JPS59228082A - Wool treating method - 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 improvements in the treatment of wool to impart shrinkage resistance to the wool, and more particularly, the present invention relates to improvements in the treatment of wool to impart shrinkage resistance to the wool, and more particularly, the present invention relates to improvements in the treatment of wool to impart shrinkage resistance to the wool. The present invention relates to the treatment of materials consisting of wool, since it contains wool that can be easily attached to wool. Wool materials available in continuous length include yarns, tops, and woven and knitted fabrics consisting of or containing wool. Such a continuous length may also be formed by sewing a knitted garment, such as socks, which is then separated after processing is complete. The invention is also applicable to loose wool. For this purpose, means are required for transferring the loose wool in a 4"% form. Such means, known to those skilled in the art, are suitable for conveyor belts and rotating rake equipment.
nothing. A two-step anti-shrinkage process is well established in which wool is first treated with a chlorinating agent and then with a preformed synthetic polymer. A wide range of different polymers, including polyamide-epichlorohydrin resins and polyacrylates, are available in the form of aqueous solutions or dispersions (e.g. Overview of Processing in this Field by J. Lewis, May 978) Wool. - Science Review, pages 23 to 42. However, despite its industrial success, the known method leaves room for improvement in various ways. (1) Drying. Traditionally processed wool requires fairly thorough drying at high temperatures. This is believed to be necessary just to cure the polymer,
However, this is a disadvantage in these plants where drying capacity is a limiting factor. In conventional such plants, capacity can be increased by increasing the drying temperature, apart from cost, but this increases yellowing and deterioration of the wool. A method with reduced drying requirements would be welcome. (II l Addition of coalescence. When this method is carried out with a pack washer, it is actually necessary to apply the polymer with a suction drum to achieve a uniform distribution on the polymer fibers at 6°C.) However, suction drums are an expensive part of the loading line, so a method that can achieve uniform distribution of polymer without the need for suction is welcome.all) Capacity. Chlorination tends to yellow and deteriorate the fibers, and polymer deposition changes the feel of the wool. Both chemicals are expensive enough to have a significant effect on the cost of the product. Methods that use less chemical agents to achieve the same degree of anti-shrink properties are welcomed. Amino-acrylic polymers are well known and are described, for example, in British Patent Nos. 1,318,781 and 1,393,273. The use of polymers to prevent shrinkage of wool is described, for example, in US Pat.
However, such a method as taught in No. 42054 is not a two-step continuous method. The present invention has discovered that certain polymers containing quaternized amide 7 groups exhibit good shrinkage resistance and other advantages when used in conventional two-step processing. Based on. A preferred form of the invention overcomes each of the three drawbacks mentioned above. According to the invention, (+1) pre-treats the wool for oxidative chlorination; (11) then treats the wool with an aqueous solution of the polymer so as to exhaust the polymer into the wool fibers; Provided is a continuous production method for shrink-resistant wool, which comprises a step of drying to a drying point, and uses a polymer containing quaternized amino groups in the step (1;) above,
In the above step Oi++, the wool is dried to a moisture content of 12 to 1818% by weight based on the weight 1'+t' of the dried wool, and at this time, the wool to be made shrink-resistant is dried to the same moisture content using the conventional continuous method. ㅅ、At least 20 more than it takes to go to 4
It is characterized by using less energy. The main advantage of the present invention is that it requires significantly less energy than other conventional anti-shrink methods to achieve comparable dryness of wool. In fact, it is expected that there will be at least 20% savings in energy over such methods. It is also clear that wool treated with the method of the invention requires less heat treatment than wool treated with known methods. Wool is preferably dried and processed to a moisture content of 12 to 15 percent by weight, whereas conventional methods dry to a much lower moisture content. Low moisture content can lead to difficulty in handling during subsequent processing of the wool. One can take advantage of these discoveries in one or both of two ways. 4't, Homura R's 1151
It is possible to reduce the power consumption and save electricity. Inui:),'i! , time can be reduced,
Production can therefore be increased by 1. Plants operating the process of the invention have greater capacity and are generally more efficient because these harsh drying requirements are reduced. Reduced energy requirements 4 This also results in significant savings in overall operating costs. Although the inventors do not wish to be bound by theory,
We currently believe that the reason for this is the ease of drying. Conventional dryers consist of a perforated chamber around which wool is fed and air is drawn into it. The wet wool forms a water-soaked blanket through which air passes, but this is done with a slight cone. Wool fibers treated with water-based resins are treated with conventional anti-shrink methods. wool fibers treated with hydrophobic resins (other than wool fibers treated with hydrophobic resins) tend to stick and retain their shape as they dry. It easily springs away, makes the wool bulky, and allows air to pass through easily.
Speed up the drying process. As mentioned above, chlorination pretreatment is a conventional method, and many suitable treatments are already well known and available. Hypochlorite or sodium dichloroisocyanurate (possibly with potassium permanganate or potassium peroxosulfate), based on the weight of dry wool (0, W, W, ,) active chlorine 0.25 JJ can be used at ~2.0% by weight, most preferably from 0.5 to 1.2% by weight. The optimum amount of chlorine to use will depend on the polymer can used in the next step. The pretreatment itself produces a small degree of shrinkage resistance in the wool. The wool is treated with sulfite anti-dialysis, washed and then subjected to a polymerization step. The 7f'f compound used contains quaternized amino groups in a sufficient proportion to exhaust the 7]f compound from an aqueous solution to the (anionic) wool fiber. When the polymer is derived from a skeleton or a polymer containing tertiary amino groups,
Some or preferably all of these are sufficiently quaternized to impart the desired cationic character to the combination. The following two groups of such polymers have been announced, of which (Bl is preferred). Heterocyclic compounds with one tertiary nitrogen JI', which can be quaternized, include pyridine and imidazole.01-mers, which can be derived from polymers, include 2- and 4-vinyl pyridine and 2- and 4-vinylimidazole. +1 terms include dimethylamino/ethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl meccrylate, dimethylaminoneopendel acrylate, dimethylaminoneopentyl methacrylate, dimethylaminopropylacrylamide, dimethylaminepropyl methacrylate. Used to include acrylic and methacrylic acids, acrylamides, methacrylates and their derivatives with tertiary nitrogen atoms. The tertiary nitrogen atoms can be quaternized before or after polymerization of the mers. The quaternization method is well known to those skilled in the art. The quaternizing agent, which is well known in the art and will not be described here, may be monofunctional or polyfunctional and may be used to achieve a certain degree of crosslinking of the polymer after being applied to the wool fibers. It is useful to use polyfunctional quaternizing agents alone or in mixtures with monofunctional quaternizing agents. Functional - methyl chloride, dimethyl sulfate, lauryl bromide, myristyl bromide, benzyl chloride, difunctional - epichlorohythrin, 1,5-dibromopencune. Monomer containing tertiary nitrogen iI, 1:f- ? may be homopolymerized or copolymerized with other monomers such as acrylamide, methacrylamide, acrylate, methacrylate, siloxane, vinyl ester, vinyl alcohol. If used, the properties of these other l)i r1 bodies may be selected to impart folding properties to the co'I penetrator.For example, acrylamide is more likely to be
9 can also produce copolymers with high water solubility. The molar proportion of the amino group-containing monogas in the polymer is (
Selection is made depending on factors such as 100% for homopolymers, it+00% for copolymers, and T'i. The proportion is large enough and at a satisfactory rate to dissolve the polymer in water at the required concentration # wool! It must be large enough to be exhausted by the vertebrae. If the proportion is too high, then the shrinkage resistance of the polymer on the wool may not develop immediately, or it may affect the subsequent drying or washing process, or it may adversely affect dye absorption and fastness. . On the other hand, if the ratio is small, it will cause agglomeration problems as discussed below. The molar ratio of the amino group-containing monomer to other monomers is 1:INl:10°, especially 1:2 to 1
:5 is preferred. The polymers can be made by solution polymerization in water-miscible organic solvents. The proportion of the amino group-containing monomer must be selected taking into account the need to carry out the polymerization reaction and subsequent quaternization reaction in solution form. A chain transfer agent may be included to create a concentrated polymer solution at the viscosity used. Impropatol is a suitable solvent and has the advantage of also acting as a chain transfer agent. Polymerization conditions are well known to those skilled in the art and there are no strict regulations. Preferred conditions result in a concentrated solution of polymer in 50:50 Improper Tool to Water. This is diluted with water to a solids content of 5% and used for final use when preparing a treatment bath. In continuous operation, the polymer concentration in the bath is generally 0.
The equilibrium value is reached in the range of 1 to 1 double stitch%. These polymers are water soluble under acidic conditions and have 1,H3~
Preferably, it is stored and transported at 6. Under alkaline conditions, crosslinking occurs, especially when quaternization is carried out using difunctional agents such as shrimp chlorohydrin. The advantage of the method of the invention is that very low concentrations of polymer can be used;
Moreover, it should still produce acceptable shrinkage resistance. As mentioned above, the proper concentration of polymer used depends on the concentration of chlorine used in the pretreatment, i.e. the use of high chlorine generally requires a lower concentration of polymer and vice versa. It means that. Typically the polymer should be applied to the wool at a concentration of 0.4 to 2.0% (o, w, w, ), preferably i;i 0.5 to 0.8%. In use, the aqueous polymer solution should be acid stabilized (preferably pH 3.5-4.0) and diluted to about 5% solids before being fed to the application bowl. The bowl itself is alkaline, H (, H7-10,
Preferably, it should be set in the range of H8.5 to 9.5), and agents such as sodium carbonate should be set to 1. should be kept at the value of the addition. It has been found that during operation the coalescing bowl becomes more cloudy than ever before and can eventually develop some agglomeration. This problem was found to be caused by the entrainment of liquid from the sulfite bath used for the plate-graining process. 1 is a protein a decomposition product, and these are anion 1 products, so small coalescence and non-phase:'8 l:'h means 1.
．． ξ will be lost. agglomerated in the bowl)l)UY
The size of t is quite small compared to the added value of small combination,
This fires with the protein i[-'=Tfi merging complex, I
If reconstituted, the amount of solubilized protein α that would be brought into the 11 coalescing bowl would be very small (because it is an eggplant, obviously), and even the amount of 11. The presence of the suction drum device 11 can have a catastrophic effect, blocking the holes in the suction drum device 11 and generally forming an adhesive jacket 1 over the entire surface. Agglomeration is clean sulphur:'23f
Solution A does not produce it, sometimes 11! ! It is true that this occurs only with liquid from the produced sulfite bath. However, this is clearly a serious Iy1 problem for continuous methods. One way to avoid I.14 during this time is to use copolymers or homopolymers containing a high proportion of quaternary nitrogen atoms. However, such polymers tend to agglomerate.

[2] Although this is thought to be rare, it can create other problems during drying. Preferred solution to the problem 1
;Ijl;--Includes the use of a water-soluble cationic external phase Fl, which can be a J-form or a polymer. This material should selectively retain the proteinaceous material Iy: I11', IL, in the form of a solution or suspension. It is true that P<'-
'%' should not be used with sufficient abbreviation so as not to give i, 2 to 201 with 1: as the base of the ID combination.
T′]・1% G1 is a good quotient. This abrasive may be added to the polymer i,"j)7i and the mixture is then diluted to the desired concentration for addition to the processing bath. Suitable abrasive materials are commercially available and their chemical 4'44 D) z,
Ingredients are often. It has not been announced in La, but they are 1. ] The bottom is mine: Unisol
sol) UA 4QQ: Ethomeen T/25 and S/20, manufactured by Ethomeen T/25 and S/20, FJthoquad 0/I
2 and HT/25 manufactured in Japan, BmpiBen BCT 4 Q: manufactured by Alfright &Wilson's Marchon Division, Nalfloc 76Q 7.8
1o2.7107: Magnafloc f (RI
20: 7 Ride Colloid Co., Ltd., Zetag 51 Near Rai)” Fist: + r
x There is one made by Ido. It will be seen that many of these materials are also a single agent. They are here referred to as protein materials.
Used for the opposite purpose of holding in a liquid or suspension. Unisol and Esomene materials have the formula -rl (wherein R is an alkyl group or alkenyl group i (1, preferably CI2 to C+s), R is H or CH3, and x
+y is from 2 to 40, preferably from 10 to 40). When included in polymer solutions, compounds of this type have been found to reduce or completely prevent the problems of turbidity and precipitation. Representative compound I1. having this effect. /I (This has its own content below. Oleylamine + 10 moles of ethylene oxide, tallow amine + 15 moles of ethylene oxide, tallow amine quaternized with dimethyl sulfate + 15
Mol of ethylene oxide, tallow amine + 40 mol of ethylene oxide (used in Example 5 below). Following application of the polymer, the wool is dried. As mentioned above, the drying step requires significantly less energy than would be required by other comparable anti-shrink methods to achieve the same degree of wool drying. In fact, care must be taken to avoid overdrying the wool, as this can lead to handling problems due to the generation of static electricity. In order to obtain successful results with the method of the invention, it is essential that the polymer be uniformly applied to the wool. The use of a suction drum bowl, a marking device found in many wool processing plants, is considered a perfectly acceptable means of achieving this. However, we have surprisingly found that a conventional pack washer - It has been found that even if the polymer is applied from a bowl, a small amount and a low cost can be achieved by improving the equipment. The following examples are for illustrating the present invention. Example 1 Examples 2 and 3 are comparative examples to demonstrate the advantages of the process of the invention over other commercially available shrink prevention methods. By way of example, Example 4 relates to a number of industrial tests conducted to demonstrate the improved drying properties exhibited by the process of the present invention. This is a comparative example illustrating the effectiveness of chlorine-containing additives. The 6411↑ hand wool top was treated with several oxidative anti-shrinkage pre-treatments. After passing through a conventional board treatment bowl, the wool was given the necessary weight to absorb 1% polymer solids. Pass the wool through the bowl containing the coalesce and finally heat the top at 134°C at 75-80°C.
I passed it through the made Inui J-■(,:). wool 2/24
It was spun into a carded worsted yarn and woven into 1.29 direct e-tex '/JJI jrl'l.Then, the swatches were machined on a cupex machine with 1+1, FE, TM18
I made a trial against 5's 3-seki Maori/Yα. The following polymers were tested (all ratios are molar ratios). Type (a1 polymer-2: l 1J14A: DI
JAEIIA was tetra+ilated with myristyl bromide. Type (bl j7j union-3, l 4: l M+
ilA: DMAEklA, quaternized with shrimp chlorohydrin. Type (cl Y1j combined-DMADMA homopolymer, pre-quaternized with shrimp chlorohydrin. Type (di polymer-DMAPMA homopolymer, quaternized with shrimp chlorohydrin). Type (0) polymer-3: l MMA: DMAP
T! A, shrimp quaternized with chlorohydrin. Type (old type combined-3: l MMA: 4-vinylpyridine, quaternized with shrimp chlorohydrin. Type (81fp (combined-3, +25: I BI
ilA: DIAAPMA, quaternized with shrimp chlorohydrin. Type (11) Polymer-5,25: I: IMIJAH Acrylamide Dl (ArM), quaternized with shrimp chlorohydrin. Type (il i4' + polymer-3,l 3: l
MMA: Quaternized with DIAAI A150/50 myristyl bromide/Ebiku r, I rj hydrin. Tights (jlff1 combination-2:1 methacrylamide:D
), lAPMA, shrimp jff i-1 was quaternized with hydrin. In the above, MIAA is methyl I tacrylate, D114AEM is dimegyl aminoethyl meccrylate, DM/', and PRIA is dimethyl amine/
Propyl methacrylamide and DMA is butyl methacrylate. The results obtained are shown below. No polymer added -2, 9-14, 9-25,
No tetrapolymer added -4946 No polymer added -45.7 Example 2 A wool top was oxidatively treated by the chlorination method of Example (1), spun, and woven into cloth. The polymer was then applied by bath exhaustion at pH 9.0. - to L6% 1g
This experiment was conducted using a batch method, but we believe that the results can also be applied to continuous methods. Example 3 Using the wool top as an industrial back washer
It was processed by the IJ method and dried by passing it through a three drum dryer operating at a high temperature of 90°C. The top layer was removed from the dryer and allowed to dry at room temperature. The sample was then immediately spun into 2724 worsted yarn, made into pongee yarn, and tested with a test material of 21.6 in the TM185 test.
μ -6,6-3,8 samples (Bl wool 18.8μ
-4,0-4,1 Example 4 Using polymer (bl), the treatment described in Example 1 (11) was carried out at steady state using the same oxidative method used for the pretreatment of these experiments. Three industrial plants in operation were subjected to a series of tests. In each case, the soil temperature and initial drying PA vorticity were the same as in regular production, and the trials lasted approximately 1 hour. Plan) A - Using normal speeds and dryer temperatures for this plant, the wool coming out was excessively overdried. The water vapor was reduced to a constant level during the ritual, and the wool was properly dried at the end. +00.90 and 85°C. Using these conditions, the resulting wool was excessively over-dried. The temperature was lowered to ~80°C, and the wool was thoroughly dried. be. The wool was over-dried and presented problems when exiting the dryer due to static charge. Opening the side door to quickly cool down the dryer improved feeding, but the wool was still dry. I met you. After turning off the water and completing the experiment, the wool was satisfactorily dry. The final drying temperature was approximately 30°C. The wool was properly dried throughout. 18% using at least 20% less energy than required
The wool was dried to a moisture content of less than Example: 32 trees of wool top sliver (21,5tt),
According to the method described in British Patent No. 1073441,
11] % 'l'l' containing an aqueous mixture of potassium peroxysulfate and sodium dichloroisocyanurate with a treatment rate of 380 Ky of wool; oxidatively treated under industrial conditions through a padded mangle of 77% . The 1j11 treated sliver was passed through four bowl back washers where it was successively subjected to anti-agglomeration treatment, water washing, polymer application and post-Q application of cationic softener. The sulfite bowl is prepared by adding a sulfite solution and a suitable alkali to a concentration of 7:1% and pH 8.5 to 1].
It was kept at 0. The polymer bowl is of type (bl
A 5% solution of l aggregate was supplied. The pH of the bath is maintained at 85-9.0 by adding alkali. After 1 hour of continuous heating, the solution in the polymer bowl became cloudy and some agglomerated material was present. Continuous operation became increasingly difficult and then suddenly impossible. In the second experiment, the same conditions were used overall except that ethyl-tosylated tallow amine (40 moles of ethylene oxide) was added to the polymer bowl at the rate of 0.4 f/f) at the start of the experiment + yij. did. History) 0.5f'
/Kp-treated wool in the polymer feed solution
- Addition was performed after the xylated amine was sufficiently dissolved. In this way, no aggregation or addition of 19 P.s. +); Processing can be continued for 8 hours without
Kibuko. Tie the tops from both trials onto 2/24 count worsted yarn, and
．． It was knitted to a coverage of 29 Direct Tex. Swatch was tested in school at II'lS, TM I 35, 3 hours A'. Area shrinkage rate (%) 1. Experiment I TM185-180 minutes 5.92 Actual, Experiment 2 TM185-180 minutes 7.6 Hikaru Adachi'h (t=
Fri Ackbottom, UK 53SP Derby Replay Amber Heights Padley Chase 22 0 Inventor Bethrus Theodorus Cornelia de Wall Netherlands Sass Van Gient Oost Card 26 0 Inventor Anthony Suzburgh, 39 Staunton Avenue, Derby Belper, UK Supplementary Procedures 0) Announcement in 1948: ], ; Japan Patent Office Disgraced Official Kazuo Wakasugi Tonosho 1 Ch. 3, Relationship with the Amendment Person Case, tbg size minister / shiright = place = residence) outside 4, agent ■ Pak Rangban

Claims (1)

[Claims] 1. (1-weight wool is pretreated with oxidative chlorination, (11)
In a method for producing shrink-resistant wool, the method comprises the steps of: subsequently treating the wool with an aqueous solution of a polymer so as to exhaust the polymer into the wool fibers; and drying the G11l wool to a constant moisture content; step (11); In step 0, a polymer containing a quaternized amino group is used.
12 to 18 weight, based on the weight of the dry wool, using at least 20% less energy than would be required to dry the wool made shrink resistant in a conventional continuous manner in 11) to the same moisture content. A method characterized by drying wool to a moisture content of %. 2. Apply chlorination pre-treatment to 1% and 0% based on the weight of dry wool.
．． The claimed ll1iIl carried out at an active chlorine concentration of 25 to 2.0% by weight! Ij. The method described in paragraph 1. 3. The polymer is a copolymer of at least one amino group-containing monomer and at least one other monomer, and the molar ratio of the amino group-containing monomer to the other monomer is 1. :1-1:10
The method according to claim 1 or 2, wherein: 4. The method according to any one of claims 1 to 3, wherein the polymer is derived from at least one aminoacrylic monomer. 5 The polymer is 0.4 to 2.0 based on dry wool weight.
5. A method as claimed in any one of claims 1 to 4, in which the wool is imparted with a weight of %. 6. The method according to any one of claims 1 to 5, wherein the polymer contains an amino group quaternized using epichlorohydrin. 7. The method according to any one of claims 1 to 6, wherein the @coalescence is applied to wool in the presence of a water-soluble cationic additive. 8. The water-soluble cationic material has the formula (wherein R is a 01-C22 alkyl group or alkenyl group, R1 is H or OH3, and
8. The method according to claim 7, wherein: 9. The method of claim 7, wherein the material is present at an Id of 2 to 20% by weight based on the weight of the polymer. 10. Wool from 12! The method according to any one of Items 1 to 9 of the Patent Si7 Requested Range, wherein the method is dried to a moisture content of 5x JA%.