JPH101873A - Durable softening and finishing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a softening and finishing agent capable of imparting both a durable softening property and a durable water-absorbing property to synthetic fibers such as cellulosic fibers or synthetic fibers such as polyester fibers, polyamide fibers or acrylic fibers. SOLUTION: This durable softening and finishing agent contains at least one compound selected from the esterification product of (A) an α-olefin/maleic anhydride copolymer of the formula (R is a 2-58C alkyl) having a mol.wt. of 2000-50000 and an acid value of 10-350 with (B) a 4-22C alcohol, its ethylene oxide adduct and/or propylene oxide adduct, a 4-22C alkylamine-ethgylene oxide and/or propylene oxide adduct, etc., having an HLB of 10-19 and the amidation product of the component A with (C) a 4-22C alkylamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a durable soft finish. More specifically, the present invention provides:
Provides flexibility and water absorbency to cellulose fibers such as cotton, rayon, hemp, etc. and composite fibers of various synthetic fibers such as polyester, polyamide, and acrylic, and excellent sewability and prevention of reduction in strength. The present invention relates to a durable soft finish capable of imparting properties.

[0002]

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

As the softening agent for fibers used in such processing, various types of softening agents are described in "Handbook of Surfactants" (published by Sangyo Tosho Co., Ltd.), pp. 473-477. Processing agents 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,
The point was that durable flexibility could not be satisfied.

Further, polyester resins, polyurethane resins, polyacrylic resins, etc., which have been conventionally used as a durable softener, are stable because of their high molecular structure, but have satisfactory durable flexibility with respect to fibers. In many cases, the initial flexibility is not sufficient, and there is a problem of lack of practicality. Furthermore, in terms of durability, compounds belonging to the domain of oligomers to polymers 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. The inventors of the present invention have previously disclosed an ether compound obtained by adding ethylene oxide and / or propylene oxide to non-oxidized or acid-modified polyethylene and nonylphenol or an alcohol having 4 to 22 carbon atoms or an alkylamine having 4 to 22 carbon atoms. It has been proposed to use an ester compound produced by an esterification reaction with HLB (HLB = 10 to 19) to impart good durability flexibility and water absorbency to various fibers (Japanese Patent Application Laid-Open No. Hei 7-166474). . However, due to recent diversification of target materials and sophistication of required performance, flexibility may still be insufficient even when these compounds are used.

[0006] Cellulose-based fibers are often required to have sufficient water absorption in addition to durable flexibility. Conventionally known soft finishes have two contradictory effects of durable flexibility and water absorption. It was difficult to satisfy the elements at a high level.

[0007]

The present invention therefore provides:
It is an object of the present invention to provide a practical durable and flexible finish capable of simultaneously satisfying the trade-offs of providing excellent durability and sufficient flexibility and water absorption to fibers.

[0008]

Means for Solving the Problems The inventors of the present invention have:
As a result of intensive studies to solve the above problems, as compared to the above ester compounds, by using an ester compound or an amide compound obtained from a copolymer of α-olefin and maleic anhydride, water resistance to various fibers is improved. It is possible to apply a flexible finish with excellent washability and dry cleaning resistance.Also, with regard to the initial flexibility, an ester compound or amide compound obtained from a copolymer of α-olefin and maleic anhydride can be used. By using the same, it was found that good flexibility with a large volume feeling can be obtained, which cannot be obtained with an ester compound using a conventional oxidation-modified or acid-modified polyethylene, and based on this finding, the present invention was completed. It has been reached.

That is, the present invention provides the following general formula (1)

[0010]

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(Wherein R represents an alkyl group having 2 to 58 carbon atoms), which is a copolymer of α-olefin / maleic anhydride having a molecular weight of 2,000 to 50,000 and an acid value of 10 to 350. Compound (A) having 4 to 4 carbon atoms
22 alcohols, ethylene oxide and / or propylene oxide adducts of alcohols having 4 to 22 carbon atoms (HLB
= 10 to 19) or an ester compound obtained by an esterification reaction of an alkylamine having 4 to 22 carbon atoms with ethylene oxide and / or propylene oxide adduct (HLB = 10 to 19) (B), and the compound (A) )
To provide a durable and flexible finish containing at least one compound selected from amide compounds obtained by an amidation reaction between the compound and an alkylamine (C) having 4 to 22 carbon atoms.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The α-olefin / maleic anhydride copolymer (A) used in the present invention is obtained by radically copolymerizing an α-olefin (having 4 to 60 carbon atoms) with maleic anhydride. Molecular weight 2000-50,000,
It has an acid value of 10 to 350, and particularly has a molecular weight of 500
Those having 0 to 20,000 and an acid value of 50 to 350 are preferred. For example, Diakarna PA manufactured by Mitsubishi Chemical Corporation
30, PA124 and PA168, X-8044, X-8040 and X-80 manufactured by Toyo Petrolite Co., Ltd.
39 and the like.

On the other hand, the esterification component (B) is a non-ionic alcohol selected from alcohols having 4 to 22 carbon atoms and ethylene oxide and / or propylene oxide adducts of alcohols having 4 to 22 carbon atoms (HLB = 10 to 19). Surfactants, ethylene oxide and / or propylene oxide adducts of alkylamines having 4 to 22 carbon atoms (HLB = 10 to 1)
A nonionic surfactant selected from 9) is preferable, and an alkylamine having 4 to 22 carbon atoms is preferable as the amidating component (C). In the present invention, by appropriately adjusting the combination and the molar ratio of the alcohol component, the nonionic surfactant component or the alkylamine component, etc., the two performances of flexibility and water absorption are achieved for various fibers. be able to.

Specific examples of the alcohol having 4 to 22 carbon atoms used in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol,
Tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, hexenol, heptinol, octenol, nonenol, decenor, undecenol, dodecenol, tridecenol, tetradecenol Pentadecenol, hexadecenol, heptadecenol, octadecenol, etc., and the alkyl group or alkenyl group may have a side chain.

Specific examples of the alkylamine having 4 to 22 carbon atoms used in the present invention include butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, docosylamine, and the like, and the alkyl group thereof may have a side chain.

The reaction between the α-olefin / maleic anhydride copolymer component (A) and the esterification component (B) and / or the amidation component (C) can be carried out, for example, by reacting the α-olefin with maleic anhydride in a reaction vessel. An alcohol equivalent to the acid value of the acid copolymer and an equivalent mole of alcohol or alkylamine and a nonionic surfactant are charged, and paratoluenesulfonic acid is further added as a catalyst. It can be performed by performing a dehydration reaction for a time. The conversion was xylene / dimethylsulfoxide (2
/ 1 to 9/1) can be traced by measuring the acid value using a mixed solvent of (1) to (9/1). The reaction rate of the reactant according to the present invention is 70
９８98%.

By emulsifying and dispersing such a reaction product in water, a high-quality and 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 impart durable flexibility. In order to respond to the diversification of fiber materials and the diversification and sophistication of required flexibility, water-soluble polyester resin, water-soluble polyurethane resin, glyceride, polyhydric alcohol fatty acid ester, polyamine Higher fatty acid amides,
Paraffin, water-soluble acrylic resin, modified silicone and the like may be blended.

The above-mentioned copolymer of α-olefin / maleic anhydride, alcohol having 4 to 22 carbon atoms, and 4 to 2 carbon atoms
Ester compound obtained by the esterification reaction of ethylene alcohol and / or propylene oxide adduct of alcohol 2 or alkylamine having 4 to 22 carbon atoms with ethylene oxide and / or propylene oxide adduct, or α-olefin / maleic anhydride By emulsifying and dispersing an amide compound obtained by an amidation reaction between an acid copolymer and an alkylamine having 4 to 22 carbon atoms in water, a high-quality and stable emulsion can be obtained. In addition, this emulsion has good affinity for various fibers, and gives a good initial flexibility and water absorption by forming a uniform resin film on the fiber surface, and also has a significant effect of improving durability. .

[0019]

Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 In a 500 ml four-necked flask, 50 g of diamond carna PA168 (manufactured by Mitsubishi Chemical Corporation, acid value 275), which is an α-olefin / maleic anhydride copolymer, and 28 mol of ethylene oxide adduct of stearyl alcohol (HLB = 16.4) 3
68 g and 0.8 g of p-toluenesulfonic acid were charged, the temperature was raised under a nitrogen stream, and a dehydration reaction was carried out at 160 to 200 ° C. for 4 hours to obtain 415 g of a light yellow-white solid product (I) having a conversion of 85%. Obtained.

Synthesis Example 2 In a 500 ml four-necked flask, 80 g of Diacarna PA124 (manufactured by Mitsubishi Chemical Corporation, acid value: 315) as an α-olefin / maleic anhydride copolymer, oleyl alcohol 6
0 g, 258 g of an adduct of stearylamine with 20 mol of ethylene oxide (HLB = 15.3) and 0.8 g of paratoluenesulfonic acid.
A dehydration reaction was performed at -200 ° C for 4 hours to obtain 395 g of a pale yellow-white solid product (II) having a conversion of 80%.

Synthesis Example 3 In a 500 ml four-necked flask, 70 g of diamond carna PA168 (manufactured by Mitsubishi Chemical Corporation, acid value 275), which is an α-olefin / maleic anhydride copolymer, and oleyl alcohol 4
6 g, 257 g of a 28 mol adduct of stearyl alcohol with ethylene oxide (HLB = 16.4) and 0.8 g of p-toluenesulfonic acid were charged, and the temperature was increased under a nitrogen stream.
Dehydration reaction at 60-200 ° C for 4 hours, reaction rate 85%
368.6 g of the product (III) was obtained as a pale yellow-white solid.

Synthesis Example 4 70 g of α-olefin / maleic anhydride copolymer Q-0048 (manufactured by Toyo Petrolite Co., Ltd., acid value 280) and behenyl alcohol 5 were placed in a 500 ml four-necked flask.
7 g, 262 g of an adduct of stearyl alcohol with 28 mol of ethylene oxide (HLB = 16.4) and 0.8 g of p-toluenesulfonic acid were charged, and the temperature was increased under a nitrogen stream.
Dehydration reaction at 60-200 ° C for 4 hours, reaction rate 85%
384.5 g of the product (IV) as a pale yellow-white solid was obtained.

Synthesis Example 5 In a 500 ml four-necked flask, 100 g of α-8olefin / maleic anhydride copolymer X-8040 (manufactured by Toyo Petrolite Co., Ltd., acid value 170), stearylamine 4
1 g, 227 g of an adduct of stearyl alcohol with 28 mol of ethylene oxide (HLB = 16.4) and 0.8 g of paratoluenesulfonic acid were charged, and the temperature was increased under a nitrogen stream.
Dehydration reaction at 60-200 ° C for 4 hours, reaction rate 85%
365.6 g of the product (V) as a pale yellow-white solid was obtained.

[0024] The product (I) is charged into an emulsification kettle, heated to 85 to 90 ° C, melted for about 1 hour, stirred, and then hot water at 80 to 90 ° C is added to emulsify. This emulsion was a pale yellowish white liquid.
The obtained emulsion is referred to as “Product 1 of the present invention”.

[0025] The product (II) is charged into an emulsification kettle, heated to 85 to 90 ° C, melted for about 1 hour, stirred, and then hot water at 80 to 90 ° C is added to emulsify. This emulsion was a white liquid. The obtained emulsion is referred to as product 2 of the present invention.

[0026] The product (III) is charged into an emulsification kettle, heated to 85 to 90 ° C, melted for about 1 hour, stirred, and then hot water at 80 to 90 ° C is added to emulsify. This emulsion was a pale yellowish white liquid. The obtained emulsion is referred to as product 3 of the present invention.

[0027] The product (IV) is charged into an emulsification kettle, heated to 85 to 90 ° C, melted for about 1 hour, stirred, and then hot water at 80 to 90 ° C is added to emulsify. This emulsion was a white liquid. The obtained emulsion is referred to as “Product 4 of the present invention”.

[0028] The product (V) is charged into an emulsification kettle, heated to 85 to 90 ° C, melted for about 1 hour, stirred, and then hot water at 80 to 90 ° C is added to emulsify. This emulsion was a pale yellowish white liquid.
The obtained emulsion is designated as product 5 of the present invention.

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

Comparative Example 2 Emulsion having the following composition (referred to as Comparative Product 2) Esterification reaction product of high wax 1105A (manufactured by Mitsui Petrochemical) and 15 mol of ethylene oxide adduct of cetyl alcohol 20 parts Water 80 parts Total 100 parts This emulsion was a pale yellow liquid.

Comparative Example 3 A commercially available water-soluble polyester resin (20% product) represented by the following structural formula (Comparative Product 3).

[0032]

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(In the formula, x is 45 and y is 15.) Comparative Example 4 A commercially available water-soluble polyurethane resin (29% product) represented by the following structural formula (referred to as Comparative Product 4).

[0034]

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(Wherein R ₁ is a block copolymer chain of ethylene oxide and propylene oxide having a molecular weight of 5000 (EO = 40%, PO = 60%), and z is 3). Comparative Example 1 The cotton knitted fabric was padded with a 5% aqueous solution of the product of the present invention or the comparative product, and its durability, flexibility and water absorption were evaluated. Test material Cotton knitted cloth Processing conditions 1 dip / 1 nip 5% aqueous solution Squeezing rate: 80% Drying: 105 ° C, 10 minutes Durability Waterproof washing tester: Home washing machine Ginga VH-300S1 (Toshiba) New Using 2 g / liter of beads (manufactured by Kao), washing at 40 ° C. for 15 minutes is performed once, and the deterioration of feeling after 5 (L-5) and 10 (L-10) washes is examined. Evaluation Hand: Judge by touch.

：: Rich in flexibility Δ: Slightly flexible ×: Coarse hard Water absorption: JIS L-1018 A method (drop method) The results are shown in Table 1 below.

[0037]

[Table 1]

From the above results, the cotton knitted fabric treated with the softening agent of the present invention not only has a good initial feeling but also has a durability which cannot be obtained with the conventional finishing agent even after repeated washing. It turns out that it has some flexibility. Also,
Good water absorption. Performance Comparative Example 2 A polyester / cotton knit fabric was padded with a 3% aqueous solution of the product of the present invention or the comparative product, and its durability, flexibility and water absorption were evaluated. Test material Polyester / cotton knit cloth Processing conditions 1 dip / 1 nip 3% aqueous solution Each squeezing rate: 70% Drying: 105 ° C, 10 minutes Durability Waterproof washing tester: Home washing machine Ginga VH-300S1 (manufactured by Toshiba Using 2 g / l of New Beads (made by Kao), wash once at 40 ° C for 15 minutes, and reduce the feeling after 5 (L-5) and 10 (L-10) washes. Find out. Evaluation Hand: Judge by touch.

：: Rich in flexibility △: Slightly flexible ×: Coarse hard Water absorption: JIS L-1018 A method (drop method) The results are shown in Table 2 below.

[0040]

[Table 2]

It can be seen that the polyester / cotton knit fabric treated with the softening agent of the present invention has high 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, Sumitomo Chemical Co., Ltd.) and a mixed 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 solution containing the amount shown in Table 3 below. After the treatment, the effect of preventing a decrease in tear strength was evaluated. Test material Cotton 40th broad bleached rayon taffeta Polyester / cotton fabric Processing conditions 1 dip / 1 nip Drawing ratio: Cotton 40th broad bleached fabric: 60% Rayon taffeta: 70% Polyester / cotton fabric: 55% Drying: 105 ° C, 3 Minutes Cure: 150 ° C., 2 minutes Evaluation Tear strength tester: Elmendorf tearing tester (manufactured by Toyo Seiki) The results are shown in Table 3 below.

[0042]

[Table 3]

The soft finish of the present invention exhibits excellent properties for preventing a reduction in tear strength when a resin such as cotton fabric, rayon fabric and polyester / cotton fabric is used in combination. Comparative Test Example 4 A cotton knit fabric and a cotton / polyester fabric were subjected to padding treatment with a 2% aqueous solution of the above-mentioned invention product and the comparison product, and their sewability and anti-fusing property were evaluated. Test material Cotton knit fabric (fluorescent dyed cloth) Cotton / polyester fabric (35/65) Processing conditions 1 dip / 1 nip 2% aqueous solution squeezing rate Cotton knit fabric: 80% Cotton / polyester fabric: 70% Drying: 105 ° C 10 minutes evaluation Sewability, anti-fusing property Tester: High-speed single-needle lockstitch industrial sewing machine (manufactured by Juki) Needle # 11, pitch 2 mm, 4-ply overlap, number of pinholes or fusion after empty sewing at 4500 rpm Read the distance to wear.

The results are shown in Table 4 below.

[0045]

[Table 4]

The softening agent of the present invention can be used as a sewable and pinhole-preventing agent for cellulose fibers treated thereby.
Furthermore, it provides excellent properties for preventing fusion of the cellulose / polyester mixed knitted fabric.

[0047]

As can be seen from the above results, according to the present invention, the problems of imparting flexibility, durability and water absorption, which were weak points common to the conventional softening agents, are practically satisfied. It can be improved to the extent possible, and also has secondary functions such as a strength reduction preventing effect which cannot be obtained by conventional durable soft finishing agents, and therefore can exert a great effect on soft finishing of textile products.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication // C08F 222/06 MLQ C08F 222/06 MLQ (72) Inventor Nobuo Akie Sono, Miyazu, Kyoto 262 Gunze Co., Ltd., Apparel Division (72) Inventor Tadahiko Kato 1-3-21 Yanagimachi, Sabae-shi, Fukui Prefecture (72) Inventor Hiroaki Miyakoshi 4-6, Tamokunaka-ku, Harue-cho, Sakai-gun, Fukui Prefecture (72) Invention Person Masanobu Ueno No.8, 43, Kongo-ji, Harue-cho, Sakai-gun, Fukui Prefecture

Claims (1)

[Claims] [Claim 1] The following general formula (1) (Wherein R represents an alkyl group having 2 to 58 carbon atoms), which is a copolymer of α-olefin / maleic anhydride, having a molecular weight of 2000 to 50,000 and a molecular weight of 10 to 350.
(A) having an acid value of 4 to 22 carbon atoms, an alcohol having 4 to 22 carbon atoms, and an ethylene oxide and / or propylene oxide adduct of an alcohol having 4 to 22 carbon atoms (HLB = 10 to 1)
9) or an ethylene oxide and / or propylene oxide adduct of an alkylamine having 4 to 22 carbon atoms (HLB =
10-19) An ester compound obtained by an esterification reaction with (B), and the compound (A) and a compound having 4 carbon atoms
A durable soft finish containing at least one compound selected from amide compounds obtained by amidation reaction with alkylamine (C).