TW201930664A - Coloured polypropylene fibre and preparation method therefor - Google Patents

Abstract

A coloured polypropylene fibre, the fibre containing component a hindered phenolic antioxidant and component b phosphite ester antioxidant and/or component c hindered amine antioxidant, component a accounting for 800-15000 ppm of the coloured polypropylene fibre; the weight ratio of component b to component a is less than 0.80, and component c accounts for 4000-50000 ppm of the coloured polypropylene fibre. The coloured polypropylene fibre has excellent antioxidant properties, low pyrolysis and heat generation, and a wide range of application.

Description

 Colored polypropylene fiber and preparation method thereof  

The invention relates to a colored polypropylene fiber with good oxidation resistance and a preparation method thereof.

Polypropylene fibers are widely used due to their advantages of light weight and fast drying. However, under the action of light and heat, polypropylene undergoes oxidative decomposition to produce alkyl radicals, and this reaction proceeds continuously. Through this chain reaction called auto-oxidation cycle, polypropylene itself oxidatively cleaves, and at the same time, the cleavage reaction is an exothermic reaction, and the polypropylene will melt, smoke or even burn under the action of self-heating.

In order to reduce the problem of oxidative heating of polypropylene, the main measure in the prior art is to add an antioxidant. For example, patent CN02112743.3 discloses a transparent polyester composition in which phenolic and phosphonite or sulfuric acid antioxidants are added in order to improve the oxidation resistance of polypropylene. However, unlike transparent polypropylene, colored polypropylene has poorer oxidation resistance, and the coloring agent in colored polypropylene, such as carbon black, has an adsorption effect on the antioxidant, which affects the distribution of the antioxidant in the polypropylene and weakens the resistance. The role of oxygen agents.

It is an object of the present invention to provide a colored polypropylene fiber which is excellent in oxidation resistance.

Technical solution of the invention:

A colored polypropylene fiber comprising a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, wherein component a possesses 800~15000ppm of color polypropylene fiber, preferably 1000~8000ppm of colored polypropylene fiber; when component b is contained, the weight ratio of component b to component a is less than 0.80, preferably greater than or equal to 0.20 less than 0.80; When it is divided into c, the component c accounts for 4000 to 50000 ppm, preferably 4000 to 20000 ppm of the colored polypropylene fiber.

Preferably, the colored polypropylene fibers contain component a, component b and component c.

The component a hindered phenolic antioxidant is preferably [β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester; β-(3,5- Tridecyl alcohol ester of di-tert-butyl-4-hydroxyphenyl)propanoate; 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4- Hydroxybenzyl)benzene or 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri At least one of -2,4,6-(1H,3H,5H)-trione.

The component b phosphite antioxidant is preferably poly(dipropylene glycol) phenyl phosphite; bis(2,6-di-t-butyl-4-methylphenyl)neopentanol diphosphate Ester; tris(2,4-di-t-butylphenyl)phenylphosphite; bis(2,4,6-tri-t-butylphenyl)neopentitol diphosphite; tetra(2) , 4-di-t-butylphenol)-4,4'-biphenyl diphosphite or 3,9-bisoctadecyloxy-2,4,8,10-tetraoxy-3,9-di At least one of phosphorus spiro[5.5]undecane.

The component c hindered amine antioxidant is preferably poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-three -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imido]]; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); N ^I , N ^II , N ^III , N ^IV -肆(2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-three -6-yl)-4,7-diazanonane-1,10-diamine; bis(1-undecane-2,2,6,6-tetramethylpiperidin-4-yl) carbonate Or 1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five At least one of methyl-4-piperidinyl)].

The invention also discloses a preparation method of colored polypropylene fiber, the polypropylene and the component a hindered phenolic antioxidant and the component b phosphite antioxidant and/or the component c hindered amine antioxidant Mixing uniformly and extruding granulation to obtain a colored polypropylene mixture, and then melt spinning the colored polypropylene mixture to obtain colored polypropylene fibers, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added. The weight ratio of b to component a is less than 0.80; when component c is added, component c is 4000 to 50000 ppm of the polypropylene mixture.

The colored polypropylene fiber of the invention has excellent oxidation resistance, low cracking heat generation and wide application.

The structure of polypropylene itself is unstable, easily oxidized, and the oxidation process is accompanied by heat generation, thus affecting the safety of articles using polypropylene fibers. Although the addition of an antioxidant can improve the oxidation resistance of the polypropylene, for a colored polypropylene containing a colorant which is less resistant to oxidation, the effect of the antioxidant is affected by the adsorption of the colorant against the oxygen. Adding too much antioxidant will reduce the physical properties of the polypropylene product and cause the colored polypropylene product to be susceptible to yellowing.

The colored polypropylene fiber provided by the invention not only has excellent oxidation resistance, but also has physical properties such as strength, and is not prone to yellowing.

The colored polypropylene fiber of the present invention contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, and component a occupies colored polypropylene fiber. 800~15000ppm. When the polypropylene fiber contains component b, the weight ratio of component b to component a is less than 0.80; when the polypropylene fiber contains component c, component c accounts for 4000 to 50000 ppm of the colored polypropylene fiber.

During the oxidative decomposition of polypropylene, alkyl radicals and peroxy radicals are formed, wherein the alkyl radicals are further oxidized to peroxy radicals. The peroxidic free radicals are unstable, and a part of the peroxidic free radicals will further form hydroperoxides, which accelerate the oxidative decomposition of the polypropylene. The above component a hindered phenolic antioxidant can capture peroxidic free radicals, component b phosphite antioxidant can capture hydroperoxide, and component c hindered amine antioxidant can simultaneously capture peroxidic free radicals And alkyl radicals.

In order to obtain a colored polypropylene fiber with certain oxidation resistance, the content of the hindered phenolic antioxidant in the fiber must be above 800 ppm, otherwise the component a hindered phenolic antioxidant is mostly adsorbed by the coloring agent in the fiber. After that, it will be difficult to improve the oxidation resistance of the colored polypropylene fiber, and the colorant itself has poor oxidation resistance, which may cause further deterioration of the oxidation resistance of the colored polypropylene fiber. When the content of the hindered phenolic antioxidant in the colored polypropylene fiber is higher than 15000 ppm, not only the preparation cost of the colored polypropylene fiber is increased, but also the excess component a hindered phenolic antioxidant is in the air. Oxidation to form terpenoids results in yellowing of colored polypropylene fibers.

The component a hindered phenolic antioxidant in the colored polypropylene fiber of the present invention preferably has a content of from 1,000 to 8,000 ppm.

In addition to the above-mentioned function of capturing a hydroperoxide, the component b phosphite antioxidant can effectively inhibit the oxidation of the component a hindered phenolic antioxidant in the air, thereby suppressing the yellowing of the polypropylene. In order to achieve the above effects at the same time, the weight ratio of component b to component a in the colored polypropylene fiber is less than 0.80. When the weight ratio of component b to component a is greater than or equal to 0.80, there is more component b phosphite antioxidant remaining in the colored polypropylene fiber relative to component a hindered phenolic antioxidant, Since there is no hydroperoxide available for capture, this component b phosphite antioxidant does not have an antioxidant effect, but will increase the preparation cost of the colored polypropylene fiber, while a large amount of component b Phosphite antioxidants reduce the strength of polypropylene fibers. In the case of containing the component b phosphite antioxidant, the weight of the component b and the component a in the colored polypropylene fiber of the present invention is preferably 0.20 or more and less than 0.80.

Component c is a hindered amine antioxidant that acts to capture alkyl radicals and peroxy radicals. When the content of the component c hindered amine antioxidant in the colored polypropylene fiber is less than 4000 ppm, the alkyl radical and the peroxy radical are not effectively captured, and the excess alkyl radical is further oxidized to peroxidic free radical. However, peroxidic free radicals generate a large amount of hydroperoxide, which further accelerates the oxidation of the polypropylene and does not improve the oxidation resistance of the colored polypropylene fibers. When the content of the component c hindered amine antioxidant is more than 50,000 ppm, the strength of the colored polypropylene fiber is lowered, and the cost is also increased. When the component c hindered amine antioxidant is contained, the content of the component c in the colored polypropylene fiber of the present invention is preferably from 4,000 to 20,000 ppm.

The colored polypropylene fiber of the present invention contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, that is, there are three cases: It contains component a and component b, second contains component a and component c, and third contains component a, component b and component c. A preferred third case is that the colored polypropylene fibers contain both component a hindered phenolic antioxidant, component b phosphite antioxidant, and component c hindered amine antioxidant.

The hindered phenolic antioxidant of the component a is not particularly limited and may be methyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; N,N'-1, 6-hexylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamine]; 1,3,5-indole-(3,5-dicyclohexyl-4- Hydroxybenzyl)isocyanurate; N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoid]indole; 3-(3,5-di Octadecyl tributyl-4-hydroxy)propionate; 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 2,6-di-t-butyl-4- Methylphenol; 4,4'-methylenebis(2,6-di-t-butylphenol); 2,2-thiobis[3-(3,5-di-t-butyl-4-hydroxyl) Phenyl)ethyl propionate]; 肆[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester; β-(3,5-di-third butyl Octadecanol ester of 4-hydroxyphenyl)propanoate; 1,3,5-trimethyl-2,4,6-anthracene (3,5-di-t-butyl-4-hydroxybenzyl) Benzene or 1,3,5-anthracene (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione; 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-- At least one of phenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, wherein 肆[β-(3,5-di Tributyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester; octadecyl ester of β-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate; 1,3, 5-trimethyl-2,4,6-indole (3,5-di-t-butyl-4-hydroxybenzyl)benzene or 1,3,5-indole (4-tert-butyl-3-hydroxyl) -2,6-dimethylbenzyl)-1,3,5-three At least one of -2,4,6-(1H,3H,5H)-trione.

The component b phosphite antioxidant is not particularly limited and may be dimethyl phosphite, bis(2,4-di-t-butylphenyl)phenylphosphite; , 2,2,6,6-pentamethylpiperidinol) phosphite; hydrazine (nonylphenol) phosphite; bis(2,6-di-t-butyl-4-methylphenyl) new Pentaerythritol diphosphite; bis(2,4,6-tri-t-butylphenyl)neopentitol diphosphite; bismuth (2,4-di-t-butylphenol)-4,4 '-Biphenyl diphosphite; Dimercaptophenyl phosphite; Diphenyl isooctyl phosphite; Poly(dipropylene glycol) phenyl phosphite; Bismuth (2,4-di-t-butyl Phenyl)phosphite; 3,9-bisoctadecyloxy-2,4,8,10-tetraoxy-3,9-diphosphorylcyclo[5.5]undecane; tribenzylphosphite Or at least one of tris(2-ethylhexyl)phosphite, wherein poly(dipropylene glycol)phenylphosphite is preferred; bis(2,6-di-t-butyl-4-methylphenyl) Neopentyl alcohol diphosphate; bismuth (2,4-di-t-butylphenyl) phosphite; bis(2,4,6-tri-t-butylphenyl)neopentitol diphosphite肆(2,4-di-t-butylphenol)-4,4'-biphenyl bisphosphite or 3,9-dual 18 At least one of alkoxy-2,4,8,10-tetraoxa-3,9-diphosphorylcyclo[5.5]undecane.

The component c hindered amine antioxidant is not particularly limited and may be bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; 3-(2 , 2,6,6-tetramethylpiperidin-4-amino)propionic acid lauryl ester; 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-chloro Benzotriazole; 2,4,6-trichloro-1,3,5-three N-butyl-1-butylamine; N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; poly{[6-[(1,1,3,3-tetra Methyl butyl)amino]]-1,3,5-three -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imido]]; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); N ^I , N ^II , N ^III , N ^IV -肆(2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-three -6-yl)-4,7-diazanonane-1,10-diamine; bis(2,2,6,6-tetramethylpiperidyl)sebacate or 1,3,5- three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]; bis(1-undecane-2,2,6,6-tetramethylpiperidin-4-yl)carbonate or 1,3,5-tri -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five At least one of methyl-4-piperidinyl)]. Among them, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-three is preferred -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imido]]; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); NI, NII, NIII, NIV-肆(2,4-bis((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-three -6-yl)-4,7-diazanonane-1,10-diamine; 1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five At least one of methyl-4-piperidinyl)] or bis(1-undecane-2,2,6,6-tetramethylpiperidin-4-yl) carbonate. Among them, component c is better 1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five When methyl-4-piperidinyl)] is used in combination with component a and component b, the spinning temperature is 260 ° C or lower.

The antioxidant of the present invention may also be used in combination with a hydroxylamine, and among them, a octadecylhydroxylamine may be mentioned.

The invention also discloses a preparation method of colored polypropylene fiber, the polypropylene and the component a hindered phenolic antioxidant and the component b phosphite antioxidant and/or the component c hindered amine antioxidant Mixing uniformly and extruding granulation to obtain a colored polypropylene mixture, and then melt spinning the colored polypropylene mixture to obtain colored polypropylene fibers, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added. The weight ratio of b to component a is less than 0.80; when component c is added, component c is 4000 to 50000 ppm of the polypropylene mixture.

The colored polypropylene fiber of the present invention may be a fiber obtained by blending a colorant masterbatch in a polypropylene chip and then spinning, or a fiber obtained by blending a polypropylene chip and a polyester, followed by spinning and dyeing.

The coloring agent may be a pigment or a dye. The type of the pigment and the dye in the present invention is not particularly limited, and may be various pigments and dyes for the polymer, such as carbon black, titanium white powder, cadmium red, and genus. Phthalocyanine green, phthalocyanine blue, water solid red, zinc yellow, Hansa yellow, TERATOP BLUE NFB GR, TERATOP RED NFR, TERATOP YELLOW NFG, TERASIL BLACK WW-KSN, and the like. The content of the colorant in the polypropylene fiber is also not particularly limited, and can be adjusted according to the application or market demand within the known range of the prior art. In addition, the manner and timing of introduction of the coloring agent are not particularly limited. For example, the coloring agent may be directly added, or the mother particle containing the coloring agent may be added; the timing of introduction may be when the polypropylene is blended with the antioxidant. Addition may also be carried out by mixing and remelting the spun after the polypropylene and the antioxidant are blended and extruded.

The colored polypropylene fiber of the invention has excellent anti-oxidation property, good physical property and not easy to yellowing due to mutual synergy between the different components of the antioxidant.

The test methods involved in the present invention are as follows:

(1) oxidation resistance test

The colored polypropylene fibers were first prepared into a cylinder and pretreated in accordance with JIS L 0217 103. Then, it was tested and evaluated in accordance with the "Test method for acidification and heating of polypropylene fibers (acceleration method)" (Japan Chemical Fiber Association Law). When the test time reached 100 hours, it did not generate heat itself, that is, it was judged that the polypropylene fiber was qualified for oxidation resistance. Otherwise, it is judged as unqualified.

(2) Yellowing value test of fiber

Put a NOx gas generating agent (85% phosphoric acid and 2% aqueous nitrous acid solution) in a closed container, and then arrange the sample and blue standard dyeing in the container. When the color of the blue standard dyeing cloth fades to the standard gray plate On the 3rd, replace the blue standard dyeing cloth. When the color reaches the standard gray board No. 3 again, take out the sample, wash it twice, and dry it. The yellowing value was measured by a Datacolor 650 spectrophotometer.

(3) Fiber strength test

Tested by a tensile tester. The test speed is 200 mm/min and the distance between the two clamps is 200 mm.

(4) Antioxidant and heat-generating properties of fibers (simple method / wt%)

Take the fiber sample, weigh the weight W1, and use a differential scanning calorimeter to raise the temperature to 30 °C/min from 25 °C to 160 °C under the condition of gas atmosphere pressure and gas flow rate of 60±0.05m1. When the weight reduction rate was obtained by analysis for 22 hours, and the weight reduction rate was 10% by weight or less, the KAKEN method judged that it was acceptable. The lower the weight reduction rate, the better the oxidation resistance.

(5) barrel braided L value

The L value of the cartridge was measured by a Datacolor 650 spectrophotometer.

(6) Testing of the types and contents of antioxidants

The sample was dissolved in a solvent and centrifuged to obtain a mixture containing an antioxidant. The mixture was further measured by HPLC, and the type and content of the antioxidant were obtained by pattern analysis.

Abbreviations of the antioxidants involved in the embodiments of the present invention are as follows.

Component a:

(1) 1,3,5-anthracene (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione (abbreviation: antioxidant 1790);

(2) 肆 [β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester) (abbreviation: antioxidant 1010);

(3) 1,3,5-trimethyl-2,4,6-indole (3,5-di-t-butyl-4-hydroxybenzyl)benzene (abbreviation: antioxidant 330);

(4) Methyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate (abbreviation: component a1);

(5) N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoid] oxime (abbreviation: antioxidant 1024);

(6) 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl]-2, 4,8,10-tetraoxaspiro[5.5]undecane (abbreviation: AO80);

(7) 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (abbreviation: antioxidant 2246);

(8) 2,6-Di-t-butyl-4-methylphenol (abbreviation: antioxidant BHT).

(9) N,N'-1,6-hexylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide] (abbreviation: antioxidant 1098).

Component b:

(1) Poly(dipropylene glycol) phenyl phosphite (abbreviation: antioxidant PDP); (2) 3,9-bisoctadecyloxy-2,4,8,10-tetraoxy-3,9 - diphosphorus spiro[5.5]undecane (abbreviation: antioxidant 619); (3) bismuth (2,4-di-t-butylphenyl) phosphite (abbreviation: antioxidant 168); 4) bis(1,2,2,6,6-pentamethylpiperidinol) phosphite (abbreviation: component b1); (5) bis(2,4,6-tri-t-butylphenyl) Pentaerythritol diphosphite (abbreviation: antioxidant 633); (6) bis(2,4-di-t-butylphenyl)phenylphosphite (abbreviation: component b2).

Component c:

(1) Poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-three -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imido]} (abbreviation: HS944); (2) N ^I , N ^II , N ^III , N ^IV -肆 (2,4-di((N-1,2,2,6,6) -pentamethyl-4-piperidinyl)-n-butylamino)-1,3,5-three -6-yl)-4,7-diazonium-1,10-diamine (abbreviation: component c1); (3) polysuccinic acid (4-hydroxyethyl-2,2,6,6 -tetramethyl-1-piperidineethanol) (abbreviation: UV622); (4) bis(2,2,6,6-tetramethylpiperidinyl) sebacate (abbreviation: TINUVIN770); (5 ) 3-(2,2,6,6-tetramethylpiperidin-4-amino)propionic acid lauryl ester (abbreviation: component c2); (6) 2,4,6-trichloro-1, 3,5-three (abbreviation: component c3); (7) N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (abbreviation: component c4); (8) 1,3,5- three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)] (abbreviation: HALS119); (9) bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (abbreviation: UV- 292); (10) bis(1-undecane-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (abbreviation: LA-81).

 [Example 1]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite), component c (poly{[6-[(1,1, 3,3-tetramethylbutyl)amino]]-1,3,5-three -2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4) -piperidinyl)imine]}) and colorant masterbatch (black) are added to a mixer for kneading and extrusion granulation, wherein component a accounts for 3000 ppm of the polypropylene mixture, component b and component a The weight ratio was 0.60, and component c was 13,000 ppm of the polypropylene mixture; finally, the pellets were melt spun into colored polypropylene fibers.

 [Embodiment 2]  

Slicing polypropylene, component a (肆[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol), component b (3,9-double ten Octaethoxy-2,4,8,10-tetraoxa-3,9-diphosphorylcyclo[5.5]undecane) and component c (N ^I , N ^II , N ^III , N ^IV -肆 ( 2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-three -6-yl)-4,7-diazonium-1,10-diamine) and colorant masterbatch (black) are added to the mixer for kneading and extrusion granulation, wherein component a accounts for polypropylene 15,000 ppm of the mixture, the weight ratio of component b to component a was 0.20, and component c was 8000 ppm of the polypropylene mixture; finally, the pellets were melt spun into colored polypropylene fibers.

 [Example 3]  

Slice polypropylene, component a (1,3,5-trimethyl-2,4,6-indole (3,5-di-t-butyl-4-hydroxybenzyl)benzene), component b (叁 (2,4-di-t-butylphenyl)phosphite) and colorant masterbatch (black) were added to a mixer for kneading and extrusion granulation, wherein component a accounted for 1100 ppm of the polypropylene mixture. The weight ratio of component b to component a was 0.75; finally, the pellets were melt spun to form colored polypropylene fibers.

 [Example 4]  

Section of polypropylene, component a (methyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), component c (polysuccinic acid (4-hydroxyethyl-2) , 2,6,6-tetramethyl-1-piperidineethanol) and colorant masterbatch (black) are added to the mixer for mixing and extrusion granulation, wherein component a accounts for 6000 ppm of the polypropylene mixture. Component c is 10,000 ppm of the polypropylene mixture; finally, the pellets are melt spun to form colored polypropylene fibers.

 [Example 5]  

Slicing polypropylene, component a(N,N'-1,6-hexylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide] and components b (bis(2,4-di-t-butylphenyl)phenylphosphite) was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 10,000 ppm of the polypropylene mixture, component b and The weight ratio of component a was 0.10; finally, the pellets were mixed with the masterbatch masterbatch (black) and melt-spun to form colored polypropylene fibers.

 [Embodiment 6]  

The polypropylene was sliced, the component a(N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanium] oxime) and the component b (叁1, 2 , 2,6,6-pentamethylpiperidinol) phosphite) was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 6000 ppm of the polypropylene mixture, component b and component a The weight ratio was 0.80; finally, the pellets were mixed with the masterbatch masterbatch (black) and melt-spun to form colored polypropylene fibers.

 [Embodiment 7]  

Polypropylene section, component a (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propenyloxy] Ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane) and component c (bis(1,2,2,6,6-pentamethyl-4-piperidinyl) The sebacate) is added to the mixer for mixing and extrusion granulation, wherein component a accounts for 1100 ppm of the polypropylene mixture, component c accounts for 5000 ppm of the polypropylene mixture; finally, the pellet and the color masterbatch (black) After mixing, melt-spun to form colored polypropylene fibers.

 [Embodiment 8]  

Polypropylene section, component a (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propenyloxy] Ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane) and component c(3-(2,2,6,6-tetramethylpiperidin-4-yl) The dodecyl propionate was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 15000 ppm of the polypropylene mixture, component c accounted for 13,000 ppm of the polypropylene mixture; finally, the pellets and the color former masterbatch ( Black) After mixing, melt-spun to form colored polypropylene fibers.

 [Embodiment 9]  

Slice polypropylene, component a (2,2'-methylenebis(4-methyl-6-tert-butylphenol)), component b (double (2,4,6-three third) Phenyl) neopentyl alcohol diphosphite) and component c (2,4,6-trichloro-1,3,5-three Adding to a mixer for mixing and extrusion granulation, wherein component a accounts for 7000 ppm of the polypropylene mixture, component b has a weight ratio of component 0.5 to 0.50, and component c accounts for 5000 ppm of the polypropylene mixture; The pellets are mixed with the masterbatch masterbatch (black) and melt-spun to form colored polypropylene fibers.

 [Embodiment 10]  

Slicing polypropylene, component a (2,6-di-t-butyl-4-methylphenol), component b (bis(2,4,6-tri-t-butylphenyl)pentaerythritol Diphosphite) and component c (N-butyl-2,2,6,6-tetramethyl-4-piperidinamine) are added to a mixer for kneading and extrusion granulation, wherein component a 1300 ppm of the polypropylene mixture, the weight ratio of component b to component a is 0.75, component c is 15000 ppm of the polypropylene mixture; finally, the pellets are mixed with the masterbatch masterbatch (black) and then melt-spun. Colored polypropylene fiber.

 [Example 11]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c (double (2, 2,6,6-Tetramethylpiperidinyl) sebacate) was added to a mixer for kneading and extrusion granulation, wherein component a 1200 ppm of the polypropylene mixture, component b and component a The weight ratio was 0.60, and the component c was 50,000 ppm of the polypropylene mixture; finally, the pellets were mixed with the color masterbatch (black) and melt-spun to form colored polypropylene fibers.

 [Embodiment 12]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c(1,3, 5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) was added to a mixer for kneading and extrusion granulation, wherein component a was 1200 ppm of the polypropylene mixture, and the weight ratio of component b to component a was 0.75. c occupies 8000 ppm of the polypropylene mixture; finally, the pellets are mixed with the masterbatch masterbatch (black) and melt-spun to form colored polypropylene fibers.

 [Example 13]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c(1,3, 5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 4000 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.60. c is 5200 ppm of the polypropylene mixture; finally, the pellets are mixed with the masterbatch masterbatch (blue) and melt-spun to form colored polypropylene fibers.

 [Embodiment 14]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c(1,3, 5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 4500 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.50. c is 5200 ppm of the polypropylene mixture; finally, the pellets are mixed with the masterbatch masterbatch (blue) and melt-spun to form colored polypropylene fibers.

 [Example 15]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component c (1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) was added to a mixer for compounding and extrusion granulation, wherein component a was 7000 ppm of the polypropylene mixture and component c was 5200 ppm of the polypropylene mixture; finally, the pellets were The colorant masterbatch (red) is mixed and melt-spun to form colored polypropylene fibers.

 [Example 16]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) was added to a mixer for mixing and extrusion Granulation, wherein component a accounts for 10000 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.10; finally, the pellet is mixed with the color masterbatch (red) and melt-spun to form colored poly Acrylic fiber.

 [Example 17]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component c (1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 4000 ppm of the polypropylene mixture, component c accounts for 4000 ppm of the polypropylene mixture; finally, the pellets are The colorant masterbatch (yellow) is mixed and melt-spun to form colored polypropylene fibers.

 [Embodiment 18]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component c (1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 1000 ppm of the polypropylene mixture, component c accounts for 50,000 ppm of the polypropylene mixture; finally, the pellets are The colorant masterbatch (blue) is mixed and melt-spun to form colored polypropylene fibers.

 [Embodiment 19]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component c (bis(2,2,6,6-tetramethylpiperidyl)sebacate) was added to a mixer Mixing and extruding granulation, wherein component a accounts for 1200 ppm of the polypropylene mixture, component c accounts for 50,000 ppm of the polypropylene mixture; finally, the pellet is mixed with the color masterbatch (red) and melt-spun to make colored Polypropylene fibers.

 [Example 20]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c (double (2, 2,6,6-tetramethylpiperidinyl) sebacate) was added to a mixer for kneading and extrusion granulation, wherein component a was 850 ppm of the polypropylene mixture, component b and component a were The weight ratio was 0.70, and the component c was 50,000 ppm of the polypropylene mixture; finally, the pellets were mixed with the masterbatch masterbatch (white) and melt-spun to form colored polypropylene fibers.

 [Example 21]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c (double (1- Undecane-2,2,6,6-tetramethylpiperidin-4-yl)carbonate) was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 4500 ppm of the polypropylene mixture, group The weight ratio of the fraction b to the component a was 0.65, and the component c was 5200 ppm of the polypropylene mixture; finally, the pellet was mixed with the masterbatch masterbatch (black) and melt-spun to form a colored polypropylene fiber.

 [Comparative Example 1]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite), component c (poly{[6-[(1,1, 3,3-tetramethylbutyl)amino]]-1,3,5-three -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imine]}) and colorant masterbatch (black) are added to a mixer for kneading and extrusion granulation, wherein component a accounts for 3000 ppm of the polypropylene mixture, component b and component a The weight ratio was 2.00, and the component c was 50,000 ppm of the polypropylene mixture; finally, the pellets were melt spun into a colored polypropylene fiber. The weight ratio of component b to component a is too large, and excess component b results in a low strength of the polypropylene fiber.

 [Comparative Example 2]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite) and component c (poly{[6-[(1,1, 3,3-tetramethylbutyl)amino]]-1,3,5-three -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imine]}) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 100 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.70, component c 5,000 ppm of the polypropylene mixture; finally, the pellets are mixed with the color masterbatch (black) and melt-spun to form colored polypropylene fibers. The content of component a is too small, resulting in poor oxidation resistance of the polypropylene fibers.

 [Comparative Example 3]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite) and component c (poly{[6-[(1,1, 3,3-tetramethylbutyl)amino]]-1,3,5-three -2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4- Piperidinyl)imine]}) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 25000 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.10, component c It accounts for 80,000 ppm of the polypropylene mixture; finally, the pellets are mixed with the color masterbatch (black) and melt-spun to form colored polypropylene fibers. The content of component c is too large, resulting in low strength of the polypropylene fiber.

 [Comparative Example 4]  

Polypropylene section, component a (1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione), component b (叁(2,4-di-t-butylphenyl)phosphite) and component c(1,3, 5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five Methyl-4-piperidinyl)]) was added to a mixer for kneading and extrusion granulation, wherein component a was 1000 ppm of the polypropylene mixture, and the weight ratio of component b to component a was 0.75. c is 3000 ppm of the polypropylene mixture; finally, the pellets are mixed with the color masterbatch (black) and melt-spun to form colored polypropylene fibers. The content of component c is too small, resulting in poor oxidation resistance of the polypropylene fiber.

Claims (9)

 A colored polypropylene fiber characterized in that the polypropylene fiber contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, wherein Component a accounts for 800-15000 ppm of colored polypropylene fibers; when component b is contained, the weight ratio of component b to component a is less than 0.80; when component c is contained, component c accounts for 4000~50000 ppm of colored polypropylene fibers. .    The colored polypropylene fiber of claim 1, wherein the component a comprises from 1000 to 8000 ppm of the colored polypropylene fiber.    The colored polypropylene fiber according to claim 1 or 2, wherein the weight ratio of the component b to the component a is 0.20 or more and less than 0.80.    The colored polypropylene fiber of claim 1 or 2, wherein the component c comprises from 4,000 to 20,000 ppm of the colored polypropylene fiber.    The colored polypropylene fiber of claim 1, wherein the colored polypropylene fiber contains component a, component b, and component c.   The colored polypropylene fiber of claim 1, wherein the component a hindered phenolic antioxidant is 肆[β-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid] Tetraol ester; octadecyl ester of β-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate; 1,3,5-trimethyl-2,4,6-tri (3) ,5-di-t-butyl-4-hydroxybenzyl)benzene or 1,3,5-indole (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 , 5-three At least one of -2,4,6-(1H,3H,5H)-trione.  The colored polypropylene fiber of claim 1, wherein the component b phosphite antioxidant is poly(dipropylene glycol) phenyl phosphite; bis (2,6-di-t-butyl-4- Methylphenyl) pentaerythritol diphosphate; tris(2,4-di-t-butylphenyl)phosphite; bis(2,4,6-tri-t-butylphenyl)nepentaerythritol Alcohol diphosphite; bismuth (2,4-di-t-butylphenol)-4,4'-biphenyl bisphosphite or 3,9-bisoctadecyloxy-2,4,8,10 At least one of tetraoxo-3,9-diphosphorylcyclo[5.5]undecane.   The colored polypropylene fiber of claim 1, wherein the component c hindered amine antioxidant is poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]- 1,3,5-three 2,4-[(2,2,6,6-tetramethyl-piperidinyl)imido]-1,6-extended hexyl[(2,2,6,6-tetramethyl-4-piperidin Iridinyl)imido]]; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); N ^I , N ^II , N ^III , N ^IV -肆(2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-three -6-yl)-4,7-diazanonane-1,10-diamine; bis(1-undecane-2,2,6,6-tetramethylpiperidin-4-yl) carbonate Or 1,3,5-three -2,4,6-triamine-N-N'''-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6,6-five Methyl-4-piperidinyl)amino]-1,3,5-triazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-five At least one of methyl-4-piperidinyl)].  A method for preparing colored polypropylene fibers of claim 1, characterized in that: polypropylene and component a hindered phenolic antioxidants and component b phosphite antioxidants and/or component c hindered amines The antioxidant is uniformly mixed and extruded and granulated to obtain a colored polypropylene mixture, and then the colored polypropylene mixture is melt-spun to obtain a colored polypropylene fiber, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added. The weight ratio of component b to component a is less than 0.80; when component c is added, component c is 4000 to 50000 ppm of the polypropylene mixture.