkylene group with 2 to 4 carbon atoms; m is an integer from 0 to 15; M 1 M is a hydrogen atom, an alkali metal, or an organic amine salt. 2 Q is a hydrogen atom, an alkali metal, or an organic amine salt, and M is a hydrogen atom. 2 Or (OA) m R 5 R 5 It is a hydrocarbon group with 6 to 22 carbon atoms, R 5 It can be a straight chain or a branched chain, Y is 1 or 2, and there are more than 2 M molecules within the molecule. 2 Or (AO) m In this case, they can be the same or different.

3. The permeability-improving agent according to claim 1 or 2, wherein, The water-permeability imparting agent comprises the surfactant (S). The surfactant (S) comprises at least one selected from dialkyl sulfosuccinic acid, dialkyl sulfosuccinate, polyol fatty acid sulfate, and polyol fatty acid sulfate salt.

4. The permeability-improving agent according to any one of claims 1 to 3, wherein, Of the non-volatile components, the total amount of phosphorus is 0-15% by weight and / or the total amount of sulfur is 0-10% by weight.

5. The permeability-improving agent according to any one of claims 1 to 4, wherein, The permeability-enhancing agent is used in nonwoven fabrics for menstrual blood.

6. The permeability-improving agent according to any one of claims 1 to 5, wherein, The water-permeability imparting agent comprises the surfactant (P). The surfactant (P) must contain: Surfactant (P-1), having an alkyl group having 12 to 18 carbon atoms and / or an alkenyl group having 12 to 18 carbon atoms; and Surfactant (P-2) having an alkyl group having 10 or fewer carbon atoms and / or an alkenyl group having 10 or fewer carbon atoms.

7. A fiber, characterized in that, It is made by imparting the permeability-improving agent according to any one of claims 1 to 6 to the raw material fiber.

8. A nonwoven fabric, characterized in that, It is made by imparting the permeability imparting agent according to any one of claims 1 to 6.

9. An absorbent article, characterized in that, It includes the nonwoven fabric as described in claim 8.

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