Nonwoven fabric treatment agents and fibers

Abstract

The present invention provides a nonwoven fabric treating agent for imparting water repellency, which can improve emulsion stability and can improve the wettability of the nonwoven fabric treating agent to fibers, and fibers using the same. The nonwoven fabric treatment agent of the present invention contains the following phosphoric acid compound (P) and the following alcohol (A), and has the following P nucleus NMR integral values ​​N Pa , N Pi Ratio of (N Pi / N Pa ) is 0.6 or more, and the acid value of the nonwoven fabric treating agent is 0.5 mgKOH / g or more and 100 mgKOH / g or less. The phosphoric acid compound (P) is a phosphoric acid compound containing a phosphoric acid ester (Pa), a phosphoric acid ester (Pb), an inorganic phosphoric acid (Pi), or the like, represented by a given formula. The alcohol (A) is a monohydric to trihydric alcohol having 3 or more and 6 or less carbon atoms.

Description

[Technical field]

[0001] The present invention relates to a treatment agent for nonwoven fabrics for imparting water repellency, which can improve emulsion stability, etc., and to fibers to which the treatment agent has been applied. [Background technology]

[0002] Generally, synthetic fibers are used as raw fibers for nonwoven fabrics. For example, nonwoven fabrics are manufactured using synthetic fibers composed of thermoplastic resins such as polyolefins. A treatment agent is applied to the raw fibers used for the nonwoven fabric or to the nonwoven fabric to impart functions such as water repellency. Nonwoven fabrics imparted with functions such as water repellency are used in a wide range of fields, including hygiene products, medical care, agriculture, and civil engineering.

[0003] For example, a conventional fiber treatment agent is disclosed in Patent Document 1. Patent Document 1 discloses a water-repellent fiber treatment agent that contains a specific phosphate ester and has an acid value of 0.5 to 680 mgKOH / g. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 7025594 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional nonwoven fabric treating agents for imparting water repellency have the problem that not only does the emulsion stability decrease, but the wettability of the nonwoven fabric treating agent to fibers also decreases. [Means for solving the problem]

[0006] As a result of research conducted by the present inventors to solve the above-mentioned problems, it was found that a composition in which the acid value of a nonwoven fabric treatment agent containing a specified phosphoric acid compound (P) and an alcohol (A) is specified within a specified range is precisely suitable.

[0007] Various aspects for solving the above problems will be described below. The nonwoven fabric treatment agent of the first embodiment contains the following phosphoric acid compound (P) and the following alcohol (A): When the total content of the phosphoric acid compound (P) and the alcohol (A) is taken as 100 mass%, the phosphoric acid compound (P) is contained in an amount of 70 mass% or more and 98.7 mass% or less, and the alcohol (A) is contained in an amount of 1.3 mass% or more and 30 mass% or less, and the content of compounds other than the phosphoric acid compound (P) and the alcohol (A) is 10 mass% or less. The nonwoven fabric treatment agent has the following phosphoric acid ester (Pa) and the following inorganic phosphoric acid (Pi) respectively having the P nucleus NMR integral value N Pa , N Pi Ratio of (N Pi / N Pa ) is 0.6 or more, and the acid value of the nonwoven fabric treating agent is 0.5 mgKOH / g or more and 100 mgKOH / g or less.

[0008] Phosphate compound (P): Contains a phosphate ester (Pa) represented by the following formula (1), a phosphate ester (Pb) represented by the following formula (2), and inorganic phosphoric acid (Pi), and optionally contains at least one selected from a phosphate ester (Pc) represented by the following formula (3), and a phosphate ester (Pd) represented by the following formula (4): When the sum of the P nucleus NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio attributable to the inorganic phosphoric acid (Pi) is 55% or less, and the P nucleus NMR integral ratio attributable to the phosphate ester (Pa) is 5% or more. A phosphate compound.

[0009] [ka] (In formula (1), R 1 : A hydrocarbon group having 3 to 5 carbon atoms. A 1 O: an alkyleneoxy group having 2 to 4 carbon atoms. n1: An integer between 0 and 3. M 1 ,M 2 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine.

[0010] [ka] (In formula (2), R 2 ,R 3 : A hydrocarbon group having 3 to 5 carbon atoms. A 2 O,A 3 O: an alkyleneoxy group having 2 to 4 carbon atoms. n2, n3: Integers between 0 and 3. M 3 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine.

[0011] [ka] (In formula (3), Q 1 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, organic amine, or -(A 5 O) n5 R 5 . R 4 ,R 5 : A hydrocarbon group having 3 to 5 carbon atoms. A 4 O,A 5 O: an alkyleneoxy group having 2 to 4 carbon atoms. n4, n5: Integers between 0 and 3. M 4 ,M 5 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine.

[0012] [ka] (In formula (4), R 6 ,R 7 ,R 8 : A hydrocarbon group having 3 to 5 carbon atoms. A 6 O,A 7 O,A 8 O: an alkyleneoxy group having 2 to 4 carbon atoms. n6, n7, n8: Integers between 0 and 3. Alcohol (A): Monohydric to trihydric alcohols with 3 to 6 carbon atoms.

[0013] In aspect 2, in the treatment agent for nonwoven fabric according to aspect 1, when the sum of the P nucleus NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio attributable to the inorganic phosphoric acid (Pi) is 25% or more.

[0014] In aspect 3, in the treatment agent for nonwoven fabric according to aspect 1 or 2, when the sum of the P nucleus NMR integral ratios assigned to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio assigned to the phosphate ester (Pc) is 15% or more.

[0015] In aspect 4, in the treatment agent for nonwoven fabric according to any one of aspects 1 to 3, when the sum of the P nucleus NMR integral ratios assigned to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio assigned to the phosphate ester (Pa) is less than 20%.

[0016] Aspect 5 is a treatment agent for nonwoven fabric according to any one of Aspects 1 to 4, in which the phosphoric acid compound (P) is contained in an amount of 80% by mass or more and 97% by mass or less, and the alcohol (A) is contained in an amount of 3% by mass or more and 20% by mass or less, assuming that the total content of the phosphoric acid compound (P) and the alcohol (A) is 100% by mass.

[0017] The fiber of the sixth aspect is characterized in that the treating agent for nonwoven fabric according to any one of the first to fifth aspects is adhered to the fiber. Effect of the Invention

[0018] According to the present invention, in a treatment agent for nonwoven fabrics for imparting water repellency, it is possible to improve the emulsion stability and also improve the wettability of the treatment agent for nonwoven fabrics to fibers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] First Embodiment A first embodiment of the treatment agent for nonwoven fabrics (hereinafter, simply referred to as the treatment agent) of the present invention will be described below. The treatment agent of this embodiment contains the following phosphoric acid compound (P) and the following alcohol (A).

[0020] (Phosphate Compounds (P)) The phosphoric acid compound (P) provided in this embodiment contains a phosphoric acid ester (Pa) represented by the following formula (1), a phosphoric acid ester (Pb) represented by the following formula (2), and inorganic phosphoric acid (Pi), and optionally further contains at least one selected from a phosphoric acid ester (Pc) represented by the following formula (3) and a phosphoric acid ester (Pd) represented by the following formula (4).

[0021] The phosphate ester (Pa) is a compound represented by the following formula (1).

[0022] [ka] (In formula (1), R 1 : A hydrocarbon group having 3 to 5 carbon atoms. A 1 O: an alkyleneoxy group having 2 to 4 carbon atoms. n1: An integer between 0 and 3. M 1 ,M 2 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. In addition, since alkaline earth metals are divalent, alkaline earth metal (1 / 2) is M 1 Or M 2 This indicates that 1 / 2 mol of the compound is added (hereinafter the same).

[0023] These phosphoric acid esters (Pa) may be used alone or in appropriate combination of two or more kinds. R 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms constituting the group include an alkyl group which is a saturated hydrocarbon group, an alkenyl group which is an unsaturated hydrocarbon group, etc. The hydrocarbon group may have a linear or branched chain structure.

[0024] R 1 Specific examples of the alkyl group constituting the formula (I) include a propyl group, a butyl group, a pentyl group, an isobutyl group, and an isopentyl group. R 1 Specific examples of the alkenyl group constituting the formula (I) include a propenyl group, a butenyl group, a pentenyl group, an isobutenyl group, and an isopentenyl group.

[0025] A 1 Specific examples of the alkyleneoxy group constituting O include an ethyleneoxy group obtained from ethylene oxide, a propyleneoxy group obtained from propylene oxide, and a butyleneoxy group obtained from butylene oxide. As the alkylene oxide, one type of alkylene oxide may be used alone, or two or more types of alkylene oxides may be used in appropriate combination.

[0026] Specific examples of the alkali metal include sodium, potassium, lithium, etc. Specific examples of the alkaline earth metal include magnesium, calcium, etc.

[0027] Specific examples of organic amines include: (1) aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, N-diisopropylethylamine, butylamine, dibutylamine, 2-methylbutylamine, tributylamine, octylamine, laurylamine, and dimethyllaurylamine; (2) aromatic amines or heterocyclic amines such as aniline, N-methylbenzylamine, pyridine, morpholine, piperazine, and derivatives thereof; (3) alkanolamines such as monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, dibutylethanolamine, butyldiethanolamine, octyldiethanolamine, and lauryldiethanolamine; (4) arylamines such as 3-aminopropene; and (5) polyoxyalkylene alkylamino ethers such as polyoxyethylene lauryl amino ether and polyoxyethylene steryl amino ether.

[0028] M 1 ,M 2 may be the same or different. The phosphate ester (Pb) is a compound represented by the following formula (2).

[0029] [ka] (In formula (2), R 2 ,R 3 : A hydrocarbon group having 3 to 5 carbon atoms. A 2 O,A 3 O: an alkyleneoxy group having 2 to 4 carbon atoms. n2, n3: Integers between 0 and 3. M 3 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. These phosphate esters (Pb) may be used alone or in appropriate combination of two or more.

[0030] R 2 or R 3 The hydrocarbon group having 3 to 5 carbon atoms constituting the formula (1) is R 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms constituting the above group include those exemplified above. A 2 O or A 3 The alkyleneoxy group constituting O is A in the formula (1). 1 Examples of the alkyleneoxy group constituting O include those exemplified above.

[0031] M 3 The alkali metal, alkaline earth metal, or organic amine constituting the compound is M of the formula (1). 1 ,M 2 Examples of the alkali metal, alkaline earth metal, or organic amine that constitutes the above compound include those exemplified above.

[0032] R 2 and R 3 , and A 2 O and A 3 Each O may be the same or different. The phosphate ester (Pc) is a compound represented by the following formula (3).

[0033] [ka] (In formula (3), Q 1 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, organic amine, or -(A 5 O) n5 R 5 . R 4 ,R 5 : A hydrocarbon group having 3 to 5 carbon atoms. A 4 O,A 5 O: an alkyleneoxy group having 2 to 4 carbon atoms. n4, n5: Integers between 0 and 3. M 4 ,M5 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. These phosphate esters (Pc) may be used alone or in appropriate combination of two or more.

[0034] Q 1 The alkali metal, alkaline earth metal, or organic amine constituting the compound is M of the formula (1). 1 ,M 2 Examples of the alkali metal, alkaline earth metal, or organic amine that constitutes the above compound include those exemplified above.

[0035] R 4 or R 5 The hydrocarbon group having 3 to 5 carbon atoms constituting the formula (1) is R 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms constituting the above group include those exemplified above. A 4 O or A 5 The alkyleneoxy group constituting O is A in the formula (1). 1 Examples of the alkyleneoxy group constituting O include those exemplified above.

[0036] M 4 Or M 5 The alkali metal, alkaline earth metal, or organic amine constituting the compound is M of the formula (1). 1 ,M 2 Examples of the alkali metal, alkaline earth metal, or organic amine that constitutes the above compound include those exemplified above.

[0037] R 4 and R 5 , A 4 O and A 5 O and M 4 and M. 5 may be the same or different. The phosphate ester (Pd) is a compound represented by the following formula (4).

[0038] [ka] (In formula (4), R 6 ,R 7 ,R 8 : A hydrocarbon group having 3 to 5 carbon atoms. A 6 O,A 7 O,A 8 O: an alkyleneoxy group having 2 to 4 carbon atoms. n6, n7, n8: Integers between 0 and 3. These phosphate esters (Pd) may be used alone or in appropriate combination of two or more.

[0039] R 6 ,R 7 , or R 8 The hydrocarbon group having 3 to 5 carbon atoms constituting the formula (1) is R 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms constituting the above group include those exemplified above. A 6 O,A 7 O or A 8 The alkyleneoxy group constituting O is A in the formula (1). 1 Examples of the alkyleneoxy group constituting O include those exemplified above.

[0040] R 6 and R 7 and R 8 , and A 6 O and A 7 O and A 8 Each O may be the same or different. The inorganic phosphate (Pi) may be inorganic phosphoric acid that does not form a salt, such as orthophosphoric acid, pyrophosphoric acid, diphosphoric acid pentoxide, etc., or an inorganic phosphate. Specific examples of inorganic phosphates include tripotassium phosphate, trisodium phosphate, tricalcium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, dicalcium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, calcium dihydrogen phosphate, potassium pyrophosphate, sodium pyrophosphate, calcium pyrophosphate, etc.

[0041] These inorganic phosphates (Pi) may be used alone or in appropriate combination of two or more. The P NMR integrals assigned to phosphate ester (Pa) and inorganic phosphate (Pi) are shown in the table below. Pa , N Pi When expressed as Pa N Pi Ratio of (N Pi / N Pa The lower limit of the ratio N is 0.6 or more, and preferably 1.0 or more. When the ratio is 0.6 or more, the emulsion stability of the treatment agent can be improved. In addition, the carding ability of the fibers to which the treatment agent is applied can be improved. In addition, the P NMR integral value N Pa N Pi Ratio of (N Pi / N Pa The upper limit of the ratio is preferably 4.0 or less. When the ratio is 4.0 or less, the carding property of the fibers to which the treatment agent is applied can be improved. Any combination of the above upper and lower limits is also contemplated.

[0042] The P nuclear NMR integral value is determined by taking the sum of the P nuclear NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and inorganic phosphoric acid (Pi) in the P nuclear NMR measurement when the phosphate compound (P) is pretreated by alkaline overneutralization as 100%.

[0043] The above-mentioned "alkaline overneutralization pretreatment" means a pretreatment in which an excess amount of alkali is added to the phosphoric acid compound (P). Specific examples of the alkali are not particularly limited, and include, for example, organic amines, hydroxides of alkali metals or alkaline earth metals, etc. Furthermore, the alkali may be the same as or different from the alkali used in synthesizing the phosphoric acid compound (P). Specific examples of the organic amines include those exemplified as organic amines constituting the phosphoric acid compound (P) described above. Specific examples of the hydroxides of alkali metals or alkaline earth metals include, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, etc.

[0044] 31 In the measurement of P-NMR, by carrying out this "alkaline superneutralization pretreatment", the peaks assigned to phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), phosphate ester (Pd), and inorganic phosphoric acid (Pi) can be clearly separated, and the P nuclear integral ratio assigned to each compound can be calculated using the following formulas (1) to (5).

[0045] The P nucleus NMR integral ratio assigned to phosphate ester (Pa) is shown by the following formula (1). The P nucleus NMR integral ratio assigned to phosphate ester (Pb) is shown by the following formula (2). The P nucleus NMR integral ratio assigned to phosphate ester (Pc) is shown by the following formula (3). The P nucleus NMR integral ratio assigned to phosphate ester (Pd) is shown by the following formula (4). The P nucleus NMR integral ratio assigned to inorganic phosphate (Pi) is shown by the following formula (5).

[0046]

number

[0047]

number

[0048]

number

[0049]

number

[0050]

number

[0051] In the treatment agent, when the sum of the P nucleus NMR integral ratios attributable to the phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), phosphate ester (Pd), and inorganic phosphoric acid (Pi) shown in the above formula (3) is taken as 100%, the P nucleus NMR integral ratio (N Pc The lower limit of the ratio (N (%)) of the NMR integrals of the P nucleus attributable to the phosphoric acid ester (Pc) shown in the above formula (3) is preferably 15% or more. By specifying the ratio within this range, the carding ability of the fibers to which the treatment agent is applied can be improved. Pc The upper limit of (%) is preferably 45% or less. By specifying it within this range, the emulsion stability of the treatment agent can be further improved. Note that any combination of the above upper and lower limits is also envisioned.

[0052] In the treatment agent, when the sum of the P nucleus NMR integral ratios attributable to the phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), phosphate ester (Pd), and inorganic phosphoric acid (Pi) shown in the above formula (1) is taken as 100%, the P nucleus NMR integral ratio attributable to the phosphate ester (Pa) (N Pa The lower limit of (%) is 5% or more. do. By specifying the range, the effects of the present invention can be further improved. In addition, the P nucleus NMR integral ratio (N Pa The upper limit of (%) is preferably less than 20%. By specifying the range as described above, the water repellency of the fiber to which the treatment agent is applied can be further improved. Note that any combination of the above upper and lower limits is also contemplated.

[0053] In the treatment agent, when the sum of the P nucleus NMR integral ratios attributable to the phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), phosphate ester (Pd), and inorganic phosphoric acid (Pi) shown in the above formula (2) is taken as 100%, the P nucleus NMR integral ratio (N Pb The lower limit of the NMR integral ratio (N Pb The upper limit of (%) is preferably less than 45%. By specifying it within such a range, the effects of the present invention can be further improved. Note that ranges that combine the above upper and lower limits in any way are also envisioned.

[0054] The phosphoric acid compound (P) can be obtained by reacting a raw material alcohol, an aliphatic alcohol having 3 to 5 carbon atoms, with, for example, diphosphorus pentoxide to obtain a phosphoric acid ester, and then, if necessary, neutralizing or overneutralizing the phosphoric acid ester with an alkali such as potassium hydroxide. In the case of the above synthesis method, the phosphoric acid ester compound is usually a phosphoric acid ester Pa, a phosphoric acid ester Pb, a phosphoric acid ester Pc, and an inorganic phosphoric acid Pi. Alternatively, the phosphoric acid ester Pa, the phosphoric acid ester Pb, the phosphoric acid ester Pc, and the inorganic phosphoric acid Pi may be mixed together to prepare the phosphoric acid ester.

[0055] The lower limit of the content of the phosphoric acid compound (P) in the treatment agent is appropriately set, but is preferably 70% by mass or more, more preferably 80% by mass or more. When the content is 70% by mass or more, the carding ability of the fiber to which the treatment agent is applied can be improved. The upper limit of the content of the phosphoric acid compound (P) is appropriately set, but is preferably 99% by mass or less, more preferably 97% by mass or less. When the content is 99% by mass or less, the wettability of the treatment agent to the fiber can be improved. Any combination of the above upper and lower limits is also envisioned.

[0056] (Alcohol (A)) The alcohol (A) used in this embodiment is a monohydric to trihydric alcohol having 3 to 6 carbon atoms. The alcohol (A) may be a saturated aliphatic alcohol, an unsaturated aliphatic alcohol, or an aromatic alcohol. The hydrocarbon group constituting the alcohol (A) may have a linear or branched structure. In addition, the alcohol (A) may be a primary alcohol or a secondary alcohol.

[0057] Specific examples of monohydric alcohols include (1) linear alkyl alcohols such as propanol, butanol, pentanol, and hexanol, (2) branched alkyl alcohols such as isobutanol, isopentanol, and isohexanol, (3) linear alkenyl alcohols such as propenol, butenol, pentenol, and hexenol, (4) branched alkenyl alcohols such as isobutenol, isopentenol, and isohexenol, (5) cyclic alkyl alcohols such as cyclopentanol and cyclohexanol, and (6) aromatic alcohols such as phenol.

[0058] Specific examples of dihydric alcohols include 1,3-butanediol, 2-methyl-1-propanol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, diethylene glycol, polyethylene glycol, propylene glycol, and dipropylene glycol.

[0059] Specific examples of trihydric alcohols include glycerin, trimethylolpropane, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-2-hydroxymethyl-1,3-propanediol, 1,2,3-pentatriol, and 1,2,4-pentatriol.

[0060] These alcohols (A) may be used alone or in appropriate combination of two or more. The lower limit of the content of the alcohol (A) in the treatment agent is set appropriately, but is preferably 1% by mass or more, more preferably 3% by mass or more. When the content is 1% by mass or more, the wettability of the treatment agent to the fiber can be improved. The upper limit of the content of the alcohol (A) is set appropriately, but is preferably 30% by mass or less, more preferably 20% by mass or less. When the content is 30% by mass or less, the carding ability of the fiber to which the treatment agent is applied can be improved. Any combination of the above upper and lower limits is also envisioned.

[0061] In the treatment agent, when the total content of the phosphoric acid compound (P) and the alcohol (A) is 100 mass%, it is preferable that the phosphoric acid compound (P) is contained in a proportion of 80 mass% or more and 97 mass% or less, and the alcohol (A) is contained in a proportion of 3 mass% or more and 20 mass% or less. By specifying the ranges as above, the effect of the present invention can be further improved. Note that a range in which the above upper and lower limits are arbitrarily combined is also assumed. In the present invention, the treatment agent contains the phosphoric acid compound (P) in an amount of 70% by mass or more and 98.7% by mass or less, and the alcohol (A) in an amount of 1.3% by mass or more and 30% by mass or less, assuming that the total content of the phosphoric acid compound (P) and the alcohol (A) in the treatment agent is 100% by mass.

[0062] (Acid value) The lower limit of the acid value of the treatment agent is 0.5 mgKOH / g or more, preferably 10 mgKOH / g or more. When the lower limit of the acid value is 0.5 mgKOH / g or more, the effect of the present invention can be further improved. The upper limit of the acid value of the treatment agent is 100 mgKOH / g or less. When the lower limit of the acid value is 100 mgKOH / g or less, the emulsion stability of the treatment agent can be particularly improved. Note that any combination of the above upper and lower limits is also envisioned.

[0063] The acid value (KOHmg / g) of the treatment agent is expressed by the following formula. The treatment agent was dissolved in ion-exchanged water to prepare a sample solution. The prepared sample solution was set in a known potentiometer and titrated with a 0.1 mol / L potassium hydroxide methanol standard solution. The acid value of the treatment agent was calculated using the following formula.

[0064] Acid value of treatment agent (KOHmg / g) = (R x f x 56.11 x 0.1) / S f: Factor of 0.1 mol / L potassium hydroxide methanol standard solution S: Sample amount (g, solid content equivalent) R: Amount of 0.1 mol / L potassium hydroxide methanol standard solution used up to the inflection point (mL) In addition, when the treatment agent is mixed with a solvent such as water, it is also possible to calculate the acid value of the treatment agent by subtracting the content of the treatment agent in the mixture from the acid value of the mixture. The content of the treatment agent in the mixture can be calculated from the mass loss of the mixture when the mixture is heat-treated to remove the solvent.

[0065] (solvent) The treatment agent of the present embodiment may contain a solvent if necessary. Examples of the solvent include water and organic solvents. Specific examples of the organic solvent include lower alcohols such as ethanol and propanol, and low polarity solvents such as hexane and normal paraffin. These solvents may be used alone or in combination of two or more. Among these, water is preferred from the viewpoints of excellent dispersibility or solubility of each component and excellent handling.

[0066] (Application) The treatment agent of the present embodiment is applied to the use of nonwoven fabrics. As long as a treated nonwoven fabric having the treatment agent of the present embodiment adhered to its surface can be obtained, the treatment agent may be adhered to the fiber surface before the nonwoven fabric is produced, or the treatment agent may be adhered to the fiber surface after the nonwoven fabric is produced.

[0067] The type of fiber is not particularly limited, and examples thereof include short fibers and long fibers. The present invention can be applied to both short and long fiber fiber applications. Short fibers are generally called staples, and do not include long fibers generally called filaments. The length of the short fibers is not particularly limited as long as it corresponds to short fibers in this technical field, and is, for example, 100 mm or less, preferably 30 mm or more and 70 mm or less. The fibers may be composed of the following synthetic fibers.

[0068] Specific examples of synthetic fibers include (1) polyolefin fibers such as polyethylene fibers, polypropylene fibers, and polybutene fibers, (2) polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-isophthalate, and polyether polyester, (3) polyamide fibers such as nylon 6 and nylon 66, and (4) composite fibers, among which composite fibers having a core-sheath structure in which either the core or the sheath or both are polyolefin fibers, such as polyethylene / polypropylene composite fibers and polyethylene / polyester composite fibers in which the sheath is a polyethylene fiber, or polyethylene / polyester composite fibers and polyethylene / polyester composite fibers having a side-by-side structure, etc. Among these, polyolefin fibers such as polyethylene fibers, polypropylene fibers, and polybutene fibers, composite fibers having a core-sheath structure in which either the core or the sheath or both are polyolefin fibers, such as polyethylene / polypropylene composite fibers and polyethylene / polyester composite fibers in which the sheath is a polyethylene fiber, or polyethylene / polyester composite fibers and polyethylene / polyester composite fibers having a side-by-side structure, are preferred. Here, the polyolefin-based synthetic fiber means a synthetic fiber synthesized using an olefin or alkene as a monomer.

[0069] The type of nonwoven fabric is not particularly limited, but examples thereof include spunbond and the like. In addition, examples of web formation methods other than the spunbond method include dry methods such as carding and airlaid methods, and wet methods such as papermaking methods, when the raw fiber material is short fibers. In addition, examples of the web formation method include meltblown and flash spinning methods, when the raw fiber material is long fibers. In addition, examples of the fiber-to-fiber bonding method include chemical bonding, thermal bonding, needle punching, spunlace, stitch bonding, and the like.

[0070] (Effects of this embodiment) The effects of the treatment agent according to the first embodiment will be described. (1-1) The treatment agent of the first embodiment contains the above-mentioned phosphoric acid compound (P) and alcohol (A), and has an acid value in the range of 0.5 mgKOH / g to 100 mgKOH / g. Therefore, in a treatment agent for imparting water repellency, the emulsion stability of the treatment agent can be improved. In particular, the emulsion stability against hard water can be improved.

[0071] In addition, the water-repellent properties of the water-repellent fibers can be maintained, and the functionality of the nonwoven fabric obtained from such fibers can be maintained. Furthermore, in a nonwoven fabric treating agent for imparting water repellency, the wettability of the treating agent to the fibers can be improved, thereby enabling the treating agent to be applied uniformly to the fibers.

[0072] Furthermore, when the fibers to which the treatment agent has been applied are passed through a card to obtain a nonwoven fabric, the carding properties can be improved, thereby obtaining a nonwoven fabric with excellent uniformity. (1-2) The P nucleus NMR integral ratio (N Pi When the (%)) is 25% or more, the emulsion stability of the treatment agent can be further improved.

[0073] (1-3) The P nucleus NMR integral ratio (N Pc When the ratio (%) is 15% or more, the carding properties of the fibers to which the treatment agent is applied can be improved.

[0074] (1-4) The P nucleus NMR integral ratio (N Pa When the ratio (%) is less than 20%, the water repellency of the fiber to which the treatment agent is applied can be further improved.

[0075] <Second embodiment> A second embodiment of the fiber according to the present invention will be described. The fiber of this embodiment is a treated fiber having the treatment agent of the first embodiment attached to its surface. A modified fiber is obtained by attaching the treatment agent to the fiber surface. The uses and types of the fiber are the same as those listed in the first embodiment.

[0076] (Treatment agent attachment treatment) There is no particular restriction on the proportion of the treatment agent of the first embodiment that is applied to the fibers, but it is preferable to apply the treatment agent that does not contain a solvent so that it is 0.1% by mass to 2% by mass relative to the fibers, and it is more preferable to apply it so that it is 0.2% by mass to 1.2% by mass.

[0077] When a treatment agent is used, a treatment agent-containing composition containing the treatment agent of the first embodiment and a solvent such as water, or a dilution solution further diluted with a solvent is used. As a method for attaching the treatment agent to the fiber, for example, a known method such as a dipping method, a spray method, a roller method, a guide oiling method using a metering pump, etc. can be applied. In addition, as a process for attaching the treatment agent to a nonwoven fabric, for example, a dipping method, a spray method, a roll coater, a gravure coater, a die coater, a curtain coater, etc. can be mentioned.

[0078] (Effects of this embodiment) The following describes the effects of the fiber of the second embodiment: In addition to the effects of the above-mentioned embodiments, the second embodiment has the following effects.

[0079] (2-1) The fiber of this embodiment is adhered with the treatment agent of the first embodiment. Therefore, a nonwoven fabric having water repellency is obtained. Therefore, the nonwoven fabric can be suitably applied to applications in which improved performance is required, such as the hygiene, medical, and civil engineering fields.

[0080] In addition, the fibers to which the treatment agent has been applied have improved carding properties, which allows for a nonwoven fabric with excellent uniformity to be obtained. In addition, the wettability of the treatment agent to the fibers is improved, which allows for a nonwoven fabric to be obtained in which the treatment agent has been uniformly applied to the fibers.

[0081] (Example of change) The above embodiment may be modified as follows: The above embodiment and the following modifications may be combined with each other to the extent that no technical contradiction occurs.

[0082] Each of the treatment agents, compositions, or dilutions of the above embodiments may further contain other components used in normal treatment agents, such as solvents, stabilizers, antistatic agents, binders, antioxidants, UV absorbers, surfactants, and pH adjusters, to maintain the quality of each treatment agent, within a range that does not impair the effects of the present invention. Note that the amount of other components used in normal treatment agents, other than the solvent, is preferably 10% by mass or less in each treatment agent, from the viewpoint of efficiently exerting the efficacy of the present invention. In addition, the other components may be stored as a separate agent from each of the above treatment agents. In the present invention, the content of compounds other than the phosphoric acid compound (P) and the alcohol (A) is 10 mass % or less. EXAMPLES

[0083] In the following, examples will be given to more specifically describe the configuration and effects of the present invention, but the present invention is not limited to these examples. In the following examples and comparative examples, parts means parts by mass, and % means % by mass.

[0084] Test category 1 (preparation of treatment agent) Example 1 The treatment agent of Example 1 was prepared by putting 92.5 parts of the phosphoric acid compound (P-1) shown in Table 1 below as the phosphoric acid compound (P) and 7.5 parts of 1-propanol (A-1) as the alcohol (A) into a container and mixing them well.

[0085] (Examples 2 to 25, Comparative Examples 1 to 6) Each of the treating agents in Examples 2 to 25 and Comparative Examples 1 to 6 was prepared in the same manner as in Example 1 using the components shown in Table 1.

[0086] The type and content of the phosphoric acid compound (P) and the type and content of the alcohol (A) in each example of the treatment agent are shown in the "Phosphate compound (P)" and "Alcohol (A)" columns of Table 1, respectively.

[0087] The acid value of the treatment agent was measured by the method described in the "Acid value" column in the embodiment section. The acid value of the treatment agent in each example is as shown in the "Acid value" column of Table 1.

[0088] [Table 1] Details of the phosphoric acid compound (P) and the alcohol (A) shown in Table 1 are as follows.

[0089] (Phosphate Compounds (P)) The phosphorus compounds (P-1) to (P-12) and (rP-1) to (rP-4) shown in Table 2 below were used.

[0090] [Table 2] The "Type" column in Table 2 shows the types of substituents and salts constituting the phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), and phosphate ester (Pd) shown in formulas (1) to (4).

[0091] The P nucleus integral ratios (%) attributable to phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), phosphate ester (Pd), and inorganic phosphoric acid (Pi) when the sum of the P nucleus NMR integral ratios attributable to phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pc), phosphate ester (Pd), and inorganic phosphoric acid (Pi) is taken as 100%, are shown in the "P nucleus NMR integral ratio" column. In Table 2, "EO" represents an ethyleneoxy group.

[0092] The acid value of the phosphoric acid compound (P) is shown in the "Acid value" column. The acid value was measured by the method described in the "Acid value" column in the embodiment section. The P NMR integrals N assigned to phosphate ester (Pa) and inorganic phosphate (Pi) Pa N Pi Ratio of (N Pi / N Pa ) to "N Pi / N Pa The P nuclear NMR measurement method is shown below.

[0093] ·P nuclear NMR measurement method Each phosphoric acid compound (P) was pretreated by adding KOH to adjust the pH to 12 or higher. Deuterium oxide was used as the solvent. 31 P-NMR (MERCURY plus NMR Spectrometer System, product name, manufactured by VALIAN, 300 MHz, the same below) was used.

[0094] Among the obtained signals, the integral value of the signal appearing at 4 ppm to 10 ppm corresponds to the P atom in inorganic phosphate (Pi). The integral value of the signal appearing between 3 ppm and 7 ppm corresponds to the P atom in the phosphate ester (Pa).

[0095] The integral value of the signal appearing between -1 ppm and 4 ppm corresponds to the P atom in the phosphate ester (Pb). The integral value of the signal appearing between 0 ppm and -3 ppm corresponds to the P atom in the phosphate ester (Pd).

[0096] The integral value of the signal appearing between -1 ppm and -15 ppm corresponds to the P atom in the phosphate ester (Pc). However, if signals are detected in overlapping ranges of the above values, signals from P atoms corresponding to inorganic phosphate (Pi), phosphate ester (Pa), phosphate ester (Pb), phosphate ester (Pd), and phosphate ester (Pc) will be detected, in that order from the low magnetic field side.

[0097] (Alcohol (A)) A-1: 1-propanol A-2: Propylene glycol A-3: Glycerin A-4: 1-butanol A-5: 2-Methyl-1-propanol A-6: 1,3-butanediol A-7: 1-Pentanol rA-1: 1-Hexadecanol Test category 2 (preparation of 5% diluted solution of treatment agent) The treatment agent of each example was added to ion-exchanged water heated to about 60° C. with stirring and completely dissolved to prepare a 5% diluted solution of the treatment agent of each example.

[0098] Test category 3 (evaluation of wettability) The 5% diluted solution of the treatment agent obtained above was added to ion-exchanged water at room temperature under stirring to prepare a 1% diluted solution. 5 μL of 1% emulsion (aqueous solution) of each treatment agent was dropped onto a polypropylene nonwoven fabric to which no treatment agent had been applied, and the time until complete penetration was recorded. The results are shown in the "Wettability" column of Table 1.

[0099] · Evaluation criteria for wettability 3 (Good): Penetrates in less than 60 seconds 2 (OK): 60 seconds or more, but less than 120 seconds 1 (defective): 120 seconds or more Test category 4 (water repellency evaluation) The 5% diluted solution of the treatment agent obtained above was further diluted with ion-exchanged water to prepare a 0.4% diluted solution. The 0.4% aqueous solution of the treatment agent thus prepared was applied by spray oiling to a composite fiber (PE / PET) obtained in the cotton manufacturing process, with a fineness of 2.2 dtex and a fiber length of 38 mm, the sheath of which was polyethylene and the core of which was polyester, so that the amount of the treatment agent applied was 0.4%.

[0100] The fibers were dried for 1 hour in a hot air dryer at 80°C to obtain treated PE / PET fibers with the treatment agent attached. 20 g of the dried short fibers were subjected to a known miniature roller carding machine under conditions of a temperature of 25°C and a humidity of 40% to form a web. Hot air at about 140°C was blown onto the web for 10 seconds to perform a hot air treatment, bonding the fibers together to obtain a basis weight of 25 g / m. 2The nonwoven fabric was produced. The water repellency was evaluated according to the hydrostatic pressure method of JIS L 1092 7.1.1A method (low water pressure method). The test environment was 20±2°C and 65±2% humidity, using a hydrotester (FX3000-III) manufactured by Swiss Textest. Five pieces of the produced nonwoven fabric (approximately 150mm x approximately 150mm) were taken and attached to the hydrotester so that water hit the front side of the nonwoven fabric. The water level was raised at a speed of 10cm / min, and the displayed value (cmw.c.) was read when the third drop of water appeared on the back side of the nonwoven fabric. This test was performed five times, and the average value of the five times was calculated. The higher the water pressure resistance, the better the water repellency. The results are shown in the "Water repellency" column of Table 1.

[0101] Water repellency evaluation criteria 3 (Good): Water pressure resistance of 5.0cmw.c. or more 2 (Acceptable): Water pressure resistance is 3.0cmw.c. or more and less than 5.0cmw.c. 1 (Poor): Water pressure resistance is less than 3.0 cmw.c. Test category 5 (evaluation of card passability) 30 g of the above-mentioned oiled PE / PET fiber was passed through a small roller card in an atmosphere of 25°C x 40% RH. The carding property was evaluated as the uniformity of the spun carded web according to the following criteria. The results are shown in the "Carding property" column in Table 1.

[0102] ·Card passability evaluation criteria 3 (Good): The web has a uniform thickness and looks very good. 2 (Acceptable): There are some areas of uneven thickness in the web, but this does not pose a problem. 1 (bad): The web thickness is not uniform. Test category 6 (evaluation of emulsion stability) A 1% diluted hard water solution was prepared by uniformly mixing 1 part of the treatment agent and 99 parts of hard water. The hard water used had an electrical conductivity of 130 μS / cm when measured at 25°C. The prepared 1% diluted hard water solution was left to stand at 25°C for 24 hours. The emulsion stability was evaluated based on the appearance of the 1% diluted hard water solution of the treatment agent after standing. The results are shown in the "Emulsion stability" column in Table 1.

[0103] ·Evaluation criteria for emulsion stability 3 (Good): No precipitate particles are observed 2 (Acceptable): When slight precipitate particles are observed 1 (bad): Precipitated particles are observed and are dispersed or precipitated. From the results in the above table, it is clear that the present invention can improve the emulsion stability of a treatment agent for imparting water repellency, improve the wettability of the treatment agent to fibers, and improve the carding properties of fibers to which the treatment agent is applied. Next, the technical ideas that can be understood from the above-described embodiment and other examples will be described below. The nonwoven fabric treatment agent of the first aspect is a nonwoven fabric treatment agent containing the following phosphoric acid compound (P) and the following alcohol (A), and has the following P nucleus NMR integral values ​​N Pa 、N Pi Ratio of (N Pi / N Pa ) is 0.6 or more, and the acid value of the nonwoven fabric treating agent is 0.5 mgKOH / g or more and 100 mgKOH / g or less. Phosphate compound (P): A phosphoric acid compound containing a phosphoric acid ester (Pa) represented by the above formula (1), a phosphoric acid ester (Pb) represented by the above formula (2), and inorganic phosphoric acid (Pi), and optionally further containing at least one selected from a phosphoric acid ester (Pc) represented by the above formula (3), and a phosphoric acid ester (Pd) represented by the above formula (4). Alcohol (A): Monohydric to trihydric alcohols with 3 to 6 carbon atoms. In aspect 2, in the treatment agent for nonwoven fabric according to aspect 1, when the sum of the P nucleus NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio attributable to the inorganic phosphoric acid (Pi) is 25% or more. In aspect 3, in the treatment agent for nonwoven fabric according to aspect 1 or 2, when the sum of the P nucleus NMR integral ratios assigned to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio assigned to the phosphate ester (Pc) is 15% or more. In aspect 4, in the treatment agent for nonwoven fabric according to any one of aspects 1 to 3, when the sum of the P nucleus NMR integral ratios assigned to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nucleus NMR integral ratio assigned to the phosphate ester (Pa) is less than 20%. Aspect 5 is a treatment agent for nonwoven fabric according to any one of Aspects 1 to 4, in which the phosphoric acid compound (P) is contained in an amount of 80% by mass or more and 97% by mass or less, and the alcohol (A) is contained in an amount of 3% by mass or more and 20% by mass or less, assuming that the total content of the phosphoric acid compound (P) and the alcohol (A) is 100% by mass. The fiber of the sixth aspect is characterized in that the treating agent for nonwoven fabric according to any one of the first to fifth aspects is adhered to the fiber.

Claims

1. A treatment agent for nonwoven fabrics comprising the following phosphoric acid compound (P) and the following alcohol (A), wherein, when the total content of the phosphoric acid compound (P) and the alcohol (A) is taken as 100 mass%, the phosphoric acid compound (P) is contained in an amount of 70 mass% or more and 98.7 mass% or less, and the alcohol (A) is contained in an amount of 1.3 mass% or more and 30 mass% or less, and the content of compounds other than the phosphoric acid compound (P) and the alcohol (A) is 10 mass% or less, The P nucleus NMR integral values ​​N Ｐａ , N Ｐｉ The ratio of (N Ｐｉ / N Ｐａ ) is 0.6 or more, The treatment agent for nonwoven fabrics, characterized in that the acid value of the treatment agent for nonwoven fabrics is 0.5 mgKOH / g or more and 100 mgKOH / g or less. Phosphate compound (P): A phosphoric acid compound containing a phosphoric acid ester (Pa) represented by the following formula (1), a phosphoric acid ester (Pb) represented by the following formula (2), and inorganic phosphoric acid (Pi), and optionally containing at least one selected from a phosphoric acid ester (Pc) represented by the following formula (3) and a phosphoric acid ester (Pd) represented by the following formula (4), in which, when the sum of the P nuclear NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nuclear NMR integral ratio attributable to the inorganic phosphoric acid (Pi) is 55% or less, and the P nuclear NMR integral ratio attributable to the phosphate ester (Pa) is 5% or more. 【Chemistry 1】 (In formula (1), R １ : a hydrocarbon group having 3 to 5 carbon atoms. A １ O: an alkyleneoxy group having 2 to 4 carbon atoms. n1: an integer between 0 and 3. M １ , M ２ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. 【Chemistry 2】 (In formula (2), R ２ , R ３ : a hydrocarbon group having 3 to 5 carbon atoms. A ２ O.A. ３ O: an alkyleneoxy group having 2 to 4 carbon atoms. n2, n3: integers greater than or equal to 0 and less than or equal to 3. M ３ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. 【Chemistry 3】 (In formula (3), Q １ : a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2), an ammonium, an organic amine, or -(A ５ O) ｎ５ R ５ . R ４ , R ５ : a hydrocarbon group having 3 to 5 carbon atoms. A ４ O.A. ５ O: an alkyleneoxy group having 2 to 4 carbon atoms. n4, n5: integers greater than or equal to 0 and less than or equal to 3. M ４ , M ５ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. 【Chemistry 4】 (In formula (4), R ６ , R ７ , R ８ : a hydrocarbon group having 3 to 5 carbon atoms. A ６ O.A. ７ O.A. ８ O: an alkyleneoxy group having 2 to 4 carbon atoms. n6, n7, n8: integers between 0 and 3. Alcohol (A): a monohydric, trihydric or trihydric alcohol having 3 or more and 6 or less carbon atoms.

2. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein when the sum of the P nuclear NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nuclear NMR integral ratio attributable to the inorganic phosphoric acid (Pi) is 25% or more.

3. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein, when the sum of the P nuclear NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nuclear NMR integral ratio attributable to the phosphate ester (Pc) is 15% or more.

4. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein when the sum of the P nuclear NMR integral ratios attributable to the phosphate ester (Pa), the phosphate ester (Pb), the phosphate ester (Pc), the phosphate ester (Pd), and the inorganic phosphoric acid (Pi) is taken as 100%, the P nuclear NMR integral ratio attributable to the phosphate ester (Pa) is less than 20%.

5. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein the treatment agent contains the phosphoric acid compound (P) in an amount of 80% by mass or more and 97% by mass or less, and the alcohol (A) in an amount of 3% by mass or more and 20% by mass or less, assuming that the total content of the phosphoric acid compound (P) and the alcohol (A) is 100% by mass.

6. A fiber having the nonwoven fabric treating agent according to any one of claims 1 to 5 adhered thereto.

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