JP2625374B2 - Durable soft finish - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a durable softener. 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. In addition, the present invention relates to a durable soft finish capable of giving excellent sewability and strength reduction prevention properties.

[0002]

2. Description of the Related Art In general, a textile garment is sewn from a yarn form through a woven or knitted fabric to produce a product. They cannot be fully satisfied, and various finishing agents are applied at the stage of fiber processing to modify them to meet consumer needs.

[0003] As a softening agent for fibers used in such processing, "Handbook of Surfactants" by the editors of Nishiichiro, Jiro Imai and Masatake Kasai (published by Sangyo Tosho Co., Ltd., p. 473, lines 25 to 477). (See page 11, line 11), various treatment chemicals are known. However, the drawback common to such conventionally known soft finishes is that both the washing resistance and the dry cleaning resistance are poor,
It was not satisfactory in terms of durability.

Further, polyester resins, polyurethane resins, polyacrylic resins, etc., which have been conventionally used as a durable softener, are stable because of having a high molecular structure, but have satisfactory durability in terms of a softening effect on fibers. In many cases, the initial flexibility is not sufficient, and the method lacks practicality. Furthermore, in terms of durability, compounds belonging to the oligomer or polymer region have a durability effect due to a specific adhesive force, but also provide adhesion between fibers, increase static friction and dynamic friction between fibers, There is a disadvantage that sufficient flexibility cannot be provided.

[0005] On the other hand, it is known that a relatively low-molecular compound having a molecular weight of about 500 to 1,000 gives a softening effect, but has a drawback of poor durability due to lack of affinity and adhesion to fibers.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a practical durable softener which can simultaneously satisfy the trade-offs of providing excellent durability and sufficient flexibility to fibers. 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) And an ester compound produced by an esterification reaction with an ethylene oxide and / or propylene oxide adduct (HLB 10 to 19) having 4 to 22 carbon atoms, and a water-soluble polyester resin and a water-soluble polyurethane represented by the following formula: There is provided a durable soft finish containing at least one selected from resins as an essential component. <Water-soluble polyester resin>

[0008]

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<Water-soluble polyurethane resin>

[0010]

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The present inventors have previously described an oxidized-modified or acid-modified polyethylene and a 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 (HLB 10-1
Molecular weight 100 produced by the esterification reaction with 9)
It has been confirmed that durability and flexibility can be obtained by an ester compound in the oligomer region of about 0 to 4000 (Japanese Patent Application Laid-Open No. 2-1).
75971). However, due to diversification of target materials and sophistication of required performance, durability may still be insufficient even when these compounds are used.

Therefore, the present inventors have obtained a high-quality and stable emulsion by using a water-soluble polyester resin or a water-soluble polyurethane resin in combination with the above ester compound in order to improve durability. It has been found that the use thereof makes it possible to apply a flexible finish to various fibers such as cellulose fibers and synthetic fibers, which is resistant to washing and dry cleaning. Also,
By this, cotton, polyester / cotton, polyester /
There is also obtained an advantage that it can be applied as an agent for preventing a decrease in tear strength during resin processing of a woven fabric such as rayon or as an agent for improving the sewability of various fibers.

Next, oxidized 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 useful in the present invention. And / or propylene oxide adduct (HLB 10-1
The ester compound (component A) produced by the esterification reaction with 9) will be described.

Examples of the oxidized or acid-modified polyethylene include polyethylene having a carboxyl group introduced by air oxidation or thermal decomposition, polyethylene and acrylic acid,
Suitable are those obtained by copolymerizing a vinyl carboxylic acid such as methacrylic acid. For example, AC-C available from Allied Chemical Co., Ltd.
629, AC-580, AC-540, Mitsui Petrochemical Co., Ltd. Mitsui High Wax 4202E, 1105A,
Sanwax E-300 manufactured by Sanyo Chemical Industries, Ltd. and the like.

On the other hand, as the adduct of ethylene oxide and / or propylene oxide, nonylphenol, higher alcohol (alkyl group having 4 to 22 carbon atoms) and higher alkylamine (alkyl group having 4 to 22 carbon atoms) can be used. Examples include block or random adducts with ionic surfactants. 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 12.
17 is good.

The reaction between the oxidized-modified or acid-modified polyethylene and the above-mentioned nonionic surfactant is carried out, for example, by charging a non-ionic surfactant equivalent to the oxidation equivalent of the oxidized-modified or acid-modified polyethylene into a reaction vessel and further adding a catalyst. As para-toluenesulfonic acid, under a nitrogen stream, 180-
It can be performed by performing a dehydration reaction at 220 ° C. for 3 to 5 hours. The conversion can be monitored by measuring the oxidation with a mixed solvent of xylene / dimethylsulfoxide (2/1 to 9/1). The conversion of the reactants according to the invention was between 80 and 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 them in water. By blending a polyhydric alcohol fatty acid ester, a polyamine higher fatty acid amide, paraffin, a water-soluble acrylic resin, an amino-modified silicone, and the like, an even better and more stable emulsion can be obtained.

The resulting emulsion is diluted with water, applied to the fiber by dipping, padding, spraying or the like, and dried to give durable flexibility.

[0019]

The oxidized or acid-modified polyethylene according to the present invention and 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 a good-quality and stable emulsion can be obtained by blending a water-soluble polyester resin and a water-soluble polyurethane resin and emulsifying in water. This composite emulsion has good affinity for various fibers, and by forming a uniform resin film on the fiber surface,
Provides good initial flexibility and water absorption, and a significant durability improvement effect.

[0020]

Next, the present invention will be further described based on examples. Synthesis Example 1 In a 500 ml four-necked flask, high wax 1105A (Mitsui Petrochemical, acid value 6
0) 187 g, 180.4 g of an ethylene oxide 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 the dehydration reaction was performed at 180 to 220 ° C. for 4 hours. Let
Product (I) 364. as a pale yellowish white solid having a conversion of 85%.
3 g were obtained.

Synthesis Example 2 In a 500 ml four-necked flask, acid-modified polyethylene AC-540 (manufactured by Allied Chemical Co., acid value 40) 14
0 g, 20 mol of ethylene oxide of cetyl alcohol and 10 mol of propylene oxide (HLB)
10.3) 170 g and p-toluenesulfonic acid 0.1 g.
6 g, and heated to 180 to 220 ° C. under a nitrogen stream.
For 4 hours to obtain 308.4 g of a product (II) as a pale yellowish white solid having a conversion of 87%.

Synthesis Example 3 In a 500 ml four-necked flask, high wax 1105A (oxidized modified polyethylene, manufactured by Mitsui Petrochemical, acid number 6)
0) 200 g, 195.7 g of a stearylamine ethylene oxide 15 mol adduct (HLB 14.2) and 0.6 g of paratoluenesulfonic acid were charged, and the temperature was increased under a nitrogen stream, followed by a dehydration reaction at 180 to 220 ° C. for 4 hours. Let
391.9 g of product (III) as a yellow solid having a conversion of 84% was obtained.

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

Emulsion Example 1 Product (I) 20 parts Water-soluble polyurethane resin 15 parts Water 65 parts Total 100 parts Emulsion vessel was charged with product (I) and water-soluble polyurethane resin, and heated to 85 to 90 ° C. Then, 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]

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Emulsion Example 2 15 parts of product (II) 30 parts of water- soluble polyester resin 55 parts of water 100 parts in total 100 parts The product (II) and the water-soluble polyester resin were charged into an emulsification vessel, and the temperature was raised to 85 to 90 ° C. Then, 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]

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[0028] The product (II) and the water-soluble polyester resin are charged into an emulsification kettle, heated to 85 to 90 ° C, melted and stirred for about 1 hour, and then the product (I) is charged into an emulsification kettle charged with 85 to 90 ° C hot water.
A molten mixture of I) and a water-soluble polyester resin is charged and emulsified. 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]

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[0030] The product (I), the water-soluble polyurethane resin and water are charged into an emulsification kettle and emulsified at 110 to 130 ° C. under high pressure 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]

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[0032] The product (I) and water are charged into an emulsification kettle and
At 30 ° C., emulsify under high pressure 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 designated as product 5 of the present invention. The water-soluble polyurethane resin used above was represented by the following formula.

[0033]

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[0034] The product (III), the water-soluble polyurethane resin and water are charged into an emulsification kettle and emulsified at 110 to 130 ° C. under high pressure 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]

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[0036] The product (IV), the water-soluble polyester resin and water are charged into an emulsification kettle and emulsified at 110 to 130 ° C. under high pressure 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]

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Comparative Example 1 An emulsion having the following composition (referred to as Comparative Product 1). AC-540 (manufactured by Allied Chemical) 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 represented by the following structural formula (manufactured by Nichika Chemical Co., Ltd., referred to as Comparative Product 2).

[0040]

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Comparative Example 3 A commercially available water-soluble polyester resin represented by the following structural formula (manufactured by Nika Chemical Co., Ltd., referred to as Comparative Product 3).

[0042]

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Comparative Example 4 In a 500 ml four-necked flask, acid-modified polyethylene type AC-540 (manufactured by Allied Chemical Co., acid value 40) 1
40 g, 93 g of stearylamine ethylene oxide 15 mol adduct (HLB 14.2) and 0.5 g of paratoluenesulfonic acid were charged, and the temperature was increased under a nitrogen stream.
A dehydration reaction was performed at 180 to 190 ° C for 4 hours, and the
% Of the product as a yellow solid.

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

Performance Test Example 1 A cotton knit was padded with a 5% aqueous liquid of the above-mentioned present invention product and comparative product, and its durability, flexibility and water absorption were evaluated. Test material Cotton knit (fluorescent dyed cloth) Processing conditions 1 dip-1 nip 5% aqueous liquid Squeezing rate: 80% Drying: 105 ° C, 10 minutes Durability Waterproof washing tester: Home-use washing machine Ginga VH-300SI (Manufactured by Toshiba) New beads (manufactured by Kao) 2 g / L, 1 at 40 ° C
Washing for 5 minutes is defined as one time, and the decrease in hand after 5 (L-5) and 10 (L-10) washings is examined. Evaluation Hand: Determined by touch. ：: Rich in flexibility △: Slightly flexible ×: Coarse hardness Water absorption: JIS L-1018 A method (drop method) Electron microscope observation (scanning electron microscope S-2400: manufactured by 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 high durability and flexibility. Also, the water absorption is good. The knitted fabric treated with the product of the present invention was confirmed by an electron microscope to have a resin film formed on each fiber.
Since this film has water-absorbing flexibility, not only good initial feeling but also durable flexibility which could not be obtained conventionally even after repeated washing can be realized.

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

Performance Test Example 2 A polyester / cotton knit was padded with a 3% aqueous liquid of the above-mentioned product of the present invention and the comparative product, and the durability and water absorption were evaluated. Test materials Polyester / cotton knit (bleaching) Processing conditions 1 dip-1 nip 3% aqueous liquid Each squeezing rate: 60% Drying: 105 ° C, 10 minutes Durability Waterproof washing tester: Household washing machine Ginga VH- 300g (made by Toshiba) New beads (made by Kao) 2g / L
Washing for 5 minutes is defined as one time, and the decrease in hand after 5 (L-5) and 10 (L-10) washings is examined. Evaluation Hand: Determined by touch. ：: Rich in flexibility Δ: Slightly flexible ×: Coarse hardness Water absorption: JIS L-1018 A method (drop 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. Also, the water absorption is good.

Performance Test Example 3 Cotton fabric, rayon fabric and polyester / cotton fabric were
Glyoxal resin (Sumitec Resin NS-1
9, a Sumitomo Chemical Co., Ltd.) and a complex metal salt-based catalyst (Sumitex Accelerator X-80, manufactured by Sumitomo Chemical Co., Ltd.) and the present invention or the comparative product in an aqueous liquid containing the amounts shown in Table 3 below. After treatment, the effect of preventing a decrease in tear strength is evaluated. Test material Cotton 40th broad bleached rayon taffeta Polyester / cotton fabric Processing conditions 1 dip-1 nip Drawing rate: Cotton 40th broad bleached 60% rayon taffeta 70% polyester / cotton fabric 55% Drying: 105 ° C for 3 minutes Cure: Evaluation at 150 ° C. for 2 minutes Tear strength tester: Elmendorf 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 for preventing a decrease 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 a 2% aqueous liquid of the product of the present invention and the comparative product, and their seamability and fusing property were evaluated. Test material Cotton knit fabric (fluorescent dyed fabric) Polyester / cotton fabric (65/35) Processing conditions 1 dip-1 nip 2% aqueous liquid squeezing rate: cotton knit fabric 80% polyester / cotton fabric 55% Drying: 105 ° C, 10 Minutes Evaluation Sewability Testing machine: High-speed single-needle lockstitch industrial sewing machine (manufactured by Juki) Four-ply cotton knit fabric is staple # 11, pitch 1 mm, 4
The number of pinholes (X) in a 20 cm needle hole (800 pieces) excluding 5 cm each before and after sewing at 500 rpm and 30 cm blank sewing
Is measured. Testability: High-speed single-needle lockstitch industrial sewing machine (manufactured by Juki) Length of four-ply polyester / cotton fabric, when needlelessly sewn at needle # 11, pitch 1 mm, 4500 rpm, before fusing Is measured. The results are shown in Table 4 below.

[0056]

[Table 4]

The product of the present invention has excellent sewability and pinhole prevention properties of the cellulose fiber treated thereby, and excellent fusion prevention properties 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 of conventional soft finishes, has been improved to an extent that can be practically satisfied, and strength not available in conventional durable soft finishes Secondary functions such as a lowering prevention effect and a sewability improvement effect are also produced, and therefore, a great effect can be brought about for a soft finish of textiles.

[Brief description of the 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.

Continued on the front page (72) Inventor Tadahiko Kato 1-3-21 Yanagimachi, Sabae-shi, Fukui Prefecture (72) Inventor Hajime Fukuda 1-20-18, Yotsui, Fukui-shi, Fukui Prefecture

Claims (1)

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