Fiber treatment agent for nonwoven fabric, aqueous liquid of fiber treatment agent for nonwoven fabric, and fiber

Abstract

The objective of this invention is to reduce the rate of change in friction of synthetic fibers coated with a nonwoven fiber treatment agent even after long-term storage, and to improve the wet friction characteristics of the synthetic fibers coated with the nonwoven fiber treatment agent, the emulsification stability of the nonwoven fiber treatment agent, and the antifoaming properties. The nonwoven fiber treatment agent contains a specific phosphate compound (A) and an alcohol (B). In the P-nuclear NMR determination during the pretreatment of alkaline excess neutralization, when the total P-nuclear NMR integral ratios of specific phosphate esters P1, P2, P3, P4, P5 and orthophosphate and their salts are set to 100%, the P-nuclear NMR integral ratios of P4 and P5 are 20% to 65% and 20% to 45%, respectively, the value calculated according to mathematical formula (1) is 8 or less, the pH of the 1% by mass water dilution at 25°C is 5.0 to 8.0 or less, and the acid value of the non-volatile components is 5 or more and less than 60. {[the NMR integral ratio of the P-nucleus to which phosphate ester P1 belongs]× 2 +[the NMR integral ratio of the P-nucleus to which phosphate ester P2 belongs]× [the concentration (mass%) of phosphate compound (A) in the nonwoven fiber treatment agent] / 100 …(1)

Description

[Technical Field]

[0001] This invention relates to a fiber treatment agent for nonwoven fabrics, an aqueous liquid of the fiber treatment agent for nonwoven fabrics, and fibers. [Previous Technology]

[0002] Generally speaking, it is known that synthetic fiber spinning and stretching steps or post-processing steps are performed in the manufacturing process of nonwoven fabrics. In addition, in the spinning and stretching steps, post-processing steps, etc., from the viewpoint of reducing the friction of synthetic fibers and improving antistatic properties, sometimes a synthetic fiber treatment agent is applied to the surface of the synthetic fibers.

[0003] Currently, synthetic fiber treatment agents disclosed in Patent Documents 1 to 3 are known. Patent Document 1 describes a fiber treatment agent for nonwoven fabric manufacturing, which contains a specific alkyl phosphate ester, wherein the acid value (KOH mg / g) of the non-volatile component of the treatment agent is less than 100.

[0004] Patent document 2 describes a treatment agent for polyolefin synthetic fibers, which contains specific organic acids, alkyl phosphate salts, and polyoxyalkylene derivatives.

[0005] Patent document 3 describes a fiber treatment agent for short fibers, which contains a specific alkyl phosphate ester.

[0006] Prior Art Documents Patent Document 1: International Publication No. 2023 / 149326 Patent Document 2: Japanese Patent Application Publication No. 2017-210693 Patent Document 3: Japanese Patent Application Publication No. 2020-73741 [Summary of the Invention]

[0007] Problems to be Solved by the Invention However, it is currently desirable to reduce the rate of change in friction of synthetic fibers after long-term storage when a synthetic fiber treatment agent (i.e., a nonwoven fiber treatment agent) is adhered to the synthetic fiber. Furthermore, it is also desirable to further improve the wet friction characteristics of the synthetic fiber with the nonwoven fiber treatment agent, the emulsification stability of the nonwoven fiber treatment agent, and the anti-foaming properties.

[0008] Means for solving the problem The inventors conducted research in order to solve the above-mentioned problem and found that nonwoven fiber treatment agents containing specific phosphoric acid compounds and alcohols are particularly effective.

[0009] The above describes various forms used to solve the above problems.

[0010] Form 1 is a nonwoven fiber treatment agent containing the following phosphoric acid compound (A) and the following alcohol (B), wherein: in the P-nuclear NMR determination of the above nonwoven fiber treatment agent during alkaline excess neutralization pretreatment, when the total P-nuclear NMR integral ratio of phosphate ester P1, phosphate ester P2, phosphate ester P3, phosphate ester P4, phosphate ester P5, orthophosphate and their salts is set to 100%, the P-nuclear NMR integral ratio of the above phosphate ester P4 is 20% or more and 65% or less, the P-nuclear NMR integral ratio of the above phosphate ester P5 is 20% or more and 45% or less, the value calculated according to the following mathematical formula (1) is 8 or less, the pH of a 1% by mass aqueous dilution of the above nonwoven fiber treatment agent at 25°C is 5.0 or more and 8.0 or less, and the acid value of the non-volatile component in the above nonwoven fiber treatment agent is 5KOH-mg / g or more and less than 60KOH-mg / g. Phosphoric acid compound (A) contains phosphate ester P3, phosphate ester P4, phosphate ester P5, and orthophosphoric acid, and further optionally contains at least one of phosphate ester P1 and phosphate ester P2. In general formula (1), M1, M2, and M3 are hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium, respectively. In general formula (2), R1 is an alkyl or alkenyl group with 8 to 12 carbon atoms, and M4 and M5 are hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium, respectively. In general formula (3), R2 and R3 are alkyl or alkenyl groups with 8 to 12 carbon atoms, and M6 is hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium. In general formula (4), R4 is an alkyl or alkenyl group with 8 to 12 carbon atoms, and M7 and M8 are hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium, respectively. In general formula (5), R5 and R6 are alkyl or alkenyl groups with 8 to 12 carbon atoms, and M9 is hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium. {[the NMR integral ratio of the P nucleus to which phosphate ester P1 belongs} × 2 + [the NMR integral ratio of the P nucleus to which phosphate ester P2 belongs]} × [the concentration (mass%) of phosphate compound (A) in the fiber treatment agent for nonwoven fabrics] / 100 … (1) Alcohols (B) are aliphatic alcohols with 8 to 18 carbon atoms.

[0011] Form 2 is a nonwoven fabric fiber treatment agent as described in Form 1, wherein the value obtained according to the above mathematical formula (1) is 3.5 or less.

[0012] Form 3 is a nonwoven fabric fiber treatment agent as described in Form 1 or 2, wherein the NMR integral of the P nucleus to which the above-mentioned phosphate ester P3 belongs is 6.5% or more and 40% or less.

[0013] Form 4 is a nonwoven fiber treatment agent as described in any of Forms 1 to 3, wherein the total percentage of the NMR integral of the P-nuclei to which the above-mentioned phosphate ester P2 and the above-mentioned phosphate ester P3 belong is greater than 0% and less than 20%.

[0014] Form 5 is a nonwoven fiber treatment agent as described in any of Forms 1 to 4, wherein when the total content of the above-mentioned phosphoric acid compound (A) and the above-mentioned alcohol (B) is set to 100% by mass, the proportion of the above-mentioned phosphoric acid compound (A) is 85% to 99.9% by mass and the above-mentioned alcohol (B) is 0.1% to 15% by mass.

[0015] Form 6 is a nonwoven fabric fiber treatment agent as described in any of Forms 1 to 5, wherein at least one of the following two conditions is met: Condition 1: It contains two or more of the above-mentioned alcohols (B) with different carbon numbers; Condition 2: It contains fatty acids (C) with 12 to 20 carbon numbers.

[0016] Form 7 is a nonwoven fiber treatment agent as described in any of Forms 1 to 6, wherein it further contains the following nonionic surfactant (D). The nonionic surfactant (D) is at least one of the following: a compound formed by adding 1 mole of a monohydric aliphatic alcohol having 22 to 50 carbon atoms to an epoxy alkane having 2 to 4 carbon atoms, totaling 5 to 100 moles; and an ester compound formed by polyglycerol with a degree of condensation of 3 to 12 and a saturated fatty acid having 12 to 18 carbon atoms.

[0017] Form 8 is a nonwoven fabric fiber treatment agent as described in Form 7, wherein when the total content of the above-mentioned phosphoric acid compound (A), the above-mentioned alcohol (B), and the nonionic surfactant (D) is set to 100% by mass, the proportion of the above-mentioned phosphoric acid compound (A) is 20% to 80% by mass, the above-mentioned alcohol (B) is 0.1% to 10% by mass, and the nonionic surfactant (D) is 10% to 75% by mass.

[0018] Form 9 is an aqueous liquid of a nonwoven fabric fiber treatment agent, characterized in that: the concentration of non-volatile components of the nonwoven fabric fiber treatment agent described in any of Forms 1 to 8 is more than 0.1% by mass and less than 10% by mass.

[0019] Form 10 is a fiber, the key feature of which is that it is coated with a nonwoven fiber treatment agent as described in any of Forms 1 to 8.

[0020] Form 11 is a fiber as described in Form 10, wherein the fiber is a polyolefin synthetic fiber.

[0021] Effects of the Invention According to the present invention, the rate of change of friction of synthetic fibers coated with a nonwoven fiber treatment agent can be reduced even after long-term storage. In addition, the wet friction characteristics of synthetic fibers coated with a nonwoven fiber treatment agent, the emulsification stability of the nonwoven fiber treatment agent, and the antifoaming properties can be improved.

Implementation Method

[0022] <First Embodiment> The first embodiment of the present invention will now be described, namely, a fiber treatment agent for nonwoven fabrics (hereinafter referred to as the treatment agent). The treatment agent of this embodiment contains the following phosphoric acid compound (A) and the following alcohol (B).

[0023] (Phosphoric acid compound (A)) Phosphoric acid compound (A) contains phosphate ester P3 of general formula (3), phosphate ester P4 of general formula (4), phosphate ester P5 of general formula (5), and orthophosphoric acid, and further optionally contains at least one of phosphate ester P1 of general formula (1) and phosphate ester P2 of general formula (2).

[0024] In general formula (1), M1, M2 and M3 are hydrogen atom, alkali metal, alkaline earth metal (1 / 2), organic amine, ammonium or phosphonium, respectively.

[0025] In general formula (2), R1 is an alkyl or alkenyl group with 8 to 12 carbon atoms, and M4 and M5 are hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium, respectively.

[0026] In general formula (3), R2 and R3 are alkyl or alkenyl groups with 8 to 12 carbon atoms, respectively, and M6 is a hydrogen atom, alkali metal, alkaline earth metal (1 / 2), organic amine, ammonium, or phosphonium.

[0027] In general formula (4), R4 is an alkyl or alkenyl group with 8 to 12 carbon atoms, and M7 and M8 are hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium, respectively.

[0028] In general formula (5), R5 and R6 are alkyl or alkenyl groups with 8 to 12 carbon atoms, respectively, and M9 is a hydrogen atom, alkali metal, alkaline earth metal (1 / 2), organic amine, ammonium, or phosphonium.

[0029] (Alkali metals) In the phosphoric acid compound (A), there are no particular restrictions on the alkali metals that constitute M1 to M9, such as sodium, potassium, lithium, etc.

[0030] (Alkaline earth metals) There are no particular restrictions on the alkaline earth metals that constitute M1 to M9. Examples include calcium, magnesium, beryllium, strontium, and barium.

[0031] In this context, since alkaline earth metals are divalent, the above-mentioned "alkaline earth metals (1 / 2)" means adding 1 / 2 moles to M1 to M9.

[0032] (Organic amines) There are no particular restrictions on the organic amines that constitute M1 to M9. Examples include methylamine, ethylamine, butylamine, octylamine, laurylamine, octadecylamine (also known as stearamine), octadeceneamine, coconutamine, and other primary amines.

[0033] (phosphonium) There are no particular restrictions on the phosphonium constituting M1 to M9. Examples of quaternary phosphonium include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetraoctylphosphonium, dibutyldihexylphosphonium, trihexyltetradecylphosphonium, triethyloctylphosphonium, trioctylmethylphosphonium, and triphenylmethylphosphonium.

[0034] The alkali metal, alkaline earth metal, organic amine, ammonium and phosphorus constituting the above M1 to M9 can each be used alone or in combination of two or more types.

[0035] (Alkyl group with 8 to 12 carbon atoms) There are no other restrictions on the alkyl group with 8 to 12 carbon atoms constituting R1 to R6. It can be a straight-chain alkyl group or a branched alkyl group. By setting the carbon number of the alkyl group to 8 to 12, it is possible to prevent the reduction of friction characteristics of the synthetic fiber with the treatment agent when wet due to too small a carbon number, and the reduction of the emulsification stability of the treatment agent due to too large a carbon number.

[0036] Specific examples of straight-chain alkyl groups include octyl, nonyl, decyl, undecyl, dodecyl, etc.

[0037] Specific examples of branched alkyl groups include isooctyl, isononyl, isodecyl, isoundecyl, isoundecyl, isododecyl, etc.

[0038] (Alkenyl group with 8 to 12 carbon atoms) There are no other restrictions on the alkenyl group constituting R1 to R6, which has 8 to 12 carbon atoms. It can be a straight-chain alkenyl group or a branched alkenyl group. By setting the number of carbon atoms in the alkenyl group to 8 to 12, it is possible to prevent the reduction of frictional properties of the synthetic fiber with the treatment agent when wet due to too small a number of carbon atoms, and the reduction of the emulsification stability of the treatment agent due to too large a number of carbon atoms.

[0039] Specific examples of straight-chain alkenyl groups include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, etc.

[0040] Specific examples of alkenyl groups with branched chains include isooctenyl, isononenyl, isodelenyl, isoundecenyl, isoundecenyl, isododecenyl, etc.

[0041] The alkyl and alkenyl groups constituting R1 to R6 with 8 to 12 carbon atoms can be used individually or in combination with two or more types.

[0042] The orthophosphoric acid contained in the phosphoric acid compound (A) can also form salts. Examples of salts of orthophosphoric acid include those formed with the aforementioned alkali metals and alkaline earth metals.

[0043] (Method for manufacturing phosphoric acid compound (A)) There are no particular limitations on the method for manufacturing phosphoric acid compound (A), and known manufacturing methods can be used. For example, phosphoric acid compound (A) can be manufactured by reacting an aliphatic alcohol as a raw material with pyrophosphoric acid such as phosphorus pentoxide to obtain a phosphate (hereinafter referred to as phosphorylation reaction), and then neutralizing the resulting phosphate. By this manufacturing method, the phosphoric acid compound (A) produced will contain at least phosphate ester P3, phosphate ester P4, and phosphate ester P5.

[0044] Aliphatic alcohols may be alcohols having alkyl or alkenyl groups having 8 or more but less than 12 carbon atoms constituting the above-mentioned R1 to R6.

[0045] It is preferable to pre-dehydrate aliphatic alcohols. When pre-dehydration is performed, it is easier to inhibit the decomposition of pyrophosphate caused by moisture in the raw material.

[0046] There are no restrictions on the reaction atmosphere of aliphatic alcohols and pyrophosphate. A nitrogen atmosphere or an atmospheric atmosphere can be used. A nitrogen atmosphere is preferred as it is easier to suppress the decomposition of pyrophosphate caused by moisture in the reaction atmosphere.

[0047] There are no particular limitations on the conditions for the above phosphorylation reaction, but it is preferred that the reaction be carried out at a temperature of 65°C to 85°C for 1 hour to 6 hours.

[0048] Furthermore, the synthesized phosphate is preferably not in contact with moisture. Contact with moisture can easily cause the decomposition of phosphate ester P2 or phosphate ester P3.

[0049] There are no particular restrictions on the above-mentioned neutralization conditions, but it is preferable to carry out neutralization for, for example, at a temperature of 85°C to 95°C for 3 to 9 hours. Neutralization at temperatures below 85°C may easily increase the content of phosphate ester P2.

[0050] (Alcohols (B)) Alcohols (B) are aliphatic alcohols with 8 to 18 carbon atoms.

[0051] Specific examples of alcohols (B) include octanol, nonanol, decanol, undecaneol, dodecaneol (lauryl alcohol), tridecaneol, tetradecaneol, pentadecaneol, hexadecaneol (cetyl alcohol), heptadecanol, octadecaneol (stearyl alcohol), etc.

[0052] Alcohols (B) can be straight-chain aliphatic alcohols or branched aliphatic alcohols.

[0053] The above-mentioned alcohol (B) can be used alone or in combination with two or more types of alcohol (B).

[0054] The alcohol (B) is preferably an alcohol (B) containing two or more different types of alcohols (B) with different numbers of carbon atoms. When it contains two or more different types of alcohols (B) with different numbers of carbon atoms, the defoaming properties of the treatment agent can be improved.

[0055] (Ratio of Phosphoric Acid Compound (A) to Alcohol (B)) There is no particular limitation on the ratio of phosphoric acid compound (A) and alcohol (B) in the treatment agent. When the total ratio of phosphoric acid compound (A) and alcohol (B) in the treatment agent is set to 100% by mass, the treatment agent preferably contains 85% to 99.9% by mass of phosphoric acid compound (A) and 0.1% to 15% by mass of alcohol (B).

[0056] When the proportions of phosphoric acid compound (A) and alcohol (B) in the treatment agent are within the above-mentioned range, the initial hydrophilicity of the synthetic fiber with the above-mentioned treatment agent attached can be improved.

[0057] (P-Nuclear NMR Integral Ratio) In the P-nuclear NMR determination of the treatment agent before alkaline excess neutralization, when the total P-nuclear NMR integral ratios of phosphate ester P1, phosphate ester P2, phosphate ester P3, phosphate ester P4, phosphate ester P5, and orthophosphate and its salts are set to 100%, the P-nuclear NMR integral ratio of phosphate ester P4 is 20% to 65%, and the P-nuclear NMR integral ratio of phosphate ester P5 is 20% to 45%. By setting the ratios of phosphate ester P4 and phosphate ester P5 within the above ranges, the reduction in the antifoaming properties of the treatment agent due to excess phosphate ester P4 and the reduction in the emulsification stability of the treatment agent due to excess phosphate ester P5 can be prevented.

[0058] In addition, the value obtained according to the following mathematical formula (1) is 8 or less, preferably 3.5 or less.

[0059] {[the NMR integral ratio of the P-nucleus to which phosphate ester P1 belongs]× 2 +[the NMR integral ratio of the P-nucleus to which phosphate ester P2 belongs]=×[the concentration (mass%) of phosphate compound (A) in the nonwoven fiber treatment agent] / 100 …(1)

[0060] When the value calculated according to mathematical formula (1) is 8 or less, the rate of change of friction of the synthetic fiber with the treatment agent can be reduced even after long-term storage. Furthermore, when the value calculated according to mathematical formula (1) is 3.5 or less, the rate of change of friction can be further reduced.

[0061] It is generally believed that the increase in orthophosphoric acid caused by the time-dependent decomposition of phosphate esters P1 and P2 has a significant impact on the frictional properties of synthetic fibers coated with the treatment agent. One mole of phosphate ester P1 decomposes to generate 2 moles of orthophosphoric acid. Another one mole of phosphate ester P2 decomposes to generate 1 mole of orthophosphoric acid. Therefore, considering the impact of orthophosphoric acid generation, the rate of change of friction of synthetic fibers can be evaluated using the above mathematical formula (1).

[0062] Here, the aforementioned "alkaline excess neutralization pretreatment" refers to a pretreatment in which an excess of alkali is added to the phosphate ester or orthophosphoric acid contained in the phosphoric acid compound (A). Specific examples of alkalis include alkali metal hydroxides. Furthermore, the alkali may be the same as or different from the alkali used in the synthesis of the phosphate ester salt. Specific examples of alkali metal hydroxides include, for example, sodium hydroxide and potassium hydroxide. In p-nuclear NMR determination, the peaks to which phosphate esters P1 to P5 and orthophosphoric acid and its salts belong can be clearly distinguished by performing an alkaline excess neutralization pretreatment. The method for determining the p-nuclear NMR integration ratio is described below.

[0063] The NMR integral ratio of the P nucleus to which the phosphate ester P3 belongs is preferably above 6.5% and below 40%.

[0064] In addition, the total percentage of the NMR integral of the P nuclei to which phosphate ester P2 and phosphate ester P3 belong is preferably greater than 0% and less than 20%.

[0065] When the NMR integral of the P nucleus to which the phosphate ester P3 belongs is 6.5% or more but less than 40%, the emulsion stability can be further improved.

[0066] Furthermore, when the total NMR integral percentages of the P-cores to which phosphate ester P2 and phosphate ester P3 belong are greater than 0% and less than 20%, the friction between the synthetic fiber with the treatment agent and the wet metal can be reduced. In other words, the frictional properties when wet can be improved.

[0067] (pH of the treatment agent) A 1% by mass aqueous solution of the treatment agent has a pH of 5.0 or higher and 8.0 or lower at 25°C.

[0068] Since a pH of 5.0 to 8.0 is weakly acidic to neutral, when nonwoven fabric containing fibers coated with a treatment agent is used as a sanitary material that comes into contact with the skin, skin irritation can be reduced.

[0069] There are no particular limitations on the method of adjusting the pH of the treatment agent. For example, the pH can be adjusted by adjusting the acid value of the treatment agent. In addition, the pH of the treatment agent can also be adjusted by using a pH adjuster that is one of the other components (E) described later.

[0070] There are no particular restrictions on the method of pH measurement. For example, a well-known pH meter (Horiba Manufacturing Co., Ltd. benchtop pH meter F-72) can be used for measurement.

[0071] (Acid value of the treatment agent) The acid value of the non-volatile components in the treatment agent is above 5 KOH-mg / g and below 60 KOH-mg / g. When the acid value of the non-volatile components in the treatment agent is within the above-mentioned range, the emulsification stability of the treatment agent can be improved.

[0072] The acid value of the non-volatile component in the treatment agent is calculated by dissolving the non-volatile component of the treatment agent in a mixed solvent of ethanol / xylene = 1 / 2 (volume ratio), then setting it on a potentiometric titration device and titrating it with a 0.1 mol / L potassium hydroxide methanol standard solution, and calculating the value from the following mathematical formula.

[0073] Acid value (KOH - mg / g) = (R × f × 56.11 × 0.1) / S

[0074] In this mathematical formula, f represents the factor of 0.1 mol / L potassium hydroxide methanol standard solution; S represents the amount of sample taken (g, converted from solid content); and R represents the amount of 0.1 mol / L potassium hydroxide methanol standard solution used up to the inversion point (mL).

[0075] The non-volatile component of the treatment agent refers to the absolute dry matter after the treatment agent has been heat-treated at 105°C until its mass no longer changes and volatile substances have been fully removed.

[0076] (Fatiodic acids (C) with 12 to 20 carbon atoms) The treatment agent may also contain fatty acids (C) with 12 to 20 carbon atoms.

[0077] Specific examples of fatty acids (C) include dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid, etc.

[0078] The above-mentioned fatty acid (C) can be used alone or in combination with two or more types of fatty acids (C).

[0079] When the treatment agent contains fatty acids (C) with 12 to 20 carbon atoms, the foam suppression property of the treatment agent can be improved.

[0080] There is no particular limitation on the content of the above-mentioned fatty acid (C), but it is preferred that the non-volatile components of the treatment agent contain more than 0% by mass and less than 2% by mass.

[0081] The treatment agent preferably meets at least one of the following two conditions. Condition 1: Contains two or more alcohols (B) with different carbon numbers. Condition 2: Contains fatty acids (C) with 12 to 20 carbon numbers.

[0082] When the treatment agent meets at least one of the above conditions 1 and 2, the foam suppression property of the treatment agent can be further improved.

[0083] (Nonionic surfactant (D)) The treatment agent preferably further contains at least one selected from the nonionic surfactant (D) below.

[0084] Specific examples of nonionic surfactants (D) include compounds formed by the addition of 1 mole of monoalbial aliphatic alcohols with 22 to 50 carbon atoms to 5 to 100 mol of epoxides with 2 to 4 carbon atoms, and ester compounds formed by polyglycerols with a degree of condensation of 3 to 12 and saturated fatty acids with 12 to 18 carbon atoms.

[0085] When the treatment agent contains the above-mentioned nonionic surfactant (D), the durable hydrophilicity of the synthetic fiber to which the treatment agent is attached can be further improved.

[0086] (Proportion of Phosphate Compound (A), Alcohol (B), and Nonionic Surfactant (D)) There are no particular restrictions on the proportion of phosphate compound (A), alcohol (B), and nonionic surfactant (D) in the treatment agent. When the total proportion of phosphate compound (A), alcohol (B), and nonionic surfactant (D) in the treatment agent is set to 100% by mass, the treatment agent preferably contains 20% to 80% by mass of phosphate compound (A), 0.1% to 10% by mass of alcohol (B), and 10% to 75% by mass of nonionic surfactant (D).

[0087] When the proportions of phosphoric acid compound (A), alcohol (B) and nonionic surfactant (D) in the treatment agent are within the above-mentioned value range, it is easier to make the acid value of the treatment agent or the value calculated according to mathematical formula (1) within the above-mentioned value range.

[0088] (Other components (E)) The treatment agent may also contain other components (E). Examples of other components (E) include stabilizers, antistatic agents, adhesives, antioxidants, ultraviolet absorbers, surfactants other than the nonionic surfactants (D) mentioned above, pH adjusters, alcohols other than the alcohols (B) mentioned above, and other components that are commonly used in the treatment agent.

[0089] Specific examples of other components (E) include, for example, lactic acid, sodium dioctyl sulfosuccinate, sodium dodecyl sulfonate, polyether-modified polysiloxane, etc.

[0090] Of the non-volatile components of the treatment agent, the content of other components (E) is preferably 15% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. Other components (E) may also be 0% by mass.

[0091] (Preservation form) The treatment agent may be configured as a dosage form 1 containing the above-mentioned components (A) to (E), or from the viewpoint of improving the stability of the formulation, it may be configured as a dosage form 2 or a dosage form 3.

[0092] (Solvent) The treatment agent of this embodiment may also be mixed with a solvent as appropriate to prepare a composition containing a nonwoven fiber treatment agent (hereinafter referred to as "composition containing treatment agent"), and stored or distributed in the form of composition containing treatment agent.

[0093] The solvent is a solvent with a boiling point below 105°C at 1 atmosphere. Examples of solvents include water and organic solvents.

[0094] Specific examples of water include, for example, ion-exchanged water, distilled water, hard water, soft water, etc. Among these, ion-exchanged water or distilled water is preferred.

[0095] Specific examples of organic solvents include lower alcohols such as ethanol and propanol, and low-polarity solvents such as hexane. One type of solvent may be used alone, or two or more may be used in appropriate combinations. Among these, polar solvents such as water and lower alcohols are preferred from the viewpoint of excellent dispersibility or solubility of each component, and water is more preferred from the viewpoint of excellent operability.

[0096] <Effects and Effects of the First Embodiment> (1-1) The treatment agent of the first embodiment contains the above-mentioned phosphoric acid compound (A) and alcohol (B). In addition, the NMR integral ratio of the P-core to which phosphate ester P4 belongs is 20% to 65%, the NMR integral ratio of the P-core to which phosphate ester P5 belongs is 20% to 45%, the value calculated according to mathematical formula (1) is 8 or less, and the acid value of the non-volatile component in the treatment agent is 5 KOH-mg / g or more and less than 60 KOH-mg / g. Therefore, the rate of change of friction of the synthetic fiber with the treatment agent attached can be reduced even after long-term storage. In addition, the wet friction characteristics, initial hydrophilicity, durable hydrophilicity, emulsification stability of the treatment agent, and antifoaming properties of the synthetic fiber with the treatment agent attached can be improved.

[0097] (1-2) Furthermore, by containing the above-mentioned nonionic surfactant (D), the durable hydrophilicity of the synthetic fiber to which the treatment agent is attached can be further improved.

[0098] (1-3) By using the treatment agent of the first embodiment, a nonwoven fabric that is better suited for final products such as diapers or wet wipes for hygiene products can be manufactured.

[0099] <Second Embodiment> Next, a second embodiment of the present invention will be described, namely, an aqueous solution of a fiber treatment agent for nonwoven fabrics (hereinafter referred to as aqueous solution). The description will focus on the differences from the first embodiment.

[0100] The aqueous solution of this embodiment contains the above-described treatment agent and water. By mixing the treatment agent and water, the aqueous solution is used in the form of an emulsion. Specifically, the same type of water as the solvent described above can be used.

[0101] There are no particular limitations on the preparation method of the aqueous liquid. For example, a method of adding a specific amount of treatment agent to pre-measured water can be cited. In addition, it can be prepared by using known mechanical emulsification methods such as a mixer or homogenizer.

[0102] There is no particular limitation on the concentration of the treatment agent in the aqueous solution. Preferably, the concentration of the treatment agent is such that the concentration of the non-volatile component of the treatment agent is 0.1% by mass or more and 10% by mass or less.

[0103] When the concentration of the treatment agent in the aqueous solution is within the above-mentioned range, the emulsion stability can be easily improved.

[0104] <Function and Effect of the Second Embodiment> In addition to the function and effect of the first embodiment, the second embodiment also has the following function and effect.

[0105] (2-1) The aqueous solution of the second embodiment described above contains the above-mentioned treatment agent and water. Therefore, the treatment agent can be applied to synthetic fibers for nonwoven fabrics in the form of an emulsion. In addition, by containing water as a solvent, the operability of the aqueous solution can be improved.

[0106] <Third Embodiment> Next, a third embodiment of the present invention, namely fiber, will be described.

[0107] The fiber in this embodiment is a treated fiber, on which the treatment agent of the first embodiment is attached. By attaching the treatment agent to the surface of the fiber, a fiber exhibiting the effects of the present invention is obtained.

[0108] There are no particular restrictions on the type of fiber, but examples include (1) polyester fibers such as polyethylene terephthalate (PET), polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate-isophthalate, polyether polyester, polylactic acid, and composite fibers formed from such polyester resins; (2) polyamide fibers such as Nylon 6 and Nylon 66; (3) polyacrylic acid fibers such as polyacrylic acid and modified acrylic acid; and (4) polyolefin fibers such as polyethylene and polypropylene. Among these, polyolefin fibers (hereinafter referred to as polyolefin synthetic fibers) are preferred.

[0109] Polyolefin synthetic fibers can also be composite fibers with a core-sheath structure. More specifically, they can be composite fibers in which either or both of the core and sheath are polyolefin fibers. Specifically, they can be polyethylene / polypropylene composite fibers with a polyethylene sheath and a polypropylene core, or polyethylene / polyester composite fibers with a polyethylene sheath and a polyester core.

[0110] The treatment agent of this embodiment is applicable to nonwoven fabrics. As long as a treated nonwoven fabric with the treatment agent of this embodiment adhering to its surface can be obtained, the treatment agent can be adhering to the fiber surface before nonwoven fabric manufacturing, or the treatment agent can be adhering to the fiber surface after nonwoven fabric manufacturing.

[0111] Furthermore, there is no particular limitation on the length of the fiber; it can be applied to either short or long fibers, but is preferably applied to short fibers. That is to say, the polyolefin synthetic fiber of this embodiment is preferably a polyolefin short fiber.

[0112] Short fibers generally refer to those called "staples" and do not include long fibers called "filaments". In addition, the length of short fibers is not particularly limited as long as it meets the definition of short fibers in this technical field, for example, 100 mm or less, preferably 30 mm or more and 70 mm or less.

[0113] (Adhesion treatment of the treatment agent) There is no particular limitation on the proportion of the treatment agent of the first embodiment adhering to the fiber. Preferably, the non-volatile component of the treatment agent is at least 0.01% by mass and less than 10% by mass relative to the fiber, more preferably at least 0.1% by mass and less than 3% by mass relative to the fiber. With this configuration, the effectiveness of each component can be effectively utilized. Furthermore, there is no particular limitation on the method of adhering the aqueous liquid; known methods can be used depending on the type, shape, and intended use of the fiber, such as roller oiling, guided oiling using a metering pump, impregnation oiling, spray oiling, etc. When using the impregnation oiling method, the impregnation time is preferably at least 1 minute and less than 5 minutes.

[0114] Fibers treated with an aqueous solution can also be dried or heated using known methods. Drying or heating causes solvents such as water to evaporate, thereby obtaining fibers with components contained in the treatment agent adhering to them. Fibers with components adhering to the treatment agent can effectively perform their functions as nonwoven fabrics.

[0115] (Manufacturing Method of Nonwoven Fabric) There is no particular limitation on the type of nonwoven fabric. For example, spunbond nonwoven fabric made using the spunbond method can be cited. In addition, carding web forming methods other than spunbond can be cited, such as dry methods like carding or air-jet methods, and wet methods like papermaking methods when the raw material fibers are short fibers. In addition, when the raw material fibers are long fibers, meltblowing or flash spinning can be cited. Furthermore, the bonding methods between fibers can be cited as chemical bonding, thermal bonding, needle bonding, water needle bonding, and stitch bonding.

[0116] The polyolefin synthetic fiber of this embodiment can also be used to manufacture nonwoven fabric by the following method. Specifically, nonwoven fabric can be obtained by the following steps.

[0117] Step 1: The step of attaching the treatment agent of the first embodiment to the polyolefin synthetic fiber.

[0118] Step 2: The step of passing the polyolefin synthetic fibers coated with the treatment agent in Step 1 through a carding machine to obtain a carded web. Step 2 is also called the carding step.

[0119] Step 3: The carding web obtained in Step 2 above is subjected to hot air treatment to fuse the fibers together and thus produce nonwoven fabric. Step 3 is also called the hot air penetration step.

[0120] Nonwoven fabric can be manufactured through the above steps. Nonwoven fabric obtained by the hot air penetration step is also called heat-bonded nonwoven fabric.

[0121] <Effects and Effects of the Third Embodiment> (3-1) The polyolefin synthetic fiber is coated with the treatment agent of the first embodiment. Therefore, the rate of change in friction can be reduced even after long-term storage. In addition, the frictional properties of the polyolefin synthetic fiber when wet can be improved.

[0122] Example

[0123] The following embodiments are provided to illustrate the structure and effects of the present invention in more detail, but the present invention is not limited to these embodiments. In the following description of the embodiments and comparative examples, parts represent parts by mass.

[0124] Test Category 1 (Preparation of fiber treatment agents for nonwoven fabrics)

[0125] (Example 1) As shown in Table 1, 23.2 parts (mass%) of phosphoric acid compound (A-1) and 16 parts (mass%) of (A-2) shown in Table 2 as phosphoric acid compound (A), 0.28 parts (mass%) of lauryl alcohol (B-1) and 0.28 parts (mass%) of octanol (B-2) as alcohol (B), 0.24 parts (mass%) of stearic acid (C-2) as fatty acid (C), and 30 parts (mass%) of polyoxyethylene (40 moles) triacontyl ether (D-1) and polyoxyethylene (50 moles) tetratetraalkyl ether (D-2) as nonionic surfactant (D) were diluted in a beaker with 900 parts of warm water at 70°C. The mixture was stirred until homogeneous to prepare a 10% (mass) aqueous solution of the nonwoven fabric fiber treatment agent of Example 1.

[0126] (Examples 2-25, Comparative Examples 1-14) The treatment agents of Examples 2-25 and Comparative Examples 1-14 were prepared in the same way as the treatment agent of Example 1, and contained phosphoric acid compound (A), alcohol (B), fatty acid (C), nonionic surfactant (D), and other components (E) in the proportions shown in Table 1.

[0127] The types and contents of phosphoric acid compounds (A), alcohols (B), fatty acids (C), nonionic surfactants (D), and other components (E) are shown in the columns “Phosphoric Acid Compounds (A),” “Alcohols (B),” “Fatty Acids (C),” “Nonionic Surfactants (D),” and “Others (E)” of Table 1, respectively. In addition, the value calculated according to mathematical formula (1), the acid value of the non-volatile components in the treatment agent, and the pH of a 1% by mass aqueous dilution of the treatment agent at 25°C are shown in the columns “Value of Mathematical Formula 1,” “Acid Value of Treatment Agent,” and “pH” of Table 1, respectively.

[0128] Table 1 Nonwoven fabric treatment agent Evaluation results Phosphoric acid compounds (A) alcohols (B) fatty acid (C) nonionic surfactants (D) other (E) The value of mathematical formula 1 Treatment agent acid value​ (KOH - mg / g) pH friction rate of change emulsification stability When moist friction Antifoaming properties Early stage hydrophilic durable hydrophilic type quality% type quality% type quality% type quality% type quality% Example 1 A-1 A-2 23.2 16 B-1 B-2 0.28 0.28 C-2 0.24 D-1 D-3 30 30 - - 0.17 10.6 6.7 3 3 3 3 3 3 Example 2 A-1 A-2 8 18 B-1 B-2 1 2 C-2 0.8 D-4 D-5 30 30.2 E-2 10 0.08 8.8 6.9 3 3 3 3 3 3 Example 3 A-2 61.5 B-1 B-2 0.5 0.5 C-1 0.5 D-2 D-3 16 16 E-5 E-6 3 2 0.26 19.9 7.1 3 3 3 3 3 3 Example 4 A-2 45 B-2 5 C-1 0.5 D-10 49.5 - - 0.19 15.0 7.0 3 3 3 3 3 3 Example 5 A-1 29.5 B-1 0.5 C-1 C-2 0.2 0.1 D-1 D-3 D-6 twenty five 24.7 5 E-2 E-3 10 5 0.14 7.6 7.3 3 3 3 3 3 3 Actual example 6 A-3 39.2 B-1 0.5 C-2 0.3 D-4 D-8 30 30 - - 0.22 19.6 7.3 3 3 3 3 3 3 Actual example 7 A-2 twenty five B-1 B-2 B-3 0.6 0.6 0.5 C-1 C-2 0.2 0.1 D-2 D-4 D-7 twenty five twenty five 18 E-4 5 0.11 7.7 7.2 3 3 3 3 3 3 Example 8 A-1 35 B-1 5 C-1 1.5 D-11 48.5 E-2 10 0.16 8.1 6.7 3 3 3 3 3 3 Example 9 A-2 30 B-1 0.5 C-1 1 D-2 D-4 D-10 28 28 12.5 - - 0.13 9.0 6.6 3 3 3 3 3 3 Example 10 A-1 98.6 B-1 0.3 C-1 1.1 - - - - 0.45 25.8 7.4 3 3 3 3 3 2 Example 11 A-3 96.5 B-1 2.5 C-2 1 - - - - 0.55 12.4 6.9 3 3 3 3 3 2 Example 12 A-1 A-2 58 40 B-1 B-2 1 1 - - - - - - 0.43 25.4 6.8 3 3 3 3 3 2 Example 13 A-1 A-2 58 40 B-1 B-2 0.7 0.7 C-2 0.6 - - - - 0.43 26.6 6.8 3 3 3 3 3 2 Example 14 A-2 90 B-2 10 - - - - - - 0.38 27.1 7.1 3 3 3 2 3 2 Example 15 A-1 99.7 B-1 0.3 - - - - - - 0.46 23.0 7.5 3 3 3 2 3 2 Example 16 A-3 99.8 B-1 0.2 - - - - - - 0.57 50.0 7.0 3 3 3 2 3 2 Example 17 A-9 28 B-2 2 - - D-1 D-3 30 40 - - 3.05 11.3 7.0 3 3 2 2 3 3 Example 18 A-8 49.5 B-2 0.5 - - D-4 D-9 25 25 - - 3.08 29.0 7.2 3 3 2 2 3 3 Example 19 A-7 92 B-1 8 - - - - - 2.85 52.0 6.4 3 3 2 2 3 2 Example 20​ A-4 94.5 B-1 5.5 - - - - - - 0.03 17.0 7.6 3 2 3 2 3 2 Example 21 A-5 93.5 B-2 6.5 - - - - - - 0.02 12.0 7.3 3 2 3 2 3 2 Example 22 A-6 98 B-1 B-3 1 1 - - - - - - 0.19 9.5 7.7 3 2 3 2 3 2 Example 23 A-5 76.5 B-2 23.5 - - - - - - 0.02 9.8 7.4 3 2 3 2 2 2 Example 24 A-8 99 B-2 1 - - - - - - 6.17 29.0 7.3 2 3 2 2 3 2 Example 25 A-8 81.2 B-2 18.8 - - - - - - 5.06 23.8 7.3 2 3 2 2 2 2 Comparative Example 1 A-15 100 - - - - - - - - 0.02 0.0 8.8 3 2 - 1 3 2 Comparative Example 2 A-10 100 - - - - - - - - 0.00 0.0 8.7 3 1 1 1 3 2 Comparative Example 3 A-11 100 - - - - - - - - 0.00 0.0 8.6 3 1 1 1 3 2 Comparative Example 4 A-9 99 B-1 1 - - - - - - 10.79 40.0 6.8 1 3 2 2 3 2 Comparative Example 5 A-1 100 - - - - - - - - 0.46 23.1 7.5 3 3 3 1 3 2 Comparative Example 6 A-10 100 - - - - - - - - 0.00 49.0 6.2 3 1 3 1 3 2 Comparative Example 7 A-10 A-11 40 25 - - - - D-4 30 E-1 5 0.00 31.1 6.0 3 1 3 1 3 3 Comparative Example 8 A-12 99.7 B-1 0.3 - - - - - - 0.46 2.0 8.1 3 3 1 2 3 2 Comparative Example 9 A-13 92 B-2 8 - - - - - - 0.13 25.0 9.8 3 1 3 3 1 1 Comparative Example 10 A-14 100 - - - - - - - - 0.31 0.0 8.9 3 3 1 1 3 1 Comparative Example 11 A-11 99 B-2 1 - - - - - - 0.00 0.0 8.6 3 1 1 1 3 2 Comparative Example 12 A-16 99.7 B-1 0.3 - - - - - - 0.03 100.0 4.7 3 1 3 2 3 2 Comparative Example 13 A-17 97 B-2 3 - - - - - - 0.44 25.0 7.7 3 3 1 3 1 1 Comparative Example 14 A-18 92 B-2 8 - - - - - - 0.13 60.0 7.9 3 1 3 2 1 1

[0129] The details of the phosphoric acid compound (A) shown in Table 1 are as follows.

[0130] <Phosphoric Acid Compound (A)> Phosphoric acid compound (A) uses A-1 to A-16 as described in Table 2. The types of phosphoric acid compound (A) are shown in the "Types of Phosphoric Acid Compound (A)" column of Table 2. In addition, the manufacturing conditions, acid value, and P-nuclear NMR integral ratio of phosphoric acid compound (A) are shown in the "Manufacturing Conditions (A / B / C / D)" column, the "Acid Value of Phosphoric Acid Compound (A)" column, and the "P-nuclear NMR Integral Ratio (%)" column of Table 2, respectively.

[0131] Table 2 Types of phosphoric acid compounds (A) Manufacturing conditions (A / B / C / D) Acid value of phosphoric acid compound (A) (KOH - mg / g) P-core NMR integration percentage (%) Phosphate P1 Phosphate P2 Phosphate P3 Phosphate P4 Phosphate P5 orthophosphoric acid A-1 Lauryl phosphate and its potassium salt A 23.1 0.00 0.46 13.82 45.61 38.13 1.98 A-2 Octyl phosphate and its potassium salt A 30.1 0.00 0.42 17.15 39.52 40.17 2.74 A-3 Lauryl phosphate and its potassium salt A 50.1 0.00 0.57 16.32 48.16 31.89 3.06 A-4 Lauryl phosphate and its potassium salt A 18.0 0.00 0.03 4.66 58.45 34.33 2.53 A-5 Octyl phosphate and its potassium salt A 12.8 0.00 0.02 3.85 62.88 32.14 1.11 A-6 Lauryl phosphate and its potassium salt A 9.7 0.00 0.19 0.86 60.22 33.24 5.49 A-7 Lauryl phosphate and its potassium salt B 56.5 0.83 1.43 35.49 26.47 26.54 9.24 A-8 Octyl phosphate and its potassium salt B 29.3 1.60 3.03 30.33 28.80 29.24 7.00 A-9 Lauryl phosphate and its potassium salt C 40.4 0.00 10.90 29.10 25.00 34.00 1.00 A-10 Potassium lauryl phosphate D 0.0 0.00 0.00 0.00 69.18 26.61 4.21 A-11 Potassium octyl phosphate D 0.0 0.00 0.00 0.00 71.45 23.74 4.81 A-12 Lauryl phosphate and its potassium salt A 2.0 0.00 0.46 13.82 45.61 38.13 1.98 A-13 Stearyl phosphate and its potassium salt B 27.2 0.01 0.12 7.19 49.82 38.50 4.36 A-14 Lauryl phosphate and its potassium salt A 0.0 0.00 0.31 9.69 39.90 50.00 0.10 A-15 Octyl phosphate and its potassium salt A 0.0 0.00 0.02 3.85 62.88 32.14 1.11 A-16 Lauryl phosphate and its potassium salt A 100.3 0.00 0.03 4.66 58.45 34.33 2.53 A-17 Butyl phosphate and its potassium salt A 25.8 0.00 0.45 18.35 32.40 23.80 25.00 A-18 Stearyl phosphate and its potassium salt A 65.2 0.01 0.12 7.19 49.82 38.50 4.36

[0132] The detailed manufacturing conditions A to D for the phosphoric acid compound (A) shown in Table 2 are shown in Table 3. In Table 3, the "Alcohol Dehydration" column indicates whether the raw material alcohol is dehydrated. The "Synthesis Environment" column indicates the atmosphere of the phosphorylation reaction. The "Phosphorylation Conditions" column indicates the temperature and time of the phosphorylation reaction. The "Addition of Water After Phosphorylation" column indicates whether water is added after the phosphorylation reaction. The "Neutralization Conditions" column indicates the temperature and time for the neutralization of the phosphate.

[0133] Table 3 Manufacturing conditions alcohol dehydration Synthetic environment Phosphorylation conditions Phosphorylation followed by hydrogenation Neutralization conditions A have N2 70±3℃×3h none 90±3℃×6h B none atmosphere 70±3℃×3h none 90±3℃×6h C none atmosphere 70±3℃×3h none 70±3℃×3h D none atmosphere 70±3℃×3h 1.8% by weight 70±3℃×3h

[0134] Further details of the manufacturing conditions A to D for the phosphoric acid compound (A) are shown below.

[0135] (Manufacturing Condition A) In Manufacturing Condition A, the raw material alcohol is one that has been dehydrated under reduced pressure at 105°C. The raw material alcohol is packed into a four-necked flask, and phosphorus pentoxide is slowly added to it under a nitrogen atmosphere. The mixture is stirred at 70±3°C for 3 hours to carry out a phosphorylation reaction. The phosphate obtained from the phosphorylation reaction is slowly packed into an aqueous solution of potassium hydroxide and stirred at 90±3°C for 6 hours to neutralize the phosphate, thereby synthesizing a phosphate ester compound.

[0136] (Manufacturing Condition B) In Manufacturing Condition B, the raw material alcohols are used directly after opening the reagent vials. The phosphorylation reaction is carried out under atmospheric conditions. Phosphorus pentoxide is placed under atmospheric conditions (room temperature: approximately 27°C, relative humidity: approximately 80%) from the time the reagent vials are opened until they are completely added. The time from the start to the end of the phosphorus pentoxide addition is approximately 30 minutes. Otherwise, phosphate ester compounds are synthesized under the same conditions as in Manufacturing Condition A.

[0137] (Manufacturing Condition C) In Manufacturing Condition C, the raw material alcohols are used directly after opening the reagent vials. The phosphorylation reaction is carried out under atmospheric conditions. Phosphorus pentoxide is placed under atmospheric conditions (room temperature: approximately 27°C, relative humidity: approximately 80%) from the time the reagent vials are opened until they are completely added. The phosphorylation reaction is carried out by stirring at 70±3°C for 3 hours. The phosphate obtained from the phosphorylation reaction is slowly added to an aqueous solution of potassium hydroxide and stirred at 70±3°C for 3 hours to neutralize the phosphate. Otherwise, phosphate ester compounds are synthesized under the same conditions as in Manufacturing Condition A.

[0138] (Manufacturing Condition D) In ​​Manufacturing Condition D, the raw material alcohol is used directly after opening the reagent vial. The phosphorylation reaction is carried out under atmospheric conditions. Phosphorus pentoxide is placed under atmospheric conditions (room temperature: approximately 27°C, relative humidity: approximately 80%) from the time the reagent vial is opened until it is completely added. It takes approximately 30 minutes from the start to the end of the addition of phosphorus pentoxide. The phosphorylation reaction is carried out by stirring at 70±3°C for 3 hours. After the phosphorylation reaction is completed, 1.8% by mass of water (the total amount of raw material alcohol and phosphorus pentoxide) is added, and the mixture is stirred at 70±3°C for 1 hour to obtain a phosphate compound. The obtained phosphate compound is slowly added to an aqueous solution of potassium hydroxide and stirred at 70±3°C for 3 hours to neutralize the phosphate compound. Otherwise, phosphate ester compounds are synthesized under the same conditions as in Manufacturing Condition A.

[0139] Among these manufacturing conditions A to D, the ratio of the raw material alcohol to phosphorus pentoxide or the neutralization conditions of the phosphate compound can be appropriately adjusted within the scope of common technical knowledge. By adjusting these conditions, the composition of the synthesized phosphate ester compound can be adjusted even under the same manufacturing conditions. Specifically, the ratio of phosphate esters P1 to P5 and orthophosphoric acid contained in the phosphate compound (A) can be adjusted.

[0140] The P-nuclear NMR integral ratio of the phosphoric acid compound (A) shown in Table 2 was determined by the following method.

[0141] (Method for determining the P-nuclear NMR integral ratio) To determine the P-nuclear NMR integral ratio of phosphate compound (A), a pretreatment is first performed by adding excess KOH to phosphate compound (A) to make the pH 12 or higher. This pretreatment allows for clear differentiation of the peaks associated with phosphate esters P1, P2, P3, P4, and P5, as well as orthophosphate and its salts, in 31P-NMR measurements.

[0142] The P-core NMR integration ratio is 31P-NMR (Valian Corporation trade name MERCURY plus NMR Spectrometer System, 300MHz).

[0143] The solvent is a mixed solvent of heavy water / tetrahydrofuran = 8 / 2 (volume ratio).

[0144] Among the obtained signals, the integral value of the single signal appearing in the range of -3ppm to -7ppm corresponds to the P atom in P1.

[0145] The sum of the integral values ​​of the dual signals appearing in the range of -3ppm to -7ppm and the integral values ​​of the dual signals appearing in the range of -7ppm to -11ppm corresponds to the P atoms in P2.

[0146] The integral value of a single signal appearing in the range of -7ppm to -14ppm corresponds to the P atom in P3.

[0147] The integral value of a single signal appearing at 3ppm to 7ppm corresponds to the P atom in P4.

[0148] The integral value of a single signal appearing in the range of -1ppm to 4ppm corresponds to the P atom in P5.

[0149] The integral value of the signal appearing in the range of 4 ppm to 10 ppm corresponds to the P atom in the orthophosphate and its salt.

[0150] When the above-mentioned value detects a signal with repeated range, signals originating from the corresponding orthophosphoric acid and its salt, phosphate esters P4, P5, P2 (-3ppm to -7ppm), P1, P2 (-7ppm to -11ppm), and P3 will be detected sequentially from the low magnetic field side.

[0151] The total proportion of the NMR integral of the P nuclei to which phosphate ester P1, phosphate ester P2, phosphate ester P3, phosphate ester P4, phosphate ester P5, and orthophosphate and its salts belong can be set to 100%, and the value according to the above mathematical formula (1) can be calculated.

[0152] The acid value of the phosphoric acid compound (A) shown in Table 2 was determined by the following method.

[0153] (Method for determining acid value) The phosphoric acid compound (A) is dissolved in a mixed solvent of ethanol / xylene = 1 / 2 (volume ratio), and then set on a potentiometric titration apparatus for titration with a 0.1 mol / L potassium hydroxide methanol standard solution. The acid value is calculated using the same mathematical formula as for the determination of the acid value of the above-mentioned treatment agent. The acid value of the phosphoric acid compound can be adjusted, for example, by the degree of neutralization when the phosphoric acid compound is obtained (see, for example, paragraph

[0044] of Japanese Patent No. 7055512).

[0154] (pH Measurement Method) The treatment agent of each example was diluted with water to prepare a 1% by mass aqueous solution. The pH of the prepared 1% by mass aqueous solution at 25°C was measured using a known pH meter (Horiba Manufacturing Co., Ltd., desktop pH meter F-72) in a conventional manner.

[0155] The details of the alcohols (B) shown in Table 1 are as follows.

[0156] <Alcohols (B)> B-1: Lauryl alcohol B-2: Octyl alcohol B-3: Stearyl alcohol

[0157] The details of the fatty acids (C) shown in Table 1 are as follows.

[0158] <Fatty Acids (C)> C-1: Lauric Acid C-2: Stearic Acid

[0159] The details of the nonionic surfactants (D) shown in Table 1 are as follows.

[0160] <Nonionic Surfactant (D)> D-1: Polyoxyethylene (40 moles) triacontyl ether D-2: Polyoxyethylene (50 moles) tetratetraalkyl ether D-3: Pentaglyceryl monooctadecanoic acid D-4: Tetraglyceryl monooctadecanoic acid D-5: Polyoxyethylene (10 moles) octadecanoic acid D-6: Polyoxyethylene (20 moles) oil ether D-7: Polyoxyethylene (10 moles) hardened castor oil ether D-8: Polyoxyethylene (15 moles) dehydrated sorbitan monolaurate D-9: Polyoxyethylene (20 moles) dehydrated sorbitan stearate D-10: Polyoxyethylene (10 moles) coconut fatty acid ester D-11: Polyoxyethylene (15 moles) palm fatty acid ester

[0161] The details of the other components (E) shown in Table 1 are as follows.

[0162] <Other Ingredients (E)> E-1: Lactic Acid E-2: Sodium Dioctyl Sulfosuccinate E-3: Sodium Dodecyl Sulfonate

[0163] Other components (E) may also be E-4 to E-6 shown in Table 4 (all of which are polyether modified polysiloxane).

[0164] Table 4 Polyether Modification Types of polysiloxane polyether end of the modified group Si% EO% kinematic viscosity average quality molecular weight (Mollbi) (mm 2 / s, 25℃) E-4 Acetyl 50 100 270 3600 E-5 Me base 35 15 500 14700 E-6 n-Bu base 17 45 1700 48000

[0165] In Table 4, "Me-group" and "n-Bu-group" refer to methyl and n-butyl groups, respectively. "Si%" refers to the mass ratio of the alkyl group after deducting the mass average molecular weight of the polyether-modified polysiloxane. "EO% (molar ratio)" refers to the molar ratio of ethylene oxide in the alkyl group. For example, when the alkyl group contains ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO), the EO% (molar ratio) can be calculated using the following formula.

[0166] EO% (Morb) = (EO mol number / (EO mol number + PO mol number)) × 100

[0167] Test Category 2 (Adhesion of nonwoven fiber treatment agents to polyolefin synthetic fibers)

[0168] A polyolefin composite fiber (2.2 dtex fineness, 51 mm length) with a polyethylene sheath and a polyester core was prepared. A 10% by mass aqueous solution of each treatment agent prepared in Test Category 1 was diluted with water to a 0.4% by mass aqueous solution and sprayed onto 100 g of the fiber, resulting in an adhesion amount of 0.40% as a non-volatile component. The fiber was then dried in a hot air dryer at 80°C for 2 hours, and then conditioned overnight at 20°C and 65% RH to obtain the polyolefin composite fiber with the treatment agent.

[0169] Test Category 3 (Production of heat-fused nonwoven fabric)

[0170] 100g of polyolefin composite fibers coated with a treatment agent were conditioned for 24 hours in a constant temperature chamber at 20°C and 65% RH. The conditioned polyolefin composite fibers coated with the treatment agent were then passed through a roller carding machine to produce a carded web with a basis weight of 20g / m2. The obtained carded web was subjected to hot air treatment at 140°C for 10 seconds to obtain a heat-fused nonwoven fabric.

[0171] Test Category 4 (Initial Hydrophilicity)

[0172] The heat-bonded nonwoven fabric obtained in test category 3 was conditioned for 24 hours in a constant temperature chamber at 20°C and 65% RH. Then, it was placed on a horizontal plate, and 0.4 mL of water was added from a height of 10 mm using a burette. The time required for the water droplet to be completely absorbed was determined and evaluated using the following evaluation criteria.

[0173] ・Evaluation criteria for initial hydrophilicity 3 (Good): Water penetration time less than 3 seconds 2 (Fair): Water penetration time more than 3 seconds but less than 6 seconds 1 (Poor): Water penetration time more than 6 seconds

[0174] Test Category 5 (Durability and Hydrophilicity)

[0175] The heat-fused nonwoven fabric obtained in test category 3 was cut into 10cm × 10cm pieces and conditioned for 24 hours in a constant temperature chamber at 20°C and 65% RH. The conditioned heat-fused nonwoven fabric was placed on top of five overlapping filter papers, and a cylinder with an inner diameter of 1cm and open at both ends was vertically erected in the center above it. 5mL of 0.9% physiological saline was then injected into the cylinder. The time required for the saline to be completely absorbed by the heat-fused nonwoven fabric was measured. The heat-fused nonwoven fabric was then removed and dried in an air-dried state at 40°C for 90 minutes. The same operation was repeated a total of 2 times, and the time of the second time was evaluated using the following evaluation criteria.

[0176] ・Evaluation criteria for durable hydrophilicity 3 (Good): The time required for physiological saline to be absorbed is less than 5 seconds 2 (Fair): The time required for physiological saline to be absorbed is more than 5 seconds but less than 10 seconds 1 (Poor): The time required for physiological saline to be absorbed is more than 10 seconds

[0177] Test Category 6 (High Temperature and High Humidity Treatment)

[0178] Polyolefin composite fibers coated with a treatment agent are aged in a constant temperature chamber at 70°C and 90% RH for 48 hours to obtain polyolefin composite fibers coated with a treatment agent that have undergone high temperature and high humidity treatment after long-term storage (hereinafter referred to as high temperature and high humidity treated fibers). In this invention, long-term storage means storage for more than 48 hours.

[0179] Test Category 7 (Friction Change Rate after Long-Term Storage)

[0180] 20g of high-temperature and high-humidity treated fiber and 20g of untreated polyolefin composite fiber with a treatment agent were conditioned in a constant temperature chamber at 20°C and 65% RH for 24 hours, and then sent to a micro carding machine to produce a carding web. The carding web was then sent to a micro sliver raker to obtain a sliver with a g / m ratio of 3 g / m. For the sliver under the above two conditions, the draft force was measured when the sliver was drafted at a sliver speed of 1 m / min and a draft ratio of 1.5, and the friction change rate with and without high-temperature and high-humidity treatment was calculated according to the following mathematical formula. The results are evaluated using the following evaluation criteria. The results are shown in the "Friction Change Rate" column of Table 1.

[0181] [Frictional Change Rate] = [Tension of polyolefin composite fibers with treatment agents but without high temperature and humidity treatment] / [Tension of fibers treated with high temperature and humidity] × 100

[0182] ・Evaluation criteria for friction change rate: 3 (Good): Friction change rate less than 5%; 2 (Fair): Friction change rate more than 5% but less than 10%; 1 (Poor): Friction change rate more than 10%.

[0183] Test Category 8 (Emulsion Stability)

[0184] 300 mg of calcium carbonate was dissolved in 1 L of distilled water to prepare hard water with a hardness of 300. Using the hard water with a hardness of 300, an aqueous solution with a concentration of 10% by mass of the treatment agent in each example was prepared. This aqueous solution was then diluted with hard water to prepare an aqueous solution with a concentration of 0.3% by mass of non-volatile components. The above aqueous solution was heated in a constant temperature room at 20°C for 24 hours, and then the state of the aqueous solution was visually confirmed. The results were evaluated using the following evaluation criteria. The results are shown in the "Emulsification Stability" column of Table 1.

[0185] ・Emulsion stability evaluation criteria 3 (Good): No precipitation or particles 2 (Fair): No precipitation but particles 1 (Poor): Precipitation present

[0186] Test Category 9 (Frictional Properties under Wet Conditions)

[0187] Dilute 10% by mass of the aqueous solution of the treatment agent prepared in test category 1 with ion-exchanged water to prepare a 0.35% by mass aqueous solution. Pour 80 mL of the prepared 0.35% by mass aqueous solution onto a metal pad measuring 60 mm in length, 230 mm in width, and 20 mm in height.

[0188] Prepare a rectangular plate-shaped weight, 30mm long × 90mm wide × 45mm high, weighing 1kg. Use double-sided tape to attach a piece of polyester spunbond nonwoven fabric of the same size as the bottom surface of the weight. Place the weight on a pad containing the above-mentioned 0.35% by mass aqueous solution, with the side with the polyester spunbond nonwoven fabric attached as the bottom side.

[0189] A tensile test was performed using a tensile testing machine (manufactured by Shimadzu Corporation, Autograph type AGS-X) equipped with a force gauge with a maximum load capacity of 50N, under conditions of pulling the weight at a horizontal speed of 100mm / min in an atmosphere of 20°C and 60%RH.

[0190] The frictional characteristics between the fiber and the metal during wetting were evaluated using the method described above. Specifically, the frictional characteristics between the fiber and the metal roller during the spinning or drawing steps were evaluated using the method described above. The evaluation of the frictional characteristics was conducted within 12 hours of preparing the 0.35% by mass aqueous solution. When the treatment agent of Comparative Example 1 was used, the friction between the fiber and the metal during wetting was relatively high. Therefore, the following evaluation criteria were used as a benchmark based on Comparative Example 1. The results are shown in the "Friction during wetting" column of Table 1.

[0191] ・Evaluation criteria for frictional properties under wet conditions 3 (Good): The ratio between the friction N measured using the 0.35% by mass aqueous solution of Comparative Example 1 and the friction M measured using the 0.35% by mass aqueous solution of each example, i.e., the M / N ratio, is 0.98 or less 2 (Fair): The above M / N ratio is greater than 0.98, but less than 0.99 1 (Poor): The above M / N ratio is greater than 0.99

[0192] Test Category 10 (Foam Suppression)

[0193] A 10% by mass aqueous solution of the treatment agent prepared in Test Category 1 was diluted with deionized water to prepare a 0.25% by mass aqueous solution. 25g of the prepared aqueous solution was placed in a 100mL stoppered graduated cylinder and vigorously shaken 30 times within 30 seconds, then allowed to stand for 30 seconds, and then vigorously shaken 30 times again within 30 seconds. After standing for 5 minutes, the height H1 from the water surface to the top surface of the foam was measured. The following evaluation criteria were used for evaluation. The results are shown in the "Foam Suppression" column of Table 1.

[0194] ・Evaluation criteria for foam suppression: 3 (Good): H1≦10.0cm 2 (Fair): 10.0cm

[0195] Test Category 11 (Acid Value of the Treatment Agent)

[0196] The acid value of the treatment agent was determined by JIS K 0070-1992 "3.2 Potentiometric titration". The solvent used was a mixture of ethanol and xylene. The results are shown in the "Acid Value of Treatment Agent" column of Table 1.

[0197] Test Category 12 (pH of the treatment agent)

[0198] The treatment agents of each example were diluted to prepare a 1% by mass aqueous solution as a treatment agent. The pH of the prepared 1% by mass aqueous solution at 25°C was measured using a known pH meter (Horiba Manufacturing Co., Ltd., desktop pH meter F-72).

[0199] As shown in Table 1, the treatment agent of Comparative Example 1 does not contain alcohol (B) and its acid value is outside the range of values ​​of the present invention, and it was confirmed that its foam suppression performance was poor. ​

[0200] The treatment agents in Comparative Examples 2 and 3 do not contain alcohols (B), and the phosphoric acid compound (A) does not contain phosphate ester P3. Furthermore, the integral ratio of phosphate ester P4 is outside the numerical range of the present invention. Consequently, the acid value is also outside the numerical range of the present invention, and it has been confirmed that the emulsification stability, friction characteristics when wetted, and antifoaming properties are all poor.

[0201] In the treatment agent of Comparative Example 4, the value calculated according to mathematical formula (1) is outside the value range of the present invention, and it was confirmed that the friction change rate was not good.

[0202] The treatment agent in Comparative Example 5 does not contain alcohol (B), and it was confirmed that its defoaming properties were poor.

[0203] The treatment agents in Comparative Examples 6 and 7 do not contain alcohols (B), and the phosphoric acid compound (A) does not contain phosphate ester P3. Furthermore, the integral ratio of phosphate ester P4 is also outside the numerical range of the present invention, and it was confirmed that the emulsification stability and antifoaming properties are both poor.

[0204] In the treatment agent of Comparative Example 8, the acid value was outside the range of values ​​of the present invention, and it was confirmed that the friction characteristics were poor when wet.

[0205] In the treatment agent of Comparative Example 9, the number of carbon atoms of the alkyl groups in the phosphate esters P3 to P5 contained in the phosphate compound (A) is outside the numerical range of the present invention, and it was confirmed that the emulsion stability, initial hydrophilicity and durable hydrophilicity are all poor.

[0206] The treatment agent of Comparative Example 10 does not contain alcohols (B), and the integral proportion of phosphate ester P5 contained in the phosphate compound (A) is outside the numerical range of the present invention. Consequently, the acid value is also outside the numerical range of the present invention, and it was confirmed that the frictional properties, antifoaming properties, and durable hydrophilicity are all poor when wetted.

[0207] In the treatment agent of Comparative Example 11, the phosphoric acid compound (A) did not contain phosphate ester P3. Furthermore, the integral ratio of phosphate ester P4 was outside the numerical range of the present invention. Consequently, the acid value was also outside the numerical range of the present invention, and it was confirmed that the emulsification stability, friction characteristics when wetted, and antifoaming properties were all poor.

[0208] In the treatment agent of Comparative Example 12, the acid value was outside the range of values ​​of the present invention, and it was confirmed that the emulsification stability was poor.

[0209] In the treatment agent of Comparative Example 13, the carbon number of the carbon chain of the phosphate compound (A) is less than 8, and it was confirmed that the friction characteristics, initial hydrophilicity and durable hydrophilicity are all poor when wetted.

[0210] In the treatment agent of Comparative Example 14, the carbon number of the carbon chain of the phosphate compound (A) exceeded 12, and it was confirmed that the emulsion stability, initial hydrophilicity and durable hydrophilicity were all poor.

[0211] On the other hand, the treatment agent according to the present invention can improve the rate of frictional change after long-term storage, emulsion stability, frictional characteristics when wet, and antifoaming properties. Furthermore, it can also improve initial hydrophilicity and durable hydrophilicity. Therefore, nonwoven fabrics containing fibers coated with the treatment agent can be preferably used in sanitary materials, etc.

Claims

1. A fiber treatment agent for nonwoven fabrics, comprising the following phosphoric acid compound (A) and the following alcohol (B), characterized in that: in the P-nuclear NMR determination of the above-mentioned fiber treatment agent for nonwoven fabrics during alkaline excess neutralization pretreatment, when the total P-nuclear NMR integral ratios of phosphate ester P1, phosphate ester P2, phosphate ester P3, phosphate ester P4, phosphate ester P5, orthophosphate and their salts are set to 100%, the P-nuclear NMR integral ratio of phosphate ester P4 is 20% or more and 65% or less, the P-nuclear NMR integral ratio of phosphate ester P5 is 20% or more and 45% or less, the value calculated according to the following mathematical formula (1) is 8 or less, the pH of a 1% by mass aqueous dilution of the above-mentioned fiber treatment agent for nonwoven fabrics at 25°C is 5.0 or more and 8.0 or less, and the acid value of the non-volatile component in the above-mentioned fiber treatment agent for nonwoven fabrics is 5 KOH-mg / g or more and less than 60 KOH-mg / g. Phosphoric acid compound (A): containing phosphate ester P3 of general formula (3), phosphate ester P4 of general formula (4), phosphate ester P5 of general formula (5), and orthophosphoric acid, and further optionally containing at least one of phosphate ester P1 of general formula (1) and phosphate ester P2 of general formula (2), (in general formula (1), M1, M2, M3: hydrogen atom, alkali metal, alkaline earth metal (1 / 2), organic amine, ammonium, or phosphonium) (in general formula (2), R1: alkyl or alkenyl with 8 to 12 carbon atoms, M4, M5: hydrogen atom, alkali metal, alkaline earth metal (1 / 2), organic amine, ammonium, or phosphonium) (in general formula (3), R2, R3: alkyl or alkenyl with 8 to 12 carbon atoms, M6: hydrogen atom, alkali metal, alkaline earth metal (1 / 2), organic amine, ammonium, or phosphonium) (in general formula (4), R4: Alkyl or alkenyl groups with 8 to 12 carbon atoms, M7, M8: Hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium) (In general formula (5), R5, R6: Alkyl or alkenyl groups with 8 to 12 carbon atoms, M9: Hydrogen atoms, alkali metals, alkaline earth metals (1 / 2), organic amines, ammonium, or phosphonium) {[NMR integral ratio of P nucleus to which phosphate ester P1 belongs} × 2 + [NMR integral ratio of P nucleus to which phosphate ester P2 belongs]} × [Concentration (mass%) of phosphate compound (A) in nonwoven fiber treatment agent] / 100 … (1) Alcohols (B): Aliphatic alcohols with 8 to 18 carbon atoms.

2. The nonwoven fabric fiber treatment agent as claimed in claim 1, wherein the value obtained according to the above mathematical formula (1) is 3.5 or less.

3. The nonwoven fabric fiber treatment agent as claimed in claim 1, wherein the NMR integral of the P nucleus to which the above-mentioned phosphate ester P3 belongs is 6.5% to 40%.

4. The nonwoven fiber treatment agent as claimed in claim 1, wherein the total percentage of the NMR integral of the P-nuclei to which the phosphate ester P2 and the phosphate ester P3 belong is greater than 0% and less than 20%.

5. The nonwoven fabric fiber treatment agent as claimed in claim 1, wherein when the content ratio of the above-mentioned phosphoric acid compound (A) and the above-mentioned alcohol (B) is set to 100% by mass, the content ratio of the above-mentioned phosphoric acid compound (A) is 85% to 99.9% by mass and the above-mentioned alcohol (B) is 0.1% to 15% by mass.

6. The nonwoven fabric fiber treatment agent as claimed in claim 1, wherein at least one of the following two conditions is met: Condition 1: contains two or more of the above-mentioned alcohols (B) with different carbon numbers; Condition 2: contains fatty acids (C) with 12 to 20 carbon numbers.

7. The nonwoven fabric fiber treatment agent as claimed in claim 1, further comprising a nonionic surfactant (D) selected from at least one of the following: a compound formed by adding 1 mole of a monohydric aliphatic alcohol having 22 to 50 carbon atoms to an epoxy alkane having 2 to 4 carbon atoms in total of 5 to 100 moles; and an ester compound formed by polyglycerol having a degree of condensation of 3 to 12 and a saturated fatty acid having 12 to 18 carbon atoms.

8. The nonwoven fabric fiber treatment agent as claimed in claim 7, wherein when the content ratio of the above-mentioned phosphoric acid compound (A), the above-mentioned alcohol (B), and the nonionic surfactant (D) is set to 100% by mass, the content ratio of the above-mentioned phosphoric acid compound (A) is 20% to 80% by mass, the above-mentioned alcohol (B) is 0.1% to 10% by mass, and the nonionic surfactant (D) is 10% to 75% by mass.

9. An aqueous liquid of a fiber treatment agent for nonwoven fabrics, characterized in that: the concentration of non-volatile components in the fiber treatment agent for nonwoven fabrics according to any one of claims 1 to 8 is 0.1% by mass or more and 10% by mass or less.

10. A fiber, characterized in that: it is coated with any one of claims 1 to 8 as a nonwoven fiber treatment agent.

11. The fiber as claimed in claim 10, wherein the fiber is a polyolefin synthetic fiber.