JP3313280B2 - Hydrophilicity improver for polyolefin fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilicity improver for polyolefin fibers, and more particularly, to imparting initial or instantaneous water permeability to a non-woven fabric made of polyolefin fibers, and at the same time improving durability water permeability. The present invention relates to a hydrophilicity improver that can be used.

[0002]

2. Description of the Related Art Polyolefin fibers, such as polyethylene fibers and polypropylene fibers, are hydrophobic fibers, and when used as surface materials such as sanitary napkins and paper diapers, the parts in contact with the skin do not have a wet feeling and feel comfortable. Therefore, it is widely used for such purposes.

In order to avoid discomfort due to sweating, urine, body fluids, etc. when wearing paper diapers, sanitary napkins, etc., it is easy to wet the touching parts of such products, and the ease of wetting is instantaneous in a short time. Is considered important. For this reason, the polyolefin fibers constituting the touching part are required to have instantaneous water permeability within a short period of time, and at the same time, infants, elderly people, and sick people who cannot themselves treat excrement with paper diapers etc. For example, since one wear does not always treat one excrement, it is necessary to avoid discomfort for several excretions. There is also a strong demand for water permeation) and low wet return (wet return). Naturally, by providing instant water permeability and durability, there is no leakage of urine or the like from the surface material.

[0004] The present invention relates to a hydrophilicity improver which satisfies the above-mentioned requirements for polyolefin fibers which are inherently inferior in hydrophilicity due to their hydrophobic properties. Conventionally, for imparting hydrophilicity to polyolefin fibers, 1) application of a low molecular weight hydrophilic compound 2) application of a hydrophilic polymer resin 3) surface modification by chemical treatment, solvent treatment, plasma treatment, corona discharge treatment, etc. Has been made.

However, in the case of a low-molecular-weight hydrophilic compound, the wetting agent does not easily adhere to the hydrophobic fiber surface due to poor wettability, and it is difficult to obtain the expected water permeability. However, there is a problem that even when the property is obtained, durability is not obtained at all, and many of them have strong skin irritation. In addition, in the case of a hydrophilic polymer resin, the durability is generally inadequate than expected, and when an imparting agent that provides a certain degree of durability is used, the water permeability becomes insufficient or the imparting agent is made of a resin. Therefore, there is a problem that various obstacles are caused in the nonwoven fabric manufacturing process.
Means by modification on the fiber surface have the advantage that relatively good results can be obtained in terms of skin irritation and water permeability, but on the other hand, the change over time of the polar group caused by the modification of the fiber surface As a result, there is a problem that the water permeability is easily reduced, the durability is also reduced, and the means itself is uneconomical.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention is to solve the above-mentioned conventional problems and to provide a treating agent capable of meeting the above-mentioned requirements.

[0007]

Means for Solving the Problems From the above-mentioned viewpoints, the present inventors have conducted intensive studies on the hydrophilicity improving agent for polyolefin fibers, and as a result, it is difficult to balance a single compound having strong hydrophobicity and strong hydrophilicity with one another. It was found that the possibility of synergistic effects can be expected by using a combination of a compound with high hydrophilicity and high water permeability and a compound with high affinity for polyolefin, which has a low possibility of development of the compound. The present inventors have found that a treating agent containing a compound and specifically a polyether-modified silicone at a predetermined ratio is a treating agent capable of meeting the above-mentioned requirements, and have completed the present invention. That is, the present invention provides a polyether compound represented by the following general formula (A),
A hydrophilicity improver for polyolefin-based fibers, comprising 90% by weight and 90 to 10% by weight of a polyether-modified silicone represented by the following general formula (B).

[0008]

HO-,-(RO) _a -,-(R'-O) _b- , -H (wherein R = propylene, R '= ethylene, a = 5)
-100, b = 1-100. )

[0009]

HO- (R'-O) _n- (RO) _m- (R'-O) _{n '}
-H (wherein, R and R 'are the same as A, m is a of the A, and n + n' is b of the A)

[0010]

Embedded image (Wherein, R ″ = ethylene group and / or propylene group,
R ″ ′ = hydrogen or an alkoxy group or carboxy group having 1 to 12 carbon atoms, c = 7 to 100, d = 1 to 10, e =
2-3, f = 20-80. Further, the present invention provides the above-mentioned hydrophilicity improver for polyolefin-based fibers, wherein the fatty acid metal salt represented by the following general formula (C) is added in an amount of 5% by weight or less,

[0011]

Embedded image General formula C: RCOOM (wherein R represents an alkyl or alkenyl group having 11 to 17 carbon atoms, M = Na or K) An alkylolamide compound represented by the following general formula (D) A hydrophilicity improver for polyolefin-based fibers, comprising 10 to 40% by weight of

[0012]

Embedded image (Wherein, R represents an alkyl group or an alkenyl group having 11 to 17 carbon atoms.) The above-mentioned polyolefin-based fiber comprising 10 to 40% by weight of an alkylamino oxide compound represented by the following general formula (E). Hydrophilicity improver,

[0013]

Embedded image (In the formula, R represents an alkyl group having 11 to 17 carbon atoms.) The hydrophilicity improvement for polyolefin-based fibers described above, which comprises 10 to 40% by weight of an alkylammonium phosphate compound represented by the following general formula (F). Agent,

[0014]

Embedded image (Wherein, R represents an alkyl group having 8 to 12 carbon atoms).

The polyether compound having a repeating unit represented by the general formula A is generally a copolymer of propylene oxide and ethylene oxide,
The copolymer may be a random copolymer or a block copolymer. In particular, the block copolymer represented by the above general formula (A ') obtained by addition polymerization of ethylene oxide to polypropylene glycol obtained by addition polymerization of propylene oxide to water or propylene glycol has an affinity for polyolefin-based fibers. It is preferably used in view of the above. The degree of polymerization of the polyether is such that the propylene oxide unit (a) is 5 to 100, preferably 1
0 to 90, and the ethylene oxide unit (b) is 1 to 1
00, preferably 5 to 70, and from the viewpoint of the balance between hydrophobicity and hydrophilicity, a is particularly preferably 60 to 90, b is particularly preferably 10 to 30, a / b is 2 to 7, and 3 to 6 is more preferable. Preferably, there is.

Specifically, there are block copolymers represented by the general formula (A ') wherein a = 65, b = 15, and a = 85, b = 25. Furthermore, the molecular weight of the polyether is related to the insolubility of what is attached to the fiber,
Further, it is necessary to set from the viewpoint of dissolving workability.
What is 00 or less, especially 1000 to 9000 is preferable from a viewpoint of durability, solubility, handleability, and the like. On the other hand, the modified polyether silicone represented by the general formula B is obtained by adding dimethylhydrogenpolysiloxane to polyethylene glycol, a block or random copolymerized polyether of polyethylene glycol and polypropylene glycol, or ethylene oxide to an alcohol having 1 to 12 carbon atoms. Modified silicone obtained by adding a monoallyl ether such as a propylene oxide / ethylene oxide block or a random copolymer adduct to an alcohol having 1 to 12 carbon atoms.

In the present invention, the characteristic feature of the modified polyether silicone is that it has low water solubility based on its structure. That is, it has a solubility in water as small as possible, or shows a solubility such that it is finally emulsified with the aid of another emulsifier. In fact, in order to obtain a satisfactory water permeability by giving the modified silicone the minimum water solubility, it is necessary that d in the general formula B be 1 or more. The resulting modified silicone has too high a water solubility, which is satisfactory in terms of water permeability, but insufficient in durability. Also,
Similarly, in order to provide the modified silicone with minimum hydrophilicity and obtain satisfactory water permeability, the above-mentioned general formula B
Is preferably in the range of 20 to 80,
If it is less than 20, satisfactory water permeability cannot be imparted, and if it is more than 80, particularly the durability of the resulting modified silicone is greatly impaired. In this case, the molar ratio of the oxyethylene unit to the oxypropylene unit also affects, and the oxyethylene unit is preferably 1/4 or more.
Further, c in the general formula B is in the range of 7 to 100,
When the value is less than 7, the modified silicone obtained has poor durability, while when it exceeds 100, the water permeability deteriorates.

The treating agent of the present invention comprises the above-mentioned polyether compound represented by the general formula A and the modified polyether silicone represented by the general formula B, the former of which is 10-9.
0% by weight, the latter containing 90 to 10% by weight, the former preferably containing 30 to 90% by weight, and the latter containing 70 to 10% by weight, the former being preferably 50 to 90% by weight,
It is more preferable that the latter be contained in a proportion of 50 to 10% by weight, and in particular, the former is 60 to 80% by weight and the latter is 20 to 80% by weight.
Those containing at a ratio of 40% by weight are more preferable because the initial water permeability and durability are balanced. By this blending, the permeation of the polyether-modified silicone alone into the polyolefin fiber is also improved. When applying the treating agent, it is also effective to apply the stock solutions individually or by mixing and directly applying them. However, it is preferable to apply them beforehand by mixing and diluting with a solvent such as water. In order to disperse evenly in the above-mentioned solvent, it is more preferable to contain 5% by weight or less of an activator such as a fatty acid metal salt represented by the general formula C. When the content of the activator exceeds 5% by weight, the performance of the treating agent is adversely affected, and more preferably, the content is 1% by weight or less.

As a method of applying the treating agent, known methods such as a dipping method, a spraying method, and a coating method (a roll coater, a gravure coater, a die, etc.) can be adopted by using a generally diluted treating agent solution. After drying, drying is performed using a drying means such as hot air or a hot roll. In the above application, when the application is mainly performed by a coating method, it is necessary that the permeation into the cloth is uniform, especially in the case of applying at a high speed, and at this time, the polyether-modified silicone, one of the components, penetrates into the cloth. In order to stabilize this permeability, the treating agent has the following properties:
Further, as a permeability stabilizer, an alkylolamide compound represented by the general formula D, an alkylaminooxide compound of the same E, an alkylammonium phosphate compound of the same F, or the like is 10 to 40% by weight, preferably 1 to 40% by weight.
The content can be 5 to 30% by weight.

The amount of the treatment agent to be applied varies depending on the performance required, but is in the range of 0.1 to 1.0% by weight with respect to the fiber. However, since it is in direct contact with the human body, it can be set to the minimum necessary. preferable. If necessary, for example, it is also important to apply the liquid only to a necessary portion of liquid permeation, such as a central portion of the surface material. The treating agent of the present invention contains the polyether compound represented by the general formula A or A 'and the polyether-modified silicone represented by the general formula B at a predetermined ratio as described above. Other compounds, for example, various surfactants as an antistatic agent, an emulsifier, a smoothing agent, and a sizing agent can be appropriately contained according to a desired purpose within a range that does not impair the effects of the present invention.

Examples of the polyolefin fibers to which the treating agent is applied include polyolefin fibers such as polyethylene and polypropylene, and core-sheath fibers having a polyolefin resin as a surface layer. Fibers of special forms such as irregular fibers are also included, and may be applied to monofilaments to form a fibrous web, or may be applied after forming a fibrous web. The shape of the fibrous web may be flat or crimped. Nonwoven fabric laminated various fiber webs such as lamination, the surface layer is a polyolefin fiber web,
A special nonwoven fabric having a hydrophilic layer or a heterogeneous web as the central layer is used. Upon application, a difference may be made in the amount of adhesion between the front and back of the fiber web as necessary.

As a joining means for joining a fiber web to form a nonwoven fabric, a thermocompression bonding point (point bonding) is used.
Method, hot air method, and other methods such as joining with a molten component (hot melt agent), and the like, but the former two methods are preferred in terms of safety. As a method for forming the web, a method in which short fibers are formed into a web by a card machine or the like, and a spun bond method directly connected to spinning, a melt blow method, and the like are not particularly limited. From the point that no other treating agent such as an oil agent is used and the point that excessive heat such as fusing at the time of joining the web is not applied, it is preferable to give after the web is joined. Spunbonded nonwoven fabrics are preferred in terms of performance stability.

[0023]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited by these examples. Various measurement methods and evaluations in the present invention are as described below. (1) Instantaneous water permeability: A measuring instrument (about 800 g, a 10 cm square hole having a diameter of 25 mm at the center, two electrodes facing the center, and a timer Is placed, and a 10 cm square (or more) test cloth is placed between the absorber and the measuring instrument, and one drop (0.1 cc / drop) of physiological saline is dropped from a dropper 15 mm above the cloth. The time from dropping to the end of surface passage was checked with an electrode, and the instantaneous water permeation rate (second) was determined.

(2) 5 cc water permeation rate (second / 5 cc) and re-wetting amount (g): As an absorber, a specific filter paper (“939”, 10 cm square × 3 by Eaton Dikeman Co., Ltd.) in order to keep the characteristics of the absorber constant. The measuring device (approximately 80
0 g, a 10 cm square having a hole with a diameter of 25 mm in the center). A test cloth (10 cm
Corner). First, 5 cc of artificial urine is dropped from the upper 25 mm. Artificial urine was prepared by adding a nonionic surfactant to physiological saline to adjust to 45 ± 3 dyne / cm (equivalent to infant urine) at 25 ° C., and the dropping rate was 3.3 seconds / 25 cc.
And This was set to 5 cc water permeation speed (second / 5 cc).
Next, artificial urine is added as it is, so that the total amount of liquid is about four times the weight of the absorber so that the amount of liquid contained in the absorber is constant. A load of 800 g / 10 cm square is applied from above the test cloth for 3 minutes to make the distribution of the liquid in the absorber constant. Next, filter paper (Eato, pre-weighed) was placed on a test cloth.
n “631” manufactured by Dikeman, 12.5 cm square x 2
Sheets were piled up and immediately applied with a 3600 g / 10 cm square (corresponding to the load applied to the baby's diaper) for 2 minutes, and the weight increase of the filter paper was measured to determine the amount of re-wetting (g).

(3) Permeation durability (number of times): The permeation rate of 5 cc of physiological saline on a certain filter paper is measured using a 5 cc water permeation rate measuring device. After determining the position of the test cloth and measuring the permeation speed, the fabric is dried with warm air of 50 ° C. or less, and the measurement of the permeation speed on a new filter paper is repeated. As a guide, a transmission speed of 60 seconds or less was effective, and the number of repetitions up to that was measured, and the number was regarded as the number of durable transmissions. (4) Thickness (mm): The thickness when a load of 100 g / cm ² is applied to the sample piece is measured. (5) Tensile test (strength / elongation): A sample with a width of 2.5 cm was grasped at a sample grasping interval of 10 cm, and a tensile speed of 20 cm /
Tested in minutes.

Preparation of nonwoven fabric: A polypropylene having a melt flow rate (MFR) of 38 is extruded quantitatively at 1300 g / mm at an extrusion temperature of 240 ° C. using an extruder having a diameter of 65 mm, and a filament group is spun using a 1540-hole spinneret. 3500 using a high-speed airflow traction device.
The web was pulled at a speed of m / min and received on a wire mesh web conveyor with a moving suction device to form a web. The web was conveyed, and the upper and lower rolls were partially thermocompressed at 135 ° C. and a pressure of 60 kg / cm by a thermocompression roll in which an engraving roll and a smoothing roll were combined, and the single yarn denier was 2.2 denier.
A polypropylene spunbond nonwoven fabric (PP nonwoven fabric) having a basis weight of 20 g / m ² was obtained. Further, by changing the speeds of a conveyor, a thermocompression roll and a winder, a polypropylene spunbond nonwoven fabric having a basis weight of 18 g / m ² was obtained.

Treatment agent component: polyether compound; propylene oxide is addition-polymerized to propylene glycol to obtain polypropylene glycol having an average degree of polymerization of 85. Next, ethylene oxide is added to the polypropylene glycol to obtain an average degree of polymerization of 25 to obtain (PO) ₈₅ · having an average molecular weight of about 6000.
(EO) ₂₅ block polyether compounds were obtained. Similarly, (PO) ₈₅ · (EO) having an average molecular weight of about 5800
₂₀ block polyether compounds were obtained.

Polyether-modified silicone; dimethylhydroxypolysiloxane to which ethylene oxide reactant of methyl alcohol is added, and c in general formula B is 2
A polyethylene ether-modified silicone (Si ₂₂ , SiE ₂ , EO ₄₀ ) having 2, d of 2, and f of 40 was obtained.

Example 1 The above PP nonwoven fabric (having a basis weight of 20)
g / m ² ), 70% by weight of a block polyether compound of (PO) _85. (EO) ₂₅ and (Si ₂₂ , SiE ₂ , E
O ₄₀₎ 1% aqueous solution of polyethylene ether modified silicone 30% by weight of comprises a mixture treating agent was applied by spraying of a 0.5% by weight of the treating agent was applied to the nonwoven fabric with respect to dried nonwoven. The instantaneous water permeability of the obtained nonwoven fabric is 0.18 (sec), the water permeability of 5 cc is 2.9 (sec / 5 cc), the wetting return amount is 0.15 (g), and the permeation durability is 5 (times) or more. Table 1 shows the obtained results. The instantaneous water permeability and durability were both excellent, and the amount of wetness and return was at a level that was not felt by the skin.

(Comparative Examples 1 and 2) The same procedures as in Example 1 were carried out except that the polyether compound and the polyether-modified silicone were not used in combination and individual components were used as treating agents.
A PP nonwoven fabric treated with the treating agent was obtained. Various physical properties of the obtained PP nonwoven fabric were measured in the same manner as in Example 1. Table 1 shows the obtained results. Polyether compounds are excellent in durability but have poor instantaneous water permeability, and polyether modified silicone alone has high instantaneous water permeability but is inferior in durability.

Example 2 A block polyether compound of (PO) ₈₅ · (EO) ₂₀ was used as a polyether compound, and 0.7% by weight of potassium laurate was further added as a fatty acid metal salt. The treatment was performed in the same manner as in Example 1 except that the temperature was set to 18 ° C. and the gravure coating method was used, to obtain a treatment agent-added PP nonwoven fabric. Various physical properties of the obtained PP nonwoven fabric were measured in the same manner as in Example 1. Table 1 shows the obtained results. There is no problem in dissolving during treatment and penetration into the cloth,
The instantaneous water permeability, durability, and wet return properties were all good.

(Example 3) Dimethylolamide laurate was further added to the treating agent for 20 minutes.
The same treatment as in Example 2 was carried out except that the addition by weight was added to obtain a treatment agent-added PP nonwoven fabric. Example 1 of obtained PP nonwoven fabric
Various physical properties were measured in the same manner as described above. Table 1 shows the obtained results. The solubility and stability of the treatment liquid were excellent, there was no problem with the penetration into the cloth, and the performance of the cloth was good. Example 4 Dimethyllaurylamine oxide was further added to the treating agent.
Except for adding 0% by weight, the same treatment as in Example 2 was performed to obtain a treatment agent-treated PP nonwoven fabric. Various physical properties of the obtained PP nonwoven fabric were measured in the same manner as in Example 1. Table 1 shows the obtained results.
Shown in It was as good as in Example 3.

Example 5 A treatment agent-treated PP nonwoven fabric was obtained by treating in the same manner as in Example 2 except that lauryl ammonium phosphate was further added to the treatment agent at 20% by weight. Various physical properties of the obtained PP nonwoven fabric were measured in the same manner as in Example 1. Table 1 shows the obtained results. As in Example 3, there was no problem in processing and the fabric performance was good. (Comparative Example 3) As a treating agent, a nonylphenol polyethylene oxide adduct (E
Using a 1% aqueous solution of (O ₁₀ added), the treatment was carried out in the same manner as in Example 2 to obtain a treated agent-added PP nonwoven fabric. As shown in Table 1, the performance of the obtained nonwoven fabric was inferior in both instantaneous water permeability and durable water permeability, and the treating agent of the present invention was excellent in instant water permeability, durability, and well-balanced wettability. Obviously.

[0034]

[Table 1]

[0035]

By using a specific polyether compound and a specific polyether modified silicone in combination, instantaneous water permeability, durable water permeability, and re-wetting property are improved, and these properties are combined with a small amount of a treating agent. The present invention provides a treatment agent for olefin fibers which can impart excellent performance and is excellent in safety.

Claims (8)

(57) [Claims] 1. A polyether compound comprising a repeating unit represented by the following general formula (A): 10 to 90% by weight, and a polyether modified silicone represented by the following general formula (B): 90 to 10% by weight. A hydrophilicity improver for polyolefin fibers characterized by the following. Embedded image General formula A: HO—, — (RO) _a —, — (R′—O) _b —, —H (where R = propylene, R ′ = ethylene, a = 5)
-100, b = 1-100. ) (Wherein, R ″ = ethylene group and / or propylene group,
R ″ ′ = hydrogen or an alkoxy group or a carboxy group having 1 to 12 carbon atoms, c = 7 to 100, d = 1 to 10, e = 2
-3, f = 20-80. ) 2. The polyether compound having a molecular weight of 1000
The hydrophilicity improver for polyolefin fibers according to claim 1, which is 0 or less. 3. In the general formula (A), a / b is 2-7.
The hydrophilicity improver for polyolefin fibers according to claim 1 or 2, wherein 4. The hydrophilicity improver for polyolefin fibers according to claim 1, wherein the polyether compound is a compound represented by the following general formula (A ′). Embedded image General formula A ′: HO— (R′—O) _n — (RO) _m — (R′—O) _{n ′}
-H (wherein, R and R 'are the same as A, m is a of the A, and n + n' is b of the A) 5. The hydrophilicity improver for polyolefin fibers according to claim 1, wherein a fatty acid metal salt represented by the following general formula (C) is added in an amount of 5% by weight or less. Embedded image General formula C: RCOOM (where R represents an alkyl or alkenyl group having 11 to 17 carbon atoms, and M represents Na or K) 6. The hydrophilicity improver for polyolefin fibers according to claim 1, wherein an alkylolamide compound represented by the following general formula (D) is blended in an amount of 10 to 40% by weight. Embedded image (In the formula, R represents an alkyl group or alkenyl group having 11 to 17 carbon atoms.) 7. The hydrophilicity improver for polyolefin fibers according to claim 1, wherein an alkylamino oxide compound represented by the following general formula (E) is blended in an amount of 10 to 40% by weight. Embedded image (In the formula, R represents an alkyl group having 11 to 17 carbon atoms.) 8. The hydrophilicity improver for polyolefin fibers according to claim 1, wherein an alkylammonium phosphate compound represented by the following formula (F) is blended in an amount of 10 to 40% by weight. Embedded image (In the formula, R represents an alkyl group having 8 to 12 carbon atoms.)