JP2002146671A - Method for preventing shrinkage of animal hair fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preventing the shrinkage of an animal hair fiber, not using chlorine-based chemicals, capable of imparting an excellent shrink prevention not inferior to that of a method for using the chlorine-based chemicals while retaining its touch feeling, color and physical properties such as strength, elongation, etc., of the animal hair fiber. SOLUTION: This method for preventing the shrinkage of the animal hair fiber by treating the animal hair fiber with a peroxycompound is characterized by (a) imparting a transition metal oxide to the animal hair fiber and then (b) treating it with a polymer peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for shrink-proofing animal hair fibers, and more particularly to a method for shrink-proofing animal hair fibers by modifying a scale tip.

[0002]

2. Description of the Related Art Conventionally, a fiber structure made of animal hair such as wool has been subjected to a shrink-proofing process using a chlorine-based chemical, a DC method, and a DC method.
The CA method is commonly used. However, AOX (absorptive organic halogen) is generated in the waste liquid after the processing, and this leads to environmental pollution. Accordingly, the movement of emission control has been strengthened especially in EC countries. Therefore, there is an urgent need to develop a shrink-proofing technique that does not use chlorine-based chemicals.

[0003] As shrink-prevention processing techniques that do not use chlorine-based chemicals, for example, methods using enzymes, monopersulfuric acid, monopersulfate, monoperoxyphthalic acid, and hydrogen peroxide have been developed. There are drawbacks such as insufficient or lowering of the texture and high elongation of animal hair fiber,
Satisfactory results have not been obtained.

[0004]

The object of the present invention is to provide an animal hair fiber having excellent shrinkage resistance, which is not inferior to the method using a chlorine-based drug, while maintaining physical properties such as texture, color, and high elongation. And a method for shrink-proofing animal hair fibers using no chlorine-based drug.

[0005]

Means for Solving the Problems The present inventors have conducted various studies in order to develop a shrink-prevention processing technique using no chlorine-based chemical. As a result, according to the following predetermined method, according to the conventional shrink-proof processing technology without using a chlorine-based chemical, for example, the above-mentioned method using enzymes, monopersulfuric acid, monopersulfate, monoperoxyphthalic acid, and hydrogen peroxide The inventors have found that all the disadvantages can be solved, and have completed the present invention.

That is, according to the present invention, there is provided a method for (1) treating animal hair fiber with a peroxide and subjecting the animal hair fiber to shrink-preventing treatment, wherein (a) converting the animal hair fiber using a transition metal oxide and / or hydrogen peroxide; And (b) treating animal hair fibers with a polymeric peroxide, and performing (a) and (b) simultaneously or sequentially. is there.

In a preferred embodiment, (2) the oxide of a transition metal is an oxide of one or more metals selected from the group consisting of metals of groups IB, IIB, VIIB and VIIIB of the periodic table. The method according to (1) above, wherein (3) the oxide of the transition metal is an oxide of one or more metals selected from the group consisting of zinc, copper, nickel, manganese, cobalt and iron. The method according to the above (1),
(4) The method according to (1) above, wherein the oxide of the transition metal is selected from zinc oxide and iron oxide. (5) The polymer peroxide is a peroxide and a homopolymer or copolymer of an unsaturated dicarboxylic anhydride. The method according to any one of the above (1) to (4), which is a reaction product with a product; (6) the method according to the above (5), wherein the peroxide is hydrogen peroxide; (7) The unsaturated dicarboxylic anhydride has 4 to 3 carbon atoms.
(8) The method according to (5) or (6), wherein the unsaturated dicarboxylic anhydride is one or more selected from the group consisting of eight unsaturated dicarboxylic anhydrides. (5) or (6) above, wherein the anhydride is one or more unsaturated dicarboxylic anhydrides selected from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride and glutaconic anhydride. (9) The above (5), wherein the unsaturated dicarboxylic anhydride is maleic anhydride and / or itaconic anhydride.
Or (6) the method according to (5) to (9), wherein the copolymer of unsaturated dicarboxylic anhydride is a copolymer of unsaturated dicarboxylic anhydride and another ethylenically unsaturated compound. The method according to any one of (1)
1) The method according to (1), wherein the ethylenically unsaturated compound is one or more substances selected from the group consisting of methyl vinyl ether, styrene, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, ethylene, and propylene. (12) The method according to the above (10), wherein the ethylenically unsaturated compound is methyl vinyl ether and / or styrene.
3) The weight average molecular weight of the polymer peroxide is from 5,000 to
The above (1) to (1), which are 3,000,000
2) The method according to any one of 2), (14) the polymer peroxide has a weight average molecular weight of 10,000 to 2,000,
(15) The method according to any one of the above (1) to (12), wherein the weight average molecular weight of the high molecular peroxide is 40,000 to 1,500,000. The method described in any one of the above (1) to (12) can be mentioned.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for shrink-proofing animal hair fibers of the present invention comprises: (a) treating animal hair fibers with a transition metal oxide and / or hydrogen peroxide; and (b) polymer Treating animal hair fibers with a peroxide.

The metal oxide and hydrogen peroxide used in step (a) both act on the polymer peroxide to generate nascent oxygen and active radicals, and the polymer peroxide oxidizing agent It is thought that the function as a function is effectively exhibited. The metal oxide is a transition metal oxide. The metal oxides are preferably of the periodic table IB, IIB, VIIB and VIIIB
An oxide of one or more metals selected from the group consisting of metals of the group III, more preferably one or more metals selected from the group consisting of zinc, copper, nickel, manganese, cobalt and iron It is an oxide. Particularly preferably, zinc oxide and / or iron oxide can be used as metal oxide.

Since the metal oxide needs to be applied to the animal hair fiber and adhere to the vicinity of the fiber surface, the particle size is preferably about 1/10 or less of the fiber diameter (usually several tens μm). . As for the particle size of the metal oxide, the average particle size is preferably 0.005 to 10 μm, more preferably 0.01 to 1 μm, and particularly preferably 0.04 to 0.2 μm.
m. Above the upper limit, the adhesion to the vicinity of the animal hair fiber surface is poor, and the shrinkage resistance of the animal hair fiber cannot be increased, and below the lower limit, the effect on the increase in the effect becomes small as the cost increases. .

In the present invention, the amount of the metal oxide used is
0.00 g per gram of animal hair fiber to be treated
1-0.5 grams, more preferably 0.005-0.2
Grams, particularly preferably 0.01 to 0.1 grams. The amount of hydrogen peroxide used is preferably 0.01 to 10 g, more preferably 0.15 to 5 g, and particularly preferably 0.2 g per gram of animal hair fiber to be treated.
~ 2.5 grams. In any case, if the upper limit is exceeded,
The effect on the increase of the effect is small at the expense of increasing the cost, and the shrinkage resistance of the animal hair fiber cannot be increased below the lower limit.

The polymeric peroxide used in step (b) is preferably a reaction product of a peroxide and a homopolymer or copolymer of an unsaturated dicarboxylic anhydride.

[0013] The unsaturated dicarboxylic anhydride is preferably one or more unsaturated dicarboxylic anhydrides selected from the group consisting of unsaturated dicarboxylic anhydrides having 4 to 38 carbon atoms, more preferably 4 to 18 carbon atoms. It is a dicarboxylic anhydride, particularly preferably one or more unsaturated dicarboxylic anhydrides selected from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride and glutaconic anhydride. Of these, maleic anhydride and / or itaconic anhydride can be particularly preferably used. Examples of the copolymer of an unsaturated dicarboxylic anhydride include a copolymer composed of two or more kinds of unsaturated dicarboxylic anhydrides, or a copolymer of the above unsaturated dicarboxylic anhydride and another ethylenically unsaturated compound. Examples of the ethylenically unsaturated compound include vinyl monomers such as methyl vinyl ether, styrene, acrylonitrile, and vinyl acetate; methyl acrylate, methyl methacrylate, ethylene, and propylene; preferably, methyl vinyl ether and / or styrene are used. Can be done.

As the peroxide, for example, hydrogen peroxide,
Ozone, formic acid, peracetic acid, percarbonate and the like can be mentioned, and preferably, hydrogen peroxide is used.

The method for producing a high molecular peroxide by reacting a copolymer of unsaturated dicarboxylic anhydride with a peroxide is not particularly limited, and a generally known method can be used. For example, when producing a high molecular peroxide by reacting a methyl vinyl ether / maleic anhydride copolymer with 35% hydrogen peroxide, the copolymer 31 is used.
The reaction is carried out by placing 2 parts by weight and 195 parts by weight of hydrogen peroxide in a reactor equipped with a stirrer and reacting at a temperature of 30 ° C. for 12 hours.

In the method of the present invention, the polymer peroxide is
The upper limit of the weight average molecular weight is preferably 3,000,000.
00, more preferably 2,000,000, particularly preferably 1,500,000, and the lower limit is preferably 5,
000, more preferably 10,000, particularly preferably 40,000. If the weight average molecular weight exceeds the above upper limit, the shrinkproof property of the animal hair fiber is not obtained after the shrinkproof processing, and if the weight average molecular weight is less than the above lower limit, the shrinkproof property of the animal hair fiber after the shrinkproof processing decreases and the texture of the fiber also decreases. I do.

In the present invention, the amount of the polymer peroxide used is preferably 0.001 to 0.5 g, in terms of the effective concentration of the oxidizing agent, per gram of the animal hair fiber to be treated.
More preferably, it is 0.005 to 0.2 g, particularly preferably 0.01 to 0.1 g. If the upper limit is exceeded, the cost will be increased and the effect on the effect will be small. If the upper limit is not exceeded, the shrink resistance of the animal hair fiber cannot be increased.

The animal hair fibers in the present invention include, for example, wool, cashmere, angora, kashigora, chinchilla and the like, and preferably wool.

In the present invention, the above steps (a) and (b) may be performed simultaneously or sequentially.

A method for sequentially carrying out the steps (a) and (b) is as follows, for example. The treatment (a) with a metal oxide and / or hydrogen peroxide is performed, for example, by placing the above-described predetermined amount of the metal oxide and / or hydrogen peroxide and animal hair fibers in a closed container and stirring the metal oxide and / or hydrogen peroxide. It is carried out by uniformly attaching hydrogen peroxide to animal hair fibers. During the application, the temperature is preferably 0 ± 10
0 ° C., more preferably 0-50 ° C., particularly preferably room temperature, the pressure is preferably 0-200 atm, more preferably 0-10 atm, particularly preferably atmospheric, and the time is preferably 5-5 atm. Seconds to 500 hours, more preferably 1
Minutes to 24 hours, particularly preferably 10 to 20 minutes.

The treatment (b) of the animal hair fiber to which the metal oxide and / or hydrogen peroxide has been applied as described above with the high molecular peroxide is usually carried out as follows. First, the predetermined amount of the polymer peroxide is mixed with water, preferably 1 to 5 times by weight, and then mixed with animal hair fiber. The mixing with the animal hair fiber is performed by uniformly immersing the animal hair fiber in the polymer peroxide at a temperature of preferably 10 to 35 ° C., preferably for 10 to 30 minutes. At the time of immersion, it is preferable to sufficiently impregnate the inside of the animal hair fiber with the polymer peroxide using a nip roller. After the immersion, preferably at a temperature of 30-70 ° C, preferably 0.5-2
Let stand for a while.

A method for simultaneously carrying out the steps (a) and (b) is, for example, as follows. The above-mentioned predetermined amount of metal oxide and / or hydrogen peroxide, and the above-mentioned predetermined amount of polymer peroxide and animal hair fiber are put in a container and stirred. Here, the polymer peroxide is preferably used by being mixed with 1 to 5 times by weight of water. During the stirring, the temperature is preferably 0 ±
90 ° C., more preferably 0 to 50 ° C., particularly preferably room temperature, the pressure is preferably 0 to 200 atm, more preferably 0 to 10 atm, particularly preferably atmospheric pressure, and the time is preferably 5 seconds to The time is 500 hours, more preferably 1 minute to 24 hours, particularly preferably 10 to 20 minutes.
After the above stirring, the animal hair fibers are uniformly immersed in the polymer peroxide by further mixing at a temperature of preferably 10 to 35 ° C., preferably for 10 to 30 minutes. After the immersion, it is left at a temperature of preferably 30 to 70 ° C., preferably for 0.5 to 2 hours.

As a method of simultaneously carrying out the steps (a) and (b), for example,
Using a homopolymer or copolymer of unsaturated dicarboxylic anhydride and excess hydrogen peroxide to obtain a mixture of high molecular peroxide and hydrogen peroxide, which can be mixed with animal hair fiber . Mixing with animal hair fiber is preferably 10
Animal hair fibers are uniformly immersed in a polymeric peroxide at a temperature of ~ 35 [deg.] C, preferably for 10-30 minutes. After the immersion, it is left at a temperature of preferably 30 to 70 ° C., preferably for 0.5 to 2 hours.

After completion of the treatment of the animal hair fiber, the animal hair fiber is washed and dried by a conventional method.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0026]

EXAMPLES Each substance used in Examples and Comparative Examples is as follows.

<Metal oxide> Zinc oxide (ZnO) powder (first grade reagent, manufactured by Hayashi Junyaku Co., Ltd.) Ultrafine zinc oxide (ZnO) powder (FINEX-25, trademark, manufactured by Sakai Chemical Industry Co., Ltd.) Iron oxide powder (Terada Pharmaceutical Co., Ltd.)

<Polymer peroxide> A reaction product of a copolymer of maleic anhydride and methyl vinyl ether with hydrogen peroxide (manufactured by Nikko Giken Co., Ltd.) having a weight average molecular weight of about 1,000,000.
And the effective H ₂ O ₂ equivalent concentration determined by back titration by the iodine method is 4.9% (abbreviated as 4-peroxide in Table 1). A reaction product of a copolymer of maleic anhydride and methyl vinyl ether with hydrogen peroxide (manufactured by Nikko Giken Co., Ltd.), a weight average molecular weight of about 200,000, and an effective H ₂ titrated back by the iodine method O ₂ conversion concentration is 5.0
% (Abbreviated as 2-peroxide in Table 1).

<Comparative substance> Hydrogen peroxide (H ₂ O ₂ ) (first-class reagent, manufactured by Wako Pure Chemical Industries, Ltd.), the effective H ₂ O ₂ conversion concentration by iodometric titration was 31.2.
%. - potassium persulfate _{(K 2 S 2 O 8)} ( reagent primary, manufactured by Wako Pure Chemical Industries, Ltd.), the effective H ₂ O ₂ concentration in terms of the back titration with potassium permanganate is 12.6%.

The evaluation of the fiber properties after the shrink-proof treatment in Examples and Comparative Examples was carried out as follows.

<Shape (Average Diameter)> The fiber after the shrink-proof treatment was loosened to lose its directivity, and then 1 g of the fiber was put into a 200 ml Erlenmeyer flask together with 50 ml of pure water. The Erlenmeyer flask was then placed at 25 ± 5 ° C. using a wrist action shaker at 310 ° C.
After shaking at 1 rpm for 1 hour, the fiber shape was visually evaluated. The average diameter of the fiber after shaking was measured using a caliper. If the fiber after shaking is spherical, measure its diameter at 3 to 5 points and calculate the average value. If the fiber is amorphous or semi-amorphous (usually semi-lunar), place the sample on a flat table. The major axis and the minor axis were measured, and the average value was calculated.

[0032] In the test, the wrist action shaker, manufactured by TAITEC Co., was used flask shaker SR-3 ^N (arcuate reciprocating shaking).

<Shrink Resistance> The shrink resistance was determined as follows based on the above evaluation of the fiber shape. Large: amorphous (average diameter 46 mm or more) Medium: eyebrows to semi-amorphous (average diameter 31 to 45 mm) Small: spherical (average diameter 23 to 30 mm) None: spherical (average diameter 22 mm or less)

<Color> The color of the fiber after the above-described shrink-proof treatment was visually judged.

<Hand feeling> The fibers after the above shrink-proof treatment were evaluated by touch. Good: Smooth, high resilience, easy to recover to original shape even when pressed. Poor: Loose and low resilience, difficult to recover to original shape when pressed.

<Strength of elongation> The single fiber before and after the shrink-proof treatment was pulled by hand, and the stretched state when the fiber was cut was qualitatively evaluated. Good: Can be stretched about 1.5 to 2 times and cut. Bad: Hardly stretched and cut almost as it is.

[0037]

Examples 1-4 and Comparative Examples 1-7 Wool was used as animal hair fiber. First, the wool top was subjected to a reflux treatment for about 2 hours in a Soxhlet extractor using ether as a solvent to remove deposits such as a fiber oil agent. The top 3 g of the wool and 0.15 g of the metal oxide shown in Tables 1 and 2 were packed in a plastic bag F with a chuck (dimensions: 170 mm × 120 mm × 0.04 m).
m, Unipack F-4, manufactured by Nippon Shokubai Co., Ltd.) and sealed in an air atmosphere.
At a temperature of ° C., the inner powder was lightly hand-punched onto a table and allowed to soar up, filled into the inner atmosphere and mixed so as to adhere uniformly to the wool fibers. Thereafter, the polymeric peroxides or comparative substances shown in Tables 1 and 2 were placed in the plastic bags.
At this time, as for the polymer peroxide, a mixture of 5 g of the polymer peroxide and 10 g of water was put in a plastic bag.
For the comparative substance, 0.8 g of hydrogen peroxide and 14.2 g of water were used for hydrogen peroxide in order to match the effective concentrations of the polymer peroxide and the oxidizing agent (H ₂ O ₂ ). Was placed in a plastic bag, and for potassium persulfate, a mixture of 1.99 grams of potassium persulfate and 13.01 grams of water was placed in a plastic bag. Then 25 ± 5 ° C
After 15 minutes, the contents of the plastic bag were gently rubbed by hand and the wool top was uniformly immersed, and then left still for 1 hour with a heater maintained at 50 ° C. After standing, the contents were taken out from the plastic bag, and the wool top was washed with water and air-dried to complete the shrink-proof processing. This was used as a sample for each of the above evaluation tests. The results are shown in Tables 1 and 2.

[0038]

[Table 1]

[0039]

[Table 2]

In Examples 1 and 2, zinc oxide (ZnO) was used as the metal oxide. In each case, the shrink resistance was large, and the texture after the shrink processing was good. Further, the fibers were whitened after the shrink-proof processing. Example 3
Uses iron oxide (III) (Fe ₂ O ₃ ) as a metal oxide. The shrink resistance was large, and the texture after the shrink processing was good. In addition, although the fibers were slightly colored red after the shrink-proof processing, they did not affect the effects of the present invention. In Example 4, iron (III) oxide (Fe ₂ O ₃ ) was used as the metal oxide, and 2-peroxide was used as the polymer peroxide. Example 3
The result equivalent to was obtained.

On the other hand, Comparative Example 1 is the result of a conventional Croi method using a chlorine-based chemical. Example 1
In Nos. To 4, it was found that almost the same good results were obtained as in the Kloi method. Comparative Example 2 is one subjected to shrink-proofing treatment using hydrogen peroxide. The shrink resistance was small and the texture was poor. Comparative Example 3 was treated with only a polymer peroxide. The shrink resistance was small. Comparative Examples 4 and 5
Is in place of the polymeric peroxide in Examples 1 and 2,
Hydrogen peroxide or potassium persulfate was used, respectively. In each case, the shrink resistance was reduced and the texture was very poor. Comparative Examples 6 and 7 use hydrogen peroxide or potassium persulfate instead of the polymer peroxide in Example 3. In each case, the shrinkage resistance was significantly reduced, and the texture was very poor.

In the following examples, animal hair fibers were subjected to shrink-prevention processing using a polymer peroxide and hydrogen peroxide at the same time.

Examples 5 to 10 and Comparative Examples 8 to 10 As shown in Table 3, copolymers of maleic anhydride and methyl vinyl ether (AN-119, trade name, manufactured by Grantrez, hereinafter sometimes abbreviated as MAMEC) )), An excess of 30 wt% aqueous hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 20 ml of each of the 30 wt%, 10 wt%, and 5 wt% aqueous solutions, and the mixture was stirred at room temperature for 24 hours. As a result, an anti-shrink treatment solution containing a polymer peroxide and hydrogen peroxide was produced. Amount of hydrogen peroxide solution added (X milliliter)
Are 2 ml and 5 ml, respectively, in the aqueous solution of the copolymer (MAMEC) at the above concentrations.
As a comparative example, the case where no hydrogen peroxide solution was used (X = 0)
Milliliters). To keep the bath ratio constant, each milliliter of water (5-X) was added to each aqueous copolymer solution together with aqueous hydrogen peroxide.

Wool was used as animal hair fiber. First, the wool top was subjected to a reflux treatment for about 2 hours in a Soxhlet extractor using ether as a solvent to remove deposits such as a fiber oil agent. Put 2 g of the wool top and 25 ml of each shrink-prevention treatment liquid in a plastic bag with a chuck (dimensions: 85 mm × 120 m).
mx 0.04 mm, Unipack F-4, manufactured by Japan Manufacturing Co., Ltd.) and sealed in an air atmosphere.
The contents of the plastic bag were gently rubbed by hand at 5 ° C. for 5 minutes to uniformly soak the wool top, and then left still for 1 hour in a heater maintained at 50 ° C. After standing, the contents were taken out of the plastic bag, the wool top was washed with water, and dried with a hot air drier at 40 ° C. to complete the shrink-proof processing. Using this as a sample, the same evaluation as described above was performed. Table 3 shows the results.

[0044]

[Table 3]

Examples 5 and 6 show 30% by weight of MAME
An anti-shrink treatment liquid produced by adding an excessive amount of hydrogen peroxide to an aqueous C solution was used. Both have high shrink resistance,
And the texture after the shrink-proof processing was good. Further, the fibers were whitened after the shrink-proof processing. Strong elongation was also good. Comparative Example 8 uses only a 30% by weight MAMEC aqueous solution. No shrink resistance was obtained. Examples 7 and 8
Used a shrink-proof treatment liquid produced by adding an excessive amount of hydrogen peroxide to a 10% by weight MAMEC aqueous solution,
In Examples 9 and 10, a shrink-proof treatment liquid produced by adding an excessive amount of hydrogen peroxide to a 5% by weight MAMEC aqueous solution was used. In each case, the shrink resistance was large, and the texture after the shrink processing was good. Further, the fibers were whitened after the shrink-proof processing. Comparative Examples 9 and 10 have 10% MAM by weight.
An EC aqueous solution or a 5% by weight MAMEC aqueous solution alone was used. No shrinkage resistance was obtained in any case.

[0046]

According to the present invention, the texture, color,
An object of the present invention is to provide a method for shrink-proofing animal hair fibers that does not use a chlorine-based drug, while giving excellent shrinkage resistance not inferior to the method using a chlorine-based drug while maintaining physical properties such as high elongation. AOX (absorptive organic halogen) is not contained in the waste liquid after the shrink-proofing treatment, and it is remarkably environmentally superior to the conventional Croi method and DCCA method using a chlorine-based chemical.

Continuing on the front page (72) Tadashi Takatsuka 2-7-1, Ayumino, Izumi City, Osaka Prefecture Inside the Osaka Prefectural Institute of Advanced Industrial Science and Technology (72) Kyohei Jokko 35, Kita Hiyoshicho, Imakumano, Higashiyama-ku, Kyoto, Kyoto, Japan Inside Kyoto Women's University (72) Inventor St. Oka 6-12 Tsumon Otsuka-cho, Nishinomiya-shi, Hyogo Prefecture Nikko Giken Co., Ltd. (72) Inventor Kenji Kitamura 1-2-2 Umeda, Kita-ku, Osaka-shi, Osaka Incorporated (72) Inventor Mio Sugai 2-7-1, Ayumino, Izumi-shi, Osaka F-term in Osaka Industrial Technology Research Institute (reference) 4L031 AA05 AB01 BA09 BA33 CA02 4L033 AA03 AB01 AC15 CA18 CA70 DA06

Claims (5)

[Claims] 1. A method for treating animal hair fibers with peroxide to prevent shrinkage, comprising: (a) treating animal hair fibers with an oxide of transition metal and / or hydrogen peroxide; A) a process for treating animal hair fibers with a polymeric peroxide, and wherein (a) and (b) are carried out simultaneously or sequentially; 2. The method according to claim 1, wherein the transition metal oxide is selected from zinc oxide and iron oxide. 3. The method according to claim 1, wherein the polymeric peroxide is a reaction product of a homopolymer or copolymer of unsaturated dicarboxylic anhydride and hydrogen peroxide. 4. The method according to claim 3, wherein the unsaturated dicarboxylic anhydride is maleic anhydride and / or itaconic anhydride. 5. The polymer peroxide has a weight average molecular weight of:
The method according to any one of claims 1 to 4, wherein the method is 5,000 to 3,000,000.