JP2022111999A - Permeability imparting agent for fibers, fibers, non-woven fabrics and water absorptive articles - Google Patents

Abstract

To provide a permeability imparting agent which can achieve both repeated water permeability and antistatic properties.SOLUTION: A permeability imparting agent contains a phosphoric acid ester metal salt (A) of aliphatic alcohol having 8 to 18 carbon atoms, and an alkylene oxide adduct (B) of a polyvalent active hydrogen compound represented by the following general formula (1), wherein an addition mole number ratio (n/m) of A1O to CH2CH2O in the following general formula (1) is 0 to 0.5, a content of the phosphoric acid ester metal salt (A) of the aliphatic alcohol having 8 to 18 carbon atoms is 8-39 wt.%, and a content of the alkylene oxide adduct (B) of the polyvalent active hydrogen compound represented by the following general formula (1) is 20-80 wt.%, based on a weight of a nonvolatile component in the permeability imparting agent. General formula (1): R-[(A1O)m-(CH2CH2O)n-H]p.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a water permeability imparting agent for fibers, fibers, nonwoven fabrics and absorbent articles.

In general, absorbent articles such as paper diapers and sanitary products have an absorbent body made of cotton pulp, superabsorbent polymer, etc., placed between a liquid-permeable topsheet and a liquid-impermeable backsheet. It is configured.
As the top sheet of the absorbent article, for example, a nonwoven fabric manufactured using fibers such as short fibers is sometimes used. The nonwoven fabric is generally manufactured by passing fibers such as short fibers through a fiber opening machine or a carding machine, and the fibers may be made of polyester or polypropylene. many. Therefore, when the fibers are passed through a fiber opening machine or a carding machine without being treated (a state in which a treatment agent or the like is not applied), static electricity is generated and problems such as winding around the carding machine may occur.
In consideration of such problems, conventionally, fibers made of materials such as polyester and polypropylene are coated with a fiber treatment agent. As such a fiber treatment agent, for example, a treatment agent containing an alkyl phosphate is known (see Patent Document 1).

Japanese Patent No. 5796922

By using a treatment agent containing an alkyl phosphate salt as a fiber treatment agent, the generation of static electricity can be suppressed in the step of passing the fibers through a fiber opening machine or a carding machine, and antistatic properties can be enhanced. However, since the alkyl phosphate ester salt has a high solubility in water, when a nonwoven fabric manufactured using fibers to which a treatment agent containing an alkyl phosphate ester salt is adhered is used as the top sheet of an absorbent article, the alkyl phosphate There is a problem that the acid ester salt tends to fall off, and the repeated water permeability (the water permeability when body fluid is repeatedly absorbed) is insufficient.

In order to improve repeated water permeability, a nonionic interface with high low HLB and high durability hydrophilicity (performance indicating how long the hydrophilicity required for synthetic fibers used for a given purpose can be maintained) It is contemplated to use a treatment containing an active agent. However, when a treatment agent containing a low HLB nonionic surfactant is used, leakage resistance increases, antistatic properties become insufficient, and adhesiveness increases. In other words, it is difficult to achieve both repeated water permeability and antistatic properties with conventional treatment agents, and improvements have been demanded.
An object of the present invention is to provide a water-permeability-imparting agent for fibers that can achieve both repeated water-permeability and antistatic properties.

The present inventors arrived at the present invention as a result of intensive studies in order to solve the above problems.
That is, the present invention contains a phosphate metal salt (A) of an aliphatic alcohol having 8 to 18 carbon atoms and an alkylene oxide adduct (B) of a polyvalent active hydrogen compound represented by the following general formula (1). A water permeability imparting agent, wherein in the following general formula (1), the ratio (n/m) of the number of added moles of A ¹ O and CH ₂ CH ₂ O is 0 to 0.5, and the water permeability imparting agent Based on the weight of the non-volatile components in the polyvalent active compound represented by the general formula (1), the content of the phosphate metal salt (A) of an aliphatic alcohol having 8 to 18 carbon atoms is 8 to 39% by weight. A water permeability imparting agent for fibers in which the content of the alkylene oxide adduct (B) of a hydrogen compound is 20 to 80% by weight; A fiber in which the weight ratio of the nonvolatile component of the imparting agent is 0.15 to 2% by weight based on the weight of the hydrophobic fiber; a nonwoven fabric using the fiber; and a water absorbent article using the nonwoven fabric.
R-[(A ¹ O) _m -(CH ₂ CH ₂ O) _n -H] _p (1)
[In general formula (1), R represents a residue obtained by removing all active hydrogens from a polyvalent active hydrogen compound. A ¹ O represents an alkyleneoxy group having 3 or 4 carbon atoms. m represents the number of moles of A ¹ O added and is a number from 4 to 50. n represents the number of added moles of CH ₂ CH ₂ O and is a number from 0 to 25; p represents a valence and is an integer of 3-6. ]

A nonwoven fabric using fibers to which the water permeability imparting agent for fibers of the present invention is attached can achieve both repeated water permeability and antistatic properties.

[Water permeability imparting agent for fibers]
The water permeability imparting agent for fibers of the present invention (hereinafter also referred to as "water permeability imparting agent") is represented by the following general formula (1) and the phosphate ester metal salt (A) of an aliphatic alcohol having 8 to 18 carbon atoms. contains an alkylene oxide adduct (B) of a polyvalent active hydrogen compound.
R-[(A ¹ O) _m -(CH ₂ CH ₂ O) _n -H] _p (1)
[In general formula (1), R represents a residue obtained by removing all active hydrogens from a polyvalent active hydrogen compound. A ¹ O represents an alkyleneoxy group having 3 or 4 carbon atoms. m represents the number of moles of A ¹ O added and is a number from 4 to 50. n represents the number of added moles of CH ₂ CH ₂ O and is a number from 0 to 25; p represents a valence and is an integer of 3-6. ]

The phosphate ester metal salt of an aliphatic alcohol having 8 to 18 carbon atoms (A) is a phosphate monoester metal salt of an aliphatic alcohol having 8 to 18 carbon atoms and a phosphate diester of an aliphatic alcohol having 8 to 18 carbon atoms. It is at least one compound selected from the group consisting of metal salts. The metal phosphate (A) of an aliphatic alcohol having 8 to 18 carbon atoms is preferably a metal phosphate monoester of an alcohol having an alkyl group of 8 to 18 carbon atoms, more preferably 10 carbon atoms. It is a phosphate monoester metal salt of an alcohol with ∼16 alkyl groups. The alkyl group may be linear or branched. Hereinafter, the "metal phosphate (A) of an aliphatic alcohol having 8 to 18 carbon atoms" may be referred to as "metal phosphate (A)" or "(A) component".

Specific examples of the phosphate metal salt (A) include octyl alcohol phosphate monoester potassium salt, octyl alcohol phosphate monoester potassium salt, 2-ethylhexyl alcohol phosphate monoester potassium salt, and decyl alcohol phosphate monoester potassium salt. acid monoester sodium salt, isodecyl alcohol phosphate monoester potassium salt, dodecyl alcohol phosphate monoester potassium salt, tridecyl alcohol phosphate monoester sodium salt, isotridecyl alcohol phosphate monoester sodium salt, Tetradecyl alcohol (myristyl alcohol) phosphate monoester potassium salt, hexadecyl alcohol phosphate monoester sodium salt, octadecyl alcohol phosphate monoester potassium salt, isooctadecyl alcohol phosphate monoester potassium salt, oleyl alcohol Phosphate monoester potassium salt, coconut oil alcohol monoester phosphate potassium salt, and the like. These phosphate ester metal salts may be used alone or in combination of two or more. As the phosphate metal salt (A), a phosphate diester metal salt may be used.
From the viewpoint of excellent antistatic properties, the phosphate metal salt (A) includes 2-ethylhexyl alcohol phosphate monoester potassium salt, oleyl alcohol phosphate monoester potassium salt, and myristyl alcohol phosphate monoester potassium salt. It is preferably at least one or more selected from salts, potassium phosphate monoester of isostearyl alcohol, and potassium phosphate monoester of coconut oil alcohol.

In the water permeability imparting agent of the present invention, the content of the phosphate metal salt (A) is 8 to 39% by weight based on the weight of the nonvolatile components in the water permeability imparting agent. When the content of the phosphate ester metal salt (A) is 8 to 39% by weight, both repeated water permeability and antistatic properties can be achieved. If the content of the phosphate ester metal salt (A) is less than 8% by weight, the antistatic property will be insufficient, and if the content exceeds 39% by weight, the repeated water permeability will be insufficient.
The content of the phosphate ester metal salt (A) is preferably 10 to 36% by weight, more preferably 15 to 34% by weight, from the viewpoint of achieving both antistatic properties and repeated water permeability. The non-volatile component in the present invention is a residue after heating and drying 1 g of a sample in an uncovered glass petri dish at 130° C. for 45 minutes in a circulating air dryer.

The water permeability imparting agent of the present invention contains an alkylene oxide adduct (B) of a polyvalent active hydrogen compound represented by general formula (1). Hereinafter, "the alkylene oxide adduct (B) of the polyvalent active hydrogen compound represented by the general formula (1)" is referred to as "the alkylene oxide adduct (B) of the polyvalent active hydrogen compound" or "component (B)". I may call
R-[(A ¹ O) _m -(CH ₂ CH ₂ O) _n -H] _p (1)

In general formula (1), R represents a residue obtained by removing all active hydrogens from the polyvalent active hydrogen compound. A ¹ O represents an alkyleneoxy group having 3 or 4 carbon atoms. m represents the number of moles of A ¹ O added and is a number from 4 to 50. n represents the number of added moles of CH ₂ CH ₂ O and is a number from 0 to 25; p represents a valence and is an integer of 3-6.

Examples of polyvalent active hydrogen compounds include polyhydric alcohols having a valence of 3 to 6, sugars, polyvalent carboxylic acids and polyvalent amines.
Among polyhydric alcohols having a valence of 3 to 6, trihydric polyhydric alcohols include glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, and 1,2,3-pentanetriol. , 1,2,4-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2 , 3,4-pentanetriol, 3-methylpentane-1,3,5-triol, 2,4-dimethyl-2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3 , 4,5-heptanetriol, 1,3,5-cyclohexanetriol, pentamethylglycerin, trimethylolethane, trimethylolpropane, castor oil and hydrogenated castor oil.
Tetrahydric polyhydric alcohols include 1,2,3,4-butanetetraol, pentaerythritol, diglycerin, sorbitan, ribose, arabinose, xylose and lyxose.
Pentahydric polyhydric alcohols include triglycerin, arabitol, xylitol, glucose, fructose, galactose, mannose, allose, gulose, idose, talose and quercitol.
Hexavalent polyhydric alcohols include dipentaerythritol, sorbitol, galactitol, mannitol, allitol, iditol, talitol and inositol.

Examples of polyhydric alcohols having a valence of 3 to 6 include animal and vegetable oils and fats other than castor oil and hydrogenated castor oil.

As the polyhydric alcohol, glycerin, trimethylolpropane, castor oil, hydrogenated castor oil, pentaerythritol, sorbitan and sorbitol are preferable, and glycerin, trimethylolpropane, sorbitol and pentaerythritol are more preferable, from the viewpoint of excellent water permeability.

Monosaccharides etc. are mentioned as saccharides.

Among polyvalent carboxylic acids having a valence of 3 to 6, trivalent carboxylic acids include 1,2,3-propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, and 1,3,5-cyclohexanetricarboxylic acid. acid, trimeric acid (C18 unsaturated carboxylic acid trimer), trimellitic acid and the like.

Examples of the tetravalent carboxylic acid include ethylenetetracarboxylic acid, cyclopentanetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid and butane-1,2,3,4-tetracarboxylic acid. .

Pentavalent carboxylic acids include 1,2,3,4,5-cyclohexanepentacarboxylic acid, benzenepentacarboxylic acid and 1,2,4,5,8-naphthalenepentacarboxylic acid.
Examples of the hexavalent carboxylic acid include cyclohexanehexacarboxylic acid, benzenehexacarboxylic acid and 1,2,3,4,5,7-naphthalenehexacarboxylic acid.

Among polyvalent amines having a valence of 3 to 6, trivalent amines include 1,2,3-propanetriamine, hexamethylenetriamine, 1,3,5-benzenetriamine and melamine.
Examples of tetravalent amines include butane-1,1,4,4-tetramine, triethylenetetramine and pyrimidine-2,4,5,6-tetramine.

The polyvalent active hydrogen compound may contain at least two active hydrogen groups selected from the group consisting of carboxyl groups, hydroxyl groups and amino groups. Examples of compounds containing two or more active hydrogen groups include citric acid, glyceric acid, and amino acids (aspartic acid, glutamic acid, lysine, arginine, serine, threonine, tyrosine, aspartic acid, glutamic acid, etc.).

The polyvalent active hydrogen compound may be a partial ester formed by a polyhydric alcohol having a valence of 3 to 6 and a fatty acid.
Examples of polyhydric alcohols having a valence of 3 to 6 include the compounds described above.
Examples of fatty acids include aliphatic carboxylic acids having 8 to 24 carbon atoms [aliphatic saturated carboxylic acids (caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, lauric acid, tridecanoic acid, isotridecanic acid, myristic acid, palmitic acid, , stearic acid and isostearic acid, etc.), aliphatic unsaturated carboxylic acids (oleic acid, linoleic acid, linolenic acid, ricinoleic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, etc.)] and the like.

When R in the general formula (1) is a residue obtained by removing all active hydrogen from an alkylene oxide adduct of a partial ester of a polyhydric alcohol with a valence of 3 to 6 and a fatty acid, the polyvalent active hydrogen compound The degree of esterification of the alkylene oxide adduct (B) is preferably 50% or less.
The degree of esterification can be calculated from the following formula (1) based on the peak areas (integrated areas) of the mono-, di-, and triesters determined by an automatic analysis method from the measurement results of gel permeation chromatography (GPC).

The conditions of GPC are as follows.
Apparatus: HLC-8220GPC [manufactured by Tosoh Corporation]
GPC column guard column: TSKguardcolumn SuperH-L (4.6 mm ID × 15 cm)
Separation column: TSKgel SuperH2000 (6 mm ID x 15 cm) + TSKgel Super H3000 (6 mm ID x 15 cm) + TSKgel Super H4000 (6 mm ID x 15 cm)
Detector: RI detector Flow medium: Tetrahydrofuran Flow rate: 0.6 ml/min
Column temperature: 40°C
Sample concentration: 0.25% by weight
Sample injection volume: 10 μl

As the polyvalent active hydrogen compound of the alkylene oxide adduct (B) of the polyvalent active hydrogen compound, from the viewpoint of excellent water permeability, a polyhydric alcohol having a valence of 3 to 6, a carboxyl group, a hydroxyl group and an amino group. Preferred are compounds containing at least two active hydrogen groups selected from the group consisting of, animal and vegetable oils and fats, etc., and at least one selected from the group consisting of glycerin, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, glutamic acid, castor oil and hydrogenated castor oil. A compound selected from the group consisting of glycerin, trimethylolpropane, sorbitol and pentaerythritol is particularly preferred.

A ¹ O in the general formula (1) represents an alkyleneoxy group having 3 to 4 carbon atoms, specifically a propyleneoxy group (hereinafter abbreviated as PO) or a butyleneoxy group (hereinafter abbreviated as BO). be. PO may be a linear propyleneoxy group or a branched propyleneoxy group (1-methylethyleneoxy group, 2-methylethyleneoxy group). BO includes linear butyleneoxy groups and branched butyleneoxy groups (1-methylpropyleneoxy group, 2-methylpropyleneoxy group, 3-methylpropyleneoxy group, 1,2-dimethylethyleneoxy group, 1,1'- dimethylethyleneoxy group, 2,2'-dimethylethyleneoxy group, etc. ^{A 1} O is preferably PO. good too.

m in the general formula (1) represents the number of moles of A ¹ O added per group [(A ¹ O) _m -(CH ₂ CH ₂ O) _n -H] bonded to R. m is a number of 4 to 50, preferably 8 to 40, more preferably 12 to 30, from the viewpoint of handleability. m is not necessarily an integer and may be a decimal number.

When two or more alkyleneoxy groups are contained in A ¹ O, PO and BO in A ¹ O may be added blockwise or randomly. “Block-like” means an embodiment in which two or more alkyleneoxy groups of one type are consecutive in the group [(A ¹ O) _m —(CH ₂ CH ₂ O) _n —H] bonded to R. Say.

CH ₂ CH ₂ O in general formula (1) represents an ethyleneoxy group (EO).
n in the general formula (1) represents the number of added moles of CH ₂ CH ₂ O per group [(A ¹ O) _m -(CH ₂ CH ₂ O) _n -H] bonded to R. , is a number from 0 to 25. From the viewpoint of excellent water permeability, n is preferably a number from 0 to 20, more preferably from 0 to 10, and particularly preferably from 0 to 8. n is not necessarily an integer and may be a decimal number.

A ¹ O and CH ₂ CH ₂ O in general formula (1) are preferably added in blocks.

In addition, in the alkylene oxide adduct (B) of the polyvalent active hydrogen compound represented by the general formula (1), either A ¹ O or CH ₂ CH ₂ O may be located at the terminal, From the viewpoint of hydrophilicity and durability of the water permeability imparting agent, it is preferable that CH ₂ CH ₂ O is located at the end.

In general formula (1), the ratio (n/m) of the number of added moles of A ¹ O and CH ₂ CH ₂ O is 0 to 0.5. The molar addition ratio is preferably 0.02 to 0.3, more preferably 0.04 to 0.2.
In addition, the ratio of the number of added moles of A ¹ O and CH ₂ CH ₂ O is calculated from theoretical calculation.

The number of added moles of A ¹ O and CH ₂ CH ₂ O in the alkylene oxide adduct (B) of the polyvalent active hydrogen compound represented by the general formula (1) is obtained by gel permeation chromatography (GPC) of (B). It can be obtained by analyzing according to the method.
In this case, the GPC measurement conditions are as follows.
Apparatus: HLC-8220GPC [manufactured by Tosoh Corporation]
GPC column guard column: TSKguardcolumn SuperH-L (4.6 mm ID × 15 cm)
Separation column: TSKgel SuperH2000 (6 mm ID x 15 cm) + TSKgel Super H3000 (6 mm ID x 15 cm) + TSKgel Super H4000 (6 mm ID x 15 cm)
Detector: RI detector Flow medium: Tetrahydrofuran Flow rate: 0.6 ml/min
Column temperature: 40°C
Sample concentration: 0.25% by weight
Sample injection volume: 10 μl

Further, the added mole number m of A ¹ O and the added mole number n of CH ₂ CH ₂ O in the alkylene oxide adduct (B) of the polyvalent active hydrogen compound represented by the general formula (1) are It can be calculated from the molar ratio of raw materials, the number of active hydrogens in the polyvalent active hydrogen compound, and the like.
For example, when glycerin (the number of active hydrogens is 3), propylene oxide (PO) and ethylene oxide (EO) are used as raw materials at a molar ratio (glycerin:PO:EO=1:90:20), glycerin ( A compound in which three groups represented by [(PO) _m -(EO) _n -H] are bonded to a residue obtained by removing all active hydrogens from a trivalent active hydrogen compound (p = 3 ), the total number of added moles of PO is 90 and the total number of added moles of EO is 20 in one molecule of the compound.
In this compound, the PO addition mole number m per group represented by [(PO) _m - (EO) _n -H] can be calculated by (total PO addition mole number/p). The number of moles n can be calculated by (total number of moles of EO added/p).

In the water permeability imparting agent of the present invention, the alkylene oxide adduct (B) of the polyvalent active hydrogen compound is a PO90 mol EO 20 mol block adduct of glycerin [in the general formula (1), from the viewpoint of excellent water permeability. , m is 30, n is 6.67, p is 3], PO 85.3 mol EO 21.8 mol block adduct of glycerol [in general formula (1), m is 28.4, n is 7.5. 3, a compound in which p is 3], PO67 mol EO 11 mol block adduct of trimethylolpropane [compound in general formula (1) in which m is 22.3, n is 3.67, and p is 3], pentaerythritol PO 104 mol adduct [compound in general formula (1) in which m is 26, n is 0 and p is 4], PO 104 mol EO 19.2 mol block adduct of pentaerythritol [in general formula (1), m is 26, n is 4.8, and p is 4], BO80 mol EO 12 mol block adduct of pentaerythritol (compound where m is 20, n is 3, p is 4), PO 60 mol adduct of trimethylolpropane (compound where m is 20, n is 0, and p is 3), PO9 mol BO0.84 mol PO78 mol block adduct of sorbitol (compound where m is 14.64, n is 0, p is 6) and the like are preferred.

The content of the alkylene oxide adduct (B) of the polyvalent active hydrogen compound is 20 to 80 wt. %. When the content of the alkylene oxide adduct (B) of the polyvalent active hydrogen compound is less than 20% by weight, repeated water permeability becomes insufficient, and when the content exceeds 80% by weight, the antistatic property is insufficient. can be.
The content of the alkylene oxide adduct (B) of the polyvalent active hydrogen compound is preferably 30 to 70% by weight, more preferably 30 to 65% by weight.

The alkylene oxide adduct (B) of the polyvalent active hydrogen compound can be produced by a known method or the like, for example, by adding an alkylene oxide to the polyhydric alcohol using potassium carbonate or sodium carbonate as a basic catalyst. can be manufactured.

The water permeability imparting agent of the present invention may contain components other than components (A) and (B). Examples of such components include surfactants (C) other than components (A) and (B), polyhydric alcohols having 2 to 10 carbon atoms (D), and additives (E). Hereinafter, "surfactant (C)" is also referred to as "component (C)".
As the component (C), an anionic surfactant (C1) excluding a metal phosphate ester (A) of an aliphatic alcohol having 8 to 18 carbon atoms, and an alkylene oxide adduct of a polyvalent active hydrogen compound (B). nonionic surfactants (C2) and betaine type amphoteric surfactants (C3). These may use 1 type and may use 2 or more types together.

Examples of the anionic surfactant (C1) include dialkylsulfosuccinate salts and alkylsulfonates. These may be used individually by 1 type, and may use 2 or more types.
As dialkylsulfosuccinate salts, those having an alkyl group of 6 to 18 carbon atoms are preferred. The alkyl group may be linear or branched, and two alkyl groups may be the same or different. As the alkylsulfonate, those having an alkyl group of 6 to 20 carbon atoms are preferred. The alkyl group may be linear or branched.

As the anionic surfactant (C1), a dialkylsulfosuccinate salt is preferable from the viewpoint of excellent initial water permeability. Specific examples of dialkylsulfosuccinate salts include di-2-ethylhexylsulfosuccinate sodium salt, didodecylsulfosuccinate sodium salt, and 1-octyl 2-hexadecylsulfosuccinate potassium salt. Among them, di-2-ethylhexyl sulfosuccinate sodium salt is preferred.

Nonionic surfactants (C2) include, for example, polyoxyalkylene alkyl ethers (C21), esters of polyhydric alcohols, polyoxyalkylene adducts and fatty acids (C22), polyoxyalkylene glycol diesters (C23), polyhydric Nonionic surfactants (C25) having an ester of alcohol and fatty acid (C24), an amide group and/or an amino group, and the like. Nonionic surfactant (C2) may be used alone or in combination of two or more

Examples of polyoxyalkylene alkyl ethers (C21) include monohydric alcohols to which alkylene oxides are added. The number of carbon atoms in the alkyl group of the monohydric alcohol is preferably 1-18, more preferably 6-16.
The number of carbon atoms in the alkyl group may be distributed, and alkylene oxide adducts of two or more monohydric alcohols may be mixed. Alkylene oxides include EO, PO, and those obtained by block polymerization or random polymerization thereof. Among these, EO is preferred. The number of moles of alkylene oxide to be added is preferably 1-20, more preferably 2-15.

The ester (C22) of a polyhydric alcohol, a polyoxyalkylene adduct, and a fatty acid is a compound that does not correspond to the alkylene oxide adduct (B) of the polyvalent active hydrogen compound, for example, a polyhydric alcohol and a fatty acid. alkylene oxide adduct (C22-1) of an ester of and ester (C22-2) of an alkylene oxide adduct of a polyhydric alcohol and a fatty acid.

Specific examples of the polyhydric alcohol constituting the alkylene oxide adduct (C22-1) of an ester of polyhydric alcohol and fatty acid include aliphatic polyhydric (tri- to hexahydric) alcohols having 3 to 6 carbon atoms (glycerin, trimethylolpropane, pentaerythritol, sorbitol and sorbitan, etc.).
Specific examples of the fatty acid constituting the alkylene oxide adduct (C22-1) of an ester of a polyhydric alcohol and a fatty acid include aliphatic carboxylic acids having 8 to 24 carbon atoms [aliphatic saturated carboxylic acids (caprylic acid, 2- ethylhexanoic acid, pelargonic acid, capric acid, lauric acid, tridecanoic acid, isotridecanic acid, myristic acid, palmitic acid, stearic acid and isostearic acid), and aliphatic unsaturated carboxylic acids (oleic acid, linoleic acid, linolenic acid, ricinoleic acid, beef tallow fatty acid, hydrogenated beef tallow fatty acid, castor oil fatty acid, hydrogenated castor oil fatty acid, etc.)].
Specific examples of the alkylene oxide (AO) constituting the alkylene oxide adduct (C22-1) of an ester of a polyhydric alcohol and a fatty acid include AO having 2 to 12 carbon atoms (EO, PO, BO). AO may be used singly or in combination of two or more. When two or more types of AO are used together, either block addition or random addition may be used.
Specific examples of the alkylene oxide adduct (C22-1) of an ester of a polyhydric alcohol and a fatty acid include an EO 15 mol adduct of glycerin beef tallow fatty acid ester, an EO 20 mol adduct of trimethylolpropane trioleate, and pentaerythritol. EO 30 mol adduct of tetraoleic acid ester, EO 20 mol adduct of sorbitan monooleate, EO 20 mol adduct of sorbitan tetraoleate, castor oil EO 10 mol adduct, castor oil EO 25 mol adduct, castor oil EO 43 mol adducts, and 43 EO mol adducts of hydrogenated castor oil and 25 EO mol adducts of esters of glycerin with castor oil fatty acids. Of these, the EO 10 mol adduct of castor oil and the EO 25 mol adduct of castor oil are preferred.

The "polyhydric alcohol", "alkylene oxide" and "fatty acid" constituting the ester (C22-2) of the alkylene oxide adduct of polyhydric alcohol and fatty acid are the same as those described in (C22-1) above. are listed.
Specific examples of esters (C22-2) of alkylene oxide adducts of polyhydric alcohols and fatty acids include stearic acid esters of EO adducts of castor oil, oleic acid esters of EO adducts of hardened castor oil, and EO adducts of castor oil. Examples include beef tallow fatty acid esters, polyesters of EO adducts of hardened castor oil, maleic acid and stearic acid, and polyesters of EO adducts of hardened castor oil, sebacic acid and stearic acid.

Examples of polyoxyalkylene glycol diesters (C23) include diesters (C23-1) of polyoxyalkylene glycol and fatty acids.
Specific examples of the alkylene oxides forming the diester (C23-1) of polyoxyalkylene glycol and fatty acid include AO (EO, PO and BO) having 2 to 12 carbon atoms. AO may be used singly or in combination of two or more. When two or more types of AO are used together, either block addition or random addition may be used.
Specific examples of the fatty acid constituting the diester (C23-1) of polyoxyalkylene glycol and fatty acid include aliphatic carboxylic acids having 8 to 24 carbon atoms [aliphatic saturated carboxylic acids (caprylic acid, 2-ethylhexanoic acid, pelargon acid, capric acid, lauric acid, tridecanoic acid, isotridecanic acid, myristic acid, palmitic acid, stearic acid and isostearic acid, etc.), aliphatic unsaturated carboxylic acids (oleic acid, linoleic acid and linolenic acid, etc.), animal and plant oils [( coconut oil, palm oil, palm kernel oil, olive oil, rice bran oil, rice germ oil, rapeseed oil, sunflower oil, castor oil, hydrogenated castor oil, beef tallow, hydrogenated beef tallow and lard, etc.)] fatty acids.
As the diester (C23-1) of polyoxyalkylene glycol and fatty acid, polyoxyethylene glycol diolate is preferable, and diolate of polyoxyethylene glycol 9 mol adduct is more preferable.

Specific examples of the polyhydric alcohol constituting the ester (C24) of polyhydric alcohol and fatty acid include aliphatic polyhydric (tri- to hexahydric) alcohols having 3 to 6 carbon atoms (glycerin, trimethylolpropane, pentaerythritol, sorbitol and sorbitan, etc.).
Specific examples of fatty acids constituting esters (C24) of polyhydric alcohols and fatty acids include aliphatic carboxylic acids having 8 to 24 carbon atoms [aliphatic saturated carboxylic acids (caprylic acid, 2-ethylhexanoic acid, pelargonic acid, caprin acid, lauric acid, tridecanoic acid, isotridecanic acid, myristic acid, palmitic acid, stearic acid and isostearic acid), aliphatic unsaturated carboxylic acids (oleic acid, linoleic acid, linolenic acid, ricinoleic acid, coconut oil fatty acid, palm oil fatty acids, palm kernel oil fatty acids, olive oil fatty acids, rice bran oil fatty acids, rice germ oil fatty acids, rapeseed oil fatty acids, sunflower oil fatty acids, beef tallow fatty acids, hydrogenated beef tallow fatty acids, castor oil fatty acids and hydrogenated castor oil fatty acids)].
Specific examples of esters of polyhydric alcohols and fatty acids (C24) include coconut oil fatty acid sorbitan esters and oleic acid sorbitan esters.

The nonionic surfactant (C25) having an amide group and/or amino group includes, for example, an amide (C25-1) of a fatty acid and a compound having 2 to 10 carbon atoms having a hydroxyl group and an amino group, and the number of carbon atoms of the amide. Examples thereof include 2 to 4 alkylene oxide adducts (C25-2), and compounds (C25-3) which are C 2 to 4 alkylene oxide adducts of aliphatic amines and have an amino group.

Fatty acids with 6 to 24 carbon atoms are preferred as the fatty acid forming the amide (C25-1) of a fatty acid and a compound with 2 to 10 carbon atoms having a hydroxyl group and an amino group. Examples of fatty acids having 6 to 24 carbon atoms include hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, eicosanoic acid, docosanoic acid and tetraconic acid. mentioned. In addition, as fatty acids having 6 to 24 carbon atoms, fatty acids derived from natural oils [fatty acids derived from vegetable oils (coconut oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, olive oil fatty acids, rice bran oil fatty acids, rice germ oil fatty acids, rapeseed oil fatty acids, castor oil fatty acids, hydrogenated castor oil fatty acids, etc.) and fatty acids derived from animal fats and oils (beef tallow fatty acids, hydrogenated beef tallow fatty acids, lard fatty acids, etc.)] may also be used.
Fatty acids derived from natural fats and oils are generally saturated fatty acids having 8, 10, 12, 14, 16, 18, 20, 22 and 24 carbon atoms and/or unsaturated fatty acids having 16, 18, 20 and 22 carbon atoms. A mixture.
Among fatty acids having 6 to 24 carbon atoms, fatty acids derived from vegetable oils are preferable from the viewpoint of skin safety, and coconut oil fatty acids (octanoic acid, decanoic acid, lauric acid, myristic acid, mixtures of palmitic acid, stearic acid and oleic acid, etc.).

Examples of compounds having 2 to 10 carbon atoms having a hydroxyl group and an amino group that constitute an amide (C25-1) of a fatty acid and a compound having 2 to 10 carbon atoms having a hydroxyl group and an amino group include monoethanolamine and diethanolamine. be done.

The amide (C25-1) of a fatty acid and a compound having 2 to 10 carbon atoms having a hydroxyl group and an amino group is the above fatty acid having 6 to 24 carbon atoms [or the above fatty acid having 6 to 24 carbon atoms and 1 to 4 with an alcohol (methanol etc.)] and the above compound having 2 to 10 carbon atoms having a hydroxyl group and an amino group are reacted by a known method.
The amide (C25-1) between a fatty acid and a compound having 2 to 10 carbon atoms and having a hydroxyl group and an amino group may be used alone or in combination of two or more.

In the alkylene oxide adduct (C25-2) having 2 to 4 carbon atoms of the amide [amide of (C25-1)], an alkylene oxide having 2 to 4 carbon atoms is added to the hydroxyl group of the amide (C25-1). An addition compound is preferred.
Examples of the alkylene oxide having 2 to 4 carbon atoms constituting the alkylene oxide adduct having 2 to 4 carbon atoms (C25-2) of the amide include ethylene oxide, 1,2- or 1,3-propylene oxide and 1,2 -, 1,3-, 1,4- or 2,3-butylene oxide. Of these, ethylene oxide is preferred.
The number of moles of the added alkylene oxide having 2 to 4 carbon atoms in the alkylene oxide adduct having 2 to 4 carbon atoms of the amide (C25-2) is preferably 2 to 20 mol.

The C2-4 alkylene oxide adduct (C25-2) of the amide can be produced by adding an alkylene oxide having 2-4 carbon atoms to the amide (C25-1) by a known method.
The C2-4 alkylene oxide adducts of amides (C25-2) may be used singly or in combination of two or more.

As an aliphatic amine constituting a compound (C25-3) having an amino group which is an alkylene oxide adduct having 2 to 4 carbon atoms of an aliphatic amine [hereinafter "a compound having an amino group (C25-3)"] Aliphatic amines having 6 to 24 carbon atoms are preferred. Examples of aliphatic amines having 6 to 24 carbon atoms include hexylamine, octylamine, and hydrogenated beef tallow amine. Among these aliphatic amines, hydrogenated tallow amine is preferred.

As the alkylene oxide having 2 to 4 carbon atoms in the compound (C25-3) having an amino group, the alkylene oxide having 2 to 4 carbon atoms exemplified in the explanation of (C25-2) above can be used. Ethylene oxide is preferred among the alkylene oxides having 2 to 4 carbon atoms.
The number of moles of the alkylene oxide having 2 to 4 carbon atoms added to the compound (C25-3) having an amino group is preferably 2 to 20 moles.

The amino group-containing compound (C25-3) can be produced by adding the above alkylene oxide having 2 to 4 carbon atoms to the above aliphatic amine by a known method.
The amino group-containing compound (C25-3) may be used alone or in combination of two or more.

Betaine-type amphoteric surfactants (C3) include betaine-type amphoteric surfactants having an alkyl group and/or an alkenyl group. Examples of the alkyl group include alkyl groups having 6 to 24 carbon atoms (hexyl group, octyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, icosyl group, docosyl group and tetracosyl group).
The alkenyl group includes alkenyl groups having 6 to 24 carbon atoms (hexenyl group, octenyl group, decenyl group, dodecenyl group, pentadecenyl group, octadecenyl group and icosenyl group).

From the viewpoint of excellent emulsifiability of the water permeability imparting agent, the surfactant (C) includes an anionic surfactant (C1) excluding metal phosphate ester (A) of aliphatic alcohol having 8 to 18 carbon atoms, and at least one surfactant selected from the group consisting of nonionic surfactants (C2) excluding the alkylene oxide adducts (B) of polyvalent active hydrogen compounds.

The content of the surfactant (C) in the water permeability imparting agent is preferably 0 to 70% by weight, more preferably 12 to 70% by weight, based on the weight of the nonvolatile component in the water permeability imparting agent. , more preferably 20 to 65% by weight.

The water permeability imparting agent of the present invention may contain a polyhydric alcohol (D) having 2 to 10 carbon atoms [hereinafter also referred to as "(D) component"].
(D) Component includes ethylene glycol, propylene glycol, glycerin, sorbitol and the like.
The water permeability-imparting agent of the present invention tends to have improved water permeability when used in combination with a polyhydric alcohol (D) having 2 to 10 carbon atoms. Therefore, when the polyhydric alcohol (D) having 2 to 10 carbon atoms is used in combination, there is a tendency that excellent water permeability can be exhibited even when the amount of the water permeability imparting agent used is small.

When the water permeability imparting agent of the present invention contains the polyhydric alcohol (D), the weight ratio of the polyhydric alcohol (D) is the weight of the nonvolatile component in the water permeability imparting agent from the viewpoint of improving the water permeability. based on 5 to 50% by weight.

The water permeability imparting agent of the present invention may optionally contain an additive (E) as a component other than the above components (A), (B), (C) and (D).
Examples of the additive (E) include solvents (water, organic solvents, etc., preferably water), lubricants such as waxes, antioxidants, ultraviolet absorbers, antifoaming agents, preservatives, fragrances, and the like.
The content of the additive (E) in the water permeability imparting agent of the present invention is preferably 5% by weight or less, more preferably 0.1 to 0.1%, based on the weight of the nonvolatile components in the water permeability imparting agent. 1% by weight.

When the water permeability imparting agent of the present invention contains component (C) together with component (A) and component (B), the weight ratio of component (A) to component (B) to component (C) [( A) / (B) / (C)] is preferably [( 8 to 39)/(20 to 75)/(12 to 70)], more preferably [(9 to 35)/(21 to 70)/(15 to 70)].

The water permeability imparting agent of the present invention comprises a phosphate salt (A), an alkylene oxide adduct of a polyvalent active hydrogen compound (B), and optionally water, a surfactant (C), and a polyhydric alcohol (D). and the additive (E), etc., and uniformly mixed at room temperature or, if necessary, heated (for example, 30 to 70° C.). There are no particular restrictions on the order and method of blending each component.

The water permeability imparting agent of the present invention is preferably used for fibers. By adhering the water permeability imparting agent of the present invention to fibers, water permeability can be imparted to the fibers.
The fibers to which the water permeability imparting agent of the present invention is attached are preferably used for nonwoven fabric products, and particularly preferably for top sheets of absorbent articles such as disposable diapers.

The water permeability imparting agent of the present invention is generally applied to hydrophobic fibers as an aqueous emulsion.
The water-based emulsion is preferably prepared by diluting a water permeability imparting agent with water at 20 to 40°C, or by adding the water permeability imparting agent to water at 20 to 40°C to emulsify.

Any concentration can be selected for the concentration of the aqueous emulsion, but the weight ratio of the non-volatile component in the water permeability imparting agent is preferably 0.05 to 20% by weight based on the weight of the aqueous emulsion. , more preferably 0.1 to 10% by weight.

[fiber]
The fibers of the present invention are fibers in which the water permeability imparting agent of the present invention is attached to hydrophobic fibers. By attaching the water permeability-imparting agent of the present invention to the hydrophobic fiber, the hydrophobic fiber can be imparted with water permeability to obtain the fiber of the present invention.

There is no particular limitation on the method of attaching the water permeability imparting agent to the hydrophobic fiber, and any process such as spinning or drawing, dip oiling method, oiling roll method, immersion method, spraying method, etc. are generally used. method can be used.

The amount of the water permeability imparting agent attached is preferably such that the weight ratio of the non-volatile component in the water permeability imparting agent is 0.15 to 2% by weight, based on the weight of the hydrophobic fiber, and 0.2%. An amount of ˜1.5% by weight is more preferred, and an amount of 0.25 to 1% by weight is particularly preferred.

The hydrophobic fiber used for the fiber material of the present invention means a fiber having a water absorption rate of 1% by weight or less at a temperature of 25° C. and a relative humidity of 65%.
The hydrophobic fibers are not particularly limited, and generally used hydrophobic synthetic fibers can be used, including fibers made of polyolefin, polyester, polyamide, and the like.
Polyolefins include polyethylene, polypropylene, ethylene-vinyl acetate copolymers, ethylene/propylene copolymers, and ethylene/propylene/1-butene copolymers.

Examples of polyester include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate/isophthalate, and polyether polyester.
Polyamides include 6,6-nylon, 6-nylon, and the like.
Among these, polyolefins and polyesters are preferably used as absorbent materials for diapers.

The fiber form using the fiber to which the water permeability imparting agent of the present invention is attached is preferably cloth-like, and examples thereof include woven fabrics, knitted fabrics, and non-woven fabrics. In addition, fibers mixed by a method such as mixed cotton, mixed spinning, mixed fiber, mixed knitting, and mixed weaving may be used as a cloth. Among these, nonwoven fabrics are particularly preferred.

[Nonwoven fabric]
The fiber to which the water permeability imparting agent of the present invention is attached can be applied as a nonwoven fabric. The nonwoven fabric of the present invention uses the fibers of the present invention.
When applying the fibers to which the water permeability imparting agent of the present invention is attached to a nonwoven fabric, the short fibers treated with the water permeability imparting agent of the present invention are formed into a fiber laminate by a dry or wet method, and then pressed with a heating roll. , The water permeability imparting agent of the present invention may be attached to a nonwoven fabric obtained by fusing with air heating or entangling fibers with a high pressure water jet, or by a spunbond method, a meltblown method, a flash spinning method, or the like. You may let

[Absorbent article]
The fiber of the present invention and the nonwoven fabric using the same are suitably used as topsheets for absorbent articles, particularly as topsheets for sanitary materials such as disposable diapers. The absorbent article of the present invention uses the nonwoven fabric of the present invention.
The fiber of the present invention and the nonwoven fabric using the same can also be used for second sheets, water absorbers, absorbent pads, and the like.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In the following, parts represent parts by weight.

<Production Example 1: Production of coconut oil alcohol phosphate potassium salt (A-2)>
A reaction vessel equipped with a stirrer and a thermometer was charged with 330 parts by weight of coconut oil alcohol and 101 parts by weight of phosphoric anhydride and allowed to react at 60°C. Acid ester potassium salt was obtained. Water was added to the obtained coconut oil alcohol monophosphate potassium salt to obtain a solution containing 50% by weight of coconut oil alcohol monophosphate potassium salt (A-2).

<Production Example 2: Production of 2-ethylhexyl alcohol phosphate potassium salt (A-1)>
A potassium phosphate salt of 2-ethylhexyl alcohol was obtained in the same manner as in Production Example 1, except that 231 parts by weight of 2-ethylhexyl alcohol was used instead of 330 parts by weight of coconut oil alcohol. rice field. Water was added to the resulting potassium 2-ethylhexyl alcohol phosphate to obtain a solution containing 73% by weight of the potassium 2-ethylhexyl alcohol phosphate (A-1).

<Production Example 3: Production of myristyl alcohol phosphate potassium salt (A-3)>
A potassium phosphate salt of myristyl alcohol was obtained in the same manner as in Production Example 1, except that 379 parts by weight of myristyl alcohol was used in place of 330 parts by weight of coconut oil alcohol. Water was added to the obtained potassium phosphate of myristyl alcohol to obtain a solution containing 50% by weight of the potassium phosphate of myristyl alcohol (A-3).

<Production Example 4: Production of oleyl alcohol phosphate potassium salt (A-4)>
A potassium phosphate ester of oleyl alcohol was obtained in the same manner as in Production Example 1, except that 475 parts by weight of oleyl alcohol was used instead of 330 parts by weight of coconut oil alcohol. Water was added to the obtained oleyl alcohol phosphate potassium salt to obtain a solution containing 25% by weight of oleyl alcohol phosphate potassium salt (A-4).

<Production Example 5: Production of isostearyl alcohol phosphate potassium salt (A-5)>
A potassium phosphate salt of isostearyl alcohol was obtained in the same manner as in Production Example 1, except that 475 parts by weight of isostearyl alcohol was used in place of 330 parts by weight of coconut oil alcohol. Water was added to the obtained isostearyl alcohol phosphate potassium salt to obtain a solution containing 90% by weight of the isostearyl alcohol phosphate potassium salt (A-5).

<Analytical method by GPC of the alkylene oxide adducts obtained in Production Examples 6 to 11>
The alkylene oxide adducts obtained in Production Examples 6 to 11 were analyzed under the following conditions.
(GPC conditions)
Apparatus: HLC-8220GPC [manufactured by Tosoh Corporation]
GPC column guard column: TSKguardcolumn SuperH-L (4.6 mm ID × 15 cm)
Separation column: TSKgel SuperH2000 (6 mm ID x 15 cm) + TSKgel Super H3000 (6 mm ID x 15 cm) + TSKgel Super H4000 (6 mm ID x 15 cm)
Detector: RI detector Flow medium: Tetrahydrofuran Flow rate: 0.6 ml/min
Column temperature: 40°C
Sample concentration: 0.25% by weight
Sample injection volume: 10 μl

<Production Example 6: PO 90 mol EO 20 mol block adduct of glycerin (B-1)>
9.21 parts by weight of glycerin [molecular weight 92.1, trade name: refined glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)] was added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping funnel, pressure reduction and nitrogen introduction line. After 0.8 parts by weight of potassium hydroxide was added and stirring was started, nitrogen was sealed, the temperature was raised to 90° C., the pressure was reduced to 0.005 MPa, and stirring was performed for 1 hour. Then, the temperature was raised to 130±10° C., and 523 parts by weight of propylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. It took 1 hour to complete the dropwise addition, and 2 hours to completely reduce the pressure. Then, 88 parts by weight of ethylene oxide was added dropwise. It took 0.5 hours to complete the dropwise addition, and 0.5 hours to completely reduce the pressure. After that, 10 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku) was charged, and after adsorption treatment at 95° C. for 1 hour, the alkali metal was removed by filtration treatment. It was cooled to 60°C and taken out to obtain 550 parts by weight of an alkylene oxide adduct. When the obtained alkylene oxide adduct was analyzed by GPC method, it was found that glycerin PO90 mol EO 20 mol block adduct (B-1) [in general formula (1), m is 30, n is 6.67, p is 3 compound] was confirmed to be contained.

<Production Example 7: PO85.3 mol EO 21.8 mol block adduct of glycerin (B-2)>
9.21 parts by weight of glycerin [molecular weight 92.1, trade name: refined glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)] was added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping funnel, pressure reduction and nitrogen introduction line. After 0.8 parts by weight of potassium hydroxide was added and stirring was started, nitrogen was sealed, the temperature was raised to 90° C., the pressure was reduced to 0.005 MPa, and stirring was performed for 1 hour. Then, the temperature was raised to 130±10° C., and 496 parts by weight of propylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. It took 1 hour to complete the dropwise addition, and 2 hours to completely reduce the pressure. Then, 96 parts by weight of ethylene oxide was added dropwise. It took 0.5 hours to complete the dropwise addition, and 0.5 hours to completely reduce the pressure. After that, 10 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku) was charged, and after adsorption treatment at 95° C. for 1 hour, the alkali metal was removed by filtration treatment. It was cooled to 60°C and taken out to obtain 560 parts by weight of an alkylene oxide adduct. The obtained alkylene oxide adduct was analyzed by GPC, and it was found to be a block adduct of 85.3 PO and 21.8 mol EO of glycerin (B-2) [where m is 28.4 and n is 7 .3, p is 3] was confirmed to be contained.

<Production Example 8: Production of PO 67 mol EO 11 mol block adduct (B-3) of trimethylolpropane>
13.4 weight of trimethylolpropane (I) [molecular weight 134, trade name trimethylolpropane (manufactured by Bayer Chemical Co., Ltd.)] was placed in a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping funnel, pressure reduction and nitrogen introduction line. and 0.8 parts by weight of potassium hydroxide were added, stirring was started, nitrogen was sealed, the temperature was raised to 90° C., the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 389 parts by weight of propylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. It took 1 hour to complete the dropwise addition, and 2 hours to completely reduce the pressure. Then, 48.4 parts by weight of ethylene oxide was added dropwise. It took 0.5 hours to complete the dropwise addition, and 0.5 hours to completely reduce the pressure. After that, 10 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku) was charged, and after adsorption treatment at 95° C. for 1 hour, the alkali metal was removed by filtration treatment. It was cooled to 60°C and taken out to obtain 400 parts by weight of an alkylene oxide adduct. The resulting alkylene oxide adduct was analyzed by GPC and found to be trimethylolpropane PO 67 mol EO 11 mol block adduct (B-3) [where m is 22.3 and n is 3.67 in general formula (1). , p is 3].

<Production Example 9: Production of PO 104 mol adduct (B-4) of pentaerythritol>
In a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping funnel, pressure reduction and nitrogen introduction line, 14 parts by weight of pentaerythritol (I) [molecular weight 136, trade name Pentalit (manufactured by Koei Chemical Industry)], hydroxylation After adding 0.8 part by weight of potassium and starting stirring, nitrogen was sealed, the temperature was raised to 90° C., the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 604 parts by weight of propylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. It took 1 hour to complete the dropwise addition, and 2 hours to completely reduce the pressure. After that, 10 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku) was charged, and after adsorption treatment at 95° C. for 1 hour, the alkali metal was removed by filtration treatment. It was cooled to 60°C and taken out to obtain 550 parts by weight of an alkylene oxide adduct. When the obtained alkylene oxide adduct was analyzed by GPC, a PO 104 molar adduct of pentaerythritol (B-4) [a compound having m of 26, n of 0 and p of 4 in the general formula (1)] was found. confirmed to be included.

<Production Example 10: Production of PO 104 mol EO 19.2 mol block adduct (B-5) of pentaerythritol>
550 parts by weight of the alkylene oxide adduct obtained in Production Example 8 was heated to 130±10° C., and 75.2 parts by weight of ethylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. It took 0.5 hours to complete the dropwise addition, and 0.5 hours to completely reduce the pressure. After that, 10 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku) was charged, and after adsorption treatment at 95° C. for 1 hour, the alkali metal was removed by filtration treatment. It was cooled to 60° C. and taken out to obtain 600 parts by weight of an alkylene oxide adduct. When the obtained alkylene oxide adduct was analyzed by GPC, it was found that pentaerythritol PO 104 mol EO 19.2 mol block adduct (B-5) [in general formula (1), m is 26, n is 4.8, compound with p=4] was confirmed to be contained.

<Production Example 11: Production of PO9 mol BO0.84 mol PO78 mol block adduct (B-6) of sorbitol>
In a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping funnel, pressure reduction and nitrogen introduction line, 26 parts by weight of sorbitol [molecular weight 182.2, trade name Sorbitol D-70 (manufactured by Mitsubishi Shoji Foodtech)] was added. It was prepared, dehydrated at 120±10° C., and then cooled to 50° C. or lower. After 1 part by weight of potassium hydroxide was added and stirring was started, nitrogen was sealed, the temperature was raised to 90° C., the pressure was reduced to 0.005 MPa, and stirring was performed for 1 hour. Then, the temperature was raised to 130±10° C., and 52.3 parts by weight of propylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. It took 1 hour to complete the dropwise addition, and 2 hours to completely reduce the pressure. Then, 6.1 parts by weight of 1,2-butylene oxide was successively added dropwise. It took 0.5 hours to complete the dropwise addition and 1 hour to completely reduce the pressure. Further, 453.2 parts by weight of propylene oxide was added dropwise. It took 1.5 hours to complete the dropwise addition and 2 hours to completely reduce the pressure. After that, 10 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku) was charged, and after adsorption treatment at 95° C. for 1 hour, the alkali metal was removed by filtration treatment. It was cooled to 60° C. and taken out to obtain 500 parts by weight of an alkylene oxide adduct. When the obtained alkylene oxide adduct was analyzed by GPC, the PO9BO0.84PO78 molar block adduct of sorbitol (B-6) [in general formula (1), m is 14.64, n is 0, and p is 6 compound] was confirmed to be contained.

<Production Example 12: Production of castor oil EO 10 mol adduct (C-1)>
459 parts by weight of castor oil and 0.1 part by weight of potassium hydroxide were added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping funnel, pressure reduction and nitrogen introduction line, and stirring was started. After the temperature was raised to °C, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 216 parts by weight of ethylene oxide was successively added dropwise while maintaining the temperature at 4 to 6.5 kPa. Thereafter, 20 parts by weight of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. After cooling to 60° C., it was taken out to obtain a castor oil EO 10 mol adduct (C-1).

<Production Example 13: Production of castor oil EO 25 mol adduct (C-2)>
A castor oil EO 25 mol adduct (C-2) was obtained in the same manner as in Production Example 10 except that 216 parts by weight of ethylene oxide was changed to 541 parts by weight in Production Example 12.

<Examples 1 to 12 and Comparative Examples 1 to 4>
Each component described in Table 1 was blended so that the amount of each component (pure content: nonvolatile component) was the amount described in Table 1. By stirring the mixture (at 40 ° C. for 30 minutes), Examples 1 to 12 and Comparative Examples 1 to 4 were obtained.

Raw materials corresponding to each component used in Examples 1 to 12 and Comparative Examples 1 to 4 are as follows. The blending amount (parts by weight) of each component shown in Table 1 is the pure amount.
(A-1): Solution containing 73% by weight of 2-ethylhexyl alcohol monophosphate potassium salt obtained in Production Example 2 (A-2): Coconut alcohol monophosphate potassium salt obtained in Production Example 1 Solution (A-3) containing 50% by weight of: Solution (A-4) containing 50% by weight of myristyl alcohol phosphate monoester potassium salt obtained in Production Example 3: Oleyl alcohol phosphate obtained in Production Example 4 Solution containing 25% by weight of ester potassium salt (A-5): Solution containing 90% by weight of isostearyl alcohol phosphate potassium salt obtained in Production Example 5 (B-1): Alkylene obtained in Production Example 6 Oxide adduct (PO 90 mol EO 20 mol block adduct of glycerin)
(B-2): Alkylene oxide adduct obtained in Production Example 7 (PO 85.3 mol EO 21.8 mol block adduct of glycerin)
(B-3): Alkylene oxide adduct obtained in Production Example 8 (PO 67 mol EO 11 mol block adduct of trimethylolpropane)
(B-4): Alkylene oxide adduct obtained in Production Example 9 (PO 104 mol adduct of pentaerythritol)
(B-5): Alkylene oxide adduct obtained in Production Example 10 (PO 104 mol EO 19.2 mol block adduct of pentaerythritol)
(B-6): Alkylene oxide adduct obtained in Production Example 11 (PO 9 mol BO 0.84 mol PO 78 mol block adduct of sorbitol)
(C-1): Castor oil EO 10 mol adduct obtained in Production Example 12 (C-2): Castor oil EO 25 mol adduct obtained in Production Example 13 (C-3): Coconut oil fatty acid sorbitan ester [product name: Ionet S-20, manufactured by Sanyo Chemical Industries Co., Ltd.]
(C-4): Sorbitan oleate ester [product name: Ionet S-80, manufactured by Sanyo Chemical Industries Co., Ltd.]
(C-5): Polyoxyethylene glycol 9-mol adduct diolate [product name: IONET DO-400, manufactured by Sanyo Chemical Industries Co., Ltd.]
(C-6): Solution containing 70% by weight of di-2-ethylhexyl sulfosuccinate sodium salt [product name: Sanmorin OT-70, manufactured by Sanyo Chemical Industries Co., Ltd.]
(D-1): Glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Measurement of surface resistance (evaluation of antistatic property)>
[Production of treated cotton]
Using the water permeability imparting agents of Examples 1 to 12 and Comparative Examples 1 to 4, treated cotton was produced by the following procedure.
Low-melt polyester synthetic fiber cotton (synthetic fiber cotton made of polyethylene terephthalate with a low melting point, single filament fiber density of 4.0 Dtex, fiber length of 51 mm) is coated with the water permeability imparting agent of each example and treated. Cotton (treated cotton of polyester synthetic fiber) was obtained. The adhesion amount of the water permeability imparting agent in each example was set to be the amount shown in Table 1.

[Measurement of surface resistance]
A web was prepared by passing 20 g of the treated polyester synthetic fiber cotton through a small opening machine and a carding machine. After the obtained web was conditioned in a constant temperature room at 25° C. and 40% RH for 24 hours, the electric resistance (Ω) was measured using a super megohmmeter manufactured by Toa Denpa Co., Ltd. The smaller the surface resistance, the better. The surface resistance is preferably less than 1.0×10 ¹⁰ Ω from the viewpoint of exhibiting sufficient antistatic properties. If the surface resistance value is less than 1.0×10 ¹⁰ Ω and the card passability evaluation result (percentage of discharged amount) described later is 60% or more, the antistatic property is excellent.

<Evaluation of Card Passability)>
[Preparation of treated cotton of polyester synthetic fiber]
Low-melt polyester synthetic fiber cotton (synthetic fiber cotton made of polyethylene terephthalate with a low melting point, single filament fiber density of 4.0 Dtex, fiber length of 51 mm) is coated with the water permeability imparting agent of each example and treated. Cotton (treated cotton of polyester synthetic fiber) was obtained. The adhesion amount of the water permeability imparting agent in each example was set to be the amount shown in Table 1.

[Evaluation of Card Passability]
After 20 g of the polyester-based synthetic fiber-treated cotton was conditioned in a constant temperature room at 25° C. and 40% RH for 24 hours, it was put into a flat card. The ratio of emissions to inputs was calculated. Table 1 shows the results.
The higher the ratio of the discharged amount to the input amount, the better the card passability. If the card passability is excellent, the generation of static electricity due to passage through the card machine can be suppressed, and as a result, the antistatic property can be enhanced. From the viewpoint of excellent card passability, the ratio of the discharged amount to the input amount is preferably 60% or more.

<Evaluation of Web Water Permeability>
The sedimentation time was measured by the following method using the web produced in the antistatic property evaluation test (web using polyester-based synthetic fiber-treated cotton). Table 1 shows the results.
(1) Measurement of First Sedimentation Time 800 mL of ion-exchanged water was added to a 1000 mL glass beaker, and the temperature was adjusted in a constant temperature room at 25° C. and 40% RH for 24 hours. 5 g of the web prepared in the surface resistance value measurement test was placed in a SUS woven basket (a cylindrical woven basket with a weight of 3 ± 0.1 g, a base diameter of 50 mm, and a height of 80 mm), and placed at a height of 25 mm from the liquid surface. The time for the drop basket to completely sink into the liquid surface was measured. Immediately after the cage submerged on the surface of the liquid, it was taken out of the water with tweezers, the web was squeezed by hand to remove the water, and subjected to a second sedimentation time measurement. The shorter the sedimentation time, the better the water permeability. If the web did not settle within 60 seconds after it was placed in the woven basket and dropped on the surface of the liquid, it was determined that the web did not settle, and was marked with x in the table.

(2) Measurement of second and third sedimentation times (i) Measurement of second sedimentation time The web after the first sedimentation time measurement (after the cage was submerged in the liquid surface, the web was taken out of water and squeezed by hand) ) was placed on water-absorbing paper and dried in a constant temperature room at 25° C. and 40% RH for 48 hours. The web was uniformly stuffed into the SUS knitting rope again, and the sedimentation time was measured in the same manner as the first sedimentation time measurement. As soon as the cage sank to the surface of the liquid, it was taken out of the water with tweezers, the web was squeezed by hand to remove the water, and the settling time was measured for the third time.
(ii) Measurement of third sedimentation time Using the web after the second sedimentation time measurement, the same operation as in (i) above was performed to measure the third sedimentation time. The shorter the sedimentation time is, the better the repeated water permeability.

<Examples 13 to 24, Comparative Examples 5 to 8: Production and evaluation of nonwoven fabric>
[Manufacturing of non-woven fabric]
The water permeability imparting agents of Examples 1 to 12 and Comparative Examples 1 to 4 were each diluted with hot water at 25° C. so that the nonvolatile component content was 1.0% by weight, thereby obtaining diluted solutions of the water permeability imparting agents. Obtained.
Next, 150 g of the water permeability imparting agent diluted solution was applied to 300 g of the main body of the fiber by a dip lubrication method, and the adhesion amount of the non-volatile component of the water permeability imparting agent adhering to the fiber was adjusted to the value shown in Table 1.
The main body of the fiber was a polyester (core)-polyethylene (sheath) composite fiber to which no fiber treatment agent such as a fiber treatment agent was attached, and had a single fiber fineness of 2.2 Dtex and a fiber length of 51 mm. . The fibers to which each water permeability imparting agent diluted solution was attached were placed in a hot air dryer at 80 ° C. for 1 hour, and then left at room temperature for 4 hours or more to dry, and the water permeability imparting agent adhered. fiber was obtained.
The resulting fibers were passed through a roller card to prepare a carded web having a basis weight of 20 g/m2. The resulting carded web was subjected to hot air treatment at 140° C. for 10 seconds to obtain an air-through nonwoven fabric.
The obtained nonwoven fabrics (Examples 13 to 24 and Comparative Examples 5 to 8) were evaluated for water permeability and repeated water permeability (durable water permeability) by the following method. Table 1 shows the results.

[Evaluation of water permeability and repeated water permeability (durable water permeability)]
From each of the nonwoven fabrics produced in Examples 13 to 24 and Comparative Examples 5 to 8, square nonwoven fabrics with a size of 10 cm×10 cm were cut out and subjected to a water permeability test.
(1) First water permeability test Under conditions of a temperature of 25 ° C. and a humidity of 65% RH, the nonwoven fabric of each example is placed on a filter paper (manufactured by Toyo Roshi Kaisha, No. 5) and placed at a height of 10 mm from the surface of the nonwoven fabric. One drop (about 0.05 mL) of physiological saline was dropped from the burette, and the time until the water drops disappeared from the surface of the nonwoven fabric was measured. A marking pen was used to mark 10 points on the surface of the non-woven fabric, and measurements were taken at the points to count the number of samples in which the saline disappeared within 5 seconds. The greater the number of locations where the disappearance time is less than 5 seconds, the better the water permeability.
(2) 2nd to 5th water permeability test (repeated evaluation of water permeability)
(i) Second water permeability test Place the non-woven fabric after the first water permeability test on a commercially available paper diaper, and place a SUS ring (inner diameter 6 cm, height 6 cm) on it, through which 50 mL of physiological saline was passed through (within the inner diameter of the ring) and absorbed by the paper diaper. After removing the non-woven fabric from the paper diaper and drying it, drop one drop of physiological saline again on the 10 marked places on the non-woven fabric surface, measure the disappearance time every 10 places, and measure the disappearance time for less than 5 seconds. The number of spots was counted.
(ii) Third to Fifth Water Permeability Tests After the second water permeability test, the nonwoven fabric was subjected to the third water permeability test in the same manner as in (i) above. Furthermore, the nonwoven fabric after the third water permeability test was subjected to the fourth water permeability test by performing the same operation as in (i) above. Furthermore, the nonwoven fabric after the fourth water permeability test was subjected to the fifth water permeability test by performing the same operation as in (i) above.
Repeated water permeability (durable water permeability) is excellent when the number of places where the disappearance time is less than 5 seconds even after repeated times is large. In the evaluation results of durable water permeability in Table 1, the number of locations where the disappearance time was less than 5 seconds was described.

A nonwoven fabric using the fibers to which the water permeability imparting agent of the present invention is attached can achieve both repeated water permeability and antistatic properties, and is therefore useful as a top sheet for absorbent articles.

Claims (7)

Water permeability-imparting fibers containing (A) a phosphate ester metal salt of an aliphatic alcohol having 8 to 18 carbon atoms and an alkylene oxide adduct (B) of a polyvalent active hydrogen compound represented by the following general formula (1) is an agent
In the following general formula (1), the ratio (n/m) of the number of added moles of A ¹ O and CH ₂ CH ₂ O is 0 to 0.5,
Based on the weight of nonvolatile components in the water permeability imparting agent, the content of the phosphate metal salt (A) of an aliphatic alcohol having 8 to 18 carbon atoms is 8 to 39% by weight, represented by the general formula (1) A water permeability-imparting agent for fibers containing 20 to 80% by weight of the alkylene oxide adduct (B) of a polyvalent active hydrogen compound.
R-[(A ¹ O) _m -(CH ₂ CH ₂ O) _n -H] _p (1)
[In general formula (1), R represents a residue obtained by removing all active hydrogens from a polyvalent active hydrogen compound. A ¹ O represents an alkyleneoxy group having 3 or 4 carbon atoms. m represents the number of moles of A ¹ O added and is a number from 4 to 50. n represents the number of added moles of CH ₂ CH ₂ O and is a number from 0 to 25; p represents a valence and is an integer of 3-6. ] The water permeability imparting agent for fibers according to claim 1, wherein n is a number from 0 to 20 in the general formula (1). 3. The polyvalent active hydrogen compound of the alkylene oxide adduct (B) of the polyvalent active hydrogen compound is at least one selected from the group consisting of glycerin, trimethylolpropane, pentaerythritol and sorbitol according to claim 1 or 2. Water permeability imparting agent for textiles. Furthermore, an anionic surfactant (C1) other than the phosphate ester metal salt (A) of an aliphatic alcohol having 8 to 18 carbon atoms, and a nonionic surfactant other than the alkylene oxide adduct (B) of the polyvalent active hydrogen compound containing at least one surfactant (C) selected from the group consisting of the agent (C2), and the content of the surfactant (C) based on the weight of the non-volatile component in the water permeability-imparting agent is 12 to 70 wt. %, the water permeability imparting agent for fibers according to any one of claims 1 to 3. The water permeability imparting agent for fibers according to any one of claims 1 to 4 is a fiber attached to a hydrophobic fiber, and the weight ratio of the nonvolatile component of the water permeability imparting agent is the weight ratio of the hydrophobic fiber. Fibers that are 0.15 to 2% by weight, based on weight. A nonwoven fabric using the fiber according to claim 5. A water absorbent article using the nonwoven fabric according to claim 6.