JPH07166474A - Durable softening agent - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a practical durable softening agent capable of simultaneously satisfying the trade-off requirements of providing fibers with excellent durability and sufficient flexibility. [Structure] Oxidation-modified or acid-modified polyethylene, nonylphenol, higher alcohol (alkyl group having 4 to 4 carbon atoms)
22) or a higher alkylamine (alkyl group having 4 to 22 carbon atoms) by esterification reaction with ethylene oxide and / or propylene oxide adduct (HLB10 to 19), and water-soluble polyester resin And a durable softening agent containing, as an essential component, at least one selected from water-soluble polyurethane resins.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a durable softening finish. More specifically, the present invention imparts flexibility and water absorbency to cellulosic fibers such as cotton, rayon and hemp, and composite fibers of various synthetic fibers such as polyester, polyamide and acrylic and cellulosic fibers. At the same time, the present invention relates to a durable softening agent which can provide excellent sewability and strength reduction prevention.

[0002]

2. Description of the Related Art Generally, a fiber garment is made into a product by being sewn from a thread form through a woven or knitted fabric. However, the nature originally possessed by the fiber and the clothing product design alone will satisfy consumer needs. It cannot be fully filled, and various finishing agents are applied at the stage of fiber processing to modify it to meet consumer needs.

As a softening agent for fibers used in such processing, "Handbook of Surfactants" by editors of Nishiichiro, Jiro Imai and Masatake Kasai (Sangyo Tosho KK, page 473, line 25-477). Various treatment agents are known, as also described in page 11, line 11). However, a drawback common to such conventionally known softening finishes is that both water-washing resistance and dry cleaning resistance are poor,
There was a point that it was not satisfactory in terms of durability.

Polyester resins, polyurethane resins, polyacrylic resins, etc., which have been conventionally used as durable softeners, are stable because they have a polymer structure, but have satisfactory durability in terms of softening effect on fibers. In many cases, the initial flexibility is not sufficient and it is not practical. Further, in terms of durability, the compound belonging to the oligomer or polymer region has a durability effect due to its unique adhesive force, but also provides adhesion between fibers, increasing static friction and dynamic friction between fibers, The drawback is that it does not provide sufficient flexibility.

On the other hand, it is known that a compound having a relatively low molecular weight of about 500 to 1000 gives a softening effect, but has a drawback that it is poor in durability because it lacks affinity for fibers and adhesive force.

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention provides a practical durable softener capable of simultaneously satisfying the trade-off requirement of providing fibers with excellent durability and sufficient flexibility. The purpose is to do.

[0007]

According to the present invention, in order to solve the above-mentioned problems, oxidation-modified or acid-modified polyethylene and nonylphenol, higher alcohol (alkyl group having 4 to 22 carbon atoms) or higher alkylamine (alkyl group). An ester-based compound produced by an esterification reaction with an ethylene oxide and / or propylene oxide adduct (HLB10-19) having 4 to 22 carbon atoms, and a water-soluble polyester resin and a water-soluble polyurethane represented by the following formula Provided is a durable softening agent containing, as an essential component, at least one selected from resins. <Water-soluble polyester resin>

[0008]

[Chemical 3]

<Water-soluble polyurethane resin>

[0010]

[Chemical 4]

The inventors of the present invention have previously prepared oxidation-modified or acid-modified polyethylene and nonylphenol, higher alcohol (alkyl group having 4 to 22 carbon atoms) or higher alkylamine (alkyl group having 4 to 22 carbon atoms) ethylene oxide. And / or propylene oxide adduct (HLB10-1
9) molecular weight 100 produced by esterification reaction with
It was confirmed that durability flexibility was obtained with an ester compound in the oligomer region of about 0 to 4000 (Japanese Patent Laid-Open No. 2-1.
75971). However, due to diversification of target materials and sophistication of required performance, durability may still be insufficient even if these compounds are used.

Therefore, the present inventors used a water-soluble polyester resin or a water-soluble polyurethane resin in combination with the above ester compound in order to improve the durability, thereby obtaining a good quality and stable emulsion, and the emulsion was obtained. It has been found that the use of various fibers such as cellulose fibers and synthetic fibers can be subjected to a soft finish with water-washing resistance and dry-cleaning resistance. Also,
This allows cotton, polyester / cotton, polyester /
There is also an advantage that it can be applied as a tear strength reduction inhibitor during resin processing of textiles such as rayon and as a sewability improver for various fibers.

Next, oxidation-modified or acid-modified polyethylene and nonylphenol, higher alcohols (having 4 to 22 carbon atoms in the alkyl group) or higher alkylamines (having 4 to 22 carbon atoms in the alkyl group), useful in the present invention, are ethylene oxide. And / or propylene oxide adduct (HLB10-1
The ester compound (component A) produced by the esterification reaction with 9) will be described.

Examples of the oxidatively modified or acid modified polyethylene are those in which a carboxyl group is introduced by air oxidation or thermal decomposition of polyethylene, polyethylene and acrylic acid,
Those obtained by copolymerizing vinyl carboxylic acid such as methacrylic acid are suitable. For example, AC-made by Allied Chemical Co.
629, AC-580, AC-540, Mitsui Petrochemical Co., Ltd. Mitsui High Wax 4202E, 1105A,
Examples include Sun Wax E-300 manufactured by Sanyo Chemical Industry Co., Ltd.

On the other hand, the adduct of ethylene oxide and / or propylene oxide is a non-phenol selected from nonylphenol, higher alcohol (alkyl group having 4 to 22 carbon atoms) and higher alkylamine (alkyl group having 4 to 22 carbon atoms). Block or random adducts with ionic surfactants are mentioned. The block or random adduct of the nonylphenol, higher alcohol or higher alkylamine with ethylene oxide and / or propylene oxide has an HLB of 10 to 19, preferably 12 to 10.
It should be 17.

The reaction between the oxidation-modified or acid-modified polyethylene and the above nonionic surfactant is carried out, for example, by charging a reaction vessel with the oxidation equivalent of the oxidation-modified or acid-modified polyethylene and an equimolar amount of the nonionic surfactant, and further adding a catalyst. Paratoluene sulfonic acid is added as
It can be carried out by dehydration reaction at 220 ° C. for 3 to 5 hours. The reaction rate can be traced by an oxidation measurement with a mixed solvent of xylene / dimethyl sulfoxide (2/1 to 9/1). The reaction rate of the reaction product according to the present invention was 80 to 98%.

In the present invention, it is possible to use the component A in combination with a water-soluble polyester resin and / or a water-soluble polyurethane resin (component B) and emulsify these in water before use. By blending a polyhydric alcohol fatty acid ester, a polyamine higher fatty acid amide, paraffin, a water-soluble acrylic resin, an amino-modified silicone, etc., a higher quality and stable emulsion can be obtained.

By diluting the obtained emulsion with water, applying it to the fibers by dipping, padding, spraying, etc., and drying it, it is possible to impart durable flexibility.

[0019]

Oxidation-modified or acid-modified polyethylene according to the present invention, nonylphenol, higher alcohol (alkyl group having 4 to 22 carbon atoms), higher alkylamine (alkyl group having 4 to 22 carbon atoms) ethylene oxide and / or propylene oxide The ester compound produced by the esterification reaction with the adduct (HLB10 to 19) has a molecular weight of 10
It is an oligomer of about 00 to 4000, and by mixing a water-soluble polyester resin and a water-soluble polyurethane resin and emulsifying them in water, a good quality and stable emulsion can be obtained. This composite emulsion has a good affinity for various fibers, and by forming a uniform resin coating on the fiber surface,
It gives good initial flexibility, water absorption, and a significant improvement in durability.

[0020]

EXAMPLES Next, the present invention will be further described based on examples. Synthesis Example 1 High wax 1105A which is an oxidation-modified polyethylene (Mitsui Petrochemical, acid value 6
0) 187 g, ethylene oxide 15 mol adduct of cetyl alcohol (HLB 14.6) 180.4 g and paratoluenesulfonic acid 0.6 g were charged, the temperature was raised under a nitrogen stream, and dehydration reaction was performed at 180 to 220 ° C. for 4 hours. Let
Light yellowish white solid product (I) 364.
3 g was obtained.

Synthetic Example 2 In a 500 ml four-necked flask, AC-540 (made by Allied Chemical, acid value 40), which is an acid-modified polyethylene, was used.
0 g, 20 mol of ethylene oxide and 10 mol of propylene oxide of cetyl alcohol (HLB
10.3) 170 g and paratoluene sulfonic acid 0.
Charge 6 g and raise the temperature under nitrogen flow to 180-220 ° C.
After dehydration for 4 hours, 308.4 g of a pale yellowish white solid product (II) having a conversion of 87% was obtained.

Synthetic Example 3 In a 500 ml four-necked flask, high-wax 1105A which is an oxidatively modified polyethylene (Mitsui Petrochemical, acid value 6
0) 200 g, ethylene oxide 15 mol adduct of stearyl amine (HLB 14.2) 195.7 g and paratoluene sulfonic acid 0.6 g were charged, the temperature was raised under nitrogen flow, and dehydration reaction was performed at 180 to 220 ° C. for 4 hours. Let
391.9 g of a yellow solid product (III) having a reaction rate of 84% was obtained.

Synthesis Example 4 In a 500 ml four-necked flask, high-wax 1105A which is an oxidatively modified polyethylene (Mitsui Petrochemical, acid value 6
0) 150 g, ethylene oxide 10 mol adduct of nonylphenol (HLB 13.3) 105.9 g, and paratoluenesulfonic acid 0.6 g were charged, the temperature was raised under a nitrogen stream, and dehydration reaction was performed at 180 to 220 ° C. for 4 hours. 253 g of a white solid product (IV) having a reaction rate of 87%
Got

Emulsion Example 1 Product (I) 20 parts Water-soluble polyurethane resin 15 parts Water 65 parts Total 100 parts The product (I) and the water-soluble polyurethane resin were charged into an emulsifying pot and the temperature was raised to 85 to 90 ° C. After melting and stirring for about 1 hour, hot water at 85 to 90 ° C. is charged and emulsified. This emulsion was a white liquid. The obtained emulsion is referred to as Product 1 of the present invention. The water-soluble polyurethane resin used above was represented by the following formula.

[0025]

[Chemical 5]

Emulsion Example 2 Product (II) 15 parts Water-soluble polyester resin 30 parts Water 55 parts Total 100 parts The product (II) and the water-soluble polyester resin were charged into an emulsifier and the temperature was raised to 85 to 90 ° C. After melting and stirring for about 1 hour, hot water at 85 to 90 ° C. is charged and emulsified. This emulsion was a slightly pale yellow liquid. The obtained emulsion is referred to as Product 2 of the present invention. The water-soluble polyester resin used above was represented by the following formula.

[0027]

[Chemical 6]

[0028] The product (II) and the water-soluble polyester resin are charged into an emulsifying kettle, the temperature is raised to 85 to 90 ° C., the mixture is melted and stirred for about 1 hour, and the product (I is charged to an emulsifying kettle charged with hot water at 85 to 90 ° C.
Charge and emulsify the molten mixture of I) and the water-soluble polyester resin. This emulsion was a slightly pale yellow liquid. The obtained emulsion is referred to as Product 3 of the present invention. The water-soluble polyester resin used above was represented by the following formula.

[0029]

[Chemical 7]

[0030] The product (I), the water-soluble polyurethane resin and water are charged in an emulsifying vessel and emulsified under high pressure at 110 to 130 ° C. for about 30 minutes to 1 hour. This emulsion was a white liquid. The obtained emulsion is referred to as Product 4 of the present invention. The water-soluble polyurethane resin used above was represented by the following formula.

[0031]

[Chemical 8]

[0032] The product (I) and water were charged into an emulsification kettle, and 110-1
Emulsify under high pressure at 30 ° C. for about 30 minutes to 1 hour,
Next, a water-soluble polyurethane resin is charged and uniformly mixed. This emulsion was a white liquid. The obtained emulsion is referred to as Product 5 of the present invention. The water-soluble polyurethane resin used above was represented by the following formula.

[0033]

[Chemical 9]

[0034] The product (III), the water-soluble polyurethane resin and water are charged into an emulsifying vessel and emulsified under high pressure at 110 to 130 ° C. for about 30 minutes to 1 hour. This emulsion was a slightly yellowish white liquid. The obtained emulsion is referred to as Product 6 of the present invention. The water-soluble polyurethane resin used above was represented by the following formula.

[0035]

[Chemical 10]

[0036] The product (IV), the water-soluble polyester resin and water are charged into an emulsifying vessel and emulsified under high pressure at 110 to 130 ° C. for about 30 minutes to 1 hour. This emulsion was a white liquid.
The obtained emulsion is referred to as Product 7 of the present invention. The water-soluble polyester resin used above was represented by the following formula.

[0037]

[Chemical 11]

Comparative Example 1 An emulsion having the following composition (referred to as Comparative Product 1). AC-540 (manufactured by Allied Chemicals) 15 parts Nonylphenol ethylene oxide 10 mol adduct 5 parts 48% KOH 1 part Water 79 parts Total 100 parts This emulsion was a white translucent liquid.

Comparative Example 2 A commercially available water-soluble polyurethane resin having the following structural formula (comparative product 2 manufactured by Nichika Chemical Co., Ltd.).

[0040]

[Chemical 12]

Comparative Example 3 A commercially available water-soluble polyester resin represented by the following structural formula (comparative product 3 manufactured by Nichika Chemical Co., Ltd.).

[0042]

[Chemical 13]

Comparative Example 4 In a 500 ml four-necked flask, acid-modified polyethylene type AC-540 (manufactured by Allied Chemical, acid value 40) 1
40 g, 93 g of ethylene oxide 15 mol adduct of stearylamine (HLB 14.2) and 0.5 g of paratoluenesulfonic acid were charged, and the temperature was raised under a nitrogen stream,
Dehydrated at 180-190 ℃ for 4 hours, reaction rate 84
% Product was obtained as a yellow solid.

An emulsion having the following composition using the above product is designated as Comparative Product 4. Product 12 parts 51 ° tallow hydrogenated oil 2 parts Sorbitan tristearate 6 parts Water 80 parts Total 100 parts

Performance Test Example 1 A cotton knit is padded with a 5% aqueous solution of the product of the present invention and the comparative product, and its durability flexibility and water absorption are evaluated. Test materials Cotton knit (fluorescent dyed cloth) Processing conditions 1 dip-1 nip 5% aqueous liquid each Squeezing ratio: 80% Drying: 105 ° C, 10 minutes Durability Water-resistant washing tester Machine: household washing machine Galaxy VH-300SI (Toshiba made) New beads (made by Kao) 2 g / L are used at 40 ° C for 1
The washing for 5 minutes is defined as one wash, and the deterioration in feeling after 5 (L-5) and 10 (L-10) washes is examined. Evaluation Feel: Judgment is made by touch. ○: Rich in flexibility Δ: Slightly flexible ×: Coarse and hard Water absorption: JIS L-1018 A method (dropping method) Electron microscope observation (scanning electron microscope S-2400: Hitachi) ・ Cross section (× 5000) It is shown in Table 1 below.

[0046]

[Table 1]

It can be seen that the knitted fabric treated with the product of the present invention has excellent durability and flexibility. Further, the water absorption is also good. It was confirmed by an electron microscope that the resin coating was formed on each fiber of the knitted fabric treated with the product of the present invention.
Since this coating film has water absorption flexibility, it is possible to realize not only good initial feeling but also durable flexibility that could not be obtained conventionally even after repeated washing.

FIG. 1 is an electron micrograph (5000 times) of a fiber cross section of a knitted fabric treated with Product 4 of the present invention after washing 10 times, and FIG. 2 is a fiber of the knitted fabric treated with Comparative Product 2 after washing 10 times. It is an electron micrograph (5000 times) of a cross section.

Performance Test Example 2 Polyester / cotton knit is padded with the 3% aqueous solution of the product of the present invention and the comparative product, and its durability and water absorption are evaluated. Test material Polyester / cotton knit (bleaching) Processing conditions 1 dip-1 nip 3% aqueous liquid each Squeezing ratio: 60% Drying: 105 ° C, 10 minutes Durability Water-resistant washing tester Machine: household washing machine Galaxy VH- 300 SI (manufactured by Toshiba) New beads (manufactured by Kao) 2 g / L are used at 1 at 40 ° C.
The washing for 5 minutes is defined as one wash, and the deterioration in feeling after 5 (L-5) and 10 (L-10) washes is examined. Evaluation Feel: Judgment is made by touch. ◯: Rich in flexibility Δ: Slightly flexible ×: Coarse and hard Water absorption: JIS L-1018 Method A (dropping method) The results are shown in Table 2 below.

[0050]

[Table 2]

It can be seen that the knitted fabric treated with the product of the present invention is rich in durability and flexibility. Further, the water absorption is also good.

Performance Test Example 3 Cotton fabric, rayon fabric and polyester / cotton fabric were
Glyoxal resin (Sumitex resin NS-1
9, manufactured by Sumitomo Chemical Co., Ltd.) and a complex metal salt catalyst (Sumitex Accelerator X-80, manufactured by Sumitomo Chemical Co., Ltd.) and the above-mentioned product of the present invention or a comparative product are padded with an aqueous liquid containing the amounts shown in Table 3 below. After the treatment, the effect of preventing reduction in tear strength is evaluated. Test material Cotton 40 broad bleached cloth Rayon taffeta Polyester / cotton fabric Processing conditions 1 dip-1 nip Squeezing ratio: Cotton 40th broad bleached cloth 60% Rayon taffeta 70% Polyester / cotton fabric 55% Dry: 105 ° C, 3 minutes Cure: 150 ° C., 2 minutes Evaluation Tear strength tester: Elemendorf tearing tester (manufactured by Toyo Seiki) The results are shown in Table 3.

[0053]

[Table 3]

The product of the present invention exhibits excellent properties in preventing reduction in tear strength when a resin such as cotton fabric, polyester / cotton fabric and rayon fabric is used in combination.

Performance Test Example 4 A cotton knit and a polyester / cotton fabric were padded with the above-mentioned inventive product and comparative product with a 2% aqueous solution, and their sewability and fusion property were evaluated. Test material Cotton knit fabric (fluorescent dyed cloth) Polyester / cotton fabric (65/35) Processing conditions 1 dip-1 nip 2% aqueous liquid Squeezing ratio: Cotton knit fabric 80% Polyester / cotton fabric 55% Dry: 105 ° C, 10 Minute evaluation Sewability tester: High-speed, single-needle, lockstitch, industrial sewing machine (made by JUKI) 4 layers of cotton knit fabric, needle # 11, pitch 1mm, 4
Number of pinholes (X) in 20 cm needle holes (800) excluding 5 cm at the front and back, 30 cm empty stitching at 500 rpm
To measure. Fusing property Tester: High-speed, single-needle, lockstitch, industrial sewing machine (made by JUKI) 4 layers of polyester / cotton fabric are sewn with needle # 11, pitch 1 mm, 4500 rpm, until they are fused To measure. The results are shown in Table 4 below.

[0056]

[Table 4]

The product of the present invention is excellent in the sewability and the pinhole preventive property of the cellulose fiber treated thereby, and the fusion preventive property of the cellulose / polyester mixed knitted fabric.

[0058]

As can be seen from the above, according to the present invention,
The problem of compatibility between flexibility and durability, which was a common weakness in conventional softening agents, has been improved to the point where it can be practically satisfied, and the strength that conventional durable softening agents does not have. A secondary function such as an effect of preventing deterioration and an effect of improving sewability is also produced, and therefore, a great effect can be brought about in the soft finishing of the textile product.

[Brief description of drawings]

FIG. 1 is an electron micrograph of a fiber cross section of a knitted fabric obtained in an example.

FIG. 2 is an electron micrograph of a fiber cross section of a knitted fabric obtained in a comparative example.

Front page continuation (72) Inventor Nobuo Akie 262 Sou Sou, Miyazu City, Kyoto Prefecture Gunze Co., Ltd. Apparel Division (72) Inventor Tadahiko Kato 1-3-2 Yanagicho, Sabae City, Fukui Prefecture (72) Inventor Hajime Fukuda Fukui 20-18 Yotsui, Fukui City, Japan

Claims (1)

[Claims] 1. An ethylene oxide and / or propylene oxide adduct of oxidation-modified or acid-modified polyethylene and nonylphenol, higher alcohol (alkyl group having 4 to 22 carbon atoms) or higher alkylamine (alkyl group having 4 to 22 carbon atoms). Durable and flexible finish containing, as essential components, an ester compound produced by an esterification reaction with (HLB10 to 19) and at least one selected from water-soluble polyester resins and water-soluble polyurethane resins represented by the following formula . <Water-soluble polyester resin> [Chemical formula 1] <Water-soluble polyurethane resin> [Chemical formula 2]