JPH0660465B2 - Hydrophilicity imparting agent for synthetic fibers - Google Patents

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a hydrophilicity-imparting agent for synthetic fibers, and in particular, improves hydrophilicity by adding it to synthetic fibers such as polyester fibers, polyolefin fibers and polyamide fibers. can do. More specifically, it relates to a hydrophilicity-imparting agent for synthetic fibers, which is suitable for underwear and the like as a fiber material for clothing, sanitary materials such as paper diapers, and can impart hydrophilicity with excellent durability to water.

[Prior art]

Synthetic fibers are used in a wide range of fields by utilizing their physical properties, but their use is limited because of their strong hydrophobicity due to the structure of their polymers. Conventionally, attempts have been made to make hydrophilic for the purpose of expanding applications, and as methods for making synthetic fiber molded articles hydrophilic, (1) to (4) can be mentioned. (1) A method of attaching a hydrophilic compound to the surface of a molded article (2) A method of graft-polymerizing a hydrophilic compound on the surface of a molded article, (3) A method of treating the molded article with a chemical solution, ultraviolet rays, etc. to make the surface hydrophilic (4) A method of adding a hydrophilic compound to a polymer of synthetic fibers, and synthetic fibers using a conventional hydrophilicity-imparting agent for synthetic fibers are described in, for example, JP-A-54-153872, sulfate ester base, An example of attaching an anionic surfactant having a phosphoric acid ester base, and published patent publication 59-5010.
No. 49 has an example of adhering a sorbitan fatty acid ester, and each of these is a method of dipping and adhering a surfactant to a porous film-like fiber molded product made of polypropylene. Further, JP-A-64-20378 and JP-A-6-206
As a surfactant, there is an example of using sorbitan fatty acid ester, polyoxyalkylene-modified silicone and alkyl phosphate in combination, an example of using sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester and alkyl phosphate in combination as a surfactant,
Both are hydrophilicity-imparting agents for polyolefin fibers,
A method of dipping and adhering in a surfactant emulsion aqueous solution is used.

[Problems to be Solved by the Invention]

However, in such a conventional hydrophilicity-imparting agent for synthetic fibers, a method of immersing the above-mentioned surfactant of the hydrophilic compound on the surface of the fiber molded article and adhering the surface active agent thereto, and therefore the above-mentioned special feature is used. In Japanese Laid-Open Patent Publication No. 54-153872, there is no water resistance to water, which is a problem in practical use. In Japanese Laid-Open Patent Publication No. 59-501049, which is used in an organic solvent system, there is a problem in handling and poor durability. However, there are problems such as insufficient hydrophilicity. Furthermore, JP-A-64-20378 and JP-A-64-
In 6172, a hydrophilic activator and a lipophilic activator are used in combination to improve durability, and this is made into an emulsion solution and attached to fibers to impart hydrophilicity, but it is still against water. Since the water resistance is weak and the fibers are washed away with water, there is a problem that the hydrophilic performance of the fibers is not fully utilized.

[Means for Solving the Problems]

The present invention has been made focusing on such conventional problems. That is, the following general formula (I) A [(C _x H _2x 0) _b (C _y H _2y 0) _c (C ₂ H _2z 0) _d H] _e (I) (where A is e Indicates a residue obtained by removing active hydrogen from a polyamine compound having an active hydrogen, a polyalkyleneimine compound, or a derivative thereof, and x is an integer of 2 to 4, y
Is an integer of 8 to 30, z is 2 or a mixture of 2 and 3, b is 0.
Or an integer of 1 to 30, c is a part of 0, or an integer of 1 to 5, and the average equivalent number of CyH2y0 per molecule is 0.2e to
5e, d is an integer of 1 to 200, and e is an integer of 6 to 300), which is a hydrophilicity-imparting agent for synthetic fibers containing as an essential component any compound. (Requirements Constituting Means) The hydrophilicity-imparting agent for synthetic fibers represented by the general formula (I) is
A polyether polyol obtained by using polyamine, polyalkyleneimine or a derivative thereof as a starting material and subjecting a specific alkylene oxide to an addition reaction in a specific order. Examples of the starting material used in the present invention include those having 6 to 300 active hydrogens in the molecule, and examples of polyamines include triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and heptaethylene. Examples include polyalkylenepolyamines such as octamine and tripropylenetetramine, polyallylamine, polyethyleneimine, and polypropyleneimine. Polyethyleneimine is usually obtained by the polymerization of ethyleneimine, but it is not a perfect linear structure.
It has a branched structure containing a primary, secondary, and tertiary amino nitrogen. Any of these linear and branched polyamine compounds is effective as long as they contain 6 to 300 active hydrogens in the molecule, and a heterocycle containing nitrogen in part may be present. Further, the polyamine and polyethyleneimine have various chemical reactivities, and the number of remaining active hydrogen is 6 to 300.
If it is within the range, the derivative can be used as a starting material. Typical examples are shown below. (a) Reaction products with aldehydes and ketones (b) Reaction products with alkyl halides (c) Reaction products with isocyanates and thioisocyanates (d) Reactions with active double bonds Products (e) Reaction products with epihalohydrins (f) Reaction products with cyanamides, guanidines, urea, etc. (g) Reaction products with carboxylic acids, acid anhydrides, acyl halides, etc. Can be used alone or in combination of two or more, and the alkylene oxide adduct can be easily produced by a usual method. That is, the starting polyamine compound is heated to 100 to 180 ° C. under an alkaline catalyst to
The target product is obtained by addition reaction of alkylene oxide at 10 atm. The hydrophilicity-imparting agent of the present invention contains a long-chain alkylene oxide having 8 to 30 carbon atoms as an essential component as shown in the general formula (I), and further ethylene oxide (hereinafter abbreviated as EO) or EO and propylene oxide (hereinafter abbreviated as PO). Is a polyether polyol obtained by addition-polymerizing a mixture of the above-mentioned starting materials. Examples of the long-chain alkylene oxide include α-olefin oxide, and it is effective that the alkyl group has 8 to 30 carbon atoms. In this case, the α-olefin oxide may be a mixture of two or more kinds having different carbon numbers. It is necessary to add-polymerize the α-olefin oxide in an average of 0.2 to 5 molar equivalents with respect to one active hydrogen, and if it is outside this range, an excellent effect of imparting hydrophilicity cannot be obtained. Examples of the alkylene oxide include EO, PO and butylene oxide (hereinafter abbreviated as BO), and the order of the addition reaction is important for obtaining an effective hydrophilicity-imparting agent. That is, the following is a specific description of the addition order of the formula (I). Starting Material-α-Alephine Oxide-EO or PO
-EO mixture Starting material-EO, PO or BO- [alpha] -olefin oxide-EO or PO-EO mixture is prepared by adding [alpha] -olefin oxide in an average of 0.2 to 5 molar equivalents to one active hydrogen of the starting material. , Further EO
Alternatively, 1 to 200 moles of PO / EO mixture is added, and 1 to 30 moles of EO, PO or BO is added, and then an average of 0.2 to 5 mole equivalents of α-olefin oxide is added, and further EO or 1-20 for PO / EO mixture
The thing added 0 mol is mentioned. It is not preferable to add PO alone to the terminal because of hydrophilicity. PO / EO
The block may be mixed with a block-shaped portion and a random-shaped portion, but more preferably, the terminal is an EO chain by the block-shaped addition method, and the degree of polymerization of the terminal EO is 1
Those added with 0 mol or more are good. The average molecular weight of the hydrophilicity-imparting agent of the present invention may be any as long as it does not deteriorate the physical properties of the resin, but preferably 5,000.
A molecular weight of ˜1,000,000, more preferably 20,000 to 500,000 is good. Synthetic fibers that can use the hydrophilicity-imparting agent of the present invention include polyolefin-based synthetic fibers, polyester-based synthetic fibers, ethylene-vinyl alcohol copolymer-based synthetic fibers, polyamide-based synthetic fibers, polyvinyl alcohol-based synthetic fibers, and polychlorinated materials. Vinylidene-based synthetic fibers and the like,
Examples of the polyolefin fiber include polypropylene, polyethylene, and modified products thereof. It is used from spun fabrics or nonwoven fabrics such as stable fibers and filament yarns obtained from these synthetic fibers, as clothing such as underwear, paper diapers, sanitary materials such as napkins, and futon lines. The amount of the hydrophilicity-imparting agent added to the synthetic fiber varies depending on the type and thickness of the fiber molded product, but is generally 0.2 to 2 as an active ingredient per 100 parts by weight of the synthetic fiber.
0 parts by weight is suitable. If the addition amount is less than 0.2 parts by weight, the hydrophilic performance is poor, and if the addition amount is less than 20 parts by weight, the hydrophilicity is not improved and the physical properties of the fiber molded product deteriorate. , Not preferable. The hydrophilicity-imparting agent of the present invention and a hydrophilicity-imparting agent having already known initial hydrophilicity, for example, fatty acid ester of polyhydric alcohol, ethylene oxide adduct thereof or ethylene oxide adduct of higher alcohol are partially contained. You may use together. In this case, the hydrophilicity can be obtained from the initial stage to the long term. As a method of use, a method of kneading with a synthetic resin polymer during a melt-spinning step of synthetic fibers is more preferable than a method of dip-coating a fiber molded article. Usually, in the extrusion spinning process, after adding to a polymer and kneading, spinning is performed to produce a stable fiber or filament yarn. Further, in the hydrophilicity-imparting agent of the present invention, in addition to the above-mentioned active ingredient, depending on the use of the fiber, an antioxidant, an ultraviolet absorber,
It does not matter at all to add an antistatic agent, a flame retardant, a coloring agent or the like.

[Action]

The processed product of the synthetic fiber to which the hydrophilicity-imparting agent of the present invention is added,
When using it, it adheres finely aggregated water that is generated depending on temperature and humidity conditions, and makes synthetic fibers with strong hydrophobicity hydrophilic, so it acts as an astonishingly wet water. The hydrophilicity-imparting agent of the present invention is different from known hydrophilicity-imparting agents in molecular structure, and has a well-balanced lipophilic group and hydrophilic group having good compatibility with a synthetic resin polymer (synthetic fiber). Due to its multi-chain structure and large molecular weight, there is very little outflow from the synthetic resin polymer (synthetic fiber) due to blooming. As a result, the durability of hydrophilicity is dramatically increased and it is durable against water. It may be a hydrophilic synthetic fiber having a certain property. Also,
By making the synthetic fiber hydrophilic, it has the effects of preventing stuffiness of the skin due to perspiration, exhibiting permanent antistatic property and antifouling property, and improving workability during manufacturing.

【Example】

The present invention will now be described with reference to examples, but the examples are merely illustrative and are not limited thereto. As target fibers, polyethylene terephthalate resin, high-density polyethylene resin, and polyamide resin were used, and stable fibers spun from each resin (single yarn fineness 3 denier, fiber length 50 mm) were prepared and the following evaluation tests were carried out. (Water durability test of hydrophilicity and hydrophilicity of the fiber) 1 g of the fiber to which the hydrophilicity-imparting agent was added was collected, and the diameter was about 5 c.
Make a spherical fiber mass of m and float it on the water surface of a beaker containing 1000 m of water. Then, water is absorbed in the fiber mass, and the time until it completely sinks under the water surface is measured. It was evaluated that the faster the immersion time is, the higher the hydrophilicity is. Next, the sunk fiber lumps are taken out, dehydrated by a centrifugal dehydrator, dried with warm air at 80 ° C. for 20 minutes, and allowed to cool, and then the above-mentioned hydrophilic immersion test is performed, and the immersion time at this time is 60 The same operation was repeated until the number of seconds was exceeded, and the number of times of this repetition was taken as the hydrophilic durability against water. The larger the number of repetitions, the higher the durability to water was evaluated. (Fiber card passability test) The fiber disentangled under the temperature and humidity conditions of 20 ° C x 70% RH is passed through a flat card and weighed with a wave of 20 g / m ² for 30 waves.
Spinning at m / min and observing the amount of the card wrapped around the needle cloth and the amount of nep generated in the wave, while 20 ° C x 35% RH
The generated amount of static electricity was observed under the temperature and humidity conditions of 1 above, and the card passing property was comprehensively determined. The result of passing the card is displayed according to the following evaluation criteria. ⊚: No winding or nep is generated, and the amount of static electricity generated is excellent. Good: Winding, generation of nep, and small amount of static electricity are good. Δ: There is wrapping, and card passing property is slightly poor. X: Poor cart passage. Table 1 shows the hydrophilicity-imparting agents of the present invention used here and comparative hydrophilicity-imparting agents. 1. Examples of polyester fiber Composition: Polyethylene terephthalate resin 100 parts by weight Hydrophilicity imparting agent of the present invention 3 parts by weight The composition having the above composition is prepared by continuously adding the hydrophilicity imparting agent of the present invention with an extrusion spinning machine for molten polymer, After mixing, the fibers were continuously spun to produce the stable fiber shown above, and the results of the evaluation test conducted are shown in Table 2. 2. Example of polyolefin fiber Composition: High-density polyethylene resin 100 parts by weight Hydrophilicity imparting agent of the present invention 4 parts by weight A formulation having the above composition was prepared in the same manner as in Example 1,
Table 3 shows the results of the evaluation test performed by making a stable fiber. 3. Example of polyamide fiber Composition: Polyamide resin 100 parts by weight Hydrophilicity-imparting agent of the present invention 3.5 parts by weight A formulation having the above composition was prepared in the same manner as in Example 1,
Table 4 shows the results of the evaluation test performed by making a stable fiber. From the above test results, tests No. 1-1 to 17 and No. 2-1 to 17 using the hydrophilicity-imparting agent of the present invention, and No. 3-1 to 17
Is a synthetic fiber such as polyester fiber, polyolefin fiber or polyamide fiber, which is capable of imparting hydrophilicity to the hydrophobic fiber surface and exhibiting hydrophilicity with durability against water. Was completed. In addition, since the hydrophilicity can be imparted, the charging property is prevented,
It is possible to improve the static electricity generated when passing cards in fiber processing and the card passing properties, thus improving workability.

【The invention's effect】

Since the hydrophilicity-imparting agent of the present invention has the property of having high durability against water and imparts hydrophilicity to the fiber, it can be processed into a synthetic fiber having hygroscopicity and excellent functionality. When a spun woven fabric or a non-woven fabric is used, and when it is used as clothing such as underwear or clothing, or when it is used as a sanitary material such as a paper diaper or a napkin and a futon wire, the feel of the fiber becomes good. Further, the prevention of stuffiness of the skin due to sweating or the like can be effectively obtained as a result of the improved hygroscopicity of the fibers. As described above, since it is excellent as a hydrophilicity-imparting agent to be added to synthetic fibers, it can widely contribute industrially to technology for improving the functionality of synthetic fibers.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08G 73/02 NTC 9285-4J D06M 101: 16

Claims (1)

[Claims] 1. The following general formula (I) A [(C _x H _2x 0) _b (C _y H _2y 0) _c (C ₂ H _2z 0) _d H] _e (I) (wherein A is A residue obtained by removing active hydrogen from a polyamine compound, a polyalkyleneimine compound, or a derivative thereof having e active hydrogens, x is an integer of 2 to 4, y
Is an integer of 8 to 30, z is 2 or a mixture of 2 and 3, b is 0.
Or an integer of 1 to 30, c is a part of 0, or an integer of 1 to 5, and the average equivalent number of CyH2y0 per molecule is 0.2e to
5e, d is an integer of 1 to 200, and e is an integer of 6 to 300).