JPH0811868B2 - Flexible smoothing agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention provides flexibility and smoothness to cellulose fibers such as cotton, rayon, and hemp, and mixed fibers of various synthetic fibers such as polyester, polyamide, and acrylic, and cellulose fibers. The present invention relates to a self-emulsifying type soft and smooth finishing agent that imparts

2. Description of the Related Art Various chemicals are known as soft and smooth finishing agents for fibers.

In general, as a soft and smooth finish, a high melting point wax such as 140 ° F paraffin, a smooth component of polyethylene and a polyhydric alcohol higher fatty acid ester, and a soft component typified by a polyamine higher aliphatic amide are added with nonylphenol or higher alcohol ethylene oxide. The thing emulsified with the nonionic surfactant of the thing is mainly used. on the other hand,
Cationic surfactants or those mixed with formic acid, acetic acid, etc. are called cationic softening and smoothing agents, and those containing anionic surfactants such as soap and sulfosuccinate sodium salt are anionic softening and smoothing agents. It is classified as a drug.

Anionic softening and smoothing agents are used as softening and smoothing agents for fluorescent dyes of cellulose fibers (for white goods) because they are highly compatible with an thione-based fluorescent dye and show little reduction in whiteness. On the other hand, since the cationic softening agent has a high adsorptivity, it is used as a coloring material for polyamide fibers such as wool and nylon, other synthetic fibers such as polyester and acrylic, and cellulose fibers such as cotton, rayon and hemp. Many are used. Further, the nonionic softening and smoothing agent is widely used for cellulose fibers, polyamide fibers and other synthetic fibers, taking advantage of the fact that there is almost no trouble concerning compatibility with anions and cation agents. .

Problems to be Solved by the Invention These anionic, cationic, and nonionic softening agents are composed of various ingredients such as smoothing ingredients and softening agents, mainly nonionic surfactants, to form stable emulsions. Has been done. However, in order to obtain a stable emulsion, a large amount of emulsifier is required, which causes a decrease in the softening / smoothing effect and a decrease in various fastnesses of the dyed fiber, and a lot of work by trial and error in selecting various emulsifiers. The current situation is that it is necessary and has become a bottleneck in the development of softening finishes.

Means for Solving the Problems The present invention is directed to an ethylene- and / or propylene oxide adduct of oxidatively modified or acid-modified polyethylene and nonylphenol (HLB 10 to 19, preferably 12 to 17), higher alcohol (carbon number of alkyl group). 4-22) ethylene oxide and / or propylene oxide adduct (HLB 10-19, preferably
12-17) or an ester produced by an esterification reaction of a higher alkylamine (having 4 to 22 carbon atoms in the alkyl group) with an ethylene oxide and / or propylene oxide adduct (HLB 10 to 19, preferably 12 to 17). Provided is a softening finish containing a system compound as an essential component.

Since the soft and smooth finishing agent of the present invention has self-emulsifying property, it is possible to reduce the amount of the emulsifier as compared with the case of using the conventional soft and smooth finishing agent. Therefore, by using this, smoothness and flexibility are significantly improved. It is also improved, and the dyeing fastness of polyester and acetate fibers is reduced, and there are few defects of color change due to discharge of dyes of dyed polyamide and cellulose fibers. Furthermore, by utilizing its self-emulsifying property, it becomes possible to develop a softening / smoothing agent in a wide HLB range.

The nonionic softening / smoothing agent of the present invention can be made into a cationic softening / smoothing agent by blending a cationic surfactant, and can also be made into an anionic softening / smoothing agent by blending an anionic surfactant.

The emulsification can be easily carried out by blending the softening agent of the present invention, an ester compound, paraffin and the like, melting the mixture, and then adding heat absorption at 90 ° C. Also,
It is also possible to collectively emulsify at a high temperature of 130 to 135 ° C in a sealed state.

The oxidation-modified or acid-modified polyethylene used in the present invention includes those having a carboxyl group introduced by polyethylene air oxidation or thermal decomposition, those obtained by copolymerizing polyethylene with vinyl carboxylic acid such as acrylic acid and methacrylic acid. is there. Typical examples include AC-629 and AC-540 manufactured by Allied Chemicals, high wax 4202E and 1105A manufactured by Mitsui Petrochemical, and sun wax E manufactured by Sanyo Kasei.
-300 etc. are mentioned.

On the other hand, as an adduct of ethylene oxide and / or propylene oxide, nonylphenol or a higher alcohol having 4 to 22 carbon atoms, preferably 12 to 18 or a higher alcohol having 4 to 22 carbon atoms,
Preferably 12 to 18 higher alkyl amines and ethylene oxide and / or propylene oxide 6 to 50 mol, preferably 8 to
There is an adduct reaction with 30 moles (HLB 12-17). Also,
The block or random addition reaction product of the above nonylphenol, higher alcohol, higher alkylamine and ethylene oxide and propylene oxide can be used if the HLB is 10 to 19, preferably 12 to 17.

The reaction between the oxidation-modified or acid-modified polyethylene and the nonionic surfactant agent is carried out, for example, by charging the acid-value equivalent of the oxidation-modified or acid-modified polyethylene and the equimolar amount of the nonionic surfactant, and further adding paratoluenesulfonic acid as a catalyst. Is added, and dehydration reaction is performed at 180 to 220 ° C. for 3 to 5 hours under a nitrogen stream. The reaction rate can be traced by measuring an acid value 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%.

Since the reaction product according to the present invention has self-emulsifying property, single emulsification is also possible, but the texture is improved by further adding glyceride, polyhydric alcohol fatty acid ester, polyamine higher fatty acid amide, paraffin and the like. , It is possible to improve the stability of the product. In general, the incorporation of other nonionic surfactants is not required.

The obtained emulsion can be diluted with water and used for dipping, padding, spraying or the like.

Since the ester of the acid value-modified or acid-modified polyethylene according to the present invention and the nonylphenol or higher alcohol or higher alkylamine ethylene oxide and / or propylene oxide adduct is in the oligomer region having a molecular weight of about 1000 to 4000, Compared with general softening and smoothing agents, it has a stronger affinity for fibers and provides a stable smoothness, flexibility and durability with a small amount used.

In addition, since it is a self-emulsifying ester that is directly bonded to polyethylene, which is a low HLB wax, it does not require any further emulsifier and the processing performance is improved.

Furthermore, these emulsions form a stable emulsion in a wide range of HLB, which is different from that of low molecular weight emulsions, due to the emulsion protective action peculiar to oligomers and colloids.

EXAMPLES Next, the present invention will be further described based on Examples.

Synthesis 1 Oxidation-modified polyethylene type high wax 1105A (Mitsui Petrochemical, oxidation 60) 1 in a 500 ml four-necked flask.
87 g, cetyl alcohol 9 mol ethylene oxide adduct (HLB 12.4) 127.6 g and paratoluene sulfonic acid
0.6 g was charged, the temperature was raised under a nitrogen stream, and dehydration reaction was carried out at 210 to 220 ° C. for 4 hours to obtain 311 g of a pale yellowish white solid product (I) having a reaction rate of 87%.

Synthesis 2 In a 500 ml four-necked flask, acid-modified polyethylene type AC-540 (Allied Chemical, acid value 40) 140 g, ethylene oxide 15 mol adduct of stearylamine (HL
B 14.2) 93 g and p-toluenesulfonic acid 0.5 g were charged, the temperature was raised under a nitrogen stream, and dehydration reaction was performed at 180 to 190 ° C. for 4 hours to obtain 231 g of a yellow solid product (II) with a reaction rate of 84%. It was

Emulsion 1 (referred to as product 1 of the present invention) Product (I) 12 parts 50 ° beef tallow oil 2 parts sorbitan tristearate 6 parts Water 80 parts Total 100 parts Properties are white liquid.

Emulsion 2 (referred to as product 2 of the present invention) Product (II) 10 parts 140 F ° paraffin 5 parts 51 ° beef tallow oil 5 parts Water 80 parts Total 100 parts Properties are white translucent liquid.

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 Properties are white translucent liquid.

Comparative product 2 Our commercial paraffin-based smoothing agent (paraffin content 20%) Properties are white translucent liquids.

EFFECT OF THE INVENTION Performance Test 1 A cotton knit is dipped in the above product and its durability is evaluated by a handling method.

Sample material Cotton knit fabric (slen dyeing) Treatment conditions 5% each owf bath ratio: 1:15 Dipping: 45 ℃ × 15 minutes Squeezing: 85% Drying: 100 ℃ × 30 minutes Durability Dry cleaning resistance tester Using a dry cleaning tester (manufactured by Daiei Kagaku Seiki Co., Ltd.) PARK REN, at room temperature, once every 10 minutes, check the deterioration of the texture after cleaning once and five times.

Water-proof washing resistance tester Household washing machine Aozora PS-522 (Hitachi) Sub (Daiichi Kogyo Seiyaku) 2g / is used, and 40 ° C for 10 minutes once, wind after washing once and five times Examine the decline.

Evaluation Judgment based on feeling of touch.

◯: Rich in flexibility Δ: Slightly flexible ×: Coarse and hard results are shown in Table 1.

It can be seen that the product of the present invention has excellent durability.

Performance test 2 A cotton yarn is dipped in the above-mentioned product and its flexibility and smoothness are evaluated.

Test material Cotton yarn No. 20 twin yarn Unfixed and fixed products Fixing agent: Neofix R-250 3% owf (manufactured by Nichika Kagaku Co., Ltd., polycationic fixing agent) Treatment conditions 3% owf bath ratio: 1:15 immersion Pickling: 45 ℃ × 15 minutes Squeezing: 90% Drying: 100 ℃ × 60 minutes Evaluation Judgment based on the feeling of touch.

○: Rich in flexibility △: Slightly flexible ×: Coarse hardness smoothness tester Eiko μmeter (manufactured by Eiko Sokki Co., Ltd.) Adjust the initial tension T ₁ of the yarn to 10 g at a yarn speed of 100 m / min. Thread tension after passing 3 rods (φ5mm) g of T ₂
The number is measured and the smoothness between the thread and the metal is checked. The smaller the value, the better the smoothness.

 The results are shown in Table 2.

When applied to a yarn, the product of the present invention gives a feeling of flexibility as well as a knitted fabric, and has good smoothness.

Performance test 3 The stability of the treatment baths is compared by the following shaking test method.

Treatment conditions 300 ml Erlenmeyer flask, 200 ml of water containing 5 g / each of the above products
Put it in, put a stopper on it, shake it vigorously up and down 100 times, and then filter with a cotton cloth (black dye # 40) to check the presence or absence of residue and the stability to some extent.

Evaluation Stability ◯: Stable, no residue Δ: A small amount of residue is seen ×: Unstable, large amount of residue is seen Table 3 shows the results.

The product of the present invention is a self-emulsifying emulsion, and has excellent processing bath stability.

Claims (1)

[Claims] 1. An ethylene oxide and / or propylene oxide adduct (HLB 10 to 19) of oxidatively modified or acid modified polyethylene and nonylphenol, an ethylene oxide and / or propylene oxide of a higher alcohol (having 4 to 22 carbon atoms in an alkyl group). Ester-based compound produced by esterification reaction of adduct (HLB 10 to 19) or higher alkylamine (alkyl group having 4 to 22 carbon atoms) with ethylene oxide and / or propylene oxide adduct (HLB 10 to 19) A soft and smooth finish containing at least one of the above as an essential component.