Treatment agent for nonwoven fabric and fiber

Abstract

To provide a treatment agent for a nonwoven fabric for imparting water repellency, capable of improving emulsion stability and wettability of the treatment agent for the nonwoven fabric to a fiber, and to provide the fiber using the same.SOLUTION: The nonwoven fabric treatment agent of the present invention is a nonwoven fabric treatment agent containing the following phosphate compound (P) and the following alcohol (A), wherein the ratio (NPi / NPa) of P-nuclear NMR integral values NPa and NPi assigned to the following phosphate ester (Pa) and the following inorganic phosphate (Pi), respectively, is 0.6 or more, and the acid number of the nonwoven fabric treatment agent is 0. 5mgKOH / g or more and 100mgKOH / 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), and the like represented by predetermined formulae. The alcohol (A) is a mono - to trihydric alcohol having 3 or more and 6 or less carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a treatment agent for nonwoven fabrics that can impart water repellency and 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. Functionality such as water repellency is imparted to the raw fibers used for the nonwoven fabric or to the nonwoven fabric by applying a treatment agent to the nonwoven fabric. Nonwoven fabrics imparted with functionalities 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 conventionally known 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 treatment agents for nonwoven fabrics intended to impart water repellency have had the problem that not only does the emulsion stability decrease, but also the wettability of the treatment agent for nonwoven fabrics to fibers decreases. [Means for solving the problem]

[0006] As a result of research conducted by the present inventors to solve the above-mentioned problems, they found that a treatment agent for nonwoven fabrics containing a predetermined phosphoric acid compound (P) and an alcohol (A) having an acid value within a predetermined range is precisely suitable.

[0007] Various aspects for solving the above problems will be described. The nonwoven fabric treatment agent of the first aspect 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 is a compound having the following P nucleus NMR integral value N Pa , N Pi The ratio (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 further 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 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. Phosphate compounds.

[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): Mono- to trihydric alcohols with 3 to 6 carbon atoms.

[0013] In a second aspect, in the treatment agent for nonwoven fabrics according to the first aspect, 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 a third aspect, in the treatment agent for nonwoven fabrics according to the first or second aspect, 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 phosphate ester (Pc) is 15% or more.

[0015] In aspect 4, in the treatment agent for nonwoven fabrics according to any one of aspects 1 to 3, 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 phosphate ester (Pa) is less than 20%.

[0016] Aspect 5 is the treatment agent for nonwoven fabrics according to any one of Aspects 1 to 4, 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, where the total content of the phosphoric acid compound (P) and the alcohol (A) is taken as 100% by mass.

[0017] The fibers of the sixth aspect are characterized in that the treating agent for nonwoven fabric according to any one of the first to fifth aspects is adhered to the fibers. [Effects 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 emulsion stability and also improve the wettability of the treatment agent for nonwoven fabrics to fibers. DETAILED DESCRIPTION OF THE INVENTION

[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) used in this embodiment includes 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 includes 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. Since alkaline earth metals are divalent, alkaline earth metal (1 / 2) is M 1 or M 2 This indicates that 1 / 2 mole of the compound is added (the same applies below).

[0023] These phosphate esters (Pa) may be used singly or in appropriate combination of two or more. 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 group 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 alkali metals include sodium, potassium, lithium, etc. Specific examples of alkaline earth metals 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 laurylamino ether and polyoxyethylene sterylamino 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 singly 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 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms that constitutes the above group include those exemplified above. A 2 O or A 3 The alkyleneoxy group constituting O is A in 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 metals, alkaline earth metals, or organic amines that constitute the above-mentioned compounds include those exemplified above.

[0032] R 2 and R 3 , and A 2 O and A 3 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 singly 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 metals, alkaline earth metals, or organic amines that constitute the above-mentioned compounds include those exemplified above.

[0035] R 4 or R 5 The hydrocarbon group having 3 to 5 carbon atoms constituting the formula (1) is 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms that constitutes the above group include those exemplified above. A 4 O or A 5 The alkyleneoxy group constituting O is A in 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 metals, alkaline earth metals, or organic amines that constitute the above-mentioned compounds 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 singly 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 1 Examples of the hydrocarbon group having 3 to 5 carbon atoms that constitutes the above group include those exemplified above. A 6 O,A 7 O or A 8 The alkyleneoxy group constituting O is A in 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 O may be the same or different. The inorganic phosphate (Pi) may be inorganic phosphate that does not form a salt, such as orthophosphoric acid, pyrophosphoric acid, or diphosphoric acid pentoxide, or may be 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, and calcium pyrophosphate.

[0041] These inorganic phosphates (Pi) may be used singly 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 The ratio (N Pi / N Pa The lower limit of the ratio N is 0.6 or more, 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 nucleus NMR integral value N Pa N Pi The ratio (N Pi / N Pa The upper limit of the ratio is preferably 4.0 or less. When this ratio is 4.0 or less, the carding properties of the fibers to which the treatment agent is applied can be improved. Note that 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" refers to a pretreatment in which an excess amount of alkali is added to the phosphoric acid compound (P). Specific examples of the alkali include, but are not limited to, organic amines, hydroxides of alkali metals or alkaline earth metals, etc. 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 amine 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 P-NMR measurements, by performing this "alkaline superneutralization pretreatment," peaks attributable 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 nucleus integral ratios attributable to each compound can be calculated using the following formulas (1) to (5).

[0045] The P NMR integral ratio attributable to phosphate ester (Pa) is shown by the following formula (1). The P NMR integral ratio attributable to phosphate ester (Pb) is shown by the following formula (2). The P NMR integral ratio attributable to phosphate ester (Pc) is shown by the following formula (3). The P NMR integral ratio attributable to phosphate ester (Pd) is shown by the following formula (4). The P NMR integral ratio attributable to inorganic phosphoric acid (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 total of the P nuclear 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 nuclear NMR integral ratio (N Pc The lower limit of the ratio (%) of the P nucleus NMR integral ratio (N 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 ranges that combine the above upper and lower limits are also contemplated.

[0052] In the treatment agent, when the total of the P nuclear 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 nuclear NMR integral ratio (N Pa The lower limit of (%) is 5% or more. do. By specifying the ratio within this 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 it within this range, the water repellency of the fiber to which the treatment agent is applied can be further improved. Note that ranges that combine the above upper and lower limits are also contemplated.

[0053] In the treatment agent, when the total of the P nuclear 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 nuclear NMR integral ratio (N Pb The lower limit of the P nucleus NMR integral ratio (N Pb The upper limit of (%) is preferably less than 45%. By specifying it within this range, the effects of the present invention can be further improved. Note that ranges that combine the above upper and lower limits are also contemplated.

[0054] The phosphoric acid compound (P) can be obtained by reacting a raw material alcohol, an aliphatic alcohol having from 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 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 inorganic phosphoric acid Pi. Alternatively, the phosphoric acid ester Pa, a phosphoric acid ester Pb, a phosphoric acid ester Pc, and inorganic phosphoric acid Pi may be synthesized and mixed together to prepare the compound.

[0055] The lower limit of the content of the phosphate compound (P) in the treatment agent is set as appropriate, 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 fibers to which the treatment agent is applied can be improved. The upper limit of the content of the phosphate compound (P) can be set as appropriate, 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 fibers can be improved. Note that ranges that combine the above upper and lower limits in any way are also contemplated.

[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 chain structure. Furthermore, 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 singly or in appropriate combination of two or more. The lower limit of the content of the alcohol (A) in the treatment agent is set as appropriate, 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 as appropriate, 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. Note that ranges that combine the above upper and lower limits are also contemplated.

[0061] In the treatment agent, when the total content of the phosphoric acid compound (P) and the alcohol (A) is taken as 100% by mass, it is preferable that the phosphoric acid compound (P) is contained in an amount of 80% by mass to 97% by mass, and the alcohol (A) is contained in an amount of 3% by mass to 20% by mass. By specifying these ranges, the effects of the present invention can be further improved. Note that ranges that combine the above upper and lower limits are also contemplated. Furthermore, in the present invention, when the total content of the phosphoric acid compound (P) and the alcohol (A) in the treatment agent 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.

[0062] (acid number) The lower limit of the acid value of the treatment agent is 0.5 mg KOH / g or more, preferably 10 mg KOH / g or more. When the lower limit of the acid value is 0.5 mg KOH / g or more, the effects of the present invention can be further improved. The upper limit of the acid value of the treatment agent is 100 mg KOH / g or less. When the lower limit of the acid value is 100 mg KOH / g or less, the emulsion stability of the treatment agent can be particularly improved. Note that ranges that combine the above upper and lower limits are also contemplated.

[0063] The acid value (KOH mg / 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 placed 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 (KOH mg / g) = (R × f × 56.11 × 0.1) / S f: Factor of 0.1 mol / L potassium hydroxide methanol standard solution S: Sample amount (g, solids equivalent) R: Amount (mL) of 0.1 mol / L potassium hydroxide methanol standard solution used to reach the inflection point Furthermore, when the treatment agent is mixed with a solvent such as water, the acid value of the treatment agent can be calculated 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 this embodiment may contain a solvent if necessary. Examples of the solvent include water and organic solvents. Specific examples of organic solvents 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 appropriate combinations of two or more. Among these, water is preferred from the viewpoints of excellent dispersibility or solubility of each component and excellent handleability.

[0066] (Application) The treatment agent of this embodiment is applied to nonwoven fabric applications. As long as a treated nonwoven fabric having the treatment agent of this 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 include short fibers and long fibers. The present invention can be applied to both short and long fiber applications. Short fibers generally refer to those called staples, and do not include long fibers generally called filaments. The length of the short fibers is not particularly limited as long as they fall under the category of short fibers in this technical field, but is, for example, 100 mm or less, preferably 30 mm to 70 mm. 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, including composite fibers with a core-sheath structure in which either the core or the sheath, or both, are polyolefin fibers, such as polyethylene / polypropylene composite fibers or polyethylene / polyester composite fibers in which the sheath is polyethylene fiber, or polyethylene / polyester composite fibers with a side-by-side structure. Among these, polyolefin fibers such as polyethylene fibers, polypropylene fibers, and polybutene fibers, and composite fibers with a core-sheath structure in which either the core or the sheath, or both, are polyolefin fibers, such as polyethylene / polypropylene composite fibers or polyethylene / polyester composite fibers in which the sheath is polyethylene fiber, or polyethylene / polyester composite fibers with a side-by-side structure, are preferred. Here, polyolefin synthetic fibers refer to synthetic fibers synthesized using olefins or alkenes as monomers.

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

[0070] (Effects of this embodiment) The effects of the treatment agent of the first embodiment will be described. (1-1) The treatment agent of the first embodiment contains the above-described 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] Furthermore, the water-repellent properties of the water-repellent fibers can be maintained, thereby maintaining the functionality of the nonwoven fabric obtained from such fibers. Furthermore, in a treatment agent for nonwoven fabrics for imparting water repellency, the wettability of the treatment agent to the fibers can be improved, thereby enabling the treatment agent to be applied uniformly to the fibers.

[0072] Furthermore, when fibers to which a 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 (%)) 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 (%)) 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. The treatment agent is attached to the surface of the fiber to obtain a modified fiber. The uses and types of the fiber are the same as those described in the first embodiment.

[0076] (Treatment agent adhesion treatment) There are no particular restrictions on the proportion of the treatment agent of the first embodiment that is applied to the fibers, but it is preferable to apply the solvent-free treatment agent so that it is 0.1% by mass or more and 2% by mass or less relative to the fibers, and it is more preferable to apply it so that it is 0.2% by mass or more and 1.2% by mass or less.

[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 diluted solution further diluted with a solvent, is used. The treatment agent can be applied to fibers by known methods, such as immersion, spraying, roller application, and guide oiling using a metering pump. Furthermore, the treatment agent can be applied to nonwoven fabrics by immersion, spraying, roll coating, gravure coating, die coating, curtain coating, or the like.

[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 fibers of this embodiment are coated with the treatment agent of the first embodiment. Therefore, a nonwoven fabric having water repellency can be obtained. This makes the fabric suitable for applications in fields such as hygiene products, medical care, and civil engineering, where improved functionality is required.

[0080] Furthermore, fibers to which the treatment agent has been applied have improved carding properties, resulting in a nonwoven fabric with excellent uniformity. Furthermore, the wettability of the treatment agent to the fibers has also improved, resulting in a nonwoven fabric 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 within the scope of technical compatibility.

[0082] Each of the treatment agents, compositions, or dilutions of the above embodiments may further contain other components commonly used in treatment agents, such as solvents, stabilizers, antistatic agents, binders, antioxidants, UV absorbers, surfactants, and pH adjusters, to maintain the quality of each treatment agent, as long as the effects of the present invention are not impaired. In order to efficiently exert the efficacy of the present invention, the amount of other components commonly used in treatment agents other than solvents is preferably 10% by mass or less in each treatment agent. Furthermore, these other components may be stored as separate agents from the treatment agents described above. In the present invention, the content of compounds other than the phosphoric acid compound (P) and the alcohol (A) is 10% by mass or less. [Example]

[0083] Examples will be given below to more specifically illustrate 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 adding 92.5 parts of the phosphate compound (P-1) shown in Table 1 below as the phosphate compound (P) and 7.5 parts of 1-propanol (A-1) as the alcohol (A) to a container and mixing them well.

[0085] (Examples 2 to 25, Comparative Examples 1 to 6) The treating agents of Examples 2 to 25 and Comparative Examples 1 to 6 were 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 in Table 1.

[0088] [Table 1] Details of the phosphoric acid compound (P) and 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 that constitute 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) are shown in the "P nucleus NMR integral ratio" column, assuming that 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 100%. Note that "EO" in Table 2 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. P nucleus NMR integrals N assigned to phosphate ester (Pa) and inorganic phosphate (Pi) Pa N Pi The ratio (N Pi / N Pa ) to "N Pi / N Pa The P NMR measurement method is shown below.

[0093] ·P nuclear NMR measurement method Each phosphate 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, trade name, manufactured by VALIAN, 300 MHz, the same applies hereinafter) was used.

[0094] Among the obtained signals, the integral value of the signal appearing between 4 ppm and 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 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 room temperature ion-exchanged water with stirring to prepare a 1% diluted solution. 5 μL of a 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] Wettability evaluation criteria 3 (Good): Penetrates in less than 60 seconds 2 (Acceptable): 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 bicomponent fibers (PE / PET) obtained in the cotton manufacturing process, with a fineness of 2.2 dtex and a fiber length of 38 mm, and consisting of a polyethylene sheath and a polyester core, so that the amount of 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 at a temperature of 25°C and a humidity of 40% to form a web. Hot air at approximately 140°C was blown onto the web for 10 seconds to perform a hot air treatment, bonding the fibers together and achieving a basis weight of 25 g / m. 2Nonwoven fabrics were fabricated. Water repellency was evaluated using the hydrostatic pressure method according to JIS L 1092 7.1.1A (low water pressure method). A Swiss-made Textest FX3000-III hydrotester was used, and the test was conducted under conditions of 20±2°C temperature and 65±2% humidity. Five pieces of the fabricated nonwoven fabric (approximately 150 mm x 150 mm) were attached to the hydrotester so that the water hit the front side of the nonwoven fabric. The water level was raised at a rate of 10 cm / min, and the reading (cmw.c.) was taken 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 was calculated. The higher the water pressure resistance, the better the water repellency. The results are shown in the "Water Repellency" column in Table 1.

[0101] Water repellency evaluation criteria 3 (Good): Water pressure resistance of 5.0 cmw.c. or more 2 (Acceptable): Water pressure resistance is 3.0cm w.c. or more and less than 5.0cm w.c. 1 (Poor): Water pressure resistance is less than 3.0 cmw.c. Test Category 5 (Card Passability Evaluation) 30 g of the oiled PE / PET fiber described above was passed through a small roller card in an atmosphere of 25°C and 40% RH. The carding performance was evaluated as the uniformity of the spun carded web according to the following criteria. The results are shown in the "Carding Performance" 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 uneven areas of thickness on the web, but this is not a problem. 1 (bad): When the web thickness is uneven Test Category 6 (Evaluation of emulsion stability) A 1% dilution in hard water was prepared by uniformly mixing 1 part of the treatment agent with 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% dilution in hard water was allowed to stand at 25°C for 24 hours. Emulsion stability was evaluated based on the appearance of the 1% dilution of the treatment agent in hard water 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, dispersed, or precipitated The results in the above table show that the present invention can improve emulsion stability in 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 has been 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 P nucleus NMR integral values ​​N Pa 、N Pi The ratio (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): Mono- to trihydric alcohols with 3 to 6 carbon atoms. In a second aspect, in the treatment agent for nonwoven fabrics according to the first aspect, 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 a third aspect, in the treatment agent for nonwoven fabrics according to the first or second aspect, 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 phosphate ester (Pc) is 15% or more. In aspect 4, in the treatment agent for nonwoven fabrics according to any one of aspects 1 to 3, 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 phosphate ester (Pa) is less than 20%. Aspect 5 is the treatment agent for nonwoven fabrics according to any one of Aspects 1 to 4, 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, where the total content of the phosphoric acid compound (P) and the alcohol (A) is taken as 100% by mass. The fibers of the sixth aspect are characterized in that the treating agent for nonwoven fabric according to any one of the first to fifth aspects is adhered to the fibers.

Claims

1. A treatment agent for nonwoven fabrics, comprising the following phosphoric acid compound (P) and the following alcohol (A): The P nucleus NMR integral values ​​N assigned to the following phosphate esters (Pa) and the following inorganic phosphoric acid (Pi) Ｐａ , N Ｐｉ The ratio (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 further 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): 【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 of 0 or more and 3 or less. 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 of 0 or more and 3 or less. M ３ : hydrogen atom, alkali metal, alkaline earth metal (1 / 2), ammonium, or organic amine. 【Transformation 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 between 0 and 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): Mono- to trihydric alcohols having 3 to 6 carbon atoms.

2. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein the P nuclear NMR integral ratio attributable to the inorganic phosphoric acid (Pi) is 25% or more when the total 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%.

3. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein the P nuclear NMR integral ratio attributable to the phosphate ester (Pc) is 15% or more when the total 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%.

4. 2. The treatment agent for nonwoven fabrics according to claim 1, wherein the P nuclear NMR integral ratio attributable to the phosphate ester (Pa) is less than 20% when the total 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%.

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, where the total content of the phosphoric acid compound (P) and the alcohol (A) is taken as 100% by mass.

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

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