CN1189605C - Process for manufacturing dyeable polypropylene - Google Patents

Abstract

The present invention relates to a preparation method for dyeable polypropylene fiber. The method adds a dyeing additive into common fibre-grade polypropylene resin, and the dyeable polypropylene fiber is manufactured through the technological processes of blending melt spinning, draft, crimp and heat setting; the content of the dyeing additive in spinning raw material is from 8 to 12%, and the spinning temperature is from 230 to 290 DEG C; the present invention is characterized in that filament tow is in the processes of the draft and the heat setting; the first draft temperature is from 80 to 90 DEG C, the second draft temperature is from 25 to 60 DEG C, the heat setting temperature is from 120 to 140 DEG C, and the heat setting time is from 7 to 15 min. Compared with the prior art, the present invention has the advantages that manufactured polypropylene fiber can be dyed by cationic dye in a boiling mode under ordinary pressure, the dye-uptake is higher and can commonly reach more than 70 %, and the color fastness reaches more than 4 levels.

Description

The manufacture method of dyeable polypropylene

Technical field

The present invention relates to the manufacture method of dyeable polypropylene, particularly improve additive, make the manufacture method of dyeable polypropylene through blend melt spinning by in general fibre grade polypropylene resin, adding dyeing.

Background technology

Polypropylene fibre have light specific gravity, intensity height, warmth retention property good, breathe freely, lead moist good, plurality of advantages such as chemical resistance is strong, and it is abundant, cheap to make raw material sources, development in recent years is rapid, its Application Areas also constantly enlarges.But because crystalling propylene degree height, structure is tight, and does not have the polar group that can combine with dye molecule on the strand, promptly lacks and dyes seat, so that can't dye with the method for routine.Usually people adopt original liquid coloring or Masterbatch method of colouring to make the colored fibre of heavy colour, but this can have high dyeing flexibility and color diversity not as fiber or fabric printing after all, is subjected to people's attention deeply so improve the dyeability of polypropylene fibre always.

In the prior art, be the method for improving the polypropylene fibre dyeability comparatively commonly used with blending modification method.It will have the dyeing group on the molecule, and can be well be incorporated in the polypropylene with the coloration additive of acrylic resin blended melting and goes, and carries out blend melt spinning then.This method is easy to implement technically, and less to the mechanical property influence of fiber.Propose acrylic resin and a certain amount of mylar blend melt spinning are made dyeable polypropylene as the flat 6-25912 of Japanese Patent Application Laid-Open.CN93114967.3, CN96105290 etc. have all proposed a kind of coloration additive and acrylic resin to be carried out blend melt spinning, and the fiber that makes has good dyeability.But the prepared dyeable polypropylene of these existent method, its good dyeability normally realizes with disperse dyeing, with cationic dyeing and have the but rare report of higher dye-uptake, and we know no matter cation dyes all are better than DISPERSE DYES from the vividness of color, the diversity and the COLOR FASTNESS of color.

Summary of the invention

Technical problem to be solved by this invention provides a kind of manufacture method of dyeable polypropylene, improve additive by in the plain polypropylene resin, adding dyeing, through blend melt spinning, make the dyeable polypropylene that can adopt cationic dyeing and have higher dye-uptake.

Below be the technical scheme that the present invention solves the problems of the technologies described above:

A kind of manufacture method of dyeable polypropylene, this method adopts in the general fibre grade polypropylene resin and adds coloration additive, through blend melt spinning, drawing-off, curling, heat setting process process manufacturing dyeable polypropylene, the content of coloration additive is 8～12% in the spinning material, spinning temperature is 230～290 ℃, and tow is in drawing-off and HEAT SETTING process, and the first road drawing temperature is 80～90 ℃; The second road drawing temperature is 25～60 ℃, is preferably 30～40 ℃; Heat setting temperature is 120～140 ℃, and heat-setting time is 7～15min.

Above-mentioned coloration additive adopt usually between terephthalic acid (TPA), 5-sulfonic acid alkali metal salts (to) copolymer that rutgers and ethylene glycol copolymerization form, its inherent viscosity [η] is generally 0.3～0.5dL/g, fusing point is 200～250 ℃.

Spinning speed is decided by the spinneret hole count, and when spinneret was 30000～60000 holes, spinning speed was 80～150m/min; When spinneret was 1000～4000 holes, spinning speed was 500～2600m/min.

As everyone knows, structure closely and do not have the polar group that can combine with dye molecule on the strand or lack that to dye seat be two main causes that influence the polypropylene fibre dyeability.Blending modification method has solved well and has dyed the problem that seat lacks in the polypropylene, but because the polypropylene structure closely mainly is that it has due to the higher degree of crystallinity, though it is very simple and easy reducing polyacrylic degree of crystallinity by adjustment spinning aftertreatment technology, the reduction of degree of crystallinity certainly will influence the physical and mechanical property of fiber.

In fact, impact polypropylene structure tightness degree be not only polyacrylic degree of crystallinity, also with the crystalline region in crystal grain big or small directly related, under the identical prerequisite of degree of crystallinity, crystal grain is more little, structure is tight more, its principle is very similar to bulk density.Also can find by test, change polypropylene crystalline region crystallite dimension in the polypropylene fibre by changing heat treatment temperature, and along with crystallite dimension becomes big, the dye-uptake of fiber be the trend of obvious rising.This is because the increase of crystallite dimension increases the free volume of fibrous inside, thereby helps the infiltration and the diffusion of dye molecule.Therefore, crystallite dimension is big more, and the dyeability of fiber is good more.Yet as long as degree of crystallinity is constant, the variation of crystallite dimension does not produce significantly influence to the physical and mechanical property of fiber.The technology that traditional blending modification method adopts in the last handling process of spinning is identical with conventional polypropylene spinning, and this perhaps is in order to guarantee the physical and mechanical property of fiber, and common first road and the second road drawing temperature are 80～90 ℃; Heat setting temperature is 90～110 ℃, and heat-setting time is 2～3min.Key of the present invention has been to adjust the technological parameter of fiber when drawing-off and HEAT SETTING, makes polyacrylic crystallization mainly occur in the HEAT SETTING process.Polyacrylic best crystallization temperature is 100～110 ℃, and sneaking into of coloration additive destroyed macromolecular compound with regular structure in the fiber to a certain extent, so its best crystallization temperature rises to 120～140 ℃.Raising heat setting temperature and time not only make polyacrylic degree of crystallinity increase, and more help the rising of crystalline rate, and this will make nucleus have adequate time to grow up into the crystal grain of large-size under high relatively temperature.Just because of this, compared with prior art, the polypropylene fibre that the present invention makes can boil under normal pressure with cation dyes and dye, and has higher dye-uptake, generally can reach more than 70%, and COLOR FASTNESS reaches more than 4 grades.

The specific embodiment

To enumerate some embodiment below and come further details of the present invention to be described, in an embodiment, the method for testing of the dye-uptake of fiber and the definition of dye-uptake are as follows.

Method of testing:

Instrument: sample dyeing machine, 721 type spectrophotometers;

Reagent: peacock green, cation dyes (yellow 8GL, red 5GN, blue RL), acetic acid;

The dye liquor preparation: bath raio is 1: 100; The consumption of 1g fiber is 0.2% peacock green or cation dyes 5ml, is equipped with deionized water 95ml, and pH value is 4.5～5.5;

Dyeing condition: go into to dye for 70 ℃, be heated to 100 ℃ in 20 minutes, boil and dye 40 minutes, stop heating and kept 30 minutes, take out sample and be cooled to the room temperature after washing;

The mensuration of dyeing residual liquid optical density: get the 20ml dyeing residual liquid, merge the back with the stained specimens water lotion and move into volumetric flask, with its optical density of spectrophotometric instrumentation;

The mensuration of dyeing stoste optical density: get 20ml dyeing stoste, the deionized water dilution of immigration volumetric flask with stained specimens water lotion same amount is with its optical density of spectrophotometric instrumentation.

[embodiment 1～8]

Coloration additive be between terephthalic acid (TPA), 5-sulfonic acid alkali metal salts (to) copolymer that rutgers and ethylene glycol copolymerization form, inherent viscosity [η] is 0.3～0.5dL/g, fusing point is 200～250 ℃.Coloration additive is sneaked into common acrylic resin after metering units is in required ratio metering, lacking melt spinning on the thread spinning plant then, produce polypropylene short fiber, its specification is 2.78dtex * 67mm (55000 hole) (embodiment 1～4) and 5.56dtex * 102mm (30000 hole) (embodiment 5～8).Spinning temperature is 230～290 ℃, and spinning speed is 80～120m/min, and the cooling wind-warm syndrome is 18～23 ℃.Carry out the first road drawing-off, the second road drawing-off behind the fiber cooling forming successively, curl, operations such as HEAT SETTING, cut-out and packing.The temperature of coloration additive content, the first road drawing-off and the second road drawing-off in each embodiment spinning material, heat set conditions sees Table 1, and the performance of fiber sees Table 2.

Table 1.

	Coloration additive content (wt%)	One drawing temperature (℃)	Two road drawing temperatures (℃)	Heat setting temperature (℃)	Heat-setting time (min)
						Embodiment 1	8	80	25	120	15
Embodiment 2	10	85	30	125	13
						Embodiment 3	10	85	30	130	13
Embodiment 4	11	87	36	130	10
						Embodiment 5	11	87	36	135	10
Embodiment 6	12	87	40	130	7
						Embodiment 7	12	87	40	140	7
Embodiment 8	12	90	60	140	7

Table 2.

	Dye-uptake (%)				Fracture strength (CN/dtex)
						Cationic yellow 8GL	Cationic red 5GN	Cationic blue RL	Peacock green
	Embodiment 1	70.6	71.2	72.6						75.5	2.85
Embodiment 2					72.5	73.8	75.0	78.2	3.10
	Embodiment 3	74.7	76.0	77.3						80.6	3.32
Embodiment 4					75.2	78.5	80.0	82.0	3.28
	Embodiment 5	78.9	81.3	82.5						83.7	3.46
Embodiment 6					80.1	82.7	83.6	86.5	3.25
	Embodiment 7	86.8	88.9	90.0						95.0	3.63
Embodiment 8					86.7	89.1	90.2	95.0	3.60

Claims (4)

1, a kind of manufacture method of dyeable polypropylene, this method adopts in the general fibre grade polypropylene resin and adds coloration additive, through blend melt spinning, drawing-off, curl, the heat setting process process is made dyeable polypropylene, the content of coloration additive is 8～12% in the spinning material, coloration additive is a terephthalic acid (TPA), between the 5-sulfonic acid alkali metal salts (to) copolymer that forms of rutgers and ethylene glycol copolymerization, the inherent viscosity of this copolymer [η] is 0.3～0.5dL/g, the fusing point of copolymer is 200～250 ℃, spinning temperature is 230～290 ℃, it is characterized in that tow in drawing-off and HEAT SETTING process, the first road drawing temperature is 80～90 ℃; The second road drawing temperature is 25～60 ℃; Heat setting temperature is 120～140 ℃, and heat-setting time is 7～15min.

2, the manufacture method of dyeable polypropylene according to claim 1 is characterized in that the described second road drawing temperature is 30～40 ℃.

3, the manufacture method of dyeable polypropylene according to claim 1 is characterized in that described spinneret is 30000～60000 holes, and spinning speed is 80～150m/min.

4, the manufacture method of dyeable polypropylene according to claim 1 is characterized in that described spinneret is 1000～4000 holes, and spinning speed is 500～2600m/min.