KR940007336B1 - Fat liquaring-compositions of leather - Google Patents

Abstract

The fatl iquoring agent composition for a leather is composed of (a) 1-15 wt.pts. of dyeing elevator of at least one of urea, melamine surfactant, urea surfactant, glyoxal resin, lower amine and polyoxyethylene alkylamine ether, (b) 20-60 wt.pts. of sulfated oil or phosphated oil contg. 20-93 wt.pts. softener, 2-20 wt.pts. C8-18 fatty alcohol, 2-30 wt.pts. sulfating agent or phosphating agent and 3-45 wt.pts. neutralizing agent, (c) 1-20 wt.pts. of emulsifying agent, (d) 3-30 wt.pts. of synthetic oil of at least one of C10-32 hydrocarbon or halogenated hydrocarbon, and C10-36 alkylbenzene, and (e) 78 wt.pts. or less of water. The fatliquoring agent composition has a good dyeing property and a dyeing levelness for leathers.

Description

Leather eggplant composition

The present invention relates to a leather eggplant composition. More specifically, the present invention relates to a leather eggplant composition which improves dyeability upon leather softening action.

Leather divides the dermal and flesh layers of skin and hide and processes them with the dermal layer. For example, leather is produced by first dividing the grain and split layers by water and lime, followed by pickling, tannin, neutralization, eggplant and dyeing, and coating in the finishing process.

In particular, the eggplant and dyeing process is a process to soften the leather by re-feeding the oil to prevent the oil contained in the raw hide is removed in the soaking and lime process to prevent this, the eggplant used here As for dyes, eggplants are used as products that are sulfated and phosphorylated in fats, oils, liquid paraffins, waxes, fatty alcohols, fatty acids, and synthetic oils, and emulsified with surfactants. Acid dyes and direct dyes are mostly used as dyes.

Looking at the dyeing mechanism (mechanism), the positive ions of the leather, that is, the amine group of the cation and the carboxyl group of the anion are charged with (-) and (+) ions depending on the pH of the salt bath, so that the pH is adjusted to 5.8 to 6.5 to negative (-). Charge with an electric charge. When the leather is charged with a negative charge, acidic and direct pigments are negative ions, so they do not combine with the leather and penetrate into the leather. The organic acid is added to the penetrated dye solution to lower the pH to fix the dye to the leather by amine bonds of the leather.

(D: dyeing machine F of dyes: fiber of leather)

This dyeing and eggplant is very important as a process for imparting flexibility and color of the leather. British Patent No. 773,825 as a patent for the composition of the branching agent used to improve the physical properties of such leather contains mineral oil and low fat, and as an emulsifier, sulfated oil as an anion, polyethylene glycol (molecular weight 200 to 400) as an anion and 8 to C A branching composition is disclosed using an aliphatic mono carboxylic acid of 22 and containing alkylate aminoamide and wool as cations. However, when the leather is treated with the conventional eggplant process using only such eggplants, the flexibility of the leather is improved, but the dyeing property is greatly lost as compared with the case where no eggplant is used.

Accordingly, it is an object of the present invention to provide a leather eggplant composition having excellent dyeing and leveling properties while exhibiting a softening effect applied to leather.

The leather eggplant composition of the present invention contains one or two or more of urea, melamine-based surfactants, urea-based surfactants, glyoxal resins, lower amines and polyoxyethylene alkylamine ethers as dyeing enhancers. The use of the composition not only significantly improves the uniformity and dyeability of the leather, but also can significantly reduce the amount of dye used in dyeing due to high dyeing efficiency.

The leather eggplant composition of the present invention may further contain a softening agent, an emulsifier, a synthetic oil and water in the above-mentioned dyed flavoring agent.

Hereinafter, the present invention will be described in more detail. ·

Leather eggplant composition of the present invention (a) 1 to 15 parts by weight of one or more dyeing enhancers selected from urea, melamine-based surfactants, urea-based surfactants, glyoxal resins, lower amines and polyoxyethylene alkylamine ether, (b) 20 to 93 parts by weight of at least one softening agent selected from animal oils, fish oils and vegetable oils and fatty acids in the form of triglycerides and 2 to 20 parts by weight of one or more fatty alcohols selected from fatty alcohols having 8 to 18 carbon atoms. Or 20 to 60 parts by weight of sulfated oil or phosphated oil containing 2 to 30 parts by weight of a phosphorylating agent and 3 to 45 parts by weight of a neutralizing agent, (c) 1 to 20 parts by weight of an emulsifier, (d) a hydrocarbon having about 10 to 32 carbon atoms or part 3 to 30 parts by weight of synthetic oil of one subphase selected from halogenated hydrocarbons, linear or branched alkylbenzenes having 10 to 36 carbon atoms, and (e) 78 parts by weight or less of wool. It is composed.

Lower amines used as the dyeing enhancer (a) in the composition of the present invention include monoethanolamine, diethanolamine or triethanolamine, and melamine surfactants, urea surfactants, polyoxyethylene alkylamine ethers, and glyoxal coefficients. It is desirable to have the following structural formula, respectively.

① Melamine Type Surfactant:

② Urea-based surfactants:

③ polyoxyethylene alkylamine ether:

(Wherein R is an alkyl group having 12 to 18 carbon atoms, m and n are each an integer of 1 or more, and the sum of m and n is 7 to 30)

④ Glyoxal Resin:

In the leather eggplant composition of the present invention, the dyeing flavoring agent (a) is 1 to 15 parts by weight based on the total weight of the composition .. However, if it is used in less than 1 part by weight, the dyeing efficiency is lowered. When used in more than 15 parts by weight, the amount of the softening agent is relatively small, so that the softening effect is insufficient.

Sulfuric acid oil mentioned as component (b) in the composition of the present invention comprises at least one softener selected from animal oils, fish oils and vegetable oils in the form of mono-, di- and triglycerides, fatty acids and fatty acid ester compounds; And at least one softening aid, sulfate or phosphorylating agent and neutralizing agent selected from fatty alcohols having 8 to 18 carbon atoms.

Particularly, the softening agent of the above components may be selected from at least one of mono-, di- and tr-glyceride forms of copper wool, fish oil and vegetable oil and ester compounds of fatty acids or fatty acids. It is preferable to select from among, barley oil, cod liver oil, cottonseed oil, lijiang oil and oleic acid. Such sulfated oil or phosphorylated oil contains 20 to 60 parts by weight of the total branching agent, more preferably 30 to 40 parts by weight.

The softening aid uses a fatty alcohol having 8 to 18 carbon atoms, preferably a fatty alcohol having 16 to 18 carbon atoms, and the softening aid contains 2 to 20 parts by weight of the total branching agent, more preferably 7 To l5 parts by weight. 、

In addition, those that can be preferably used as the sulfate or phosphating agent include 98% sulfuric acid, fuming sulfuric acid, colosulphonic acid, SO gas, phosphoric anhydride, phosphorus oxychloride (POCl), such a sulfate or phosphoric acid It is preferable to use 5-30 weight part of agents for the whole branching agent.

Preferred examples of the neutralizing agent include sodium hydroxide (50%), triethanolamine, diethanolamine, monoethanolamine, ammonia, and the like. Such neutralizing agents use from 2 to 35 parts by weight based on the total branching agent.

Such sulfated oil or phosphorylated oil may be prepared by the following method, by mixing the softening agent and softening aid, stirring at 40 to 80 rpm, and adding a sulfate or phosphorylating agent while maintaining a temperature of 40 ° C. or lower. After 8 hours of sulfation or phosphorylation, a neutralizing agent is added while maintaining a temperature of 50 ° C. or lower and neutralized for 4 to 8 hours.

On the other hand, the emulsifying agent (c) component in the composition of the present invention includes a polyoxyethylene alkylphenyl ether and a polyoxyethyllian alkyl glycol fatty acid ester as a bayone, and the polyoxyethylene alkylphenyl ether has 8 to 12 carbon atoms, preferably 8 To 9 alkyls and 2 to 30 moles, preferably 2 to 12 moles of ethylene oxide, and polyoxyedylene alkylglycol fatty acid esters are 5 to 20 moles of ethylene oxide as single or mixed fatty acids having 12 to 18 carbon atoms, Preferably 5 to 9 mole added. As the anion, alpha-olefin sulfonate, linear alkylbenzene sulfonate, synthetic or natural fatty alcohol sulfonate, polyoxyedylene alkyl ether sulfonate, containing 1 to 20 parts by weight of ethylene oxide alone or in combination of 1 to 20 parts by weight good.

In addition, the synthetic oil as component (d) in the composition of the present invention may contain 3 to 30 wt% of hydrocarbons having 10 to 32 carbon atoms or partially halogenated hydrocarbons, linear or branched alkylbenzenes having 10 to 36 carbon atoms, alone or in combination. Minor mixture is good.

The following describes the present invention in detail with reference to the examples. The scope of the present invention is not limited to these examples.

[Production Example 1]

64 parts by weight of right angle oil and l3 parts by weight of oleyl alcohol were mixed and stirred at 50 rpm, and maintained at 40 ° C. or lower, followed by 10 parts by weight of 98% sulfuric acid to be sulfated for 5 hours, and then maintained at 50 ° C. or lower. 50% sodium hydroxide was added to neutralize for 6 hours to obtain sulfated oil.

[Production Example 2]

50 parts by weight of cottonseed oil and 20 parts by weight of oleic acid were mixed, stirred at 50 rpm, and maintained at 40 ° C. or lower, followed by 14.1 parts by weight of 98% sulfuric acid, followed by sulfate for 3 hours, and then 13.9 parts by weight of 50% hydroxide. Sodium was neutralized for 4 hours to obtain sulfated oil.

[Manufacture example 3]

61.7 parts by weight of cod liver oil and 10.1 parts by weight of lauryl alcohol were mixed, stirred at 60 rpm, and maintained at 40 ° C. or lower, followed by 12.4 parts by weight of 98% sulfuric acid, followed by sulfate for 4 hours. The sodium sulfate was neutralized for 5 hours to obtain sulfated oil.

[Production Example 4]

58.8 parts by weight of oleic acid and 7.4 parts by weight of lauryl alcohol were mixed, stirred at 60 rpm, and phosphorylated for 1 hour by adding 14.7 parts by weight of phosphoric anhydride while maintaining at 40 ° C. or lower, and then 19.1 parts by weight of 50% hydroxide. Sodium was added and neutralized for 6 hours to obtain phosphorylated oil.

Production Example 5

51.2 parts by weight of rice bran oil and 6.1 parts by weight of lauryl alcohol and 8.9 parts by weight of oleic acid were mixed, stirred at 60 rpm, and maintained at 40 ° C. or lower, followed by the addition of 14.3 parts by weight of 98% sulfuric acid for 6 hours, followed by 50 ° C. or lower. 16.5 parts by weight of 50% sodium hydroxide was added thereto and neutralized for 7 hours to obtain sulfated oil.

[Application Example 1]

Wash raw skin with clean water, add alkali, water and degreasing agent, soak for 24 hours, and wash again with clean wool. After washing with water, lime lime, soda oil and soda oil are limed for 12 hours. The limed finished leather is divided and demineralized, pickled and tannin processed as a grain layer. Tannin finished leather is called wet blue and is neutralized to suit dyeing and eggplanting (pH 5.5-6.2).

Thickness: 0.7-0.9mm, shaved, used for eggplant experiments.

[Application Example 2]

1. Experimental leather: Neutralized wet blue of the application example 1 (tanned leather)

Thickness: 0.7-0.9mm

2.process

1) Water washing: Put water at 50 ° C in a drum about 100 parts by weight of wet blue weight level and wash it while rotating (hereinafter, the weight standard in the process is wet blue weight standard).

2) Dyeing and eggplant: 250 parts by weight of water at 50 ℃.

2 parts by weight of the dye (black) and 15 parts by weight of dry eggplant composition were added to Examples 1 to 8 and rotated for 40 minutes. Add 1 part by weight of formic acid and rotate for 10 minutes.

3) Water washing: Wash with water using 100 parts by weight of cold water.

4) Precursor: Allow to dry naturally in places where sunlight is not directly exposed.

5) Aji, mill and toggle for proper moisture content and flexibility.

[Examples 1 to 8]

Examples 1 to 8 are applied to the test piece of the neutralized leather collected in Application Example 1 by the process of Application Example 2 dyeing and eggplant work using 15% of the leather eggplant composition prepared in the ratio shown in Table 1 The dyeing property of the leather is observed using a color difference meter.

[Comparative Examples 1 to 7]

Comparative Examples 1 to 7 were dyed and eggplanted in the same manner as in Examples 1 to 8 using 15% of the leather eggplant composition prepared at the ratio shown in Table 1, and observed the dyeability of the leather using a color difference meter. do.

Table 1. Eggplant composition]

The following is a description of the visual observation sensory test, uniformity test and leather color test method and results in the dyeing test using the leather eggplant composition prepared according to Examples 1 to 8 and Comparative Examples 1 to 7 of Table 1 above. do.

(1) Visual observation sensory test

Twenty specimens (Examples 1 to 8 and Comparative Examples 1 to 7) were divided into 4 grades (very good, excellent, normal, and poor) for 15 specimens (absolute evaluation), and absolute staining was observed. The results are shown in Table 2 below (symbols in the table are very good, ○ is good, △ is normal, and × is bad).

[Table 2] Unit: Person

(2) leveling test

Hunter whiteness is measured on a 10 x 10 cm specimen using a calorimeter (colorimeter) using a colorimeter to compare the difference and measure the leveling.

1) Psalms

Hunt whiteness for any of the three sections is measured using a sensor 1 cm in diameter.

2) results

The result is judged using the numerical deviation of Hunt whiteness.

Table 3. Crack Test Results

(3) Leather color test result

The whiteness value observed in the color of the leather using a color difference meter is shown in Table 4, where W is whiteness by Lab 켸 and WB is Hunter whiteness.

WB = Z / 1.18, W = 100-[(100-L) ² + a ² + b ² ] ^1/2

The numerical value is a comparative value with standard values (Y = 94.75, X = 92.84, Z = 112.05, WB = 94.95, N = 0.07).

The results of the following Table 4 shows that the larger the value, the greater the whiteness, so that the eggplant using the dyeing enhancer is superior to the one not used.

[Table 4. Leather color test results]

Claims (9)

A leather eggplant composition comprising at least one dyeing enhancer selected from urea, melamine-based, surfactants, urea-based surfactants, glyoxal resins, lower amines and polyoxyethylene alkylamine ethers. The leather eggplant composition according to claim 1, wherein the dyeing enhancer is a melamine-based surfactant having the following structural formula. The leather eggplant composition according to claim 1, wherein the dyeing enhancer is a urea surfactant selected from the following structural formulas. The leather branch composition of claim 1 wherein the dyeing enhancer is a polyoxyethylene alkylamine ether having the structure: _Wherein R is an alkyl group of C _12-18 , m and n are each an integer of at least 1, and the sum of m and n is 7 to 30; The composition of claim 1, wherein the dyeing enhancer is a glyoxal resin having the structure 2. The composition of claim 1, wherein the dyeing enhancer is a lower amine selected from monoethanolamine, diethanolamine or triethanolamine. The leather branch composition according to claim 1, further comprising a softening agent, an emulsifier, a synthetic oil, and water. The leather branch composition according to any one of claims 1 to 6, wherein the dye enhancer contains 1 to 15% by weight based on the total weight of the composition. The leather branch composition according to claim 7, which contains 20 to 60% by weight of a softening agent, 1 to 20% by weight of emulsifier, 3 to 30% by weight of synthetic oil, and 78% by weight of water.