CN1488790A - Long-persistence/mminous polyamide fiber and preparing method thereof - Google Patents

Abstract

The present invention discloses a long-afterglow luminous polyamide fibre and its preparation method. The described long-afterglow luminous polyamide fibre is formed from polyamide fibre and alkaline earth aluminate which has luminous effective quantity and is activated by Eu (2+). The preparation method of said fibre includes the following steps: using luminous polyamide prepared by in-situ polymerization method as raw material, adopting conventional method to directly make melt spinning or co-mixing it with polyamide and making spinning so as to obtain the invented product long-afterglow luminous polyamide fibre. The fluorescent powder adopted by said invention is non-toxic, has no radioactivity, high luminous intensity, long afterglow time and stable chemical property.

Description

Light-emitting polyamide fiber of long fluorescent lag and its preparation method

Technical field

The present invention relates to a kind of polyamide fiber, be specifically related to a kind of long-persistence luminous fiber and preparation method thereof.

Technical background

Polyamide fiber is a kind of purposes synthetic fiber very widely, needs along with science and technology development and people's real life, polyamide fiber is had higher requirement, wherein, the long persistence luminous polyamide fiber be numerous scientific and technical personnel the research contents very paid close attention to.

Luminescent fibre can be used in different aspects according to the difference of luminous kind.Light-accumulated luminous fiber can be made easy suit, full dress, caution clothes, ornament, safety sign etc.The International Maritime conference is clearly stipulated: the relevant positions such as passage, fire-fighting equipment and safe life-saving facility on the passenger-cargo vessel more than staffing 25 people that produced later in 1998 must be provided with luminous safety sign, to ensure safety.The irradiation luminescent fibre can be used as the evening dress in anti-false sign, the dance hall etc.

The development technique of luminescent fibre and the development technique of phosphor are closely related, and the conventional fluorescent powder is because of poor stability, have shortcoming such as radioactivity and are difficult to use in exploitation luminescent fibre with practical value.Chemical stability is good, the Eu nontoxic, "dead", that brightness is high, persistence is long ²⁺The exploitation of the alkali earth metal aluminate fluorescent material that activates, a series of luminescent plastics that market prospects are arranged, rubber, coating, printing ink, fiber etc. are succeeded in developing in succession, and the long persistence luminous polyamide fiber yet there are no report.

Compare with other luminous high polymer material, the technology of preparing of fiber is had relatively high expectations to fluorescent material, so the difficulty of preparation technology of luminescent fibre is also bigger.Generally speaking, can be divided into three kinds of methods: (1) coating; (2) co-blended spinning method; (3) light emitting polymer direct spinning.

Patent CN1346857 discloses a kind of luminous coating composition, but by the coating composition that adhesive and luminescent fibre are formed, is used for the mark of object.Coating or method for printing are simple relatively, and applicable to multiple fiber and fabric, its shortcoming is to be easy to peel off, and service life is shorter.

The co-blended spinning method is the method for preparing luminescent fibre commonly used.Patent CN1081210 discloses a kind of manufacture method of luminous fibre at night, is to add 5～20% luminous agent to carry out spinning and prepare the luminous artificial fiber in the spinning viscose.Patent CN1374415 discloses a kind of manufacture method of RE luminous fiber, be in stated polyesters section, add luminous agent and nano assistant make the noctilucence master batch after with big bright PET chips co-blended spinning, but fibre strength is on the low side.Equally, patent US6162539 discloses a kind of method for preparing the high brightness fluorescent fiber, be with fluorescent RE powder and polyolefin blend as sandwich layer, polyolefin carries out composite spinning as cortex and prepares industrial luminous polyamide fiber.Japan Patent JP-A-7-300722 is that the method by composite spinning prepares luminescent fibre equally, and cortex is polyester, polycaprolactam or polyhexamethylene adipamide, but the fluorescent material moisture-sensitive of being added and influence its luminosity.

Summary of the invention

The technical issues that need to address of the present invention are to disclose a kind of Light-emitting polyamide fiber of long fluorescent lag and its preparation method, to overcome the above-mentioned defective that prior art exists, satisfy the demand of relevant department.

The said long persistence luminous polyamide fiber of the present invention is by the Eu of polyamide and luminous effective dose ²⁺The alkali earth metal aluminate that activates is formed, and preferred ingredients and weight percent content comprise: polyamide 70%～98%, Eu ²⁺The alkali earth metal aluminate 2%～30% that activates.

Said polyamide comprises a kind of in polyamide 6, polyamide 66, polyamide 46, polyamide 1010, polyamide 6 10. polyamide, 11. polyamide 12 or the polyamide 6 12;

Said Eu ²⁺The alkali earth metal aluminate that activates is the compound with following general structure:

M _XAl _YO _Z:Eu ²⁺，N ³⁺

Wherein: M represents a kind of among Sr, Ca, Mg or the Ba;

N represents a kind of among Dy, Nd or the Pr;

The integer of X=1～4;

The integer of Y=2～14;

The integer of Z=4～25;

Preferred Eu ²⁺The alkali earth metal aluminate that activates comprises SrAl ₂O ₄: Eu ²⁺, Dy ³⁺, Sr ₄Al ₁₄O ₂₅: Eu ²⁺, Dy ³⁺, CaAl ₂O ₄: Eu ²⁺, Nd ³⁺, BaAl ₂O ₄: Eu ²⁺, Pr ³⁺, MgAl ₂O ₄: Eu ²⁺, Nd ³⁺In a kind of;

The Eu that is addressed ²⁺The alkali earth metal aluminate that activates can adopt CN1212988 and CN1403533 patent or document (Chen Zhonglin. Wan Tizhi. Zhang Yuqi. Yan Dezhong, the illuminating engineering journal, 1999,10 (2), 35) disclosed method is prepared, also can adopt the commercially available prod, the trade mark of producing as Shanghai Yuelong New Material Co., Ltd. is the fluorescent material of YLAG.

The fiber of being addressed is drafted fibre or elastic filament, and filament number is 1.5～20dtex, fibre strength＞3.0cN/dtex.

Long persistence luminous polyamide fiber preparation method of the present invention comprises the steps:

With the luminous polyamide is raw material, adopts conventional method, directly carry out melt spinning or with polyamide blended back spinning, can obtain long persistence luminous polyamide fiber of the present invention.

Can preferably adopt following step to make fiber:

Luminous polyamide is carried out extracting, and melt spinning is carried out in dry back under 260～295 ℃, carries out drawing-off then or adds bullet, preparation luminous polyamide fiber;

Perhaps with the dried luminous polyamide of extracting by a certain percentage with the polyamide blended melt spinning that carries out of dried conventional fibre level, drawing-off or add bullet, preparation luminous polyamide fiber.

Can preferably adopt the luminous polyamide of situ aggregation method preparation, its architectural feature and preparation method thereof is at inventor's Chinese patent formerly, and application number is existing detailed description in 03142085.0, is summarized as follows:

Monomer of polyamide, auxiliary agent and water and the fluorescent material addressed are mixed, in inert atmosphere, under the pressure of normal pressure～2.0Mpa,, vacuumize then and continue reaction 0.2～1hr, promptly obtain long persistence luminous polyamide in 200～300 ℃ of reaction 2～8hr.

Said monomer of polyamide comprises caprolactam, adipic acid, hexamethylene diamine, decanedioic acid, decamethylene diamine, butanediamine, 11-aminoundecanoic acid, ten dicaprolactams, 12 diacid. one or more in polyamide fibre 66 salt, polyamide fibre 1010 salt or polyamide fibre 46 salt;

Said auxiliary agent comprises catalyst or/and stabilizing agent;

A kind of in preferred aminocaproic acid of said catalyst or the caprolactam;

A kind of in preferred adipic acid of said stabilizing agent or the decanedioic acid;

In the weight of monomer of polyamide, the addition of catalyst is 1～3%;

The addition of stabilizing agent is 0.1～0.6%;

The addition of water is 1～35%.

Advantage of the present invention is very significant, and the fluorescent material that (1) is adopted is Eu ²⁺The alkali earth metal aluminate series that activates, nontoxic, "dead", luminosity is high, persistence is long, and chemical property is stablized.And can develop the fiber of different emission wavelengths as required; (2) the prepared luminous polyamide of in-situ polymerization, the chemical bonding effect is arranged between fluorescent material and the polyamide, fluorescent material is uniformly dispersed, incrust, good spinnability, the luminous polyamide of (3) in-situ polymerization, molecular weight can be adjusted as required, the luminescent fibre of spinning different size, the fibre strength height; (4) compare with other fibrous material, polyamide fiber is widely used in fields such as decoration, clothes, fishery, industry, thereby the luminous polyamide fiber has application promise in clinical practice.

The specific embodiment

Embodiment 1

The preparation of long afterglow daiamid-6 fiber

Raw material: caprolactam 190.4g

Aminocaproic acid 4.00g

Adipic acid 0.5g

Distilled water 6.00ml

Fluorescent material: CaAl ₂O ₄: Eu ²⁺, Dy ³⁺10.36g, average grain diameter: $\stackrel{\‾}{D_{50}}=18.5\mathrm{\μm}$

The preparation method:

(1) above-mentioned raw materials is added in the reactor, mix, logical nitrogen protection slowly is heated to 140 ℃, stirs, and slowly is warming up to 250 ℃, behind the isothermal reaction 5hr, vacuumizes and continues 0.5hr, obtains luminous polyamide 6.

(2) luminous polyamide 6 in the step (1) is carried out extracting 0.5hr in boiling water, dry after the taking-up, in vacuum drying chamber, descend dry 18hr in 95 ℃.

(3) dried luminous polyamide 6 is sent into the screw extruder fusion, 275 ℃ of following spinning of spinning temperature, spinning speed is 1200m/min, stretches then, the draw ratio ratio is 3.3 times.

The result: luminous polyamide 6 drawn yarn specifications, 100dtex/20f, intensity 3.8cN/dtex, emission wavelength 420～440nm behind the illumination 10min, in the dark places 2hr, and after-glow brightness is 1.06mcd/m ²

Embodiment 2

The preparation of long afterglow daiamid-6 fiber

Raw material: caprolactam 190.4g

Aminocaproic acid 4.00g

Adipic acid 0.5g

Distilled water 6.00ml

Fluorescent material: SrAl ₂O ₄: Eu ²⁺, Dy ³⁺31.08g, average grain diameter: $\stackrel{\‾}{D_{50}}=2.5\mathrm{\μm}$

Polyamide 66 600g, molecular weight 12000

The preparation method:

(1) add caprolactam, aminocaproic acid, adipic acid, distilled water in the reactor according to the above ratio; mix, logical nitrogen protection slowly is heated to 140 ℃; stir; slowly be warming up to 210 ℃, behind the reaction 1hr, add fluorescent material; continue to be warming up to 250 ℃; behind the isothermal reaction 4.5hr, vacuumize and continue 0.5hr, obtain luminous polyamide 6.

(2) luminous polyamide 6 in the step (1) is carried out extracting 0.5hr in boiling water, dry after the taking-up, in vacuum drying chamber, descend dry 18hr in 95 ℃.

(3) get polyamide 6 600g, in vacuum drying chamber, descend dry 18hr in 95 ℃, with send into the screw extruder fusion after luminous polyamide 6 blend in the step (2), 280 ℃ of following spinning of spinning temperature, spinning speed is 3000m/min, add bullet at false twisting machine then, 1.6 times of draw ratios, preparation drawn yarn.

The result: luminous polyamide 6 drawn yarn specifications, 167dtex/72f, intensity 4.1cN/dtex, emission wavelength 515～525nm behind the illumination 10min, in the dark places 2hr, and after-glow brightness is 1.23mcd/m ²

Embodiment 3

The preparation of long persistence luminous polyamide 66 fibers

Raw material: PA66 salt 200g

Adipic acid 1.80g

Caprolactam 4.00g

Distilled water 60g

Fluorescent material: SrAl ₁₄O ₂₅: Eu ²⁺, Dy ³⁺40g, average grain diameter: $\stackrel{\‾}{D_{50}}=8.5\mathrm{\μm}$

The preparation method:

(1) above-mentioned raw materials is added in the autoclave, mix, logical N ₂Drive away air, airtight, slowly be heated to 210 ℃, reaction 2hr, stirring continues slowly to be warming up to 270 ℃, and controlled pressure 1.47～1.96Mpa behind the continuation reaction 2hr, is released into normal pressure, after continuing to react 3hr, vacuumizes and continues to react 0.5hr, obtains polyamide 66.

(2) luminous polyamide 66 in the step (2) is carried out extracting 15min in boiling water, dry after the taking-up, in vacuum drying chamber, descend dry 16hr in 90 ℃.

(3) dried luminous polyamide 66 is sent into the screw extruder melt spinning, 290 ℃ of following spinning of spinning temperature, spinning speed is 2000m/min, 3.0 times of draw ratios.

The result: luminous polyamide 66 drawn yarn specification 200dtex/10f, intensity 4.08cN/dtex, emission wavelength 485～495nm behind the illumination 10min, in the dark places 2hr, and after-glow brightness is 1.52mcd/m ²

Embodiment 4

The preparation of long persistence luminous polyamide 66 fibers

Raw material: PA66 salt 200g

Adipic acid 1.80g

Caprolactam 4.00g

Distilled water 60g

Fluorescent material: SrAl ₂O ₄: Eu ²⁺, Dy ³⁺50g, average grain diameter: $\stackrel{\‾}{D_{50}}=5.25\mathrm{\μm}$

Polyamide 66,200g, molecular weight 13800

The preparation method:

(1) PA66 salt, adipic acid, caprolactam, distilled water, fluorescent material in the above-mentioned raw materials are added in the autoclave, mix, logical N ₂Drive away air, airtight, slowly be heated to 210 ℃, reaction 2hr, stirring continues slowly to be warming up to 270 ℃, and controlled pressure 1.47～1.96Mpa behind the continuation reaction 2hr, is released into normal pressure, after continuing to react 3hr, vacuumizes and continues to react 0.5hr, obtains polyamide 66.

(2) luminous polyamide 66 in the step (1) is carried out extracting 15min in boiling water, dry after the taking-up, in vacuum drying chamber, descend dry 16hr in 90 ℃.

(3) get polyamide 66 200g, in vacuum drying chamber in 90 ℃ of following dry 16hr, then with step (2) in luminous polyamide 66 blend, send into the screw extruder melt spinning, 295 ℃ of following spinning of spinning temperature, spinning speed is 1200m/min, 3.3 times of draw ratios.

The result: luminous polyamide 66 drawn yarn specification 60dtex/24f, intensity 4.25cN/dtex, emission wavelength 515～525nm behind the illumination 10min, in the dark places 2hr, and after-glow brightness is 1.38mcd/m ²

Claims (9)

1. a long persistence luminous polyamide fiber is characterized in that, by the Eu of polyamide and luminous effective dose ²⁺The alkali earth metal aluminate that activates is formed.

2. long persistence luminous polyamide fiber according to claim 1 is characterized in that, component and weight percent content comprise: polyamide 80%～95%, Eu ²⁺The alkali earth metal aluminate 5%～20% that activates.

3. long persistence luminous polyamide fiber according to claim 1, it is characterized in that said polyamide comprises a kind of in polyamide 6, polyamide 66, polyamide 46, polyamide 1010, polyamide 6 10, polyamide 11, polyamide 12 or the polyamide 6 12;

Said Eu ²⁺The alkali earth metal aluminate that activates is the compound with following general structure:

M _XAl _YO _Z:Eu ²⁺，N ³⁺

Wherein: M represents a kind of among Sr, Ca, Mg or the Ba;

N represents a kind of among Dy, Nd or the Pr;

The integer of X=1～4;

The integer of Y=2～14;

The integer of Z=4～25.

4. long persistence luminous polyamide fiber according to claim 1 is characterized in that, preferred Eu ²⁺The alkali earth metal aluminate that activates comprises SrAl ₂O ₄: Eu ²⁺, Dy ³⁺, Sr ₄Al ₁₄O ₂₅: Eu ²⁺, Dy ³⁺, CaAl ₂O ₄: Eu ²⁺, Nd ³⁺, BaAl ₂O ₄: Eu ²⁺, Pr ³⁺, MgAl ₂O ₄: Eu ²⁺, Nd ³⁺In a kind of.

5. according to each described long persistence luminous polyamide fiber of claim 1～4, it is characterized in that the fiber of being addressed is drafted fibre or elastic filament, filament number is 1.5～20dtex.

6. according to each described long persistence luminous polyamide fiber preparation method of claim 1～5, it is characterized in that, comprise the steps:

With the luminous polyamide is raw material, directly carry out melt spinning or with the spinning of polyamide blended back, can obtain long persistence luminous polyamide fiber of the present invention.

7. long persistence luminous polyamide fiber preparation method according to claim 6 is characterized in that, adopts the luminous polyamide of situ aggregation method preparation.

8. according to claim 6 or 7 described long persistence luminous polyamide fiber preparation method, it is characterized in that, luminous polyamide is carried out extracting, melt spinning is carried out in dry back under 260～295 ℃, carries out drawing-off then or adds bullet, preparation luminous polyamide fiber.

9. according to claim 6 or 7 described long persistence luminous polyamide fiber preparation method, it is characterized in that, with the dried luminous polyamide of extracting by a certain percentage with the polyamide blended melt spinning that carries out of dried conventional fibre level, drawing-off or add bullet, preparation luminous polyamide fiber.