JPS6286100A - Leather treating agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel leather treatment agent and a leather treatment method using the same. More specifically, the present invention particularly relates to leather (in this specification-3, "leather" refers to leather and The purpose of the present invention is to provide a leather treatment agent that can easily obtain both of the following: The leather treated with the leather treatment agent of the present invention is washable like cloth, has excellent stretchability (&"drawability), and It also has excellent features such as being able to be sewn with a home sewing machine.

Conventional technology Conventionally, in order to make leather washable like cloth, the raw hide is recalcified and fermented, then rubbed and dyed, and then fattened with cow leg tallow or sulfated oil. However, the resulting leather had drawbacks such as becoming hard and discoloring after washing several times with water, and these drawbacks could not be overcome. Traditionally, dry cleaning was done when it was unavoidable to wash leather.
Even so, troubles such as bleaching could not be avoided (Yasuda: "Problems Raised by Clothing and Leather Roundtable Discussion", Leather Technology Vol. 1.23.Nc2.p.20-27.1982).

W of the present invention (= Problems to be Solved) The present invention has a problem in that the use of 1, K leather for clothing etc. is severely limited because leather produced by conventional methods becomes hard and loses color when washed. The purpose of the present invention is to provide a leather treatment agent that can easily handle leather that can be treated like cloth by solving the above problems. Because it improves
This also makes it possible to make effective use of work-in-progress, semi-finished products, and finished product scraps, such as pre-cut, double-jar scraps, punched I backs, and source leather scraps. In the case of leather for leather products, such scraps as PIJ are loosened and made into cells, which are then made into mat-like products using paper-making methods or methods similar to non-woven fabrics, such as sound-absorbing materials, low-density materials, etc. It can be used for. The shredded leather treated with the leather treatment agent of the present invention has a mucoid content of, for example, 1.0 per weight of the absolutely dry leather.
Since the percentage by weight or less is effectively removed, the yarn obtained by bathing the leather with the leather treatment agent of the present invention, chemically modifying it as necessary, and spinning it by a conventional method is a beam. This makes it possible to use it for woven fabrics, knitted fabrics, etc., as well.

Furthermore, the percentage of raw hides that are unusable due to damage during layer slaughter is 20% in developed countries and about 50% in ten developing countries, and the loss of raw hides on a global scale would cost 3 billion dollars. However, it has also been found that these raw hides can be made into leather with excellent performance by a treatment method using the leather treating agent of the Ari invention.

'A-: According to Akira, (A) 3-6 functional polyalkylene oxide polyol, (B) 2-4 valent metal, preferably 3-4 valent metal, most preferably C3 valent metal. Salt, (C)
Aromatic compounds substituted with 11 amino groups, hydroxyl groups, sulfone groups, and/or hydroxyl groups with 3 to 6 functional groups? A leather treatment composition 11 is provided comprising an aromatic incyanate terminated with a realkylene oxide polyol and (D) a surfactant.

The leather treatment agent of the present invention preferably includes components (A) and (B).
When the total of 1, <C) and l) is 100 wt%, (A) 6-6 functional polyalkylene oxide polyol 55-9Z51 is 6, preferably 65-96.5 weight%, preferably 75-94.5% by weight, (B) 2-4 valent gold, preferably 3-4 valent gold, most preferably 5-valent gold salt 0.1-8 ．． C1 weight%, preferably 0
．． 2 to 6.0% by weight, most preferably 0.3 to 5.0% by weight, (C) directly substituted with amine groups, hydroxyl groups, sulfonic groups and/or hydroxy groups, preferably is 0.0005 to 3.0% by weight of an aromatic incyanate terminated with a mono-, non- or tri-functionalized aromatic compound or a 6- to 6-functional polyalkylene oxide polyol;
Preferably from 0.001 to 2.0% by weight, most preferably from 0.002 to 1.0% by weight and (I)''If, and from 0.3 to 65% by weight, preferably from 0.6 ~30
It is a leather treatment agent containing heavy needles, most preferably 0.3 to 25% by weight.

If the above component (, f) exceeds 97.5% by weight, it is not preferable as there is no particular effect, and if it is too small, below 55% by weight, the softness of the leather will be lost and the wearability will be reduced. So I don't like it. Further, if the amount of component (B) is too high (more than 8.0% by weight), the strength of the leather decreases, which is undesirable, while if it is less than 0.1% by weight, the washing resistance decreases, which is undesirable. In addition, if the amount of component (C) is too large (more than 3.0% by weight), the strength of the leather will be lowered, which is undesirable, and if it is still too small (less than 0.0005i% by weight), the washing resistance will deteriorate, so it is not preferable. do not have. CD> component is 55
If the amount is too high (more than 0.3% by weight), it is not preferable since there is no particular effect, and if it is too small (less than 0.3% by weight), elution of mucoids etc. will be insufficient.

The molecular weight of the 3- to 6-functional polyalkylene oxide polyol as component (A) is preferably 1,000 to 10,00.
0, more preferably 2,000 to 7,000, most preferably 3,000 to 6,000. OOO's stuff is coming out.

Among the 6-6′ self-functional polyalkylene oxide polyols, I7< is 3-4 functional, particularly preferable is < ”
3 Official Ti'F2 sex, I? Realkylene oxide polyols are used.

(A) Ingredients 3 to O functional polyalkylene oxide.
The raw material alkylene oxide for polyol has 2 or more carbon atoms.
Preferred are alkylene oxides of No. 4, and examples of such alkylene oxides include d1 ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, etc., and combinations of two or more thereof, but preferred. Propylene oxide and ethylene oxide, as well as combinations thereof, may be used.

Examples of the 3- to 6-functional polyalkylene oxide polyol as component (A) include polypropylene oxide trimenalol prono-ξ triol, polyzolopylene oxide-hexane triol, polypropylene oxide-glycerin triol, and random Alternatively, block copolymerized zolopylene oxide/ethylene oxide-glycerin triol, random or block copolymerized ethylene oxide/propylene oxide-ethylenesoamine tetraol, polypropylene oxide-sorbitol hexaol, and the like can be mentioned. (A
) Component 3- to 6-functional polyalkylene oxide polyols may be used in combination of two or more.

The most preferred component (A) is polyalkylene oxide i
j? The reols are random copolymerized polyethylene oxide/glopylene oxide triols (preferably about 70 weight percent ethylene oxide) and polypropylene oxide triols (preferably about 98 weight percent propylene oxide).

Examples of divalent metal salts of component ()3 include zinc salts; hexavalent metal salts include aluminum salts, chromium salts, and iron salts; and zirconium salts as 4-sided salts; Norconium salts are preferred. Examples of Al salts include aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum fluoride, and aluminum lactate, and examples of norconium salts include turconium sulfate. The most preferred component (CB) is an aluminum salt, and among these, aluminum sulfate or a combination of aluminum sulfate and another hexavalent metal salt is preferred.

(Examples of aromatic compounds substituted with an amino group, a halogen, a sulfone group and/or a hydroxy group, preferably mono-, no- or tri-substituted as component (D') include aniline, 2,4-soaminotolu: r -n, 2, 6-
diamine)・Luene, '1'-phenylenesoamine, O
-Finyl diamine, ? Roofenilensoamine, 0
-Toluylene diamine, m-toluylene diamine, p-
1-lylensoamine, O-chloroaniline, m-chloroaniline, p-chloroaniline, p-sochlorobenzene, m-sochlorobenzene, O-sochlorobenzene, trichlorobenzene, monochlorobenzene, O-nopromobenzene, m -Sobromobenzene, p-sobromobenzene, phenol, p~aminephenol, ? Examples include /l-amine phenol, p-amine phenol, nosola-sosulfonated benzene, and monosulfonated benzene. Among the aromatic compounds substituted with an amino group, a halogen, a sulfone group and/or a hydroxy group, benzene substituted with B'' or FA with an amino group or a halogen is preferred, and among these, aniline and p-sochlorobenzene are preferred.

An example of the 3- to 6-functional polyalkylene oxide polyol terminal-treated aromatic incyanate of component (C) is the excess equivalent of the 3-6 M functional rtF realkylene oxide polyol of component (A). Aromatic inocyanates, preferably aromatic polyisocyanates, whose terminal isocyanate groups are treated with the OH groups of polyols by reaction can be mentioned. 4- or 2,6-isomer mixing ratio is 80:20
aromatic polyisocyanate such as 4,4'-sobutenylmethane soinocyanate (including crude, refined, and modified ones), phenylene twin cyanate, naphthalene 1,5-twin cyanate, xylylene twin cyanate, Examples include anate, a tolylene diisocyanate adduct of trimethylolpropane, and a polyincyanate having the formula %.

Among these, tolylene diisocyanates and the polyisocyanate of the above formula (I) are preferred.

The above component (C) may be used in combination of two or more.

As the surfactant component (D), nonionic surfactants are preferred, and ethylene oxide adducts of alkylphenols are particularly preferred. The number of carbon atoms in the alkyl group of such alkylphenol is preferably 7 to 12, more preferably 8 to 10, particularly preferably 9, and the number of moles of ethylene oxide added is 8 to 12 moles, preferably 9 to 11 moles. .

Two or more surfactants as component (D) may also be used in combination.

In the method for producing the leather treatment agent of the present invention, components (A) to (D) may be added in an appropriate order or simultaneously, but preferably component (A) is a 3- to 6-functional polyalkylene oxide.・Add and mix component (C) into polyol, then (B)
) 3-side compound salt or its aqueous solution is added and finally CD
> Add and mix the surfactant component. (If the aromatic incyanate terminal-treated with a polyalkylene oxide polyol is used as the component, add and mix the corresponding aromatic incyanate into an excess amount of the polyalkylene oxide triol. Aromatic incyanates and the like terminally treated with alkylene oxide can be produced during mixing.

The leather treatment agent of the shy invention includes (A), (B), (C) and CD>
The ingredients are essential, but the three-side joint is blended in the form of an aqueous solution (2): Water can be contained in the furnace chamber. Preferably, the moisture content per 100 parts by weight of the leather of the present invention is preferably 1 part by weight or more, preferably 6 parts by weight or more, and most preferably 10 parts by weight or more.

The pH of the leather treatment agent of the present invention is preferably 3.5 to 6.
5 more preferably 4 to 5.5, most preferably 4.5 to
It is 5.2.

The raw leather to be treated with the leather treatment agent of the present invention is not particularly limited, and includes raw leather, bare leather, pickled leather, treated leather,
The degree of dyeing, fattened skin, etc. are preferably treated, but raw hides, naked hides, and pickled hides are more preferably treated, and among them, raw hides are particularly preferably treated.

In the method of using the leather treatment agent of the present invention, in the case of treating raw leather, soaking in water and liming after pounding is done by adding 10 to 25% by weight of the converted leather into slaked lime emulsion. The leather treatment agent of the invention is added and the treatment is carried out simultaneously with liming.

In addition, in the treatment of bast, acid-soaked leather, shabby leather, dyed leather, fattened leather, etc., the weight is 10 to 25 times the conversion weight! The leather treatment agent of the present invention is used in a proportion of 9 g.

It is used after being appropriately diluted with about 5 to 100 times the amount of water so that it can be easily carried out.

The raw leather to be treated with the leather treatment agent of the present invention is preferably raw material fabric used in the summer in industry, such as cowhide (cow: cattle group), sheepskin (sheep: sheep group), goatskin. (goat: boat group), horsehide (
Horses: Eefing Group), pigskin (Pig: Big Group), deerskin (Deer: Deer Groove), Kangaroo skin (Kangaroo: Kangaru-group), aquatic animal skin (Aquatic Animal Group), etc. can. Among these, pigskin, cowskin, sheepskin and goatskin are preferred, and cowskin is particularly preferred.

Effects of the present invention The leather treatment agent of the present invention can be applied to raw hides, lining hides, pickled hides, pickled hides,
Dyed leather or oiled leather can be treated with the simple method described above, and this is effective even when the mucoid content in the leather is, for example, 1□0% by weight or less, preferably 0.1% by weight or less. Therefore, the leather treated with the leather treatment agent of the present invention has a rope-like layer of leather fiber drainage waves (JIS P8
121 Canadian standard type) is good at 580 m or more, and the electrical conductivity (22°C, 62RH%) is also reduced to 20Ω or less.

The leather treated with the leather treatment agent of the present invention can therefore be repeatedly washed with water, has the extensibility to allow deep drawing, can be equipped in a private mine, and can be chrome-plated. It has excellent properties such as chromium absorption > Me and also high tear strength of leather. Furthermore, in the case of pigskin, the pores are not sufficiently blocked by the conventional method and the pores are clearly visible even after treatment, but with the present invention, the pores are no longer distinguishable.

Furthermore, the leather treated with the leather treatment agent of the present invention has no strange odor, has high water absorption, does not develop mold even when stored for a long period of time, is resistant to slipping, does not lose weight, and, on the other hand, does not lose its properties after washing. It has the advantage that it does not become hard and stiff even when the leather containing multiple moisture content such as leather is left to dry in sunlight, and it has heat resistance that allows it to be steam ironed, and there is little chance of short fibers falling off due to breakage. It has the following.

Since the leather treated with the leather treatment agent of the present invention has the above-mentioned advantages, it can be used not only for clothing, underwear, upper leather, buckskin, gloves, etc., but also for shoes, knots, hats, knox, etc. It has a wide range of uses, including drawing-molded products made of one grass such as covers, leather paper with dimensions of 1 to 100 degrees, and mat-like products made by loosening leather and paper.

The leather treatment agent of the present invention further includes woven fabrics made of wood, animal hair, cellulose fibers, chemical fibers, silk fibers, and synthetic fibers,
It also has excellent performance as a treatment agent for nonwoven fabrics and artificial rebels.

In addition, Fig. 1 shows an optical microscope overhead photograph at 200x magnification of the shape of the leather fibers inside the leather of the raw pig hide treated using the leather treatment agent of the present invention. Figure 2 shows an optical microscope photograph of the shape at 200x magnification.

Example 1 The raw hide (pork stirrup i vinegar skin) was treated as follows.

(a) Misuse of leather treatment agents: Polyol, polyoxyethylene, oxyproglylene triol (Sanyo Kasei Sunix FA1031462.
5F and polyoxypropylene triol (Mitsui Nisso M
A'-3050)462.5P mixture total 9252
Add and mix Ani IJN 102, then aluminum sulfate 8
% aqueous solution was added and mixed. Furthermore, surfactants polyoxyethylene nonylphenyl ether (Sanyo Kasei Nonypho'110) 10F and 4-lyoxyethylene nonylphenyl ether (Asahi Denka Adecatol NP-700)
305' was added and mixed to make a homogeneous solution, and a leather treated paris was obtained.

(b) Treatment of raw hide: 381 liters of saturated milk of lime (pH 12.5) was placed in a household washing machine, and 5601 liters of the treatment agent manufactured by A as described above was added and stirred to form a homogeneous liquid. Into this, 2.23 kg of raw hide (pork, fresh skin) in terms of converted weight was placed, immersed, stirred for 10 hours, and then taken out. After taking it out, it was washed in running water for 0.5 hours. Furthermore, 381 liters of water was added to the washing machine, and lactic acid was added to adjust the pH of the solution to 4. The leather treated as described above was added to the washing machine and stirred for 1 hour. After .5d, water was drained and hair was removed according to a conventional method.

Next, demineralization using conventional silicic acid is carried out without reliming treatment, fermentation treatment, or acid pickling treatment, and further according to the conventional method, chromium is rubbed and weighed per initial weight (9a) (approximately (The chromium adsorption rate was 90% or more.) After washing with water, neutralization, dyeing, fatliquing, and toggle drying were carried out in the usual manner to produce finished leather.

The results of measurements on the characteristics of the leather treated in this way are
Shown in the table.

Examples 2 to 10.12 and 16 Using the same raw hides as in Example 1, comparative treatments were carried out under the same conditions as in Example 1, except that the composition ratio of the leather treatment agent was changed as in the first example below.

The results of measurements on the properties of the treated leather are shown in Table 1.

Example 11 Using pigskin leather that has been treated, dyed, and fat-liquored,
The treatment was performed using a treatment agent whose composition ratio was changed as shown in the table.

That is, put water 581 into a household washer, and then add water as described above.
', 5601 of the adjusted processing agent was added and stirred to form a homogeneous solution. In this, the above leather (converted weight conversion) is 2.2
3 kl? The mixture was soaked in water, stirred for 6 hours, and then taken out. After taking it out, it was washed in running water for 0.5 hours, then dehydrated and dried.

The properties of the leather treated in this way are shown in Table 1.

Comparative Example 1 The raw skin (fresh pig skin) used in the example was treated according to the conventional method as described below. Liming, water washing, re-liming, water washing,
Decalcification: Fermentation, acidification, rubbing and peeling - Chromium amount per unit: 6
%), washed with water, neutralized, washed with water, dyed, fattened, squeezed with water, dried, flavored, toggle dried and made into finished leather. It was used as clothing leather.

Example 14 Sannix FA105, component (A) in Example 1
462.5? and Mitsui Nisso, V#-3050462,5
The test was repeated under the same conditions as in Example 1, except that Sannix FA 1039252 was used instead of F.

The results are shown in Table 2. However, the leather is brushed and has some dullness and a flat, cold feel.

Example 15 Sannix FA103925 of Example 14? Except that Mitsui Nichikai MA'-3050925F was used instead of.
The test was repeated under the same conditions as in Example 14. Second result
Shown in the table. However, the leather has a rich nap, making it fluffy, bulky, and warm.

Example 16 The test was repeated under all the same conditions as in Example 1 except that a mixture of equal amounts of aluminum sulfate and aluminum chloride was used in place of the aluminum sulfate in Example 1. Second result
Shown in the table. However, the treated leather may be damaged.

Example 17 Example 10k The test was repeated under all the same conditions as Example 1 except that a mixture of equal amounts of aluminum sulfate and aluminum lactate was used instead of 1M aluminum. The results are shown in Table 2. Additionally, treated leather becomes slippery.

Example 18 The test was repeated under all the same conditions as in Example 1 except that p-sochlorobenzene was used instead of aniline. The results are shown in Table 2.

Example 19 The test was repeated under all the same conditions as in Example 1 except that a mixture of toluene quincyanate C2T4- and 2-6 was used instead of aniline. The results are shown in the second layer.

Example 20 The test was repeated under all the same conditions as in Example 1, except that bengano monosulfonic acid was used instead of aniline. The results are shown in Table 2.

Example 21 The test was repeated under all the same conditions as in Example 1 except that amine phenol was used instead of aniline. The results are shown in Table 2.

Example 22 In Example 1, 102 nonipoles 110 and 307
The test was repeated under the same conditions as in Example 1, except that Adekatol J'/P-700409 was used instead of Adekatol NP-700.

The results are shown in Table 2. In addition, the level dyeing property of the obtained leather is improved.

Example 23 The test was carried out under the same conditions as in Example 11, except that Nonipol 40f was used instead of 30t of Noni, 19-L 10F and Hyatecatol MP-700 in Example 11, and the pickled skin (pig) was treated. went. The results are shown in Table 2.

In Tables 1 and 2, water resistance and washing resistance means that when leather is repeatedly washed in a household washing machine using tap water in a conventional manner, it loses its original flexibility and begins to feel hard. It is expressed in number of times.

Furthermore, the sewability is expressed by the thread count of the thinnest sewing machine hook that can be sewn when leather is sewn with a sewing machine.

10,000 Chromium adsorption and level dyeing properties (by Bayer LEVAFIX E) during chrome smearing were evaluated as follows.

Toshihide 20・ Q: ○ Possible: △ Defective: ×

[Brief explanation of drawings]

Figures 1 and 2 are optical microscope photographs of the shape of leather fibers at points within the reticular layer of leather. Procedural amendment (voluntary) January 1986 278 Commissioner of the Patent Office Michi Uga Bf! IR1, Indication of the case 1985 Patent Application No. 2249172, Name of the invention Leather treatment agent 3, Person making the amendment Relationship to the case Patent applicant 4, Agent 〒107 ■, Scope of claims in the specification The description in the column is corrected as follows: "[Claims] 1. (A13-6 functional polyalkylene oquine P polyol, (D2-4 valent metal salt, (C') amine group, halogen , an aromatic compound substituted with a sulfone group and/or a hydroxyl group, or an aromatic inanate end-treated with a 3- to 6-functional polyalkylene oxide polyol, as well as K [1) 1 surfactant. 2. Ingredients (A+, (t3+, (C"l and (D)
1O polyol 55-97.5% by weight, t12-tetravalent metal salt 0.1-8.0% by weight (H%, (C
0.0005 to 3.0% by weight of aromatic incyanates terminated with aromatic compounds substituted with 1 amino, halogen, sulfone, and/or hydroxy groups or 5- to 6-functional polyalkylene oxide polyols and (D) a surfactant 0.5 to 55% by weight. The leather treating agent according to claim 1. 3, (,'113~6-functional polyalkylene oxide・
Polyol, (B) di- to tetravalent metal salt, (C+ amino group,
Leather treatment containing 7 aromatic incyanates and K tD + surfactants terminated with aromatic compounds substituted with halogens, sulfone groups and/or hydroxy groups or 6-6 functional polyalkylene oxide polyols A leather treatment method that treats leather with a chemical. 4. A treatment method according to claim 3, in which a leather treatment agent is added to a lime emulsion and the lime immersion process is performed to treat raw hides. ” ■, The statement in the Detailed Description of the Invention column of the specification is corrected as follows: (]) “1.5” between “pli” and “1, preferably” on page 14, line 4 of the specification. ~aJ is a swordsman.

Claims (1)

[Scope of Claims] 1. (A) 3- to 6-functional polyalkylene oxide polyol, (B) 2- to 4-valent metal salt, (C) substituted with amino group, halogen, sulfone group and/or hydroxy group 1. A leather treating agent comprising: an aromatic isocyanate terminal-treated with an aromatic compound or a 3- to 6-functional polyalkylene oxide polyol; and (D) a surfactant. 2. The total of components (A), (B), (C) and (D) is 1
00% by weight, based on the total (A) 55 to 97.5% by weight of 3- to 6-functional polyalkylene oxide polyol, (B) 0.1 to 8.0% by weight of trivalent metal salt, (C ) 0.0005 to 3.0% by weight of aromatic isocyanates terminated with aromatic compounds substituted with amino groups, halogens, sulfone groups, and/or hydroxy groups or 3- to 6-functional polyalkylene oxide polyols; (D) The leather treatment agent according to claim 1, which contains 0.3 to 35% by weight of a surfactant. 3, (A) 3-6 functional polyalkylene oxide polyol, (B) 2-4 valent metal salt, (C) aromatic compound substituted with amino group, halogen, sulfone group and/or hydroxy group, or 3 - A leather treatment method of treating raw hide with a leather treatment agent containing an aromatic isocyanate terminal-treated with a hexafunctional polyalkylene oxide polyol and (D) a surfactant. 4. The treatment method according to claim 3, wherein the leather treatment agent is added to the lime emulsion and the raw hide is treated in a lime soaking step.