JPH1161644A - Method of giving hydrophobic synthetic fiber hydrophilicity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart durable hydrophilicity to hydrophobic synthetic fiber by applying specific polyoxyalkylene ether and specific polyester derivative to the hydrophobic synthetic fiber under specific conditions. SOLUTION: The hydrophilicity is imparted to hydrophobic synthetic fiber by applying a polyoxyalkylene ether of the formula (R<1> is a 4-22C alkyl, a 4-22C alkenyl, a 4-12C alkyl-substituted phenyl; R<2> is a 1-4C alkyl; A is a 2-3C oxyalkylene) and one or two or more kinds of polyester derivatives selected from polyether-ester and polyether-ester amide to hydrophobic synthetic fiber as polyester fiber so that the total amount of the polyoxyalkylene ether and the polyester derivative may becomes 0.05-3 wt.% and the weight ratio of the polyoxyalkylene ether/the polyester derivative may becomes 10/90-60/40.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for imparting hydrophilicity to a hydrophobic synthetic fiber. Hydrophobic synthetic fibers such as polyester-based fibers have excellent physical properties and chemical properties, as well as excellent economic efficiency. Therefore, they have been widely used for clothing, bedding, industrial use, and the like. . In recent years, the development of applications that take advantage of the advantages has been actively carried out, and as one of them, it is required that the fiber surface, such as sanitary materials and papermaking, has excellent hydrophilicity. Applications are increasing. In particular, in the production of wet nonwoven fabrics typified by papermaking applications, when a hydrophobic synthetic fiber bundle is put into water, it is quickly mixed with water in order to improve the quality of the product and speed up the papermaking process. Excellent hydrophilicity has been required to be dispersed in fibers and to maintain a stable dispersion state. The present invention relates to a method for imparting hydrophilicity to a hydrophobic synthetic fiber that meets such a demand.

[0002]

2. Description of the Related Art Hitherto, as a method for imparting hydrophilicity to a hydrophobic synthetic fiber, the following method for attaching various hydrophilic compounds to the hydrophobic synthetic fiber has been proposed. 1) Example of attaching hydrophilic polyester having various hydrophilic groups introduced thereto (Japanese Patent Publication No. 45-10)
794, JP-A-60-134071, USP 44106
87), 2) Examples of adhering a hydrophilic polyester and another water-soluble polymer (JP-A-57-112411, JP-A-57-112411)
0-146081), 3) Example of attaching hydrophilic polyester and reactive compound (JP-A-61-12978, JP-A-62-162077), 4) Adhesion of hydrophilic polyester and anionic surfactant Examples (JP-B-47-2512, JP-A-51-26400) and the like. In particular, 1) an example of attaching a polyetherester having a polyalkylene glycol ether group to a polyester fiber for producing a nonwoven fabric by a wet method (JP-A-58-208500); 2) hydrophilicity having a sulfonic acid group Example of attaching polyester (JP-A-1-298297)
3) Example of attaching polyether polyol (JP-A-5
6-169814). Further, there is an example in which a polyalkylaminoacrylate is attached to an acrylic fiber (JP-A-60-81052).

However, all of these conventional methods include:
There is a drawback that the hydrophilicity is originally insufficiently imparted, or the durability is inferior even if the hydrophilicity can be imparted initially. In the conventional method, when these are applied to the production of a nonwoven fabric by a wet method, for example, when a short fiber bundle of hydrophobic synthetic fibers to which a hydrophilicity-imparting agent is adhered is poured into water, the short fiber bundle is quickly In other words, they are not dispersed in single fibers, or even if they are dispersed in single fibers at the beginning, the dispersed state is not maintained stably.

[0004]

The problem to be solved by the present invention is that, in the conventional method, the imparting of hydrophilicity is originally insufficient, or even if the hydrophilicity can be imparted at first at the time, the durability of the method is not enough. It is inferior in sex.

[0005]

Means for Solving the Problems Thus, the present inventors have
As a result of researching to solve the above-mentioned problem, a specific polyoxyalkylene ether compound and a specific polyester derivative are determined so that the total amount of the both is a predetermined amount and the both are in a predetermined ratio with respect to the hydrophobic synthetic fiber. It has been found that the method of adhering to is correct and suitable.

That is, the present invention relates to a method in which a polyoxyalkylene ether compound represented by the following formula 1 and the following polyester derivative are added to a hydrophobic synthetic fiber as a total amount of the polyoxyalkylene ether compound and the polyester derivative. Hydrophobic, characterized in that the polyoxyalkylene ether compound / the polyester derivative is attached so as to have a ratio of 0.05 to 3% by weight and a ratio of 10/90 to 60/40 (weight ratio). The present invention relates to a method for imparting hydrophilicity to a hydrophilic synthetic fiber.

[0007]

[Formula 1] R ¹ -A-O-R ²

[0008] In Formula 1, R ^1: an alkyl group having 4 to 22 carbon atoms, a substituted phenyl group substituted with an alkenyl group or an alkyl group having 4 to 12 carbon atoms having 4 to 22 carbon atoms R ^2:. 1 to carbon atoms 4 alkyl groups A: a polyoxyalkylene group composed of repeating oxyalkylene units having 2 or 3 carbon atoms, wherein the number of repeating oxyalkylene units is 3 to 30, and oxyethylene is used as the oxyalkylene unit. 50 units
Polyoxyalkylene group having at least mol% polyester derivative: one or more selected from the following polyetheresters and the following polyetheresteramides

Polyetherester: a structural unit formed from an aromatic dicarboxylic acid, a structural unit formed from an ester-forming derivative of an aromatic dicarboxylic acid, a structural unit formed from an aliphatic dicarboxylic acid, and a structural unit formed from an aliphatic dicarboxylic acid One or more structural units A selected from structural units formed from ester-forming derivatives, structural units B formed from glycol, and structural units formed from polyether diol and polyether monool Number average molecular weight of 1000 to 100 composed of one or more structural units C selected from the formed structural units
000 polyetheresters

Polyetheresteramide: a structural unit formed from an aromatic dicarboxylic acid, a structural unit formed from an ester-forming derivative of an aromatic dicarboxylic acid, a structural unit formed from an aliphatic dicarboxylic acid, and an aliphatic dicarboxylic acid One or more structural units a selected from the structural units formed from ester-forming derivatives of the above, a structural unit b formed from a glycol, a structural unit formed from a polyether diol, and a polyether monool A number average molecular weight of 1000 to 10 composed of one or more structural units c selected from structural units formed from and a structural unit d formed from an amide-forming compound
0000 polyetheresteramide

The polyoxyalkylene ether compound represented by the formula 1 used in the present invention includes: 1) a polyoxyalkylene group having one end blocked by an alkyl group and the other end having a carbon number equal to or less than the carbon number of the alkyl group having one end blocked. A polyoxyalkylene ether compound blocked with an alkyl group having a number, 2) an alkyl group having one or less carbon atoms of an alkenyl group in which one end of the polyoxyalkylene group is blocked by an alkenyl group and the other end is blocked by one end 3) one end of the polyoxyalkylene group is blocked with a substituted phenyl group substituted with an alkyl group, and the other end is not more than the carbon number of the alkyl group of the substituted phenyl group having one end blocked. A polyoxyalkylene ether compound blocked with an alkyl group having a carbon number is included.

In the polyoxyalkylene ether compound represented by the formula 1, R ¹ which blocks one end of the polyoxyalkylene group is 1) a butyl group, a propyl group, an octyl group, a lauryl group, an isotridecyl group, a stearyl group or the like. An alkyl group having 4 to 22 carbon atoms, 2) a hexenyl group, a palmitooleyl group, an oleyl group or the like having 4 to 2 carbon atoms.
2) an alkenyl group, 3) a substituted phenyl group substituted with an alkyl group having 4 to 12 carbon atoms such as a butylphenyl group, an octylphenyl group, a nonylphenyl group, and the like.
Among them, an alkyl group having 4 to 16 carbon atoms is preferable.

In the polyoxyalkylene ether compound represented by the formula (1), R ² which blocks the other end of the polyoxyalkylene group has 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. And an alkyl group of 4, and among them, a methyl group is preferable.

In the polyoxyalkylene ether compound represented by the formula 1, the oxyalkylene unit constituting the polyoxyalkylene group is an oxyethylene unit or an oxyethylene unit and an oxypropylene unit.
5 oxyethylene units as the oxyalkylene unit;
It has 0 mol% or more, preferably 70 mol% or more. Such polyoxyalkylene groups include 1) those composed solely of oxyethylene units, and 2) those in which 50 mol% or more of oxyethylene units and 50 mol% or less of oxypropylene units are combined in a block and / or random manner. And those consisting of The number of repeating oxyalkylene units constituting such a polyoxyalkylene group is from 3 to 30, preferably from 4 to 10.

The present invention does not particularly limit the method for synthesizing the polyoxyalkylene ether compound represented by the formula 1, but includes any known synthesis method, for example, Japanese Patent Publication No. Sho 49-1.
The synthesis method described in Japanese Patent No. 4841 can be applied.

The polyester derivative used in the present invention includes:
1) Polyetherester composed of specific structural units and 2) Polyetheresteramide composed of specific structural units are included.

The above-mentioned polyetherester has the above-mentioned constitutional unit A, constitutional unit B and constitutional unit C as constitutional units. Such a polyetherester is obtained by subjecting a compound that forms the structural unit A, a compound that forms the structural unit B, and a compound that forms the structural unit C to a condensation polymerization reaction.

Compounds that form the structural unit A include aromatic dicarboxylic acids, ester-forming derivatives thereof,
One or more selected from aliphatic dicarboxylic acids and ester-forming derivatives thereof. Such aromatic dicarboxylic acids or their ester-forming derivatives include: 1) monocyclic aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid; 2) 2,6-naphthalenedicarboxylic acid; 2,3-naphthalenedicarboxylic acid Acid, polycyclic aromatic dicarboxylic acid such as 1,4-naphthalenedicarboxylic acid, 3) 5
-Aromatic dicarboxylic acids having a sulfonic acid group such as -sulfoisophthalic acid, sulfoterephthalic acid, and 4-sulfonaphthalene-2,6-dicarboxylic acid; 4) ester-forming properties of the above 1) such as dimethyl terephthalate and dimethyl isophthalate; Derivatives, 5) dimethyl 2,6-naphthalenedicarboxylate, dimethyl 1,4-naphthalenedicarboxylate and the like ester-forming derivatives of the above 2), 6) diethyl 5-sulfoisophthalate, dimethyl sulfoterephthalate and the like 3) And the like. Among them, monocyclic aromatic dicarboxylic acids and ester-forming derivatives thereof are preferable.

The above-mentioned aliphatic dicarboxylic acids or their ester-forming derivatives include: 1) saturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; 2) maleic acid and fumaric acid. 3) an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, etc .; 4) an ester-forming derivative of the above 1) such as dimethyl succinate and diethyl adipate;
5) The ester-forming derivatives of the above 2) such as diethyl maleate and dimethyl fumarate; and 6) The ester-forming derivatives of the above 3) such as dimethyl cyclohexanedicarboxylate. Among them, saturated aliphatic dicarboxylic acids, Ester-forming derivatives are preferred.

The compound that forms the structural unit B is glycol. Such glycols include 1) ethylene glycol, 1,2-propylene glycol,
1,4-butanediol, neopentyl glycol,
Aliphatic glycols such as 1,6-hexanediol, 2)
Alicyclic glycols such as cyclohexanedimethanol and 2,2'-bis (4-hydroxycyclohexyl) propane; 3) 2,2 '-{bis (4-hydroxyethoxyphenyl)} propane; 2,2'-bis (4-hydroxypropoxyphenyl) methane} and other aromatic glycols containing an aromatic group, 4) aliphatic glycols such as diethylene glycol and dipropylene glycol, and among them, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol is preferred.

The compound forming the structural unit C is one or more compounds selected from polyether diols and polyether monols. Examples of such polyether diols include 1) aliphatic polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and 2) structural unit B.
3) Polyether diols obtained by adding ethylene oxide or propylene oxide to the above-mentioned aliphatic glycol, alicyclic glycol or aromatic glycol; 3) Ethylene oxide or propylene oxide to aliphatic primary amine Is added. As such a polyether diol, those having a molecular weight of 400 to 6000 are preferable, and those having a molecular weight of 1000 to 4000 are more preferable.

The polyether monol as described above includes 1) methyl alcohol, ethyl alcohol,
Polyether monool in which ethylene oxide or propylene oxide is added to aliphatic monool such as butyl alcohol; 2) polyphenol in which ethylene oxide or propylene oxide is added to aromatic monool such as phenol or alkyl-substituted phenol substituted by alkyl group; Ether monool, 3) polyether monool obtained by adding ethylene oxide or propylene oxide to alicyclic monool such as cyclohexanol, 4) polyether monool obtained by adding ethylene oxide or propylene oxide to aliphatic secondary amine Is mentioned. Such polyether monol has a molecular weight of 400-6.
000 is preferable, and 1000 to 4000 is more preferable.

The polyetherester used in the present invention is
It is composed of the structural units A to C as described above. The present invention does not particularly limit the ratio of the structural units A to C constituting the polyetherester.
Is preferably 5 to 40% by weight, more preferably 5 to 30% by weight.
% By weight, preferably 0.1 to 10% by weight of the structural unit B,
More preferably, 0.5 to 10% by weight, and the structural unit C is preferably 50 to 94.9% by weight, more preferably 60 to 9% by weight.
It has 4.5% by weight.

As the structural unit A constituting the polyetherester, a structural unit formed from an aliphatic dicarboxylic acid and / or an ester-forming derivative thereof and a monocyclic aromatic dicarboxylic acid and / or an ester thereof as the structural unit A It is preferable that the structural unit A has a total of 60 to 90% by weight in the structural unit A.

The polyetherester used in the present invention is
The number average molecular weight is assumed to be 1,000 to 100,000.
It is preferably from 000 to 15,000.

The present invention does not particularly limit the method for synthesizing the polyetherester used in the present invention. For this purpose, a known synthesis method, for example, a synthesis method described in JP-B-45-10794 can be applied. .

The polyetherester amide used in the present invention together with or instead of the polyetherester described above is a structural unit having the above-mentioned structural unit a
And a structural unit b, a structural unit c, and a structural unit d. Such polyetheresteramides are
A condensation polymerization reaction of a compound that forms structural unit a, a compound that forms structural unit b, a compound that forms structural unit c, and a compound that forms structural unit d Is obtained by

The compound which forms the structural unit a is the same as the compound which forms the structural unit A, and the compound which forms the structural unit b forms the structural unit B described above. The compounds that form the structural unit C are the same as the compounds that form the structural unit C, and the description thereof is omitted.

The compound that forms the structural unit d is an amide-forming compound. Examples of such amide-forming compounds include 1) aliphatic diamines such as hexamethylenediamine and nonamethylenediamine, 2) 4,4′-diaminodiphenylether, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenylsulfone. 3) lactams such as ε-caprolactam,
4) Aminocarboxylic acids such as 6-aminohexanecarboxylic acid and 11-aminoundecanecarboxylic acid are exemplified, and among them, hexamethylenediamine and ε-caprolactam are preferable.

The polyetheresteramide used in the present invention comprises the structural units a to d as described above. Although the present invention does not particularly limit the proportion of the structural units a to d constituting the polyetheresteramide, the polyetheresteramide preferably accounts for 3 to 20% by weight of the structural unit a in all of these structural units. , More preferably 5 to 15% by weight, structural unit b is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, and structural unit c is preferably 50 to 94.9% by weight. Preferably 60 to 89.5% by weight, structural unit d is preferably 2 to 20% by weight, more preferably 5 to 15% by weight.
In the ratio of

Regarding the structural unit a constituting the polyetheresteramide, as the structural unit a, a structural unit formed from an aliphatic dicarboxylic acid and / or an ester-forming derivative thereof, and a monocyclic aromatic dicarboxylic acid and / or And a structural unit formed from an ester-forming derivative, which preferably accounts for 60 to 90% by weight of the structural unit A in total.

The polyetheresteramide used in the present invention has a number average molecular weight of 1,000 to 100,000, preferably 2,000 to 15,000.

The present invention does not particularly limit the method for synthesizing the polyetheresteramide used in the present invention, and includes known synthetic methods, for example, Japanese Patent Publication No. 45-10794.
Can be applied.

In the present invention, the above-mentioned polyoxyalkylene ether compound and polyester derivative are added to the hydrophobic synthetic fiber in a total amount of 0.05 to 3
%, Preferably 0.1 to 1.0% by weight.
Attach so that the ratio is weight%. If the total amount is less than 0.05% by weight, it is difficult to obtain the desired effect stably. Conversely, if the total amount exceeds 3% by weight, no appropriate effect can be obtained.

In the present invention, the ratio of the polyoxyalkylene ether compound to the polyester derivative is 10/90 to 60/40 (weight ratio) based on the hydrophobic synthetic fiber. As such, preferably 15/85 to 50/50
(Weight ratio). This is to obtain the desired hydrophilicity and its durability.

In the practice of the present invention, the polyoxyalkylene ether compound and the polyester derivative are preferably used as an aqueous dispersion or an aqueous solution. When preparing an aqueous dispersion, a dispersant can be used as an auxiliary. Examples of such dispersants include: 1) nonionic surfactants such as polyoxyethylene (hereinafter, referred to as POE) alkyl ether, POE alkyl phenyl ether, and POE alkyl ester; 2) alkyl sulfate;
Anionic surfactants such as alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, and alkyl phosphate are exemplified. The use ratio of these dispersants is preferably 15% by weight or less based on the above-mentioned polyoxyalkylene ether compound or polyester derivative. When preparing an aqueous dispersion or an aqueous solution, an organic solvent can be appropriately used in combination. When preparing an aqueous dispersion or aqueous solution, the solid content concentration is usually 1 to 2
It is adjusted to 0% by weight, preferably 3 to 15% by weight, and when adhering to the hydrophobic synthetic fiber, it can be used after further diluting it with water.

The present invention does not particularly limit the method of adhering the above-described polyoxyalkylene ether compound and polyester derivative to hydrophobic synthetic fibers. Examples of the method include: 1) a polyoxyalkylene ether compound and a polyester derivative And 2) separately attaching them to the hydrophobic synthetic fiber. In the case of the above method 1), it is preferable to attach a polyoxyalkylene ether compound to a hydrophobic synthetic fiber and then attach a polyester derivative.

[0038] The adhesion method includes a dipping method, a spray method,
A roller method and the like can be mentioned, and examples of the attaching step include a spinning step, a drawing step, a spinning step, and an interval between these steps.

As the hydrophobic synthetic fibers to which the present invention is applied, in addition to polyester fibers, polyacrylonitrile fibers, polypropylene fibers, etc., conjugate fibers using two or more of these fibers can be mentioned. Above all, the effect of the present invention is high with respect to polyester fibers, and the effect of the present invention is particularly remarkable with polyester fibers for producing a nonwoven fabric by a wet method. Such polyester fibers include, in addition to polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., modified polyester fibers obtained by copolymerizing various monomers for various purposes, such as basic or acidic dyeable polyester fibers. And antistatic polyester fibers and flame retardant polyester fibers.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the method for imparting hydrophilicity according to the present invention include the following 1) to 12). 1) Lauryl polyoxyethylene (the number of repetition of oxyethylene units is 5, hereinafter referred to as n = 5) methyl ether {in the formula 1, R ¹ is a lauryl group, R ² is a methyl group;
Is a polyoxyethylene group (n = 5) {hereinafter referred to as polyoxyalkylene ether compound (H-1)}.
And the following polyetherester (P-1) in a ratio of 0.3% by weight as a total amount of the polyoxyalkylene ether compound (H-1) and the polyetherester (P-1) to the polyester fiber. And the polyoxyalkylene ether compound (H-1) / polyether ester (P-1) = 36/64 (weight ratio) at the same time. Polyetherester (P-1): Of all the structural units, a total of 13% by weight of a structural unit formed of dimethyl terephthalate and a structural unit formed of dimethyl isophthalate, and 3 structural units formed of ethylene glycol Polyetherester having a number average molecular weight of 9500 and a structural unit formed of polyethylene glycol having an average molecular weight of 3100% by weight and a weight ratio of 84% by weight.

2) The polyoxyalkylene ether compound (H-1) and the following polyether ester (P-2) were mixed with the polyester fiber to form a polyoxyalkylene ether compound (H-1) and the polyether ester (P −
2) and the polyoxyalkylene ether compound (H-1) /
A method in which polyetherester (P-2) is simultaneously adhered so as to have a ratio of 28/72 (weight ratio). Polyetherester (P-2): a total of 15% by weight of a total of the constituent units formed of dimethyl terephthalate and the constituent units formed of dimethyl isophthalate, and a constituent unit formed of ethylene glycol and 1 4,4-butanediol in a total amount of 4% by weight, and a polyoxyethylene laurylaminoether having an average molecular weight of 4,000 is 81
Polyetherester having a number average molecular weight of 7,500 and having a weight percentage of 7500

3) The polyoxyalkylene ether compound (H-1) and the following polyether ester (P-3) were mixed with the polyester fiber to obtain a polyoxyalkylene ether compound (H-1) and the polyether ester (P-3). −
3) and the polyoxyalkylene ether compound (H-1) /
A method in which polyetherester (P-3) is simultaneously adhered so as to have a ratio of 18/82 (weight ratio). Polyetherester (P-3): A total of 29 parts by weight of the structural units formed from dimethyl terephthalate, the structural units formed from adipic acid, and the structural units formed from dimethyl 5-sulfoisophthalate, among all the structural units. %, A structural unit formed from ethylene glycol at 6% by weight,
A polyetherester having a number average molecular weight of 9000 and a structural unit formed from a bisphenol A ethylene oxide adduct having an average molecular weight of 1100 at a ratio of 65% by weight.

4) Polyoxyalkylene ether compound (H-1) and the following polyetheresteramide (A-
1) with respect to the polyester fiber so that the total amount of the polyoxyalkylene ether compound (H-1) and the polyetheresteramide (A-1) is 0.3% by weight, and Ether compound (H-1) / polyetheresteramide (A-1) =
A method of simultaneously adhering to a ratio of 36/64 (weight ratio). Polyetheresteramide (A-1): Of all the structural units, a total of 11% by weight of a structural unit formed of dimethyl terephthalate and a structural unit formed of dimethyl isophthalate, and a structural unit formed of ethylene glycol. Polyetheresteramide having a number-average molecular weight of 7,500 and having a weight-average molecular weight of 7,500 and a structural unit formed of polyethylene glycol having an average molecular weight of 1,500 at 81% by weight and a structural unit formed of ε-caprolactam at 7% by weight.

5) Polyoxyalkylene ether compound (H-1) and the following polyether ester amide (A-
2) with respect to the polyester fiber so that the total amount of the polyoxyalkylene ether compound (H-1) and the polyetheresteramide (A-2) is 0.5% by weight, and Ether compound (H-1) / polyetheresteramide (A-2) =
A method of simultaneously adhering to a ratio of 36/64 (weight ratio). Polyetheresteramide (A-2): a total of 13% by weight of a total of the constituent units formed from dimethyl terephthalate, the constituent units formed from dimethyl isophthalate, and the constituent units formed from adipic acid in all the constituent units; A number average having 1% by weight of a constituent unit formed of ethylene glycol, 83% by weight of a constituent unit formed of polyethylene glycol having an average molecular weight of 1500, and 3% by weight of a constituent unit formed of hexamethylenediamine. 8000 molecular weight polyetheresteramide

6) Polyoxyalkylene ether compound (H-1) and the following polyetheresteramide (A-
3) with respect to the polyester fiber so that the total amount of the polyoxyalkylene ether compound (H-1) and the polyetheresteramide (A-3) is 0.8% by weight, and Ether compound (H-1) / polyetheresteramide (A-3) =
A method of simultaneously adhering to a ratio of 36/64 (weight ratio). Polyetheresteramide (A-3): A total of 10% by weight of a constituent unit formed from dimethyl terephthalate and a constituent unit formed from dimethyl 5-sulfoisophthalate in all constituent units, and formed from ethylene glycol. A polyetherester having a number average molecular weight of 7000, comprising 1% by weight of a structural unit, 83% by weight of a structural unit formed from polyethylene glycol having an average molecular weight of 1500, and 6% by weight of a structural unit formed from ε-caprolactam. Amide

7) A polyoxyalkylene ether compound (H-1), a polyether ester (P-1) and a polyether ester amide (A-2) are added to a polyester fiber to form a polyoxyalkylene ether compound (H-
1), the polyetherester (P-1) and the polyetheresteramide (A-2) in a total amount of 0.3% by weight and the polyoxyalkylene ether compound (H-1) / ｛ Polyetherester (P-
1) + polyetheresteramide (A-2)｝ = 36
/ 64 (weight ratio) at the same time.

8) Oleyl polyoxyethylene (n = 1)
0) Methyl ether {In the formula 1, R ¹ is an oleyl group, R ² is a methyl group, A is a polyoxyethylene group (n =
10) {hereinafter referred to as polyoxyalkylene ether compound (H-2)} and polyetherester (P
-1) in a proportion of 0.3% by weight as a total amount of the polyoxyalkylene ether compound (H-2) and the polyether ester (P-1) to the polyester fiber, and Ether compound (H
-2) / polyetherester (P-1) = 36/64
(Weight ratio).

9) Nonylphenylpolyoxyethylene (n = 5) polyoxypropylene (repeating number of oxypropylene units is 3 and m = 3) methyl ether {in the formula 1, R ¹ is a nonylphenyl group, R ² is When the methyl group and A are a polyoxyalkylene group comprising a polyoxyethylene group (n = 10) and a polyoxypropylene group (m = 3) {hereinafter referred to as a polyoxyalkylene ether compound (H-3)}, Ether ester (P-
2) with respect to the polyester fiber so that the total amount of the polyoxyalkylene ether compound (H-3) and the polyether ester (P-2) is 0.3% by weight, and Compound (H-
3) / polyetherester (P-2) = 36/64
(Weight ratio).

10) The total amount of the polyoxyalkylene ether compound (H-1) and the polyether ester (P-1) is 0.3% by weight with respect to the polyester fiber, and the polyoxyalkylene ether is used. Compound (H-1) / polyetherester (P-1) = 30
A method in which a polyoxyalkylene ether compound (H-1) is first attached so that the ratio becomes / 70 (weight ratio), and then a polyether ester (P-1) is attached.

11) The total amount of the polyoxyalkylene ether compound (H-1) and the polyetheresteramide (A-1) is 0.33% by weight with respect to the polyester fibers, and the polyoxyalkylene is used. First, the polyoxyalkylene ether compound (H-) was added so that the ratio of ether compound (H-1) / polyetheresteramide (A-1) was 30/70 (weight ratio).
1) adhering, followed by adhering polyetheresteramide (A-1).

12) The total amount of the polyoxyalkylene ether compound (H-1) and the polyether ester (P-2) is 0.30% by weight with respect to the polyester fiber, and the polyoxyalkylene ether is used. Compound (H-1) / polyetherester (P-2) = 5
A method in which a polyoxyalkylene ether compound (H-1) is first adhered so that the ratio becomes 0/50 (weight ratio), and then a polyether ester (P-2) is adhered.

Examples will be given below to more specifically show the constitution and effects of the present invention, but the present invention is not limited to these examples. In the following examples and the like, parts mean parts by weight or% means% by weight.

[0053]

【Example】

Test Category 1 (Synthesis of polyester derivative) ・ Synthesis of polyetherester (P-1) 90 parts (0.45 mol) of dimethyl terephthalate, 10 parts (0.05 mol) of dimethyl isophthalate, 68 parts of ethylene glycol (1) .10 mol), 403 parts (0.15 mol) of polyethylene glycol having an average molecular weight of 3100, and 0.15 part of manganese acetate tetrahydrate and 0.05 part of antimony trioxide as a catalyst were charged in a nitrogen gas stream.
After transesterification at ~ 230 ° C, a predetermined amount of methanol was distilled off, and 0.035 parts of phosphorous acid was added.
The pressure was gradually reduced while raising the temperature over 2 hours, and finally a condensation polymerization reaction was carried out at 270 ° C. for 40 minutes under a reduced pressure of 1 mmHg to obtain a polymer. When this polymer was analyzed, a total of 13% of a terephthalic acid residue and an isophthalic acid residue corresponding to the structural unit A and 3% of an ethylene glycol residue corresponding to the structural unit B in all the structural units were obtained. 84 polyethylene glycol residues corresponding to unit C
% And a number average molecular weight of 9500 (GPC method in terms of polystyrene, the same applies hereinafter) polyetherester (P
-1).

Polyetherester (P-2), (P
Synthesis of -3) Polyetheresters (P-2) and (P-3) were synthesized in the same manner as polyetherester (P-1). The contents are summarized in Table 1.

Polyetheresteramide (A-1)
58 parts (0.30 mol) of dimethyl terephthalate, 10 parts (0.05 mol) of dimethyl isophthalate, 50 parts (0.80 mol) of ethylene glycol, 375 parts (0.25 mol) of polyethylene glycol having an average molecular weight of 1500 ), Ε
-Caprolactam (34 parts, 0.30 mol), and manganese acetate tetrahydrate (0.10 part) and antimony trioxide (0.03 part) as catalysts were charged into a nitrogen gas stream at 160 to 23 parts.
After heating at 0 ° C. to distill off a predetermined amount of methanol, 0.024 part of phosphorous acid was added, and a polycondensation reaction was performed at 270 ° C. for 60 minutes to obtain a polymer. When this polymer was analyzed, a total of 9% of terephthalic acid residues and isophthalic acid residues corresponding to the structural unit a and 1% of ethylene glycol residues corresponding to the structural unit b in all the structural units were obtained. Polyetheresteramide (A-1) having a number-average molecular weight of 7,500 and a polyethylene glycol residue corresponding to the unit c at 81% and an amide-forming compound residue corresponding to the structural unit d at a ratio of 7%. Was.

Polyetheresteramide (A-
2) Synthesis of (A-3) Polyetheresters (A-2) and (A-3) were synthesized in the same manner as for the polyetheresteramide (A-1). Table 1 summarizes the contents of the synthesized polyester derivatives.

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[Table 1]

In Table 1, the amounts used: parts a-1: dimethyl terephthalate a-2: dimethyl isophthalate a-3: adipic acid a-4: dimethyl sodium sulfoisophthalate b-1: ethylene glycol b -2: 1,4-butanediol c-1: polyethylene glycol having an average molecular weight of 1500 c-2: polyethylene glycol having an average molecular weight of 3100 c-3: polyoxyethylene lauryl amino ether having an average molecular weight of 4000 c-4: average molecular weight of 1100 Bisphenol A ethylene oxide adduct d-1: hexamethylene diamine d-2: ε-caprolactam Structural unit C or c equivalent ratio: Ratio of structural unit C or c in the total structural units of the polyester derivative (weight) %)

Test Category 2 (Preparation of Treatment Agent) Preparation of Treatment Agent (m-1) In a 2000 ml beaker, as a dispersant, the number of repetitions of polyoxyethylene / oxyethylene units was 6, hereinafter referred to as POE.
910 g of a 30 ° C. aqueous liquid in which 10 g of a nononylphenyl ether sulfate ammonium salt (6) is dissolved
While weighing it vigorously with a homomixer,
After adding 90 g of polyetherester (P-1) previously melted at 170 to 180 ° C, the mixture is cooled to 40 ° C or lower while stirring, and the polyetherester (P-1) is melted.
-1) was prepared as a 9% treating agent (m-1).

Preparation of treating agents (m-2) to (m-6) In the same manner as in the preparation of treating agent (m-1), treating agent (m-2)
~ (M-6) was prepared. Table 3 summarizes the contents of the prepared treatment agents.

Preparation of treating agents (m-7) and (m-8) In a 200 ml beaker, 98 g of water at room temperature was weighed, and while stirring, the polyoxyalkylene ether compound (H-
1) 2 g was added to prepare a 2% treating agent (m-7) for the polyoxyalkylene ether compound (H-1). Similarly, polyoxyalkylene ether compound (H-2)
Was prepared as a 2% treating agent (m-8).

Test Category 3 (Preparation of Treatment Agent) Preparation of Treatment Agent (T-1) In a 2000 ml beaker, 627 g of room-temperature water was weighed, and the treatment agent (m- 1)
After adding and diluting 355 g, 18 g of a polyoxyalkylene ether compound (H-1) was further added to prepare a treating agent (T-1).

The treating agents (T-2) to (T-9) and (t
Preparation of treatment agent (T-2) in the same manner as in the preparation of treatment agent (T-1)
To (T-9) and (t-1) to (t-8) were prepared.
Tables 2 and 3 summarize the contents of the prepared treatment agents.

Test Category 4 (Adhesion to Hydrophobic Synthetic Fiber and Its Evaluation) Examples 1 to 9 and Comparative Examples 1 to 15 Using the treating agent prepared in Test Category 3, a polyoxyalkylene ether compound and a polyester derivative were used. A 300 ml treatment bath having a total solid content of 1% was prepared. Using the prepared treatment bath, 10 g of defatted polyester staple cotton (2.0 denier × 50 mm) was treated by the immersion method under the conditions of a bath temperature of 25 ° C. and an immersion time of 30 seconds.
As a result, a sample cotton having the adhesion amount shown in Tables 2 and 3 was obtained. This sample cotton was subjected to the following evaluation without drying. The results are summarized in Tables 2 and 3.

Evaluation of initial dispersibility 70 ml of water at 25 ° C. was put into a test tube having a diameter of 2.8 cm × height 20 cm, and 0.1 g of a sample cotton was gently dropped into the test tube. Was inverted twice and allowed to stand. 1
The state of dispersion of the cotton after 0 minute was visually evaluated according to the following criteria.

Evaluation criteria of initial dispersibility ：: All settled, no coagulated fiber was observed. ○: All settled, but coagulated fiber was slightly observed. Δ: Partial floating fiber was observed or coagulated. Fibers are clearly observed. ×: remarkably large amount of floating fibers or aggregated fibers

Evaluation of Durability After evaluating the initial dispersibility, the test tube was shaken for 1 minute using a paint shaker (manufactured by Toyo Seiki Seisaku-sho, Ltd.). The bubble adhesion to cotton and the sedimentation amount of cotton after 10 minutes were visually evaluated according to the following criteria.

Criteria for evaluation of air bubble adhesion A: No air bubbles are observed O: Slight air bubbles are observed Δ: Air bubbles are partially observed X: Air bubbles are observed throughout the fiber Is recognized

Criteria for determining the amount of sedimentation ：: All fibers settled ご: Very few floating fibers △: Some fibers are floating ×: Half or more fibers are floating

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[Table 2]

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[Table 3]

In Tables 2 and 3, the amounts used: parts H-1 to H-3, h-1 to h-4: those described in Table 4 e-1: POE (6) nonylphenyl ether sulfate ammonium salt e -2: POE (6) lauryl ether sulfate triethanolamine salt

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[Table 4]

In Table 4, the ratio of EO: the ratio (mol%) of oxyethylene units in the oxyalkylene units constituting the polyoxyalkylene group

Test Category 5 (Adhesion to Hydrophobic Synthetic Fiber and Its Evaluation) Examples 10 to 15 The same defatted polyester staple cotton as in Test Category 4 was prepared using the treating agent prepared in Test Category 2 as follows. This was processed to produce a sample cotton. First, as a pretreatment, the treatment agent 1 shown in Table 5 is spray-lubricated so as to have a predetermined adhesion amount, and the treatment agent 2 shown in Table 4 is continuously spray-lubricated so as to have a predetermined adhesion amount without drying. Thus, a sample cotton was obtained. This sample cotton was tested in the same manner as in Test Category 3 without drying, and used for evaluation of initial dispersibility, air bubble adhesion, and settling amount.
Table 5 shows the results.

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[Table 5]

In Table 5, type A: type of treating agent prepared in test category 2 type B: type of polyoxyalkylene ether compound or polyester derivative

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As is clear from the above, the present invention described above has an effect that hydrophilic synthetic fibers having excellent durability can be imparted to hydrophobic synthetic fibers.

Claims (6)

[Claims] 1. A polyoxyalkylene ether compound represented by the following formula 1 and the following polyester derivative:
The total amount of the polyoxyalkylene ether compound and the polyester derivative is 0.1% with respect to the hydrophobic synthetic fiber.
And the polyoxyalkylene ether compound / the polyester derivative = 10
A method for imparting hydrophilicity to hydrophobic synthetic fibers, wherein the hydrophobic synthetic fibers are attached so as to have a ratio of / 90 to 60/40 (weight ratio). Formula 1 R ¹ -A-O-R ² (In the formula 1, R ¹ is substituted with an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, or an alkyl group having 4 to 12 carbon atoms. Substituted phenyl group R ² : an alkyl group having 1 to 4 carbon atoms A: a polyoxyalkylene group composed of repeating oxyalkylene units having 2 or 3 carbon atoms, wherein the number of repeating oxyalkylene units is 3 to 30, and 50 oxyethylene units as the oxyalkylene unit.
Polyoxyalkylene group having at least mol% Polyester derivative: one or more selected from the following polyetheresters and the following polyetheresteramides Polyetheresters: structural units formed from aromatic dicarboxylic acids, aromatic dicarboxylic acids Structural units formed from acid ester-forming derivatives, structural units formed from aliphatic dicarboxylic acids, and one or more structures selected from structural units formed from aliphatic dicarboxylic acid ester-forming derivatives Unit A, a structural unit B formed from glycol, and one or more structural units C selected from a structural unit formed from polyether diol and a structural unit formed from polyether monol. Polyetherester having a number average molecular weight of 1,000 to 100,000 Rietheresteramide: a structural unit formed from an aromatic dicarboxylic acid, a structural unit formed from an ester-forming derivative of an aromatic dicarboxylic acid, a structural unit formed from an aliphatic dicarboxylic acid, and ester formation of an aliphatic dicarboxylic acid One or two or more structural units a selected from the structural units formed from the acidic derivative, the structural unit b formed from the glycol, and the structural unit formed from the polyether diol and the polyether monool. A polyetheresteramide having a number average molecular weight of 1,000 to 100,000, comprising one or two or more structural units c selected from structural units and a structural unit d formed from an amide-forming compound) 2. The polyoxyalkylene ether compound represented by the formula 1, wherein A in the formula 1 is a polyoxyethylene group having 4 to 10 repeating oxyethylene units, and R ¹
The method for imparting hydrophilicity to a hydrophobic synthetic fiber according to claim 1, wherein R is a C 4-16 alkyl group and R ² is a methyl group. 3. The hydrophobic synthetic fiber according to claim 1, wherein the polyetherester has the structural unit C in a proportion of 50 to 94.9% by weight in all the structural units. how to. 4. The hydrophobic synthetic fiber according to claim 1, 2 or 3, wherein the polyetheresteramide has a structural unit c in a proportion of 50 to 94.9% by weight in all the structural units. How to give the property. 5. The method according to claim 1, wherein the polyoxyalkylene ether compound represented by the formula 1 is previously attached to the hydrophobic synthetic fiber, and then the polyester derivative is attached.
A method for imparting hydrophilicity to the hydrophobic synthetic fibers according to the above. 6. The method for imparting hydrophilicity to a hydrophobic synthetic fiber according to claim 1, wherein the hydrophobic synthetic fiber is a polyester fiber for producing a nonwoven fabric by a wet method.