WO2017203808A1

WO2017203808A1 - Treatment agent for polyolefin-based synthetic fibers, aqueous solution of same, treatment method for polyolefin-based synthetic fibers, polyolefin-based synthetic fibers and thermally bonded nonwoven fabric

Info

Publication number: WO2017203808A1
Application number: PCT/JP2017/010830
Authority: WO
Inventors: 昌武森田; 利広小室
Original assignee: 竹本油脂株式会社
Priority date: 2016-05-25
Filing date: 2017-03-17
Publication date: 2017-11-30
Also published as: KR20180126610A; JP2017210693A; TW201741521A; TWI617714B; KR101978950B1; JP6057489B1; CN109072539A; CN109072539B

Abstract

Provided are: a treatment agent for polyolefin-based synthetic fibers, which is capable of imparting a nonwoven fabric with high hydrophilicity, while maintaining good antistatic properties and card passing properties, and which is also capable of making the nonwoven fabric weakly acidic; an aqueous solution of this treatment agent; a treatment method for polyolefin-based synthetic fibers, which uses this aqueous solution; polyolefin-based synthetic fibers to which this treatment agent is adhered; and a thermally bonded nonwoven fabric which is formed from these polyolefin-based synthetic fibers. The present invention uses a treatment agent for polyolefin-based synthetic fibers, which contains 0.3-18% by mass of a specific organic acid, 10-50% by mass of an alkyl phosphate salt B having 4-11 carbon atoms, 10-50% by mass of an alkyl phosphate salt C having 12-22 carbon atoms and 25-65% by mass of a specific polyoxy alkylene derivative (with the total of the components being 100% by mass), and which provides a specific aqueous solution having a pH of 3 or more but less than 7.

Description

Polyolefin synthetic fiber treatment agent, aqueous solution thereof, polyolefin synthetic fiber treatment method, polyolefin synthetic fiber, and thermal bond nonwoven fabric

The present invention relates to a treatment agent for polyolefin-based synthetic fibers, an aqueous solution thereof, a method for treating polyolefin-based synthetic fibers, a polyolefin-based synthetic fiber, and a thermal bond nonwoven fabric. In recent years, nonwoven fabrics used for sanitary materials such as paper diapers and sanitary napkins are required to have high hydrophilicity and the same weak acidity as the skin, and can also be obtained as a treatment agent used in the production of such nonwoven fabrics. It is required that the nonwoven fabric can be provided with such characteristics. The present invention is a polyolefin synthetic fiber treatment agent that meets such requirements, an aqueous liquid of such a treatment agent, a method of treating a polyolefin synthetic fiber using such an aqueous liquid, a polyolefin synthetic fiber to which such a treatment agent is attached, and such a polyolefin. The present invention relates to a thermal bond nonwoven fabric made of a synthetic fiber.

Conventionally, as treatment agents for synthetic fibers, those containing an alkyl phosphate ester salt (see, for example, Patent Document 1), polyoxyalkylene-modified silicones having a specific functional group and a specific molecular weight, and a specific surfactant (For example, see Patent Document 2), those containing a nonionic surfactant having a specific functional group and an alkyl phosphate ester salt (for example, see Patent Document 3), etc. Has been. However, these conventional synthetic fiber treatment agents impart high hydrophilicity to the resulting nonwoven fabric while maintaining good antistatic properties and card passage properties even when they are used in polyolefin synthetic fibers. In addition, there is a problem that the nonwoven fabric cannot be modified to be weakly acidic.

JP-A-8-188965 Japanese Patent Laid-Open No. 2-80672 JP 2001-3271 A

The problem to be solved by the present invention is a polyolefin capable of imparting a high degree of hydrophilicity to the resulting nonwoven fabric while maintaining good antistatic properties and card passing properties, and capable of weakly acidifying the nonwoven fabric. -Based synthetic fiber treatment agent, aqueous solution of such treatment agent, method of treating polyolefin-based synthetic fiber using such aqueous solution, polyolefin-based synthetic fiber to which such a treatment agent is adhered, and thermal bond nonwoven fabric made of such polyolefin-based synthetic fiber It is in place to provide.

As a result of researches to solve the above-mentioned problems, the present inventors have found that it is correctly and suitably used a treatment agent for polyolefin-based synthetic fibers containing specific four components in a specific ratio.

That is, the present invention includes 0.3 to 18% by mass of the following organic acid, 10 to 50% by mass of the following alkyl phosphate ester salt B, 10 to 50% by mass of the following alkyl phosphate ester salt C, and A treatment for polyolefin-based synthetic fibers, comprising a polyoxyalkylene derivative in a proportion of 25 to 65% by mass (100% by mass in total), and having the following aqueous liquid having a pH of 3 to less than 7. Concerning. The present invention also relates to an aqueous liquid of such a treatment agent, a synthetic fiber treatment method using such an aqueous liquid, a polyolefin synthetic fiber to which such a treatment agent is attached, and a thermal bond nonwoven fabric made of such a polyolefin synthetic fiber.

Organic acid: At least one selected from organic hydroxy acid, organic sulfonic acid and organic phosphoric acid

Alkyl phosphate ester salt B: C4-11 alkyl phosphate ester salt

Alkyl phosphate ester salt C: C12-22 alkyl phosphate ester salt

Polyoxyalkylene derivative: A compound in which ethylene oxide and / or propylene oxide is added in a total proportion of 5 to 100 moles per mole of monohydric aliphatic alcohol having 22 to 50 carbon atoms

Aqueous liquid: An aqueous liquid containing 400 to 100000 parts by mass of water with respect to 100 parts by mass of the polyolefin synthetic fiber treating agent.

First, the treatment agent for polyolefin synthetic fibers according to the present invention (hereinafter referred to as the treatment agent of the present invention) will be described. As described above, the treatment agent of the present invention comprises four specific components in a specific ratio.

The organic acid used for the treating agent of the present invention is at least one selected from organic hydroxy acids, organic sulfonic acids, and organic phosphoric acids. Specific examples of the organic hydroxy acid include glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. Examples of the organic sulfonic acid include p-toluene sulfonic acid and dodecylbenzene sulfonic acid. Include octyl phosphoric acid, dodecyl phosphoric acid and the like.

The alkyl phosphate ester salt B used for the treating agent of the present invention is an alkyl phosphate ester salt having 4 to 11 carbon atoms. Specific examples thereof include butyl phosphate ester salt, hexyl phosphate ester salt, octyl phosphate ester salt, Nonyl phosphate ester salts, decyl phosphate ester salts, and the like can be mentioned. Among them, C6-C8 alkali metal salts such as hexyl phosphate alkali metal salts and octyl phosphate alkali metal salts are preferable.

The alkyl phosphate ester salt C used in the treating agent of the present invention is an alkyl phosphate ester salt having 12 to 22 carbon atoms, and specific examples thereof include dodecyl phosphate ester salt, tridecyl phosphate ester salt, isotridecyl phosphate ester. Salt, tetradecyl phosphate ester, hexadecyl phosphate ester, octadecyl phosphate ester salt, octadecenyl phosphate ester salt, isooctadecyl phosphate ester salt, docosyl phosphate ester salt, etc. Acid ester alkali metal salt, tridecyl phosphate alkali metal salt, isotridecyl phosphate alkali metal salt, tetradecyl phosphate alkali metal salt, hexadecyl phosphate alkali metal salt, octadecyl phosphate alkali metal salt, oct Desenirurin ester alkali metal salts, alkali metal salts of 12-18 carbon atoms, such as iso-octadecyl phosphate ester alkali metal salts are preferred.

Alkyl phosphate ester salt B and alkyl phosphate ester salt C are synthesized by a reaction between an aliphatic monohydric alcohol and a phosphorylating agent represented by anhydrous phosphoric acid, and a subsequent neutralization reaction with an alkali metal hydroxide. However, the aliphatic monohydric alcohol used may be a single substance or a mixture of two or more kinds. In general, an alkali metal salt of an alkyl phosphate ester is a mixture composed of a polyester containing a monoester, a diester, and a P—O—P bond, but the constituent ratio is not particularly limited. Further, the impurities contained in the synthetic raw material are allowed if they are within general raw material specifications. This includes, for example, various impurities and by-products such as sodium components contained in potassium hydroxide and heavy metals and arsenic compounds contained in anhydrous phosphoric acid which is one of phosphorylating agents.

The polyoxyalkylene derivative used for the treating agent of the present invention is a compound in which ethylene oxide and / or propylene oxide is added in a ratio of 5 to 100 mol in total with respect to 1 mol of a monovalent aliphatic alcohol having 22 to 50 carbon atoms. It is. Specific examples of the polyoxyalkylene derivative include carbons such as docosyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octacosyl alcohol, triacontyl alcohol, tetracontyl alcohol, dotetracontyl alcohol, and pentacontyl alcohol. Examples include those in which ethylene oxide and / or propylene oxide are added in a total proportion of 5 to 100 moles with respect to 1 mole of monohydric aliphatic alcohol having a number of 22 to 50. Ethylene oxide and / or propylene oxide is added at a ratio of 8 to 60 mol in total with respect to 1 mol of monohydric aliphatic alcohol having 26 to 40 carbon atoms such as cosyl alcohol, triacontyl alcohol and tetracontyl alcohol. Is preferred. In such polyoxyalkylene derivatives, the addition form of ethylene oxide or propylene oxide is not particularly limited, and may be either block addition or random addition.

The treating agent of the present invention comprises 0.3 to 18% by mass of the organic acid, 10 to 50% by mass of the alkyl phosphate ester salt B, 10 to 50% by mass of the alkyl phosphate ester salt C, and The polyoxyalkylene derivative is contained in an amount of 25 to 65% by mass (total of 100% by mass). The organic acid is 0.3 to 18% by mass, and the alkyl phosphate ester salt B is 15 to It is preferable to contain 45% by mass, 15 to 45% by mass of alkyl phosphate ester salt C, and 25 to 65% by mass of polyoxyalkylene derivatives (total 100% by mass).

Further, as described above, the treatment agent of the present invention has an aqueous liquid containing 400 to 100000 parts by mass of water and having a pH of 3 or more and less than 7 with respect to 100 parts by mass of the polyolefin synthetic fiber treatment agent. It is.

Next, the aqueous liquid of the treatment agent of the present invention (hereinafter referred to as the aqueous liquid of the present invention) will be described. The aqueous liquid of the present invention is an aqueous liquid containing 400 to 100000 parts by mass of water with respect to 100 parts by mass of the treatment agent of the present invention, and having an pH of 3 or more and less than 7. .

Examples of the water used for the aqueous liquid of the present invention include ion exchange water, distilled water, hard water, soft water, etc. Among them, ion exchange water, distilled water and the like are preferable.

Next, a method for treating a polyolefin synthetic fiber according to the present invention (hereinafter referred to as the treatment method of the present invention) will be described. The treatment method of the present invention is a method in which the aqueous liquid of the present invention is adhered to a polyolefin-based synthetic fiber so as to be 0.1 to 1% by mass as the treatment agent of the present invention. As the adhesion method, a known method can be applied, and examples thereof include a roller touch method, a spray method, a shower method, and an immersion method. The step of attaching the aqueous liquid of the present invention may be any of a spinning step, a drawing step, and a finishing step. In adhering the aqueous liquid of the present invention to the polyolefin-based synthetic fiber, other components other than the treatment agent of the present invention can be used in combination for the purpose, but the combined use of such other components is as much as possible. A small amount is preferable.

Next, the polyolefin-based synthetic fiber according to the present invention (hereinafter referred to as the synthetic fiber of the present invention) will be described. The synthetic fiber of the present invention is a polyolefin-based synthetic fiber to which the treatment agent of the present invention is attached.

Examples of the polyolefin-based synthetic fibers include polyolefin fibers such as polyethylene fibers, polypropylene fibers, and polybutene fibers, and composite fibers having a core-sheath structure in which either the core or the sheath portion or both are polyolefin-based fibers, for example, sheath Examples thereof include polyethylene / polypropylene composite fiber, polyethylene / polyester composite fiber, polyethylene / polypropylene composite fiber having a side-by-side structure, and polyethylene / polyester composite fiber.

Finally, the thermal bond nonwoven fabric of the present invention (hereinafter referred to as the nonwoven fabric of the present invention) will be described. The nonwoven fabric of the present invention is a thermal bond nonwoven fabric to which the treatment agent of the present invention is attached.

As the thermal bond nonwoven fabric, air through, a nonwoven fabric obtained by a point bond process, and the like can be used. Among them, those by air through are preferable.

According to the present invention, there is an effect that a high degree of hydrophilicity can be imparted to the obtained nonwoven fabric while maintaining good antistatic property and card passing property, and the nonwoven fabric can be weakly acidified.

Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test category 1 (Preparation of polyolefin synthetic fiber treatment agent)
Example 1
2.8 g of 90% aqueous solution of lactic acid (A-1) listed in Table 1, 15.0 g of alkyl phosphate ester salt (B-1), 15.0 g of alkyl phosphate ester salt (C-1) and polyoxy 17.5 g of the alkylene derivative (D-1) was mixed, 949.7 g of water was added, and the mixture was stirred to obtain an aqueous dispersion to obtain a 5% aqueous liquid of the polyolefin synthetic fiber treating agent of Example 1.

Examples 2 to 9, Reference Examples 10 to 13 and Comparative Examples 1 to 7
In the same manner as in Example 1, 5% aqueous liquids of the treating agents for polyolefin synthetic fibers of Examples 2 to 9, Reference Examples 10 to 13, and Comparative Examples 1 to 7 were prepared. The contents of the polyolefin-based synthetic fiber treating agents prepared in the above examples are summarized in Table 1.

In Table 1,
A-1: Lactic acid A-2: Citric acid A-3: Paratoluenesulfonic acid A-4: Octyl phosphoric acid

B-1: Hexyl phosphate potassium salt B-2: Octyl phosphate potassium salt B-3: Octyl phosphate sodium salt B-4: Butyl phosphate potassium salt B-5: Decyl phosphate potassium salt Rb-1 : Propyl phosphate potassium salt

C-1: Dodecyl phosphate potassium salt C-2: Octadecyl phosphate potassium salt C-3: Docosyl phosphate potassium salt Rc-1: Tetracosyl phosphate potassium salt

D-1: Polyoxyethylene (10 mol) octacosyl ether D-2: Polyoxyethylene (25 mol) polyoxypropylene (25 mol) octacosyl ether D-3: Polyoxyethylene (35 mol) octatria contyle ether D-4: Polyoxyethylene (10 mol) tetracosyl ether D-5: Polyoxyethylene (10 mol) octatetracontyl ether D-6: Polyoxyethylene (6 mol) octacosyl ether D-7: Polyoxyethylene (80 mol) octacosyl ether Rd-1: polyoxyethylene (10 mol) octadecyl ether Rd-2: polyoxyethylene (10 mol) hexacontyl ether Rd-3: polyoxyethylene (3 mol) octacosyl ether Rd- 4: Polyoxyethylene (60 mol) polyoxypropylene (60 mol) octacosyl ether

Test Category 2 (Adhesion and evaluation of polyolefin synthetic fiber treatment agent)
-Adhesion of polyolefin synthetic fiber treatment agent Aqueous liquid of polyolefin synthetic fiber treatment agent prepared in Test Category 1 is a polyolefin composite fiber whose sheath is polyethylene and whose core is polyester (fineness 2.2 decitex). To a fiber length of 51 mm) by a spray oiling method so as to have an adhesion amount shown in Table 2, and dried for 1 hour with a hot air dryer at 80 ° C. to obtain a treated polyolefin synthetic fiber-treated cotton. However, in Example 8, other components (E-1: oxypropylene unit / oxyethylene unit as a modifying group = 50/50 (mass%) with respect to 100 parts of the polyolefin synthetic fiber treating agent prepared in Test Category 1 ) And sprayed with an aqueous liquid in which a polyoxyalkylene-modified silicone having an average molecular weight of 5000 having a polyoxyalkylene group composed of 50% by mass in a proportion of 10 parts is used in a proportion of 10 parts. In Example 9, An aqueous liquid in which 10 parts of another component (E-2: potassium octylate) was used in combination with 10 parts of the polyolefin synthetic fiber treatment agent prepared in Test Category 1 was sprayed. Is a combination of 25 parts of the other component (E-1) described above with respect to 100 parts of the polyolefin synthetic fiber treating agent prepared in Test Category 1. The aqueous solution was spray refueling.

Evaluation The antistatic property and card passing property of the treated polyolefin synthetic fiber treated cotton obtained above were evaluated as follows. The results are summarized in Table 2.

・ Evaluation of antistatic property After 5g of the above treated polyolefin synthetic fiber-treated cotton was conditioned at 20 ° C in a constant temperature room of 45% RH for 24 hours, the electrical resistance (Ω) was measured using a resistance measuring device. And evaluated according to the following evaluation criteria.

Evaluation standard for antistatic property ◎: Surface resistance is less than 1.0 × 10 ⁹ Ω ○: Surface resistance is 1.0 × 10 ⁹ Ω or more and less than 1.0 × 10 ¹⁰ Ω ×: Surface resistance is 1.0 × 10 ¹⁰ Ω or more

Evaluation of Card Passability 20 g of the above treated polyolefin synthetic fiber-treated cotton was conditioned at 20 ° C. in a constant temperature room of 65% RH for 24 hours, and then subjected to a roller card. The ratio of the amount discharged to the input amount was calculated and evaluated according to the following evaluation criteria.

Evaluation criteria for card passability ◎: Emission is 80% or more ○: Emission is 60% or more and less than 80% ×: Emission is less than 60%

Test category 3 (Production and evaluation of thermal bond nonwoven fabric)
-Preparation of thermal bond nonwoven fabric 100g treated polyolefin synthetic fiber-treated cotton obtained in Test Category 2 was conditioned at 20 ° C in a constant temperature room of 65% RH for 24 hours, and then subjected to a roller card to a weight of 20g / An m ² card web was prepared. The obtained card web was subjected to hot air treatment at 140 ° C. for 10 seconds to obtain a thermal bond nonwoven fabric.

Thus, about the thermal bond nonwoven fabric produced in this way, initial hydrophilic property, durable hydrophilic property, wet-back prevention property, and pH of the nonwoven fabric were evaluated as follows. The results are summarized in Table 2.

Evaluation of initial hydrophilicity The thermal bond nonwoven fabric was conditioned at 20 ° C. in a constant temperature room of 60% RH for 24 hours, then placed on a horizontal plate, and 0.4 ml from a height of 10 mm using a burette. Then, the time required for the water droplets to be completely absorbed was measured and evaluated according to the following evaluation criteria.

Evaluation criteria for initial hydrophilicity ◎: Time required for water permeation is less than 1 second ○: Time required for water permeation is 1 second or more and less than 2 seconds ×: Time required for water permeation is 2 seconds or more

-Evaluation of durable hydrophilic property The above-mentioned thermal bond nonwoven fabric was cut into small pieces of 10 cm x 10 cm, and conditioned for 24 hours at 20 ° C in a constant temperature room of 60% RH. Place a non-woven fabric that has been conditioned on the five stacked filter papers, and then vertically place a cylinder with an inner diameter of 1 cm with both ends open at the center, and inject 5 ml of 0.9% physiological saline into this cylinder. The time until the saline solution was completely absorbed by the nonwoven fabric was measured. Thereafter, the nonwoven fabric was taken out and dried by blowing at 40 ° C. for 90 minutes. The same operation was repeated a total of 3 times, and the following evaluation criteria were evaluated from the third time.

Evaluation criteria for durable hydrophilicity ◎: Time required for absorption of physiological saline is less than 3 seconds ○: Time required for absorption of physiological saline is 3 seconds or more and less than 5 seconds ×: Absorption of physiological saline More than 5 seconds

-Wet back prevention evaluation The said thermal bond nonwoven fabric was cut | judged to the small piece of 10 cm x 10 cm, and humidity control was carried out for 24 hours in the constant temperature room of 60% RH at 20 degreeC. A 10 cm × 10 cm piece of non-woven fabric was cut out from the outermost non-woven fabric material of a commercially available paper diaper, and the 10 cm × 10 cm piece of moisture that had been conditioned was attached to the cut portion to obtain a wetback prevention evaluation sample. Place the sample to evaluate wetback prevention horizontally so that the attached small piece is facing upward, and stand a 6 cm inner diameter cylinder open at both ends at the center of the small piece, and inject 80 ml of water into this cylinder for 5 minutes. The water was absorbed inside the disposable diaper. Next, 15 sheets of 10 cm × 10 cm filter paper are stacked on the attached small piece, and further, a 2.8 kg weight plate of 10 cm × 10 cm is mounted thereon, loaded for 2 minutes, and the total of the 15 sheets of filter paper stacked. The mass was measured, the rate of increase in the mass was calculated, and evaluated according to the following evaluation criteria.

Evaluation criteria for wet back prevention ◎: Mass increase rate is less than 1% ○: Mass increase rate is 1% or more and less than 2% ×: Mass increase rate is 2% or more

-Evaluation of pH The above-mentioned thermal bond nonwoven fabric was conditioned at 20 ° C in a constant temperature room of 60% RH for 24 hours. Using a flat-type pH meter, the pH of the conditioned nonwoven fabric surface was measured and evaluated according to the following evaluation criteria.

Evaluation criteria of pH A: The pH of the nonwoven fabric is 3 or more and less than 7 ×: The pH of the nonwoven fabric is less than 3 or 7 or more

As is clear from the results of Table 2 corresponding to Table 1, according to the present invention, high hydrophilicity can be imparted to the obtained nonwoven fabric while maintaining good antistatic properties and card passing properties. Moreover, a nonwoven fabric can be weakly acidified.

Claims

0.3 to 18% by mass of the following organic acid, 10 to 50% by mass of the following alkyl phosphate ester salt B, 10 to 50% by mass of the following alkyl phosphate ester salt C, and the following polyoxyalkylene derivative. A polyolefin-based synthetic fiber treating agent, which is contained in a proportion of 25 to 65% by mass (total 100% by mass) and has the following aqueous liquid having a pH of 3 or more and less than 7.
Organic acid: At least one selected from organic hydroxy acid, organic sulfonic acid and organic phosphoric acid Alkyl phosphate ester salt B: Alkyl phosphate ester salt having 4 to 11 carbon atoms Alkyl phosphate ester salt C: 12 to 22 carbon atoms Alkyl phosphate ester salt of polyoxyalkylene derivative: Compound in which ethylene oxide and / or propylene oxide is added in a ratio of 5 to 100 mol in total with respect to 1 mol of monovalent aliphatic alcohol having 22 to 50 carbon atoms : An aqueous liquid containing 400 to 100000 parts by mass of water with respect to 100 parts by mass of the polyolefin-based synthetic fiber treatment agent
2. The polyolefin synthetic fiber treating agent according to claim 1, wherein the alkyl phosphate ester salt B is an alkali metal salt having 6 to 8 carbon atoms.
3. The polyolefin synthetic fiber treating agent according to claim 1, wherein the alkyl phosphate ester salt C is an alkali metal salt having 12 to 18 carbon atoms.
The polyoxyalkylene derivative is a compound in which ethylene oxide and / or propylene oxide is added in a ratio of 8 to 60 mol in total with respect to 1 mol of a monohydric aliphatic alcohol having 26 to 40 carbon atoms. The polyolefin-based synthetic fiber treating agent according to any one of the items.
0.3 to 18% by mass of organic acid, 15 to 45% by mass of alkyl phosphate ester salt B, 15 to 45% by mass of alkyl phosphate ester salt C, and 25 to 65% by mass of polyoxyalkylene derivative (100 in total) The processing agent for polyolefin-based synthetic fibers according to any one of claims 1 to 4, which is contained at a ratio of (mass%).
An aqueous polyolefin-based synthetic fiber treatment agent comprising 100 to 100 parts by mass of the polyolefin-based synthetic fiber treatment agent according to any one of claims 1 to 5 in a ratio of 400 to 100,000 parts by mass of water. An aqueous liquid characterized in that the pH is 3 or more and less than 7.
A method for treating a polyolefin-based synthetic fiber, comprising attaching the aqueous liquid according to claim 6 to a polyolefin-based synthetic fiber so as to be 0.1 to 1% by mass as a polyolefin-based synthetic fiber treating agent.
A polyolefin-based synthetic fiber, wherein the treatment agent for polyolefin-based synthetic fibers according to any one of claims 1 to 5 is adhered thereto.
A thermal bond nonwoven fabric, characterized in that the treatment agent for polyolefin synthetic fibers according to any one of claims 1 to 5 is adhered thereto.